Micron-Sized Nanoporous Antimony with Tunable Porosity for High

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Micron-Sized Nanoporous Antimony with Tunable Porosity for High Performance Potassium-Ion Batteries Yongling An, Yuan Tian, Lijie Ci, Shenglin Xiong, Jinkui Feng, and Yitai Qian ACS Nano, Just Accepted Manuscript • DOI: 10.1021/acsnano.8b08740 • Publication Date (Web): 27 Nov 2018 Downloaded from http://pubs.acs.org on November 27, 2018

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Micron-Sized Nanoporous Antimony with Tunable Porosity for High Performance Potassium-Ion Batteries Yongling An,† Yuan Tian,† Lijie Ci,† Shenglin Xiong,‡ Jinkui Feng,*,† Yitai Qian§ †SDU & Rice Joint Center for Carbon Nanomaterials, Key Laboratory for Liquid-Solid Structural

Evolution & Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, P. R. China. E-mail: [email protected] ‡ School

of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, P. R.

China. §

Hefei National Laboratory for Physical Science at Microscale, Department of Chemistry,

University of Science and Technology of China, Hefei 230026, P. R. China.

ACS Paragon Plus Environment

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KEYWORDS potassium-ion batteries, nanoporous antimony, micron-sized, tunable porosity, vacuum distillation, anode ABSTRACT Potassium-ion batteries (KIBs) are considered as favorable candidates for post-lithium-ion batteries, ascribing to its low-cost, abundant resource and high working potential (-2.93 V for K+/K). Owning to its relatively low potassiation potential and high theoretical capacity, antimony (Sb) is one of the most favorable anodes for KIBs. However, the large volume changes during KSb alloying-dealloying cause fast capacity degradation. In this report, nanoporous-Sb (NP-Sb) is fabricated by an environmental-friendly vacuum distillation method. The NP-Sb is formed via evaporating low boiling-point zinc (Zn). The by-product Zn can be recycled. It is further found that the morphology and porosity can be controlled by adjusting Zn-Sb composition and distillation temperature. The nanoporous structure can accommodate volume expansion and accelerate ion transport. The NP-Sb anode delivers an improved electrochemical performance. These results suggest that the vacuum distillation method may provide a direction for green, large-scale and tunable fabrication of nanoporous materials.

Owning to the continuous depletion of conventional fossil fuel resources and the rapid deterioration of global environment, developing sustainable and clean energy systems have attracted considerable attention.1-4 Secondary batteries have been considered as one of the most favorable devices to store energy due to its portability and high energy‐conversion efficiency.5-9 With low-cost, abundant nature resources and analogous chemical qualities of sodium and potassium elements, great research efforts on potassium-ion batteries (KIBs) and sodium-ion


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batteries (NIBs) have been devoted.10-13 Owning to the redox voltage of potassium (-2.93 V) is lower than that of sodium (-2.71 V), and closer to that of lithium (-3.04 V), KIBs have been developed as low-cost batteries.14-20 Recently, significant studies have been done to investigate the optional electrode materials for KIBs.21-26 As for anode materials, carbon-based anodes for KIBs have been explored due to its low-cost and high electronic conductivity character.27-32 However, the capacities of carbon-based anodes (Na+ > Li+, 1.38 Å>1.02 Å>0.76 Å), which is quite complicated to discover an appropriate electrode material that can accommodate huge volume expansion of potassium ion insertion/extraction to obtain an enhanced electrochemical performance.35-37 Hence, exploring a high capacity anode material is an urgent demand for KIBs. Recently, the alloy-based electrodes with high theoretical capacity and suitable potential have attracted great interest.37,38 Among numerous alloy-type electrode materials, antimony (Sb) is one of the most promising anodes attributing to the low reaction potential and high theoretical capacity (660

mAh

g-1).39-41

Nevertheless,

huge

volume

change

(about

300%)

