An Efficient Halogen‐Free Electrolyte for Use in Rechargeable Magnesium Batteries

Tutusaus, Oscar; Mohtadi, Rana; Arthur, Timothy S.; Mizuno, Fuminori; Nelson, Emily G.; Sevryugina, Yulia

doi:10.1002/anie.201412202

Cited by 417 publications

(405 citation statements)

References 30 publications

(40 reference statements)

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“…This structure consists of shoulder(s) on the low side attributed to 1s→4s transition(s), and the principal peak attributed to the transition 1s→4p, made of two peaks whose relative intensities should depend on the type of calcium involved according to the dipole transition selection rule. 31,42 In addition, the edge position is affected by the coordination number of the calcium, 43 as shown by the similar edge positions shown by CaF 2 and CaC 2 O 4 , which has eight nearest neighbors, as compared to the edges for CaCO 3 and Ca(OH) 2 , which has six-fold coordination.…”

Section: Resultsmentioning

confidence: 95%

Utilization of Ca K-Edge X-ray Absorption Near Edge Structure to Identify Intercalation in Potential Multivalent Battery Materials

Proffit

Fister

Kim

et al. 2016

J. Electrochem. Soc.

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Multivalent-ion batteries have been under investigation as a technology that can provide energy densities beyond that provided by lithium ion batteries. An emerging cation of interest is calcium, as it has similar electrochemical properties and size to sodium, and systems incorporating it have high theoretical density. Common techniques used to investigate intercalation, such as NMR, are currently unable to distinguish calcium's role in energy storage materials. In this work, we investigated the ability of calcium XANES to provide fingerprint identification of intercalated species using Ca ion exchanged Na x CoO 2 and a Ca(PF 6 ) 2 -based electrolyte as a case study. Ca XANES was able to detect intercalation down to concentrations of ∼1 Ca per 950 Å 3 , even with residual electrolyte on the surface. The ability to observe the structure of the intercalated ion will enable the discovery of new electrolytes and intercalation cathodes by helping to confirm theoretical predictions, allowing multivalent batteries to become a viable high energy density storage 8 but understanding and improving upon multivalent intercalation requires experimental observation of the intercalated species and correlating it with the resulting structural changes, in combination with the electrochemistry of interest. In the case of Mg ion intercalation, spectroscopic tools such as 25 Mg nuclear magnetic resonance (NMR) 7,9 have been developed, in combination with transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and energy dispersive spectroscopy (EDS), to provide strong evidence of magnesium ion intercalation, and in some cases, identify cases of solvent co-intercalation, the presence of structural protons, or nanoscale decomposition.10,11 Whereas magnesium (Mg 2+ ) and aluminum (Al 3+ ) cations have received the most attention as multivalent alternatives to lithium (Li + ), calcium cations (Ca 2+ ) have been identified as a promising candidate ion for transport of multiple electrons due to the high theoretical volumetric capacity of a calcium metal anode.12 Calcium may also provide advantages as compared to magnesium due to its more negative reduction potential and larger ionic radius, which may allow for faster diffusion. Unlike for magnesium and yttrium ions, however, NMR is not currently a practical diagnostic tool for determining the local structure of the calcium ion to confirm intercalation because of the low abundance and poor sensitivity of 43 Ca, the most active calcium isotope. Therefore, different approaches need to be developed to validate the alternative design paradigm, notably using the Materials Project, 3 which hypothesizes that cations in undesirable coordination environments are more likely to have high diffusivity than ones in stable coordination environment. By providing data for such models, the process of screening potential intercalation cathodes can be narrowed. In addition, this * Electrochemical Society Member.c Present Address: Spectrum Brands -Rayovac, Madison...

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Section: Resultsmentioning

confidence: 95%

Utilization of Ca K-Edge X-ray Absorption Near Edge Structure to Identify Intercalation in Potential Multivalent Battery Materials

Proffit

Fister

Kim

et al. 2016

J. Electrochem. Soc.

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“…complex electrolyte (APC-all phenyl complex) (Tutusaus et al, 2015). Wang et al tested the chemical magnesiation of α-MnO2 using di-n-butylmagnesium/heptane and diphenylmagnesium/ THF and failed to observe any intercalated product.…”

Section: −1mentioning

confidence: 99%

“…Coin cells constructed with this configuration delivered a stable performance to >2,000 cycles. After 15 years of research, the development of practical rMB has seen lights from several breakthroughs such as the discovery of electrolytes with wider operation window and less corrosive capability (Muldoon et al, 2012;Yoo et al, 2013;Tutusaus et al, 2015). Meanwhile, the Chevrel phase used in Aurbach's work is still by far the most successful cathode with remarkable reversibility and cyclability for rMB.…”

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confidence: 99%

Manganese Dioxide As Rechargeable Magnesium Battery Cathode

Ling¹,

Zhang²

2017

Front. Energy Res.

