Ultrafast Rechargeable Zinc Battery Based on High Voltage Graphite

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Ultrafast Rechargeable Zinc Battery Based on High Voltage Graphite Cathode and Stable Nonaqueous Electrolyte Ning Zhang, Yang Dong, Yuanyuan Wang, Yixuan Wang, Jiajun Li, Jianzhong Xu, Yongchang Liu, Lifang Jiao, and Fangyi Cheng ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b10399 • Publication Date (Web): 16 Aug 2019 Downloaded from pubs.acs.org on August 19, 2019

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ACS Applied Materials & Interfaces

Ultrafast Rechargeable Zinc Battery Based on High Voltage Graphite Cathode and Stable Nonaqueous Electrolyte Ning Zhang,*,†,§,+ Yang Dong,†,+ Yuanyuan Wang,† Yixuan Wang,† Jiajun Li,† Jianzhong Xu,*,† Yongchang Liu,*,‡,§ Lifang Jiao,§ and Fangyi Cheng§ †College of Chemistry & Environmental Science, Key Laboratory of Analytical Science and Technology of Hebei Province, Hebei University, Baoding 071002, China ‡Beijing Advanced Innovation Center for Materials Genome Engineering, Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China §Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China KEYWORDS: rechargeable zinc batteries, zinc anode, nonaqueous electrolyte, graphite cathode, energy storage

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ABSTRACT: Zinc-based battery chemistries have lately drawn great attention for grid-scale energy storage due to their materials abundance and high safety. However, the low Coulombic efficiency (CE) and dendrite growth of zinc (Zn) anodes, and the limited working voltage of current oxides cathodes are the major barriers hindering the development of rechargeable Znbased batteries (RZBs). Here we report an ultrafast and high-voltage Zn battery in a new cell configuration employing graphite cathode, Zn anode, and nonaqueous 1 M zinc bis(trifluoromethanesulfonate)imide (Zn(TFSI)2) in acetonitrile (AN) electrolyte. This RZB operates through the (de)intercalation of TFSI- anions into the graphite and the electrochemical Zn2+ plating/stripping at the anode. The optimized Zn(TFSI)2/AN electrolyte features high reductive/oxidative stability, good ionic conductivity (~28 mS cm-1), and low viscosity (~0.4 mPa·s), enabling the unprecedented cycling stability (over 1000 h) of Zn anode with a dendritefree morphology, the ultrafast Zn plating/stripping with a high CE (>99%), and the good compatibility to graphite cathode. Consequently, this RZB exhibits a high average output voltage (2.2 V), a high energy/power density (86.5 Wh kg-1 at 4400 W kg-1), and a long cycle life (97.3% capacity retention after 1000 cycles). The present work offers new insights and opportunities to the Zn-based electrochemistry.


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1. INTRODUCTION Lithium-based batteries with high energy density have been widely applied in portable electronics and considered as promising power supplies for electric vehicles, as well as grid-scale energy storage systems. However, the growing concerns about safety, price, and the availability of lithium resources impede their large-scale deployment, and motivate the pursuit of alternative battery chemistries.1-4 Owing to the high abundance, low-cost, non-toxicity, low-flammability, and two-electron redox properties of metallic zinc (Zn), rechargeable Zn-based batteries (RZBs) are attracting extensive attention as a promising candidate for the large-scale energy storage.5-7 Nevertheless, the low Coulombic efficiency (CE), uncontrolled Zn dendrites growth, and irreversible by-products (e.g., ZnO or Zn(OH)2) formation are the main issues for Zn metal anodes in traditional alkaline electrolytes.8-10 Although recently developed neutral/mild-acidic aqueous electrolytes can minimize the dendrite growth, the low Zn plating/stripping CE, and the hydrogen evolution still remain challenges.11-13 Moreover, the narrow electrochemical window (1.2 V) of water would inevitably limit the energy density of aqueous Zn-based batteries. The hot concept of highly concentrated aqueous electrolytes has been proposed for RZBs that can significantly improve the stability of Zn anodes compared to the diluent counterparts, but it generally increases the cost and viscosity.2,14-16 Recently, exploring non-aqueous electrolyte has been regarded as another choice for the future direction of RZBs, which in principle could provide an extended working window and minimize the side reactions facing Zn anodes in water-based electrolytes.17-20 However, the development of nonaqueous Zn chemistries is still at an incipient stage, and research on the electrode/electrolyte compatibility and the Zn reversibility in non-aqueous electrolytes remains deficient. Up to date, the ever reported non-aqueous Znbased batteries generally show low average output voltages (below 1.8 V vs. Zn2+/Zn), limited


