Advanced Low-Cost, High-Voltage, Long-Life Aqueous Hybrid Sodium

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Energy, Environmental, and Catalysis Applications

Advanced Low-Cost, High-Voltage, Long-Life Aqueous Hybrid Sodium/Zinc Batteries Enabled by A DendriteFree Zinc Anode and Concentrated Electrolyte Wei Li, Kangli Wang, Min Zhou, Houchao Zhan, Shijie Cheng, and Kai Jiang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b04085 • Publication Date (Web): 08 Jun 2018 Downloaded from http://pubs.acs.org on June 8, 2018

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ACS Applied Materials & Interfaces

Advanced Low-Cost, High-Voltage, Long-Life Aqueous Hybrid Sodium/Zinc Batteries Enabled by A Dendrite-Free Zinc Anode and Concentrated Electrolyte Wei Li,1,2 Kangli Wang,1,* Min Zhou,1 Houchao Zhan,2 Shijie Cheng,1 and Kai Jiang 1,* 1. State Key Laboratory of Advanced Electromagnetic Engineering and Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan 430074, P. R. China. 2. State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, P. R. China. *Corresponding authors. E-mail: [email protected], [email protected]

Abstract Aqueous batteries are promising energy storage systems but hindered by the limited selections of anodes and narrow electrochemical window to achieve satisfactory cyclability and decent energy density. Here, we design aqueous hybrid Na-Zn batteries by using a carbon coated Zn (Zn@C) anode, 8 M NaClO4+0.4 M Zn(CF3SO3)2 concentrated electrolyte coupled with NASICON-structured cathodes. The Zn@C anode achieves stable Zn stripping/plating and improved kinetics without Zn dendrite formation due to the porous carbon film facilitating homogeneous current distribution and Zn deposition. Furthermore, the concentrated electrolyte offers a large electrochemical window (~2.5 V) and permits stable cycling of cathodes. As a result, the hybrid batteries exhibit extraordinary performance including high voltage, high energy density (100~150 Wh kg-1 for half battery and 71 Wh kg-1 for full battery), and excellent cycling stability of 1000 cycles.

Key words: Aqueous hybrid sodium/zinc batteries, Zn dendrite, concentrated electrolyte, NASICON-structured cathodes, high voltage, high energy density 1

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Introduction Rechargeable aqueous batteries using low-cost, non-flammable and environmentally friendly water-based electrolytes are particularly attractive for static energy storage applications compared with the non-aqueous batteries,1-4 among which aqueous sodium-ion batteries are very appealing due to their abundant natural reserves and cheap raw materials.5-8 However, restricted by the narrow electrochemical window (1.23 V for water) of aqueous electrolyte and the limited selections of anodes (dominated by NaTi2(PO4)3), the energy density (~20-60 Wh kg-1) and cycling stability (~100-500 cycles) of aqueous sodium-ion batteries are still far from satisfactory.5 Alternatively, metallic zinc integrates the attractive features of low cost, good conductivity, chemical stability, non-toxicity, large hydrogen evolution overpotential and high theoretical capacity (819 mAh g-1).9-11 These distinctive merits of Zn enable the possibility to design an aqueous hybrid Na-Zn battery to circumvent the predicament encountered by sodium-ion batteries, based on the mechanism of Na+ ions intercalation in cathode and Zn2+ ions deposition in anode. However, Zn dendrite, one of the most detrimental drawbacks that pose severe threat to battery durability, is highly imperative to be addressed.12-14 Successful examples to alleviate Zn dendrites by employing 3D Zn sponges and manipulating Zn deposited into backside in alkaline Zn/Ni(OH)2 batteries have been reported.12,

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Nevertheless, the costly and

complicated procedures prevent them from implementing in scalable manufacture, and developing more effective and practical strategies to suppress the Zn dendrite still remains a great challenge. The limited window and high solubility of electrode materials in water are another critical issues challenging the battery voltage output, energy density and cyclability. In general, reducing the activity of free water molecules in electrolyte by raising the solute concentration and addition surfactant has been 2


