A short review on the comparison between Li battery systems and rechargeable magnesium battery technology (original) (raw)

Rechargeable Magnesium Battery: Current Status and Key Challenges for the Future

Progress in Materials Science, 2014

There is a tremendous need to have perennial and continuous access to cost-effective electricity generated from the intermittent energy sources (wind, solar, geothermal, hydropower, wave etc.). This will require development of inexpensive and efficient electrical energy storage (EES) devices such as stationary battery for uninterrupted electricity (power storage back up) and load leveling as well as grid energy storage systems [6]. Magnesium based secondary batteries are a viable 'environmental friendly, non-toxic' alternative compared to the immensely popular Li-ion systems owing to its high volumetric capacity (3833 mA h/cc for Mg vs. 2046 mA h/cc for Li) for stationary EES applications. Following the successful demonstration of a prototype magnesium cell capable of offering energy density 60Wh/kgintheearly2000,thelastdecadehaswitnessedtremendousamountofworkdedicatedtomagnesiumbatteryanditscomponents.Thepresentreviewisanearnestattempttocollectallofthecomprehensivebodyofresearchperformedintheliteraturehithertotodevelopnon−aqueousnucleophilic/non−nucleophilicliquidelectrolytes,ionicliquidbasedpolymeraswellassolid/gelpolymerelectrolytes;intercalahttp://dx.journalhomepage:www.elsevier.com/locate/pmatscition/insertion/conversiontypecathodes;metallicmagnesiumandtheiralloys/intermetallic/compositesasanodes;andelectronicallyconductivebutchemicallyandelectrochemicallyinertcurrentcollectorsformagnesiumbattery.Thelimitedelectrochemicaloxidativestabilityofcurrentgenerationofelectrolyteswithinherentlyslowmagnesium−iondiffusionintoelectrodesaswellastheinabilityofMg2+toreversiblycycleinallbutafewmaterialssystemsimpedethegrowthofhighpowerandhighenergydensitymagnesiumcells,analogoustoLi−ionsystems.Beforethesuccessfulfabricationofaprototypemagnesiumbattery,optimizationofelectrolyteperformance,therealizationofsuitableintercalation/insertioncathodesandtheidentificationofalternativealloys,intermetallics,compositesandcompoundsasanodesarehighlycritical.ExplorationofthecompatibilityofvariousbatterypartsincludingmetalliccurrentcollectorswithcurrentlyusedorganochloroelectrolytesshedslightontheelectrochemicalcorrosionofmetalssuchasCu,Al,stainlesssteel(SS)towardchlorinatedGrignard′ssaltswarrantingfurtherinvestigationforidentifying,electricallyconductingandelectrochemicallyinertcurrentcollectors.Resultstodateshowthepreferentialselectivityofcertainelectronicallyconductingmetallicandnon−metalliccurrentcollectorsforrechargeablemagnesiumbatteriesowingtoitshighanodicstabilityinthepresentelectrolyte.Developmentofmagnesium−ionbatterythereforerequiresaninterdisciplinaryapproachwithasoundunderstandingoforganometallicandinorganicchemistry,adequateknowledgeofmaterialschemistry,materialsscienceandengineering,aswellaselectrochemistry,andacomprehensiveknowledgeofmetalliccorrosionprinciplesinbasic/acidicelectrolyticenvironmentsinorderthatasystemwithacceptableenergydensity(60 W h/kg in the early 2000, the last decade has witnessed tremendous amount of work dedicated to magnesium battery and its components. The present review is an earnest attempt to collect all of the comprehensive body of research performed in the literature hitherto to develop non-aqueous nucleophilic/non-nucleophilic liquid electrolytes, ionic liquid based polymer as well as solid/gel polymer electrolytes; intercalahttp://dx.j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / p m a t s c i tion/insertion/conversion type cathodes; metallic magnesium and their alloys/intermetallic/composites as anodes; and electronically conductive but chemically and electrochemically inert current collectors for magnesium