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by the current employed cathodes, such as V2O5 (~0.85 V),21 MnO2 (~1.35 V),22 KCuFe(CN)6 (~1.65 V),17 ZnNi1/2Mn1/2CoO4 (~1.75 V),23 and ZnAlxCo2-xO4 (~1.75 V).24 In addition, unlike Li+ ions, the large mass and the high desolvated energy barrier of divalent Zn2+ would result in poor reaction kinetics and undesirable rate performance of Zn plating/stripping.25-27 Graphite with stable layered structure can serve as cathode enabling the intercalation of anions (e.g., PF-, TFSI-) at high charging voltage, whereas the reactions in terms of metal cations electroplating or alloying take place on the anode side, just like the cases of graphite cathodes in Ca2+- and Al3+-based batteries.28-30 Considering the advantages of Zn anode, there is also a strong interest in the Zn-graphite battery chemistry that can in concept promise high working voltage, cost-effectiveness, and high safety. However, graphite cathodes typically operate at high oxidizing potentials (theoretically >1.3 V vs. standard hydrogen electrode (SHE); i.e., >2.0 V vs. Zn2+/Zn), making the water-based electrolyte incompatible to the Zn-graphite battery. In the previously reported nonaqueous battery systems employing graphite as cathodes (vs. Li, Na, or Al), the high working potential would cause side reactions between graphite and electrolytes, and thus induce an inadequate cycling life.31-34 Then the use of high concentration organic electrolytes35-38 or ionic liquids39-41 has been demonstrated to enhance the stability of electrode/electrolyte interface, while the high cost and low ionic conductivity should be further taken into account. From the above considerations, seeking a non-aqueous electrolyte with a normal salt-concentration for Zn-graphite battery that can simultaneously enable the good compatibility to graphite cathode and stabilize the Zn anode with high reversibility and fast kinetics is particularly important. Herein, we develop a high-performance Zn-graphite battery system using Zn anode, graphite cathode, and non-aqueous electrolyte with a normal concentration (i.e., 1 M zinc


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bis(trifluoromethanesulfonate)imide (Zn(TFSI)2) in acetonitrile (AN)). The Zn(TFSI)2/AN electrolyte displays good compatibility to both Zn anode and graphite cathode, high ionic conductivity (~28 mS cm-1), low viscosity (~0.4 mPa·s), high anodic stability up to 2.8 V (vs. Zn2+/Zn), stable and dendrite-free cycling of Zn anode (over 1000 h), and ultrafast Zn plating/stripping performance with a high CE (>99%). As a result, this RZB achieves a high average output voltage (2.2 V), high rate capability (39.3 mAh g-1 at 2.0 A g-1; 86.5 Wh kg-1 at 4400 W kg-1, in ~1 min), and long-term cyclability (97.3% capacity retention after 1000 cycles at 1.0 A g-1). Furthermore, the underlying reaction mechanism of the Zn-graphite battery has been revealed that TFSI- anions reversibly (de)intercalate into the graphite cathode and Zn2+ cations electroplate/strip at the anode during charging/discharging processes, as evidenced by means of electrochemical measurements, X-ray diffraction (XRD) patterns, Raman spectra, X-ray photoelectron spectra (XPS), transmission electron microscope (TEM), Fourier transform infrared (FTIR) spectra, and scanning electron microscope (SEM) analyses. 2. EXPERIMENTAL SECTION 2.1 Materials. Commercial KS6 graphite power, Zn metal foil, and Zn(TFSI)2 are purchased form Alfa Aesar. The electrolytes (e.g., 0.5, 1, and 2 M Zn(TFSI)2 in acetonitrile (AN); 1 M Zn(TFSI)2 in diethyl carbonate (DEC)/ethylene carbonate (EC) (volume ratio of 1:1)) were prepared by dissolving the desired amount of salts in the selected solvents in a glove-box. 2.2 Characterizations. The morphology of the sample was investigated by scanning electron microscopy (SEM, JEOL JSM-7500F). Raman spectra were recorded on a confocal Raman microscope (DXR, Thermo-Fisher Scientific) using 532 nm excitation. XRD patterns were obtained on a Bruker D8 ADVANCE (Cu Kα radiation). TEM measurements were conducted on