during

potassiation/depotassiation process may lead to pulverization of electrode material, causing rapid capacity reduction, low Coulombic efficiency, and inferior electrochemical properties.14,19,32,36 To address these crucial issues, various strategies have been introduced to retard the volume change and improve the electrochemical capabilities of Sb-based anodes in NIBs, such as a series of Sbtype intermetallics and alloys (Al-Sb,42 Cu-Sb,43,44 Fe-Sb,45 Mo-Sb,46 Sn-Sb,47,48 Bi-Sb,49 Sn-GeSb50), Sb@C composites (Sb@C nanotubes,51 Sb@C nanofibers,52-54 Sb@C yolk-shell spheres,55,56 Sb@C nanosheets,57 Sb@graphene47,58-60), and metalline Sb with extraordinary structure (hollow nanospheres Sb,55,61 nanorod array Sb,62 nanocrystals Sb,63 bulk Sb,64


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nanoporous Sb57,65). The Sb-based anode materials with the porous structure have indicated enhanced electrochemical performance due to the void space and holes in such porous morphology can accommodate huge volume change during the potassiation/depotassiation process.61,65 However, the exploration of the Sb-type anodes for the KIBs is quite limited. Mao and Guo et al. studied that Sb/C powders showed an improved cycling property in the carbonate electrolyte for KIBs.41 Mai et al. reported antimony nanoparticle with carbon network as anode for KIBs, delivering the high capacity and improved rate capabilities.40 However, obtaining anode material for KIBs reminds a big challenge. Dealloying is an ordinary corrosion process that alloys are “parted” by selectively dissolving the most electrochemically active elements.42 Chemical dealloying has been used to prepare threedimensional (3D) porous structure with interconnected ligaments.42,65,66 This process can be executed at ambient temperature, which is facile to manufacture on a large scale due to the alloys commercially obtained.67 Our group has explored the Sb,65 Si,67 Bi,68 and Ge69 by the chemical dealloying method. The porous Sb was prepared via this chemical dealloying method, delivering an improved electrochemical performance as anode for NIBs.65 Nevertheless, most of these processes demand the deleterious, contaminative, and hazardous chemicals to dissolve the active elements, which is negative to the workers and environment. Herein, we report a vacuum distillation method to prepare the 3D NP-Sb from the commercial Zn-Sb alloy as anode for KIBs. This approach is a ordinary process that the laigh boiling point materials are evaporated to attain a pure high boiling point sample.70,71 To obtain pore structure, the evaporation temperature must be under the smelting point of precursor material.70,71 Thus, the continuous NP-Sb skeleton is achieved via the vacuum distillation method at an appropriate temperature under the smelting point of Zn-Sb alloy. The void structure of NP-Sb can be regulated


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by controlling the evaporation temperature and alloy proportion. Furthermore, the zinc metal, removed from Zn-Sb alloy via this method, can be recycled. The NP-Sb exhibits the improved electrochemical capability. The enhanced performance can be attributed to the 3D porous structure, relieving the large volume expansion and accelerating ion transport of NP-Sb anode for KIBs during charge/discharge process. These results illustrate that the vacuum distillation method may allow for production-scale of high-capacity Sb anode for KIBs and other energy storage systems, furnishing a direction to fabricate other nanoporous materials. Results and Discussion Figure 1 illustrates the schematic of different ratio Zn-Sb alloy via vacuum distillation method. Initially, as illustrated in Figure 1, the Zn-Sb alloy has a uniformly dispersed structure (i). While Zn-Sb alloy is handled at 400 oC, few Zn atoms are removed and few voids can be formed (ii). When the distillation temperature reaches to 500 oC, the Zn atoms are entirely sublimated, a great deal of voids or vacancies can be produced, and the pure NP-Sb is acquired (iii). Figure 1b is similar to the Figure 1a. As illustrated in Figure 1b, the content of Zn elements in the Zn-Sb alloy increases, compared to the Figure 1a. As a result, the quantities and diameters of voids or vacancies are improved, which may accommodate huge volume expansion and accelerate ion transport of Sb anode for KIBs during charge/discharge process to achieve an enhanced electrochemical performance. The SEM evolution of different ratio Zn-Sb alloy via vacuum distillation method at 2 h are explored, as illustrated in Figure S1. Figure S1b, S1e, S1h, and S1k illustrate the SEM images of Zn20Sb80, Zn40Sb60, Zn60Sb40, and Zn80Sb20 alloy precursor, which show the smooth surface. The XRD patterns in Figure S2a (Zn20Sb80), Figure S2b (Zn40Sb60), Figure S2c (Zn60Sb40), and Figure S2d (Zn80Sb20) indicate the formation of Zn elements and Sb elements. When Zn-Sb alloy is distillated at 400 oC, more and more voids or vacancies can be produced (as shown in


