On the Feasibility of Practical Mg-S Batteries: Practical Limitations

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On the Feasibility of Practical Mg-S Batteries: Practical Limitations Associated With Metallic Magnesium Anodes Michael Salama, Ran Attias, Baruch Hirsch, Reut Yemini, Yosef Gofer, Malachi Noked, and Doron Aurbach ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b11123 • Publication Date (Web): 08 Oct 2018 Downloaded from http://pubs.acs.org on October 9, 2018

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ACS Applied Materials & Interfaces

On the Feasibility of Practical Mg-S Batteries : Practical Limitations Associated with Metallic Magnesium Anodes Michael Salama, Ran Attias, Baruch Hirsch, Reut Yemini, Yosef Gofer, Malachi Noked, and *Doron Aurbach Department of Chemistry, Bar-Ilan University, Ramat-Gan 5290002, Israel Keyword: magnesium battery, sulfur battery, surface chemistry, electrochemistry, passivation films.

Abstract Rechargeable magnesium batteries (RMB) have attracted a lot of attention in recent decades, due to the theoretical properties of these systems in terms of energy density, safety and price. Nevertheless, to date, fully rechargeable magnesium battery prototypes with sufficient longevity and reversibility were realized only with low voltage and low capacity intercalation cathode materials based on Cheverel phases. The community is therefore actively looking for high capacity cathodes that can work with metallic magnesium anodes in viable RMB systems. One of the most promising cathode materials, in terms of very high theoretical specific capacity, is, naturally, sulfur. A number of recent works studied the electrochemical performances of rechargeable sulfur cathodes in RMB, with success to some extent on the cathode side. Nevertheless, as known from the lithium- sulfur rechargeable battery systems, the formation of soluble polysulfides (PS) during discharge affects strongly the behavior of the anode side. In this paper and the work in describes we focus on this effect in Mg-S systems. We carefully designed herein conditions that mimic Mg-S battery prototypes containing balanced Mg and elemental sulfur electrodes. Under these conditions, we extensively studied the Mg anode behavior. The study shows that when elemental sulfur cathodes are discharged Mg-S cells containing electrolyte solutions in which Mg anodes behave reversibly, the polysulfide species thus formed migrate to the anode and eventually fully passivate it by formation of very stable surface layers. The work involved electrochemical, spectroscopic and microscopic studies. The present study clearly shows that in order to realize practical rechargeable Mg-S batteries, the transport of any sulfide moieties from the sulfur cathode to the magnesium anode has to be completely avoided. Such a condition is mandatory for the operation of secondary Mg-S batteries.

Introduction Rechargeable magnesium batteries are anticipated to be highly attractive, cost effective, safe and environmentally friendly technology for energy storage and conversion. Magnesium is highly abundant element in earth crust It possesses high volumetric specific capacity (3833 mAh/cm3),

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and a low reduction potential (-2.37 V vs. SHE defined for aqueous system). 1–3 It is therefore a natural candidate for secondary high energy density batteries anode material. Research related to magnesium batteries has started in the 1920's with the discovery that Grignard reagents solutions enable reversible electrochemical magnesium deposition.4 However the low conductivity and low anodic stability of such solutions renders them impractical for batteries application. Several decades later (at 1990) Gregory et. al. presented a groundbreaking study in the field and developed, for the first time, feasible electrolyte solutions that can be utilized in rechargeable Mg batteries.5 The best performing electrolyte solution they obtained was 0.25 M Mg(BBu 2Ph2)2 in tetrahydrofuran (THF). This solution enabled highly reversible magnesium deposition and improved electrochemical stability window with nearly 1 V beyond Grignard reagents.4 Nevertheless, the study of Gregory et. al. was short of demonstrating sufficiently attractive properties critical for reversible Mg batteries. A major breakthrough in the field was made at the early 2000's with the demonstration of fully reversible Mg-MgxMo6S8 (Chevrel phase, 0X>3). This simple synthesis allows the preparation of pure lithium polysulfides solutions in DME, with accurately controlled concentrations. LiPS, at the ppmlevel, in magnesium ions electrolytic solutions, are used in this study to examine the influence of trace levels PS on the cycleability of magnesium anodes. It is important to note that Li ions existence in MgTFSI2/DME solutions does not hamper the electrochemical characteristics of Mg anodes, even at very high concentrations.11 Moreover, it is fair to assume that the Li+ in these systems cannot be reduced on the magnesium anode since reduction of Li ions requires much lower voltages. It is also reasonable to assume that a chemical reaction between Mg metal and LiPS species in solution on Mg electrodes surface, should form MgS as a most thermodynamically stable species. It is also expected that the solubility MgS should be much smaller than that of Li2S. As a most suitable non-electrophilic electrolyte solution we used in this study MgTFSI2/MgCl2 in a molar ratio of 1:2 in DME. This electrolyte solution is well-studied, exhibiting high columbic efficiencies and low overpotential for magnesium deposition and dissolution.11,39 The as-prepared electrolyte solution requires a conditioning step (either chemical or electrochemical) which remove any species that reacts on the Mg electrodes surface, leading to passivation (e.g. trace oxygen, water, CO2, acidic species) in order to demonstrate a fully reversible behavior of Mg