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a Talos F200x G2 microscope, AEMC. XPS and FTIR spectra were collected on a PHI 1600 ESCA spectrometer (Perkin-Elmer) and a Nicolet iS10 spectrometer (Thermo-Fisher Scientific), respectively. The viscosity of electrolyte was tested on a MDJ-5S viscometer (Shanghai, China) at 25 °C. 2.3 Electrochemical Measurements. The Zn plating/stripping performance in different electrolytes was characterized by cyclic voltammograms (CVs) at a potential sweeping rate of 1 mV s−1 using Ti foil as the working electrode and Zn foil as the reference and counter electrodes. The Coulombic efficiency of Zn stripping/plating was tested using Zn/Ti cells at 0.2 mA cm-2 with a deposition capacity of 0.1 mAh cm-2. The reversibility and stability of the selected electrolyte were evaluated in symmetric Zn/Zn cells at various current densities. Electrochemical performance was examined using CR2032 coin-type cells, in which graphite served as the cathode, Zn foil as the anode, and 1 M Zn(TFSI)2 in AN as the electrolyte. The electrolyte added in one coin-type cell is 60 μL, and the density of 1 M Zn(TFSI)2/AN electrolyte is 1.18 g mL-1. The graphite cathode was prepared by blending graphite powder and sodium carboxymethyl cellulose (CMC, binder) in a weight ratio of 9:1 using water as solvent. The obtained slurry is pasted onto a Ti foil or a stainless steel foil, and then vacuum-dried at 100 oC for 10 h. The asprepared electrode was cut into round slices with a diameter of 1 cm. The typical loading mass of active material is ~4 mg cm-2. The weight ratio of electrolyte/graphite is calculated to be ~22.55. In addition, both a lower loading mass of ~2 mg cm-2 and a higher loading mass of ~10 mg cm-2 are prepared. The charge/discharge experiments were performed on a LAND-CT2001A batterytesting instrument at room temperature. The cell is firstly charged and then discharged during charge/discharge tests. CV was carried out using a CHI660E electrochemical work station (Shanghai Chenhua, China) at different scan rates. Calculation of specific capacities was based


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on the initial graphite mass. Electrochemical impedance (EIS) spectra were performed on a CHI660E electrochemical workstation over the frequency from 100 kHz to 100 mHz with the ac perturbation signal of 5 mV. 3. RESULTS AND DISCUSSION

Figure 1. Electrolyte and Zn anode characterizations. (a) Electrochemical window of the Zn/Ti cell using 1 M Zn(TFSI)2 in AN electrolyte at a scan rate of 1 mV s-1. (b) Coulombic efficiency and typical Zn plating/stripping profiles (inset) of the Zn/Ti cell at 0.2 mA cm-2. (c)


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Galvanostatic cycling at 0.5 mA cm-2 and (d) rate performance of the Zn/Zn symmetrical cells. Insets display the selected Zn plating/stripping curves. SEM images of (e) the pristine Zn anode, and Zn anodes after the (f) 10th, (g) 50th, and (h) 200th cycles. The properties of the 1 M Zn(TFSI)2 in AN electrolyte (denoted as Zn(TFSI)2/AN) were evaluated in unsymmetrical Zn/Ti and symmetrical Zn/Zn cells. Figure 1a displays the electrochemical stability of the Zn(TFSI)2/AN electrolyte at 1 mV s-1 from -0.25 V to 3.0 V using a Zn/Ti cell. Reversible Zn plating/stripping behavior on the Ti foil can be observed, indicating the good compatibility between Zn anode and Zn(TFSI)2/AN electrolyte. The electrochemical window of the AN-based electrolyte is up to 2.8 V vs. Zn2+/Zn, which is much higher than that of the carbonate electrolyte (e.g., 1 M Zn(TFSI)2 in EC/DEC electrolyte, Figure S1). Figure 1b presents the cycling performance of the Zn/Ti cell at 0.2 mA cm-2 with a deposition time of 0.5 h and a stripping cut-off potential of 0.5 V. The Coulombic efficiencies of Zn plating/stripping are 87.3% and 99.5% at the 1st and 10th cycles, respectively, and retain an average value of 99.8% up to 200 cycles. This demonstrates that the Zn(TFSI)2/AN electrolyte enables a high utilization and a high stability of the metallic Zn anode. The typical Zn plating/stripping curves at the 10th, 100th, and 200th cycles are well overlapped with a small overpotential of ~168 mV (the inset of Figure 1b). The initial discharge/charge curve of Zn/Ti cell is provided in Figure S2. For comparison, the Zn/Ti cell using the 1 M Zn(TFSI)2 in EC/DEC electrolyte exhibits an initial CE of 76%, and then the CE increases to 98.6% after 10 cycles (Figure S3). The polarization of Zn plating/stripping in the AN-based electrolyte is smaller than that in the EC/DEC-based counterpart (168 mV vs. 235 mV), mainly attributed to the lower viscosity (~0.4 mPa·s) and higher ionic conductivity (~28 mS cm-1) of the AN-based electrolyte compared to those of the EC/DEC-based electrolyte (~2.8 mPa·s; ~3.2 mS cm-1).


