Liubin Ben, Jin Zhou, Hongxiang Ji, Hailong Yu, Wenwu Zhao, Xuejie Huang. Si nanoparticles seeded in carbon-coated Sn nanowires as an anode for high-energy and high-rate lithium-ion batteries[J]. Materials Futures, 2022, 1(1): 015101. DOI: 10.1088/2752-5724/ac3257
Citation:
Liubin Ben, Jin Zhou, Hongxiang Ji, Hailong Yu, Wenwu Zhao, Xuejie Huang. Si nanoparticles seeded in carbon-coated Sn nanowires as an anode for high-energy and high-rate lithium-ion batteries[J]. Materials Futures, 2022, 1(1): 015101. DOI: 10.1088/2752-5724/ac3257
Liubin Ben, Jin Zhou, Hongxiang Ji, Hailong Yu, Wenwu Zhao, Xuejie Huang. Si nanoparticles seeded in carbon-coated Sn nanowires as an anode for high-energy and high-rate lithium-ion batteries[J]. Materials Futures, 2022, 1(1): 015101. DOI: 10.1088/2752-5724/ac3257
Citation:
Liubin Ben, Jin Zhou, Hongxiang Ji, Hailong Yu, Wenwu Zhao, Xuejie Huang. Si nanoparticles seeded in carbon-coated Sn nanowires as an anode for high-energy and high-rate lithium-ion batteries[J]. Materials Futures, 2022, 1(1): 015101. DOI: 10.1088/2752-5724/ac3257
Songshan Lake Materials Laboratory, Dongguan 523808, Guangdong Province, People’s Republic of China
2.
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China
3.
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of China
High-capacity and high-rate anode materials are desperately desired for applications in the next generation lithium-ion batteries. Here, we report preparation of an anode showing a structure of Si nanoparticles wrapped inside Sn nanowires. This anode inherits the advantages of both Si and Sn, endowing lithiation/delithiation of Si nanoparticles inside the conducting networks of Sn nanowires. It demonstrates a high and reversible capacity of 1500 mAh g-1 over 300 cycles at 0.2 C and a good rate capability (0.2 C-5 C) equivalent to Sn. The excellent cycling performance is attributed to the novel structure of the anode as well as the strong mechanical strength of the nanowires which is directly confirmed by in-situ lithiation and bending experiments.
Rechargeable lithium-ion batteries (LIBs) have developed significantly over the past two decades for the applications in portable electronics and electric vehicles [1-3]. For the anode of LIBs, due to the outstanding cycling performance of graphite, it was the earliest candidate and is still the most commonly candidate in today’s commercial LIBs [4]. However, graphite anodes are becoming extremely problematic to meet the demands of next-generation LIBs due to its relatively low capacity of 372 mAh g-1 as well as poor rate capability. Recently, lithium-alloys with high capacity have attracted considerable attention for applications in next-generation LIBs [5-13]. Alloys involving Si and Sn are particularly interesting for the applications of anode materials due to their superior theoretical specific capacities of 4200 mAh g-1 [14, 15] and 990 mAh g-1 [16-19], respectively, calculated from the ultimately lithiated products. Nevertheless, the alloying of both Li4.4Si and Li4.4Sn results in drastic volume expansion of approximately 300%, leading to the fracture and pulverization of the electrode, an unstable solid electrolyte interface. Furthermore, the expansion will cause disconnection between anode components, and consequently, poor electrochemical performance [20-23].
To overcome the above problems such anode materials, many works have been undertaken, focusing on constructing Sn and Si anode materials with various morphologies to tolerate this volume change. Si nanoparticles (NPs) [24, 25], nanowires (NWs) [15], and thin films [26] have been prepared and results showed considerably enhanced electrochemical performance. Similar morphologies have also been produced for Sn anode materials [17, 27-30]. Unfortunately, Si or Sn have not yet been successfully commercialized due to their limitations. Though the theoretical capacity of Si is high, it shows a poor electrical conduction with a value of only 10-3 S cm-1 [31]. Previous works also showed that the lithium diffusion of Si is many orders lower than that of Sn [32]. Although carbon coating may alleviate the conduction issues of Si to some extent, it can lead to many drawbacks, such as reduced specific capacity and lower columbic efficiency [33, 34]. In contrast, both electronic [35] and ionic conductivities of Sn are high [36], but its specific capacity is only 990 mAh g-1. Investigations on composite anodes have demonstrated interesting electrochemical and structural information; however, the cycling performance has only been marginally improved.
In this work, we designed an anode showing Si NPs (30 nm) are wrapped (seeded) inside the NWs of Sn (SiNPs-in-SnNWs), which inherits the capacity advantage of Si and the conductivity advantage of Sn. The synthesis of the anode was via a facile method similar to that reported previously [37, 38], The theoretical capacity is 1608 mAh g-1, based on the starting material with a mole ratio of Si:Sn = 1:1. Electrochemical performance the anode exhibited a high and stable capacity and a good rate capability. A combination of characterization techniques directly explained the excellent capacity retention and rate capability of the anode material.
2.
Methods
2.1
Materials synthesis
The anode consists of Si NPs wrapped inside Sn NWs (SiNPs-in-SnNWs) was prepared by heat-treated of mixed Si (30 nm) and SnO2 (200 nm) powders. The mole ratio of the Si and SnO2 mixture was 1:1. The mixture was placed in a quartz boat in the center of a tube furnace for heat-treatment at 700 C for 2 h. A mixture gas of C2H2/Ar was flowing into the furnace. At high temperature, SnO2 NPs were reduced to Sn NPs, which further changed into NWs. After the heat-treatment, a black powder was obtained. In addition, for comparison, SiNPs and SnNWs were also prepared with the similar conditions.
