2021 Vol. 28, No. 10
Silicon (Si) is widely considered to be the most attractive candidate anode material for use in next-generation high-energy-density lithium (Li)-ion batteries (LIBs) because it has a high theoretical gravimetric Li storage capacity, relatively low lithiation voltage, and abundant resources. Consequently, massive efforts have been exerted to improve its electrochemical performance. While some progress in this field has been achieved, a number of severe challenges, such as the element’s large volume change during cycling, low intrinsic electronic conductivity, and poor rate capacity, have yet to be solved. Methods to solve these problems have been attempted via the development of nanosized Si materials. Unfortunately, reviews summarizing the work on Si-based alloys are scarce. Herein, the recent progress related to Si-based alloy anode materials is reviewed. The problems associated with Si anodes and the corresponding strategies used to address these problems are first described. Then, the available Si-based alloys are divided into Si/Li-active and inactive systems, and the characteristics of these systems are discussed. Other special systems are also introduced. Finally, perspectives and future outlooks are provided to enable the wider application of Si-alloy anodes to commercial LIBs.
All-solid-state Li-ion batteries (ASSLIBs) have been widely studied to achieve Li-ion batteries (LIBs) with high safety and energy density. Recent reviews and experimental papers have focused on methods that improve the ionic conductivity, stabilize the electrochemical performance, and enhance the electrolyte/electrode interfacial compatibility of several solid-state electrolytes (SSEs), including oxides, sulfides, composite and gel electrolytes, and so on. Garnet-structured Li7La3Zr2O12 (LLZO) is highly regarded an SSE with excellent application potential. However, this type of electrolyte also possesses a number of disadvantages, such as low ionic conductivity, unstable cubic phase, and poor interfacial compatibility with anodes/cathodes. The benefits of LLZO have urged many researchers to explore effective solutions to overcome its inherent limitations. Herein, we review recent developments on garnet-structured LLZO and provide comprehensive insights to guide the development of garnet-structured LLZO-type electrolytes. We not only systematically and comprehensively discuss the preparation, element doping, structure, stability, and interfacial improvement of LLZOs but also provide future perspectives for these materials. This review expands the current understanding on advanced solid garnet electrolytes and provides meaningful guidance for the commercialization of ASSLIBs.
In the past few years, the all-solid lithium battery has attracted worldwide attentions, the ionic conductivity of some all-solid lithium-ion batteries has reached 10−3–10−2 S/cm, indicating that the transport of lithium ions in solid electrolytes is no longer a major problem. However, some interface issues become research hotspots. Examples of these interfacial issues include the electrochemical decomposition reaction at the electrode–electrolyte interface; the low effective contact area between the solid electrolyte and the electrode etc. In order to solve the issues, researchers have pursued many different approaches. The addition of a buffer layer between the electrode and the solid electrolyte has been at the center of this endeavor. In this review paper, we provide a systematic summarization of the problems on the electrode–solid electrolyte interface and detailed reflection on the latest works of buffer-based therapies, and the review will end with a personal perspective on the improvement of buffer-based therapies.
Silicon (Si) particles were functionalized using carbon dots (CDs) to enhance the interaction between the Si particles and the binders. First, CDs rich in polar groups were synthesized using a simple hydrothermal method. Then, CDs were loaded on the Si surface by impregnation to obtain the functionalized Si particles (Si/CDs). The phases and microstructures of the Si/CDs were observed using Fourier-transform infrared reflection, X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. Si/CDs were used as the active material of the anode for electrochemical performance experiments. The electrochemical performance of the Si/CD electrode was assessed using cyclic voltammetry, electrochemical impedance spectroscopy, and constant current charge and discharge experiment. The electrodes prepared with Si/CDs showed good mechanical structure stability and electrochemical performance. After 150 cycles at 0.2 C, the capacity retention rate of the Si/CD electrode was 64.0%, which is twice as much as that of pure Si electrode under the same test conditions.
Silicon anodes are considered to have great prospects for use in batteries; however, many of their defects still need to be improved. The preparation of hybrid materials based on porous carbon is one of the effective ways to alleviate the adverse impact resulting from the volume change and the inferior electronic conductivity of a silicon electrode. Herein, a chain-like carbon cluster structure is prepared, in which MOF-derived porous carbon acts as a shell structure to integrally encapsulate Si nanoparticles, and CNTs play a role in connecting carbon shells. Based on the exclusive structure, the carbon shell can accommodate the volume expansion more effectively, and CNTs can improve the overall stability and conductivity. The resulting composite reveals excellent rate capacity and enhanced cycling stability; in particular, a capacity of 732 mA·h·g−1 at 2 A·g−1 is achieved with a reservation rate of 72.3% after cycling 100 times at 1 A·g−1.
