Synergy of Black Phosphorus-Graphite-Polyaniline Based Ternary

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Energy, Environmental, and Catalysis Applications

Synergy of Black Phosphorus-Graphite-Polyaniline Based Ternary Composite for Stable High Reversible Capacity Na-ion Battery Anodes Hongchang Jin, Taiming Zhang, ChengHao Chuang, Ying-Rui Lu, Ting-Shan Chan, Zhenzhen Du, Hengxing Ji, and Li-Jun Wan ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b04088 • Publication Date (Web): 15 Apr 2019 Downloaded from http://pubs.acs.org on April 15, 2019

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ACS Applied Materials & Interfaces

Synergy of Black Phosphorus-Graphite-Polyaniline Based Ternary Composite for Stable High Reversible Capacity Na-ion Battery Anodes Hongchang Jin,† Taiming Zhang,† Chenghao Chuang,‡ Ying-Rui Lu,§ Ting-Shan Chan,§ Zhenzhen Du,† Hengxing Ji†,* and Li-jun Wan†,# †Department

of Applied Chemistry, CAS Key Laboratory of Materials for Energy Conversion,

iChEM, University of Science and Technology of China, Hefei 230026, China ‡Department

§National

#CAS

of Physics, Tamkang University, Tamsui 25137, New Taipei City, Taiwan

Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan

Key Laboratory of Molecular Nanostructure and Nanotechnology and CAS

Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, China *Corresponding Author: [email protected] KEYWORDS. anode material; black phosphorus; phosphorus utilization; high reversible capacity; sodium ion batteries

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ABSTRACT. In recent times, few-layer black phosphorus (BP) has attracted tremendous attention as a promising anode material for sodium-ion batteries due to its particular two-dimensional structure, good electron conductivity and high theoretical capacity. The main disadvantages of BP based materials are the lower practical specific capacity of the BP based composite than expectation because of the low P atom utilization, and the structural fracture due to the large volume expansion that occurs during sodiation/desodiation cycles. In this work, we report a ternary composite comprising BP, graphite and polyaniline (BP-G/PANI) with a BP mass content of ~65 wt.%. The ternary composite provides an optimized ion pathway (electrolyte → PANI → BP-G → BP), which reduces the charge transfer resistance of the electrode. And further ex-situ X-ray absorption spectroscopy(XAS) measurements demonstrate the presence of graphite in the BP-G composite allows a deep sodiation of BP and also leads to a higher sodiation/desodiation reversibility. In addition, the uniformly coated PANI also restricts the huge volume expansion of BP electrode through discharge/charge processes, which promise stable cycling performance of BP-G/PANI. Thus, our composite shows a high reversible gravimetric capacity of 1530 mAh gcompo.-1 at 0.25 A g-1 and a capacity retention of 520 mAh gcompo.-1 after 1000 cycles at a high current density of 4 A g-1.


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INTRODUCTION Sodium-ion batteries (SIBs) have been considered as a promising candidate to replace lithium-ion batteries (LIBs) for large-scale energy storage considering sodium’s superiority in cost and abundance.1 However, Na ion suffers sluggish electrochemistry kinetic process when intercalating/deintercalating in the electrode compared with Li ion, which lead low reversible capacity and cyclic performance of cathode and anode materials. Therefore, to overcome this disadvantage, a number of cathode materials with performances comparable to those of LIBs have been reported for SIBs.2-4 And many different anode materials have also been investigated, some examples being carbonaceous materials,5-7 transition metal oxides,8-9 metal sulfides,10-11 organic salts12-13 and alloy-type material.14-20 Although many progresses have been made, an anode materials with high reversible capacity and long lifespan are still the research hotspots in both academia and industry for SIBs, owing to the growing demands for high energy and low price electrical power sources. Recently, black phosphorus (BP) has drawn much attentions owing to its high theoretical capacity of 2600 mAh g-1 and a low working potential (0.3 V vs. Na/Na+). Furthermore, thanks to the unique two-dimensional puckered honeycomb structure, BP displays many features, such as high electrical conductivity of ~300 S m-1;21 a larger interlayer spacing than graphite (3.08 Å vs. 1.86 Å) that facilitates the intercalation of both Li+ (0.76 Å) and Na+ (1.02 Å), and a fast Na ion diffusion capability along the zigzag direction ensuring a high level of sodiation for phosphorus atoms.22. Thus, a number of BP-based composites was synthesized for SIBs anodes. Cui et al. first reported a phosphorene/graphene composite with a capacity of 1179 mAh g-1 (calculated based on the total mass of composite, 93.8% P utilization) at 0.05 A g-1 and remains 516 mAh g-1 after 100 cycles at 8 A g-1.23 Amine and co-workers prepared a BP/ketjenblack/CNT composite which


