多电子转移镁/铝电池体系能量密度热力学计算

doi:10.12028/j.issn.2095-4239.2018.0063

摘要/Abstract

摘要： 镁离子电池和铝离子电池因其高能量密度、地壳储量丰富、安全等优良特性有望成为下一代新型高能量密度储能体系，是未来二次电池研究的热点之一。本文采用热力学方法计算和分析了近300种镁离子和铝离子电池体系的理论质量能量密度、体积能量密度和电压。在所得数据的基础上，以目前商业化锂离子电池正极材料钴酸锂为对比参考，综合考虑质量能量密度、体积能量密度、标准电极电位、毒性、腐蚀性、易燃性、环境友好性等诸多因素，逐步筛选出符合条件的一系列镁离子正极材料（O₂、S、MnO₂、MoO₃、Fe₂O₃、Fe₃O₄、NiO、MoO₂、CuO、Cu₂O）和铝离子的正极材料（O₂、S、MnO₂、MoO₃、NiO、CuO、Cu₂O）。

关键词: 镁离子电池, 铝离子电池, 质量能量密度, 体积能量密度, 正极

Abstract: Magnesium (Mg) ion batteries and aluminum (Al) ion batteries have become new hot spots in beyond lithium ion batteries due to their high energy densities, abundant reserves as well as safety. In this work, the theoretical gravimetric energy densities (GED), volumetric energy densities (VED) and output voltage (OV) of nearly 300 electrochemical couples of Mg/Al ion batteries are calculated by thermodynamic method. As our evaluation, considering of gravimetric energy density, volumetric energy density, output voltage, toxicity, corrosion, flammability and environmental friendliness and so on, a series of materials are screened out as promising candidates including Mg ion cathodes (O₂, S, MnO₂, MoO₃, Fe₂O₃, Fe₃O₄, NiO, MoO₂, CuO and Cu₂O) and Al ion cathodes (O₂, S, MnO₂, MoO₃, NiO, CuO and Cu₂O).

Key words: magnesium ion batteries, aluminum ion batteries, gravimetric energy density, volumetric energy density, cathode

中图分类号:

O646.21

曹文卓, 汪君洋, 陈汝颂, 索鎏敏, 李泓. 多电子转移镁/铝电池体系能量密度热力学计算[J]. 储能科学与技术, 2018, 7(3): 437-449.

CAO Wenzhuo, WANG Junyang, CHEN Rusong, SUO Liumin, LI Hong. Thermodynamic calculation on energy densities of multi-electron transfer Mg/Al batteries[J]. Energy Storage Science and Technology, 2018, 7(3): 437-449.