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Figure 1c shows the galvanostatic cycling of the Zn/Zn symmetric cell at 0.5 mA cm-2 with a discharge/charge time of 0.5 h. As revealed in the enlarged voltage profiles (inset of Figure 1c), the Zn(TFSI)2/AN electrolyte exhibits a decreased overpotential from the initial 270 mV (Figure S4) to 98 mV at the 10th cycle, to 70 mV at the 100th cycle, and then the overpotential maintains nearly constant for more than 1000 cycles (over 1000 h), demonstrating the excellent cyclic stability. The initial polarization decrease is associated with the electrode activation process. Even at a higher current of 1.0 mA cm-2, the exceptional Zn plating/stripping behavior can also be obtained with a small overpotential of 85 mV after 500 cycles (Figure S5). Furthermore, the Zn(TFSI)2/AN electrolyte allows a high-rate Zn plating/stripping behavior in the Zn/Zn cell (Figure 1d). The voltage profiles show negligible changes as the current increases from 0.1 to 1.0 mA cm-2, and display a small rise from 2.0 mA cm-2 (~95 mV) to 5.0 mA cm-2 (~140 mV) (Figure S6). The excellent performance of the Zn(TFSI)2/AN electrolyte mainly arises from its unique features such as, high oxidative/reductive stability, low viscosity (~0.4 mPa·s), high ionic conductivity (~28 mS cm-1), and facilitated cations transport due to the weaker interaction between Zn2+ and N-donor solvents (e.g., AN) compared with O-donor solvents (e.g., EC/DEC), which further favors the ultrafast charge/discharge and stable cycling of the Zn-graphite battery. In addition, the morphology evolution of Zn anodes in the Zn(TFSI)2/AN electrolyte during Zn/Zn cells cycling at 0.5 mA cm-2 was analyzed. Figure 1e-h records the SEM images of Zn anodes at selected states of the pristine, and after the 10th, 100th, and 200th cycles, respectively. The uncycled Zn anode displays a smooth surface (Figure 1e). Upon cycling, nodule-like Zn deposits are characterized on the Zn anode (Figure 1f,g). Even after 200 plating/stripping cycles, the Zn anode shows a dense and dendrite-free surface morphology (Figure 1h) without byproducts (e.g., ZnO) formation (XRD, Figure S7). Furthermore, no obvious dendrite growth is


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detected when the Zn anode is performed at a high current density of 2.0 mA cm-2 after 160 repeated cycles (Figure S8). These results demonstrate that the Zn(TFSI)2/AN electrolyte enables the good compatibility to Zn anode, accounting for the high stability of Zn-graphite battery.


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Figure 2. Rechargeable Zn-graphite battery performances. (a) Schematic illustration of the Zngraphite battery during discharge using 1 M Zn(TFSI)2 in AN electrolyte. (b) Representative charge/discharge curves at 50 mA g-1. (c) Rate capability and (d) the corresponding charge/discharge profiles at variable current densities. Inset shows the typical charge/discharge curves at 2.0 A g-1. (e) Long-term cycling stability at 1.0 A g-1 after the rate test. Thereafter, a Zn-graphite battery with a new configuration was built using the formulated Zn(TFSI)2/AN electrolyte, graphite cathode, and Zn metal anode (schematically illustrated in Figure 2a). Note that the specific capacity values in this work are calculated based on the graphite mass. Figure 2b presents the typical charge/discharge profiles of the Zn-graphite battery at a current density 50 mA g-1 in the voltage range of 1–2.55 V (vs. Zn2+/Zn). The cell displays an average discharge voltage of 2.2 V vs. Zn2+/Zn, which is the highest value among the reported Zn-based batteries. The reversible capacity gradually increases during initial cycles and maintains 47.5 mAh g-1 after 10 cycles (Figure S9), which is mainly due to the electrode activation, as confirmed by the reduced charge-transfer resistance according to the electrochemical impedance spectra (EIS, Figure S10). We note that the CE is below 100% (from the initial 73% increasing to ~95% after 10 cycles), mainly attributed to the formation of solid electrolyte interface (SEI) film and the slight decomposition of electrolyte at a high working voltage and a low test current of 0.05 A g-1. This phenomenon was also observed in other reported dual-ion battery systems using graphite cathodes (Table S1).28-30,35 When the cell was performed at a higher current rate (e.g., 0.5 A g-1; 1.0 A g-1), the CE values can approach 100% (shown below). It is worth mentioning that the Zn-graphite battery using a low-concentration electrolyte (e.g., 0.5 M) displays a much reduced CE (Figure S11), and a concentrated electrolyte (e.g., 2.0 M) shows negligible performance improvement but an inferior ionic conductivity (1.8