2.2
Materials characterization
The morphology was investigated by a scanning electron microscope (SEM, Hitachi S-4800), combined with a focused ion beam (FIB). A Bruker D8 Advance x-ray diffractometer with Cu K radiation ( = 1.5405 ) was used to collect ex-situ x-ray diffraction (XRD) patterns. The scan range for the XRD analysis was 10-80 for all the samples. In situ XRD analysis upon galvanostatic cycling was also carried out using a self-designed in situ cell. After resting, the cell was galvanostatically cycled at a current rate of C/15 between 2 and 0.005 V with a constant voltage step at the lower cut-off voltage. In situ lithiation under scanning transmission electron microscope (STEM) was performed by constructing a NW of SiNP-in-SiNWs as the anode, and the counter electrode was a bulk of Li metal under a JEM-ARM 200F transmission electron microscope operated at 200 kV. The solid electrolyte was unavoidable surface oxidation on the Li metal. A constant voltage (-2 V) was applied through an external source meter. The lithiation process started instantaneously once the contact was established between the SiNPs-in-SnNWs and the Li electrode. The process stopped until no significant changes of the morphology of the NW were observed. In situ bending experiment under STEM was performed by pressing the above NW of SiNPs-in-SnNWs with the bulk of the Li metal.
2.3
Electrochemical cycling
The anode slurry was obtained by mixing the SiNPs-in-SnNWs powders with sodium alginate and carbon black (weight ratio 8:1:1). The slurry was then spread on a copper foil, followed by drying in a vacuum oven for 12 h at 110 C. The half-cell was prepared in a 2032-type coin-cell in a Ar-filled glovebox. The counter electrode was Li metal and the separator was Celgard 2250. A 1.0 M LiPF6 in a 1:1 (volume ratio) of DEC: EC was used as the electrolyte, with 2 mol% FEC as electrolyte additive. The galvanostatic cycling was performed on a LANHE CT2001A battery tester. The cut-off voltage was 0.8-0.005 V (vs. Li/Li+). The theoretical capacity of the SiNPs-in-SnNWs is 1608 mAh g-1, calculated from the initial Si/Sn mixture (mole ratio of 1:1). For each half-cell, the loading level was 10 mg cm-2. For comparison with the SiNPs-in-SnNWs electrode, separate electrodes of SiNPs and SnNWs were also prepared.
3.
Results
3.1
Morphology, structure, and formation mechanism of SiNPs-in-SnNWs
The anode was prepared using a mixed nano-sized Si (30 nm in diameter, figure 1(a1)) and nano-sized SnO2 (200 nm, figure 1(a2)) particles in flowing C2H2/Ar gas at 700 C. The XRD patterns of the Si and SiO2 starting materials are shown in figure S1 (available online at stacks.iop.org/MF/1/015101/mmedia). After the heat-treatment, large agglomerates of NWs with a length of 1-2 m (60 nm in diameter) were obtained, and are seen in figures 1(a3)-(a4). Further investigation was performed by cutting the agglomerates of NWs with a FIB. A typical cross-sectional SEM image of the cut agglomerate, shown in figure S2, demonstrates a 3D structure consisting of a significant number of voids between the NWs. STEM, figures 1(b1) and (b2), combined with energy dispersive spectroscopy (EDS), elemental mapping of the NWs clearly shows the presence of silicon, tin, and carbon, figures 1(b3)-(b5).
Figure
1.
A typical SEM image of (a1) Si and (a2) SnO2 NPs and (a3), (a4) SiNPs-in-SnNWs anode. (b1), (b2) STEM-BF images of SiNPs-in-SnNWs with the green bean shaped NWs and associated EDS mapping of (b3) C, (b4) Sn, and (b5) Si. (c) Schematic showing the formation of Si NPs seeded in Sn NWs with green bean shaped NWs and Sn NWs with straight shaped NWs. (d1) and (d2) STEM-BF images of SnNWs with straight shaped NWs.
The formation mechanism of the NWs is a vapor-solid reaction growth as described in the literature [39, 40]. Sn atoms in SnO2 are initially reduced from the oxidation state +2 to 0 in the flowing C2H2/Ar atmosphere. These unstable Sn atoms may aggregate into more stable nanosized Sn clusters. At the reaction temperature 700 C, many of the Sn nanoclusters should be in the liquid state. They could diffuse on the surface, coalesce with each other, and grow anisotropically into wires. With the presence of solid-state Si NPs whose melting temperate is 1410 C, liquid-state Sn nanoclusters grow on solid-state Si NPs to form green bean’ shaped NWs. In contrast, without the presence of Si NPs, only Sn NWs are obtained with relatively straight shape. Schematic of the formation of Si NPs seeded in Sn NWs with green bean shaped NWs and Sn NWs with straight shaped NWs is shown in figure 1(c). For comparison, STEM images of the Sn NWs prepared in a manner similar to SiNPs-in-SnNWs in also shown in figures 1(d1), (d2) and EDS elemental mapping is shown in supporting information figure S3.
The Rietveld refinement of the XRDs of the SiNPs-in-SnNWs anode confirms that they are indeed a mixture of Sn (space group I41/amd) [41] with a small amount of Si (space group Fd-3m) [42], figure S4. There is no evidence of the presence of SnO or SnO2. Reflections associated with carbon are not observed, likely attributed to its limited amount or amorphous nature. The mole ratio of Si and Sn calculated from the Rietveld refinement method is generally agreed with ICP measurements (table S1) and the initial starting materials. TG analysis revealed that the amount of carbon is 7.0 wt%, figure S5. The amounts of carbon detected by ICP is 7.2 wt%, similar to that of TG analysis. Furthermore, the oxygen concentration in all the anode materials is minimal. XPS analysis also confirms the presence of mainly Sn and limited oxygen in the anode, figure S6.
3.2
STEM analysis of SiNPs-in-SnNWs
By employing a Cs-corrected STEM, the structured anode with SiNPs seeded in the SnNWs is directly revealed for the first time. A typical STEM-HAADF image of the NW is shown in figure 2(a1). EELS mapping of carbon in the SiNPs-in-SnNWs anode clearly shows surface coverage by a 12 nm layer of carbon after the heat-treatment, figure 2(a2). The presence of oxygen is minimal, according to the EELS mapping analysis. The enlarged STEM images of the surface regions of the NWs in figures 2(b1) and (b2), clearly demonstrate an arrangement of atoms analogous with that of Sn (I41/amd) viewed in the [1 -1 1] crystallographic direction. Fast Fourier transforms (FFTs) of the surface region (inlaid in panel b1) and simulated reflections (figures S7(a1)-(a3)), further confirm the reflections of the surface region to agree with a tetragonal structure. The detailed index of FFTs is shown in figure S7. In contrast, when appropriately tilted, the central region of the NW shows a layered-like arrangement of atoms with an interlayer distance of 3.09 , figures 2(c1) and (c2), in agreement with the Si (Fd-3m) viewed along the [0 -1 1] direction. FFTs of the center region (inlaid in panel c1) and simulated reflections (figures S7(b1)-(b3)), respectively, further confirm the reflections of this region to be associated with the cubic structure. The above analysis of STEM-HAADF images and STEM-EDS mapping confirms that the SnO2 NPs are converted to the SnNWs with SiNPs seeded in the latter after the heat-treatment.
