Abstract
High-voltage, oxide-based insertion cathodes are commercial favorites for lithium-ion batteries. However, due to the double charge density, the magnesium cation (Mg2+) tends to bond covalently with the oxygen in the electrode structure which precludes its smooth and reversible intercalation. With the exception of lithium titanate, reversible magnesium intercalation has only been reported for sulfide-based electrodes which offer a low energy density due to low voltage and capacity. However, higher reversibility and energy density have been reported with conversion cathodes such as selenium and iodine. The current challenge for the development of a suitable cathode for a rechargeable magnesium battery with a metal anode is improving the rates of battery charge/discharge as well as increasing the cycle life. The use of modern magnesium electrolytes will accelerate this effort.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Bucur CB, Gregory T, Oliver AG, Muldoon J (2015) Confession of a magnesium battery. J Phys Chem Lett 6:3578–3591. https://doi.org/10.1021/acs.jpclett.5b01219
God C, Bitschnau B, Kapper K et al (2017) Intercalation behaviour of magnesium into natural graphite using organic electrolyte systems. RSC Adv 7:14168–14175. https://doi.org/10.1039/C6RA28300D
Pontiroli D, Aramini M, Gaboardi M et al (2013) Ionic conductivity in the Mg intercalated fullerene polymer Mg2C60. Carbon 51:143–147. https://doi.org/10.1016/j.carbon.2012.08.022
Zhang R, Mizuno F, Ling C (2014) Fullerenes: non-transition metal clusters as rechargeable magnesium battery cathodes. Chem Commun 51:1108–1111. https://doi.org/10.1039/C4CC08139K
Kawaguchi M, Kurasaki A (2012) Intercalation of magnesium into a graphite-like layered material of composition BC2N. Chem Commun 48:6897–6899. https://doi.org/10.1039/C2CC31435E
Moundanga-iniamy M, Touzain P (1994) Study of the cointercalation of magnesium and cobalt chlorides into graphite. Mol Cryst Liq Cryst Sci Technol Sect Mol Cryst Liq Cryst 244:65–70. https://doi.org/10.1080/10587259408050084
Pruvost S, Hérold C, Hérold A, Lagrange P (2004) Co-intercalation into graphite of lithium and sodium with an alkaline earth metal. Carbon 42:1825–1831. https://doi.org/10.1016/j.carbon.2004.03.014
Giraudet J, Claves D, Guérin K et al (2007) Magnesium batteries: towards a first use of graphite fluorides. J Power Sources 173:592–598. https://doi.org/10.1016/j.jpowsour.2007.04.067
Stumpp E, Alheid H, Schwarz M et al (1996) Ternary graphite intercalation compounds of type M(NH3)xCy with M = Be, Mg, Al, Sc, Y, La. Electrochemical synthesis, stability and NMR studies. Proc 8th Int Symp Intercalation Compd 57:925–930. https://doi.org/10.1016/0022-3697(95)00375-4
Wu N, Yin Y-X, Guo Y-G (2014) Size-dependent electrochemical magnesium storage performance of spinel lithium titanate. Chem Asian J 9:2099–2102. https://doi.org/10.1002/asia.201402286
Wu N, Yang Z-Z, Yao H-R et al (2015) Improving the electrochemical performance of the Li4Ti5O12 electrode in a rechargeable magnesium battery by lithium–magnesium co-intercalation. Angew Chem Int Ed 54:5757–5761. https://doi.org/10.1002/anie.201501005
Arthur TS, Singh N, Matsui M (2012) Electrodeposited Bi, Sb and Bi1-xSbx alloys as anodes for Mg-ion batteries. Electrochem Commun 16:103–106. https://doi.org/10.1016/j.elecom.2011.12.010
Singh N, Arthur TS, Ling C et al (2012) A high energy-density tin anode for rechargeable magnesium-ion batteries. Chem Commun 49:149–151. https://doi.org/10.1039/C2CC34673G