electrodes. Figure 2 presents a typical response of repeated magnesium deposition–dissolution cycling in galvanostatic experiments with a well-conditioned electrolyte solution. The average cycling efficiency for this experiment was 98% over 50 cycles, with fairly stable low overpotentials (0.1V for dissolution and 0.15V for deposition) and total capacity retention of 90% over 50 cycles (DOD of 10%). Adding 10 PPM of Li2S8 to this electrolyte system and cycling under the same conditions showed significant effect on the electrochemical response. In Figure 3, an ever increasing oxidation overpotentials as a function of cycle number is clearly seen, up to 0.2V. The final capacity retention decreased to 50%, accounting to an average of 90% macro cycling efficiency. The increase in dissolution overpotentials, coupled with the spike-shaped peaks clearly seen from the 15th cycle and on (at the very beginning of each charging step, and towards the end of each of the discharge) is attributed to surface phenomena that increase the potential required for dissolution. This is a clear sign for magnesium anode electrochemical kinetics worsening. The first clear evidence for passivation-like phenomenon is seen at the very first instance of the first oxidation cycle. A very large, spike-like, over potential has developed (figure 3). A probable cause for this is that prior to the initiation of cycling, magnesium metal is reacting with polysulfide moieties to form a very thin and fragile passivating surface film. This required a relatively high overpotential to break-down and commence electrochemical oxidation at the constant current used. Such a phenomenon is not seen in identical cycling efficiency measurements without the presence of PS species in solutions. Interestingly, no increase in the reduction (metal deposition) overpotential was observed, apart from the overpotential spikes seen from the 20th cycle and on, at the very initial step of magnesium deposition. This spike increases in magnitude with cycle number. We hypothesize that this behavior represents an increased overvoltage that is needed to break the thin MgPS layer formed on the electrode surface during the previous step. It is important to note that the initial magnesium layer deposition was, in all experiments, carried out from a freshly synthesized and well-conditioned electrolyte solution, in order to yield fresh and surface films free magnesium metal deposits. In these experiments the first step was the formation of a thin film of fresh Mg metal on Pt, which served as the working Mg. The polysulfides were always added after the initial magnesium layer deposition, in order to prevent any contamination of the deposited magnesium. Adding 50 PPM of Li2S8 resulted in a much more dramatic decrease in the electrochemical performance, as seen in figure 4. The system overall capacity retention was 0%, from the 7th cycle and on. This means that all the pre-deposited magnesium was already consumed. Obviously, this shows that 50 ppm PS in these solutions is more than enough to severely damage the electrochemical reversibility of the Mg anodes and to render its full passivation in a very short time. In order to further illustrate the effect of PS moieties on magnesium anodes, we discharged a sulfur electrode galvanostaticaly (figure S1), in a well-conditioned MgTFSI2/MgCl2/DME electrolyte solution. We then conducted cyclic voltammetric (CV) measurements in a 3-electrodes cell containing a Pt working electrode, comparing the electrochemical response in the solution after the sulfur electrode discharge to that of a fresh solution. Figure 5 shows steady-state CVs of


