A Rechargeable Zinc-Aqueous Polysulfide Battery with a Mediator-Ion

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A Rechargeable Zinc-Aqueous Polysulfide Battery with a Mediator-Ion Solid Electrolyte Martha M Gross, and Arumugam Manthiram ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b00981 • Publication Date (Web): 21 Mar 2018 Downloaded from http://pubs.acs.org on March 22, 2018

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ACS Applied Materials & Interfaces

A Rechargeable Zinc-Aqueous Polysulfide Battery with a Mediator-Ion Solid Electrolyte Martha M. Gross and Arumugam Manthiram* Materials Science & Engineering Program and Texas Materials Institute, The University of Texas at Austin, Austin, Texas 78712, United States AUTHOR INFORMATION Corresponding Author *Email: [email protected] KEYWORDS: Sulfur batteries, zinc batteries, polysulfides, solid electrolyte, aqueous batteries

ACS Paragon Plus Environment

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ABSTRACT

Large scale energy storage for the electric grid will require low cost and high energy density solutions. We demonstrate in this letter a rechargeable zinc-aqueous polysulfide battery in which a metallic zinc anode is separated from a liquid aqueous polysulfide catholyte by an alkali-metal-ion solid-state electrolyte, wherein the alkali metal ion is Na+ or Li+. The solid-state electrolyte effectively separates the anode from the reactive polysulfide catholyte, preventing the crossover of the polysulfide species and maintaining good electrochemical performance with a reversible discharge capacity of 822 mA h g-1 with nearly 100% Coulombic efficiency.


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Grid reliability and penetration of renewable energy are driving demand for large-scale energy storage systems. The intermittent nature of renewables and a large projected increase in electricity consumption are making the need for large-scale energy storage more urgent.1-5 There has been a strong focus on batteries that make use either of high energy-density or low-cost active materials. Sulfur has attracted much attention in this regard, as it is widely abundant, inexpensive, and exhibits a high theoretical capacity. Efforts have focused on exploiting the high energy density of sulfur in such systems as the lithium-sulfur battery (1675 mA h g-1) and capturing its low cost in systems such as the redox-flow polysulfide-bromine battery.6,7

Dissolved sulfur in the form of polysulfide has attracted attention as a candidate energy storage media, as it has a large solubility in both aqueous and organic solvents.8,9 Batteries containing a high density of dissolved redox active sulfur in the form of polysulfides allows for a high system-wide energy density, as these batteries do not require inactive materials such as binders or conductive additives, or excess electrolyte typically needed for solid sulfur cathodes.5 Polysulfide in aqueous solvent has a particularly high solubility, achieving up to 8.5 molal concentrations in the case of K2S4.8 Initial work with aqueous polysulfide focused on static primary batteries, and only recently the static secondary batteries with polysulfide active material have been explored.10-16 A summary of prior work on static batteries with aqueous polysulfide active material can be found in Table SI in the supporting information.

Zinc is an attractive anode material due to its low cost and widespread use as an industrial metal. It offers a voltage of -1.22 V (versus standard hydrogen electrode (SHE)) and reasonable stability and cyclability in alkaline electrolytes.17 When used in a zinc-sulfur battery, however, zinc rapidly reacts with polysulfides to form a passivating zinc sulfide (ZnS) film on the anode


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surface, which prevents discharge of the anode. Bendikov et al. successfully demonstrated a single compartment (no separator) zinc-aqueous polysulfide battery with a strongly alkaline electrolyte (pH ≥ 15), which prevented passivation of the anode, allowing the battery to discharge.11 However, the cell was not rechargeable.18 Complete separation of the zinc anode and polysulfide catholyte is necessary for the battery to be rechargeable.

Recently Li et al. demonstrated a lithium-aqueous polysulfide battery that used a lithium ion-conducting solid-state electrolyte (SSE) to separate a metallic lithium anode from an aqueous polysulfide catholyte.14 Demir-Cakan et al. employed a lithium ion-conducting SSE to separate a LiMn2O4 cathode from a polysulfide anolyte.13 The SSE, as demonstrated in these studies, is so effective at separating the reactive polysulfide catholyte that Visco et al. are working to commercialize a lithium-sulfur battery based on the use of the SSE.12 In the case of a zinc anode, however, a Zn2+ ion SSE that operates at room temperature is not practically available.19,20

Herein we demonstrate for the first time, to the best of the authors’ knowledge, a rechargeable zinc aqueous polysulfide (ZAPS) battery by means of a mediator-ion SSE. The ZAPS battery consists of a Zn anode, an alkaline anolyte, a mediator-ion SSE, an aqueous polysulfide catholyte, and catalytically active cobalt sulfide (CoS) electrode. We demonstrate the concept and electrochemical characteristics of our rechargeable ZAPS battery with both a lithium and sodium mediator ion. Figure 1 presents a schematic of the ZAPS battery on discharge. On discharge, Zn is oxidized to form the zincate ion by the following reaction:

Zn + 4OH- → [Zn(OH)4 ]2- + 2e-

1.22 V vs. SHE


(1)

4

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At the cathode, dissolved S42- (predominant) is reduced to S2- by the following simplified reaction for extremely high concentrations of polysulfide,

2S24 + 6e → 4S

~ - 0.50 V vs. SHE

(2)

and by the following simplified reaction for moderate to low concentrations of polysulfide:8

S24 + 6e + 4H2 O → 4HS + 4OH

~ - 0.50 V vs. SHE

(3)

Charge balance is maintained by Li+ or Na+ mediator ions shuttling from the anolyte, through the mediator-ion SSE to the catholyte. On charge, the reverse reactions occur. The proof-of-concept battery demonstrated in this work uses moderate concentrations of polysulfide, so the balanced reaction of this cell can be described as

3Zn + 8OH − + S42− 4H2 O → 3[Zn(OH)4 ]2− + 4HS −

(4)

Participation of the hydroxide at the anode reduces the overall capacity of the battery from the theoretical 550 mA h g-1 for a ZnS reaction product to a still high capacity of 349 mA h g-1.


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e-

e-

� �

Zn Anode

Zn(OH)42M+

M+

M+

M+

OH–

� �

Catalytic Electrode

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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MOH, aq. SSE

Figure 1. Illustration of the zinc-aqueous polysulfide battery, in which alkali metal M is either Na or Li. SSE is an alkali-metal-ion-conducting solid-state electrolyte.

It should be noted that sulfur, when dissolved in aqueous media in the presence of sulfides, forms a multitude of species including HS-, H2S, S2- and polysulfide species Sx2- (x = 2 – 5), as confirmed by the UV-Visible spectroscopy in Figure S1.21 The concentration distribution of these species is largely dependent on the pH of the solution, as well as the initial concentrations of sulfide and nonvalent sulfur.22 Electrochemical activity comes from the sulfide and polysulfide species according to reactions 5-7.

23S24 + 2e → 4S3

- 0.48 V vs. SHE

(5)

22S23 + 2e → 3S2

- 0.50 V vs. SHE

(6)

2S22 + 2e → 2S

- 0.52 V vs. SHE

(7)


6

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In our system, the catholyte is at a high pH of ~13 due to added sodium or lithium hydroxide, which shifts the specie distribution so that S42- dominates at equilibrium. For this reason, in this report we describe our catholyte as containing Na2S4 or Li2S4 as a nominal description. Based on the high concentration of S42- in our system, the theoretical voltage is expected to be about 0.74 V. Despite this low voltage, due to the high capacity of the zinc and polysulfide active materials the ZAPS battery has a theoretical energy density of 251 W h kg-1 of total active material.

It should also be noted that the polysulfide in alkaline media is known to be unstable, disproportionating into S2O32- by the reaction,

− 4Sdissolved + 4OH − → S2 O2− 3 + 2HS + H2 O

(8)

At room temperature, the rate of degradation is very low, and can be further slowed by tailoring the solution composition such that the concentration of dissolved sulfur in the form of polysulfide is high and the concentration of hydroxide is relatively low22.

A CoS electrocatalyst was prepared for use in the ZAPS battery as it is a well-known catalyst for polysulfide reduction.23,24 CoS was prepared by first electrodepositing cobalt on a stainless steel mesh substrate as Co@SS followed by pretreating the Co@SS in 1 M Na2S4 solution to form CoS@SS, as detailed in the experimental section in the supporting information. Figure 2 shows the scanning electron microscopy (SEM) images, transmission electron microscopy (TEM) images with selected area electron diffraction (SAED) patterns, and energy dispersive spectroscopy (EDS) composition maps of the catalyst. The Co deposited as a hierarchical nanoflake structure, fully covering the steel surface except for small patches, as


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shown in Figure 2a. The patches of bare steel are likely due to incomplete stripping of the native oxide scale before deposition. Despite this, stainless steel was chosen as a substrate over a more traditional brass substrate due to its higher stability in polysulfide solution, as is demonstrated by Figures S2 and S3 in the supporting information. The Co deposit is highly polycrystalline. Figures 2b and S4 show that pretreatment of the Co to form CoS resulted in a uniform sulfur distribution and an unchanged surface morphology. TEM and EDS show the CoS layer to be 4080 nm thick, and it retains the highly polycrystalline nature of the Co deposit. X-ray photoelectron spectroscopy (XPS) shows Co 2p and S 2p peaks characteristic of mixed-phase cobalt sulfide, as shown in Figure S625. This is further corroborated by SAED in which peaks of multiple Co-S phases can be matched. Surface morphology and XPS spectra remained relatively unchanged after cycling in a ZAPS battery for 50 cycles, as shown in Figures 2c, S5 and S6. TEM shows that after cycling, the surface of the CoS has become more amorphous and the thickness of the sulfide layer has increased. The SAED pattern is unchanged after cycling, indicating that crystalline Co-S phases persist after cycling. Furthermore, EDS shows some Zn signal on the catalyst surface after cycling, which may be indicative of a minor leak between the anode and cathode chambers of the battery.


