Electrochemically Activated NickelâCarbon Composite as Ultrastable

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Electrochemically Activated Nickel-Carbon Composite as Ultrastable Cathodes for Rechargeable Nickel-Zinc Batteries Lingyi Meng, Dun Lin, Jing Wang, Yinxiang Zeng, Yi Liu, and Xihong Lu ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b04006 • Publication Date (Web): 02 Apr 2019 Downloaded from http://pubs.acs.org on April 2, 2019

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ACS Applied Materials & Interfaces

Electrochemically

Activated

Nickel-Carbon

Composite as Ultrastable Cathodes for Rechargeable Nickel-Zinc Batteries Lingyi Meng,1 Dun Lin,2* Jing Wang,2 Yinxiang Zeng,2 Yi Liu,3 and Xihong Lu2,* 1

Department of Mechanics Engineering, School of Civil Engineering and Transportation, South

China University of Technology, Guangzhou, 510641, China 2

MOE of the Key Laboratory of Bioinorganic and Synthetic Chemistry, KLGHEI of Environment

and Energy Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, P. R. China. E-mail: [email protected] (D. Lin); [email protected] (X. Lu) 3

School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University,

Guangzhou 510006, P. R. China.

ABSTRACT

Aqueous rechargeable nickel-zinc batteries are highly attractive for large-scale energy storage for their high output voltage, low cost and excellent safety; however, their inferior cycling durability due to the degradation of Ni-based cathode is a major obstacle for their applications. In

ACS Paragon Plus Environment

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this context, we develop a new kind of porous electrochemically activated Ni nanoparticles/nitrogen doped carbon (Ni/NC) composite material as ultrastable cathodes for advanced aqueous rechargeable nickel-zinc batteries. The in-situ formation of highly active NiOx(OH)y layer on Ni nanoparticles and unique hydrophilic porous architecture endow the activated Ni/NC composite with high accessible area, abundant active sites, easy electrolyte permeation and shortened charge/ion transport pathway. Consequently, a high capacity of 381.2 μAh cm-3 with outstanding rate capability is achieved by the Ni-Zn battery using the optimized activated Ni/NC composite as cathode (about 30-fold enhancement compared to that with pristine Ni/NC composite as cathode). More impressively, the as-assembled Ni-Zn battery achieves an unprecedented cyclic stability with no capacity loss after 36000 charge/discharge cycles. This is the highest cyclic durability ever for Ni-Zn batteries and other ARBs. This novel efficient electrochemical activation strategy to achieve high-performance cathode and demonstration of ultrastable aqueous rechargeable Ni-Zn battery may open up new vistas on the development of more advanced and reliable energy storage materials and devices.

KEYWORDS Ni-Zn battery, Ni nanoparticles, N doped carbon, composite, stable

1. Introduction Energy crisis and environmental deterioration have urgently called for the advance of the exploit and utilization of renewable energy, which simultaneously demand the further development of energy conversion and storage devices.1-3 With the concern of higher safety, better performances and lower cost compared to the prevailing Li-based batteries, researches have paid great attention to the rise of aqueous rechargeable batteries (ARBs), which use aqueous solutions rather than


