Encapsulation of Metallic Na in an Electrically Conductive Host with

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Encapsulation of Metallic Na in an Electrically Conductive Host with Porous Channels as a Highly Stable Na Metal Anode Wei Luo, Ying Zhang, Shaomao Xu, Jiaqi Dai, Emily Michelle Hitz, Yiju Li, Chunpeng Yang, Chaoji Chen, Boyang Liu, and Liangbing Hu Nano Lett., Just Accepted Manuscript • Publication Date (Web): 02 May 2017 Downloaded from http://pubs.acs.org on May 3, 2017

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Encapsulation of Metallic Na in an Electrically Conductive Host with Porous Channels as a Highly Stable Na Metal Anode Wei Luo,1,2,‡ Ying Zhang,1,‡ Shaomao Xu,1 Jiaqi Dai,1 Emily Hitz,1 Yiju Li,1 Chunpeng Yang,1 Chaoji Chen,1 Boyang Liu,1 Liangbing Hu1,* 1

Department of Materials Science and Engineering, 2Department of Mechanical Engineering, University of Maryland, College Park, MD 20742, United States

Keywords: Metallic Na Anode, Conductive Host, Porous Channel, Low Over-Potential, Long-Term Stability

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Abstract Room-temperature Na-ion batteries (NIBs) have attracted great attention because of the widely available, abundant sodium resources and potentially low cost. Currently, the challenge of the NIBs development is due primarily to the lack of a high-performance anode, while Na metal anode holds great promise considering its highest specific capacity of 1165 mAh/g and lowest anodic potential. However, uneven deposit, relatively infinite volume change and dendritic growth upon plating/stripping cycles cause low Coulombic efficiency, poor cycling performance and severe safety concerns. Here, a stable Nacarbonized wood (Na-wood) composite anode was fabricated via a rapid melt infusion (about 5 seconds) into channels of carbonized wood by capillary action. The channels function as a high-surface-area, conductive, mechanically stable skeleton, which lower the effective current density, ensure a uniform Na nucleation and restrict the volume change over cycles. As a result, Na-wood composite anode exhibited flat plating/stripping profiles with smaller overpotentials and stable cycling performance over 500 hours at 1.0 mA/cm2 in a common carbonate electrolyte system. In sharp comparison, the planar Na metal electrode showed a much shorter cycle life of 100 hours under the same test conditions.


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Introduction Recently, battery technologies based on Na-ion chemistry have raised great interest as alternatives to Li-ion batteries, especially for grid-scale applications owing to the wide availability and sustainability advantages of Na resources.1-3 Over the past several years, extensive research efforts have been undertaken to develop cathode materials for Na-ion batteries, which already showed great promise.4-8 As for anodes, however, the commercially available graphite failed to store enough Na ions.9-11 Hence, recent attempts mainly focused on the exploitation of anode materials, including carbon,12-16 phosphorus,17-19 and alloy anodes.20-22 Compared to other anode candidates, metallic Na shows great potential with the highest theoretical specific capacity of 1165 mAh/g and the lowest anode potential of −2.714 V vs. standard hydrogen electrode.23 More notably, Na metal anode is indispensable for these high-energy-density batteries where cathode materials cannot supply Na ions, such as Na-O2 batteries,24-27 Na-S batteries,28-31 and NaCO2 batteries.32, 33 Previous investigations have revealed that metallic anodes typically suffer from several problems in liquid electrolyte systems: i) unstable solid electrolyte interphase (SEI), ii) uneven metallic deposition and dendritic growth, and iii) large volume change upon repeated plating/stripping cycles.34-41 These issues have been discovered as well when metallic Na was applied as anodes for Na batteries.33, 42 As schematically shown in Figure 1a, porous and dendritic Na eventually forms on bare Na anode due to the unstable SEI and the relatively infinite volume change upon long-term cycling, which have significantly prevented Na metal anode from practical applications due to the resulting low Coulombic efficiency, poor cycling performance and safety concerns. To address 3 ACS Paragon Plus Environment