Figure
2.
(a1) A low-magnification STEM-HAADF image of a part of NW of the SiNPs-in-SnNWs anode and (a2) corresponding EELS mapping of elemental carbon. (b1) and (b2) Enlarged surface regions of panel a1. (c1) and (c2) Enlarged centre regions of panel a1. FFTs corresponding to the surface (I41/amd) and center (Fd-3m) regions are inlaid in panels b2 and c2, respectively. The detailed index of FFTs is shown in supporting information figure S7.
The SiNPs-in-SnNWs anode naturally inherits the advantages of Si and Sn. Meanwhile, the presence of voids between the carbon-coated NWs can reduce the volume expansion during lithium insertion, guaranteeing excellent capacity retention. Figure 3 shows the cycling of the SiNPs-in-SnNWs half-cell at 0.2 C, along with that of SiNPs and SnNWs half-cells for comparison. For SiNPs half-cell, although its initial discharge capacity is high (3259 mAh g-1), which quickly decreases with cycling (figures 3(a1), (b1)), and it is only 500 mAh g-1 after the 300th cycle. The Sn NWs half-cell shows a stable and reversible discharge capacity of only 600 mAh g-1, though its capacity retention is 84.6% after the 300th cycle (figures 3(a2) and (b2)). In contrast, the SiNPs-in-SnNWs half-cell exhibits an first cycle discharge capacity of 2036 mAh g-1, a charge capacity of 1488 mAh g-1, and a coulombic efficiency of 73.1%, figure 3(a3). The coulombic efficiency increases to 96.3% (2nd cycle) after the initial cycle and remains 99.0%. The capacity retention is 81.8% after the 300th cycle, figure 3(b3).
Figure
3.
Electrochemical performance of SiNPs, SnNWs, and SiNPs-in-SnNWs half-cells. Charge-discharge curves (at 0.2 C) in the 1st and 2nd cycles for (a1)-(a3) SiNPs, SnNWs, and SiNPs-in-SnNWs half-cells. Capacity retention and coulombic efficiency over 300 cycles (at 0.2 C) at room temperature for (b1)-(b3) SiNPs, SnNWs, and SiNPs-in-SnNWs half-cells, respectively. Rate capability (0.2 C-5 C) for (c1)-(c3) SiNPs, SnNWs half-cells and SiNPs-in-SnNWs, respectively.
A major issue for an anode of high capacity, primarily of Si, is the poor electrical conductivity resulting in poor rate capability at high current densities, making them unfavorable for LIBs [6, 43]. This could be solved entirely in the SiNPs-in-SnNWs anode where SiNPs are seeded in SnNWs of fast electronic and ionic conduction. For a conventional SiNP half-cell, the capacity decreases quickly to 19.8% from 0.2 C to 5 C, figure 3(c1). In contrast, the capacity remains 69.3% for SiNPs-in-SnNWs half-cell (figure 3(c3)), which is equivalent to that of SnNWs half-cell of 72.5% at 5 C (figure 3(c2)). The improved rate capability of the SiNPs-in-SnNWs anode is attributed to the increased electrical conduction and is confirmed by electrochemical impedance spectroscopy of the half-cell, as shown in figure S8.
3.4
dQ/dV analysis
The lithiation and delithiation of Si and Sn in the SiNPs-in-SnNWs anode can be further understood via combined dQ/dV and in-situ XRD investigations. The dQ/dV of the charge-discharge process (1st and 2nd) of SiNPs-in-SnNWs half-cell is shown in figure 4, along with SiNPs and SnNWs half-cells for comparison. In general, the dQ/dV (after the 1st cycle) of SiNPs-in-SnNWs half-cell (figure 4(a3)) is a mixture that of SiNPs (figure 4(a1)) and SnNWs (figure 4(a2)). Reduction peaks at 0.10 and 0.25 V and Sn 0.40, 0.52, and 0.64 V are associated with lithiation of Si and Sn, respectively. Oxidation peaks at 0.30 and 0.45 V and 0.60, 0.72 and 0.78 V are associated with associated with delithiation of LixSi and LixSn, respectively [9, 10, 44].
Figure
4.
The first and second dQ/dV curves for (a1) SiNPs, (a2) SnNWs and (a3) SiNPs-in-SnNWs. dQ/dV curves of the SiNP-in-SnNWs half-cell during (b1) 2nd charge and (b2) 3rd-20th charge cycles. -dQ/dV curves of the SiNP-in-SnNWs half-cell during (c1) 2nd discharge and (c2) 3rd-20th discharge cycles.
The dQ/dV curves as a function of voltage of the SiNP-in-SnNWs half-cell during prolonged charge and discharge cycles are separated into the dQ/dV curves during the charge cycle and -dQ/dV curves during the discharge cycle. Note the dQ/dV curves during the discharge cycle are plotted as -dQ/dV for better observation purpose. An example of the separation of the dQ/dV curves of the second charge-discharge cycle is shown in figures 4(b1), and (c1). The dQ/dV curves during the third to the twentieth charge cycles (figures 4(b1) and (b2)) and -dQ/dV curves during the second to the twentieth discharge cycles (figures 4(c1) and (c2)) clearly demonstrate stable peaks associated with lithiation and delithiation of Si and Sn, respectively.
3.5
In-situ XRD analysis
The lithiation and delithiation of Si and Sn in the SiNPs-in-SnNWs anode was investigated by in-situ XRD, figure 5. The C-rate during the experiment was 0.05 C. Successive XRD scans (140 scans for the first discharge, 112 scans for the first charge) were collected (figure 5(a1)), which were converted into an isoplot for the purpose clearer presentation (figure 5(a2)). The detailed peak intensity associated with voltage is also shown in figures 5(b1)-(b4) and (c).
Figure
5.
