锂离子电池基础科学问题(Ⅺ)----锂空气电池与锂硫电池

doi:10.3969/j.issn.2095-4239.2014.05.012

摘要/Abstract

摘要： 提高能量密度是可充放锂电池研发最重要的目标.近年来,锂硫电池与锂空气电池由于具有高的理论能量密度而受到广泛关注,这两种电池仍然面临较多的科学与技术问题,处于电池开发早期研究阶段.在本文中,重点介绍了锂空气电池的基本工作原理,基本结构组成,所面临的问题和两种特殊体系的锂空气电池, 同时简要介绍了锂硫电池.

关键词: 可充放金属锂电池, 锂空气电池, 锂硫电池

Abstract: In recent years, rechargeable nonaqueous lithium air battery has attracted wide attention due to its very high theoretical energy density. However, it is at early stage of research because there are still many challenges for developing lithium air battery. In this paper, the concept, structures, challenges of lithium air battery and two special types of lithium air batteries are briefly summarized. In addition, the lithium sulfur battery which also belongs to rechargeable lithium metal battery and has high energy density was introduced.

Key words: rechargeable lithium metal batteries, lithium air battery, lithium sulfur battery

中图分类号:

O646.21

彭佳悦, 刘亚利, 黄杰, 李泓. 锂离子电池基础科学问题(Ⅺ)----锂空气电池与锂硫电池[J]. 储能科学与技术, 2014, 3(5): 526-543.

PENG Jiayue, LIU Yali, HUANG Jie, LI Hong. Fundamental scientific aspects of lithium ion batteries(Ⅺ)--Lithium air and lithium sulfur batteries[J]. Energy Storage Science and Technology, 2014, 3(5): 526-543.

参考文献

[1] Barber W A,Feldman A M,Fraioli A V. Composite paper electrode for a voltaic cell:US,3551205A[P/OL]. 1970-12-29. http://www.google.com/patents/US3551205.
[2] Moser J R,Schneider A A. Primary cells and iodine containing cathodes therefor:US,3674562A[P/OL]. 1972-07-04. http://www.google.com/ patents/US3674562.
[3] Weast R. The Redox Potentials Against the Standard Hydrogen Electrode (SHE) for Various Reactions, Usually Called "Electrochemical Series"//Handbook of Chemistry and Physics [M]. 51st ed. Boca Raton:CRC Press Inc.,1970.
[4] Rauh R D,Brummer S B. Effect of additives on lithium cycling in propylene carbonate[J]. Electrochimica Acta ,1977,22(1): 75-83.
[5] Newman G H,Francis R W,Gaines L H, et al . Hazard investigations of LiClO 4 -dioxolane electrolyte[J]. Journal of the Electrochemical Society ,1980,127(9):2025-2027.
[6] Nishi Y,Azuma H,Omaru A. Non aqueous electrolyte cell:US,4959281A[P/OL]. 1990-09-25. http://www.google. com/patents/US4959281.
[7] Girishkumar G,Mccloskey B,Luntz A C, et al . Lithium-air battery:Promise and challenges[J]. Journal of Physical Chemistry Letters ,2010,1(14):2193-2203.
[8] Abraham K M,Jiang Z. A polymer electrolyte-based rechargeable lithium/oxygen battery[J]. Journal of the Electrochemical Society ,1996,143(1):1-5.
[9] Read J. Ether-based electrolytes for the lithium/oxygen organic electrolyte battery[J]. Journal of the Electrochemical Society ,2006,153(1):A96-A100.
[10] Ogasawara T,Debart A,Holzapfel M, et al . Rechargeable Li 2 O 2 electrode for lithium batteries[J]. Journal of the American Chemical Society ,2006,128(4):1390-1393.
[11] Visco S J,Katz B D,Nimon Y S, et al. Prevents the active metal from deleterious reaction with the environment on the other (cathode) side of the impervious layer, which may include aqueous or non-aqueous liquid electrolytes (catholytes) and/or a variety electrochemically active materials, including liquid, solid and gaseous oxidizers:US,2005175894-A1[P/OL]. 2005-08-11. http://www.google.com/patents/US20050175894.
[12] Kowalczk I,Read J,Salomon M. Li-air batteries:A classic example of limitations owing to solubilities[J]. Pure and Applied Chemistry ,2007,79(5):851-860.
[13] Kumar B,Kumar J,Leese R, et al . A solid-state, rechargeable, long cycle life lithium-air battery[J]. Journal of the Electrochemical Society ,2010,157(1):A50-A54.
[14] Wang Y,Zhou H. A lithium-air battery with a potential to continuously reduce O 2 from air for delivering energy[J]. Journal of Power Sources ,2010,195(1):358-361.