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these issues, Cui’s group demonstrated a compact inorganic SEI using NaPF6-glyme electrolytes, which enabled a relatively uniform and stable plating/stripping process.43 A concentrated NaFSI-glyme electrolyte or NaAlCl4·2SO2 inorganic electrolyte was also proposed to offer a high efficiency for metallic Na anodes.44, 45 Our group proposed that an artificial SEI can effectively passivate the Na metal,46 which was confirmed by Sun’s group using atomic layer deposition (ALD)47 and Archer’s group with ionic liquid48. Meanwhile, inspired by a stable Li-reduced graphene oxide (Li-rGO) composite electrode,49 Chen and coworkers reported a Na-rGO electrode, which exhibited great stability in Na-CO2 batteries.50 Their results suggested that confining metallic anodes in a host can greatly enhance the stability.51-53 Despite the recent progress provided a partial solution to address the problems, research on Na metal anode is in its early stage, and developing an effective approach for highly reversible Na metal anode is still a major challenge. Here, by encapsulating metallic Na into an electrically conductive host with porous channels, we propose a Na-carbonized wood (Na-wood) composite electrode that tackles nearly all of these problems. Our design is inspired by the structure of natural wood, where water and ions are transported through the channels. In this case, Na plating/stripping process are restricted in the channels of carbonized wood over long-term cycling that no amplified and uncontrolled Na deposition occur (Figure 1b). In addition, the high conductive surface area would lower the effective local current density and result in a uniform Na nucleation. Benefiting from this unique structure, the Na-wood composite electrodes remain stable and spatially confined, resulting in flat


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plating/stripping profiles, low overpotential of 30 mV at 0.5 mA/cm2 and superior cyclability over 500 hours at 1.0 mA/cm2.

Figure 1. The concept of encapsulating metallic Na in carbonized wood with vertical channels as a stable anode. (a) Large volume change occurs during repeated plating/stripping cycles of planar Na electrode, leading to the formation of porous and dendritic morphology. (b) A stable Na-carbonized wood (Na-wood) composite anode was achieved by restricting the repeated plating/stripping process in channels of carbonized wood.

Results and Discussion A generic illustration of fabricating the Na-carbonized wood (Na-wood) composite electrode is schematically shown in Figure 2a. In the first step, a piece of original wood was annealed in a tube furnace under argon at 1000 °C to give the black carbonized wood (Figure 2b). Encapsulation of metallic Na in the carbonized wood was accomplished by a spontaneous infusion of molten Na into the vertical channels in an argon-filled glove box (see Experimental Section and Movie S1 in Supporting Information). The spontaneous


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and instantaneous infusion (about 5 seconds) is driven by capillary forces from the vertical-channel structured carbonized wood, which agrees with previous observation of encapsulating molten Li or Na into porous carbon matrix.49, 50, 54 The black carbonized wood exhibited metal luster after this step, indicating the successful intake of metallic Na into these porous channels. Our approach used earth-abundant, low cost precursors and simple set-up/material-processing, which offers great potential for scalable production with good reproducibility.

Figure 2. Encapsulation of metallic Na into carbonized wood by a spontaneous and instantaneous infusion (5 seconds). (a) Schematics of the first carbonization step and the second step of infusion molten Na into porous, vertical channels to form Nacarbonized wood (Na-wood) composite electrodes. (b) Photos of a piece of wood before carbonization, after carbonization at 1000 °C, and after melt infusion of metallic Na.

To prove the successful encapsulation of metallic Na in carbonized wood channels, we conduct morphology analysis using scanning electron microscopy (SEM) and energy 6 ACS Paragon Plus Environment