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expensive, toxic, inflammable and poor-conductive organics as electrolyte.4-5 ARBs generally consist of metal-ion (i.e. Li+, Na+, K+, Zn2+, Al3+, etc.) batteries6-8, zinc-based (i.e. Zn-air, Zn-Mn, etc.) batteries9-10 and nickel-based (i.e. Ni-Zn, Ni-Cd, Ni-MH, Ni-Fe, Ni-Bi, etc.) batteries11-15. Among various kinds of ARBs, aqueous rechargeable Ni-Zn battery has been recognized as a promising candidate for large-scale energy storage because of its outstanding merits including natural abundance of Ni and Zn sources as well as the high operating voltage (~ 1.75 V).16-17 However, the widespread application of these Ni-Zn batteries has been severely impeded by their unsatisfactory cyclic stability consequent form the irreversibility of Ni-based cathodes as well as the self-corrosion and dendrite growth of Zn-based anodes.16, 18-19 One of the effective strategies to solve this challenge is developing new Ni-based nanostructured cathodes with improved durability and high capacity. For example, a yarn-like Ni-Zn battery with a high energy density of 0.12 mWh cm-2 (1.5 A cm-3) and good cycling performance (60% retention after 1000 cycles) was achieved by using nickel cobalt hydroxide nanosheets as cathode.20 Wang et al. anchored NiO nanosheets onto carbon nanotubes via hydrothermal synthesis and calcination, and constituted a high-performance Ni-Zn battery with long life span (~35% capacity loss after 500 cycles) based on this composite cathode.21 Similarly, Xu et al. fabricated Co-doped Ni(OH)2 onto nickel nanowire arrays via a three-step process as cathode.22 The battery successfully exhibited a satisfactory energy density of 4.05 Wh L-1 and superior longevity (up to 88% capacity retention after 5000 cycles). With those achievements, the cycle life of developed Ni-Zn batteries is still unable to satisfy the practical needs. Additionally, the tedious synthetic procedures for the most reported Ni-based nanostructured cathodes are unfavorable for industrialization application. Therefore, it is urgently pursued to develop simple, low-cost and efficient protocol for constructing robust and stable Ni-based nanostructures for high-performance Ni-Zn batteries.


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Herein, we demonstrate porous electrochemically activated Ni nanoparticles/nitrogen doped carbon matrix (A-Ni/NC) composite as ultrastable cathode for advanced rechargeable Ni-Zn batteries. The porous A-Ni/NC composite cathode is readily prepared via embedding Ni nanoparticles in the nitrogen doped carbon skeleton through facile calcination and electrochemical activation processes. Benefitting from increased accessible sites, excellent wettability and fast ion/charge transport rate, the optimized A-Ni/NC composite cathode delivers remarkably enhanced electrochemical properties over the pristine Ni nanoparticles/nitrogen doped carbon composite (Ni/NC) cathode. It delivers an extraordinary capacity of 381.2 μAh cm-3 and excellent rate capability as well as exceptionally ultrastable durability.

2. Experimental Section 2.1 Synthesis of the aqueous precursor solution All chemicals are of analytical grade and directly used without further purification. The aqueous precursor solution containing 12 wt% polyvinylpyrrolidone (PVP), 2 M nickel chloride (NiCl2) ̅ =24000, and 0.5 M zinc chloride (ZnCl2) is prepared by firstly dissolving 5.88 g PVP (Aladdin, 𝑀 K23-27) in 20 mL water by stirring at 85 °C oil bath. Subsequently 9.51 g NiCl 2∙6H2O is added into the PVP aqueous solution and dissolved. After adding 13.6 g ZnCl2, the solution is stirred at 95 °C oil bath until all solid dissolved. The obtained aqueous precursor solution is viscous, clear, dark-green and stable for months. 2.2 Synthesis of Ni/NC


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Carbon cloth is first dip-coated with the aqueous precursor solution followed by drying at 70 °C for 3 h. Then the carbon cloth with dried precursors is calcinated in N2 atmosphere at 800 °C for 1 h in a tube furnace. The mass loading of Ni/NC is 4 mg cm-2. 2.3 Electrochemical activation of Ni/NC into A-Ni/NC Ni/NC composite electrode (0.5 ×1.0 ×0.08 cm3) is electrochemical oxidized in a standard threeelectrode cell in 6 M KOH aqueous solution using graphite rod as counter electrode and mercury/mercury oxide (Hg/HgO) electrode as reference electrode under a constant voltage. 2.4 Material Characterization The microstructures and compositions of the electrode materials are analyzed using fieldemission SEM (FE-SEM, JSM-6330F, JEOL, Japan; FE-SEM, SU8010, Hitachi, Japan), transmission electron microscopy (TEM, FEI Tecnai G2 F30), XPS (XPS, ESCALab250, Thermo VG) and X-ray diffractometry (XRD, D8 ADVANCE). Nitrogen adsorption/desorption analysis of film samples was carried out at 77 K using a physisorption analyzer (JW-BK200c). The samples were degassed under vacuum at 150 °C for 6 h before sorption measurements. 2.5 Electrochemical measurements Cyclic voltammetry (CV), galvanostatic charge/discharge measurements and electrochemical impedance spectroscopy are conducted on an electrochemical workstation (CHI 760E). Data are collected after ageing of 2000-cycle galvanostatic charge/discharge (GCD) at 20 mA cm-2. The electrochemical studies of individual electrodes (0.5 × 1.0 × 0.08 cm3) are performed in a threeelectrode cell using graphite rod as counter electrode and mercury/mercury oxide (Hg/HgO) electrode as reference electrode in 6 M KOH + 0.5 M zinc acetate (Zn(Ac)2) aqueous solution. The