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Figure 2. SEM images, TEM image (inset: SAED pattern), and EDS mapping of (a) Co@SS surface after deposition on SS mesh substrate, with the arrows highlighting regions of bare substrate, (b) CoS@SS surface after pretreatment in 1M Na2S4 (inset: EDS map of sulfur) and (c) CoS@SS surface after cycling in a ZAPS battery for 50 cycles


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The ZAPS batteries were assembled with a metallic Zn anode, 0.5 M NaOH anolyte, Na3Zr2Si2PO12 (NZSP) SSE, 0.1 M Na2S4 + 0.1 M NaOH catholyte, and CoS@SS catalytically active electrode. Open-circuit voltage (OCV) of the battery was 0.89 V. A full explanation of the high OCV value compared to the theoretical 0.74 V noted earlier can be found in the supporting information. Batteries were assembled with an excess of Zn and anolyte, so performance was analyzed based on the limiting polysulfide catholyte. Voltage limits of the battery during cycling were determined by first discharging the battery at 0.5 mA cm -2 current density to completion. The onset voltage of the hydrogen evolution reaction (HER) was determined to be 0.19 V, as shown in Figure 3a. To achieve a deep discharge of the battery a discharge voltage of 0.3 V was chosen. A separate battery was discharged at 0.5 mA cm-2 current density to 0.3 V, then charged to completion. Figure 3b shows two plateaus, one for the conversion of S2- to S42-, and other for the conversion from S42- to nonvalent sulfur (S0). These plateaus correspond to the redox peaks demonstrated by cyclic voltammetry (CV) in Figure S7a. An upper voltage limit of 0.9 V was chosen to ensure that no solid sulfur precipitation occurred during cycling.

Electrochemical stability of the ZAPS battery was studied by cycling the battery for 50 cycles. Figure 3c shows the voltage profile of the cycling ZAPS battery. The first discharge shows a relatively flat plateau, while all subsequent charge and discharge cycles display a sloped voltage profile. The initial discharge capacity is 966 mA h g-1, which is above the theoretical capacity of Na2S4 (924 mA h g-1). All reported capacities and energy densities are per gram of Na2S4 unless otherwise specified. This higher-than-theoretical capacity achieved may be due to a thin film of deposited sulfur on the CoS@SS electrode after pretreatment not visible by SEM, or due to some electrochemical participation of the catalyst. CV of the ZAPS battery with and


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without polysulfide shows that even without polysulfide, the ZAPS battery demonstrates a minor amount of electrochemical activity which may be attributed to the known pseudocapacitance of CoS (Figure S7b).26 The electrochemical performance reveals that the ZAPS battery maintains a highly reversible discharge capacity of 822 mA h g-1 after 50 cycles (Figure 3d). The coulombic efficiency of the battery was ~100% throughout cycling. Despite the low discharge voltage of ~ 0.64V, the ZAPS battery displayed a maximum energy density of 586 W h kg -1, and retained an energy density of 529 W h kg-1 after 50 cycles. The energy density can be improved with improved catalysts to lower the discharge overpotential. No change is observed in overpotential during cycling, or in the SSE phase as measured by x-ray diffraction, implying good stability of the SSE in alkaline and polysulfide media, as seen in Figures S8 and S9.


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Figure 3. (a) Discharge voltage profile to the HER regime and (b) charge voltage profile to precipitate nonvalent sulfur. (c) Discharge-charge curves of ZAPS battery. (d) Cycling performance of the ZAPS battery, presenting discharge capacity and coulombic efficiency.

Figure 4 presents the rate and power performances of the ZAPS batteries built with Na+ and Li+ mediator ions. The ZAPS batteries with the Na+ mediator ion (Na-ZAPS) were built as previously described. ZAPS batteries with the Li+ mediator ion (Li-ZAPS) were assembled with a metallic Zn anode, 0.5 M LiOH anolyte, Li1+x+yAlxTi2-xP3-ySiyO12 (LATP) SSE, 0.1 M Li2S4 + 0.1 M LiOH catholyte, and CoS@SS catalytically active electrode. Each battery was cycled at increasing current densities from 0.1 mA cm-2 to 2.5 mA cm-2 with a lower voltage limit of 0.2 V imposed to prevent ingression into the HER regime. The Na-ZAPS battery consistently


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performed better than the Li-ZAPS battery, as shown in Figure 4a. The Na-ZAPS battery had a lower overpotential at every current density including the lowest rate of 0.1 mA cm-2. The LiZAPS battery showed a degrading charge profile at a current density of 1.5 mA cm-2, and cycling was stopped at 1.75 mA cm-2 due to the Li-ZAPS battery reaching the 0.2 V lower voltage limit. The Na-ZAPS battery, on the other hand, was able to cycle to 2.5 mA cm -2 without degradation to its voltage profile. The Li-ZAPS battery reached a peak power density of 0.35 mW cm-2 as shown in Figure 4b, while the Na-ZAPS battery reached a peak power density of 1.05 mW cm-2, three times that of the Li-ZAPS battery.