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Figure S1c, Figure S1f, Figure S1i, and Figure S1l) while the intensity of Zn characteristic peaks is weakened and the intensity of Sb characteristic peaks is enhanced (in Figure S2a (400 oC), Figure S2b (400 oC), Figure S2c (400 oC), and Figure S2d (400 oC) with the Sb content increasing in ZnSb alloy, attributing to the sublimation of amplified Zn elements. This consequence is conformable with Raman result in the Figure S3a (400 oC), Figure S3b (400 oC), Figure S3c (400 oC), and Figure S3d (400 oC). When Zn-Sb alloy is distillated at 500 oC, more and more uniform nanopores are achieved due to the entire Zn elements are sublimated, as illustrated in Figure S1d, S1g, S1j, and S1m. With the increasing of the Sb content in Zn-Sb alloy, the nanopores of porous structure become more well-distributed, which may promote the transfer of potassium ion and buffer huge volume change during potassiation/depotassiation process. The XRD patterns (in Figure S2a (500 oC),

Figure S2b (500 oC), Figure S2c (500 oC), and Figure S2d (500 oC)) reveal that the pure NP-

Sb is achieved and Zn elements in Zn-Sb alloy are entirely removed when the temperature reaches to 500 oC, which is accordant with Raman spectra in the Figure S3a (500 oC), Figure S3b (500 oC), Figure S3c (500 oC), and Figure S3d (500 oC). The EDS and mapping results of the different ratio Zn-Sb alloy are also given and consistent with the XRD results, as illustrated in Figure S4-S7. Besides, SEM images of Zn-Sb alloy (Zn:Sb=4:1) at higher vacuum distillation temperature of 600 oC,

700 oC, 800 oC and 900 oC are explored, as illustrated in Figure S8. With the increasing of

vacuum distillation temperature, the pores are gradually fused and the particle size NP-Sb is more larger. The successful synthesis of NP-Sb can be expected to provide the improved electrochemical performance due to this porous structure can facilitate potassium ion insertion/extraction and accommodate the volume change of Sb anode in KIBs during charge/discharge process. Figure 2 shows the morphological and structural characterization of Zn-Sb alloy (Zn:Sb=4:1) via vacuum distillation method at 500 oC. The continuous porous structure with uniformly