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reported.15-20 For example, a “water-in-salt” electrolyte designed by Suo.et al can ensure a 2.3 V aqueous lithium-ion battery to cycle up to 1000 cycles.15 Therefore, if a low cost and advanced electrolyte can be developed for aqueous hybrid Na-Zn battery, the voltage output ,energy density and cycling stability of aqueous battery are expected to be greatly improved. Herein, we propose a facile and general strategy to develop dendrite-free Zn@C anode by simply coating the Zn foil surface with a porous carbon layer, serving as nucleation sites and reservoirs to capture Zn ions from the electrolyte and alter the prioritization of Zn2+ ions transfer toward the “hot spots” on Zn foil. Therefore, the Zn@C anode can be cycled in water-based electrolyte hundreds to thousands of times without dendrite formation. Moreover, we discovered that a low-cost 8 M NaClO4+0.4 M Zn(CF3SO3)2 concentrated electrolyte(viscosity, 4.3 mPa s; ionic conductivity, 47 mS cm-1 at 25 oC) can broaden the electrochemical window to ~2.5 V and simultaneously enhance the cathode cycling stability. When coupled with high voltage or high capacity NASICON-structured cathodes, aqueous Na-Zn batteries are demonstrated, which achieve high voltage, high energy density and stable cyclability.

Experimental sections Materials synthesis Preparation of carbon coated Zn foil (Zn@C). In a typical procedure, 80 wt% active carbon (average size, ~10 µm) were mixed with 20 wt% polyvinylidene fluoride in N-methylpyrrolidone solution for 0.5 h, and then pressed onto a Zn foil (thickness, ~80 µm). After dried at 120 oC in vacuum, the carbon coated Zn foil (Zn@C) was cut into disk of ~1cm2. Preparation of carbon coated Na3V2(PO4)2F3 (NVPF@C). The synthesis of NVPF@C was according to our previous work.31 In a typical procedure, raw materials of 30 mmol NaF, 20 mmol NH4VO3, 20 mmol NH4H2PO4 and 10 mmol C6H8O7·H2O were dissolved into 60 ml deionized water with continuous stirring 3



at 80 oC to volatilize the water thoroughly and dried at 120 oC for 10 h in an oven. Finally, the precursor was grinded into fine powders and heated to 650 oC for 6 h with the protect gas flow of Ar+5v%H2. Preparation of carbon coated Na3V2(PO4)3 (NVP@C). In a similar procedure, raw materials of 30 mmol Na2CO3, 40 mmol NH4VO3, 60 mmol NH4H2PO4 and 20 mmol C6H8O7·H2O were dissolved into 60 ml deionized water with continuous stirring at 80 oC to volatilize the water thoroughly and dried at 120 oC for 10 h in an oven. Finally, the precursor was grinded into fine powders and heated to 700oC for 6 h with the protect gas flow of Ar+5v%H2. Materials characterizations X-ray diffraction (XRD) characterizations were performed on a XRD-7000S diffractometer (Japan) to detect the products structures. Field scanning electron microscopy (SEM) characterizations were conducted on a JEM 7600F microscope (Japan) to observe the products morphologies. Thermogravimety (TG) characterizations measurement were recorded by a Netzsch STA449F3 thermogravimetic analyzer (Germany) to determine the products carbon contents. X-ray photoelectron spectroscopy (XPS) characterizations were collected by an Axis Ultra DLD system (England) to analyze the surface chemical states of products. Electrochemical measurements The investigations of electrochemical properties were operated in CR2016 coin cells. The stripping/plating tests of Zn and Zn@C were performed in symmetrical cells on a LANHE Battery Tester (China). Electrochemical impedance spectroscopy (EIS) were measured on a PGSTAT302N Autolab (Germany) electrochemistry workstation. Cyclic voltammetric (CV) measurements were conducted to test of electrochemical window of electrolytes on a CHI606E electrochemisty workstation (China). To examine the electrochemical performance of Zn@C/NVPF@C and Zn@C/NVP@C batteries, 70 wt% NVPF@C or 4