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the conditioned electrolyte solution before and after the introduction of PS moieties by the partial reduction of the sulfur cathode (5a, 5b respectively). During the discharge process of the sulfur cathode, a total charge of 0.6 coulombs passed, equivalent to ~ 3.1 µmol of MgS8. This amount translates to ca. 174 ppm of MgS8 in this specific experiment. Figure 5b shows CVs measured with the PS containing solution and a fresh platinum electrode, which assess the impact of the presence of PS species in solution. Very poor electrochemical performance, even in the very first cycle, is demonstrated. The current decay with cycling is consistent with an increasing electrode’s passivation scenario. This poor electrochemical response is attributed to the reduction of PS species on the electrode’s surface. This reduction, either directly on the Pt electrode, or as a consequence of reaction with initially deposited magnesium, forms passivating surface films that completely hamper Mg2+ deposition\dissolution when they fully cover all the electrode’s active sites (Pt or Mg deposits on Pt). Apparently, electroactive magnesium species, such as Mg++3DME or MgCl+, do not have the ability to cross passivation barriers, at least not on the time scale of these experiments. Deeper understanding of the nature of the passivating film could be gained from microscopy and spectroscopic measurements. Figure 6a shows HRSEM images of magnesium deposited from the well-conditioned DME/MgTFSI2/MgCl2 (our standard) solution on a clean Pt electrode. The shape of the deposits and their chemical composition (by EDS Fig S2 , table S1) are in very good agreement with the reported metallic magnesium films deposited from electrolyte solutions in which Mg electrodes are fully reversible. Once the electrolyte solution is even slightly contaminated with PS species, the morphology and composition of the deposited film is completely different. The film is contaminated with sulfur and the appearance of the magnesium surface is of large, globular, noncrystalline deposits as depicted in figure 6b. After the sulfur electrode was discharged into a preconditioned solution a fresh Pt electrode was introduced into the solution and magnesium was deposited from this solution on the Pt electrode. EDS mapping (Figure S3-S4, Table S2) shows that in the contaminated electrolyte solutions the deposits obtained are chemically non-uniform, containing islands of sulfur-containing surface species. This observation is in-line with the poor electrochemical performance obtained with the solutions containing PS. It had been exemplified numerous times, that metallic magnesium deposits formed in solutions that render high reversibility of Mg electrodes, always exhibit sharp microcrystalline morphology.11,14 In turn, in solutions in which the reversibility of Mg electrodes is poor (yet allowing electrochemical Mg deposition), the morphology of the Mg deposits is nodular, pit-holes and amorphous.46,47 The deposits obtained on Pt electrodes from PS contaminated DME 0.25M MgTFSI2 0.5M MgCl2 solutions solution were analyzed by XPS. The results were clear and conclusive without the need of sophisticated spectra analysis. Figure 7 shows a representative S 2p spectrum. Overall, all element spectrum is presented in figure 5S, while spectra related to F 1s, O 1s, C 1s, N 1s, Cl 2p, Mg 2p and Pt 2F are presented in figures S6 – S12 respectively. The sulfur spectrum in figure 7



clearly shows that cathodic processes in these solutions yield deposits containing MgS as a major surface component. The strong peak at ca. 160 eV in the sulfur 2p spectrum is typical for sulfur in MgS.32,40 As presented in the SI (figures S5-12) the Mg deposits surfaces include also species which include F, O, C, and Cl. Surface species containing these elements exist also on Mg deposits formed in PS free DME/MgTFSI2/MgCl2 solutions. The XPS spectra of oxygen and carbon relate to contaminants resulting from the ex-situ measurements. The Cl spectrum reflects residual surface MgCl2 and the F spectrum reflects some products resulting from interactions of the TFSI anions and the Mg surfaces.11 Based on the XPS data, it is clear that the MgS formed on the electrode’s surface in the PS contaminated solutions relates to the presence of the PS moieties and not to the reduction of the TFSI anions in the presence of Mg cations, because TFSI anions are not reduced by Mg metal to MgS, but rather to sulfur species at higher sulfur oxidation states48 .Therefore we can safely assume by relying on our experimental work and as well as the work of Canepa et al.43, which predict large overpotential (900meV) for magnesium migration through MgS, that the poor electrochemical performance are the result of the MgS formation.