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dispersive X-ray spectroscopy (EDX). Figure 3a shows a typical low-magnification SEM image of the as-prepared carbonized wood, which is composed of porous, vertical channels with channel diameters ranging from 5 µm to 50 µm and channel wall thickness of ~1 µm (Figure 3b). More pores can be observed on the channel walls (Figure 3c) that the hierarchical porous structure offers larger specific area and leads to more homogeneous Na nucleation and deposition on this unique conductive skeleton by lowering the effective current density. More SEM images can be found in Figure S1 and S2 of Supporting Information to show the detailed structure of carbonized wood. After melt infusion of metallic Na, the channels of carbonized wood were almost fully filled, as shown in Figure 3d. A zoomed-in image reveals that the carbonized wood structure was well maintained upon the metallic Na intake (Figure 3e). EDX elemental mapping images in Figure 3f-3h confirmed the SEM observations that elemental Na occupied the channels while carbonized wood acted as a stable host. Detailed SEM and EDX mapping images of Na-wood composite in Figure S3 and S4 indicated that metallic Na exists along the whole length of the channels spatially from bottom to top. The observation of metallic Na peaks in the X-ray diffraction (XRD) pattern of Na-wood composite further confirmed the encapsulation of metallic Na within the carbonized wood channels (Figure S5 in Supporting Information).


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Figure 3. Evidence of encapsulating metallic Na in the channels of carbonized wood. (a) A low-magnification SEM image of carbonized wood. (b, c) Zoomed-in images corresponding to the area marked by red and yellow squares in (a). (d, e) SEM images of carbonized wood after melt infusion of metallic Na, where metallic Na was encapsulated in the channels of carbonized wood as outlined by the yellow dotted line. (f-h) Corresponding Na, C, and overlapped elemental mapping images of Na-wood composite electrode indicate that channels of carbonized wood were filled up by metallic Na.


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Prompted by this unique design, the stability of the Na-wood composite electrode is expected to improve in comparison to the bare Na metal electrode. In order to evaluate the electrochemical performance, 2032-type coin cells were assembled using two identical Na-wood electrodes with 1.0 M NaClO4 in ethylene carbonate/diethyl carbonate (EC:DEC = 1:1 by volume) solution as the electrolyte. Bare Na electrodes were also employed to assemble cells as control. The cells were first galvanostatically cycled at 0.5 mA/cm2 within a protective cut-off voltage window of -3.0−3.0 V. Each plating/stripping step was set to be 30 minutes. As shown in Figure 4a, the voltage profile of the Na-wood cell exhibited small overpotential while the voltage of the bare Na cell gradually increased. Zoomed-in voltage profiles of the first 5 cycles showed that bare Na cell delivered flat plating/stripping curves as Na-wood cell in the first cycle, but dips and dumps appeared from the 2nd cycle (Figure 4b). This phenomenon has been previously observed in bare Li electrodes, which was mainly caused by the large volume change during plating/stripping.52 Such a large volume change inevitably resulted in the cracking of SEI and direct contact between newly deposited metallic Na with liquid electrolyte, which promoted the consumption of electrolyte, formation of excessive SEI and increase of overpotential. Consequently, after cycled for less than 150 hours, the bare Na cell stopped due to the voltage reaching the protective cut-off voltage, indicative of a poor cyclic life (Figure 4c). Nyquist plots confirmed the observation that the bare Na cell exhibited a small impendence after the 1st cycle but a much larger impendence after 100 cycles (Figure 4d). When the same procedure was applied to the Na-wood cell, stable plating/stripping curves with a much lower overpotential of ~30 mV (Figure 4a and Figure S6). This stable cycling performance is consistent with the constant impendence


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of Na-wood cell (Figure 4d), indicating a great stability due to the encapsulation of metallic Na in a stable matrix. Since the cycling stability is closely related to the electrode structure, ex situ SEM measurements were conducted on bare Na electrode and Na-wood composite electrode after cycling. During sample preparation, it is worth noting that the bare Na cell was almost dried out after the 148-hour cycling test and severe electrode pulverization occurred. The corresponding SEM image in Figure 4e demonstrated a cracked Na electrode with three-dimensional (3D) porous structures, which confirmed that the large volume change upon cycling would lead to the consumption of electrolyte and formation of porous morphology. On the other hand, metallic Na was still confined in vertical channels of carbonized wood after the long-term 250-hour cycling test (Figure 4f-4j). Notably, the Na-wood electrode maintained its initial structure and the Na-wood cell was still wet when it was disassembled. The significantly enhanced stability of Na-wood electrode compared to bare Na electrode proves that confinement of metallic Na in a conductive matrix and good mechanical stability of the whole composite electrode are critical for metallic anodes.49, 50, 52