(a1) In-situ XRD scans (140 scans for the first discharging cycle, 112 scans for the first charging cycle and 130 scans for the second discharging cycle) collected, (a2) an isoplot converted from the collected XRD scans. Charge-discharge curves in the first-charge, first discharge and second charge cycle for the in-situ XRD experiment is also shown. The maximum peak intensity extracted from the in-situ XRD patterns for the (b1) Sn (002), (b2) Li2Sn5 (001), (b3) LiSn (010), (b4) Li22Sn5 (066) and (c) Si (111) peaks. Charge discharge curves in the first cycle are shown in (d). The dashed line across panels d indicates the start of the decrease in the Si (111) peak intensity. The unit a.u. in the panel is the abbreviation of arbitrary unit.
In general, the results show that the lithiation of the SiNPs-in-SnNWs initially follows the formation of discrete Li-Sn phases, i.e. Li2Sn5, -LiSn, and Li22Sn5 [42, 45], followed by the formation of Li-Si phases [41, 46], which generally correlates with the dQ/dV curves. Briefly, upon discharge, a drastic decrease in intensity of the Sn peaks (e.g. 200, 101) is observed immediately upon the first discharge, figures 5(a2) and (b1). When the voltage is below 0.35 V, the Sn peaks become invisible. As the discharging proceeds, peaks (e.g. 001) associated with a Li2Sn5 phase start to appear, figures 5(a2) and (b2), and when the voltage is <0.29 V, peaks (e.g. 010) associated with a -LiSn phase are observed, figures 5(a2) and (b3). On further discharging the half-cell to <0.27 V, peaks (e.g. 066) of a Li22Sn5 phase appear and grow in intensity, figures 5(a2) and (b4) [45]. During the remainder of the discharge (0.27-0.005 V), these peaks maintain their intensity, and no peaks associated with other phases are observed. The formation of Li-Si phases during discharge is generally similar to that reported previously [45]. The peak intensity associated with Si (111) remains constant until the voltage approaches 0.21 V, at which point Sn is lithiated to Li22Sn5, figures 5(a2) and (c), which is also in agreement with previous works [41, 46].
The results suggest that the lithiation and delithiaton of Sn reaction occurs before that of Si. The formed Li-Sn phases act as a nano-size conducting network for a further Li-Si lithiation and delithiation, resulting in improved rate capabilities in the SiNPs-in-SnNWs anode, explaining the electrochemical results observed above.
The phase change behavior of the SiNPs-in-SnNWs during the first charge is generally in the reverse order of that observed in the first discharge with slight variations. It shows that immediately upon charging, no significant change in the peaks was observed before the voltage reached >0.50 V, at which point peaks of Li22Sn5 (e.g. 660) shifted to a lower angle, figures 5(a2) and (b4). Such shifting was not observed during the first discharge. This may be associated with the phase transformation of Li22Sn to Li17Sn, before transforming into LiSn. Further increasing the voltage to >0.60 V, the shifted peaks diminished, and the peaks of LiSn became detectable, figures 5(a2) and (b3). Upon voltage >0.62 V, peaks from both Li22Sn5 and LiSn were no longer detected. The formation of the Li2Sn5 during the first charge was first detected >0.61 V and faded away until completely it disappeared at 0.72 V, figures 5(a2) and (b2). Peaks from a Sn phase were first observed when the voltage was >0.68 V and grew until the end of charging, as shown in figures 5(a2) and (b1).
The amorphization of Si occurs irreversibly in the first discharge cycle, resulting in absence of the Si (1 1 1) peak in the following cycles [9, 44]. However, as shown in figure 4, the dQ/dV curves clearly demonstrate the stable lithiation and delithiation of SiNPs inside the SnNWs after the first charge-discharge cycle.
3.6
Mechanical stability analysis
The SiNPs-in-SnNWs anode exhibits excellent morphology without showing strong evidence of fracture or pulverization after 100th cycle at RT (0.2 C), figures 6(a1) and (a2). This behavior is attributed to the unique structure of SiNPs seeded in SnNWs as explained above and the good mechanical strength of the NWs themselves [15, 47]. The latter is further confirmed via an in-situ lithiation and bending experiment under STEM. A sequence of STEM images of a typical NW undergoing continuous lithiation is shown in figures 6(c1)-(c3). The images were captured at time intervals of approximately one second and the experiment stopped until no significant changes of the morphology. The in-situ lithiation shows that the initial thickness of the NW is 54.8 nm in width (figure 6(c1)), which expands immediately to 55.8 nm after lithiation (after 1 s, figure 6(c2)). The final stable width of the NW reaches 57.6 nm (after 15 s, figure 6(c3)), indicating an expansion of the NW of only 46.9%. The video for the in-situ lithiation is supplied as supporting information V1.
Figure
6.
(a1) and (a2) A SEM image of the SiNPs-in-SnNWs anode after the 100th cycle. (c1)-(c3) a series of low-magnification STEM images of a continuous lithiation process of a single NW of SiNPs-in-SnNWs anode material. The total lithiation time is 15 s. (d1) and (d2) a series of low-magnification STEM images of a continuous bending and recovery process of a single NW of SiNPs-in-SnNWs anode after lithiation. The bending time is 4 s and the recovery time is 3 s. (d3) schematic shows the calculation of the bending strain.
The NW was further stressed after lithiation by applying stress to the above lithiated NW using a Li2O tip. A sequence of STEM images of a typical NW undergoing a continuous stress process after lithiation is shown in figures 6(d1) and (d2) (video supplied as supporting information V2). The bending strain of the NW was calculated according to the traditional formula bent = r/(r + R)% [48], where R is the bending curvature, r is the radius of the NW, and bent is the largest bending strain (figure 6(d3)). The strain in the NW increases to approximately 21.8% (figure 6(d1)), with a strain rate of approximately 5.5 s-1 (after 4 s). The NW completely recovers to its original morphology without showing any fracture when the stress is removed (figure 6(d2)), with a remarkably high strain rate of 7.3 s-1 (after 3 s) The observations are direct evidence responsible for the excellent cycling performance of the anode.
4.