Conclusion Despite the theoretical promise behind utilization of sulfur as a cathode material for RMB, surface passivation of the metallic magnesium anodes remain a key issue that the scientific community needs to address. We have shown that during the reduction of sulfur cathode, the formation of polysulfide moieties leads to detrimental reactions on the magnesium anode surface that severely reduces its activity due to passivation. We believe that MgS formation on the anode, as revealed in the current study, is the process that dominates the electrochemical response of Mg electrodes in any ethereal solutions that contain polysulfide moieties. Thereby, all conventional battery configuration based on Mg anode and sulfur cathode are supposed to demonstrate very limited cycling capability, since sooner or later, the Mg anode will become fully blocked when the MgS layer thus formed covers all active anode’s sites. Hence, any future advance toward practical magnesium-sulfur battery systems must address the anode-soluble PS species compatibility of such systems. We strongly believe that the only viable way to address this issue is by fixating the sulfur in the cathode by some sort of encapsulation that should prevent any introduction of soluble polysulfide species into the solution. This could be achieved by adding protective layer that can conduct Mg ions selectively, like metal chalcogenide materials,25,49 and prevent PS dissolution from the cathode. Alternatively, one can contemplate on developing solid-state electrolytes for rechargeable magnesium batteries or Mg anodes protected by solid electrolyte films that can somehow conduct Mg ions. Another option that might be of interest is the development of active separators that allow transport of Mg ions but avoid passage of polysulfide moieties from the cathode to the anode sides. All the above options are somewhat utopic at the current stage, and may be very hard to achieve.


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Experimental Materials and measurements conditions.

MgTFSI2 (99.95%) was purchased from Solvionic. 99% pure dimethoxyethane, MgCl2 (99.99%), Lithium sulfide Li2S (99.98%), and sulfur S8 (99.998%). were purchased from Sigma-Aldrich. All electrochemical measurements and solution preparations were performed in an highly pure Ar filled glove box. Cell configuration and electrodes materials. All electrochemical measurements were performed in flooded 3 electrode glass cells. Mg foil/strips were used as the counter/reference electrodes in all measurements. Pt was used as the working electrode for all Mg metal deposition/dissolution measurements. For the preparation of sulfur cathodes carbon cloth were cut to 14mm discs which were impregnated with sulfur. The carbon discs were sealed in a stainless steel vessel (swagelock) along with elemental sulfur. Than the sealed vessel was heated to 150 0C overnight. The final sulfur load was 3 mg per electrode. Analytical work. Electrochemical measurements were performed with a VMP-3 potentiostat, Bio-Logic Co. MgTFSI2/MgCl2 solutions were cycled between -0.8 – 2.5V vs Mg. For macro-reversibility measurements ca. 1 micrometer Mg (0.5 coulombs/cm2) was deposited at 1 mA/cm2 on Pt. Then, 10% of the initially deposited film was electrochemically dissolved and re-deposited at current



density of 1 mA/cm2 in order to measure cycleability and cycling efficiency of thin Mg electrodes. After 50 cycles (in the relevant cases), the remaining Mg deposit was electrochemically dissolved at 1 mA/cm2 until the voltage steeply rose, indicating the measurement end point. XPS Analysis— XPS analyses were performed in a Kratos AXISHS spectrometer, using a monochromatized Al Ka source. Survey and high resolution scans were acquired at 150 W. All acquisitions were performed in a hybrid mode (using electrostatic and magnetic lenses) and detection pass energies of 80 or 40 eV for survey and high resolution scans, respectively. All acquisitions were made with low energy electron flood gun for charge neutralization. Samples were transferred from the glove box to the XPS load-lock under inert Ar atmosphere using proprietarily made, air-tight, transfer system. All XPS measurements were carried out at room temperature, under vacuum conditions of (1.0–3.0) 10–9 Torr. The spectrometer energy scale was routinely calibrated according to the ISO TC/201 SC7 international procedure for binding energy (BE) with Au 4f7/2) 83.98 and Cu2p3/2 ) 932.67. Data processing was done with either VISION2.1 software (“Kratos”). In most cases a Shirley background was used. HR-SEM - SEM images were obtained by a Magellan XHR 400L FE-SEM (FEI Company)

