Revealing Quasi-1D Volume Expansion in Na-/K-Ion Battery Anodes: A Case Study of Sb ₂ O ₃ Microbelts

Abstract

Open AccessCCS ChemistryRESEARCH ARTICLE1 May 2021Revealing Quasi-1D Volume Expansion in Na-/K-Ion Battery Anodes: A Case Study of Sb2O3 Microbelts Zheng Yi†, Daliang Fang†, Wanqun Zhang, Jie Tian, Shimou Chen, Jianbo Liang, Ning Lin and Yitai Qian Zheng Yi† Department of Applied Chemistry, Hefei National Laboratory for Physical Science at Microscale, University of Science and Technology of China, Hefei 230026 , Daliang Fang† Beijing Key Laboratory of Ionic Liquid Clean Process, CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 , Wanqun Zhang Chemistry Experiment Teaching Center, University of Science and Technology of China, Anhuli 230026 , Jie Tian Experimental Center of Engineering and Material Science, University of Science and Technology of China, Hefei 230026 , Shimou Chen *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] Beijing Key Laboratory of Ionic Liquid Clean Process, CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 , Jianbo Liang *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] Department of Chemistry, Capital Normal University, Beijing 100048. , Ning Lin *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] Department of Applied Chemistry, Hefei National Laboratory for Physical Science at Microscale, University of Science and Technology of China, Hefei 230026 and Yitai Qian *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] Department of Applied Chemistry, Hefei National Laboratory for Physical Science at Microscale, University of Science and Technology of China, Hefei 230026 https://doi.org/10.31635/ccschem.020.202000321 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesTrack Citations ShareFacebookTwitterLinked InEmail Tailoring a rational structure to control the huge volume variation is practical in regulating alkali-ion battery performance on the basis of the anisotropic properties of crystallized anode materials. Here, a double-serrated orthorhombic antimony oxide (Sb2O3) microbelt was prepared by a thermally induced recrystallization/sublimation process. In situ transmission electron microscopy (TEM), in situ X-ray powder diffraction (XRD), and ex situ scanning electron microscopy (SEM) measurements demonstrate that Sb2O3 microbelts exhibit a quasi-one-dimensional expansion perpendicular to the belt (along the [100] direction) during sodiation. The unconstrained microbelt surface space can appropriately accommodate the oriented volume variation. Thus, Sb2O3 microbelts exhibit enhanced cycling and rate performance in half-cell sodium-ion batteries samples. Via support of reduced graphene oxide (RGO), Sb2O3@RGO composites deliver good rate capability (312.3 mAh g−1 at 3 A g−1) for sodium-ion full-cell batteries and good cycling performance (473.9 mAh g−1 at 100 mA g−1 after 100 cycles) for half-cell potassium-ion batteries. In situ Raman measurements reveal that the conversion/alloying-type Sb2O3 anode undergoes a fully reversible alloying reaction and partially reversible conversion mechanism, which explains its irreversible capacity during the first cycle. The delicate structural design and clarification of the alkali-ion storage mechanisms facilitate the development of Sb2O3 anodes for energy storage applications. Download figure Download PowerPoint Introduction Sodium-ion batteries (SIBs) have been considered as one of the most promising post-lithium-ion batteries (LIBs).1–6 Due to the inactive nature of graphite for sodium storage, developing high-capacity electrode materials with rational structures is imperative for high-performance SIBs.7,8 Inspired by the high-capacity features of conversion/alloying-type anode materials such as Sn- or Sb-based oxides or sulfides in LIBs, these kinds of anode materials have attracted significant attention for SIBs. Particularly, antimony oxide (Sb2O3) exhibits inherent superiority of high theoretical capacity (1102 mAh g−1) and moderate working potential.9,10 However, high capacity means more sodium-ion storage in the electrode material at the expense of huge volume changes during the sodiation/desodiation process, thus leading to adverse pulverization of the primary structure, and, accordingly, fast capacity fading. 11–13 To circumvent these issues, nanoengineering strategies have proven to be one of the most effective approaches to enhance the sodium-storage performance, such as reducing anode materials to nanoscale, reserving porous voids in active materials, or coating carbonaceous additives and other buffer layers onto the active materials. For instance, by using a colloidal template with large pore interconnects in the three-dimensional (3D) scaffold, a 3D Ni-supported Sb2O3 anode was fabricated for SIBs with a capacity of about 445 mA h g−1 with a capacity retention of 89% after 200 cycles at 200 mA g−1.14 Considering the anisotropy of crystallized anode materials, the volume change during cycling also undergoes anisotropic behaviors. Thus, advanced material designs for sophisticated nanostructures to controllably accommodate volume expansion are relevant and urgent, such as, leaving larger space along the direction of larger expansion. Accordingly, some low-dimensional, crystallized anode materials have been structurally/morphologically optimized, so that the maximum performance, in terms of capacity and stability, was achieved in the alkali-ion battery. For example, Chan et al.15 circumvented the huge volume change of Si by designing one-dimensional (1D) Si nanowires to induce radial volume expansion and accommodate the large strain without pulverization. Few-layer antimonene was reported with anisotropic volume expansion along the a/b plane, which maintained a stable structure. This few-layer antimonene delivered a large capacity of 642 mAh g−1 at 66 mA g−1 and a high rate capability of 429 mAh g−1 at 3.3 A g−1, much higher than the Sb powders.16 Similarly, few-layer bismuthene also showed anisotropic expansion in SIBs applications with high areal capacity.17 The advancement motivated us to tailor an ideal Sb2O3-based anode to manipulate the anisotropic volume variation and promote the sodium-storage performance. In this study, we designed a double-serrated microbelt of orthorhombic Sb2O3 quasi-single-crystals to manipulate the volume change with oriented expansion. Single-crystalline Sb2O3 microbelts (axial direction along [001]) were obtained through solid-state recrystallization and followed by a sublimation-etching procedure by annealing the presynthesized Sb2O3 nanorods. In situ X-ray powder diffraction (XRD), in situ transmission electron microscopy (TEM), and ex situ scanning electron microscopy (SEM) measurements confirmed the anisotropic volume expansion of the as-prepared Sb2O3 microbelts during sodiation. The in/ex situ measurement results suggested that the microbelts have a quasi-1D expansion only perpendicular to the belt (along the [100] direction). As a result, the directionally dependent volume expansion endowed the double-serrated Sb2O3 microbelts with good structural stability and enhanced sodium-storage performance including good rate capability and cycling performance in half/full SIBs and half potassium-ion batteries (PIBs). In addition, in situ Raman measurements revealed that the conversion/alloying-type Sb2O3 anode underwent a fully reversible alloying reaction and partially reversible conversion process, which disclosed the origin of irreversible capacity in the first discharge/charge process. Experimental Section Sample preparation and characterization Sb2O3 microbelts were fabricated by a thermally induced recrystallization/sublimation process. First, the Sb2O3 nanorod precursor was prepared according to a previously reported method,18 as shown in the Supporting Information. Subsequently, the obtained Sb2O3 nanorod precursors were loaded into a silica boat and maintained at 400 °C for 5 h under Ar flow. After cooling to room temperature naturally, Sb2O3 microbelts were produced. In comparison, rod-like Sb2O3 nanorods and octahedral Sb2O3 microstructure were obtained by calcinating the Sb2O3 nanorod precursor at 350 and 500 °C for 5 h in inert atmosphere, respectively. Other detailed synthesis procedures and characterization methods are available in the Supporting Information. Results and Discussion Double-serrated Sb2O3 microbelts were prepared by controllably calcinating presynthesized rod-like Sb2O3 at 400 °C for 5 h. The rod-like Sb2O3 has a diameter of hundreds of nanometers and length of several microns ( Supporting Information Figure S1). The XRD pattern of the as-prepared double-serrated Sb2O3 microbelts is exhibited in Figure 1a, indicating an orthorhombic structure (JCPDS 71-0383). As presented in Figure 1b, the orthorhombic Sb2O3 microbelts consist of infinite chains running parallel to the z-axis. The Sb2O3 microbelts have a width of about 0.8 μm (Figure 1c), thickness of about 0.25 μm ( Supporting Information Figure S2), and belt length of several microns. Figure 1d exhibits the TEM image of the double-serrated Sb2O3 microbelts. It can be seen that both of the sides have formed the well-aligned double-serrated array onto the belt-like body. Compared with the rod-like sample, the formation of the double-serrated morphology has no obvious enhancement of the Brunauer–Emmett–Teller (BET) specific surface area ( Supporting Information Figure S3). The high-resolution TEM (HR-TEM) image (Figure 1e) shows that the lattice fringes can reach to the end of the belt, indicating that the sample is crystalline. The lattice spacing of 1.246 and 0.264 nm was determined to be the (010) and (012) planes of the orthorhombic phase ( Supporting Information Figure S4). Figure 1f is the selected area electron diffraction (SAED) pattern of the double-serrated Sb2O3 microbelts, suggesting the microbelt is quasi-single-crystal in nature.18 The HR-TEM image (Figure 1e) and the SAED pattern(Figure 1f) imply the axis of the microbelts is along the [001] direction, and the sawtooth formed along the [010] direction (inset of Figure 1f). The scanning TEM (STEM) image and energy-dispersive X-ray (EDX) mapping pictures in Figures 1g–1i indicate that both the Sb and O mapping are uniformly distributed on all of the Sb2O3 microbelts. Figure 1 | Structural and morphological features of Sb2O3 microbelts. (a) XRD pattern, (b) schematic crystal structure, (c) SEM image, (d) TEM images, (e) HR-TEM image, (f) SAED pattern, (g) STEM image, and (h and i) EDX mapping of (h) Sb and (i) O elements. Download figure Download PowerPoint To understand the formation procedure, a series of contrast experiments were conducted. The thermogravimetric (TG) curve ( Supporting Information Figure S5a) and in situ optical photographs ( Supporting Information Figure S6) of presynthesized nanorods in the inert atmosphere suggested that the orthorhombic Sb2O3 began to sublimate mildly at 400 °C, according to the thermodynamic equation19: 2 Sb 2 O 3 ( s ) → Sb 4 O 6 ( g ) The XRD patterns ( Supporting Information Figure S5b) imply that the orthorhombic phase was locally transformed into cubic Sb2O3 during longer-time or higher-temperature heating treatments. The effect of temperature on the morphology was also studied. Coupled rod-like morphology was observed at 350 °C ( Supporting Information Figure S7a). Accordingly, it is reasonable to speculate that the adjacent nanorods would couple into crystallographically identical orientations derived by the high surface energy of nanorods during heat treatment.20,21 Regarding the mechanism of the double-serrated framework, the temperature gradient on the surface of the Sb2O3 microbelts at sintering is not identical, which is similar to the crystallization process in solution. The locally overheated parts may be preferentially sublimated and some grooves may be left, thus forming a saw-like structure. Above all, a thermally induced solid-state recrystallization and sublimation-etching process are responsible for the formation of the double-serrated microbelt structure. To directly observe the anisotropic expansion of the Sb2O3 microbelts during the sodiation process, in situ TEM and ex situ SEM measurements were conducted. For the in situ TEM characterization, the nanobattery configuration is schematically presented in Figure 2a. Figure 2b (detailed in Supporting Information Video S1) presents the time-dependent morphological evolution of the Sb2O3 microbelts during the sodiation process. No evident change in the microbelt width could be detected (Figure 2c). Figure 2d shows the SAED pattern after sodiation, in which the d-spacing converted from the rings can be well indexed to the hexagonal Na3Sb, suggesting the electrochemical sodiation of Sb2O3 caused a phase change. The electrochemical sodiation reactions are also demonstrated by the homogeneous distribution of elemental sodium in the microbelt (Figure 2e). Figure 2f shows an SEM image of the Sb2O3 microbelts before sodiation. Belt-like microstructure with dentation on both sides is presented. During step-by-step sodium insertion (Figures 2g and 2h), the belt was gradually swelled along the direction perpendicular to the belt, while the microbelt width and dentation were well maintained, in agreement with the in situ TEM results (Figure 2b). The above in situ TEM and ex situ SEM images reveal that the double-serrated Sb2O3 microbelts undergo anisotropic volume change, which is a quasi-1D expansion along the direction perpendicular to the microbelt surface (along [100] direction). Figure 2 | Structural evolution of Sb2O3 microbelts during the sodium-storage process. (a) Schematic illustration of the nanobattery setup for in situ TEM characterization, (b) time-lapse TEM images and (c) width change of the Sb2O3 microbelts during sodiation. (d) SAED pattern after in situ sodiation. (e) TEM images and EDX mapping for Sb, O, and Na elements after in situ sodiation. (f–h) Ex situ SEM images (f) before sodiation and (g and h) during first sodiation, and (i) average thickness change before and after desodiation (derived from Supporting Information Figure S15). Download figure Download PowerPoint The structural change of a single Sb2O3 nanorod during sodiation is also illustrated by time-dependent TEM images shown in Supporting Information Figure S8. The diameter of the rod before sodiation is about 310 nm, which increased to about 435 nm after sodiation, suggesting obvious volume expansion along the direction of the diameter. Supporting Information Figure S9 shows the size change of the Sb2O3 nanorods upon the sodium insertion process. Evidently, compared with the huge volume expansion of Sb2O3 nanorods ( Supporting Information Figure S9), the width variation of the Sb2O3 microbelts (Figure 2c) is unobvious, because the large lattice spacing of the (010) planes (1.246 nm) of orthorhombic Sb2O3 can accommodate the sodiation-induced volume change along the radial direction of the microbelt. The ex situ SEM images before and after the first discharge process are provided to further observe the width and thickness changes of the microbelts during sodiation. As shown in Supporting Information Figures S10–S12, there is no obvious change in the width of the microbelts, which is in agreement with the in situ TEM measurements (Figure 2c). However, the thickness of the microbelts changed obviously from 251 to 397 nm (Figure 2i and Supporting Information Figures S13–S15), suggesting expansion in this direction, which is also consistent with the in situ TEM images observed along the direction parallel to the belt ( Supporting Information Figure S16). To further confirm the quasi-1D expansion of microbelts, the in situ XRD patterns during the initial sodiation process are provided, as shown in Figure 3a (detailed in Supporting Information Figure S17). As previously reported in literature, when the crystalline material underwent lattice stain, the Bragg angle, that is, the position of the X-ray diffraction peak, can be changed. To determine the lattice strains, the diffraction peak shifts could be measured, which represent an average value in a given direction.22–24 For the Sb2O3 microbelts during sodiation, the conversion reaction process leads to volume expansion, thus resulting in increased lattice strains in the microbelts, which may cause X-ray diffraction peak shifting in the expansion direction. From Figure 3a, it can be seen that there is no peak shift in the (040) lattice plane, but there is an obvious shift in the (200) lattice plane. This phenomenon further suggests the expansion-induced lattice strains along the [100] direction and implies the volume expansion of the Sb2O3 microbelts along the direction perpendicular to the belt. Figure 3 | (a) In situ XRD pattern evolution of the (040) and (200) lattice planes of the Sb2O3 microbelts during the initial sodiation stage. It is noted that the peak at ∼28.5° is assigned to the window (detailed in Supporting Information Figure S17). (b) Schematic illustration of the volume expansion of the double-serrated Sb2O3 microbelts. (c) Stereoscopic view of the Sb2O3 microbelts. Download figure Download PowerPoint Overall, the sodium insertion of Sb2O3 microbelts exhibited an anisotropic volume variation, as schematically illustrated in Figure 3b. The well-demonstrated quasi-1D expansion perpendicular to the belt can be accommodated because of the large double-surface space of the microbelt, that is, the oriented expansion is unconstrained. Meanwhile, volume expansion of microbelts along the [010] direction can be accommodated by the large lattice spacing of (010) planes (1.246 nm), as stereoscopically viewed in Figure 3c. The anisotropic volume change of the Sb2O3 microbelts motivated us to study the relationship between the anisotropic volume change and sodium-storage performance. Figure 4 and Supporting Information Figure S18 and S19 show the sodium-storage properties of the Sb2O3 microbelts. The cyclic voltammetric (CV) curves were obtained at a scan rate of 0.1 mV s−1 (Figure 4a). A reduction peak located at 0.35 V during the first cycle may be assigned to the conversion reaction of Sb2O3 and formation of the solid electrolyte interface (SEI) layer.25,26 In the following cycles, the reduction peaks located at 0.7 and 0.42 V, and the oxidation peaks at 0.72 and 1.52 V can be attributed to the related conversion and alloying reaction, respectively. The detailed sodium-storage mechanism was also explored by in situ Raman spectrum, detailed in subsequent discussion. The first and second discharge capacities of the Sb2O3 microbelts are 762.3 and 495.6 mAh g−1, respectively (Figure 4b). At current densities of 50 mA g−1, the discharge capacities of the Sb2O3 microbelts were maintained at 470 mAh g−1 after 50 cycles. In contrast, the rod-like sample showed poor capacity retention with capacities of only 368 mAh g−1. Figure 4 | Sodium-storage performance in the half and full cell. (a) CV curves at a scan rate of 0.1 mV s−1, (b) comparison of galvanostatic cycling performance of Sb2O3 microbelts and rods. Rate capability of the Sb2O3@RGO (c) at current densities from 0.05 to 5 A g−1, and (d) at 1 A g−1. (e–h) Full-cell performance of the Sb2O3@RGO: (e) typical charge/discharge curves of the Na3V2(PO4)3@C/Sb2O3@RGO full cell at 0.5 A g−1, (f) rate capability at current density from 0.2 to 3 A g−1, (g) cycling performance at 0.5 A g−1, and (h) comparison of the rate capability with the reported Sb-based references. Download figure Download PowerPoint To further improve the conductivity and rate performance, we also fabricated the reduced graphene oxide (RGO)-supported Sb2O3 microbelts (Sb2O3@RGO) with 15 wt% of RGO, as shown in Supporting Information Figures S20–S22. Figure 4c and Supporting Information Figure S23 exhibit the rate capability of the Sb2O3@RGO with increasing current densities from 50 to 5000 mA g−1. Due to the enhanced conductivity, the capacity of the Sb2O3@RGO was increased in comparison with the pure double-serrated Sb2O3 microbelts. At a current density of 50 mA g−1, the Sb2O3@RGO could deliver an average reversible capacity of 584 mAh g−1. The capacity of 316.6 and 219.4 mAh g−1 was maintained even at 2000 and 5000 mA g−1, respectively. Furthermore, at a higher current density of 1000 mA g−1 (Figure 4d), a capacity of 388.5 mAh g−1 was maintained over 200 cycles. Compared with the pure Sb2O3 microbelts, the enhanced rate capability and cycling stability of the Sb2O3@RGO composite could be attributed to the good flexibility and buffering effect of RGO ( Supporting Information Figure S24). Good full-cell performance of the Sb2O3@RGO is expected based on its good electrochemical performance in the half cell. A home-made Na3V2(PO4)3@C was employed as the cathode, which delivered a reversible capacity of 96 mAh g−1 with good cycling stability ( Supporting Information Figure S25). The typical charge/discharge curves of the Na3V2(PO4)3@C/Sb2O3@RGO full cell are illustrated in Figure 4e and Supporting Information Figure S26. It can be seen that the medium voltage of the full cell is 2.4 V in discharge and 2.8 V in charge. The difference between the initial charge curve and those of subsequent cycles may be attributed to the irreversible capacity loss or unreasonable capacity ratio of the electrodes during the first charging.27 The rate capability of the full cell is presented in Figure A reversible discharge capacity of mAh g−1 can be obtained at 200 mA g−1 based on the of the at current densities of and mA g−1, the full cell could also capacities of and mAh g−1, respectively. at a current density of 500 mA g−1, the full cell could deliver a reversible capacity of mAh g−1 after 50 cycles (Figure As exhibited in Figure in comparison with the previously reported Sb-based full the rate capability of the Na3V2(PO4)3@C/Sb2O3@RGO is For the full cell based on the of the anode and materials, a practical energy density of and density of was Furthermore, with increasing current the medium voltage has no obvious suggesting good rate capability ( Supporting Information Figure The sodium-storage mechanisms of the double-serrated Sb2O3 microbelts were The in situ XRD patterns ( Supporting Information Figure show that the peaks of the Sb2O3 microbelts located at of and gradually and during the first discharge process, the sodiation of However, no crystallized phase was during subsequent sodiation/desodiation cycles, which that the sodiation of the double-serrated Sb2O3 microbelts were or of crystal To further the sodium-storage mechanism, the in situ Raman was as shown in Figure at and were indexed to the with the first these peaks gradually and a between and This is assigned to the of Sb and suggesting that Sb2O3 was partially transformed to Subsequently, this peak step-by-step and a peak at which implies the conversion of Sb2O3 to Sb and The peak is by a peak at at the end of the first This peak is indexed to the suggesting the alloying reaction between Sb and During the process, the peak at at the and a peak at is which is attributed to the of to the peak is by a peak between and after the first process, indicating that Sb has been transformed into the However, no peaks are well indexed to pure that the electrochemical conversion reaction from Sb to Sb2O3 is partially The HR-TEM and SAED images ( Supporting Information Figure of the Sb2O3 after to V further reveal that the reaction from Sb to Sb2O3 is not fully The mechanism for the partially reversible conversion reaction may be attributed to the of Sb in the which conversion of into Sb2O3 during sodium the second discharge/charge process is similar to that of the first cycle. Sb 2 O 3 6 Na 6 → 3 Na 2 O 2 Sb ( partially reversible ) Sb 3 Na 3 → Na 3 Sb ( reversible ) Na 3 Sb → Sb 3 Na 3 ( reversible ) 3 Na 2 O 2 Sb → Sb 2 O 3 6 Na 6 ( partially reversible ) Figure 5 | (a) Sodium-storage mechanism of the double-serrated Sb2O3 microbelts microstructure by in situ Raman (b) Schematic illustration of the sodium-storage mechanism of the double-serrated Sb2O3 microbelts. Download figure Download PowerPoint The in situ Raman exhibited the sodium-storage mechanism of double-serrated Sb2O3 microbelts, as schematically illustrated in Figure and the sodium-storage mechanisms of double-serrated Sb2O3 microbelts a sodiation/desodiation process, including a partially reversible conversion reaction and reversible process. The partially reversible conversion process is partially responsible for the initial Sb-based anode materials have attracted for Here, the performance of the Sb2O3@RGO was also Supporting Information Figures and show the CV and charge/discharge As the mechanism of the double-serrated Sb2O3 microbelts is also a process, similar to that in SIBs. A capacity of mAh g−1 at 100 mA g−1 after 100 cycles was maintained ( Supporting Information Figure At current densities of and 2 A g−1, the composite capacities of and 200 mAh g−1, respectively ( Supporting Information Figure The capacity can be appropriately after suggesting good The ex situ XRD and Raman were provided to the mechanism of the as shown in Supporting Information Figure Double-serrated Sb2O3 microbelts have been fabricated by annealing presynthesized Sb2O3 nanorods with a thermally induced recrystallization/sublimation process. in situ including and Raman were to understand the anisotropic volume variation and electrochemical reaction It was demonstrated that Sb2O3 microbelts have a quasi-1D expansion perpendicular to the belt (along [100] direction) during sodiation, and, structural During the discharge/charge process, conversion/alloying-type Sb2O3 underwent a fully reversible alloying reaction and partially reversible conversion mechanism, leading to irreversible capacity during the first electrochemical measurements indicate that Sb2O3 microbelts showed sodium-storage performance in half/full than that of the Sb2O3 nanorods. In addition, the performance of the Sb2O3 microbelts was also The delicate structural design and clarification of the electrochemical mechanisms facilitate the development of Sb2O3 anodes for practical which can also to design other electrode materials with morphology and performance. 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