Shao Y, Gu M, Li X et al (2014) Highly reversible Mg insertion in nanostructured Bi for Mg ion batteries. Nano Lett 14:255–260. https://doi.org/10.1021/nl403874y
Periyapperuma K, Tran TT, Purcell MI, Obrovac MN (2015) The reversible magnesiation of Pb. Electrochimica Acta 165:162–165. https://doi.org/10.1016/j.electacta.2015.03.006
Murgia F, Weldekidan ET, Stievano L et al (2015) First investigation of indium-based electrode in Mg battery. Electrochem Commun 60:56–59. https://doi.org/10.1016/j.elecom.2015.08.007
Murgia F, Monconduit L, Stievano L, Berthelot R (2016) Electrochemical magnesiation of the intermetallic InBi through conversion-alloying mechanism. Electrochimica Acta 209:730–736. https://doi.org/10.1016/j.electacta.2016.04.020
Gregory TD, Hoffman RJ, Winterton RC (1990) Nonaqueous electrochemistry of magnesium. Applications to energy storage. J Electrochem Soc 137:775–780. https://doi.org/10.1149/1.2086553
Crowe AJ, Bartlett BM (2016) Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte. J Solid State Chem 242(Part 2):102–106. https://doi.org/10.1016/j.jssc.2016.04.011
Bruce PG, Krok F, Nowinski J et al (1991) Chemical intercalation of magnesium into solid hosts. J Mater Chem 1:705–706. https://doi.org/10.1039/JM9910100705
Kaveevivitchai W, Huq A, Manthiram A (2017) Microwave-assisted chemical insertion: a rapid technique for screening cathodes for Mg-ion batteries. J Mater Chem A 5:2309–2318. https://doi.org/10.1039/C6TA09497J
Novák P, Desilvestro J (1993) Electrochemical insertion of magnesium in metal oxides and sulfides from aprotic electrolytes. J Electrochem Soc 140:140–144. https://doi.org/10.1149/1.2056075
Novák P, Imhof R, Haas O (1999) Magnesium insertion electrodes for rechargeable nonaqueous batteries — a competitive alternative to lithium? Electrochimica Acta 45:351–367. https://doi.org/10.1016/S0013-4686(99)00216-9
Novák P, Scheifele W, Haas O (1995) Magnesium insertion batteries—an alternative to lithium? Proc Seventh Int Meet Lithium Batter 54:479–482. https://doi.org/10.1016/0378-7753(94)02129-Q
Novák P, Scheifele W, Joho F, Haas O (1995) Electrochemical insertion of magnesium into hydrated vanadium bronzes. J Electrochem Soc 142:2544–2550. https://doi.org/10.1149/1.2050051
Byeon A, Zhao M-Q, Ren CE et al (2017) Two-dimensional titanium carbide MXene as a cathode material for hybrid magnesium/lithium-ion batteries. ACS Appl Mater Interfaces 9:4296–4300. https://doi.org/10.1021/acsami.6b04198
Pan B, Feng Z, Sa N et al (2016) Advanced hybrid battery with a magnesium metal anode and a spinel LiMn2O4 cathode. Chem Commun 52:9961–9964. https://doi.org/10.1039/C6CC04133G
Su S, NuLi Y, Huang Z et al (2016) A high-performance rechargeable Mg2+/Li+ hybrid battery using one-dimensional mesoporous TiO2(B) nanoflakes as the cathode. ACS Appl Mater Interfaces 8:7111–7117. https://doi.org/10.1021/acsami.6b00106
Sun X, Bonnick P, Nazar LF (2016) Layered TiS2 positive electrode for Mg batteries. ACS Energy Lett 1:297–301. https://doi.org/10.1021/acsenergylett.6b00145
Sun X, Bonnick P, Duffort V et al (2016) A high capacity thiospinel cathode for Mg batteries. Energy Environ Sci 9:2273–2277. https://doi.org/10.1039/C6EE00724D
Liu M, Jain A, Rong Z et al (2016) Evaluation of sulfur spinel compounds for multivalent battery cathode applications. Energy Environ Sci 9:3201–3209. https://doi.org/10.1039/C6EE01731B