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NVP@C were mixed with 20 wt% polytetrafluoroethylene binder and 10 wt% acetylene black in isopropanol and extruded into a thin film by a rolling machine, and then cut into 8 mm disks, finally pressed onto Ti mesh under 10 MPa pressure to fabricate NVPF@C or NVP@C electrodes. The mass loading of active materials in electrodes were ~7-10 mg cm-2 for NVPF@C and ~5-8 mg cm-2 for NVP@C. Prior to battery assembly, the 8 M NaClO4+0.4 M Zn(CF3SO3)2 concentrated electrolyte was purged with N2 flow to remove dissolved oxygen. The Zn@C/NVPF@C and Zn@C/NVP@C batteries were constructed by sandwiching Zn@C anode and NVPF@C or NVP@C cathode between a glass fiber separator that pre-soaked by electrolyte. The battery galvanostatic charge/discharge tests were recorded using a LANHE Battery Tester (China) at 25 oC in 0.8-1.9 V for Zn@C/NVPF@C and 0.8-1.8V for Zn@C/NVP@C, respectively. For Zn@C/NVPF@C pouch battery, 70wt% Zn powders, 20wt% polytetrafluoroethylene binder and 10wt% acetylene black were mixed in isopropanol and rolled into Zn film by a rolling machine. After drying, it was coated by carbon slurry (identical procedure to the preparation of Zn@C), cut into ~25×25 mm and pressed onto stainless steel collector. Likewise, the NVPF@C cathode (~25×25 mm) was also prepared by pressing NVPF@C film onto a stainless steel collector. The Zn@C and NVPF@C electrodes were then sandwiched between a separator that pre-soaked in 8 M NaClO4+0.4 M Zn(CF3SO3)2 electrolyte, pasted on the surface of PET film and sealed using a vacuum sealer. The mass ratio of Zn to NVPF was controlled as ~1:10, and the capacity and energy density of pouch battery are calculated based on the total weight of Zn@C and NVPF@C.

Results and discussion Carbon coated Zn (Zn@C) film was prepared by blade coating active carbon layer (average size, ~10 µm; thickness, ~90 µm) on a planar Zn foil (thickness, ~80 µm), as illustrated in Figure 1a-b. SEM and 5



XRD characterizations were used to check the morphology and structure of Zn and Zn@C. The bare Zn foil shows planar and smooth surface (Figure 1c). After coating a carbon layer, the Zn@C features much rougher surface with considerable voids (Figure 1d), leaving sufficient space for electrolyte penetration and Zn deposition as well as stress release during cycling. The cross-sectional SEM image (Figure S1, Supporting Information) of Zn@C film and the comparable XRD peak intensity (Figure 1e) of Zn@C with Zn further reveal a non-compact carbon layer, coinciding well with the SEM image in Figure 1d.

Figure 1. (a) Schematic illustration of carbon coated Zn (Zn@C) film. (b) Photograph of Zn@C. SEM images of (c) Zn and (d) Zn@C. The insert of d is the SEM image of Zn@C at high magnification. (e) XRD patterns of Zn and Zn@C. The insert of e is narrow degree XRD pattern of Zn@C.

To evaluate the stability of Zn foil and Zn@C film during galvanostatic cycling, symmetrical coin cells with two identical Zn and Zn@C were assembled with concentrated aqueous electrolyte of 8 M NaClO4+0.4 M Zn(CF3SO3)2 (the reason for choosing this electrolyte will be discussed below). The cycling curves of Zn symmetrical cell show serious fluctuation during 100 cycles at 1 mA cm-2 (Figure 2a), which is likely attributed to the inhomogeneous current distribution caused by the surface morphological change during the stripping/plating.22 In contrast, much stable curves of Zn@C symmetrical cell imply the smaller morphological change of Zn@C. At a high current density of 2.5 mA cm-2, likewise, Zn@C symmetrical