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distributed pores of the as-produced NP-Sb-20 is observed, as indicated in Figure 2a and 2b. The corresponding EDX mapping in Figure 2c shows the elemental distribution of Sb and clearly reveals the porous structure of NP-Sb-20. The size of whole NP-Sb-20 particle is about dozens of microns in Figure S9. The 0.30 nm lattice fringe is observed in Figure 2d and 2e, which can be ascribed to the typical (012) crystal planes of Sb.72 The SAED patterns illustrate that NP-Sb-20 is polycrystalline in Figure S10. The XRD patterns are indexed well with the standard data (JCPDS No. 35-0732) in Figure 2f.72 The Zn peaks are vanished from Zn-Sb alloy after vacuum distillation, demonstrating that Zn elements in the Zn-Sb precursor are entirely removed. The weak XRD peak of Sb may attribute to the small size of Sb nanoparticles, according with the TEM observation, which may provide an improved electorchemical performance. Besides, more structure data of the NP-Sb-20 is furnished by the Raman spectra in Figure 2g. The peaks located at 147.8 cm-1 and 109.7 cm-1 exhibit the optical mode of crystalline Sb.72 In addition, the TEM evolution of different ratio Zn-Sb alloy via vacuum distillation method at 500 oC are also studied, as illustrated in Figure S11-S13. The pores are more uniform and large with the increasing of the Zn content in Zn-Sb alloy, which may favor the potassiation/depotassiation and accommodate huge volume change of Sb anode in KIBs. These results demonstrate that different ratio Zn-Sb alloy changes into NP-Sb product when temperature approaches 500 °C and these pores are more uniform and large with the increasing of Zn content, which are expected to achieve the enhanced electrochemical performance. The porous properties of NP-Sb-20 are probed via BET in the Figure 2h. The specific BET is calculated to be around 12.3 m2 g-1. The pore size distribution (Figure 2i) illustrates that major apertures are under 100 nm. These pores are obtained due to the vacancy space remanent after removing Zn components in Zn-Sb alloy to form the NP-Sb-20. Furthermore, the porous properties of different ratio Zn-Sb alloy via vacuum distillation method at 500 oC are also investigated, as


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illustrated in Figure S14. With the increasing of Zn content in Zn-Sb alloy, the BET surface area and pore sizes of porous structure become larger, facilitating the less-resistance diffusion of potassium ion and accommodating the volume change of Sb anode in KIBs during cycling process to achieve improved electrochemical property. The electrochemical performance of bulk-Sb and NP-Sb as the KIBs anodes is explored between 0.01 V and 1.2 V in Figure 3. Figure 3a illustrates cyclic voltammograms (CVs) of NP-Sb-20 anode for the first five cycles at 0.05 mV s-1. The first cathodic sweep is dissimilar to the following scans, implying activation process and SEI film formation during the initial cycle.39,40 Specifically, the reduction peaks at 0.21 and 0.1 V correspond to electrochemical reaction of Sb to shape amorphous KxSb and then cubic K3Sb alloy phase.39,40,73 While for the anodic sweep, a broad oxidation peak from 0.65 V to 0.95 V may be ascribed to depotassiation reaction of the KxSb alloy.65,67,73 To further investigate the potassiation/depotassiation process of NP-Sb-20 in KIBs, the ex situ XRD experiments are executed of pristine, potassiation and depotassiation electrodes, as shown in Figure 3b. Corresponding to (012) face of crystalline Sb, a peak located at 28.6° is observed in the XRD patterns of pristine electrode.39 After full potassiation, two new peaks located at 29.7° and 35° emerge, which can be well indexed to K3Sb, suggesting that the NP-Sb-20 is fully transported to the K3Sb phase and confirming that the reversible capacity of NP-Sb-20 may be ascribed to the K3Sb formation.40 Besides, after full depotassiaton, the characteristic peaks of the K3Sb phase vanish completely, however, no evident characteristic peaks of Sb are observed, implying that the amorphous Sb may be acquired from the K3Sb phase.39,40 The ex situ XRD results illustrate that the NP-Sb-20 changes to the K3Sb phase in the potassiation process, while the K3Sb phase transforms to amorphous Sb in the depotassiation process. Ex situ Raman spectrum is further measured to explore the electrochemical reaction of Sb and K by testing the pristine, full


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potassiation and depotassiation electrode, respectively. As shown in Figure 3c, the fresh electrode exhibits two Raman peaks at 109.7 cm-1 and 147.8 cm-1. Nevertheless, after full potassiation, a wide peak located at 145 cm-1 is observed, which is indexed to the K3Sb phase. Besides, after full depotassiation, this peak is replaced by a feeble weak at 160 cm-1, further exhibiting the formation of amorphous Sb. As a result, the potassiation/depotassiation mechanism of the Sb-based anode can be summarized as the following reactions: Sb + x K+ + x e- ↔ KxSb KxSb + (3-x) K+ + (3-x) e- ↔ K3Sb40,73 The curves of NP-Sb-20 (Figure 3d and S18) and bulk-Sb (Figure S19) anodes for KIBs are tested at 100 mA g-1. More specifically, in first cycle, comparable with 734 mAh g-1 capacity and 70.5 % Coulombic efficiency of the bulk-Sb anode, the NP-Sb-20 electrode achieves 728 mAh g1