Aurbach D, Lu Z, Schechter A et al (2000) Prototype systems for rechargeable magnesium batteries. Nature 407:724–727. https://doi.org/10.1038/35037553
Ichitsubo T, Yagi S, Nakamura R et al (2014) A new aspect of Chevrel compounds as positive electrodes for magnesium batteries. J Mater Chem A 2:14858–14866. https://doi.org/10.1039/C4TA03063J
Liang Y, Feng R, Yang S et al (2011) Rechargeable Mg batteries with graphene-like MoS2 cathode and ultrasmall Mg nanoparticle anode. Adv Mater 23:640–643. https://doi.org/10.1002/adma.201003560
Liu B, Luo T, Mu G et al (2013) Rechargeable Mg-ion batteries based on WSe2 nanowire cathodes. ACS Nano 7:8051–8058. https://doi.org/10.1021/nn4032454
Herb JT, Nist-Lund CA, Arnold CB (2016) A fluorinated alkoxyaluminate electrolyte for magnesium-ion batteries. ACS Energy Lett 1:1227–1232. https://doi.org/10.1021/acsenergylett.6b00356
Nelson EG, Brody SI, Kampf JW, Bartlett BM (2014) A magnesium tetraphenylaluminate battery electrolyte exhibits a wide electrochemical potential window and reduces stainless steel corrosion. J Mater Chem A 2:18194–18198. https://doi.org/10.1039/C4TA04625K
Tutusaus O, Mohtadi R, Arthur TS et al (2015) An efficient halogen-free electrolyte for use in rechargeable magnesium batteries. Angew Chem Int Ed 54:7900–7904. https://doi.org/10.1002/anie.201412202
Arthur TS, Zhang R, Ling C et al (2014) Understanding the electrochemical mechanism of K-αMnO2 for magnesium battery cathodes. ACS Appl Mater Interfaces 6:7004–7008. https://doi.org/10.1021/am5015327
Zhang R, Arthur TS, Ling C, Mizuno F (2015) Manganese dioxides as rechargeable magnesium battery cathode; synthetic approach to understand magnesiation process. J Power Sources 282:630–638. https://doi.org/10.1016/j.jpowsour.2015.02.067
Okamoto S, Ichitsubo T, Kawaguchi T et al (2015) Intercalation and push-out process with spinel-to-rocksalt transition on Mg insertion into spinel oxides in magnesium batteries. Adv Sci 2(8):1500072. https://doi.org/10.1002/advs.201500072
NuLi Y, Yang J, Li Y, Wang J (2010) Mesoporous magnesium manganese silicate as cathode materials for rechargeable magnesium batteries. Chem Commun 46:3794–3796. https://doi.org/10.1039/C002456B
Pan W, Liu X, Miao X et al (2015) Molybdenum dioxide hollow microspheres for cathode material in rechargeable hybrid battery using magnesium anode. J Solid State Electrochem 19:3347–3353. https://doi.org/10.1007/s10008-015-2971-z
Du X, Huang G, Qin Y, Wang L (2015) Solvothermal synthesis of GO/V2O5 composites as a cathode material for rechargeable magnesium batteries. RSC Adv 5:76352–76355. https://doi.org/10.1039/C5RA15284D
Miao X, Chen Z, Wang N et al (2017) Electrospun V2MoO8 as a cathode material for rechargeable batteries with Mg metal anode. Nano Energy 34:26–35. https://doi.org/10.1016/j.nanoen.2017.02.014
Minella CB, Gao P, Zhao-Karger Z et al (2017) Interlayer-expanded vanadium oxychloride as an electrode material for magnesium-based batteries. ChemElectroChem 4:738–745. https://doi.org/10.1002/celc.201700034
An Q, Li Y, Deog Yoo H et al (2015) Graphene decorated vanadium oxide nanowire aerogel for long-cycle-life magnesium battery cathodes. Nano Energy 18:265–272. https://doi.org/10.1016/j.nanoen.2015.10.029
Inamoto M, Kurihara H, Yajima T (2014) Electrode performance of sulfur-doped vanadium pentoxide gel prepared by microwave irradiation for rechargeable magnesium batteries. Curr Phys Chem 4:238–243