Supporting Information EDS mapping, additional electrochemistry measurements, XPS spectra of F,N,O,Mg,Pt. Corresponding Author E-mail: *[email protected]; Phone +9723-5318317 (D.A.)

Aknowledgements We thank the Israeli Ministry of Scirnce and Technology for partial support in the framework of the School of Batteries research projects. We also thank Israel Committee of High Education and the Prime Minister Office for a partial support in the framework of INREP consortium.

Figures


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Figure 1- UV-vis spectrum of MgTFSI2 0.25 M + MgCl2 0.5 M/DME electrolyte solution after sulfur cathode reduction.



Figure 2- Macro reversibility measurements for a conditioned MgTFSI2 0.25 M + MgCl2 0.5 M/DME solution. 0.5 coulombs per cm2 of magnesium was deposited on a clean Pt electrode. This Mg (on Pt) electrode was cycled galvanostatically 50 times at 10% depth of discharge at 1 mA/cm2. Mg foils served as CE and RE. The last half cycle was galvanostatic oxidation, at the same current density, with a cutoff voltage of 2.0V, corresponding to Mg-metal free Pt electrode.


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Figure 3- Macro cycling efficiency measurements for conditioned MgTFSI2 0.25 M + MgCl2 0.5 M/DME solution with 10 PPM of Li2S8 . The sulfide as added to the formerly conditioned solution after the initial magnesium deposition. The electrochemical cycling conditions are identical in all experiments. Inset: Magnification of the chrono-potentiometric response and the evolution of the overpotential for Mg dissolution.



Figure 4- Macro reversibility measurements for conditioned MgTFSI2 0.25 M + MgCl2 0.5 M/DME solution. 50 PPM of Li2S8 were added after conditioning. Certain amounts of magnesium were deposited on Pt electrodes (corresponding to 0.5 Coulombs per cm2). These Mg (on Pt) electrodes were cycled galvanostatically 50 times at 10% depth of discharge at 1 mA/cm2. Mg foils served as CE and RE.


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Figure 5 – a) CV cycles of conditioned MgTFSI2 0.25 M with MgCl2 0.5 M in DME solution. Pt served as the WE, and Mg as the RE and CE, scan rate 25 mV/sec. b) CV cycles of conditioned MgTFSI2 0.25 M with MgCl2 0.5 M in DME solution after discharging a sulfur cathode at the same cell and solution. Pt served as the WE, and Mg as the RE and CE, scan rate 25 mV/sec. c) Efficiencies of repeated CV cycles conditioned MgTFSI2 0.25 M with MgCl2 0.5 M in DME solution. d) Efficiencies of CV cycles of conditioned MgTFSI2 0.25 M with MgCl2 0.5 M in DME solution after discharging a sulfur cathode at the same cell and solution.



Figure 6. SEM images of a 1 micron thick (calculated) Mg deposits on Pt electrode. The Mg was deposited from: (a) MgTFSI2 0.25 M + MgCl2 0.5 M/ DME solution at 1 mA/cm2, (b) MgTFSI2 0.25 M + MgCl2 0.5 M/DME solution after sulfur cathode discharge at 1 mA/cm2


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figure 7–XPS S 2p spectrum of deposits on a Pt electrode formed by a cathodic processes of a PS contaminated 0.25 M MgTFSI and 0.5 M MgCl2 DME solution.

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On the Feasibility of Practical Mg-S Batteries: Practical Limitations

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