6


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cell exhibits a stable cycling during 300 cycles (>250 h), while Zn symmetrical cell can only survive for several hours before short circuit (Figure 2b). Even at higher current densities of 5 and 10 mA cm-2, the Zn@C symmetrical cell can also stably run 100 hours with overpotential below 0.1 V (Figure S2d-e, Supporting Information).These two different behaviors shed light upon the decisive role of carbon film in

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Of note, the thickness of carbon layer exerts significant influence on Zn@C cycling performance (Figure 3). With a carbon layer thickness of 28 µm, the Zn@C cell only operates 75 h at 1 mA cm-2 before short circuit (Figure 3a). When the carbon layer thickness is increased to 65 µm, the Zn@C cell shows less fluctuation in cycling curve and successfully runs 200 h without short circuit (Figure 3b). When the carbon layer thickness is further increased to 90 µm, the Zn@C cell displays much smooth curves, small 7



overpotential and stable cycling compared with Zn (Figure 3b). However, further increasing the carbon layer thickness to 124 µm incurs a large Zn stripping/plating overpotential. Therefore, Zn@C with optimized 90 µm carbon thickness can both improve the stippling/plating of Zn and facilitate the kinetics of Zn2+ ions flux, and it is chosen as the anode for Na-Zn battery.

Figure 3. Stripping/plating performance of Zn@C symmetrical cells with different thickness carbon layers at 1 mA cm-2 with 1mAh cm-2. (a) 28 µm, (b) 65 µm, (c) 90 µm and (d) 124 µm. The insertions are the cross-section SEM images of Zn@C with different thickness carbon layers

SEM observations (Figure 4) were conducted to check the surface morphological changes of Zn and Zn@C after repeated stippling/plating. Noticeable plate-like Zn dendrites (Figure 4a) and cracks (Figure S2a, Supporting Information) appear on the Zn foil surface after 100 round-trip cycles (200 hours) at 1 mA cm-2, which is well response to the fluctuation of Zn plating/stripping curves. Without porous carbon layer modification, the dendrites on Zn foil at the nucleation step cause the charge accumulation at the sharp ends, 8


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which further lure Zn to deposit around the sharp ends and results in the stacking growth of dendrites in repeated cycling.22 The plate-like Zn dendrites become more obvious in both top-view image (Figure 4b) and cross-section images (Figure 4c-d) at 2.5 mA cm-2, and can even penetrate and adhere to the glass fiber separator (Figure S2b, Supporting Information). Moreover, the Zn dendrite formation is accompanied by a sharp increase of contact resistance from the electrochemical impedance spectroscopy (EIS, Figure 4i), which is related to the deteriorative interface caused by dendrite and poorly conductive ZnO (Figure 4k).

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Figure 4. Top view SEM images of Zn electrode cycled at (a) 1mA cm-2 and (b) 2.5mA cm-2, and Zn@C electrode cycled at (e) 1mA cm-2 and (f) 2.5mA cm-2. Cross-section view SEM images of (c) fresh Zn and (g) Zn@C electrode, and cycled (d) Zn and (h) Zn@C electrode at 2.5 mA cm-2. Nyquist plots of (i) Zn and (j) Zn@C symmetrical cell before and after 100 cycles. (k) XRD patterns of Zn before and after 100 cycles

In contrast, the morphology of Zn@C after continuous plating/stripping is non-dendrite at 1 mA cm-2 9