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Rechargeable magnesium battery (rMB) has received increased attention as a promising alternative to current Li-ion technology. However, the lack of appropriate cathode that provides high-energy density and good sustainability greatly hinders the development of practical rMBs. To date, the successful Mg 2+ -intercalation was only achieved in only a few cathode hosts, one of which is manganese dioxide. This review summarizes the research activity of studying MnO2 in magnesium cells. In recent years, the cathodic performance of MnO2 was impressively improved to the capacity of >150-200 mAh g −1 at voltage of 2.6-2.8 V with cyclability to hundreds or more cycles. In addition to reviewing electrochemical performance, we sketch a mechanistic picture to show how the fundamental understanding about MnO2 cathode has been changed and how it paved the road to the improvement of cathode performance.

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“…The use of aromatic ligands enabled to develop electrolyte solutions with wider electrochemical windows > 3 V. 4 It should be noted that in recent years, several families of electrolyte solutions for Mg batteries which exhibit wide electrochemical windows were developed by other groups. [5][6][7][8][9][10][11] Recently we demonstrated organometallic-free electrolyte solutions named MACC. These solutions were comprised of the reaction products between MgCl 2 and AlCl 3 in THF.…”

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confidence: 99%

Evaluation of (CF₃SO₂)₂N⁻(TFSI) Based Electrolyte Solutions for Mg Batteries

Shterenberg

Salama

Yoo

et al. 2015

J. Electrochem. Soc.

316

445

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MgTFSI 2 is the only ether-soluble "simple" magnesium salt. The poor electrochemical performance of Mg electrodes in its solutions hinders its practicality as a viable electrolyte for Mg batteries. MgTFSI 2 /DME solutions were demonstrated to dissolve large quantities of MgCl 2 and produce electrolyte solutions with superior performance, though the electrochemical performance, mainly in terms of reversibility, of MgTFSI 2 /MgCl 2 (DME) solutions cannot yet compete with that of organometallic based electrolyte solutions. We believe that the solutions' purity level governs the overall electrochemical performance, especially in solutions where a strong reductant (i.e Grignard reagent) is not present to act as an impurity scavenger. In this work, we alter the performance of the MgTFSI 2 /MgCl 2 (DME) solutions through chemical and electrochemical conditioning and demonstrate the effect on the solutions' electrochemical characteristics. We demonstrate relatively high reversible behavior of Mg deposition/dissolution with crystalline uniformity of the Mg deposits, complemented by a fully reversible intercalation/de-intercalation process of Mg ions into Mo 6 S 8 cathodes. We also investigated LiTFSI/MgCl 2 solutions which exhibited even higher reversibility than MgTFSI 2 /MgCl 2 (DME) solutions, which we attribute to the higher purity level available for the LiTFSI salt. Magnesium is a natural candidate anode material for "next generation" rechargeable batteries due to its high volumetric capacity (3833 mAh/cm 3 ), low reduction potential (−2.3 V) wide abundance, and low price.1 Rechargeable Mg battery research had been developing very slowly since the 1920's but had recently gained a big momentum. Magnesium battery systems will have great difficulties to outperform lithium systems In terms of energy and power density. However, they possess several properties that make them desirable, as they are expected to benefit from a cheaper price and lower hazard levels. One of the core issues developing rechargeable magnesium batteries is the formulation of electrolytic solutions that support reversible magnesium deposition. Other properties such as sufficient ionic conductivity, adequate magnesium ion concentration, and a wide electrochemical window are also mandatory. 15 years ago we synthesized electrolyte solutions that possessed most of the key features listed above. These electrolyte solutions were the product of a Lewis acid/base reaction in which R 2 Mg moieties such as Bu 2 Mg served as the base component, and RAlCl 2 species such as EtAlCl 2 served as the acid component.Hence, we could demonstrate a family of organometallic electrolyte solutions for rechargeable Mg batteries known as di-chloro complex solutions (DCC).2,3 Unfortunately, even the best DCC electrolyte solution does not possess the minimum requirement needed for next generation rechargeable magnesium batteries, e.g. wide electrochemical stability window (>2.2 V), chemical stability and safety. The use of aromatic ligands enabled to develop electrolyte solu...

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An Efficient Halogen‐Free Electrolyte for Use in Rechargeable Magnesium Batteries

Cited by 417 publications

References 30 publications

Utilization of Ca K-Edge X-ray Absorption Near Edge Structure to Identify Intercalation in Potential Multivalent Battery Materials

Utilization of Ca K-Edge X-ray Absorption Near Edge Structure to Identify Intercalation in Potential Multivalent Battery Materials

Manganese Dioxide As Rechargeable Magnesium Battery Cathode

Evaluation of (CF₃SO₂)₂N⁻(TFSI) Based Electrolyte Solutions for Mg Batteries

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An Efficient Halogen‐Free Electrolyte for Use in Rechargeable Magnesium Batteries

Cited by 417 publications

References 30 publications

Utilization of Ca K-Edge X-ray Absorption Near Edge Structure to Identify Intercalation in Potential Multivalent Battery Materials

Utilization of Ca K-Edge X-ray Absorption Near Edge Structure to Identify Intercalation in Potential Multivalent Battery Materials

Manganese Dioxide As Rechargeable Magnesium Battery Cathode

Evaluation of (CF3SO2)2N−(TFSI) Based Electrolyte Solutions for Mg Batteries

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Evaluation of (CF₃SO₂)₂N⁻(TFSI) Based Electrolyte Solutions for Mg Batteries