specific capacity with 71.0 % Coulombic efficiency. The irreversible capacity may be ascribed

to the SEI formation.11,39,40,65,71,73,74 The profiles of NP-Sb-20 are overlapped comparable to the bulk-Sb, indicating the enhanced cycling performance and reversibility of NP-Sb-20 anode for KIBs. Figure 3e compares the cycling capability of NP-Sb-20 and bulk-Sb anode at 100 mA g-1. The NP-Sb-20 anode achieves a 510 mAh g-1 capacity in second cycle and retains 318 mAh g-1 after 50 cycles (62.35 % capacity retention, relative to the second cycle). In contrast, the specific capacity of bulk-Sb delivers an decrease in the cycling capability test and maintains 19 mAh g-1 (the capacity retention is 3.92 %, relative to the second cycle). In addition, the cycling performance of NP-Sb-80, NP-Sb-60, and NP-Sb-40 are also tested in Figure S20, Figure S21, and Figure S22, respectively. Compared to the bulk-Sb, the NP-Sb-80, NP-Sb-60 and NP-Sb-40 showed improved cycling capability. The rate performance of bulk-Sb and NP-Sb-20 anodes for KIBs is explored in Figure 3f. As illustrated, the NP-Sb-20 persistently precedes the bulk-Sb counterpart. Specifically,


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the average capacities of bulk-Sb are 539, 400, 242, 146, 81, and 30 mAh g-1 at 50, 100, 200, 300, 400, and 500 mA g-1. A 110 mAh g-1 capacity can be achieved while the current density backs to 50 mA g-1. This result reveals inferior rate property of bulk-Sb anode. For the NP-Sb-20 anode, the average specific capacities are 560, 430, 373, 312, and 265 mAh g-1 at current densities of 50, 100, 200, 300, 400, and 500 mA g-1. When current density backs to 50 mA g-1, the 497 mAh g-1 capacity is obtained. The charge/discharge curves of bulk-Sb and NP-Sb-20 anodes at different current densities are also illustrated in Figure S23. This result illustrates the enhanced rate capability of NP-Sb-20 anode for KIBs, which may be ascribed to the structure stability of NP-Sb20. Furthermore, the electrochemical performance of NP-Sb-20 is compared with that of the previously reported anode materials for KIBs, as illustrated in Figure 4.14,18-21,26,29,33,41,55,75-104 The NP-Sb-20 delivers the high reversible capacity among these reported results. Besides, the electrochemical property of NP-Sb-20 as NIBs anode is also measured, as shown in Figure S24. A survey of Sb-based anodes for NIBs is listed in Table S1. As a result, the NP-Sb-20 anode for NIBs exhibits an improved capability. Figure 5 illustrates the schematic of potassiation process for bulk-Sb and NP-Sb. The potassium ion insertion may cause the large volume expansion and crumble the conductive network between Sb particles and current collector in Figure 5a and S25.84 Thus, the NP-Sb with different porosities as active materials is designed. The pores in NP-Sb anode can accommodate huge volume change and efficiently promote the potassium ion transport, providing the improved the capacity retention and rate performance, as illustrated in Figure 5b.84 The volume change of NP-Sb during cycling process is less than that of bulk-Sb, corresponding to the preceding results (Figure 3e) that the cycling capability is NP-Sb-20>bulk-Sb. To further investigate the mechanical stability of NP-Sb20 anode for KIBs, the ex situ TEM and EIS are probed in Figure S26 and S27. For the bulk-Sb