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delivered a capacity of 1505 mAh g-1 at 0.2 A g-1 (77.3% P utilization) and a capacity retention of 1190 mAh g-1 at 1.3 A g-1 after 100 cycles.24 Dou et al. demonstrated a functionalized few-layer BP, the electrode displayed a discharge capacity of 1597 mAh g-1 (69% P utilization) and remain 1050 mAh g-1 after 100 cycles at 0.1 A g-1.25 Although these works led to noteworthy enhancement in the reversible capacity of BP-based materials, the cycling stability of high-capacity anodes with long term at high current densities is urgently to be improved. Specifically, the main reasons of the low capacity and poor lifespan at high current density are as follows. First, the utilization of P determined the reversible capacity of BP based materials during sodiation/desodiation processes. Pristine BP shows a low BP utilization of < 70% due to its inferior wettability (in the electrolyte) which hinder the ion diffusion from electrolyte into electrode.25 Second, phosphorus suffers huge volume expansion (~490%) after sodiation process, and solid electrolyte interphase (SEI) generated on the surface of fractured BP, which leading the contact loss with current collector, result in the fast capacity fading. Therefore, it is critical to find an approach to enhance P utilization and conquer the huge volume expansion, which could achieve stable high reversible capacity of BP based material for SIBs. In this work, we present a BP based composite with rational design containing few-layer BP flakes, graphite and polyaniline (BP-G/PANI) to be applied as SIB’s anode to realize both high reversible capacity and a stable cyclic performance at high current densities. The electrochemical impedance spectroscopy (EIS) results demonstrate that graphite in the BP-G hybrid reduces the charge transfer resistance (Rct) compared with pristine BP. And the presence of graphite also enhances the P utilization during sodiation/desodiation process, which represented through X-ray absorption spectroscopy (XAS) measurements. Further uniform PANI coating layer shows swelling property in the electrolyte, which ensures an efficient access of Na ion to the BP-G hybrid


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and enables high reversible capacity at high rate. PANI also accommodates the volume expansion and provide conductive network, which make the stability of our composite during long term sodiation/desodiation cycles. Thus, an optimized ion pathway (electrolyte → PANI → BP-G → BP) was constructed. Benefiting from the well-designed ternary structure, our BP-G/PANI composite delivered a high reversible capacity of 1530 mAh g-1 (90% P utilization) at a current density of 0.25 A g-1 (here, we calculate the capacity taking the total mass of the composite into account). Most significantly, the reversible capacity still remains 520 mAh g-1 after 1000 cycles at a high current density of 4 A g-1 with an extremely low capacity fading rate of 0.024%. The superior performance of BP-G/PANI can be ascribed the rational structure of BP-G/PANI with reduced Rct, enhanced P utilization and long terms stability.


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RESULTS AND DISCUSSION

Figure 1. Structure characterization of BP based materials. (a) Schematic diagram of the sodiation of BP-G and BP-G/PANI electrodes. (b) Raman spectra and (c) XRD patterns of BP-G/PANI and BP. (d) TEM and (e) HRTEM images of BP-G/PANI. (f-i) TEM elemental mapping images of BP-G/PANI. Figure 1 describes the structural characterization of BP-G/PANI. Figure 1a shows the different steps in the fabrication of the ternary composite BP-graphite-PANI, the ternary structure conquer the volume changes of BP during (de)sodiating processes and thereby prevent a loss of


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contact of BP-G with the current collector during battery cycling. Few-layer BP was used as the starting material (Figure S1) and the BP-G particles (Figure S2) are well coated with PANI (Figures 1b and c). And the schematic in the right of Figure 1a describes the unique structure of BP-G/PANI. The PANI offers Na ion pathway between electrolyte and active material (BP-G) and electron conductive network, and the graphite in the BP-G reduce the ion charge transfer resistance. Raman spectrum (Figure 1b) shows intense bands at 363, 440 and 467 cm-1, which represent the feature peaks of BP.23 Two broad peaks are also seen at 1323 and 1604 cm-1, ascribed to the D and G bands of the graphite and two low-intensity broad peaks appear at 850 and 1200 cm-1, which are characteristic of PANI.26 X-ray diffraction (XRD) patterns show characteristic diffraction peaks of BP at 2 values of 16.8°, 26.5°, 34.1° and 34.9° in both samples (Figure 1c) and a broad peak originating from PANI appears around 22° (black). Raman spectra and XRD pattern thus confirm that BP remains intact while forming the composite BP-G/PANI. The microstructure of BP-G/PANI was characterized by transmission electron microscope (TEM) , our BP-G/PANI sample is made up of small BP-G particles coated by the cross-linked polymer PANI; the HRTEM image shows a detailed view of the edge of graphene where a lattice spacing of 4.41 Å is measured, corresponding to a zigzag edge of BP (Figure 1d).27 Graphite lattice plane with a spacing of 2.06 Å is also present.28 The amorphous part outside BP and graphite corresponds to PANI (Figure 1e). Furthermore, TEM mapping images show that C, P, and N are evenly distributed in the BP-G/PANI particle (Figures 1f–i).


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Figure 2. The function of graphite and PANI in BP based composite during discharge/charge process. (a) P K-edge XAS spectra of BP and BP-G. Ex-situ XAS P K-edge spectra of (b) BP-G and (c) BP. Cross sectional SEM images of (d) BP-G/PANI and (e) BP-G electrodes before and after three cycles. To further investigate the effect of graphite on the improved P utilization and the effect of PANI on the improved cycling stability, first, we recorded X-ray absorption spectra to understand the P state in BP and BP-G (Figure 2a). The absorption edge of BP-G is at 2145.7 eV, which is higher than that of BP (2145.5 eV) due to the strong charge transfer from P to C owing to the much higher electron affinity of C (1.262 eV) than P (0.746 eV). Furthermore, we test the ex-situ XAS of BP and BP-G at different states of charge. the P K-edge of BP-G is up-shifted to 2146.0 eV and a pre-edge appears after sodiation (Figure 2b), indicating the formation of NaxP (1

Synergy of Black Phosphorus-Graphite-Polyaniline Based Ternary

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