Zinc Secondary Battery with a Bio-Ionic LiquidâWater

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A prussian blue/zinc secondary battery with a bio-ionic liquid-water mixture as electrolyte Zhen Liu, Giridhar Pulletikurthi, and Frank Endres ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b01592 • Publication Date (Web): 27 Apr 2016 Downloaded from http://pubs.acs.org on May 4, 2016

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ACS Applied Materials & Interfaces

A Prussian Blue/Zinc Secondary Battery with a Bio-Ionic Liquid-Water Mixture as Electrolyte

Zhen Liu*, Giridhar Pulletikurthi, Frank Endres*

Institute of Electrochemistry, Clausthal University of Technology, Arnold-SommerfeldStrasse 6, 38678 Clausthal-Zellerfeld, Germany E-mail: [email protected], [email protected]

ABSTRACT The development of rechargeable zinc ion batteries with high capacity and high cycling stability is a great challenge in aqueous solution due to hydrogen evolution and dendritic growth of zinc. In this study, we present a zinc ion secondary battery, comprising a metallic zinc anode, a bio-ionic liquid-water electrolyte and a nanostructured prussian blue analogue (PBA) cathode. Both the Zn anode and the PBA cathode exhibit good compatibility with the bio-ionic liquid-water electrolyte, which enables the electrochemical deposition/dissolution of zinc at the zinc anode, and reversible insertion/extraction of Zn2+ ions at the PBA cathode. The cell exhibits a well-defined discharge voltage plateau of ~1.1 V with a specific capacity of about 120 mAh g–1 at a current of 10 mA g–1 (~ 0.1 C). The Zn anode shows great reversibility and dendrite-free Zn deposits were obtained after 100 deposition/dissolution cycles. The integration of an environmental-friendly PBA cathode, a non-toxic and low-cost Zn anode and a biodegradable ionic liquid-water electrolyte provides new perspective to develop rechargeable zinc ion batteries for various applications in electric energy storage.

KEYWORDS: Ionic liquids, Zinc, Prussian blue, Battery, Biodegradable

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1. INTRODUCTION The development of low-cost, environmentally-benign and efficient energy storage devices is crucial for the storage of electrical energy, especially on larger scales.1-2 Rechargeable Zn-ion batteries are potential candidates as zinc is non-toxic, abundant and cheap. In a rechargeable zinc ion battery, anodic zinc is oxidized to Zn2+ ions, it diffuses to the cathodic electrode/electrolyte interface and is subsequently intercalated into the cathode material during discharging. Upon charging, the above-mentioned process is reversed. Manganese dioxide with layer and tunnel structures, including α-MnO2, β-MnO2, γ-MnO2, λ-MnO2, has been extensively studied as cathode material for Zn-ion batteries.3-4 It can be prepared economically and can produce a discharge capacity of more than 200 Wh kg−1. However, the extensively studied MnO2 based cathode materials, which enable a reversible insertion of Zn2+ in aqueous electrolytes, are suffering from a sharp initial capacity fading, low Columbic efficiency and poor reversibility.3-7 Prussian blue and its analogues (PBAs) are non-toxic, inexpensive and easy to synthesize.8 They have a general formula of AxM1[M2(CN)6]y·nH2O and possess a face centered cubic structure with a Fm-3m space group, in which two metal ions (M1 and M2) are linked together by cyanide (CN) ligands (A: mobile alkaline metal ions).9 The open-framework structure has large channels, and allows the rapid diffusion of a wide variety of metal ions. PBAs have demonstrated an excellent cycle life and high-rate capability as cathode materials in aqueous electrolytes for monovalent metal-ion batteries (Li+, Na+, and K+)10-15 as well as for multivalent metal-ion batteries (Mg2+, Al3+ and Zn2+).16-20 In the case of zinc-ion batteries,16-18 the employed aqueous solutions suffer from hydrogen evolution and the formation of a passivation layer, e.g. ZnO, which decrease the cycle life of the battery.17 Alkaline electrolytes, like potassium hydroxide, are commonly used in zinc based batteries. However, the alkaline electrolyte can permeate small creaks and holes, causing severe problems as they are corrosive and environmentally less friendly. Furthermore, alkaline 2 ACS Paragon Plus Environment