参考文献

[1] WU CHUAN B Y, WU FENG, et al. Novel ternary metal boride Mg-Co-B alloys as anode materials for alkaline secondary batteries[J]. Electrochemistry Communications, 2009, 11(11):2173-2176.
[2] 罗锐, 黄永鑫, 陈人杰, 吴锋. 基于多电子反应机制的高比能二次电池[C]//第三届全国储能科学与技术大会, 2016. LUO Rui, HUANG Yongxin, CHEN Renjie, WU Feng. Secondary battery with high specific energy based on multi-electron reaction mechanism[C]//Proceedings of the Third National Conference on Energy, 2016.
[3] 李泓, 许晓雄. 固态锂电池研发愿景和策略[J]. 储能科学与技术, 2016, 5(5):607-614. LI Hong, XU Xiaoxiong. R&D vision and strategies on lithium batteries[J]. Energy Storage Science and Technology, 2016, 5(5):607-614.
[4] AURBACH D, LU Z, SCHECHTER A, et al. Prototype systems for rechargeable magnesium batteries[J]. Nature, 2000, 407(6805):724-727.
[5] RANKIN W J. Minerals, metals and sustainability:Meeting future material needs[M]//PRESS C. Boca Raton, Fla. 2011.
[6] B SAHOO N C, A SAMANTARAY, P KUMAR. Inorganic chemistry[M]. PHI Learning, 2012.
[7] HARRIS J. Nature's building blocks:an A-Z guide to the elements[J]. Interdisciplinary Science Reviews, 2002, 27(1):79-80.
[8] 郑育培, 努丽燕娜, 杨军, 陈强, 王久林. 可充镁电池正极材料研究进展[J]. 化工进展, 2011, 30(5):1024-1032. ZHENG Yupei, NULI Yanna, YANG Jun, et al. Research progress of cathode materials for rechargeable magnesium batteries[J]. Chemical Industry and Engineering Progress, 2011, 30(5):1024-1032.
[9] 马正青, 左列, 庞旭, 曾苏民. 铝电池研究进展[J]. 船电技术, 2008, 28(5):257-261. MA Zhengqing, ZUO Lie, PANG Xu, et al. Advance in Aluminum Batteries[J]. Ship Electricity Technology, 2008, 28(5):257-261.
[10] NOVAK P, DESILVESTRO J. Electrochemical insertion of magnesium in metal oxides and sulfides from aprotic electrolytes[J]. J. Electrochem. Soc., 1993, 140(1):140-144.
[11] BRUCE P G, KROK F, NOWINSKI J, et al. Chemical intercalation of magnesium into solid hosts[J]. J. Mater. Chem., 1991, 1(4):705-706.
[12] KUMAGAI N, KOMABA S, SAKAI H, et al. Preparation of todorokite-type manganese-based oxide and its application as lithium and magnesium rechargeable battery cathode[J]. Journal of Power Sources, 2001, 97/98:515-517.
[13] GREGORY T D, HOFFMAN R J, WINTERTON R C. Nonaqueous electrochemistry of magnesium-applications to energy-storage[J]. J. Electrochem. Soc., 1990, 137(3):775-780.
[14] LI X L, LI Y D. MoS₂ nanostructures:Synthesis and electrochemical Mg²⁺ intercalation[J]. J. Phys. Chem. B, 2004, 108(37):13893-13900.
[15] MAKINO K, KATAYAMA Y, MIURA T, et al. Electrochemical insertion of magnesium to Mg_0.5Ti₂(PO₄)₃[J]. Journal of Power Sources, 2001, 99(1-2):66-69.
[16] FENG Z, YANG J, NULI Y, et al. Sol-gel synthesis of Mg_1.03Mn_0.97SiO₄ and its electrochemical intercalation behavior[J]. Journal of Power Sources, 2008, 184(2):604-609.
[17] WANG R Y, WESSELLS C D, HUGGINS R A, et al. Highly reversible open framework nanoscale electrodes for divalent ion batteries[J]. Nano Letters, 2013, 13(11):5748-5752.
[18] NULI Y, GUO Z, LIU H, et al. A new class of cathode materials for rechargeable magnesium batteries:Organosulfur compounds based on sulfur-sulfur bonds[J]. Electrochemistry Communications, 2007, 9(8):1913-1917.
[19] GIRAUDET J, CLAVES D, GUERIN K, et al. Magnesium batteries:Towards a first use of graphite fluorides[J]. Journal of Power Sources, 2007, 173(1):592-598.
[20] REED L D, MENKE E. The roles of V₂O₅ and stainless steel in rechargeable Al-ion batteries[J]. J. Electrochem. Soc., 2013, 160(6):A915-A917.
[21] KULISH V V, MANZHOS, S. Comparison of Li, Na, Mg and Al-ion insertion in vanadium pentoxides and vanadium dioxides[J]. RSC Adv., 2017, 7(30):18643-18649.
[22] LIU S, HU J J, YAN N F, et al. Aluminum storage behavior of anatase TiO₂ nanotube arrays in aqueous solution for aluminum ion batteries[J]. Energy & Environmental Science, 2012, 5(12):9743-9746.
[23] JURAN T R, SMEU M. Hybrid density functional theory modeling of Ca, Zn, and Al ion batteries using the Chevrel phase Mo₆S₈ cathode[J]. Phys. Chem. Chem. Phys., 2017, 19(31):20684-20690.