To probe the differences between the Na-ZAPS and Li-ZAPS batteries rate and power performances, electrochemical impedance spectroscopy (EIS) was performed on uncycled cells. The EIS spectra show that the Na-ZAPS battery has a lower relative bulk impedance and chargetransfer impedance than the Li-ZAPS battery (Figure 4c). The improved performance of the NaZAPS over the Li-ZAPS battery may be partly attributed to the higher conductivity of the NZSP membrane ( = ~1.0 x 10-3 S cm-1) compared to that of the LATP membrane ( = ~1.0 x 10-4 S cm-1). To separate the effects of the SSE’s conductivities, EIS measurements were taken of the catholyte alone. EIS confirms that the impedance of the Na2S4 catholyte is lower than the Li2S4 catholyte, with or without the use of a CoS catalyst, as shown in Figure 4d and 4e. This implies better reaction kinetics for the Na-based catholyte. Due to the better performance of the NaZAPS battery and the higher capacity of Na2S4 as discussed in the supporting information, future work will focus on the development of the ZAPS battery with Na2S4 rather than Li2S4 catholyte.


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0

0.8 0.4 0

-10

Z" (Ω /1000)

(c)

-8

0.25

10

0.5

0.75

1.0

20

1.25

-6 -4 -2

1.75

30 Time (h)

(d)

NNa a+ Li Li+

1.5

-32 -24

40

2.0

2.25

2.5

50

(e)

NNa a+ Li Li+

-16 -8 0

0 0 2 4 6 8 10 12 14 16 Z' (Ω /1000)

1.2 1.0 0.8 0.6 0.4 0.2 0.0

0 10 20 30 40 50 60 70 Z' (Ω /1000)

Z" (Ω /1000)

0.1

Power Density (mW cm-2)

Na+ Li+

1.2

0.0

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(b)

Z" (Ω /1000)

Cell Potential (V)

1.6

Li+ Na+

2.0

2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0

10

(a)

Cell Potential (V)

20

3 Tim

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Na+ Na+ Li+ Li+

0.0 0.5 1.0 1.5 2.0 2.5 3.0 Current Density (mA cm-2) -300 -250 -200 -150 -100 -50 0

NNa a+ Li+ Li

0

200 400 600 800 Z' (Ω /1000)

Figure 4. Comparison of the Na-ZAPS and Li-ZAPS batteries performances, presenting (a) voltage profiles of the cells at different current densities ranging from 0.1 mA cm-2 to 2.5 mA cm-2 with the numbers in blue indicating current density in mA cm-2, and (b) polarization curves obtained from an average discharge voltage over 5 cycles. Nyquist plots from the EIS data of (c) uncycled Na-ZAPS and Li-ZAPS batteries, (d) Na2S4 and Li2S4 catholyte with CoS@SS electrode, and (e) Na2S4 and Li2S4 catholyte with planar stainless steel electrodes.

We demonstrate, for the first time, a rechargeable zinc-aqueous polysulfide battery. This novel battery was achieved by the separation of the zinc anode from the reactive polysulfide catholyte by a mediator-ion solid-state electrolyte. Charge balance is maintained by the mediator alkali metal ions (Na+ or Li+) that shuttle through the solid-state electrolyte. This proof-ofconcept battery exhibited good performance, maintaining 822 mA h g-1 of reversible capacity after 50 cycles with ~ 100% Coulombic efficiency. It was shown that the ZAPS batteries with a Na+ mediator ion produced superior rate and power performance over those with a Li+ mediator


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ion. Optimization of parameters such as solid-state electrolyte conductivity and catalyst performance could improve battery impedance, which could in turn improve the power density of the cell. Increased concentration of polysulfide in the catholyte could greatly improve the energy density of the system. Overall, the rechargeable ZAPS battery shows promise as a technology that utilizes high energy-density and low-cost electrode materials.

ASSOCIATED CONTENT Supporting Information. Experimental methods, calculation of ZAPS battery open-circuit voltage, supporting discussion of Na2S4 and Li2S4 capacity. AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. ACKNOWLEDGMENT This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering under Award No. DE-SC0005397.


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A Rechargeable Zinc-Aqueous Polysulfide Battery with a Mediator-Ion

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