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anode in Figure S26(a), the structure is destroyed, and many Sb particles are aggregated. However, the morphology of NP-Sb-20 in Figure S26(b) retains its original porous structure, indicating that this structure can alleviate Sb nanoparticles aggregation and accommodate huge volume change. The resistance of bulk-Sb anode in Figure S27(c) shows an improvement of 2350 Ω after 1 cycle, 2840 Ω after 5 cycles, 3780 Ω after 10 cycles, 4010 Ω after 20 cycles, and 4720 Ω after 50 cycles. However, the resistance of the NP-Sb-20 anode in Figure S27(d) illustrates a lower change of 770 Ω after 1 cycle, 1250 Ω after 5 cycles, 1640 Ω after 10 cycles, 1980 Ω after 20 cycles, and 2260 Ω after 50 cycles. Thus, the NP-Sb-20 anode for KIBs exhibits an enhanced electrochemical performance due to its porous structure that can facilitate the less-resistance diffusion of potassium ion and accommodate the volume change during cycling process. Conclusion In summary, we have successfully synthesized the nanoporous Sb (NP-Sb) with tunable morphology and porosity using a physical vacuum distillation method, which show an enhanced electrochemical performance as anode for KIBs. In this method, the NP-Sb has been obtained by the evaporation of low boiling point Zn from Zn-Sb alloy precursor, and the zinc by-products can be recycled. By adjusting Zn-Sb alloy composition and distillation temperature, the void structure of NP-Sb can be controlled. The optimized NP-Sb delivers a 560 mAh g-1 capacity at 50 mA g-1 and 265 mAh g-1 capacity at 500 mA g-1. Enhanced electrochemical performance of NP-Sb can be ascribed to the porous structure with interconnected ligaments, which can accommodate huge volume expansion and accelerate the ion transport of NP-Sb anode for KIBs during charge/discharge process. These results illustrate that the vacuum distillation method may achieve production-scale of high-capacity Sb anode for KIBs and other energy storage systems, furnishing a direction to fabricate nanoporous materials.


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Experimental Section Material Synthesis The Zn20Sb80, Zn40Sb60, Zn60Sb40 and Zn80Sb20 alloy powders (99.99 %) were purchased from the Materialsnet Industrial (China). The bulk-Sb powder (99.5 %) was purchased Shanghai Aladdin Industrial Co. Ltd (The XRD and Raman were shown in Figure S15, the SEM was illustrated in Figure S16, the BET was measured in Figure S17). Then, the vacuum distillation operation was manipulated at 400 oC and 500 oC (5 °C min-1) for 2 h in dynamic high vacuum conditions by a pipe furnace (OTF-1200X-S-II, MTI). During the experiment process, the vacuum degree was maintained below 10 Pa or lower. Ultimately, the NP-Sb-80 (from Zn20Sb80), NP-Sb60 (from Zn40Sb60), NP-Sb-40 (from Zn60Sb40), and NP-Sb-20 (from Zn80Sb20) was obtained. Characterization Methods The crystallographic phases, structure, and composition were measured via X-ray diffraction (Rigaku Dmax-rc diffractometer), Raman spectrometer (LabRAM HR800) and X-ray photoelectron spectroscopy (ESCALAB 250). The morphology was delineated by high-resolution transmission electron microscopy (JEM-2100, JEOL) and scanning electron microscopy (Zeiss SUPRA 55). Nitrogen adsorption-desorption isotherms was analyzed by BET theory (ASAP 2020). Electrochemical Measurements The NP-Sb anode was prepared via mixing 0.06 g active material, 0.02 g Super P carbon, and 0.02 g carboxymethyl cellulose (CMC) binder (6:2:2, a weight ratio) to shape a homogeneous slurry stirring at room temperature for 20 h, coating on Cu foil and drying at 100 oC under vacuum condition for 24 h. The mass loading of active materials on anode was 1.5-1.6 mg cm-2. To explore the electrochemical property of NP-Sb, the 2032-coin cells were collected using K foil as reference and counter electrode, NP-Sb anode as working electrode, Whatman GF/C glass fiber as separator,