Kim J-S, Kim R-H, Yun D-J et al (2016) Cycling stability of a VOx nanotube cathode in mixture of ethyl acetate and tetramethylsilane-based electrolytes for rechargeable Mg-ion batteries. ACS Appl Mater Interfaces 8:26657–26663. https://doi.org/10.1021/acsami.6b05808
Perera SD, Archer RB, Damin CA et al (2017) Controlling interlayer interactions in vanadium pentoxide-poly(ethylene oxide) nanocomposites for enhanced magnesium-ion charge transport and storage. J Power Sources 343:580–591. https://doi.org/10.1016/j.jpowsour.2017.01.052
Yin J, Pelliccione CJ, Lee SH et al (2016) Communication—sol-gel synthesized magnesium vanadium oxide, MgxV2O5 · nH2O: the role of structural Mg2+ on battery performance. J Electrochem Soc 163:A1941–A1943. https://doi.org/10.1149/2.0781609jes
Gershinsky G, Yoo HD, Gofer Y, Aurbach D (2013) Electrochemical and spectroscopic analysis of Mg2+ intercalation into thin film electrodes of layered oxides: V2O5 and MoO3. Langmuir 29:10964–10972. https://doi.org/10.1021/la402391f
Kim D-M, Kim Y, Arumugam D et al (2016) Co-intercalation of Mg2+ and Na+ in Na0.69Fe2(CN)6 as a high-voltage cathode for magnesium batteries. ACS Appl Mater Interfaces 8:8554–8560. https://doi.org/10.1021/acsami.6b01352
Pan B, Zhou D, Huang J et al (2016) 2,5-Dimethoxy-1,4-Benzoquinone (DMBQ) as organic cathode for rechargeable magnesium-ion batteries. J Electrochem Soc 163:A580–A583. https://doi.org/10.1149/2.0021605jes
Pan B, Huang J, Feng Z et al (2016) Polyanthraquinone-based organic cathode for high-performance rechargeable magnesium-ion batteries. Adv Energy Mater 6:n/a–n/a. https://doi.org/10.1002/aenm.201600140
Kim HS, Arthur TS, Allred GD et al (2011) Structure and compatibility of a magnesium electrolyte with a sulphur cathode. Nat Commun 2:427. https://doi.org/10.1038/ncomms1435
Yu X, Manthiram A (2016) Performance enhancement and mechanistic studies of magnesium–sulfur cells with an advanced cathode structure. ACS Energy Lett 1:431–437. https://doi.org/10.1021/acsenergylett.6b00213
Zhang Z, Cui Z, Qiao L et al (2017) Novel design concepts of efficient Mg-ion electrolytes toward high-performance magnesium–selenium and magnesium–sulfur batteries. Adv Energy Mater. https://doi.org/10.1002/aenm.201602055
Shiga T, Hase Y, Kato Y et al (2013) A rechargeable non-aqueous Mg–O2 battery. Chem Commun 49:9152–9154. https://doi.org/10.1039/C3CC43477J
Esch TR, Bredow T (2016) Bulk and surface properties of magnesium peroxide MgO2. Appl Surf Sci 389:1202–1207. https://doi.org/10.1016/j.apsusc.2016.07.141
Smith JG, Naruse J, Hiramatsu H, Siegel DJ (2017) Intrinsic conductivity in magnesium-oxygen battery discharge products: MgO and MgO2. Chem Mater. 29(7):3152–3163. https://doi.org/10.1021/acs.chemmater.7b00217
Tian H, Gao T, Li X et al (2017) High power rechargeable magnesium/iodine battery chemistry. Nat Commun 8:14083. https://doi.org/10.1038/ncomms14083
Yao X, Luo J, Dong Q, Wang D (2016) A rechargeable non-aqueous Mg-Br2 battery. Nano Energy 28:440–446. https://doi.org/10.1016/j.nanoen.2016.09.003
Author information
Authors and Affiliations
Rights and permissions
Copyright information
© 2018 The Author(s)
About this chapter
Cite this chapter
Bucur, C.B. (2018). Magnesium Electrodes. In: Challenges of a Rechargeable Magnesium Battery. SpringerBriefs in Energy. Springer, Cham. https://doi.org/10.1007/978-3-319-65067-8_3
Download citation
DOI: https://doi.org/10.1007/978-3-319-65067-8_3
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-65066-1
Online ISBN: 978-3-319-65067-8
eBook Packages: EnergyEnergy (R0)