(Figure 4e), 2.5 mA cm-2 (Figure 4f-h) and even 5 mA cm-2 (Figure S2c, Supporting Information). Moreover, Zn@C still remains non-dendritic at an increased plating/stripping capacity of 3 and 5 mAh cm-2(Figure S3, Supporting Information). The remarkably enhancement of carbon film in inhibiting dendritic Zn is partial due to it increased surface area that adsorbs and guides Zn to preferentially fill the voids between carbon particles in sphere shape (average size of ~100 nm) rather than the perpendicular growth of dendrites,22-28 which is reconfirmed by the SEM images of Zn@C after 5, 20, 50 and 400 cycles (Figure S4, Supporting Information). The deposited Zn mainly goes into the voids between carbon particles without obvious dendrite formation, indicating that the porous carbon layers can well accommodate Zn during the cycling. From the sawtooth-like Zn/carbon edge and relatively flat Zn@C surface (Figure 4g-h), it can be speculated that Zn deposition mainly takes place in the interface between Zn and carbon layer, as well as within the carbon layer (inner space and surface voids). Consequently, with the spatially confinement of carbon, the volume change and physical contact of Zn are effectively improved, which is also verified by the smaller increase of charge transfer resistance of Zn@C cell (Figure 4j). Furthermore, application of other types of carbon coatings such as carbon nanotubes and acetylene black also achieves comparable effect (Figure S5, Supporting Information).These results reveal that it is a general strategy to inhibit Zn dendrite through carbon coating. The unexpected capability of Zn@C in suppressing dendritic Zn opens up the opportunity to construct high-specific-energy hybrid Na-Zn batteries with high voltage or high capacity cathodes, for example, Na3V2(PO4)2F3,29-33 or Na3V2(PO4)3.34-37 The synthesis details for carbon coated Na3V2(PO4)2F3 (NVPF@C) and Na3V2(PO4)3 (NVP@C) were given in Experimental Section and the corresponding characterizations are shown in Figure S6 (Supporting Information). Aqueous Na-Zn batteries using Zn@C anode, 8 M NaClO4+0.4 M Zn(CF3SO3)2 electrolyte and NVPF@C or NVP@C cathode, are designated as 10


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Zn@C/NVPF@C and Zn@C/NVP@C, respectively. We firstly examine the influence of electrolytes on battery behavior. Compared with dilute electrolytes (eg. 1 M NaClO4+0.4 M Zn(CF3SO3)2 and 4 M NaClO4+0.4 M Zn(CF3SO3)2), the 8 M NaClO4+0.4 M Zn(CF3SO3)2 concentrated electrolyte can afford a maximum voltage of 2.5 V, 0.3 and 0.4 V higher than dilute electrolytes, respectively (Figure S7a, Supporting Information). More importantly, it can effectively reduce the water-induced side reactions, such as the dissolution and self-discharge of host materials (Figure S7-S9, Supporting Information), benefitting the stable cycling of electrode in aqueous solutions. In addition, co-insertion reactions (eg. Na+ and Zn2+ ions insertion) at the anode and Zn2+ ions at the cathode are negligible in this concentrate electrolyte (Figure S10, Supporting Information). 2.0

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⊗ NaTi2(PO4)3/Na2CuFe(CN)6 (Ref.42) ⊗ (Ref.48) ⊗ Zn@C/NVP@C This work (Ref.47) ⊗ Zn/Na3V2(PO4)3 ⊗ ⊗ Zn/Na2MnFe(CN)6 (Ref.55) NaTi2(PO4)3/Na3V2O2(PO4)2F ⊗ NaTi ⊗ ⊗ Zn/Na4Fe(CN)6 2(PO4)3/Na0.44MnO2 (Ref.40) (Ref.49) ⊗ NaTi (PO ) /Na NiFe(CN) ⊗ (Ref.45) ⊗ ⊗ 2 43 2 6 (Ref.43) MnHCMn/CuHCFe NaTi2(PO4)3/Na2FeP2O7 (Ref.41) ⊗ Na3Ti2(PO4)3/Na0.24MnO2 (Ref.44) MoO3/Na0.35MnO2 NaTi (PO ) /Na [Mn Ti ]O 0.66 0.34 2 (Ref.39) 2 43 0.66 (Ref.46) Zn/Na0.95MnO2

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Figure 5. Charge/discharge profiles of (a) Zn@C/NVPF@C and (b) Zn@C/NVP@C battery at current densities from 0.1 to 5 A g-1. (c) Comparison of capacity, average discharge voltage and energy density reported for aqueous Na-ion and Na-Zn batteries. (d) Cycling performances of Zn/NVPF@C, Zn@C/NVPF@C and Zn@C/NVP@C batteries at 2 A g-1.