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Figure 4. Electrochemical performance of symmetric cells using Na-wood electrodes and bare Na metal electrodes and their structural evaluation after cycling. (a) Longterm cycling performance at 0.5 mA/cm2 with 30 minutes for each plating/stripping process and a protective cut-off voltage window of -3.0−3.0 V. Detailed voltage profiles of (b) the first 5 cycles and (c) marked by green rectangles in (a). (d) EIS spectra of the 11 ACS Paragon Plus Environment

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Na-wood and bare Na cells collected after 1 cycle and 100 cycles. (e) SEM image of bare Na electrode after cycling (148 hours), which exhibited 3D porous morphology. (f) SEM image of Na-wood electrode after long-term cycling (250 hours), showing stable morphology. (g-j) Corresponding EDX elemental mapping images of Na-wood electrode after long-term cycling marked by yellow rectangle in (f), where metallic Na was still confined in the channels of carbonized wood.

The carbonized wood with porous channels can also function as a high-surface-area conductive host to greatly decrease the effective current density and ensure a uniform Na nucleation, affording an improved rate performance. Figure 5a and 5b show the voltage profiles of Na-wood and bare Na symmetric cells cycled at 1.0 mA/cm2 with 1 hour or 2 hours for each cycle. Obviously, the Na-wood electrode exhibited stable cycling performance for more than 250 cycles at both conditions while bare Na cell can only run for less than 90 cycles and 50 cycles. Detailed voltage profiles of Na-wood cells displayed stable plating/stripping curves with small hysteresis over hundreds of cycles (insets of Figure 5a and 5b). The above observations are consistent with previous reports that a conductive matrix can reduce the effective current and result in a better rate performance for both metallic Li and metallic Na.50,

55-59

It should be noted that the

excellent cyclic stability of Na-wood cells was achieved in common carbonate based electrolyte system without any additives, revealing the advantages from the composite anode design. We believe that the cycling performance of the Na-wood composite electrode could be further improved using an optimized electrolyte system.


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Figure 5. Electrochemical performance of symmetric cells using Na-wood electrodes and bare Na metal electrodes at 1.0 mA/cm2 with capacity of 0.5 mAh/cm2 and 1.0 mAh/cm2, respectively. Long-term cycling performance at 1.0 mA/cm2 with (a) 1 hour and (b) 2 hours for each plating/stripping cycle. Insets are detailed voltage profiles marked by rectangles in (a) and (b).

Conclusion In conclusion, we have demonstrated the encapsulation of metallic Na into an electrically conductive matrix with porous channel structure that can be rapidly accomplished by a melt infusion (5 seconds). The protocol for fabricating Na-wood composite electrode 13 ACS Paragon Plus Environment

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involves only abundant precursors and simple processing. The conductive, porous framework provided by the carbonized wood offers an ideal host for metallic Na during electrochemical plating/stripping cycles, which enables much improved cycling performance by its good mechanical stability and confinement of metallic Na. Furthermore, the rate performance is enhanced by lowering the effective current density and ensuring a uniform Na nucleation due to the high conductive surface area. We believe that this unique design promises a potential solution for metallic Na anode and can also be extended to other metallic anodes for multiple applications.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge via the Internet at http://pubs.acs.org. Details for experimental and characterizations; Movie S1; Figures (S1-S6) of SEM images of carbonized wood, SEM and EDX elemental mapping images of Na-wood electrode, XRD patterns of carbonized wood and Na-wood electrode, detailed voltage profiles of a symmetric cell using Na-wood electrodes.

AUTHOR INFORMATION ‡These authors contributed equally

Corresponding Author *Email: [email protected]

Notes The authors declare no competing financial interest.


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Acknowledgement The authors acknowledge the supported by Nanostructures for Electrical Energy Storage (NEES), an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Basic Energy Sciences under Award number DESC0001160.

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Nano Letters

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Keywords: Metallic Na Anode, Conductive Host, Porous Channel, Low Over-Potential, Long-Term Stability

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Page 18 of 18

Encapsulation of Metallic Na in an Electrically Conductive Host with

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