The silicon-based material exhibits a high theoretical specific capacity and is one of the best anode for the next generation of advanced lithium-ion batteries (LIBs). However, it is difficult for the silicon-based anode to form a stable solid-state interphase (SEI) during Li alloy/de-alloy process due to the large volume change (up to 300%) between silicon and Li4.4Si, which seriously limits the cycle life of the LIBs. Herein, we use strontium fluoride (SrF2) particle to coat the silicon−carbon (Si/C) electrode (SrF2@Si/C) to help forming a stable and high mechanical strength SEI by spontaneously embedding the SrF2 particle into SEI. Meanwhile the formed SEI can inhibit the volume expansion of the silicon−carbon anode during the cycle. The electrochemical test results show that the cycle performance and the ionic conductivity of the SrF2@Si/C anode has been significantly improved. The X-ray photoelectron spectroscopy (XPS) analysis reveals that there are fewer electrolyte decomposition products formed on the surface of the SrF2@Si/C anode. This study provides a facile approach to overcome the problems of Si/C electrode during the electrochemical cycling, which will be beneficial to the industrial application of silicon-based anode materials.
Antimony sulfide (Sb2S3) is a promising anode for lithium-ion batteries due to its high capacity and vast reserves. However, the low electronic conductivity and severe volume change during cycling hinder its commercialization. Herein our work, a three-dimensional (3D) Sb2S3 thin film anode was fabricated via a simple vapor transport deposition system by using natural stibnite as raw material and stainless steel fiber-foil (SSF) as 3D current collector, and a carbon nanotube interphase was introduced onto the film surface by a simple dropping-heating process to promote the electrochemical performances. This 3D structure can greatly improve the initial coulombic efficiency to a record of 86.6% and high reversible rate capacity of 760.8 mAh·g−1 at 10 C. With carbon nanotubes interphase modified, the Sb2S3 anode cycled extremely stable with high capacity retention of 94.7% after 160 cycles. This work sheds light on the economical preparation and performance optimization of Sb2S3-based anodes.
Anion-immobilized solid composite electrolytes (SCEs) are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries (ASSLMBs). Herein, a novel SCEs based on metal-organic frameworks (MOFs, UiO-66-NH2) and superacid ZrO2 (S-ZrO2) fillers are proposed, and the samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS), thermo-gravimetric analyzer (TGA) and some other electrochemical measurements. The –NH2 groups of UiO-66-NH2 combines with F atoms of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) chains by hydrogen bonds, leading to a high electrochemical stability window of 5 V. Owing to the incorporation of UiO-66-NH2 and S-ZrO2 in PVDF-HFP polymer, the open metal sites of MOFs and acid surfaces of S-ZrO2 can immobilize anions by strong Lewis acid-base interaction, which enhances the effect of immobilization anions, achieving a high Li-ion transference number (t+) of 0.72, and acquiring a high ionic conductivity of 1.05×10–4 S·cm–1 at 60°C. The symmetrical Li/Li cells with the anion-immobilized SCEs may steadily operate for over 600 h at 0.05 mA·cm–2 without the short-circuit occurring. Besides, the solid composite Li/LiFePO4 (LFP) cell with the anion-immobilized SCEs shows a superior discharge specific capacity of 158 mAh·g–1 at 0.2 C. The results illustrate that the anion-immobilized SCEs are one of the most promising choices to optimize the performances of ASSLMBs.
To improve the sulfur loading capacity of lithium-sulfur batteries (Li–S batteries) cathode and avoid the inevitable “shuttle effect”, hollow N doped carbon coated CoO/SnO2 (CoO/SnO2@NC) composite has been designed and prepared by a hydrothermal-calcination method. The specific surface area of CoO/SnO2@NC composite is 85.464 m2·g–1, and the pore volume is 0.1189 cm3·g–1. The hollow core-shell structure as a carrier has a sulfur loading amount of 66.10%. The initial specific capacity of the assembled Li–S batteries is 395.7 mAh·g–1 at 0.2 C, which maintains 302.7 mAh·g–1 after 400 cycles. When the rate increases to 2.5 C, the specific capacity still has 221.2 mAh·g–1. The excellent lithium storage performance is attributed to the core-shell structure with high specific surface area and porosity. This structure effectively increases the sulfur loading, enhances the chemical adsorption of lithium polysulfides, and reduces direct contact between CoO/SnO2 and the electrolyte.
The commercial development of lithium–sulfur batteries (Li–S) is severely limited by the shuttle effect of lithium polysulfides (LPSs) and the non-conductivity of sulfur. Herein, porous g-C3N4 nanotubes (PCNNTs) are synthesized via a self-template method and utilized as an efficient sulfur host material. The one-dimensional PCNNTs have a high specific surface area (143.47 m2·g−1) and an abundance of macro-/mesopores, which could achieve a high sulfur loading rate of 74.7wt%. A Li–S battery bearing the PCNNTs/S composite as a cathode displays a low capacity decay of 0.021% per cycle over 800 cycles at 0.5 C with an initial capacity of 704.8 mAh·g−1. PCNNTs with a tubular structure could alleviate the volume expansion caused by sulfur and lithium sulfide during charge/discharge cycling. High N contents could greatly enhance the adsorption capacity of the carbon nitride for LPSs. These synergistic effects contribute to the excellent cycling stability and rate performance of the PCNNTs/S composite electrode.
Ultrafine nano-scale Cu2Sb alloy confined in a three-dimensional porous carbon was synthesized using NaCl template-assisted vacuum freeze-drying followed by high-temperature sintering and was evaluated as an anode for sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs). The alloy exerts excellent cycling durability (the capacity can be maintained at 328.3 mA·h·g−1 after 100 cycles for SIBs and 260 mA·h·g−1 for PIBs) and rate capability (199 mA·h·g−1 at 5 A·g−1 for SIBs and 148 mA·h·g−1 at 5 A·g−1 for PIBs) because of the smooth electron transport path, fast Na/K ion diffusion rate, and restricted volume changes from the synergistic effect of three-dimensional porous carbon networks and the ultrafine bimetallic nanoalloy. This study provides an ingenious design route and a simple preparation method toward exploring a high-property electrode for K-ion and Na-ion batteries, and it also introduces broad application prospects for other electrochemical applications.
p-Benzoquinone (BQ) is a promising candidate for next-generation sodium-ion batteries (SIBs) because of its high theoretical specific capacity, good reaction reversibility, and high resource availability. However, practical application of BQ faces many challenges, such as a low discharge plateau (~2.7 V) as cathode material or a high discharge plateau as anode material compared with inorganic materials for SIBs and high solubility in organic electrolytes, resulting in low power and energy densities. Here, tetrahydroxybenzoquinone tetrasodium salt (Na4C6O6) is synthesized through a simple neutralization reaction at low temperatures. The four –ONa electron-donating groups introduced on the structure of BQ greatly lower the discharge plateau by over 1.4 V from ~2.70 V to ~1.26 V, which can change BQ from cathode to anode material for SIBs. At the same time, the addition of four –ONa hydrophilic groups inhibits the dissolution of BQ in the organic electrolyte to a certain extent. As a result, Na4C6O6 as the anode displays a moderate discharge capacity and cycling performance at an average work voltage of ~1.26 V versus Na/Na+. When evaluated as a Na-ion full cell (NIFC), a Na3V2(PO4)3 || Na4C6O6 NIFC reveals a moderate discharge capacity and an average discharge plateau of ~1.4 V. This research offers a new molecular structure design strategy for reducing the discharge plateau and simultaneously restraining the dissolution of organic electrode materials.
Aqueous zinc-ion batteries (ZIBs) are deemed as the idea option for large-scale energy storage systems owing to many alluring merits including low manufacture cost, environmental friendliness, and high operations safety. However, to develop high-performance cathode is still significant for practical application of ZIBs. Herein, Ba0.23V2O5·1.1H2O (BaVO) nanobelts were fabricated as cathode materials of ZIBs by a typical hydrothermal synthesis method. Benefiting from the increased interlayer distance of 1.31 nm by Ba2+ and H2O pre-intercalated, the obtained BaVO nanobelts showed an excellent initial discharge capacity of 378 mAh·g−1 at 0.1 A·g−1, a great rate performance (e.g., 172 mAh·g−1 at 5 A·g−1), and a superior capacity retention (93% after 2000 cycles at 5 A·g−1).
The microstructural properties and electrochemical performance of zinc (Zn) sacrificial anodes during strain-induced melt activation (SIMA) were investigated in this study. The samples were subjected to a compressive ratio of 20%–50% at various temperatures (425–435°C) and durations (5–30 min). Short-term electrochemical tests (anode tests) based on DNV-RP-B401 and potentiodynamic polarization tests were performed in 3.5wt% NaCl solution to evaluate the electrochemical efficiency and corrosion behavior of the samples, respectively. The electrochemical test results for the optimum sample confirmed that the corrosion current density declined by 90% and the anode efficiency slightly decreased relative to that of the raw sample. Energy-dispersive X-ray spectroscopy, scanning electron microscopy, metallographic images, and microhardness profiles showed the accumulation of alloying elements on the boundary and the conversion of uniform corrosion into localized corrosion, hence the decrease of the Zn sacrificial anode’s efficiency after the SIMA process.
Mg–Sn–Y alloys with different Sn contents (wt%) were assessed as anode candidates for Mg-air batteries. The relationship between microstructure (including the second phase, grain size, and texture) and discharge properties of the Mg–Sn–Y alloys was examined using microstructure observation, electrochemical measurements, and galvanostatic discharge tests. The Mg–0.7Sn–1.4Y alloy had a high steady discharge voltage of 1.5225 V and a high anodic efficiency of 46.6% at 2.5 mA·cm−2. These good properties were related to its microstructure: small grain size of 3.8 μm, uniform distribution of small second phase particles of 0.6 μm, and a high content (vol%) of (
Synthesizing atomically precise Ag nanoclusters (NCs), which is essential for the general development of NCs, is quite challenging. In this study, we report the synthesis of high-purity atomically precise Ag NCs via a kinetically controlled strategy. The Ag NCs were prepared using a mild reducing agent via a one-pot method. The as-prepared Ag NCs were confirmed to be Ag49(D-pen)24 (D-pen: D-penicillamine) on the basis of their matrix-assisted laser desorption ionization time-of-flight mass spectrometric and thermogravimetric characteristics. The interfacial structures of the Ag NCs were illustrated by proton nuclear magnetic resonance and Fourier-transform infrared spectroscopy. The Ag NCs were supported on activated carbon (AC) to form Ag NCs/AC, which displayed excellent activity for the catalytic reduction of 4-nitrophenol with a kinetic reaction rate constant k of 0.21 min−1. Such a high k value indicates that the composite could outperform several previously reported catalysts. Moreover, the catalytic activity of Ag NCs/AC remained nearly constant after six times of recycle, which suggests its excellent stability.
The properties of γ-ray-reduced graphene oxide samples (GRGOs) were compared with those of hydrazine hydrate-reduced graphene oxide (HRGO). Fourier transform infrared spectroscopy, X-ray diffractometry, Raman spectroscopy, Brunauer–Emmett–Teller surface area analysis, thermogravimetric analysis, electrometry, and cyclic voltammetry were carried out to verify the reduction process, structural changes, and defects of the samples, as well as to measure their thermal, electrical, and electrochemical properties. Irradiation with γ-rays distorted the structure of GRGOs and generated massive defects through the extensive formation of new smaller sp2-hybridized domains compared with those of HRGO. The thermal stability of GRGOs was higher than that of HRGO, indicating the highly efficient removal of thermally-labile oxygen species by γ-rays. RRGO prepared at 80 kGy showed a pseudocapacitive behavior comparable with the electrical double-layer capacitance behavior of HRGO. Interestingly, the specific capacitance of GRGO was enhanced by nearly three times compared with that of HRGO. These results reflect the advantages of radiation reduction in energy storage applications.
MnO2/biomass carbon nanocomposite was synthesized by a facile hydrothermal reaction. Silkworm excrement acted as a carbon precursor, which was activated by ZnCl2 and FeCl3 combining chemical agents under Ar atmosphere. Thin and flower-like MnO2 nanowires were in-situ anchored on the surface of the biomass carbon. The biomass carbon not only offered high conductivity and good structural stability but also relieved the large volume expansion during the charge/discharge process. The obtained MnO2/biomass carbon nanocomposite electrode exhibited a high specific capacitance (238 F·g−1 at 0.5 A·g−1) and a superior cycling stability with only 7% degradation after 2000 cycles. The observed good electrochemical performance is accredited to the materials’ high specific surface area, multilevel hierarchical structure, and good conductivity. This study proposes a promising method that utilizes biological waste and broadens MnO2-based electrode material application for next-generation energy storage and conversion devices.