battery. The limited electrochemical oxidative stability of current generation of electrolytes with inherently slow magnesium-ion diffusion in to electrodes as well as the inability of Mg 2+ to reversibly cycle in all but a few materials systems impede the growth of high power and high energy density magnesium cells, analogous to Li-ion systems. Before the successful fabrication of a prototype magnesium battery, optimization of electrolyte performance, the realization of suitable intercalation/ insertion cathodes and the identification of alternative alloys, intermetallics, composites and compounds as anodes are highly critical. Exploration of the compatibility of various battery parts including metallic current collectors with currently used organochloro electrolytes sheds light on the electrochemical corrosion of metals such as Cu, Al, stainless steel (SS) toward chlorinated Grignard's salts warranting further investigation for identifying, electrically conducting and electrochemically inert current collectors. Results to date show the preferential selectivity of certain electronically conducting metallic and non-metallic current collectors for rechargeable magnesium batteries owing to its high anodic stability in the present electrolyte. Development of magnesium-ion battery therefore requires an interdisciplinary approach with a sound understanding of organometallic and inorganic chemistry, adequate knowledge of materials chemistry, materials science and engineering, as well as electrochemistry, and a comprehensive knowledge of metallic corrosion principles in basic/acidic electrolytic environments in order that a system with acceptable energy density (60Wh/kgintheearly2000,thelastdecadehaswitnessedtremendousamountofworkdedicatedtomagnesiumbatteryanditscomponents.Thepresentreviewisanearnestattempttocollectallofthecomprehensivebodyofresearchperformedintheliteraturehithertotodevelopnon−aqueousnucleophilic/non−nucleophilicliquidelectrolytes,ionicliquidbasedpolymeraswellassolid/gelpolymerelectrolytes;intercalahttp://dx.journalhomepage:www.elsevier.com/locate/pmatscition/insertion/conversiontypecathodes;metallicmagnesiumandtheiralloys/intermetallic/compositesasanodes;andelectronicallyconductivebutchemicallyandelectrochemicallyinertcurrentcollectorsformagnesiumbattery.Thelimitedelectrochemicaloxidativestabilityofcurrentgenerationofelectrolyteswithinherentlyslowmagnesium−iondiffusionintoelectrodesaswellastheinabilityofMg2+toreversiblycycleinallbutafewmaterialssystemsimpedethegrowthofhighpowerandhighenergydensitymagnesiumcells,analogoustoLi−ionsystems.Beforethesuccessfulfabricationofaprototypemagnesiumbattery,optimizationofelectrolyteperformance,therealizationofsuitableintercalation/insertioncathodesandtheidentificationofalternativealloys,intermetallics,compositesandcompoundsasanodesarehighlycritical.ExplorationofthecompatibilityofvariousbatterypartsincludingmetalliccurrentcollectorswithcurrentlyusedorganochloroelectrolytesshedslightontheelectrochemicalcorrosionofmetalssuchasCu,Al,stainlesssteel(SS)towardchlorinatedGrignard′ssaltswarrantingfurtherinvestigationforidentifying,electricallyconductingandelectrochemicallyinertcurrentcollectors.Resultstodateshowthepreferentialselectivityofcertainelectronicallyconductingmetallicandnon−metalliccurrentcollectorsforrechargeablemagnesiumbatteriesowingtoitshighanodicstabilityinthepresentelectrolyte.Developmentofmagnesium−ionbatterythereforerequiresaninterdisciplinaryapproachwithasoundunderstandingoforganometallicandinorganicchemistry,adequateknowledgeofmaterialschemistry,materialsscienceandengineering,aswellaselectrochemistry,andacomprehensiveknowledgeofmetalliccorrosionprinciplesinbasic/acidicelectrolyticenvironmentsinorderthatasystemwithacceptableenergydensity(150-200 W h/kg) and operational voltage $2-3 V can be developed in the near future.