[15] Peng Z,Freunberger S A,Hardwick L J, et al . Oxygen reactions in a non-aqueous Li + electrolyte[J]. Angewandte Chemie-International Edition ,2011,50(28):6351-6355.
[16] McCloskey B D,Scheffler R,Speidel A, et al . On the mechanism of nonaqueous LiO 2 electrochemistry on C and its kinetic overpotentials:Some implications for Li-air batteries[J]. Journal of Physical Chemistry C ,2012,116(45):23897-23905.
[17] Laoire C O,Mukerjee S,Plichta E J, et al . Rechargeable lithium/TEGDME-LiPF 6 /O 2 battery[J]. Journal of the Electrochemical Society ,2011,158(3):A302-A308.
[18] Lu Y C,Gallant B M,Kwabi D G, et al . Lithium-oxygen batteries:Bridging mechanistic understanding and battery performance[J]. Energy & Environmental Science ,2013,6(3):750-768.
[19] Bruce P G,Freunberger S A,Hardwick L J, et al . LiO 2 and LiS batteries with high energy storage[J]. Nature Materials ,2012,11(1):19-29.
[20] Zu C X,Li H. Thermodynamic analysis on energy densities of batteries[J]. Energy & Environmental Science ,2011,4(8):2614-2624.
[21] Peng Jiayue(彭佳悦),Zu Chenxi(祖晨曦),Li Hong(李泓). Fundamental scientific aspects of lithium batteries(I) Thermodynamic calculations of theoretical energy densities of chemical energy storage systems[J]. Energy Storage Science and Technology (储能科学与技术),2013,2(1):55-62.
[22] Guo Xiangxin(郭向欣),Huang Shiting(黄诗婷),Zhao Ning(赵宁),Cui Zhonghui(崔忠慧),Fan Wugang(范武刚),Li Chilin(李驰麟),Li Hong(李泓). Rapid development and critical issues of secondary lithium-air batteries[J]. Journal of Inorganic Materials (无机材料学报),2014,29(2):113-123.
[23] Lu J,Li L,Park J B, et al . Aprotic and aqueous LiO 2 batteries[J]. Chemical Reviews ,2014,114(11):5611-5640.
[24] Xu K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries[J]. Chem. Rev. ,2004,104(10):4303-4317.
[25] Aurbach D,Gofer Y,Langzam J. The correlation between surface-chemistry, surface-morphology, and cycling efficiency of lithium electrodes in a few polar aprotic systems[J]. Journal of the Electrochemical Society ,1989,136(11):3198-3205.
[26] Aurbach D,Daroux M,Faguy P, et al . The electrochemistry of noble-metal electrodes in aprotic organic-solvents containing lithium-salts[J]. Journal of Electroanalytical Chemistry ,1991,297(1):225-244.
[27] Mizuno F,Nakanishi S,Kotani Y, et al . Rechargeable Li-air batteries with carbonate-based liquid electrolytes[J]. Electrochemistry ,2010,78(5):403-405.
[28] Zhang Z,Lu J,Assary R S, et al . Increased stability toward oxygen reduction products for lithium-air batteries with oligoether-functionalized silane electrolytes[J]. The Journal of Physical Chemistry C ,2011,115(51):25535-25542.
[29] Xu W,Xu K,Viswanathan V V, et al . Reaction mechanisms for the limited reversibility of LiO 2 chemistry in organic carbonate electrolytes[J]. Journal of Power Sources ,2011,196(22):9631-9639.
[30] Xu W,Viswanathan V V,Wang D, et al . Investigation on the charging process of Li 2 O 2 -based air electrodes in LiO 2 batteries with organic carbonate electrolytes[J]. Journal of Power Sources ,2011,196(8):3894-3899.
[31] McCloskey B D,Bethune D S,Shelby R M, et al . Solvents' critical role in nonaqueous lithium-oxygen battery electrochemistry[J]. The Journal of Physical Chemistry Letters ,2011,2(10):1161-1166.
[32] Freunberger S A,Chen Y,Peng Z, et al . Reactions in the rechargeable LiO 2 battery with alkyl carbonate electrolytes[J]. Journal of the American Chemical Society ,2011,133(20):8040-8047.
[33] Bryantsev V S,Giordani V,Walker W, et al . Predicting solvent stability in aprotic electrolyte Li-air batteries:Nucleophilic substitution by the superoxide anion radical(O2 • - )[J]. Journal of Physical Chemistry A ,2011,115(44):12399-12409.
[34] Bryantsev V S,Blanco M. Computational study of the mechanisms of superoxide-induced decomposition of organic carbonate-based electrolytes[J]. The Journal of Physical Chemistry Letters ,2011,2(5):379-383.
[35] Peng Z,Freunberger S A,Hardwick L J, et al . Oxygen reactions in a non-aqueous Li + electrolyte[J]. Angewandte Chemie International Edition ,2011,50(28):6351-6355.