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electrochemical characterizations of the aqueous A-Ni/NC//Zn batteries are conducted in a twoelectrode pouch cell using A-Ni/NC as cathode (active area 0.5 ×1.0 ×0.08 cm3), Zn foil as anode (0.5 ×1.0 ×0.08 cm3) and 6 M KOH + 0.5 M Zn(Ac)2 aqueous solution as electrolyte. All current densities are based on the area of A-Ni/NC. 2.6 Fabrication of aqueous Ni-Zn pouch cell An A-Ni/NC cathode (active area 0.5 × 1.0 × 0.08 cm3) and a Zn foil anode (0.5 × 1.0 × 0.08 cm3) are fixed respectively with a titanium lug at the tail end of the electrode. Aqueous 6 M KOH + 0.5 M Zn(Ac)2 electrolyte is injected into a small polyethylene valve bag (2.5 × 3 cm2, 0.2 mm thick) and the two electrodes are placed parallel to each other at both sides. Subsequently the valve bag is heat-sealed with a laminator and further mended with epoxy, leaving the tail ends of the two Ti lugs outside the pouch cell for connection. 3. Results and discussion The porous A-Ni/NC composite is synthesized via a simple two-step process. As shown in Figure 1a, the carbon cloth (CC) coated with precursor hydrogel composed of moderate PVP, NiCl2 and ZnCl2 is firstly annealed at 800 °C in N2 atmosphere to obtain the intermediate Ni nanoparticles/nitrogen doped carbon (denoted as Ni/NC) composite. In the precursors, PVP serves as the sources of carbon and nitrogen, NiCl2 serves as the source of Ni nanoparticles, and ZnCl2 is employed as activator. The viscosity and penetrability of this inorganic-organic hydrogel can enable the uniform dispersion and tight conjugation of precursors on carbon cloth, which are favorable for the homogeneous formation of product on carbon clothe surface. Scanning electron microscope (SEM) images reveals that the Ni nanoparticles with diameters about 50-200 nm are homogeneously embedded on porous carbon framework (Figure S1). Then, the A-Ni/NC


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composite is obtained by electrochemical activation of Ni/NC sample in 6 M KOH at 1 V for 100 s, and the possible activation reactions are shown in supporting information. As shown in Figure 1b and Figure S2, the morphology of A-Ni/NC sample is highly similar to that of Ni/NC sample, indicating that the electrochemical oxidation process has negligible effect on their morphology. Figure 1c is the typical transmission electron microscopy (TEM) image of the A-Ni/NC composite, showing that a large amount of Ni nanoparticles are closely encapsulated into the porous carbon matrix. The high-resolution TEM (HRTEM) image in Figure 1d clearly reveals that there are very thin carbon layers with well graphitization at the outer edge of Ni nanoparticles. The inner domain of the Ni nanoparticle exhibits lattice fringes with interplanar spacing of 0.204 nm (Figure 1e) and 0.173 nm (Figure 1f), which match the d111 spacing and d200 spacing of metallic Ni (JCPDS (Joint Committee on Powder Diffraction Standards) #65-2865), respectively. The outer domain of the nanoparticle shows lattice fringes with interplanar spacing of 0.233 nm corresponded to the (101) plane of Ni(OH)2 (JCPDS #14-0117, Figure 1g), 0.210 nm corresponded to the (200) plane of NiO (JCPDS #47-1049), and 0.239 nm corresponded to the (011) plane of NiOOH (JCPDS #270956, Figure 1h). The results implie the formation of a core-shell structure with a hybrid shell of NiOx(OH)y after electrochemical oxidation in alkaline electrolyte. Figure S3 presents the typical X-ray diffraction (XRD) spectra of Ni/NC and A-Ni/NC samples. However, in addition to C, only metallic Ni peaks (JCDPS #65-2865) are observed for the A-Ni/NC sample, which is likely attributed to the predominance of Ni in bulk Ni nanoparticles and small amount of those activated products.23


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Figure 1. (a) Schematic illustration of the synthesis of porous A-Ni/NC; (b) SEM images, (c) TEM image, and (d-h) HRTEM images of the A-Ni/NC composite.