Progress in Rechargeable Magnesium Battery Technology

Advanced Materials, 2007

Rechargeable magnesium batteries were first presented about seven years ago. Their components included magnesium metal or a Mg alloy anode, Mg x Mo 6 S 8 (0 < x < 2) Chevrel phase cathodes, and electrolyte solutions that contained an ether solvent and a complex electrolyte, a product of the reaction between a MgBu 2 Lewis base and an AlCl 2 Et Lewis acid (Bu = butyl, Et = ethyl). These systems, while demonstrating impressive cycleability, suffered from several drawbacks: i) The micrometric size Mg 0-2 Mo 6 S 8 Chevrel phase cathode suffers from some kinetic limitation and the phenomenon of partial charge trapping (of Mg ions) at low temperatures. ii) The electrochemical window of the first generation of electrolyte solutions, THF/Mg(AlCl 2 BuEt) 2 was around 2.2 V, which limited the possible use of cathode materials with a higher redox potential (and higher capacity) than Chevrel phases. iii) For practical use, the synthesis of the components of rechargeable Mg batteries needs simplification.

Electrolyte Solutions with a Wide Electrochemical Window for Rechargeable Magnesium Batteries

Journal of The Electrochemical Society, 2008

Electrolyte solutions for rechargeable Mg batteries were developed, based on reaction products of phenyl magnesium chloride ͑PhMgCl͒ Lewis base and AlCl 3 Lewis acid in ethers. The transmetallation of these ligands forms solutions with Mg x Cl y + and AlCl 4−n Ph n − ions as the major ionic species, as analyzed by multinuclei nuclear magnetic resonance spectroscopy. Tetrahydrofuran ͑THF͒ solutions of ͑PhMgCl͒ 2 -AlCl 3 exhibit optimal properties: highly reversible Mg deposition ͑100% cycling efficiency͒ with low overvoltage: Ͻ0.2 V and electrochemical windows wider than 3 V. A specific conductivity of 2-5 ϫ 10 −3 ⍀ −1 cm −1 could be measured between −10 and 30°C for these solutions, similar to that of standard electrolyte solutions for Li batteries. Mg ions intercalate reversibly with Chevrel phase ͑Mg x Mo 6 S 8 ͒ cathodes in these solutions. These systems exhibit high thermal stability. The solutions may enable the use of high voltage, high-capacity Mg insertion materials as cathodes and hence open the door for research and development of high-energy density, rechargeable Mg batteries.

High energy density rechargeable magnesium battery using earth-abundant and non-toxic elements

Scientific reports, 2014

Rechargeable magnesium batteries are poised to be viable candidates for large-scale energy storage devices in smart grid communities and electric vehicles. However, the energy density of previously proposed rechargeable magnesium batteries is low, limited mainly by the cathode materials. Here, we present new design approaches for the cathode in order to realize a high-energy-density rechargeable magnesium battery system. Ion-exchanged MgFeSiO 4 demonstrates a high reversible capacity exceeding 300 mAh?g 21 at a voltage of approximately 2.4 V vs. Mg. Further, the electronic and crystal structure of ion-exchanged MgFeSiO 4 changes during the charging and discharging processes, which demonstrates the (de)insertion of magnesium in the host structure. The combination of ion-exchanged MgFeSiO 4 with a magnesium bis(trifluoromethylsulfonyl)imide-triglyme electrolyte system proposed in this work provides a low-cost and practical rechargeable magnesium battery with high energy density, free from corrosion and safety problems. R echargeable batteries have become quintessential energy conversion devices, that are widely used in portable electronic devices and hybrid electric vehicles. However, their energy density and safety still require improvement, particularly considering their future demand as larger power sources for electric vehicles and smart grid communities 1. Rechargeable magnesium metal batteries are one potential solution. As an anode, magnesium metal provides two electrons per atom, giving it an attractive volumetric capacity of 3837 mAh?cm 23 , which is approximately five times higher than that of the conventional graphite anodes in lithium ion batteries (LIBs). In addition to the high capacity, the relatively high negative reduction potential of magnesium metal can provide high energy density. Moreover, the terrestrial abundance and melting point of elemental magnesium by far surpass that of lithium, translating to a cheap and safe battery system. These advantages of magnesium metal anodes have been previously recognized 2,3 , and a rechargeable magnesium battery cell was first proposed in 2000 4. In this system, sulfide clusters in Chevrel-type Mo 6 S 8 were used as cathodes, and a magnesium organohaloaluminate salt in tetrahydrofuran (THF) was used as the electrolyte. However, the energy density remained rather constrained by the cathode material, and the narrow potential window, corrosion, and safety problems posed by the electrolyte have hampered the commercial realization of these batteries. Recently, magnesium deposition and dissolution obtained by using magnesium bis(trifluoro-methylsulfonyl)imide (Mg(TFSI) 2) with glyme-diglyme have been reported 5. The anodic stability of this elec-trolyte is higher than 3.0 V vs. Mg 21 /Mg, and high-voltage cathode materials can be used in this electrolyte. Even though extensive research has been performed on cathode materials 6 , breakthroughs are awaited for the development of practically usable rechargeable magnesium batteries. In this study, we have attempted to address the problems related to cathode materials by using an ion-exchanged polyanion cathode (i.e., MgFeSiO 4) and constructed a rechargeable magnesium battery using this high-energy-density cathode material.

Electrolyte roadblocks to a magnesium rechargeable battery

Low cost, non-dendritic magnesium metal is an ideal anode for a post lithium ion battery. Currently,development of magnesium electrolytes governs the rate of progress in this field, because electrolyteproperties determine the class of cathodes utilized. A review of the latest progress in the area ofmagnesium battery electrolyte and a perspective on mitigating present challenges is presented herein.Firstly, density functional theory has been shown to predict the potential window of magnesiumelectrolytes on inert electrodes. Secondly, we report initial efforts aimed to overcome the corrosiveproperty of these magnesium organohaloaluminates towards less noble metals such as stainless steel.This is a major challenge in developing high voltage magnesium electrolytes essential for batterieswhich operate above 3V. We lastly touch on cathode candidates including the insertion and conversionclasses. One conversion cathode we pay particular attention to is electrophilic sulfur which can bemarried with magnesium metal anodes by utilizing non-nucleophilic electrolytes obtained by simplecrystallization ofin situgenerated magnesium organohaloaluminates. Effectively, non-nucleophilicelectrolytes open the door to research on magnesium/sulfur batteries. Electrolyte roadblocks to a magnesium rechargeable battery. Available from: https://www.researchgate.net/publication/235430753\_Electrolyte\_roadblocks\_to\_a\_magnesium\_rechargeable\_battery [accessed Sep 28, 2016].