[24] MORI T, ORIKASA Y, NAKANISHI K, et al. Discharge/charge reaction mechanisms of FeS₂ cathode material for aluminum rechargeable batteries at 55 degrees C[J]. Journal of Power Sources, 2016, 313:9-14.
[25] PHILLIPS J, GIBBARD H F. Thermodynamics of Li(Al)-FeS battery system[J]. J. Electrochem. Soc., 1978, 125(8):C369.
[26] LIU S, PAN G L, LI G R, et al. Copper hexacyanoferrate nanoparticles as cathode material for aqueous Al-ion batteries[J]. J. Mater. Chem. A, 2015, 3(3):959-962.
[27] XU J T, DOU Y H, WEI Z X, et al. Recent progress in graphite intercalation compounds for rechargeable metal (Li, Na, K, Al)-ion batteries[J]. Adv. Sci., 2017, 4(10):14.
[28] RANI J V, KANAKAIAH V, DADMAL T, et al. Fluorinated natural graphite cathode for rechargeable ionic liquid based aluminum-ion battery[J]. J. Electrochem. Soc., 2013, 160(10):A1781-A1784.
[29] HUDAK N S. Chloroaluminate-doped conducting polymers as positive electrodes in rechargeable aluminum batteries[J]. J. Phys. Chem. C, 2014, 118(10):5203-5215.
[30] DONAHUE F M, MANCINI S E, SIMONSEN L. Secondary aluminum iron(Ⅲ) chloride batteries with a low-temperature molten-salt electrolyte[J]. J. Appl. Electrochem., 1992, 22(3):230-234.
[31] SUTO K, NAKATA A, MURAYAMA H, et al. Electrochemical properties of al/vanadium chloride batteries with AlCl₃-1-ethyl-3-methylimidazolium chloride electrolyte[J]. J. Electrochem. Soc., 2016, 163(5):A742-A747.
[32] BRABSON G D, FANNIN A A, KING L A, et al. Prototype high-power density aluminum-chlorine battery[J]. J. Electrochem. Soc., 1973, 120(3):C85.
[33] GAO T, LI X G, WANG X W, et al. A rechargeable Al/S battery with an ionic-liquid electrolyte[J]. Angewandte Chemie-International Edition, 2016, 55(34):9898-9901.
[34] ZU Chenxi, LI H. Thermodynamics analysis on energy densities of batteries[J]. Energy & Environmental Science, 2011, 4(8):2614-2624.
[35] HAYNES W M. CRC handbook of chemistry and physics,97th edition[M]. Boca Raton:CRC Press, 2016-2017.
[36] JAMES G SPEIGHT. Lange's handbook of chemistry,16th edition[M]. New York:McGraw Hill, 2005.
[37] BARIN I. Thermochemical date of pure substances, 3rd edition[M]. New York:VCH publisher, 1995.
[38] National Institute of Standards and Technology (NIST)-JANAF Thermochemical Tables[DB/OL]. https://janaf.nist.gov/
[39] SMITH J G, NARUSE J, HIRAMATSU H, et al. Theoretical limiting potentials in Mg/O₂ batteries[J]. Chemistry of Materials, 2016, 28(5):1390-1401.
[40] IMAMURA D, MIYAYAMA M. Characterization of magnesium-intercalated V₂O₅/carbon composites[J]. Solid State Ionics, 2003, 161(1-2):173-180.
[41] 司玉昌, 孙文军, 王贺孔, 邓昌辉, 牟心红, 焦丽芳, 袁华堂. MoO₃纳米材料的合成及电化学嵌镁性能研究[J]. 南开大学学报(自然科学版), 2010, 43(6):5-8. SI Yuchang, SUN Wenjun, WANG Hekong, et al. Synthesis and Electrochemical insertion of magnesium in MoO₃ nanomaterials[J]. Acta Scientiarum Naturalium Universitatis Nankaiensis(Natural Science Edition), 2010, 43(6):5-8.
[42] ARTHUR T S, ZHANG R G, LING C, et al. Understanding the electrochemical mechanism of K-alpha MnO₂ for magnesium battery cathodes[J]. ACS Appl. Mater. Interfaces, 2014, 6(10):7004-7008.
[43] WANG L, ASHEIM K, VULLUM P E, et al. Sponge-like porous manganese(Ⅱ,Ⅲ) oxide as a highly efficient cathode material for rechargeable magnesium ion batteries[J]. Chemistry of Materials, 2016, 28(18):6459-6470.
[44] SUTTO T E, DUNCAN T T. Electrochemical and structural characterization of Mg ion intercalation into Co₃O₄ using ionic liquid electrolytes[J]. Electrochim Acta, 2012, 80:413-417.
[45] LIU Y C, JIAO L F, WU Q, et al. Synthesis of rGO-supported layered MoS₂ for high-performance rechargeable Mg batteries[J]. Nanoscale, 2013, 5(20):9562-9567.
[46] JAYAPRAKASH N, DAS S K, ARCHER L A. The rechargeable aluminum-ion battery[J]. Chem. Commun., 2011, 47(47):12610-12612.
[47] DAS S K, MAHAPATRA S, LAHAN H. Aluminium-ion batteries:Developments and challenges[J]. J. Mater. Chem. A, 2017, 5(14):6347-6367.
[48] LIU Y, SANG S, WU Q, et al. The electrochemical behavior of Cl^- assisted Al³⁺ insertion into titanium dioxide nanotube arrays in aqueous solution for aluminum ion batteries[J]. Electrochim Acta, 2014, 143:340-346.