[36] Xu D,Wang Z L,Xu J J, et al . Novel DMSO-based electrolyte for high performance rechargeable LiO 2 batteries[J]. Chemical Communications ,2012,48(55):6948-6950.
[37] Lu Y C,Kwabi D G,Yao K P C, et al . The discharge rate capability of rechargeable LiO 2 batteries[J]. Energy & Environmental Science ,2011,4(8):2999-3007.
[38] Xu W,Hu J,Engelhard M H, et al . The stability of organic solvents and carbon electrode in nonaqueous LiO 2 batteries[J]. Journal of Power Sources ,2012,215:240-247.
[39] Assary R S,Curtiss L A,Redfern P C, et al . Computational studies of polysiloxanes:Oxidation potentials and decomposition reactions[J]. The Journal of Physical Chemistry C ,2011,115(24):12216-12223.
[40] Assary R S,Lau K C,Amine K, et al . Interactions of dimethoxy ethane with Li 2 O 2 clusters and likely decomposition mechanisms for LiO 2 batteries[J]. The Journal of Physical Chemistry C ,2013,117(16):8041-8049.
[41] Bryantsev V S,Faglioni F. Predicting autoxidation stability of ether- and amide-based electrolyte solvents for Li-air batteries[J]. The Journal of Physical Chemistry A ,2012,116(26):7128-7138.
[42] Hsu C W,Chen P,Ting J M. Microwave-assisted hydrothermal synthesis of TiO 2 mesoporous beads having C and/or N doping for use in high efficiency all-plastic flexible dye-sensitized solar cells[J]. Journal of the Electrochemical Society ,2013,160(3):H160-H165.
[43] Mccloskey B D,Scheffler R,Speidel A, et al . On the efficacy of electrocatalysis in nonaqueous LiO 2 batteries[J]. Journal of the American Chemical Society ,2011,133(45):18038-18041.
[44] McCloskey B D,Bethune D S,Shelby R M, et al . Limitations in rechargeability of LiO 2 batteries and possible origins[J]. Journal of Physical Chemistry Letters ,2012,3(20):3043-3047.
[45] Xu W,Xiao J,Zhang J, et al . Optimization of nonaqueous electrolytes for primary lithium/air batteries operated in ambient environment[J]. Journal of the Electrochemical Society ,2009,156(10):A773-A779.
[46] Black R,Oh S H,Lee J H, et al . Screening for superoxide reactivity in LiO 2 batteries:Effect on Li 2 O 2 /LiOH crystallization[J]. Journal of the American Chemical Society ,2012,134(6):2902-2905.
[47] Jung H G,Hassoun J,Park J B, et al . An improved high-performance lithium-air battery[J]. Nature Chemistry ,2012,4(7):579-585.
[48] Shui J L,Okasinski J S,Kenesei P, et al . Reversibility of anodic lithium in rechargeable lithium-oxygen batteries[J]. Nature Communications ,2013,4:2255.
[49] Zhang L,Zhang S,Zhang K, et al . Mesoporous NiCo 2 O 4 nanoflakes as electrocatalysts for rechargeable LiO 2 batteries[J]. Chemical Communications ,2013,49(34):3540-3542.
[50] Xu J J,Xu D,Wang Z L, et al . Synthesis of perovskite-based porous La 0.75 Sr 0.25 MnO 3 nanotubes as a highly efficient electrocatalyst for rechargeable lithium-oxygen batteries[J]. Angewandte Chemie International Edition ,2013,52(14):3887-3890.
[51] Lei Y,Lu J,Luo X, et al . Synthesis of porous carbon supported palladium nanoparticle catalysts by atomic layer deposition:Application for rechargeable LiO 2 battery[J]. Nano Letters ,2013,13(9):4182-4189.
[52] Freunberger S A,Chen Y,Drewett N E, et al . The lithium-oxygen battery with ether-based electrolytes[J]. Angewandte Chemie International Edition ,2011,50(37):8609-8613.
[53] Jung H G,Kim H S,Park J B, et al . A transmission electron microscopy study of the electrochemical process of lithium-oxygen cells[J]. Nano Letters ,2012,12(8):4333-4335.
[54] Laoire C O,Mukerjee S,Abraham K M, et al . Influence of nonaqueous solvents on the electrochemistry of oxygen in the rechargeable lithium-air battery[J]. The Journal of Physical Chemistry C ,2010,114(19):9178-9186.
[55] Lopez N,Graham D J,Mcguire R, et al . Reversible reduction of oxygen to peroxide facilitated by molecular recognition[J]. Science ,2012,335(6067):450-453.