Conclusion
In summary, the excellent electrochemical cycling performance of the anode is attributed to the novel structure consisting of SiNPs seeded in SnNWs. This anode has the advantages of the high specific capacity of Si and the high electrical conductivity of Sn. The SnNWs provide shorter lithium-ion diffusion distances due to their narrow diameter and long continuous paths for electron transport down their length, resulting in improved rate capability. The SnNWs also endow lithiation/delithiation of SiNPs in the conducting networks of SnNWs, solving the poor conduction issue of Si during cycling. The strong mechanical strength of the NWs and the structure with a highly porous architecture allows volume variation, leading to significantly improved capacity retention after prolonged cycling.
Acknowledgments
This work was supported by the Key Research and Development Program of Guangdong Province, China (2019B121204002). Liubin Ben and Zhou Jin contributed equally to this work.
Tarascon J M, Armand M 2001 Issues and challenges facing rechargeable lithium batteries Nature414 359-67 DOI: 10.1038/35104644
[2]
Armand M, Tarascon J M 2008 Building better batteries Nature451 652-7 DOI: 10.1038/451652a
[3]
Goodenough J B, Kim Y 2010 Challenges for rechargeable Li batteries Chem. Mater.22 587-603 DOI: 10.1021/cm901452z
[4]
Aurbach D, Markovsky B, Weissman I, Levi E, Ein-Eli Y 1999 On the correlation between surface chemistry and performance of graphite negative electrodes for Li ion batteries Electrochim. Acta45 67-86 DOI: 10.1016/S0013-4686(99)00194-2
[5]
Idota Y, Kubota T, Matsufuji A, Maekawa Y, Miyasaka T 1997 Tin-based amorphous oxide: a high-capacity lithium-ion-storage material Science276 1395-7 DOI: 10.1126/science.276.5317.1395
[6]
Li H, Huang X, Chen L, Zhou G, Zhang Z, Yu D, Mo Y J, Pei N 2000 The crystal structural evolution of nano-Si anode caused by lithium insertion and extraction at room temperature Solid State Ion.135 181-91 DOI: 10.1016/S0167-2738(00)00362-3
[7]
Chen J, Cheng F Y 2009 Combination of lightweight elements and nanostructured materials for batteries Acc. Chem. Res.42 713-23 DOI: 10.1021/ar800229g
[8]
Li H, Wang Z X, Chen L Q, Huang X J 2009 Research on advanced materials for Li-ion batteries Adv. Mater.21 4593-607 DOI: 10.1002/adma.200901710
[9]
Park C M, Kim J H, Kim H, Sohn H J 2010 Li-alloy based anode materials for Li secondary batteries Chem. Soc. Rev.39 3115-41 DOI: 10.1039/b919877f
[10]
Xu Y H, Zhu Y J, Liu Y H, Wang C S 2013 Electrochemical performance of porous carbon/tin composite anodes for sodium-ion and lithium-ion batteries Adv. Energy Mater.3 128-33 DOI: 10.1002/aenm.201200346
[11]
Obrovac M N, Chevrier V L 2014 Alloy negative electrodes for Li-ion batteries Chem. Rev.114 11444-502 DOI: 10.1021/cr500207g
[12]
Su X, Wu Q L, Li J C, Xiao X C, Lott A, Lu W Q, Sheldon B W, Wu J 2014 Silicon-based nanomaterials for lithium-ion batteries: a review Adv. Energy Mater.4 1300882-905 DOI: 10.1002/aenm.201300882
[13]
Aravindan V, Lee Y S, Madhavi S 2015 Research progress on negative electrodes for practical Li-ion batteries: beyond carbonaceous anodes Adv. Energy Mater.5 1402225-68 DOI: 10.1002/aenm.201402225
[14]
Obrovac M N, Christensen L 2004 Structural changes in silicon anodes during lithium insertion/extraction Electrochem. Solid-State Lett.7 A93-A6 DOI: 10.1149/1.1652421
[15]
Chan C K, Peng H, Liu G, Mcllwrath K, Zhang X F, Huggins R A, Cui Y 2008 High-performance lithium battery anodes using silicon nanowires Nat. Nanotechnol.3 31-35 DOI: 10.1038/nnano.2007.411
[16]
Todd A D W, Ferguson P P, Fleischauer M D, Dahn J R 2010 Tin-based materials as negative electrodes for Li-ion batteries: combinatorial approaches and mechanical methods Int. J. Energy Res.34 535-55 DOI: 10.1002/er.1669
[17]
Chen J S, Lou X W 2013 SnO2-based nanomaterials: synthesis and application in lithium-ion batteries Small9 1877-93 DOI: 10.1002/smll.201202601
[18]
Li Z, Ding J, Mitlin D 2015 Tin and tin compounds for sodium ion battery anodes: phase transformations and performance Acc. Chem. Res.48 1657-65 DOI: 10.1021/acs.accounts.5b00114
[19]
Liu Y C, Zhang N, Jiao L F, Chen J 2015 Tin nanodots encapsulated in porous nitrogen-doped carbon nanofibers as a free-standing anode for advanced sodium-ion batteries Adv. Mater.27 6702 DOI: 10.1002/adma.201503015
[20]
Liu X H, Zhong L, Huang S, Mao S X, Zhu T, Huang J Y 2012 Size-dependent fracture of silicon nanoparticles during lithiation ACS Nano6 1522-31 DOI: 10.1021/nn204476h
[21]
Jo H, Kim J, Nguyen D T, Kang K K, Jeon D M, Yang A R, Song S-W 2016 Stabilizing the solid electrolyte interphase layer and cycling performance of silicon-graphite battery anode by using a binary additive of fluorinated carbonates J. Phys. Chem. C120 22466-75 DOI: 10.1021/acs.jpcc.6b07570
[22]
Mao O, Dunlap R A, Dahn J R 1999 Mechanically alloyed Sn-Fe(-C) powders as anode materials for Li-ion batteries-I. The Sn2Fe-C system J. Electrochem. Soc.146 405-13 DOI: 10.1149/1.1391622
[23]
Li H, Shi L H, Lu W, Huang X J, Chen L Q 2001 Studies on capacity loss and capacity fading of nanosized snsb alloy anode for Li-ion batteries J. Electrochem. Soc.148 A915-A22 DOI: 10.1149/1.1383070
[24]
McDowell M T, Lee S W, Nix W D, Cui Y 2013 25th anniversary article: understanding the lithiation of silicon and other alloying anodes for lithium-ion batteries Adv. Mater.25 4966-84 DOI: 10.1002/adma.201301795