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the 0.8 M potassium hexafluorophosphate (KFP6) in the diethyl carbonate/ethylene carbonate (DEC/EC, v/v, 1:1) as electrolyte. All cells were assembled in glovebox full of high-purity argon with oxygen and water lower than 1 ppm. Cyclic voltammetry tests were performed form 0.01 V to 1.2 V at 0.05 mV S-1 by CHI 660E electrochemical workstation. Charge/discharge cycles were executed between 0.01 V and 1.2 V at different current densities by galvanostatic programmable battery charger. Electrochemical impedance spectroscopy was checked in a frequency ranging from 0.01 Hz to 100 kHz.


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Figure 1. Schematic of evolution of the different ratio Zn-Sb alloy by vacuum distillation approach. (a) The atom ratio of Zn and Sb is about 1:4. (b) The atom ratio of Zn and Sb is about 4:1. (i) Initially, the Zn-Sb alloy has a uniformly distributed structure. (ii) While the Zn-Sb alloy is distillated at 400 oC, only few Zn atoms are removed and few voids can be formed. (iii) While the distillation temperature reaches to 500 oC, Zn atoms are entirely sublimated, a great deal of voids or vacancies can be produced, and the pure NP-Sb is acquired.


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Figure 2. Morphological and structural characterization of Zn-Sb alloy (Zn:Sb=4:1) via vacuum distillation method at 500 oC. (a, b) TEM images with different magnifications. (c) Corresponding EDX mapping of Sb. (d, e) HRTEM images with different magnifications. (f) XRD pattern. (g) Raman diagram. (h) Nitrogen adsorption-desorption isotherm. (i) Corresponding pore size distribution.


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Figure 3. Electrochemical property of NP-Sb-20 and bulk-Sb anodes for KIBs between 0.01 and 1.2 V. (a) Cyclic voltammetry curves at 0.05 mV s-1 of NP-Sb-20 anode. The ex situ XRD (b) and Raman (c) of the pristine NP-Sb-20, potassiation and depotassiation electrodes. (d) Galvanostatic charge/discharge profiles of NP-Sb-20 anode at 100 mA g-1. (e) Cycling property of NP-Sb-20 and bulk-Sb anodes at 100 mA g-1 (f) Rate capability of bulk-Sb and NP-Sb-20 at different current densities from 50 to 500 mA g-1.


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Figure 4. Comparison with electrochemical property of previously reported anodes for KIBs with our work.


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Figure 5. Schematic of potassiation process for bulk-Sb and NP-Sb anodes. (a) A large volume expansion of bulk-Sb with low electrical conductivity to cause crack and disassembly of electrode. (b) A small volume expansion of NP-Sb with high electrical conductivity to accommodate huge volume expansion and prevent electrode cracks.


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ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI: Detailed experimental methods, additional Raman, XRD, TEM, SEM, BET, EDS and electrochemical capability. AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] (J. K. Feng) ORCID Yongling An: 0000-0002-2666-3051 Yuan Tian: 0000-0003-1242-0216 Lijie Ci: 0000-0002-1759-105X Shenglin Xiong: 0000-0002-8324-4160 Jinkui Feng: 0000-0002-5683-849X Author Contributions J. K. Feng and Y. L. An proposed this work. Y. L. An executed the synthesis, characterization and electrochemical property tests. Y. L. An and Y. Tian wrote this manuscript. J. K. Feng, L. J. Ci, S. L. Xiong and Y. T. Qian further polished the manuscript. ACKNOWLEDGMENT This work was supported by Shandong Provincial Natural Science Foundation (China, ZR2017MB001), Shandong Provincial Science and Technology Key Project (2018GGX104002), Independent Innovation Foundation of Shandong University, The Young Scholars Program of Shandong University (2016WLJH03), The State Key Program of National Natural Science of


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Micron-Sized Nanoporous Antimony with Tunable Porosity for High

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