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solutions absorb carbon dioxide readily, forming carbonates. The precipitate will block the electrode or the catalyst. In addition, the traditional alkaline electrolytes and the neutral ZnSO4 solutions remain great challenges for rechargeable Zn-ion batteries due to hydrogen evolution, the formation of dendrites and passivation products of the Zn anodes, which can block the surface and subsequently decrease Zn2+ ion diffusion.21-26 The exploration of alternative non-aqueous electrolytes to eliminate these problems is crucial for the development of rechargeable Zn-based batteries. The electrodeposition of Zn from ionic liquids has been previously reported.27-33 Their applications in Zn-polymer battery34 and Zn-ion battery35-36 have already been demonstrated. Nevertheless, most of the ILs had imidazolium and pyrrolidinium cations and trifluoromethylsulfonate (TfO–), bis(trifluoromethylsulfonyl)amide (TFSA–) and dicyanamide (DCA–) counter ions. Their applications might be limited by eco-toxicity, biodegradability and biocompatibility.37 An alternative approach that is capable of overcoming these drawbacks is the development of biodegradable and biocompatible ILs.38-39 The ionic liquid choline acetate can be easily prepared, and it is rather cheap and most importantly it is biodegradable and biocompatible, as it is based on vitamine B4. The integration of an environmental-friendly PBA cathode, a non-toxic and low-cost Zn anode and a biodegradable ionic liquid-water electrolyte for zinc ion batteries has been the focus of our interest. In this paper, we show the reversible electrochemistry of zinc in ionic liquid/water mixtures.

The

synthesized

PBA

with

nanostructured crystals exhibits reversible

insertion/extraction of Zn2+ ions. Finally, the cycling performance of our zinc ion battery with PBA as cathode, a bio-IL-water mixture as electrolyte and Zn as anode will be demonstrated.



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2. EXPERIMENTAL SECTION The ionic liquid, choline acetate ([Ch]OAc), was purchased from (IO-LI-TEC, Germany, 99%). Zinc acetate, Zn(OAc)2, was obtained from Sigma-Aldrich (99 %). The electrolyte was prepared by dissolving 1.0 mol/L Zn(OAc)2 in [Ch]OAc + 30 wt% water. Iron (III) hexacyanoferrate(III), FeFe(CN)6, nanoparticles were prepared by a solution precipitation method. Briefly, 100 mL of 0.05 mol/L aqueous K3Fe(CN)6 (Sigma-Aldrich, Germany) and 100 mL of 0.025 mol/L aqueous FeCl3 (Sigma-Aldrich, Germany) with several drops of HCl (37%) (to inhibit hydrolysis of FeCl3) were added drop-wise to 60 mL H2O under constant stirring. A brown solution was formed immediately. The resulting solution was maintained at 100 oC for 4 h to allow water and HCl to evaporate. Subsequently, the solution was centrifuged and washed several times with deionized water. Finally, a dark green precipitate was obtained. The as-obtained precipitate was dried in an oven at 100 oC for 12 h before use. The PBAs cathode electrodes were prepared by mixing a slurry of 80 wt % FeFe(CN)6, 10 wt % amorphous carbon (Nergy Super C65, Imery, Belgium Ltd.), 2 wt % graphite (Timrex SFG 6, Imery, Switzerland Ltd.) and 8 wt % polyvinylidene fluoride (Sigma-Aldrich, Germany) binder solution in N-methylpyrrolidone (Sigma-Aldrich, Germany). The mass loading of FeFe(CN)6 is about 5 mg per cm2. The zinc foil and zinc wire (99.99 %, SigmaAldrich, Germany) were polished using an abrasive paper (3M) and washed with acetone before use. Electrochemical measurements of the FeFe(CN)6 cathode were performed on a flooded cell containing a FeFe(CN)6 working electrode, 1.0 mol/L Zn(OAc)2/([Ch]OAc + 30 wt% water) electrolyte, and a Zn wire/sheet as counter and reference electrodes. Electrochemical measurements of the Zn anode were also performed on a flooded cell containing a Zn sheet as working electrode and a Zn wire/sheet as counter and reference electrodes. The cyclic voltammetry (CV) and galvanostatic charge–discharge test experiments were carried out 4 ACS Paragon Plus Environment

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using a VersaStat III (Princeton Applied Research) potentiostat/galvanostat controlled by Power-CV and Power-Step software. The deposits were characterized by Scanning Electron Microscopy (Carl Zeiss DSM 982 Gemini), Energy-Dispersive X-ray spectroscopy, Transmission Electron Microscopy (JEM2100, JEOL) and X-ray Diffraction patterns (PANalytical Empyrean Diffractometer). The FTIR measurements were performed on a Bruker VERTEX 70 FTIR spectrometer at room temperature. Thermogravimetric Analysis (TGA) was carried out on a TGA 2950, and Differential Scanning Calorimetry (DSC) was carried out on a DSC 2920 instrument (TA Instruments). Induction Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) was performed on Spectroflame Modulat 2000 (SPECTRO Analytical Instruments GmbH, Germany). Elemental analysis (C, H and N) was performed on Vario EL Instruments, Germany.

3. RESULTS AND DISCUSSION 3.1 Structure and morphology of PBAs The

formula

of

the

as-synthesized

PBAs

nanocrystals

was

K0.05Fe(III)[Fe(III)(CN)6]·2.6H2O (abbreviated as FeFe(CN)6), as determined by ICP-OES for K and Fe, elemental analysis for C, H, and N and TGA-DSC for water content. The morphology and particle size of FeFe(CN)6 were characterized by SEM and TEM as shown in Figure 1a, b and c. The FeFe(CN)6 particle shows a nanocubic-shaped structure with an average size of ~150 nm. The TEM image in Figure 1c clearly shows a cubic symmetry, indicating that the synthesized PBAs are highly crystalline. The TGA and DSC curves in Figure 1d show a weight loss of 15.2% below 200 oC due to the evaporation of bound water and that FeFe(CN)6 begin to decompose at temperatures higher than 300 oC. The water content is 2.6 mol per mol FeFe(CN)6 calculated on the basis of TGA analysis. The interstitial H2O was found to have a negative effect on the structural and electrochemical performance of 5 ACS Paragon Plus Environment


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the material.40 Our acid treated sample contains a lower amount of water than stated by others, where water contents of 4 (in molar ratio) were reported.9, 41 The XRD pattern in Figure 1e shows a high degree of crystallinity and all the peaks can be indexed as the face-centered cubic lattice with lattice parameter of a = 10.24 Å (space group Fm3m, JCPDS no. 73-0687). Figure 1f illustrates the crystal structure of FeFe(CN)6, where the Fe1 ions are octahedrally surrounded by N atoms and the Fe2 ions are 6-fold coordinated to C atoms of the C≡N ligands.9


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Figure 1. Characterization of the as-prepared FeFe(CN)6 nanocubic structure. (a) SEM image, (b) and (c) TEM images at lower and higher magnifications, (d) TGA-DSC curves, (e) XRD pattern and (f) the lattice structure of FeFe(CN)6. 3.2 Reversible electrochemistry of zinc in ionic liquid/water mixtures The ionic liquid choline acetate, [Ch]OAc, is solid at room temperature, however, it is miscible with water giving thus a room temperature electrolyte. We have previously investigated

the

structure

of

the

ionic

liquid

1-ethyl-3-methylimidazolium

trifluoromethylsulfonate with different amounts of water (water content ranging from 5-80 wt%) by FTIR and Raman spectra. We observed that the solution changed from an ionic liquid-like solution to an aqueous-like solution when the water content was above 40 wt%.42 We have also found that the zinc morphology was compact and dense with 20 wt% water, but rough zinc deposits with several discrete thin platelets, perpendicular to the electrode surface, were obtained with water contents of more than 50 wt%. In addition, hydrogen bubbles were found on the surface during the deposition process at higher water concentrations.27 Based on these results, choline acetate with 30 wt% of water was employed as an electrolyte for our biodegradable zinc ion battery. In simple words, this electrolyte is in-between an ionic liquid and an aqueous electrolyte. The electrochemical cycling behavior of the Zn anode in [Ch]OAc + water mixtures has also been investigated. Figure 2a shows the CV of 1.0 M Zn(OAc)2 in [Ch]OAc + water mixtures on a Zn electrode at a scan rate of 10 mV s-1. The redox couple is associated with the deposition and dissolution of Zn. Galvanostatic charge/discharge profiles at a current density of 0.2 mA cm-2 for 100 cycles is shown in Figure 2b. In the initial 20 cycles, a voltage difference of 0.15 V was observed. However, in the subsequent cycles, the difference decreased to 0.1 V. During the charge/discharge cycling, the Zn morphology seems highly stable in the IL-water electrolyte providing a platelet-like morphology as shown in Figure 2c and d. The initial morphology of the Zn deposits has a flower-like structure, comprised of thin platelets. After 100 charge/discharge cycles, a thin plate-like structure with 7 ACS Paragon Plus Environment


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the platelets perpendicular to the surface was found on the surface. The XRD results of the Zn anodes in Figure 2e show only the diffraction peaks of Zn even after 100 charge/discharge cycles, indicating a high stability of the Zn anode in IL-water mixtures. However, it was reported that in aqueous ZnSO4 solution, ZnO and basic zinc sulfate (Zn4SO4(OH)6·H2O) were found.43 From these results, it is concluded that the cycle stability of the Zn anode was greatly enhanced in IL-water mixtures and the [Ch]OAc-water seems to be quite a promising electrolyte for a rechargeable Zn-ion battery.

Figure 2. Electrochemical characterization of the Zn anode in 1.0 M Zn(OAc)2/ ([Ch]OAc + 30 wt% water mixtures): (a) CV at a scan rate of 10 mV s-1, (b) voltage profiles for 100 cycles at a current density of 0.2 mA cm-2, (c) and (d) SEM images of initial Zn deposits and after 100 cycles, (e) XRD patterns of initial Zn deposits and after 100 cycles.


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3.3 Insertion and extraction of Zn2+ ions in PBAs The electrochemical insertion and extraction of Zn2+ ions in FeFe(CN)6 was confirmed by FTIR, XRD and EDX as shown in Figure 3. Samples with different states (ZnxFeFe(CN)6 with x = 0, 0.1, 0.3 and 0.5) were prepared by galvanostatic discharge and charge at 10 mAh g-1 (~0.1 C) (based on the mass of the active material). A schematic demonstration of the insertion of Zn2+ ions in FeFe(CN)6 is shown in Figure 3a. The cyanide stretching vibration mode, ν(CN), is sensitive to the coordination environment.11 In fully charged PBA, the peaks at 2183 and 2106 cm-1 (Figure 3b, red curve) are attributed to the ν(CN) of Fe(III)Fe(III)(CN)6 and of Fe(III)Fe(II)(CN)6, respectively. The latter has a weaker intensity than the former. In the discharged state (Figure 3b, black curve), these peaks shift to a lower wavenumber of 2168 and 2067 cm-1 and change their relative intensities, indicating that Zn2+ ions were inserted into FeFe(CN)6 and Fe(III) was reduced to Fe(II). Furthermore, the XRD peaks shift gradually toward higher diffraction angles with increasing of Zn content during discharge (i.e., Zn2+ ions insertion), indicating reduced lattice parameters as shown in Figure 3c. Similar behaviors were reported on the insertion of Mg2+ ions and Al3+ ions, respectively in PBAs.44-45 This can be attributed to that the reduced [Fe(II)(CN)6]4- ion has a smaller radius than that of the oxidized [Fe(III)(CN)6]3- ions.46 Correspondingly, the XRD peaks shift gradually back to their original positions during charge (i.e., Zn2+ ions extraction). These results suggest a high reversibility of the PBA structure during the Zn2+ insertion/extraction process. The insertion of Zn2+ in PBA was also confirmed by EDX (Figure 3d and e), which shows a Fe to Zn molar ratio of ~ 3:1 in fully discharged FeFe(CN)6 (Figure 3e).



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Figure 3. (a) schematic demonstration of the insertion of Zn2+ ions in FeFe(CN)6, (b) FT-IR spectra of fully charged and discharged FeFe(CN)6, (c) XRD patterns of the FeFe(CN)6 at different depths of charge and discharge along with corresponding lattice parameters, (d) EDX of as-prepared FeFe(CN)6 and (e) EDX of fully discharged FeFe(CN)6. 3.4 Electrochemical performance of zinc-ion battery The electrochemical performance of FeFe(CN)6 as a positive electrode in the [Ch]OAc + water mixtures was thoroughly investigated. Figure 4a presents CV of the FeFe(CN)6 cathode in 1.0 M Zn(OAc)2/([Ch]OAc + 30 wt% water) electrolyte at a scan rate of 0.1 mV s-1 in the regime of 1.0–2.0 V vs. Zn2+/Zn for ten successive cycles. The open-circuit potential (OCP) was 1.56 V. The observed redox couple at 1.34/1.47 V is related to the reduction/oxidation of the Fe(III)/Fe(II) couple as a result of the insertion/extraction of Zn2+ ions in FeFe(CN)6. The shapes of the redox couple remain unchanged during successive scans, revealing a reversible Zn insertion/extraction. Figure 4b shows the charge–discharge cycling performance of the FeFe(CN)6 electrode between 0.8 and 2.0 V at a current of 10 mA g-1 (~ 0.1 C). The 10 ACS Paragon Plus Environment

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FeFe(CN)6 electrode exhibits potential plateaus of ~1.1 V during discharge and of ~1.6 V during charge. The observed polarization potential (ca. 0.5 V) might be attributed to the high viscosity of the electrolyte (87 mPa·s at room temperature). The initial discharge capacity of the FeFe(CN)6 cathode is 122 mAh g-1. The theoretical capacity of Fe[Fe(CN)6]·2.6H2O is 170 mAh g-1, assuming that the two Fe(III) can be fully reduced. In our case, it was found that ~70% of Fe(III) atoms are reduced during Zn2+ insertion. It was reported that the high spin Fe(III) ions coordinated with N atoms of C≡N ligands are more reactive than the low spin Fe(III) ions bond with C atoms of C≡N ligands.47 In the following cycles, the discharge capacities slightly decreased and a specific capacity of 115 mAh g-1 was obtained after the 10th cycle, indicating the retention of the capacity. Figure 4c shows the charge-discharge voltage profiles of the FeFe(CN)6 cathode at various currents from 10 mA g-1 to 60 mA g-1 (~0.6 C). The discharge capability of the FeFe(CN)6 cathode decreases with increasing charge-discharge rates. The cell was able to deliver a capacity of about 30 mAh g-1 at a high discharge rate of 60 mA g-1. It was reported that in IL-based electrolytes, the capacity decreases rapidly with increasing the current density.48-50 This might be attributed to the high viscosity of the electrolyte, which in turn limits Zn2+ diffusion in the electrolyte. Figure 4d shows a plot of the variations of discharge capacity and Columbic efficiency during the cycles at various rates. The discharge capacity is slightly decreased with increasing cycling numbers at each charge-discharge rate. Furthermore, the discharge capacity decreases apparently with increasing the charge-discharge rate. Except for the initial cycle, the Columbic efficiency is higher than 99% at each charge-discharge rate. These results indicate that the electrolyte and electrode materials are compatible and enable reversible Zn2+ ions insertion/extraction into the cathode material.



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Figure 4. Electrochemical characterization of the FeFe(CN)6 electrode in 1.0 M Zn(OAc)2/([Ch]OAc + 30 wt% water mixtures). (a) 10 successive CV curves. Scan rate: 0.1 mV s-1, (b) charge and discharge profiles at a current of 10 mA g-1 for 10 cycles, (c) rate capability of the battery and (d) cycling behavior at different current.

CONCLUSIONS We have investigated the structural and electrochemical properties of FeFe(CN)6 as cathode material in a bio-ionic liquid + water electrolyte for rechargeable Zn-ion batteries. A welldefined and high-quality FeFe(CN)6 with particle sizes of 150 nm was obtained. The structure shows a great stability during Zn2+ ion insertion/extraction processes. FeFe(CN)6 showed good compatibility with the employed ionic liquid + water electrolyte, and exhibited a reversible behavior when cycled against a Zn electrode. FeFe(CN)6 can deliver a reversible discharge capacity of 120 mAh g-1 with a Columbic efficiency of 99% at a current of 10 mA g-1 (~ 0.1 C). The Zn anode shows platelet-like structure upon cycling in the investigated 12 ACS Paragon Plus Environment

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electrolyte. The combination of low-cost Zn anode, eco-friendly PBA cathode and a biocompatible ionic liquid in a battery is of great interest for applications in large-scale energy storage devices.

ACKNOWLEDGEMENTS Financial support by the BMBF project LUZI (BMBF: 03SF0499A) is gratefully acknowledged. We would like to thank Karin Bode from the Institute of Inorganic and Analytical Chemistry for Elemental Analysis, FT-IR and TGA-DSC measurements, and Petra Sommer from the Institute of Mineral and Waste Processing, Waste Disposal and Geomechanics for ICP-OES measurement.

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