X-ray photoelectron spectroscopy (XPS) is applied to examine the composition evolution during the electrochemical activation process. The XPS survey spectrum of N/NC and A-Ni/NC both present obvious peaks with binding energies corresponding to Ni, O, C and N (Figure S4). After electrochemical activation, the content of O is remarkably increased from 9.61% to 20.01%, while the content shows no obvious change for Ni (from 3.28% to 3.54%) and N (from 2.23% to 2.72%)


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(Table S1). As displayed in Figure 2a, the core level Ni 2p spectrum of Ni/NC shows the presence of characteristic Ni 2p3/2 (852.9 eV) and Ni 2p1/2 (869.7 eV) peaks of Ni0 as well as Ni 2p3/2 (856.8 eV) and Ni 2p1/2 (874.6 eV) peaks of Ni2+. The Ni2+ singles possibly come from the NiO and Ni(OH)2 generated on the surface of the Ni nanoparticles when exposed to air. In comparison to the Ni/NC sample, the more obvious characteristic Ni3+ peaks and diminished intensity of the characteristic Ni0 peaks of the A-Ni/NC sample demonstrate that the surface of these Ni nanoparticles have been oxidized into highly active nickel oxide and oxyhydroxide after electrochemical activation.24 More evidences can be further confirmed by their O1s core-level XPS spectra (Figure 2b). The substantially enhanced intensities of Ni-O bond (531.0 eV), Ni-O-H bond (531.8 eV) and X-O (X = C, H, N) bond (533.1 eV) after electrochemical oxidation show the increase of NiOx(OH)y and other oxygen-containing functional groups on carbon.25-26 Additionally, the higher intensities of the C-O peak (centered at 285.6 eV) and C=O peak (centered at 288.9 eV) for A-Ni/NC sample than the Ni/NC sample indicate it possesses more oxygencontaining functional groups after activation (Figure 2c), which is beneficial for electrolyte permeation.27-28 The N signal is also identified in both Ni/NC and A-Ni/NC (Figure S5), implying the successful doping of PVP-derived nitrogen. The wettability of the Ni/NC and A-Ni/NC samples is evaluated by contact angle (CA) test (Figure 2d). Interestingly, the hydrophobic Ni/NC (CA: 120°) is transformed into super-hydrophilic A-Ni/NC (CA: 0°) after electrochemical activation. The porous structures of the Ni/NC and A-Ni/NC samples are further confirmed by nitrogen adsorption/desorption isotherms. Ni/NC and A-Ni/NC has similar porous structures, both showing the type IV isotherms with an obvious hysteresis loop, which suggest the presence of plentiful mesopores within the samples (Figure S6a). The calculated surface area of Ni/NC and ANi/NC are 113.1 m2 g-1 and 125.9 m2 g-1 respectively. Both Ni/NC and A-Ni/NC have a narrow


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pore size distribution below 10 nm, while A-Ni/NC has more meso/macropores than Ni/NC (Figure S6b). The increase of surface area and meso/macropores after electrochemical activation may be due to the slight exfoliation of some Ni particles that leaves the pores they etched during calcination. The above results fully confirm the successful generation of highly porous A-Ni/NC core-shell structure.

Figure 2. Normalized core–level (a) Ni 2p XPS spectra, (b) O 1s XPS spectra and (c) C 1s spectra of Ni/NC and A-Ni/NC; (d) Contact angle of Ni/NC (upper image) and A-Ni/NC (lower images).