Mg rechargeable batteries: an on-going challenge

Energy & Environmental Science, 2013

The first working Mg rechargeable battery prototypes were ready for presentation about 13 years ago after two breakthroughs. The first was the development of non-Grignard Mg complex electrolyte solutions with reasonably wide electrochemical windows in which Mg electrodes are fully reversible. The second breakthrough was attained by demonstrating high-rate Mg cathodes based on Chevrel phases.

Principles and prospects of high-energy magnesium-ion batteries

Science progress, 2015

In the last decade or so, lithium batteries have gained important niche positions in the market for electrochemical storage systems. Their energy capacities per unit weight (or volume) are remarkably better than those of traditional batteries--yet they appear to be approaching their practical limit, and alternative cell systems are under active investigation. The potential advantages of replacing lithium by magnesium have long been recognised, but for years it was thought that materials limitations and technical problems would prevent them from being realised. However, a combination of commercial pressures and recent scientific breakthroughs has made it likely that magnesium batteries will soon be available for a wide range of applications; they are expected to be cheaper and safer than those based on lithium, with comparable performance. This article briefly reviews the current situation and looks at the general background, principles and cell components, outlining some of the tech...

Uncovering electrochemistries of rechargeable magnesium-ion batteries at low and high temperatures

Energy Storage Materials, 2021

Rechargeable magnesium ion batteries, which possess the advantages of low cost, high safety, high volumetric capacity, and dendrite free cycling, have emerged as one of the potential contenders alleviate the burden on existing lithium ion battery technologies. Within this context, the electrochemical performance of Mg-ion batteries at high and ultra-low temperatures have attracted research attention due to their suitability for use in extreme environments (i.e. military and space station purposes). To meet the requirements for operation over wide temperature ranges, extensive studies are being conducted to explore different cathodes, anodes, electrolytes, and interfacial phenomena. There is no review that compares the characteristics of magnesium ion batteries in terms of their working mechanism, current challenges, working voltages, possible cathode materials, and resultant electrochemistry at different temperatures. To fulfil this research gap, we summarize the recent advances made in the development of magnesium ion batteries, including high-capacity cathodes, nucleophilic and non-nucleophilic electrolytes, hybrid ion tactics, working mechanisms, their high temperature and ultra-low temperature electrochemical performances. Future recommendations for the development of magnesium ion batteries with high energy densities capable of operating under extreme environmental conditions are also presented.

Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries

The need for economical and sustainable energy storage drives battery research today. While Li-ion batteries are the most mature technology, scalable electrochemical energy storage applications benefit from reductions in cost and improved safety. Sodium- and magnesium-ion batteries are two technologies that may prove to be viable alternatives. Both metals are cheaper and more abundant than Li, and have better safety characteristics, while divalent magnesium has the added bonus of passing twice as much charge per atom. On the other hand, both are still emerging fields of research with challenges to overcome. For example, electrodes incorporating Na+ are often pulverized under the repeated strain of shuttling the relatively large ion, while insertion and transport of Mg2+ is often kinetically slow, which stems from larger electrostatic forces. This review provides an overview of cathode and anode materials for sodium-ion batteries, and a comprehensive summary of research on cathodes for magnesium-ion batteries. In addition, several common experimental discrepancies in the literature are addressed, noting the additional constraints placed on magnesium electrochemistry. Lastly, promising strategies for future study are highlighted.

A High-Performance Magnesium Triflate-based Electrolyte for Rechargeable Magnesium Batteries

Cell Reports Physical Science, 2020

The quest for a suitable electrolyte formulation is pivotal to the success of rechargeable magnesium batteries. A simple conventional electrolyte having high compatibility with magnesium anode and cathode material is in great demand. Herein, we report a simple yet effective electrolyte formulation, comprising magnesium triflate (Mg(OTf)2) and magnesium chloride in monoglyme, that can enable highly reversible, conditioning-free, and homogeneous magnesium deposition. Galvanostatic Mg plating/stripping demonstrates an average Coulombic efficiency of 99.4% over 1000 cycles. The cells show excellent performance at current densities up to 3 mA cm-2 and areal capacities up to 5 mAh cm-2. Post-mortem analysis unveils the formation of a robust solid electrolyte interphase, which leads to improved kinetics at the 2 magnesium electrode. A prototype Mg battery with Mo6S8 cathode demonstrates stable cycling performance over 100 cycles. This study shows that rational design of Mg(OTf)2-based electrolytes is a promising direction towards the realization of high-performance magnesium batteries.