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mS cm-1) (Figure S12) compared to the normal concentration counterpart (i.e., 1 M). Note that graphite cathode using stainless steel foil as the current collector can also deliver similar electrochemical behaviors to that of the cathode using Ti as the current collector (Figure S13). In addition, the 1 M Zn(TFSI)2 in EC/DEC electrolyte cannot well support the operation of Zngraphite cell accompanied with side reactions during charging (Figure S14), due to its poor anodic stability (Figure S1). Figure 2c shows the rate behaviors of the Zn-graphite cell in 1 M Zn(TFSI)2/AN electrolyte by progressively increasing the test current from 0.1 to 4.0 A g-1 with 20 cycles staying for each rate. Stable capacities of 42.3, 42.5, 42.3, 42, 41.2, 39.3, 37.5, and 35.7 mAh g-1 are characterized at 0.1, 0.2, 0.5, 1.0, 1.5, 2.0, 3.0, and 4.0 A g-1, respectively. When the rate returns to 0.1 A g-1, the reversible capacity shifts up to 43.5 mAh g-1 swiftly. The corresponding discharge profiles at various rates are depicted in Figure 2d, and it can be observed that increasing the current density has a very small effect on the discharge voltage platform. From 0.1 A g-1 to 2.0 A g-1, the delivered capacity realizes a high capacity retention of 92.9%. Impressively, the charge/discharge time is around one minute (inset of Figure 2d) at 2.0 A g-1 with an energy density of 86.5 Wh kg-1 at a power density of 4400 W kg-1 based on the cathode, demonstrating the superior rate capability. Such an ultrafast Zn-graphite battery shows great prospects in many applications that are critical to the charge/discharge speed. After the rate test, the long-term cycle life of the Zn-graphite battery at 1.0 A g-1 was evaluated (Figure 2e). An impressive capacity retention of 97.3% is available after 1000 cycles, and more than 82% is maintained even after 4000 repeated cycles. Remarkably, the highest obtained capacity (42.7 mAh g-1 at 1.0 A g-1) is delivered in ~2 min of charge/discharge time. In addition, the Coulombic efficiency sustains around 100%, further suggesting the high reversibility. The ratio of electrolyte for anion


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intercalation to the total amount of electrolyte addition can be estimated to ~4.88% at 0.05 A g-1 (Figure 2b) and ~4.17% at 1.0 A g-1 (Figure 2e). The calculation details have been given in Supplementary Note 1 (Supporting Information). The selected charge/discharge curves for the 1st, 500th, 1000th, 2000th cycles are provided in Figure S15. Furthermore, the electrochemical performances of graphite cathodes with different loading masses were evaluated. The cathode with a lower loading mass (e.g., 2 mg cm-2) exhibits a higher initial discharge capacity of 50 mAh g-1 and maintains ~53 mAh g-1 after 4 cycles (Figure S16). The higher loading mass (e.g., 10 mg cm-2) leads to a reduced initial discharge capacity of ~34 mAh g-1 which gradually increases to 45 mAh g-1 with an areal capacity of 0.45 mAh cm-2 after 20 cycles (Figure S17). The ultrafast and durable performances of this rechargeable Zn-graphite battery are comparable to those of other multivalent cations (e.g. Al3+, Ca2+) based batteries employing graphite as cathodes (Table S1).28-30,35 Considering the flammability and toxicity of AN solvents that would pose safety issues of battery, more efforts should be made to develop safe and efficient electrolyte systems for the Zn/graphite battery. Towards better understanding of the high rate performance, the electrode process kinetics was studied by cyclic voltammetry (CV) analysis to identify the capacitance-type contribution in the graphite cathode. Previous reports indicate that pseudocapacitance is always observed in nanostructured or layer-structured materials, and is beneficial for the rate and cycling properties.34,42 Figure 3a exhibits the CV profiles of the graphite cathode recorded at different scan rates from 0.2 to 1.6 mV s-1. Three pairs of redox peaks (i.e., labeled as O1, O2, O3, R1, R2, and R3) correspond to the gradual anions (de)intercalation processes into the layered structure of graphite, similar to the behaviors of Al-graphite batteries.35 With the sweep rate increasing, the intensities of the redox peaks increase significantly, while the overpotentials