[25]
Zhang X H, Kong D B, Li X L, Zhi L J 2019 Dimensionally designed carbon-silicon hybrids for lithium storage Adv. Funct. Mater.29 24 DOI: 10.1002/adfm.2018-6061
[26]
Liu J, Yang Y, Lyu P, Nachtigall P, Xu Y 2018 Few-layer silicene nanosheets with superior lithium-storage properties Adv. Mater.30 1800838 DOI: 10.1002/adma.201800838
[27]
Zhou X S, Yu L, Lou X W 2016 Nanowire-templated formation of SnO2/carbon nanotubes with enhanced lithium storage properties Nanoscale8 8384-9 DOI: 10.1039/C6NR01272H
[28]
Li Q Q, et al 2019 Real-time TEM study of nanopore evolution in battery materials and their suppression for enhanced cycling performance Nano Lett.19 3074-82 DOI: 10.1021/acs.nanolett.9b00491
[29]
Xu H, Li S, Zhang C, Chen X L, Liu W J, Zheng Y H, Xie Y, Huang Y, Li J 2019 Roll-to-roll prelithiation of Sn foil anode suppresses gassing and enables stable full-cell cycling of lithium ion batteries Energy Environ. Sci.12 2991-3000 DOI: 10.1039/C9EE01404G
[30]
Wu H B, Chen J S, Lou X W, Hng H H 2011 Synthesis of SnO2 hierarchical structures assembled from nanosheets and their lithium storage properties J. Phys. Chem. C115 24605-10 DOI: 10.1021/jp208158m
[31]
Pollak E, Salitra G, Baranchugov V, Aurbach D 2007 In situ conductivity, impedance spectroscopy, and ex situ Raman spectra of amorphous silicon during the insertion/extraction of lithium J. Phys. Chem. C111 11437-44 DOI: 10.1021/jp0729563
[32]
Ding N, Xu J, Yao Y X, Wegner G, Fang X, Chen C H, Lieberwirth I 2009 Determination of the diffusion coefficient of lithium ions in nano-Si Solid State Ion.180 222-5 DOI: 10.1016/j.ssi.2008.12.015
[33]
Xue L, Xu G, Li Y, Li S, Fu K, Shi Q, Zhang X 2013 Carbon-coated Si nanoparticles dispersed in carbon nanotube networks as anode material for lithium-ion batteries ACS Appl. Mater. Interfaces5 21 DOI: 10.1021/am3027597
[34]
Zhou M, Cai T, Pu F, Chen H, Wang Z, Zhang H, Guan S 2013 Graphene/carbon-coated Si nanoparticle hybrids as high-performance anode materials for Li-ion batteries ACS Appl. Mater. Interfaces5 3449 DOI: 10.1021/am400521n
[35]
Tamura N, Ohshita R, Fujimoto M, Fujitani S, Kamino M, Yonezu I 2002 Study on the anode behavior of Sn and Sn-Cu alloy thin-film electrodes J. Power Sources107 48-55 DOI: 10.1016/S0378-7753(01)00979-X
[36]
Shi J J, Wang Z G, Fu Y Q 2016 Density functional theory study of diffusion of lithium in Li-Sn alloys J. Mater. Sci.51 3271-6 DOI: 10.1007/s10853-015-9639-z
[37]
Heitsch A T, Akhavan V A, Korgel B A 2011 Rapid SFLS synthesis of Si nanowires using trisilane with in situ alkyl-amine passivation Chem. Mater.23 2697-9 DOI: 10.1021/cm2007704
[38]
Jin Z, Ben L, Yu H, Zhao W, Huang X 2020 A facile method to synthesize 3D structured Sn anode material with excellent electrochemical performance for lithium-ion batteries Prog. Nat. Sci.30 456-60 DOI: 10.1016/j.pnsc.2020.06.007
[39]
Hu J T, Odom T W, Lieber C M 1999 Chemistry and physics in one dimension: synthesis and properties of nanowires and nanotubes Acc. Chem. Res.32 435-45 DOI: 10.1021/ar9700365
[40]
Wang H Y, Huang H Q, Chen L, Wang C G, Yan B, Yu Y T, Yang Y, Yang G 2014 Preparation of Si/Sn-based nanoparticles composited with carbon fibers and improved electrochemical performance as anode materials ACS Sustain. Chem. Eng.2 2310-7 DOI: 10.1021/sc500290x
[41]
Wang F, Wu L, Key B, Yang X-Q, Grey C P, Zhu Y, Graetz J 2013 Electrochemical reaction of lithium with nanostructured silicon anodes: a study by in-situ synchrotron x-ray diffraction and electron energy-loss spectroscopy Adv. Energy Mater.3 1324-31 DOI: 10.1002/aenm.201300394
[42]
Im H S, Cho Y J, Lim Y R, Jung C S, Jang D M, Park J, Shojaei F, Kang H S 2013 Phase evolution of tin nanocrystals in lithium ion batteries ACS Nano7 11103-11 DOI: 10.1021/nn404837d
[43]
Zhou G W, Zhang Z, Bai Z G, Feng S Q, Yu D P 1998 Controlled Li doping of Si nanowires by electrochemical insertion method Appl. Phys. Lett.73 677 DOI: 10.1063/1.121945
[44]
Jin Y, Tan Y, Hu X, Zhu B, Zheng Q, Zhang Z, Zhu G, Yu Q, Jin Z, Zhu J 2017 Scalable production of the silicon-tin Yin-Yang hybrid structure with graphene coating for high performance lithium-ion battery anodes ACS Appl. Mater. Interfaces9 15388-93 DOI: 10.1021/acsami.7b00366
[45]
Rhodes K J, Meisner R, Kirkham M, Dudney N, Daniel C 2012 In situ XRD of thin film tin electrodes for lithium ion batteries J. Electrochem. Soc.159 A294-A9 DOI: 10.1149/2.077203jes
[46]
Yang X-Q, McBreen J, Yoon W-S, Yoshio M, Wang H, Fukuda K, Umeno T 2002 Structural studies of the new carbon-coated silicon anode materials using synchrotron-based in situ XRD Electrochem. Commun.4 893-7 DOI: 10.1016/S1388-2481(02)00483-6
[47]
Luo B, Wang B, Liang M H, Ning J, Li X L, Zhi L J 2012 Reduced graphene oxide-mediated growth of uniform tin-core/carbon-sheath coaxial nanocables with enhanced lithium ion storage properties Adv. Mater.24 1405-9 DOI: 10.1002/adma.201104362
[48]
Zheng K, Han X D, Wang L H, Zhang Y F, Yue Y H, Qin Y, Zhang X, Zhang Z 2009 Atomic mechanisms governing the elastic limit and the incipient plasticity of bending Si nanowires Nano Lett.9 2471-6 DOI: 10.1021/nl9012425
Zhou, J.-E., Li, Y., Lin, X. et al. Prussian Blue Analogue-Templated Nanocomposites for Alkali-Ion Batteries: Progress and Perspective. Nano Micro Letters, 2025, 17(1): 9.