[56] Sun B,Zhang J,Munroe P, et al . Hierarchical NiCo 2 O 4 nanorods as an efficient cathode catalyst for rechargeable non-aqueous LiO 2 batteries[J]. Electrochemistry Communications ,2013,31:88-91.
[57] Trahan M J,Mukerjee S,Plichta E J, et al . Studies of Li-air cells utilizing dimethyl sulfoxide-based electrolyte[J]. Journal of the Electrochemical Society ,2013,160(2):A259-A267.
[58] Chen Y,Freunberger S A,Peng Z, et al . LiO 2 battery with a dimethylformamide electrolyte[J]. Journal of the American Chemical Society ,2012,134(18):7952-7957.
[59] Walker W,Giordani V,Uddin J, et al . A rechargeable LiO 2 battery using a lithium nitrate/ N , N -dimethylacetamide electrolyte[J]. Journal of the American Chemical Society ,2013,135(6):2076-2079.
[60] Allen C J,Mukerjee S,Plichta E J, et al . Oxygen electrode rechargeability in an ionic liquid for the Li-air battery[J]. The Journal of Physical Chemistry Letters ,2011,2(19):2420-2424.
[61] Peng Z,Freunberger S A,Chen Y, et al . A reversible and higher-rate LiO 2 battery[J]. Science ,2012,337(6094):563-566.
[62] Cecchetto L,Salomon M,Scrosati B, et al . Study of a Li-air battery having an electrolyte solution formed by a mixture of an ether-based aprotic solvent and an ionic liquid[J]. Journal of Power Sources ,2012,213:233-238.
[63] Xie B,Lee H S,Li H, et al . New electrolytes using Li 2 O or Li 2 O 2 oxides and tris (pentafluorophenyl) borane as boron based anion receptor for lithium batteries[J]. Electrochemistry Communications ,2008,10(8):1195-1197.
[64] Zheng D,Lee H S,Yang X Q, et al . Electrochemical oxidation of solid Li 2 O 2 in non-aqueous electrolyte using peroxide complexing additives for lithium-air batteries[J]. Electrochemistry Communications ,2013,28:17-19.
[65] Xu W,Xiao J,Wang D, et al . Effects of nonaqueous electrolytes on the performance of lithium/air batteries[J]. Journal of the Electrochemical Society ,2010,157(2):A219-A224.
[66] Chen Y,Freunberger S A,Peng Z, et al . Charging a LiO 2 battery using a redox mediator[J]. Nature Chemistry ,2013,5(6):489-494.
[67] Lim H D,Song H,Kim J, et al . Superior rechargeability and efficiency of lithium-oxygen batteries:Hierarchical air electrode architecture combined with a soluble catalyst[J]. Angewandte Chemie ,2014,53(15):3926-3931.
[68] Xiao J,Mei D,Li X, et al . Hierarchically porous graphene as a lithium-air battery electrode[J]. Nano Letters ,2011,11(11):5071-5078.
[69] Zhang S S,Foster D,Read J. Discharge characteristic of a non-aqueous electrolyte Li/O 2 battery[J]. Journal of Power Sources ,2010,195(4):1235-1240.
[70] Xiao J,Wang D,Xu W, et al . Optimization of air electrode for Li/air batteries[J]. Journal of the Electrochemical Society ,2010,157(4):A487-A492.
[71] Yang X H,He P,Xia Y Y. Preparation of mesocellular carbon foam and its application for lithium/oxygen battery[J]. Electrochemistry Communications ,2009,11(6):1127-1130.
[72] Kuboki T,Okuyama T,Ohsaki T, et al . Lithium-air batteries using hydrophobic room temperature ionic liquid electrolyte[J]. Journal of Power Sources ,2005,146(1-2):766-769.
[73] Qin Y,Lu J,Du P, et al . In situ fabrication of porous-carbon-supported α-MnO 2 nanorods at room temperature:Application for rechargeable LiO 2 batteries[J]. Energy & Environmental Science ,2013,6(2):519-531.
[74] Zhang J G,Wang D,Xu W, et al . Ambient operation of Li/air batteries[J]. Journal of Power Sources ,2010,195(13):4332-4337.
[75] Mitchell R R,Gallant B M,Thompson C V, et al . All-carbon-nanofiber electrodes for high-energy rechargeable LiO 2 batteries[J]. Energy & Environmental Science ,2011,4(8):2952-2958.
[76] Mitchell R R,Gallant B M,Shao-Horn Y, et al . Mechanisms of morphological evolution of Li 2 O 2 particles during electrochemical growth[J]. The Journal of Physical Chemistry Letters ,2013,4(7):1060-1064.
[77] Gallant B M,Mitchell R R,Kwabi D G, et al . Chemical and morphological changes of Li/O 2 battery electrodes upon cycling[J]. The Journal of Physical Chemistry C ,2012,116(39):20800-20805.