Figure 5a illustrates the charge/discharge profiles of Zn@C/NVPF@C battery at different current 11



densities. The capacities for Zn@C/NVPF@C battery are 63.1, 58.6, 58.0, 54.8, 49.1 and 34.2 mAh g-1 at 0.1, 0.2, 0.5, 1, 2 and 5 A g-1 in an optimal range of 0.8-1.9 V (Figure S11, Supporting Information), respectively. Besides, Zn@C/NVPF@C system shows an impressive voltage of 1.68 V, equating to a maximum energy density of 100 Wh kg-1 (for NVPF@C only). If this battery is cycled in a wide range of 0.8-2.3 V, a high voltage plateaus (>2.0 V) is utilized and the energy density can reach to 135 Wh kg-1 (Figure S12, Supporting Information). When Zn@C anode is coupled with NVP@C cathode, a higher capacity of 111 mAh g-1 along with a slightly lower voltage of 1.36 V is delivered by Zn@C/NVP@C system at 0.1 A g-1 (Figure 5b), corresponding to a maximum energy density over 150 Wh kg-1 (for NVP@C only), and 60% capacity retention can be preserved at 5 A g-1. Compared with recently reported aqueous Na-ion and Na-Zn batteries (Figure 5c, the energy densities are calculated on the basis of cathodes according reported papers),38-55 these two battery systems exhibit impressive voltage (~1.4-1.7 V) and energy density (~100-150 Wh kg-1). In addition to high energy densities, both Zn@C/NVP@C and Zn@C/NVPF@C batteries also exhibit good cyclability (Figure 5d). The capacity of Zn@C/NVP@C system is slightly decreased from 89 mAh g-1 in the 1st cycle to 58 mAh g-1 of the 1000th cycle at 2 A g-1, reflecting 65.2% capacity retention. In the case of Zn@C/NVPF@C battery, the capacity is stabilized at 44.5 mAh g-1 with nearly ~100% capacity retention after 1000 cycles. Also, from the charge/discharge curves and cycled electrodes, no overpotential increase, dendritic Zn formation and NVPF@C structural change are observed (Figure S13-14, Supporting Information). As a contrast, battery built from bare Zn foil and NVPF@C (designated as Zn/NVPF@C) only sustains less than 100 cycles prior to internal short. These results indicate the high stability of Zn@C/NVP@C and Zn@C/NVPF@C systems, which reconfirms that Zn@C can withstand long-term cycling in battery application and demonstrates the feasibility to construct advanced aqueous Na-Zn 12


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batteries. To further test the practical validity, a soft package battery was assembled. Taking Zn@C/NVPF@C system as an example, a pouch battery (see detail in Experimental section) with NVPF@C mass loading of 28.3 mg cm-2 was illustrated and demonstrated in Figure 6a-b. Interestingly, the pouch battery successfully drives a LED light (threshold voltage of ~1.4 V) at different bending modes (Figure 6c-f). After activated at 0.025 A g-1, this pouch battery can achieve 1.57 V voltage and 71 Wh kg-1 energy density (for both Zn@C and NVPF@C) at 0.117 A g -1 (Figure 6g-h), which is also comparable with recently reported aqueous batteries (Table 1).16, 19, 42, 43, 56-67 Furthermore, the pouch battery keeps 85.2% capacity retention after 100

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Figure 6. (a) Structure illustrations and (b) phtograph of Zn@C/NVPF@C pouch battery. (c) Open and (d) close circuit Zn@C/NVPF@C pouch battery. (e-f) Close circuit Zn@C/NVPF@C pouch battery in different bending conditions. (g) Cycling performance and (h) charge/discharge curves of selected cycles of Zn@C/NVPF@C pouch battery at 0.117 A g-1.