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between cathodic and anodic peaks enlarge slightly. Particularly, the main cathodic peaks (R1-3) show no obvious shifts, demonstrating the excellent reaction kinetics. The capacitive effect of a battery chemistry can be determined according to the relation of i = avb or logi = b × logv + loga, where a and b are adjustable parameters, i and v are the current density and the scan rate, respectively.43,44 When b value is close to 1.0, the redox reaction is mainly controlled by the capacitance, and when b value approaches 0.5, the reaction process is dominated by the Faradaic ion intercalation. According to the logi vs. logv plots at different oxidation/reduction states (Figure 3b), the b values for the O1, O2, O3, R1, R2, and R3 peaks are 0.97, 0.91, 0.82, 0.93, 0.98, and 0.96, respectively. This implies that the combination of diffusion and capacitive behaviors synergistically control the charge storage process, which leads to the fast ions (de)insertion kinetics.


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Figure 3. Electrode process kinetics and SEM characterization. (a) CV profiles of the graphite cathode at various sweep rates, and (b) the corresponding logi vs. logv plots at different oxidation/reduction states. (c) Typical CV curve at 0.8 mV s-1 showing the capacitive contribution (grey region) to the total current. (d) SEM image of the graphite cathode after a high-rate test of 180 cycles. The ratios of capacitance-type contribution can be further quantified using the equation of i(V) = k1v + k2v1/2 to separate the current response i at a fixed potential V into capacitive effects (k1v) and diffusion-controlled reactions (k2v1/2).45 It is found that around 51.7% fraction of the total charge comes from the capacitance-type contribution at 0.8 mV s-1 (Figure 3c), and the role of capacitive property further strengthens to a value of 61.5% at 1.2 mV s-1 (Figure S18). This is responsible for the unprecedentedly high rate capability of the graphite cathode in the Zn(TFSI)2/AN electrolyte. In addition, SEM image (Figure 3d) of the graphite cathode after the rate test (180 cycles) shows a similar morphology to that of the pristine electrode (Figure S19), and no obvious decomposition of electrolytes can be observed. This demonstrates the good compatibility between Zn(TFSI)2/AN electrolyte and graphite cathode, favoring the long-term cycling stability of battery. The reaction mechanism of the Zn-graphite battery was systematically investigated by a combination study of electrochemical, ex-situ Raman, ex-situ XRD, TEM, XPS, FTIR, and SEM analyses. Figure 4a displays the 1st charge/discharge profiles of the Zn-graphite cell, where the marked states (A-G) were collected for Raman characterizations (Figure 4b) to probe the structural transformation of graphite cathode. Upon charging, the initial G band peak of graphite at ~1580 cm-1 (E2g2 vibration mode) splits into two peaks at 1584 cm-1 (E2g2(i) mode) and 1605 cm-1 (E2g2(b) mode), respectively, related to the vibrations of C atoms in the interior and


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bounding graphene layers.34,37,46 At the fully charged state, the E2g2(i) peak obviously weakens and the E2g2(b) band shifts to a higher wavenumber of 1610 cm-1 as a result of more anions intercalation. The discharging process can well reverse the spectral changes of charging, and the graphite G band is recovered when fully discharged, demonstrating the highly reversible structural evolution of graphite cathode.