DOI:10.1007/s40820-024-01517-y
2.
Abdel-Karim, R., El-Sheikh, E., Mitwally, M.E. Electrodeposition and characterization of C/Sn thin films as a high-performance anode for li-ion batteries: effect of pulsed electrodeposition parameters. Materials for Renewable and Sustainable Energy, 2025, 14(2): 30.
DOI:10.1007/s40243-025-00302-0
3.
Zhong, Q., Mo, Y., Zhou, W. et al. Changing the pore structure and surface chemistry of hard carbon by coating it with a soft carbon to boost high-rate sodium storage | [软炭包覆优化孔结构和表面化学提升硬炭的高倍率储钠性能]. Xinxing Tan Cailiao New Carbon Materials, 2025, 40(3): 650-664.
DOI:10.1016/S1872-5805(25)60979-6
4.
Wang, C., Ding, Z., An, W. et al. Rapid Ion Migration and High Stability in SiOx Anodes Enabled by Co Doping and Core-Shell Architecture. ACS Applied Energy Materials, 2025, 8(9): 6100-6111.
DOI:10.1021/acsaem.5c00506
5.
Cao, B., Du, M., Ma, Y. et al. Preparation of low-cost pitch-derived carbon-sulfur hybrids as anodes for potassium storage. Carbon, 2025.
DOI:10.1016/j.carbon.2025.120033
6.
Zhang, W., Han, P., Liu, Y. et al. Improvement strategies and research progress of silicon/graphite composites in lithium-ion batteries. Flatchem, 2025.
DOI:10.1016/j.flatc.2025.100833
7.
Yang, J., Li, J., Xu, C. et al. Recent Advancements in Metal-Organic Frameworks-Derived Metal Phosphides as Anode for Lithium-Ion Batteries. Chemnanomat, 2025, 11(2): e202400504.
DOI:10.1002/cnma.202400504
8.
Ou, H., Li, P., Jiang, C. et al. Synergistic enhancement of Ni2P anode for high lithium/sodium storage by N, P, S triply-doping and soft template-assisted strategy. Journal of Colloid and Interface Science, 2025.
DOI:10.1016/j.jcis.2024.08.182
9.
Zhou, J.-E., Li, Y., Zou, M. et al. Self-Sacrificial Templated Lithium Manganese Oxide as a Longevous Cathode: The Intermarriage of Oxygen Defects and Zeolitic Imidazolate Framework Glass. Advanced Functional Materials, 2025.
DOI:10.1002/adfm.202501603
10.
Chen, Y., Li, P., Huang, M. et al. Elucidating the role of embedding dispersed cobalt sites in nitrogen-doped carbon frameworks in Si-based anodes for stable and superior storage. Journal of Energy Chemistry, 2024.
DOI:10.1016/j.jechem.2024.06.022
11.
Ou, H., Huang, M., Li, P. et al. Tailoring and understanding the lithium storage performance of triple-doped cobalt phosphide composites. Journal of Colloid and Interface Science, 2024.
DOI:10.1016/j.jcis.2024.06.049
12.
Zhang, W., Qi, Y., Fang, J. et al. Progress and Prospect of Sn-Based Metal-Organic Framework Derived Anode Materials for Metal-Ion Batteries. Batteries and Supercaps, 2024, 7(10): e202400227.
DOI:10.1002/batt.202400227
13.
Huang, M., Chen, Y., Zeng, W. et al. Enhancing lithium storage performance with silicon-based anodes: a theoretical study on transition metal-integrated SiOx/M@C (M = Fe, Co, Ni) heterostructures. Dalton Transactions, 2024, 53(37): 15481-15490.
DOI:10.1039/d4dt02205j
14.
Huang, B., Zhang, Y., Zhong, H. et al. Strategy for the Preparation of ZnS/ZnO Composites Derived from Metal-Organic Frameworks toward Lithium Storage. Inorganic Chemistry, 2024, 63(26): 12281-12289.
DOI:10.1021/acs.inorgchem.4c01680
15.
Hossain, M.A.M., Tiong, S.K., Hannan, M.A. et al. Recent advances in silicon nanomaterials for lithium-ion batteries: Synthesis approaches, emerging trends, challenges, and opportunities. Sustainable Materials and Technologies, 2024.
DOI:10.1016/j.susmat.2024.e00964
16.
Yang, J., Yu, H., Zhen, F. et al. Sea urchin-inspired VS4 morphology for superior electrochemical performance in high-energy batteries. Journal of Alloys and Compounds, 2024.
DOI:10.1016/j.jallcom.2024.174171
17.
Yang, J., Guan, N., Xu, C. et al. The synthesis and modification of LiFePO4 lithium-ion battery cathodes: a mini review. Crystengcomm, 2024, 26(26): 3441-3454.
DOI:10.1039/d4ce00507d
18.
Zhou, J.-E., Liu, Y., Peng, Z. et al. Unveiling the tailorable electrochemical properties of zeolitic imidazolate framework-derived Ni-doped LiCoO2 for lithium-ion batteries in half/full cells. Journal of Energy Chemistry, 2024.
DOI:10.1016/j.jechem.2024.02.005
19.
Ou, G., Huang, M., Lu, X. et al. A Metal-Organic Framework-Derived Strategy for Constructing Synergistic N-Doped Carbon-Encapsulated NiCoP@N-C-Based Anodes toward High-Efficient Lithium Storage. Small, 2024, 20(17): 2307615.
DOI:10.1002/smll.202307615
20.