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Table 1. Comparison of recently reported full aqueous batteries with Zn@C/NVPF@C full battery Systems

Average voltage/V

Energy density/(Wh kg-1)

Reference

Polymide/I

0.8

65

56

NaTi2(PO4)3/Na2V3(PO4)3

1.2

29

57

NaTi2(PO4)3/NaMnO2

0.9

30

58

NaTi2(PO4)3Na0.58/MnO2·0.48 H2O

1.3

65

59

Na3MnTi(PO4)3/Na3MnTi(PO4)3

1.4

40

60

Na1.2V3O8/NaFe0.95V0.05PO4@C

0.3

30

61

Polymide/LiCoO2

1.2

80

62

Polymide/NaVPO4F

1.0

45

62

SNDI/CoCuHCF

1.1

30

63

LiTi2(PO4)3/LiMn2O4

1.5

32

64

LiTi2(PO4)3/Li1.1Mn2O4

1.5

63

65

LiTi2(PO4)2.88F0.12/LiMn2O4

1.5

70

66

LiVPO4F/LiVPO4F

2.4

141

67

TiO2/LiMn2O4

2.1

100

19

NaTi2(PO4)3/Na2CuFe(CN)6

1.4

48

42

NaTi2(PO4)3/Na2NiFe(CN)6

1.27

43

43

Li4Ti5O12/LiCoO2

2.35

130

16

Zn@C/NVPF@C

1.57

71

This work

Conclusions In summary, a facile, scalable and extendable strategy of carbon coating Zn foil to inhibit Zn dendrite is developed and demonstrated effective. The stable plating/stripping and improved Zn electrodeposition kinetics can be ascribed to the uniform charge distribution and abundant accommodation for Zn deposition after introduction of carbon layer. Moreover, the use of 8 M NaClO4 +0.4 M Zn(CF3SO3)2 concentrated 14


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electrolyte can expand electrochemical window (up to ~2.5 V) and reduce the cathode dissolution. By virtue of its rational design, we have successfully demonstrated aqueous hybrid Na-Zn batteries with Zn@C anode, 8 M NaClO4+0.4 M Zn(CF3SO3)2 concentrated electrolyte and NVPF@C and NVP@C cathodes, realizing high voltage (1.68 V for NVPF@C; 1.36 V for NVP@C) and energy density (100 Wh kg-1 for NVPF@C; 150 Wh kg-1 for NVP@C) as well as long durability (100% and 65.2% capacity retention for NVPF@C and NVP@C after 1000 cycles, respectively). Furthermore, an energy density of 71 Wh kg-1 is also demonstrated in Zn@C/NVPF@C full battery. We believe that these strategies and key findings are extendable to create high performance aqueous batteries.

Supporting Information SEM images of cycled Zn@C electrode with different current densities, areal capacities, cycles and carbon types; XRD, SEM and TG characterizations of NVPF@C and NVP@C; Electrochemical window of different electrolytes, electrochemical performances of Zn@C/NVPF@C batteries in different electrolytes and voltage ranges; XPS, SEM, XRD characterizations of pristine and cycled NVPF@C and Zn@C.

Conflicts of interest There are no conflicts to declare.

Acknowledgements We are greatly thankful to the final support by the National Natural Science Foundation of China (Grants: 51774148, 51622703, 21703073), the Fundamental Research Funds for the Central Universities (Grant: 2015ZDTD030, 2017KFKJXX001), China Postdoctoral Science Foundation Funded Project (Grant: 2017M622421) and the National Thousand Talents Program of China.

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Graphical Abstract

21



A facile, scalable and extendable strategy of carbon coating Zn foil to inhibit Zn dendrite is developed. The carbon film can greatly improve Zn plating/stripping behavior. Aqueous hybrid Na-Zn batteries using this carbon coated Zn anode, 8 M NaClO4+0.4 M Zn(CF3SO3)2 concentrated electrolyte and Na3V2(PO4)3 and Na3V2(PO4)2F3 cathodes are constructed and demonstrated excellent cyclability

22


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Advanced Low-Cost, High-Voltage, Long-Life Aqueous Hybrid Sodium

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