To assess the electrochemical performance of A-Ni/NC electrode, electrochemical measurements are firstly performed in a three-electrode cell with 6 M KOH aqueous solution as electrolyte. Cyclic


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voltammetric (CV) curves of Ni/NC and A-Ni/NC electrodes at 10 mV s-1 are collected in Figure S7. After electrochemical activation, a pair of well-defined redox peaks that correspond to the Faradaic reactions between Ni(OH)2 and NiOOH are clearly observed for the A-Ni/NC electrode, showing its remarkably boosted capacity. Figure 3a shows the representative galvanostatic charge/discharge (GCD) curves of the Ni/NC and A-Ni/NC electrodes at 12 mA cm-2. Compared to the original Ni/NC sample, both the charge and discharge plateau of A-Ni/NC electrode are drastically extended, again verifying its excellent electrochemical property. The capacities obtained from the discharge curves (Figure S8) are demonstrated in Figure 3b. At the high current density of 12 mA cm-2, the A-Ni/NC electrode reaches a considerably high capacity of 954 μAh cm-3, much larger than that of the Ni/NC electrode (71 μAh cm-3). When the current density rises to 32 mA cm-2, it still can afford 581 μAh cm-3 (more than 60.8% retention), suggesting the superior rate performance of the A-Ni/NC. To better understand the improved capacity after electrochemical activation, Figure 3c compares the Nyquist plots of the Ni/NC and A-Ni/NC electrodes. The corresponding equivalent circuit fittings are demonstrated in the Nyquist plot, and the fit values are listed in Table S2. It is worth noting that both the equivalent series resistance (Rs) and the charge transfer resistance (Rct) are significantly lowered after electrochemical activation, which is attributed to the improved electrode/electrolyte contact originated from enhanced hydrophilicity of the electrode after electrochemical activation. The increase of Warburg impedance, which defines the resistance due to ion diffusion, indicates that a large amount of redox active materials (mainly NiOx(OH)y) are generated on electrode surface after electrochemical activation. The change of double-layer capacitance corresponds the surface change of Ni@NiOx(OH)y particles. The constant phase element (CPE) impedance, which represents the capacitance of porous NC matrix, decreases along with an increased frequency power (n value).


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This can be explained by that the double-layer capacitive performance of NC matrix prevails the pseudocapacitive performance of Ni species because of the enhanced wettability after electrochemical activation. The bode plots of the Ni/NC and A-Ni/NC electrodes are correspondingly contrasted in Figure 3d. The resistance of A-Ni/NC is significantly lower than that of Ni/NC in a wide frequency range from 1 Hz to 106 Hz, which is accordant with the interpretation of the Nyquist plots. Moreover, the phase angle at 1 Hz reaches -3.1°for the Ni/NC electrode and -60.6°for the A-Ni/NC electrode, which has substantially manifested the facilitated charge transfer at electrode/electrolyte interfaces of hydrophilic A-Ni/NC. Notably, for the Ni/NC electrode, the characteristic frequency f0 at the phase angle of -45°is ~0.03 Hz, and subsequently the relaxation time constant τ0 is calculated to be ~33.33 s according to the equation τ0=1/f0. When it comes to A-Ni/NC, f0 drastically reaches ~4.64 Hz and consequently τ0 decreases to only ~0.22 s, illustrating the relatively quick electrochemical response due to fast ion transport.25, 29-30 The excellent performances of A-Ni/NC listed above can be concluded as the formation of unique coreshell structure and the increase of oxygen-containing functional groups on carbon after efficient electrochemical activation. The NiOx(OH)y serves as redox active materials to remarkably enhance the specific capacity, while the direct contact of conductive Ni core and NiOx(OH)y shell effectively promote the interfacial charge transfer.25 Moreover, the hydrophilic oxygen-containing functional groups and NiOx(OH)y together with the porous N-C framework contribute to the close contact between electrode and electrolyte, accelerating charge transfer and ion transport. 31 The effects of the anodic potential and time on the performance of the A-Ni/NC composite are also analyzed. From Figure S9, it is found that the A-Ni/NC composite prepared at 1 V for 100 s exhibited the optimized capacity, and this condition is chosen for further study.


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Figure 3. (a) GCD curves of Ni/NC and A-Ni/NC at 12 mA cm-2. (b) Volumetric capacity of Ni/NC and A-Ni/NC as a function of current density obtained from the GCD curves. (c) Nyquist plots of Ni/NC and A-Ni/NC. (d) Bode plots of Ni/NC and A-Ni/NC.