Qiao, R., Yu, H., Ben, L. et al. Utilizing hydrolysis resistance of compressed Li3PS4 films to eradicate surface hydroxyls and form conformal coatings through atomic layer deposition. Chemical Engineering Journal, 2024.
DOI:10.1016/j.cej.2024.149877
21.
Chen, Y., Huang, M., Deng, G. et al. MOF-derived cobalt nanoparticles in silicon suboxide-based anodes for enhanced lithium storage. Chemical Engineering Journal, 2024.
DOI:10.1016/j.cej.2024.150111
22.
Shen, X., Yu, H., Ben, L. et al. High energy density in ultra-thick and flexible electrodes enabled by designed conductive agent/binder composite. Journal of Energy Chemistry, 2024.
DOI:10.1016/j.jechem.2023.10.052
23.
Wang, Y., Lu, H., Jia, X.-M. et al. Entropy-Induced Localization and Sliding Dynamics of Rings on Polyrotaxane. Macromolecules, 2024, 57(4): 1846-1858.
DOI:10.1021/acs.macromol.3c01805
24.
Huang, J., Wu, Z., Zeng, W. et al. Zeolitic imidazolate framework derivatives as anode materials for sodium and potassium-ion batteries: a mini review. Crystengcomm, 2024, 26(8): 1049-1066.
DOI:10.1039/d4ce00011k
25.
Fan, L., Shu, G., Liu, Y. et al. Cu-substituted nickel hexacyanoferrate with tunable reaction potentials for superior ammonium ion storage. Journal of Materials Science and Technology, 2024.
DOI:10.1016/j.jmst.2023.06.010
26.
Guo, Y., Huang, M., Zhong, H. et al. Metal-organic frameworks-derived MCo2O4 (M = Zn, Ni, Cu) two-dimensional nanosheets as anodes materials to boost lithium storage. Journal of Colloid and Interface Science, 2023.
DOI:10.1016/j.jcis.2023.07.099
27.
Zhang, Q., Zhu, J., Nie, Y. et al. Hierarchical carbon nanofibers-based ternary conductive network built for improving electrochemical performance of SiOx@C anodes. Materials Chemistry and Physics, 2023.
DOI:10.1016/j.matchemphys.2023.128431
28.
Ou, G., Peng, Z., Zhang, Y. et al. A metal-organic framework-derived engineering of carbon-encapsulated monodispersed CoP/Co2P@N[sbnd]C electroactive nanoparticles toward highly efficient lithium storage. Electrochimica Acta, 2023.
DOI:10.1016/j.electacta.2023.143098
29.
Huang, Q., Zeb, A., Xu, Z. et al. Fe-based metal-organic frameworks and their derivatives for electrochemical energy conversion and storage. Coordination Chemistry Reviews, 2023.
DOI:10.1016/j.ccr.2023.215335
30.
Ou, H., Peng, Y., Sang, X. et al. Recent advances in silicon-based composite anodes modified by metal-organic frameworks and their derivatives for lithium-ion battery applications. Journal of Alloys and Compounds, 2023.
DOI:10.1016/j.jallcom.2023.170713
31.
Tian, M., Jin, Z., Song, Z. et al. Domino Reactions Enabling Sulfur-Mediated Gradient Interphases for High-Energy Lithium Batteries. Journal of the American Chemical Society, 2023, 145(39): 21600-21611.
DOI:10.1021/jacs.3c07908
32.
Shi, J., Yang, S., Zhang, D. et al. C-Doped LiVO3 Honeycombs Derived from the Biomass Template Strategy for Superior Lithium Storage. Langmuir, 2023, 39(39): 14074-14083.
DOI:10.1021/acs.langmuir.3c01903
33.
Ju, P., Ben, L., Li, Y. et al. Designer Particle Morphology to Eliminate Local Strain Accumulation in High-Nickel Layered Cathode Materials. ACS Energy Letters, 2023, 8(9): 3800-3810.
DOI:10.1021/acsenergylett.3c01272
34.
Ji, H., Qiao, R., Yu, H. et al. Electrolysis Process-Facilitated Engineering of Primary Particles of Cobalt-Free LiNiO2 for Improved Electrochemical Performance. ACS Applied Materials and Interfaces, 2023, 15(33): 39291-39303.
DOI:10.1021/acsami.3c06908
35.
Cen, Z., Tang, Y., Huang, J. et al. Two-Dimensional Molecular Brush-Based Ultrahigh Edge-Nitrogen-Doped Carbon Nanosheets for Ultrafast Potassium-Ion Storage. Batteries, 2023, 9(7): 363.
DOI:10.3390/batteries9070363
36.
Chen, G., Wang, L., Liu, Y. et al. Construction of hierarchical multilayered nanomaterials derived from Co-MOFs supported by pyromellitic acid for advanced lithium storage performance. New Journal of Chemistry, 2023, 47(30): 14169-14176.
DOI:10.1039/d3nj02280c
37.
Liu, R., Yang, L., Wang, W. et al. Surface redox pseudocapacitance-based vanadium nitride nanoparticles toward a long-cycling sodium-ion battery. Materials Today Energy, 2023.
DOI:10.1016/j.mtener.2023.101300
38.
Tian, C., Qin, K., Suo, L. Concentrated electrolytes for rechargeable lithium metal batteries. Materials Futures, 2023, 2(1): 012101.
DOI:10.1088/2752-5724/acac68
39.
Tang, B., Liu, Q., Fan, H. et al. Study on Electrochemical Performance of Modified Zn Anodes on Different Metal Substrates | [不同金属基底改性 Zn 负极的电化学性能研究]. Shiyou Huagong Gaodeng Xuexiao Xuebao Journal of Petrochemical Universities, 2022, 35(6): 66-73.
DOI:10.3969/j.issn.1006-396X.2022.06.008
40.
Liu, R., Li, N., Zhao, E. et al. Facile molten salt synthesis of carbon-anchored TiN nanoparticles for durable high-rate lithium-ion battery anodes. Materials Futures, 2022, 1(4): 045102.
DOI:10.1088/2752-5724/ac9cf7
41.
Tian, M., Ben, L., Yu, H. et al. Designer Cathode Additive for Stable Interphases on High-Energy Anodes. Journal of the American Chemical Society, 2022, 144(33): 15100-15110.
DOI:10.1021/jacs.2c04124
DownLoad:
