Introducing Artificial Solid Electrolyte Interphase onto the Anode of

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Introducing Artificial Solid Electrolyte Interphase onto the Anode of Aqueous Lithium Energy Storage Systems Moin Ahmed, Alireza Zehtab Yazdi, Aly Mitha, and Pu Chen ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b09268 • Publication Date (Web): 09 Aug 2018 Downloaded from http://pubs.acs.org on August 11, 2018

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ACS Applied Materials & Interfaces

Introducing Artificial Solid Electrolyte Interphase onto the Anode of Aqueous Lithium Energy Storage Systems Moin Ahmed, ‡ Alireza Zehtab Yazdi, ‡ Aly Mitha, P. Chen* Department of Chemical Engineering and Waterloo Institute for Nanotechnology, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2L3G1, Canada ‡ These authors contributed equally to this work.

Keywords: graphene; dendrite; aqueous electrolyte; artificial solid-electrolyte interphase (SEI); rechargeable batteries; zinc anode

Abstract

Aqueous lithium energy storage systems (ALESS) offer several advantages over the commercially available non-aqueous systems, most noteworthy higher ionic conductivity, safety and environmentally friendly. The ALESS, however, exhibit faster capacity fading than their non-aqueous counterparts after repeated cycles of charge and discharge; this limits their widerange applications. Excessive corrosion of metallic anodes in the aqueous electrolyte and

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accelerated growth of dendrites during the charge/discharge process are found to be the main reasons that severely impact ALESS’s lifespan. Here, we introduce ultra-thin graphene films as an artificial solid electrolyte interface (G-SEI) on the surface of a zinc anode to improve cycling stability of an aqueous lithium battery system. The G-SEI is fabricated at different thicknesses and areas ranging from ~ 1 – 100 nm and ~ 1 – 10 cm2, respectively, via a Langmuir-Blodgett trough method, and deposited onto the surface of the zinc anode. Electrochemical characterizations show a significant reduction in corrosion current density (0.033 mAcm-2 vs. 1.046 mAcm-2 for the control), suppression of dendritic growth (~ 50%) and reduction in charge transfer resistance (222Ω vs. 563Ω for the control) when the G-SEI is utilized. The aqueous battery system with the G-SEI (100 nm thickness) on the anode exhibits ~ 17% improvement in cycling stability (82% capacity retention after 300 cycles) compared to the control system. Comprehensive microscopy and spectroscopy characterizations reveal that the G-SEI not only controls the ion transport between the electrolyte and the anode surface (lower corrosion), but also promotes a uniform deposition (less dendritic growth) of zinc on the anode.

Introduction The demand for portable and more environmentally friendly energy storage systems, particularly batteries, has been significantly grown over the past decade. While great progress have been made in the current commercially available batteries, they still suffer from major drawbacks. For example, nickel (Ni) and lead (Pb)-based battery systems typically utilize toxic heavy metals and/or precursors that are naturally low in abundance. The benchmark lithium ion batteries with organic electrolytes also have toxicity and flammability issues with high costs


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associated with their assembly at large-scale.1–3 In contrast, aqueous lithium energy storage systems (ALESS) are considered as the most attractive alternative since they can deliver higher power density, use inexpensive and safer electrolytes, and their assembly is much simpler than their non-aqueous counterparts.4,5 One major drawback that limits large-scale applications of ALESS, however, is corrosion of their anodes followed by formation of metallic dendrites leading to a significant capacity fading and ultimately short-circuit.6 During the charging process of ALESS, metal ions (e.g., Zn2+) from the electrolyte adsorb on the anode surface, and convert to metal atoms (e.g., Zn). The surface roughness of the anode localizes the current density, and causes a non-uniform deposition of the atoms leading to formation of dendrites.7 During successive cycles of charge and discharge, the dendrites gradually grow perpendicular to the anode surface, penetrating through the separator, and eventually come in contact with the cathode, a process so-called short-circuit.8 In addition, the formation and growth of dendrites increase the surface area of the anode leading to higher corrosion rates, and accelerated kinetics of detrimental surface dominant reactions.6,9 Whereas extensive studies have been conducted to suppress lithium dendrites in non-aqueous systems; limited solutions have been proposed for ALESS. Introducing additives into the aqueous electrolytes and replacing aqueous with gel electrolyte are the two main proposed methods.9–11 One common strategy in both aqueous and non-aqueous systems is to use additives in the electrolyte to suppress the dendritic growth of the anode. These additives form a physical barrier at the interface between the anode and the electrolyte. The barrier is supposed to prevent the propagation of dendrites towards the cathode.12–14 However, these physical barriers have limited mechanical strength and chemical stability, and may be easily removed after several chargedischarge battery cycles.15,16 Another strategy is to fabricate gel-like structures in the aqueous


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electrolytes.17 These gel electrolytes mainly consist of fused silica that can inhibit both corrosion of the anode and its dendrite growth. Large-scale fabrication of gel electrolytes, however, is limited, and difficult to implement in the ALESS. Facile methods using 2D materials with high mechanical and chemical stabilities to prevent corrosion and dendritic growth of anodes have yet to be developed for ALESS. Our group recently introduced the concept of artificial solid electrolyte interface (SEI) in the cathodes of ALESS.5 Graphene flakes in a continuous film with a thickness of 1 – 100 nm and length of 1 – 10 cm2 were introduced on the cathode surface, where an artificial SEI (G-SEI) was formed. The G-SEI showed a great improvement in the cycling stability of an aqueous lithium battery through suppression of the Jahn-Teller effect and degradation of carbon materials in the cathode during charge and discharge process. In fact, the G-SEI nicely controlled both the ion transport and the gas permeation processes on the cathode surface. In this work, we similarly propose the G-SEI on the anode surface to control those processes with the objective to reduce corrosion rate and dendritic growth of the anode. The graphene flakes in the G-SEI has high mechanical strength and chemical stability, while can control permeation of hydrated lithium and zinc ions into a zinc anode. The Young’s modulus of a graphene monolayer is found to be ~ 200 GPa, more than two times higher than that of zinc (~ 90 GPa).18 The high mechanical strength of the graphene layers ensures that zinc dendrites do not penetrate through the layers. While the mechanical properties of the graphene film can be measured via an AFM equipped with a nanoindentation probe on a specific substrate,19,20 this measurement would have been challenging on top of an extremely rough surface of the zinc anode with both microscopic and macroscopic features. In this work, Young’s modulus is used as a standard mechanical property to assess the strength of the graphene layers in comparison with the zinc dendrites. The impact of other


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mechanical properties, such as rupture strength and fracture toughness, of the graphene layers on suppression of dendrites can also be further explored. It is also reported that graphene oxide layers allowed ions with of hydrated radii of < 4.5 Å to permeate through.21 Hence, graphene layers are expected not to add impedance to the ionic conductivity of the zinc and lithium ions. Ionic permeation through reduced graphene oxide mainly occurs through the nano-channels that exist in spaces within each individual graphene flake (line/point defects) as well as between the flakes. Chemical stability of the G-SEI ensures that it does not affect the columbic efficiency of the aqueous battery system during cycling. The G-SEI in this work is fabricated as we previously reported based on the Langmuir – Blodgett trough method5, and deposited on the zinc anode surface of the similar lithium battery system. Comprehensive electrochemical, microscopy and spectroscopy characterizations are employed to evaluate the corrosion properties, dendritic growth and the battery performance with the G-SEI on the anode. The lowest corrosion rate and the best dendrite suppression are obtained in a G-SEI with the thickness of 10 nm. The anode also shows the reversible capacity of around 95 mAh/g and a capacity retention of 82% after 300 cycles of charge and discharge. We hypothesize that these improvements mainly come from a uniform zinc deposition process on the anode surface during charging. The uniform zinc deposition minimizes the dendritic growth. Experimental Section Materials Crystalline graphite powder (325 mesh, 99%) and polyethylene film were acquired from Alfa Aesar. Polyvinylidene fluoride (PVDF; HSV 900) was purchased from Kynar. Conductive graphite powders (KS-6) and lithium manganese oxide (LiMn2O4) and were purchased from MTI. Polyacrylamide was bought from Scientific Polymer Products, Inc. 1,2-dichloroethane


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(anhydrous 99.8%), diethyl ether (99%), ethanol (denatured, reagent grade), hydrazine monohydrate (N2H4·H2O; 98%), hydrochloric acid (HCl; 38%), hydrogen peroxide [H2O2; 30 wt % in H2O], hydroxypropyl methylcellulose (HPMC), lithium sulfate (Li2SO4; ≥99% purity), 1methyl-2-pyrrolidinone (NMP; ≥99.5% purity), phosphoric acid (H3PO4; 85%), polyvinyl alcohol (PVA;80% hydrolyzed), potassium permanganate (KMnO4; 99%), sulfuric acid (H2SO4; 95%), and zinc sulfate (ZnSO4; ≥99% purity)were all purchased from Sigma-Aldrich. Fabrication of porous zinc anode To prepare the binder, 2.5 g of HPMC, 1.25 g of PAA and 1.25 g of PVA was mixed in 200 ml of distilled water. To ensure that polymers are fully dissolved, the mixture was stirred in a hot plate at 135-1400C for 72 hours. After heating, the mixture was left to cool at room temperature for 24 hours while stirring. Subsequently, the porous zinc anode was prepared using this binder. First, 8 g of zinc purum, 84.3 mg of Pb3O4 and 84.3 mg of Bi2O3 were mixed and ground using mortar and pestle. 6.74 g of the binder was added to the powder mixture, and the resulting mixture was mixed. This mixture was cast onto the brass substrate and then dried in an oven at 600C for 24 hours. Synthesis of GO GO synthesis was based on improved Hummer’s method with slight modification in its procedure. First, a mixture of 3 g of graphite flakes in 360 ml of concentrated H2SO4 was prepared and stirred for roughly 1 hour. 40 ml of H3PO4 was then added and the resulting mixture was throughly stirred for 15 minutes. Then, 18 g of KMnO4 was added to this mixture slowly and the resulting mixture was stirred for another 1 hour at room temperature. This mixture is stirred at 500C for 12 hours in a water bath. The mixture was dark-brown in color after this step, which indicates that the graphite flakes are oxidized. To stop this oxidation, the mixture


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is poured onto 400 ml of cold solution of 30% H2O2 in distilled water. To obtain purified solid GO, the solution was centrifuged at 4000 rpm for approximately 4 hours and the resulting supernatant was disposed of. The solid was dried in air under the fume hood. Approximately 3 g of purified GO was obtained as the final product. LB coating procedure An organic suspension of GO was prepared to coat graphene monolayer on the anode surface. 2.75 g of GO was first mixed in 0.79 ml of ethanol and sonicated for 15 minutes. Then, 10.2 ml of 1,2-dichloroethane was added and the resulting mixture was stirred until a homogenous GO suspension was obtained. The Langmuir-Blodgett isotherm method was used to coat the anode with GO monolayers. The trough was first thoroughly cleaned using ethanol and DI water. The anode substrate was placed inside the trough. 275 ml of DI water was used as the subphase and was poured inside the trough. The water was first cleaned by pouring it in the trough and ensuring that the surface pressure was below 0.2 mNm-1. If the surface pressure was above 0.2 mNm-1, the water-air interface was cleaned by vacuum suction. A pre-determined amount of organic suspension of GO was then transferred on top of the subphase from a plastic syringe with the dripping rate of 0.1 ml/min. This dripping rate was controlled by a syringe pump. After dripping, the trough was left in air for 30 minutes to evaporate organic solvents. The barriers of the trough were then closed (barrier closing rate of 10 mm/min) until the final surface area inside of the barrier was 65 mm2. The water subphase was sucked out using a gentle suction to lower the water level slowly, which resulted in GO coating onto the substrate. Finally, the substrate was left to dry overnight.


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GO coated on the surface of the anode was then reduced using water vapor. The surface of anode was subjected to a continuous flow of water vapor for 5 hour. The resulting anode was left to cool and dry overnight in air. Characterization techniques SEM images were taken from Zeiss LEO 1530 FESEM with 5 kV acceleration voltage. AFM images were taken using Bruker Dimensions Icon machine using Antimony (n) doped Si tip. PANalytical X’Pert Pro MRD diffractometer with Cu Kα radiation of 1.54 Å and incidence angle of 0.30 was used for GIXRD characterizations. Raman Spectroscopy was performed using Bruker Senterra Raman microscope with the following settings: 785 nm radiation wavelength, integration time of 20 s, power of 20 mW, and objective of x10. XPS characterizations were performed using

Thermo-VG Scientific ESCALab under the following settings: a

monochromatic aluminum source, energy of 1486.6 eV, power of 49.3W, chamber pressure of 2.0× 10-9 Pa, beam diameter of 200.0 µm, and take-of angle of 45°. All binding energies were measured relative to C1s at 284.8 eV. The samples were mounted on a piece of conductive carbon tape before testing. A double neutralization - a low energy electron beam and low energy Ar+ beam - were used during spectrum acquisition. For each sample, a wide energy range (0 eV - 1350 eV) was used to obtain a high sensitivity mode spectrum (survey scan) to ascertain the elemental composition of the sample’s surface. The survey scan was followed by a high energy resolution spectra to quantitatively measure the chemical environment of the elements present in the sample. High energy resolution spectra were obtained using a narrow binding energy window, with a pass energy of 23.50 eV. For contact angle measurement, the sample and the syringe tip were positioned 1 cm apart. The water drop from the syringe was dropped on the sample at a constant dropping rate using a stepping motor. The drop image was captured using a


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high-speed camera and microscope system and the images were exported to a computer for contact angle determination. Assembly of ReHABs A solution (pH 4) consisting of 1 M Li2SO4 and 2 M ZnSO4 in deionized water was used as the electrolyte. Lithium manganese oxide (LMO) coated on polyethylene (PE) film substrate was used as the cathode. To prepare the LMO cathode, a slurry containing 86 wt.% LiMn2O4, 7 wt.% KS-6 and 7 wt.% PVDF in NMP solvent was casted on the PE film using a doctor-blade. The cathode was vacuum dried at 60 0C for 24 hours. Graphene coated anodes were assembled with lithium manganese oxide as cathode, absorbed glass mat (NSG Corporation; 1.15cm diameter and 0.5mm thickness) as separator. Battery testing The batteries were assembled in coin cell configuration and were tested using Neware battery tester. Galvanostatic cycling (charge-discharge) was done at room temperature at 4 C. The potential was varied between 1.4 V and 2.1 V. During float charge current tests, the coin-cells were first charged to 2.1 V at 0.2 C and then this this voltage (2.1 V) was maintained for 24 hours. The current was monitored during this period. . Rate capability test was conducted from 0.2 C to 4 C. OCV was test was conducted for 24 and 72 hours. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were conducted on Bio-Logic VMP3 electrochemical workstation, using Pt wire, Ag/AgCl and1 M Li2SO4/2 M ZnSO4 as counter electrode, reference electrode and electrolyte, respectively. Results and Discussion The zinc anode was fabricated by casting zinc powder slurry onto brass current collector (Experimental section). Graphene oxide (GO) was produced using improved synthesis method22


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with slight modifications to obtain the GO nano-sheets with desired lateral size for better coverage on the anode surface (Experimental section). The GO nano-sheets were transferred to the surface of anode via Langmuir-Blodgett (L-B) isotherm method using Langmuir trough (Materials and Methods). The investigated parameters in this study include concentration of GO, surface pressure (mN m-1), and film thickness. Figure 1a inset shows the schematic of L-B isotherm method. Figure 1a shows the characteristic surface pressure (mN m-1) change with GO film area during barrier compression.5,23 Three different regions in this curve can be observed. Initially, at the very large GO film area, the GO nanosheets are very far from each other (phase I). Upon compression, these nano-sheets come close to each other, and the surface pressure increases with compression (which decreases the GO film area). The steady increase in surface pressure with GO film area comes under phase II region. Further compression causes the conversion of 2D structure to 3D structure (phase III). The anodes were coated at the surface pressure near the end of phase II, right before the start of phase III, to make sure maximum GO surface coverage is achieved without damaging the 2D structure. GO films with five different thicknesses were coated on the entire surface of the anode: 1-layer (1G), 5 layer (5G), 10 layer (10G), 50 layer (50G) and 100 layer (100G). These GO coating were reduced to reduced graphene oxide (RGO) via exposure to the water vapor (Materials and Methods). Scanning electron microscopy (SEM) and atomic force microscopy (AFM) methods were used to observe the surface of the blank, 10G and 100G zinc anodes (Figure 1b-d and Figure 1e, respectively). As can be seen from the SEM images (Figure 1c and d), increasing the thickness of the graphene coating makes the anode surface features less evident. Furthermore, wrinkles of the graphene nano-sheets become more apparent (Figure 1d). Energy dispersive spectroscopy on


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10G and 100G (Fig S2) confirms the presence of carbon from the G-SEI. Also note that the carbon content increases with increasing the G-SEI thickness. The AFM image in Figure 1e confirms that the G-SEI can create a distinct boundary among zinc particles on the anode surface. SEM images of 100G before and after reduction (compare Fig S1 to Figure 1d) also show that there was no obvious structural change when GO was reduced. Contact angle measurements were also done using water droplet on the blank and 100G before (GO) and after reduction on the zinc anode (Figure 1f-h). The results show that the G-SEI anode has a much lower contact angle before the reduction of GO (6O) compared to the blank (650), mainly due to the presence of oxygen functionalities on the basal plane and edges of GO.24 After the reduction of GO (RGO), the contact angle became higher (260), as it was anticipated, possibly due to the partial reduction of GO.5 Note that the surface of the G-SEI anode is still smoother than that of the blank.25


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Figure 1. Characterization of RGO coatings on zinc porous anode. (a) Surface pressure as a function of trough area in the Langmuir method. Inset: Schematic of the isotherm method. SEM images of (b) blank, (c) 10G and (d) 100G. (e) AFM images of blank and 100G. Contact angle measurement of (f) blank, (g) 100G and (h) 100GO. The basic electrochemical properties of the anodes with the graphene coating were tested via Tafel, Chronoamperometry (CA) and Cyclic Voltammetry (CV) techniques. Linear polarization curves of zinc anode with and without the G-SEI layers are presented in Figure 2a. The corrosion


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current density and corrosion potential were obtained by fitting the Tafel plots. All the G-SEI anodes show lower corrosion current density than that of the blank, with the 10G anode as the lowest corrosion current density (Figure 2a). The corrosion current density of blank, 1G, 10G, 50G and 100G are 1.0455 mAcm-2, 0.1067 mAcm-2, 0.0333 mAcm-2, 0.6280 mAcm-2and 0.2704 mAcm-2, respectively. It is evident that the graphene layers can significantly inhibit the corrosion of the anode surface. The corrosion improvement of zinc via coating with graphene oxide has been also previously reported.26 A profile of the current density over time for the G-SEI anodes after exposure to the aqueous electrolyte (for 30 seconds) is presented in Figure 2b inset. For the blank sample (no graphene coating), the current density dropped to 7 mA/cm2 after 10 seconds suggesting a fast nucleation on the zinc anode. The G-SEI anodes, however, (except 50G) shows a much less severe drop in the current density. For example, 10G shows a current density drop to 5 mA/cm2, and this current drop occurred over a longer period, 7 seconds vs 12 seconds for the blank. Furthermore, a more gradual drop in the current density (less severe) can be translated to a longer adsorption process of zinc ions, and more uniform deposition of the zinc atoms. Currenttime profile for G-SEI anodes over a time span of 1 hour is shown in Figure 2b. Again, the current density drop in all G-SEI anodes is less than that of the blank. 10G shows the lowest current drop after 1 hour (-11.6 mA/cm2) followed by 100G (-12.6 mA/cm2), 50G (-16.3 mA/cm2), 1G (-18.0 mA/cm-2) and blank (-18.6mA/cm-2). It is interesting to note that even though initially (in less than 30 seconds) 1G had lower current drop compared to 50G, after a while (roughly 750 seconds), 50G outperforms 1G. This can be due to the physical damage in the graphene sheets in thin coated RGO sample (such as 1G) from dendrites, and it will be discussed in more details in the following sections. Moreover for 10G, 100G and 50G change in current density after 1000 seconds is much more gradual than that of 1G and blank. This increase in


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current density relates to increase in surface area of the anode from dendrite formation and growth.27 Since the G-SEI anodes (except 1G) created smaller/smoother surface area, the dendritic growth is lower than the blank anode. For 1G after a certain time, the graphene sheets crack due to the zinc dendrite growth and penetration into the G-SEI leading to a situation similar to the blank. The CVs in the three-electrode system are presented in Figure 2c. The area under the curve for each of the samples was measured, where the 10G and 100G show significantly higher area under the reduction region of the CV curve compared to the blank. SEM images of blank, 10G and 100G after 170 millisecond of chronoamperometry is shown in Figure 2d-f. This time span (170 milliseconds) corresponds to the dendrite nucleation, as evident from current-time profile (figure 2b inset). Sharp flake-like zinc dendrites appear to grow densely on the blank anode surface. For the 10G anode, there appears to be little to no dendrite growth for regions covered by the graphene nano-sheets. However dendrite with flake-like morphology grow on uncovered exposed zinc surrounding the graphene nano-sheets. For 100G anode, again dendrites seem to be suppressed underneath the graphene nano-sheets. It should also be observed that 100G sample have a better graphene coverage compared to that of 10G. SEM images for blank, 10G and 100G after 1 hour of CA are presented in Figure 2g-i. We observe irregular zinc deposition and further dendrite growth in blank sample. For 10G sample, we observe dendrite suppression by graphene nano-sheets. However, dendrites from underneath seemed to pierced through the graphene nano-sheets, which leads to the breakage of these nanosheets. At the lower magnifications (Figure 2j), these breakages in the graphene nano-sheets expand to the graphene layers underneath. The 100G sample seems to be intact after 1 hour CA, and has suppressed dendrites underneath of that. At high magnifications (Figure 2k), polygonal features of the zinc flakes parallel to the anode surface are evident. Angled SEM images of


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100RGO before and after 1 hour CA are shown in Figure 2l and 2m, respectively. An obvious increase in the G-SEI thickness from 100 nm to 500 nm was observed after the CA test. This can be attributed to zinc deposition on top of the G-SEI as well as between the graphene layers (i.e. intercalation of the graphene layers by the zinc ions).28


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Figure 2. Electrochemical characterization of RGO coated zinc porous anode. (a) Tafel plot (b) chronamperometry for 1 hour. Inset: chronoamperometry for 30 seconds. (c) CV plot of blank, 10G and 100G. SEM images of blank, 10G and 100G after (d-f) 170ms and (g-i) 1hr of chronoamperometry. SEM images of (j) demagnified new of 10G after 1 hour of CA. Angled


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SEM sample of 100G (k) showing close-up zinc deposition, (l) showing RGO layer thickness before and (m) after 1 hour of chronoamperometry.

The G-SEI anodes were assembled and tested in a rechargeable hybrid rechargeable aqueous battery (ReHAB) system (Experimental section). CV curves of the batteries containing blank, 1G, 10G, 50G and 100G anodes are shown in Figure 3a. The two redox couples, located at 1.88 V / 1.7 V and 2.00 V / 1.85 V versus Zn2+/Zn, correspond to Li+ ion de-intercalation and intercalation from/into the host spinel structure of lithium manganese oxide in the aqueous electrolyte, respectively.5,29 Furthermore, the symmetric peaks show that Li+ extraction insertion process in the cathode is highly reversible.30 It is evident that the G-SEI has minimal impact on the peak shape and position of the CV profile. Thus, it is expected that the G-SEI would not impact the charge-discharge process in the battery system. The cyclic stability of ReHABs with the blank and the G-SEI anodes is shown in Figure 2b. The highest initial discharge capacity was observed for 100G (at 102.72 mAh/g), followed by 10G (95.36 mAh/g), blank (91.15mAh/g), 50G (88.75 mAh/g) and 1G (86.14 mAh/g). All the G-SEI anodes show significant improvement in discharge capacity retention after 300 cycles (Figure S3a): 100G with a has discharge capacity retention of 81.88%, 10G of 80.94%, 50G of 77.78% and 1G of 76.79%, while the blank only showed capacity retention of 64.74%. The columbic efficiency for the blank, 10G and 100G samples (Figure S3b) are consistent with the previously reported columbic efficiency of lithium manganese oxide aqueous batteries (90 to 100 %).31,32 The rate performance of ReHABs under different C-rates (0.2C, 0.5C, 1C, 2C, 4C) are presented in Figure 3c. 1G, 50G and 100G show much higher discharge capacity for all C-rates compared to the blank, especially for higher Crates. For example, at 4C, 1G, 50G and 100G show discharge capacity around 75 mAh/g,


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whereas blank has discharge capacity of only 60 mAh/g. Galvanostatic charge-discharge curves for blank and 100G after 1st and 300th cycles are presented in Figure 3d. The two plateaus observed in charge-discharge profile correspond to CV profile, and are related to two stages of Li+ de-intercalation/intercalation behavior in the cathode.5 100G shows higher charge and discharge capacity after 1st and 300th cycle compared to that of the blank. EM images of the anode surface of the blank and 100G after 300 cycles are presented in Figure 3e, f, respectively. In the blank sample, an uneven zinc deposition leads to flake-like zinc dendritic growth (compare Figure 3E with Figure 1B). In the 100G sample, however, the dendritic growth is suppressed as the anode surface is fairly flat and uniform. Moreover, a polygonal feature of zinc flakes parallel to the anode surface can be observed.


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Figure 3. Battery performance with RGO coated porous zinc anode. (a) CV profile at scan rate of 1mVs-1. (b) Cycle Life under current density of 4C. (c) Discharge capacities at different C rates. (d) Galvanostatic charge-discharge curves of blank and 100G after 1 and 300 cycles. SEM images of (e) blank and (f) 100G after 300 cycles.


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Electrochemical impedance spectroscopy (EIS) was performed on blank, 10G and 100G samples to measure the change in impedance during the charge/discharge cycles (Figure 4). The diameter of the semicircle in the Nyquist plot corresponds to the charge transfer resistance (Rct). EIS data was fitted using equivalent circuit (Figure S4). Rct of the blank, the 10G and the 100G samples were calculated to be 563 Ω, 243 Ω and 222 Ω, respectively, before the cycling stability test (Figure 4a), indicating an improvement in the transport behavior of zinc ions into the G-SEI anode. After cycling, Rct of the blank, the 10G and the 100G were calculated to be 568 Ω, 331 Ω and 230 Ω respectively (Figure 4b). Note that the Rct for the blank and 100G samples are more stable than the 10G sample. An increase in the Rct of the 10G suggests a change in the properties of the G-SEI between the electrolyte and anode surface during cycling. This finding is in agreement with our previous observation in Figure 2h, where the dendrites pierce through the graphene layers in the 10G sample. In other words, when the dendrites break the graphene layer in the 10G anode, the underneath anode surface will be exposed to the electrolyte, and a nonhomogeneous growth of dendrites will be accelerated (higher Rct).

Figure 4. Impedance characterizations of blank, 10G and 100G (a) before cycling (b) after 100 battery cycles.


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In order to further explore the effect of the G-SEI in suppression of dendrites in the aqueous battery systems, detailed analysis of Raman, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were conducted (Figure 5). The Raman spectra of the anodes show a strong presence of the D and G bands after the CA test in the 10G sample, at 1380 cm-1 and 1450 cm-1, respectively (Figure 5a). The significant increase in the D and G bands intensities might be due to intercalation of the G-SEI by the zinc ions that can create surface Plasmon resonance effect.33 A similar increase in the intensities of the 100G sample was observed, although the ID/IG was maintained before and after the CA test, indicating that the G-SEI did not undergo an oxidation or reduction reaction during the zinc deposition. The GIXRD was also conducted on the blank and the 100G samples before and after the CA test (Figure 5b). The presence of major peaks corresponding to the (002), (100), (101), (102), (103) and (110)) planes of zinc is evident.34,35 The peak intensities of all the samples in the figure have been normalized with the (101) peak. The intensity of (002) plane relative to (101) plane for the 100G sample after CA (I002/I101~0.26) is higher than that of the blank (I002/I101~0.20). The zinc crystal growth in the (002) and (101) planes are parallel and perpendicular to the anode surface, respectively, suggesting that the GSEI promotes more zinc deposition parallel to the anode surface than does the blank sample.36 The later finding confirms the earlier observation in the SEM images (Figure 2g, k). High resolution XPS spectrum of the zinc peaks (Zn 2p (3/2)) before and after 1 hour the CA test of the blank and the 100G anodes, and cycling stability tests of the corresponding batteries are shown in Figure 5c,d, respectively. A higher zinc content (in at.%) was found after the CA (20.8%) and the cycling stability tests (6.6%) than that of the blank (9.9% and 2.9%, respectively. The higher zinc content might indicate that the G-SEI effectively reduces the corrosion rates of the anode. The deconvolution of the Zn 2p (3/2) peaks, based on a Lorentz-


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Guass algorithm, shows predominately pure zinc (62.7% at 1020.1 eV) followed by zinc hydroxide (24.8% at 1024.3 eV) and zinc oxide (12.5% at 1022.7 eV). After the CA test of the blank anode, there is a drastic decrease in the contribution of the pure zinc peak (8.9% at 1019.9eV) and increase in zinc hydroxide (50.8% at 1023eV) and zinc oxide (40.3% at 1021.8eV). In the 100G anode, however, the decrease in the pure zinc peak (16.3%) is not as significant as the blank anode, representing a more efficient deposition/dissolution processes of zinc ions in the presence of the G-SEI. Note that the 100G anode has initially lower contribution of pure zinc (27.7%) and higher zinc oxide (45.8%) and zinc hydroxide (26.5%) than that of the blank anode. This might be due to binding Zn(II) to the residual oxygen functional groups of the G-SEI from the synthesis process (COOH- + Zn2+ → COO-Zn2+ + H+ and 2OH- + Zn2+ → ZnO + H+).37


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Figure 5. Characterizations of anode before and after 1 hour of CA (a) Raman (b) GIXRD and (c) a survey XPS spectrum (d) high resolution XPS spectra of Zn 2p3/2 Conclusion An artificial solid electrolyte interface based on graphene films (G-SEI) was successfully introduced to the anode surface in an aqueous lithium battery system with a thickness and area of


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1 – 100 nm and 1 – 10 cm2, respectively. The G-SEI anodes exhibited lower corrosion current density and dendritic growth in a zinc anode as evident from the Tafel and CA measurements using a 3-electrode system. SEM images after 1 hour of CA confirmed that dendrites were suppressed underneath the G-SEI. Furthermore, a uniform zinc deposition process was observed in the regions covered with the G-SEI. SEM and Raman results confirmed an increase in the thickness of the G-SEI after the electrochemical testing, possibly due to the intercalation of the graphene layers by the zinc ions. The lithium batteries with the G-SEI anodes showed a considerable improvement in cycling stability (82% after 300 cycles). The EIS measurement also showed a lower charge transfer resistance in the G-SEI anodes.

ASSOCIATED CONTENT Supporting Information. Supporting information contains the following figures: Figure S1: SEM image of 100GO (100G before water vapor reduction) Figure S2: EDX of (a) 10G and (b) 100G Figure S3: (a) Retention in discharge capacity (b) Self discharge for 72 hours and (c) Float Capacity loss after 72 hours of blank and G-coated samples. (d) EIS of blank and 100G of aqueous battery in coin cell configuration. Figure S4: Relevant equivalent circuit model for EIS data in Fig.4 AUTHOR INFORMATION Corresponding Author


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*Email: [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. ‡These authors contributed equally. Funding Sources This work was supported by Mitacs through the Mitacs Accelerate program (IT08228). ACKNOWLEDGMENT We thank Mitacs for funding this project. We also thank N. Oh and S. Khan for their help. REFERENCES (1)

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Introducing Artificial Solid Electrolyte Interphase onto the Anode of

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