Figure 4. Reaction mechanism. (a) The first charge/discharge curves of the Zn-graphite cell at 50 mA g-1. The points A–G marked the states where data were collected for Raman analyses. (b) Raman spectra and (c) XRD patterns of the graphite cathodes at the selected charge/discharge states. (d) The typical charge/discharge profiles of the Ti-graphite cell at 50 mA g-1. (e) XRD patterns of the fully charged and discharged Ti electrodes. Insets, schematic drawings of the Zn-


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graphite (Fig. 4a) and Ti-graphite (Fig. 4d) cells. SEM and optical (insets) images of the (f) pristine Ti and (g) fully charged Ti electrodes. XRD measurements of the graphite cathodes at selected states further confirm the TFSIintercalation/deintercalation processes during charging/discharging (Figure 4c). At the fully charged state, the original sharp (002) peak at 26.55o of the pristine graphite vanishes, while two new signals appear at ~24.43o and ~30.15o, corresponding to the (00n + 1) and (00n + 2) peaks, respectively,28,36 where n represents the number of graphite layers between two adjacent intercalated planes (schematically illustrated in Figure S20). After analyzing the peak separation between the (00n + 1) and (00n + 2) peaks (see Supporting Information), the dominant state (n) of graphite intercalation compound reaches 4 for the final charged product. The gallery expansion (Δd) value is ~4.7 Å, similar to that for the TFSI- intercalation into graphite in Libased cells employing ionic liquid electrolytes,39 which indicates that almost no AN molecule co-inserts with anions into the graphite layers. During discharging process, the distance between the (00n + 1) and (00n + 2) peaks becomes smaller upon anions deintercalation, and the (002) peak of graphite reappears at the fully discharged state. The reversible (de)intercalation of TFSIanions into the graphite layers without AN solvent co-intercalation is also validated by the Fourier transform infrared (FTIR) analyses (Figure S21). In addition, Ti-graphite cells using Ti foil as the counter electrode, graphite as the cathode, and Zn(TFSI)2/AN as the electrolyte were performed to probe the reaction on the anode side. The electrochemical performance of the Ti-graphite cell has been provided in Figure S22. Figure 4d presents the typical charge/discharge profiles at 50 mA g-1 of the Ti-graphite cell (schematically shown in the inset), where Ti electrodes at states I (fully charged) and II (fully discharged) are collected for analyses. When charged to 2.55 V, the characteristic XRD peaks of metallic zinc


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(Zn) electroplated onto the Ti electrode can be detected without any other by-products (Figure 4e). The discharging process leads to the Zn stripping from the Ti substrate. These results manifest that the electrochemical deposition and dissolution of Zn take place at the anode during cell charge/discharge. Furthermore, SEM and optical images show that the smooth surface of the pristine Ti foil (Figure 4f) is uniformly coated by the deposited Zn micro-plates (Figure 4g) without obvious dendrites after the fully charged process.

Figure 5. Chemical probing of graphite cathodes. XPS data of (a) C 1s, (b) F 1s, (c) S 2p, and (d) Zn 2p spectra of the pristine, and the first fully charged/discharged graphite electrodes. STEM element mapping images of graphite cathodes at the first fully (e) charged and (f) discharged states. Scale bars, 100 nm. Afterwards, XPS and scanning transmission electron microscopy (STEM) with element mapping images (Figure 5) were carried out to investigate the chemical contents of the fully


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charged and discharged graphite cathodes. To minimize the effect of trapped electrolytes, the reobtained electrodes were thoroughly washed with AN solvent. XPS spectra show that the pristine C 1s peak (284.4 eV) develops a shoulder at a higher energy (286.3 eV) upon charging (Figure 5a), suggesting the electrochemical oxidation of graphitic carbon due to anions intercalation. Meanwhile, the strong XPS signals of F 2p and S 2p appear at the charged state (Figure 5b,c), confirming the successful TFSI- intercalation. Upon discharging, the C 1s spectrum reverts to the pristine state, and the F 2p and S 2p peaks are substantially reduced, attributed to the anions deintercalation. The weak signals of F and S mainly arise from the SEI film and a small amount of intercalated TFSI- anions trapped in the cathode. Almost no Zn signal is detected in the pristine and fully charged/discharged electrodes (Figure 5d). STEM mapping images reveal that the C, F, O, and S elements are uniformly distributed in the fully charged graphite sheet, directly demonstrating the TFSI- anions intercalation reaction (Figure 5e). The anions de-intercalation from the graphite cathode upon discharging is then confirmed by the significant reduction of F, O, and S elements signals (Figure 5f). The tiny Zn traces originate from the absorbed Zn2+ salt on the electrode surface. Furthermore, the anions intercalation reaction into graphite was analyzed by high resolution transmission electron microscopy (HRTEM, Figure S23). The pristine graphite shows well-ordered lattice fringes with a spacing of ~0.335 nm ((002) plane). After been fully charged, the layers become wrinkled and disordered associated with the anion insertion, and the interlayer distance of (002) plane is enlarged to ~0.367 nm, which is consist with the XRD analysis. When fully discharged, the well-ordered planes with a reduced lattice spacing of ~0.339 nm re-emerge. More impressively, no obvious exfoliation/damage of graphite layers can be observed, demonstrating the structural stability of graphite cathode. Additionally, the TFSI- anions (de)intercalation into the graphite was also