[78] Yoo E,Zhou H. Li-air rechargeable battery based on metal-free graphene nanosheet catalysts[J]. ACS Nano ,2011,5(4):3020-3026.
[79] Zheng H,Xiao D,Li X, et al . New insight in understanding oxygen reduction and evolution in solid-state lithium-oxygen batteries using an in situ environmental scanning electron microscope[J]. Nano Letters ,2014,14(8):4245-4249.
[80] Zhong L,Mitchell R R,Liu Y, et al . In situ transmission electron microscopy observations of electrochemical oxidation of Li 2 O 2 [J]. Nano Letters ,2013,13(5):2209-2214.
[81] Wang Z L,Xu D,Xu J J, et al . Graphene oxide gel-derived, free-standing, hierarchically porous carbon for high-capacity and high-rate rechargeable Li/O 2 batteries[J]. Advanced Functional Materials ,2012,22(17):3699-3705.
[82] Gallant B M,Kwabi D G,Mitchell R R, et al . Influence of Li 2 O 2 morphology on oxygen reduction and evolution kinetics in Li/O 2 batteries[J]. Energy & Environmental Science ,2013,6(8):2518-2528.
[83] Ottakam T M,Freunberger S A,Peng Z, et al . The carbon electrode in nonaqueous Li/O 2 cells[J]. Journal of the American Chemical Society ,2013,135(1):494-500.
[84] Ottakam T M,Freunberger S A,Peng Z, et al . A stable cathode for the aprotic LiO 2 battery[J]. Nat. Mater. ,2013,12(11):1050-1056.
[85] Dong S,Chen X,Wang S, et al . 1D coaxial platinum/titanium nitride nanotube arrays with enhanced electrocatalytic activity for the oxygen reduction reaction:Towards Li-air batteries[J]. Chem. Sus. Chem. ,2012,5(9):1712-1715.
[86] Li F,Tang D M,Chen Y, et al . Ru/ITO:A carbon-free cathode for nonaqueous LiO 2 battery[J]. Nano Letters ,2013,13(10):4702-4707.
[87] Jian Z,Liu P,Li F, et al . Core-shell-structured CNT@RuO 2 composite as a high-performance cathode catalyst for rechargeable LiO 2 batteries[J]. Angewandte Chemie : International Edition , 2014,53(2):442-426.
[88] Kichambare P,Kumar J,Rodrigues S, et al . Electrochemical performance of highly mesoporous nitrogen doped carbon cathode in lithium-oxygen batteries[J]. Journal of Power Sources ,2011,196(6):3310-3316.
[89] Kichambare P,Rodrigues S,Kumar J. Mesoporous nitrogen-doped carbon-glass ceramic cathodes for solid-state lithium-oxygen batteries[J]. ACS Applied Materials & Interfaces ,2012,4(1):49-52.
[90] Cheng F,Liang J,Tao Z, et al . Functional materials for rechargeable batteries[J]. Advanced Materials ,2011,23(15):1695-1715.
[91] Cheng F,Chen J. Metal-air batteries:From oxygen reduction electrochemistry to cathode catalysts[J]. Chemical Society Reviews ,2012,41(6):2172-2192.
[92] Debart A,Bao J,Armstrong G, et al . An O 2 cathode for rechargeable lithium batteries:The effect of a catalyst[J]. Journal of Power Sources ,2007,174(2):1177-1182.
[93] Debart A,Paterson A J,Bao J, et al . α-MnO 2 nanowires:A catalyst for the O 2 electrode in rechargeable lithium batteries[J]. Angewandte Chemie : International Edition ,2008,47(24):4521-4524.
[94] Giordani V,Freunberger S A,Bruce P G, et al . H 2 O 2 decomposition reaction as selecting tool for catalysts in LiO 2 cells[J]. Electrochemical and Solid State Letters ,2010,13(12):A180-A183.
[95] Miyazaki K,Kawakita K I,Abe T, et al . Single-step synthesis of nano-sized perovskite-type oxide/carbon nanotube composites and their electrocatalytic oxygen-reduction activities[J]. Journal of Materials Chemistry ,2011,21(6):1913-1917.
[96] Yuasa M,Nishida M,Kida T, et al . Bi-functional oxygen electrodes using LaMnO 3 /LaNiO 3 for rechargeable metal-air batteries[J]. Journal of the Electrochemical Society ,2011,158(5):A605-A610.
[97] Fu Z,Lin X,Huang T, et al . Nano-sized La 0.8 Sr 0.2 MnO 3 as oxygen reduction catalyst in nonaqueous Li/O 2 batteries[J]. J. Solid State Electrochem. ,2012,16(4):1447-1452.
[98] Suntivich J,Gasteiger H A,Yabuuchi N, et al . Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries[J]. Nature Chemistry ,2011,3(7):546-550.
[99] Chen Z,Higgins D,Yu A, et al . A review on non-precious metal electrocatalysts for PEM fuel cells[J]. Energy & Environmental Science ,2011,4(9):3167-3192.
[100] Li F,Ohnishi R,Yamada Y, et al . Carbon supported TiN nanoparticles:An efficient bifunctional catalyst for non-aqueous Li/O 2 batteries[J]. Chemical Communications ,2013,49(12):1175-1177.
[101] Kitaura H,Zhou H. Electrochemical performance of solid-state lithium-air batteries using carbon nanotube catalyst in the air electrode[J]. Advanced Energy Materials ,2012,2(7):889-894.
[102] Shui J L,Karan N K,Balasubramanian M, et al . Fe/N/C composite in LiO 2 battery:Studies of catalytic structure and activity toward oxygen evolution reaction[J]. Journal of the American Chemical Society ,2012,134(40):16654-16661.
[103] Lu Y C,Gasteiger H A,Parent M C, et al . The influence of catalysts on discharge and charge voltages of rechargeable Li-oxygen batteries[J]. Electrochemical and Solid State Letters ,2010,13(6):A69-A72.
[104] Lu Y C,Xu Z,Gasteiger H A, et al . Platinum-gold nanoparticles:A highly active bifunctional electrocatalyst for rechargeable lithium-air batteries[J]. Journal of the American Chemical Society ,2010,132(35):12170-12171.
[105] Li F,Chen Y,Zhou H, et al . Performance-improved LiO 2 battery with Ru nanoparticles supported on binder-free multiwalled carbon nanotube paper as cathode[J]. Energy & Environmental Science ,2014,7:1648-1652.
[106] Xu J J,Wang Z L,Xu D, et al . Tailoring deposition and morphology of discharge products towards high-rate and long-life lithium-oxygen batteries[J]. Nature Communications ,2013,4:24-38.
[107] Ren X,Zhang S S,Tran D T, et al . Oxygen reduction reaction catalyst on lithium/air battery discharge performance[J]. Journal of Materials Chemistry ,2011,21(27):10118-10125.
[108] Mccloskey B D,Scheffler R,Speidel A, et al . On the efficacy of electrocatalysis in nonaqueous Li/O 2 batteries[J]. Journal of the American Chemical Society ,2011,133(45):18038-18041.
[109] Imanishi N,Hasegawa S,Zhang T, et al . Lithium anode for lithium-air secondary batteries[J]. Journal of Power Sources ,2008,185(2):1392-1397.
[110] Hassoun J,Jung H G,Lee D J, et al . A metal-free, lithium-ion oxygen battery:A step forward to safety in lithium-air batteries[J]. Nano Letters ,2012,12(11):5775-5779.
[111] Aurbach D. Review of selected electrode-solution interactions which determine the performance of Li and Li ion batteries[J]. Journal of Power Sources ,2000,89(2):206-218.
[112] Cohen Y S,Cohen Y,Aurbach D. Micromorphological studies of lithium electrodes in alkyl carbonate solutions using in situ atomic force microscopy[J]. The Journal of Physical Chemistry B ,2000,104(51):12282-12291.
[113] Choi N S,Lee Y M,Cho K Y, et al . Protective layer with oligo (ethylene glycol) borate anion receptor for lithium metal electrode stabilization[J]. Electrochemistry Communications ,2004,6(12):1238-1242.
[114] Singh M,Gur I,Eitouni H B, et al . Solid Electrolyte material manufacturable by polymer processing methods:US,20090075176A1[P/OL]. 2009-03-19. http://www.google.com/patents/ US20090075176.
[115] Visco S J,Katz B D,Nimon Y S, et al . Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture:CN,100568613C[P/OL]. 2009-12-09. http://www.google.com/patents/ CN100568613C?cl=en.
[116] Zhang D,Li R,Huang T, et al . Novel composite polymer electrolyte for lithium air batteries[J]. Journal of Power Sources ,2010,195(4):1202-1206.
[117] Baker R W. Future directions of membrane gas separation technology[J]. Industrial & Engineering Chemistry Research ,2002,41(6):1393-1411.
[118] Zhang J,Xu W,Liu W. Oxygen-selective immobilized liquid membranes for operation of lithium-air batteries in ambient air[J]. Journal of Power Sources ,2010,195(21):7438-7444.
[119] Zhang J,Xu W,Li X, et al . Air dehydration membranes for nonaqueous lithium-air batteries[J]. Journal of the Electrochemical Society ,2010,157(8):A940-A946.
[120] Crowther O,Keeny D,Moureau D M, et al . Electrolyte optimization for the primary lithium metal air battery using an oxygen selective membrane[J]. Journal of Power Sources ,2012,202:347-351.
[121] Fu Z,Wei Z,Lin X, et al . Polyaniline membranes as waterproof barriers for lithium air batteries[J]. Electrochimica Acta ,2012,78:195-199.
[122] Lau K C,Curtiss L A,Greeley J. Density functional investigation of the thermodynamic stability of lithium oxide bulk crystalline structures as a function of oxygen pressure[J]. Journal of Physical Chemistry C ,2011,115(47):23625-23633.
[123] Radin M D,Rodriguez J F,Tian F, et al . Lithium peroxide surfaces are metallic, while lithium oxide surfaces are not[J]. Journal of the American Chemical Society ,2011,134(2):1093-1103.
[124] Gerbig O,Merkle R,Maier J. Electron and ion transport in Li 2 O 2 [J]. Advanced Materials ,2013,25(22):3129-3133.
[125] Garcia-Lastra J M,Bass J D,Thygesen K S. Communication:Strong excitonic and vibronic effects determine the optical properties of Li 2 O 2 [J]. Journal of Chemical Physics ,2011,135(12):121101.
[126] 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.
[127] Ong S P,Mo Y,Ceder G. Low hole polaron migration barrier in lithium peroxide[J]. Physical Review B ,2012,85(8):81105.
[128] Hummelsh J J S,Blomqvist J,Datta S, et al . Communications:Elementary oxygen electrode reactions in the aprotic Li-air battery[J]. The Journal of Chemical Physics ,2010,132(7):71101.
[129] Lau K C,Assary R S,Redfern P, et al . Electronic structure of lithium peroxide clusters and relevance to lithium-air batteries[J]. The Journal of Physical Chemistry C ,2012,116(45):23890-23896.
[130] Lu J,Jung H J,Lau K C, et al . Magnetism in lithium-oxygen discharge product[J]. Chem. Sus. Chem. ,2013,6(7):1196-1202.
[131] Yang J,Zhai D,Wang H H, et al . Evidence for lithium superoxide-like species in the discharge product of a Li/O 2 battery[J]. Physical Chemistry Chemical Physics ,2013,15(11):3764-3771.
[132] Aetukurin B,McCloskey B D,Garc A J M, et al . On the origin and implications of Li 2 O 2 toroid formation in nonaqueous LiO 2 batteries[EB/OL]. 2014-07-12. http://arxiv.org/abs/1406.3335.
[133] Zhang T,Zhou H. A reversible long-life lithium-air battery in ambient air[J]. Nature Communications ,2013,4:1817.
[134] Zhang T,Zhou H. From LiO 2 to Li-air batteries:Carbon nanotubes/ionic liquid gels with a tricontinuous passage of electrons, ions, and oxygen[J]. Angewandte Chemie-International Edition ,2012,51(44):11062-11067.
[135] Takechi K,Shiga T,Asaoka T. A LiO 2 /CO 2 battery[J]. Chemical Communications ,2011,47(12):3463-3465.
[136] Gowda S R,Brunet A,Wallraff G M, et al . Implications of CO 2 contamination in rechargeable nonaqueous LiO 2 batteries[J]. Journal of Physical Chemistry Letters ,2013,4(2):276-279.
[137] McCloskey B D,Speidel A,Scheffler R, et al . Twin problems of interfacial carbonate formation in nonaqueous LiO 2 batteries[J]. Journal of Physical Chemistry Letters ,2012,3(8):997-1001.
[138] 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.
[139] Wang R,Yu X,Bai J, et al . Electrochemical decomposition of Li 2 CO 3 in NiO-Li 2 CO 3 nanocomposite thin film and powder electrodes[J]. Journal of Power Sources ,2012,218:113-118.
[140] Liu Y,Wang R,Lyu Y, et al . Rechargeable Li/CO 2 -O 2 (2∶1) battery and Li/CO 2 battery[J]. Energy & Environmental Science ,2014,7(2):677-681.
[141] Pensado-Rodriguez O,Urquidi-Macdonald M,Macdonald D D. Electrochemical behavior of lithium in alkaline aqueous electrolytes - I. Thermodynamics[J]. Journal of the Electrochemical Society ,1999,146(4):1318-1325.
[142] Urquidi-Macdonald M,Macdonald D D,Pensado O, et al . The electrochemical behavior of lithium in alkaline aqueous electrolytes[J]. Electrochimica Acta ,2001,47(5):833-840.
[143] Kemp D D L E L,Momye W R, et al . Proceeding of the 11th IECECC[C]//Lake Tahoe,1976.
[144] Ding Fei(丁飞),Zhang Jing(张晶),Yang Kai(杨凯), et al . Study on lithium electrode corrosion in KOH aqueous electrolytes (I)[J]. Chin. J. Power Sources (电源技术),2008,32(2):91-94.
[145] Kim J K,Yang W,Salim J, et al . Li-water battery with oxygen dissolved in water as a cathode[J]. Journal of the Electrochemical Society ,2013,161(3):A285-A289.
[146] Danuta H,Juliusz U. Electric dry cells and storage batteries: US,3043896A[P/OL]. 1962-07-10. http://www.google.com/patents/ US3043896.
[147] Yao N P,HeredY L A,Saunders R C. Secondary lithium-sulfur battery[J]. Journal of the Electrochemical Society ,1970,117(8):8.
[148] Rauh R D,Abraham K M,Pearson G F, et al . Lithium-dissolved sulfur battery with an organic electrolyte[J]. Journal of the Electrochemical Society ,1979,126(4):523-527.
[149] Evers S,Nazar L F. New approaches for high energy density lithium-sulfur battery cathodes[J]. Accounts of Chemical Research ,2013,46(5):1135-1143.
[150] Xiong S,Xie K,Diao Y, et al . Oxidation process of polysulfides in charge process for lithium-sulfur batteries[J]. Ionics ,2012,18(9):867-872.
[151] Kolosnitsyn V S,Karaseva E V. Lithium-sulfur batteries:Problems and solutions[J]. Russ. J. Electrochem. ,2008,44(5):506-509.
[152] Mikhaylik Y V,Akridge J R. Polysulfide shuttle study in the Li/S battery system[J]. Journal of the Electrochemical Society ,2004,151(11):A1969-A1976.
[153] Kumaresan K,Mikhaylik Y,White R E. A mathematical model for a lithium-sulfur cell[J]. Journal of the Electrochemical Society ,2008,155(8):A576-A582.
[154] Shin E S,Kim K,Oh S H, et al . Polysulfide dissolution control:The common ion effect[J]. Chemical Communications ,2013,49(20):2004-2006.
[155] Zhang S S. Liquid electrolyte lithium/sulfur battery:Fundamental chemistry, problems, and solutions[J]. Journal of Power Sources ,2013,231:153-162.
[156] Aurbach D,Pollak E,Elazari R, et al . On the surface chemical aspects of very high energy density, rechargeable Li/S batteries[J]. Journal of the Electrochemical Society ,2009,156(8):A694-A702.
[157] Zhang S S. Role of LiNO 3 in rechargeable lithium/sulfur battery[J]. Electrochimica Acta ,2012,70:344-348.
[158] Xiong S,Xie K,Diao Y, et al . Properties of surface film on lithium anode with LiNO 3 as lithium salt in electrolyte solution for lithium-sulfur batteries[J]. Electrochimica Acta ,2012,83:78-86.
[159] Liang X,Wen Z,Liu Y, et al . Improved cycling performances of lithium sulfur batteries with LiNO 3 -modified electrolyte[J]. Journal of Power Sources ,2011,196(22):9839-9843.
[160] Xiong S,Kai X,Hong X, et al . Effect of LiBOB as additive on electrochemical properties of lithium-sulfur batteries[J]. Ionics ,2012,18(3):249-254.
[161] Song M S,Han S C,Kim H S, et al . Effects of nanosized adsorbing material on electrochemical properties of sulfur cathodes for Li/S secondary batteries[J]. Journal of the Electrochemical Society ,2004,151(6):A791-A795.
[162] Zhang Y,Zhao Y,Yermukhambetova A, et al . Ternary sulfur/polyacrylonitrile/Mg 0.6 Ni 0.4 O composite cathodes for high performance lithium/sulfur batteries[J]. Journal of Materials Chemistry A ,2013,1(2):295-301.
[163] Choi Y J,Jung B S,Lee D J, et al . Electrochemical properties of sulfur electrode containing nano Al 2 O 3 for lithium/sulfur cell[J]. Physica Scripta ,2007,2007(T129):62-75.
[164] Ji X,Evers S,Black R, et al . Stabilizing lithium-sulphur cathodes using polysulphide reservoirs[J]. Nat. Commun. ,2011,2:325.
[165] Su Y S,Manthiram A. Lithium-sulphur batteries with a microporous carbon paper as a bifunctional interlayer[J]. Nat. Commun. ,2012,3:1166.
[166] Zu C,Su Y S,Fu Y, et al . Improved lithium-sulfur cells with a treated carbon paper interlayer[J]. Physical Chemistry Chemical Physics ,2013,15(7):2291-2297.
[167] Su Y S,Manthiram A. A new approach to improve cycle performance of rechargeable lithium-sulfur batteries by inserting a free-standing MWCNT interlayer[J]. Chemical Communications ,2012,48(70):8817-8819.
[168] Suo L,Hu Y S,Li H, et al . A new class of solvent-in-salt electrolyte for high-energy rechargeable metallic lithium batteries[J]. Nat. Commun. ,2013,4:1481.