In order to shed light on the A-Ni/NC composite as promising cathode in Ni-Zn batteries, an ANi/NC as cathode, a Zn foil as anode and 6 M KOH and 0.5 M Zn(Ac)2 aqueous solution as electrolyte are fabricated into an aqueous Ni-Zn pouch battery (denoted as A-Ni/NC//Zn). As a comparison, the aqueous Ni-Zn battery with the Ni/NC cathode is also assembled (denoted as Ni/NC//Zn). The GCD curves of the A-Ni/NC//Zn battery at different current densities are


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displayed in Figure S10. It can be observed from the curves that the aqueous device possesses the wide potential range of 1.40 ~ 1.90 V. From the comparison of GCD curves in Figure 4a, the ANi/NC//Zn battery exhibits more evident plateaus and substantially larger capacity than those of the Ni/NC//Zn battery. The capacity of the A-Ni/NC//Zn battery achieves 381.2 μAh cm-3, 30.5fold enhancement with respect to the Ni/NC//Zn battery (12.5 μAh cm-3). Moreover, our ANi/NC//Zn battery also exhibits excellent reversible stability and rate capability (Figure 4b). It can offer high reversible capacities of 381.2 and 250 μAh cm-3 at 6 and 16 mA cm-2, respectively. Notably, its capacity is fully recovered as current density reset to 6 mA cm-2 after 30 cycles, demonstrating its outstanding reversible and stable performance. Energy and power densities of A-Ni/NC//Zn battery are also calculated in Figure 4c. Notably, an excellent power density of 28 mW cm-2 is achieved (350 mW cm-3) at the energy density of 0.035 mWh cm-2, greatly superior to many

other

aqueous

rechargeable

batteries

and

even

supercapacitors

such

as

MnO2/ZnO//MnO2/ZnO (0.014 mW cm-2);32 PANI/SWCNT//PANI/SWCNT (0.145 mW cm-2);33 rGO/CNT//rGO/CNT (0.19 mW cm-2);34 NiO//ZnO (0.275 mW cm-2);19 NiCo2O4//Bi (0.665 mW cm-2);14 PPy@MnO2@rGO//PPy@MnO2@rGO (1.33 mW cm-2);35 PPy//PPy (3.6 mW cm-2);36 Ni(OH)2//OMC (7.3 mW cm-2);37 pen ink fiber supercapacitor (9 mW cm-2, denoted as pen ink);38 Ni-NiO//Zn (20.2 mW cm-2);39 etc. Meanwhile, the maximum energy density of 53 μWh cm-2 (0.66 mWh cm-3) can be delivered at the power density of 10.5 mW cm-2, outperforming most developed aqueous batteries and supercapacitors.20, 32-39 The favorable output performances suggest the great potential in future applications.


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Figure 4. (a) GCD curves of Ni/NC//Zn and A-Ni/NC//Zn at 6 mA cm-2; (b) Discharge capacity of A-Ni/NC//Zn at different current densities; (c) Ragone plots of A-Ni/NC//Zn. The values corresponded to other reported aqueous rechargeable energy storage devices are added for comparison.14, 19-20, 32-39

The cycling durability is a crucial issue for the wide commercialization of the most current NiZn batteries. Thus, the consecutive charging/discharging stability of the assembled A-Ni/NC//Zn battery is studied at 10 mA cm-2, and the result is presented in Figure 5a. Exhilaratingly, our ANi/NC//Zn battery achieves an unprecedented durability with no capacity decay after 36000 cycles. Specifically, the capacity of the aqueous device gradually increases to 145.6% of the initial