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evidenced by SEM and energy dispersive spectrometer (EDS) mapping images, as provided in Figure S24. Based on the aforementioned discussions, the corresponding redox reactions of the Zn-graphite battery can be described as follows: On cathode: x TFSI- + Graphite ↔ Graphite[TFSI-]x + x eOn anode: 0.5x Zn2+ + x e- ↔ 0.5x Zn

(1)

(2)

Overall: 0.5x Zn2+ + xTFSI- + Graphite ↔ Graphite[TFSI-]x + 0.5x Zn

(3)

4. CONCLUSIONS In summary, we have developed an ultrafast and high-voltage rechargeable Zn battery with a novel configuration (graphite | Zn(TFSI)2/AN electrolyte | Zn), employing commercialized graphite cathode, 1 M Zn(TFSI)2/AN electrolyte, and zinc metal anode. This Zn-graphite battery exhibits an admirable average output voltage of 2.2 V, which is the highest value among the reported Zn-based batteries. Furthermore, this battery system features an ultralong cycling life (i.e., 97.3% and 82% capacity retentions after 1000 and 4000 cycles at 1.0 A g-1, respectively) and an ultrafast charge/discharge ability (i.e., 39.3 mAh g-1 at 2.0 A g-1; 86.5 Wh kg-1 at 4400 W kg-1, in ~1 min). The exceptional electrochemical performance is mainly attributed to the proper selection of Zn(TFSI)2/AN electrolyte with high oxidative/reductive stability, high ionic conductivity (~28 mS cm-1), and low viscosity (~0.4 mPa·s), enabling a good compatibility to graphite cathode, a high-rate behavior of Zn2+ plating/stripping, and a stable cycling (over 1000 h, ~100% CE) of Zn anode without dendrite formation. The pseudocapacitive behavior of graphite cathode is also identified to facilitate the ions insertion/extraction, accounting for the excellent


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rate capability. In addition, the reaction mechanism of the Zn-graphite battery operating through electrochemical plating/stripping of Zn at the anode and reversible (de)intercalation of TFSIanions into the graphite was revealed by a combination study of electrochemical, XRD, Raman, TEM, XPS, FTIR, and SEM measurements. Although the specific capacity of this RZB may be further improved by modifying the graphite cathode and optimizing the electrolyte system, the present work opens up a new avenue for the highly efficient utilization of Zn anode and broadens the horizons of Zn-based battery chemistries.

ASSOCIATED CONTENT Supporting Information Additional characterizations (XRD pattern, SEM and HRTEM images, FTIR spectra, etc.), additional electrochemical performances (charge−discharge curves, Zn plating/stripping curves of the Zn/Zn and Zn/Ti cells in Zn(TFSI)2/AN electrolyte, CV and Zn plating/stripping profiles of the Zn/Ti cell in Zn(TFSI)2-EC/DEC electrolyte, EIS profiles, CV profiles with pseudocapacitive contribution, the performances of graphite cathodes with different loading masses, Ti-graphite cell performance, etc.), and schematic diagram of selected stages of graphite intercalation compounds. AUTHOR INFORMATION Corresponding Authors *(N.Z.) E-mail: [email protected]; *E-mail: (J.Z.X.) [email protected];


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*(Y.C.L.) E-mail: [email protected] ORCID Ning Zhang: 0000-0002-6176-7278 Yongchang Liu: 0000-0003-1998-9309 Lifang Jiao: 0000-0002-4676-997X Fangyi Cheng: 0000-0002-9400-1500 Author Contributions +N.Z.

and Y.D. contributed equally to this work.

Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China (21805066, 21805007), Natural Science Foundation of Hebei Province (B2019201160), Top Young Talents Project of Hebei Education Department (BJ2019052), Advanced Talents Incubation Program of the Hebei University (801260201156), Young Elite Scientists Sponsorship Program by CAST (2018QNRC001), China Postdoctoral Science Foundation (2019T120191; 2018M640244), and 111 project (B12015).

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Ultrafast Rechargeable Zinc Battery Based on High Voltage Graphite

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