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capacity till the 10000th GCD cycle, and afterwards reaches 130.9% at the 36000th GCD cycle. The increased capacity of the battery at the initial stage of GCD cycles might be associated with the continuous transformation of exposed Ni into NiOx(OH)y during electrochemical redox cycles.25 Moreover, the coulombic efficiency of our battery is nearly 100% during the cyclic process. To the best of our knowledge, this excellent long-term stability has substantially surpassed the Ni-Zn batteries already reported (Figure 5b),11, 18-22, 40-42 such as Ni2S3//Zn (83.3% after 100 cycles);42 NiO//Zn (65% after 500 cycles);21 Co3O4@NiO//Zn (90% after 500 cycles);18 NiAlCo//Zn (90% after 600 cycles);11 NiCo//Zn (60% after 1000 cycles);20 Ni(OH)2//Zn (96% after 1200 cycles);41 NiO//ZnO (72.90% after 2400 cycles);19 Co-Ni(OH)2//Zn (88% after 5000 cycles);22 Ni//Zn (88% after 9000 cycles);40 etc. The GCD curves at different cycles show that the curves well maintain their shapes during GCD cycling and that each curve achieves congruity in charge and discharge time, which strongly verify the electrochemical perseverance and reversibility of the A-Ni/NC//Zn battery (Figure 5c). Additionally, SEM and TEM images reveal that the morphology and structure of the A-Ni/NC composite are well preserved after 36000-cycle GCD test (Figs. S11), implying that the robust porous N doped carbon matrix effectively prevents the degradation and aggregation of Ni@NiOx(OH)y core-shell nanoparticles that usually occur during long-term charge/discharge cycles.43-45 Finally, we connect two A-Ni/NC//Zn pouch cells in series and successfully light up a 3 V LED indicator (Figure 5d), which readily demonstrates its potential in practical utilization.


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Figure 5. (a) Cycling performance of A-Ni/NC//Zn battery at 10 mA cm-2; (b) The comparison of cycling performance among A-Ni/NC//Zn and other aqueous rechargeable Ni-Zn batteries;11, 18-22, 40-42

(c) GCD curves of A-Ni/NC//Zn battery at different cycles; (d) Optical photographs of two

aqueous A-Ni/NC//Zn pouch cells connected in series before (left) and during (right) powering an LED signboard.


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4. Conclusions In summary, a high-performance and ultrastable cathode for aqueous rechargeable Ni-Zn battery has been successfully constituted by using electrochemical activation of Ni nanoparticles/nitrogen doped carbon (A-Ni/NC) composite material. The A-Ni/NC composite can be easily obtained by the carbonization of inorganic-organic hybrid precursors and subsequent electrochemical activation. Taking the advantages of highly active NiOx(OH)y shell, open porous structure, enhanced electrolyte permeation, facile charge and mass diffusion, the Ni-Zn battery based on the A-Ni/NC cathode exhibits significantly boosted electrochemical performance compared to that of Ni/NC cathode. A remarkable high capacity of 381.2 μAh cm-3 and good rate performance has been delivered by the A-Ni/NC//Zn battery. More excitingly, this A-Ni/NC//Zn battery exhibits a high retention of more than 130.9% of original capacity after 36000 charge/discharge cycles, which turns out to be the best cycling performance achieved among Ni-Zn batteries and even ARBs. The efficient electrochemical activation strategy and the successful application in ultrastable Ni-Zn batteries in this work are ought to hold great potential in future materials for energy storage and conversion devices. ASSOCIATED CONTENT Supporting Information. Supporting Information Available: Mechanism analysis, calculations, SEM and TEM images, XRD patterns, XPS data, surface area and pore analysis data, and electrochemical tests data. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION


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Corresponding Author *E-mail: [email protected] (D. Lin) *E-mail: [email protected] (X. Lu)

Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was ﬁnancially supported by the National Natural Science Foundation of China (21822509, U1810110, 11602088 and 31530009), Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program (2015TQ01C205), and Pearl River Nova Program of Guangzhou (201610010080), Technology Planning Project of Guangdong Province (2016A010103039 and the110th file of 2015) and the opening project of the State Key Laboratory for Strength and Vibration of Mechanical Structures (Xi'an Jiaotong University) (No. SV2018KF-33). REFERENCES (1) Holdren, J. P. Energy and Sustainability. Science 2007, 315 (5813), 737. (2) Winter, M.; Brodd, R. J. What Are Batteries, Fuel Cells, and Supercapacitors? Chem. Rev. 2004, 104 (10), 4245-4270. (3) Jabeen, N.; Hussain, A.; Xia, Q.; Sun, S.; Zhu, J.; Xia, H. High-Performance 2.6 V Aqueous Asymmetric Supercapacitors based on In Situ Formed Na0.5MnO2 Nanosheet Assembled Nanowall Arrays. Adv. Mater. 2017, 29 (32), 1700804.


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Electrochemically Activated NickelâCarbon Composite as Ultrastable

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