Anode For Lithium-ion Batteries Research Articles

Poly(ethylene) Oxide Electrolytes for All-Solid-State Lithium Batteries Using Microsized Silicon/Carbon Anodes with Enhanced Rate Capability and Cyclability.

Silicon (Si) has been widely studied as one of the promising anodes for lithium-ion batteries (LIBs) because of its ultrahigh theoretical specific capacity and low working voltage. However, the poor interfacial stability of silicon against conventional liquid electrolytes has largely impeded its practical use. Therefore, the combination of silicon-based anodes and solid electrolytes has attracted a great deal of attention in recent years. Here, we demonstrate three types of microsized porous silicon/carbon (Si/C) electrodes (i.e., pristine, prelithiated by liquid electrolyte, and preinfiltrated by polymer electrolyte) that are paired with poly(ethylene) oxide (PEO)-based electrolytes for all-solid-state lithium batteries (ASSLBs). We found that when compared with ionic conductivity, the mechanical stability of the PEO electrolyte dominates the electrochemical performance of ASSLBs using Si/C electrodes at elevated temperature. Additionally, both prelithiated and preinfiltrated Si/C electrodes show higher specific capacity in comparison to the pristine electrode, which is attributed to continuous lithium-ion conducting pathways within the electrode and thus improved utilization of active material. Moreover, owing to good interfacial lithium-ion transport in the electrode, a solid-state half-cell with preinfiltrated Si/C electrode and PEO-lithium bis (trifluoromethanesulfonyl)imide electrolyte delivers a specific capacity of ∼1,000 mAh g-1 after 100 cycles under 800 mA g-1 at 60 °C with average Coulombic efficiency >98.9%. This work provides a strategy for rationally designing the microstructure of silicon-based electrodes with solid electrolytes for high-performance all-solid-state lithium batteries.

The Effect of TiO2 on the Electrochemical Performance of Sb2O3 Anodes for Li-Ion Batteries

Antimony (Sb) and its composites have been recognized as potentially good anode materials for lithium-ion batteries (LIBs) due to their relatively high theoretical capacity of 660 mAh g−1 and to their low cost. However, Sb-based anodes suffer from a high-volume change during the lithiation/delithiation process that results in capacity fading and anode degradation after prolonged charge/discharge cycles. To address this issue, Sb2O3/TiO2 nanocomposite electrodes can be synthesized and used as anodes for LIBs with high capacity and good electrochemical stability. In the present work, TiO2@Sb2O3 composites with different (TiO2:Sb2O3) ratios of 0:1, 1:1, 1:4 and 3:1 were synthesized and directly used as anode materials for LIBs. The electrochemical performance of the TiO2/Sb2O3 composite anode with different ratios of TiO2 to Sb2O3 was evaluated by galvanostatic charge/discharge, rate performance and cyclic voltammetry. The 3:1 (TiO2:Sb2O3) composite anode delivered the highest capacity compared to those of the TiO2, SbO3, 1:1 (TiO2:Sb2O3) and 1:4 (TiO2:Sb2O3) electrodes. The TiO2@Sb2O3 composite anode with a 3:1 ratio exhibited a stabilized capacity of 536 mAh g−1 after 100 cycles at 100 mA g−1 and showed excellent rate performance, with current densities between 50 and 500 mA g−1. The improved electrochemical performance was attributed to the synergistic effect of TiO2 (i.e., the coating of Sb2O3 with TiO2) on reducing the volume change of the Sb anode material after prolonged charge/discharge cycles and on maintaining a stable interface between the electrolyte and the composite electrode material.

Amorphous titanium dioxide and polyaniline dual modifying silicon for highly enhanced lithium-ion storage

Silicon (Si) anode material is promising in the next generation of lithium-ion batteries (LIBs) with high energy densities for its much higher capacity (4200 mAh/g) than that of commercial graphite (372 mAh/g). However, silicon anode material with low electronic conductivity suffers a huge volume variation and accompanies side reactions during alloyed and de-alloyed process. Here, we design an inner amorphous titanium dioxide (TiO2) and an outer flexible conductive polyaniline (PANI) network dual modified Si@TiO2@PANI material for LIBs, where the TiO2 avoids the side reactions and the PANI network layer buffers the volume expansion and increases the electronic conductivity. The as-prepared Si@TiO2@PANI exhibits a high initial discharge capacity of 3050 mAh/g and maintains 1583 mAh/g after 200 cycles at 0.5 A/g. It even delivers the discharge capacity of 1002 mAh/g after 600 cycles at 1 A/g, as well as an excellent rate ability with discharge capacity of 1890, 1260 and 432 mAh/g at the high current density of 1, 2 and 5 A/g, respectively. Our strategy shows that the innovative design of double buffer layers on Si can synergistically promote stability and accelerate kinetics of Li+ transport, offering novel resolution strategy to enhance the performance of Si-based anodes for LIBs.

Multifunctional Cross-Linking Composite Binder Enables the Stable Performance of Si-Based Anodes for High-Energy-Density Lithium-Ion Batteries.

The intrinsic volumetric stress during cycling is the main obstacle for developing Si-based materials as high-energy-density lithium-ion battery anodes. Elastic binders have been demonstrated as an efficient approach to alleviate the stress of Si. Herein, we design a tough 3D hard/soft polymeric network (LPTS) using lithiated poly(acrylic acid), silk sericin, and highly branched tannic acid. Covalent cross-linking provides a robust mechanical strength to endure the large stress. The formed multiple hydrogen bonds with bonding energies between 3.46 and 25 kcal mol-1 can effectively dissipate the stress through sequential hydrogen bond disassociation. The multifunctional LPTS binder maintains the integrity of the Si-based electrodes during repeated discharging/charging. Additionally, Li+ can be transferred via a Li-conducting group (-COOLi), thereby enhancing the ionic conductivity of electrodes. Consequently, the Si/LPTS electrode exhibits an improved initial Coulombic efficiency and excellent durability over 400 cycles. Meanwhile, this binder is also suitable for Si-C anodes, enabling stable cycling at a high areal capacity >3.6 mAh cm-2 and delivering 72.2% capacity retention for the LFP||Si-C/LPTS full cell after 200 cycles. This study provides insight into developing efficient Si-based binders that are facile and low-cost for next-generation high-energy-density systems.

A room-temperature liquid eutectic GaSn anode with regulated wettability for lithium ion batteries

The alloy-type anodes in lithium ion batteries (LIBs) often suffer from the pulverization/failure of active materials caused by the drastic volume variations during cycling. Liquid Ga-based materials with low melting points and intrinsic self-healing feature are one of the best candidates for enhancing the Li storage property. Herein, a liquid eutectic GaSn (EGaSn) electrode was fabricated based upon a simple painting method and directly used as the anode for LIBs at room temperature. Furthermore, the wettability of liquid EGaSn alloy on the current collector in the Ar atmosphere was greatly improved through the construction of Ag3Ga modified layer on the stainless steel mesh (ssm) surface. And the Ag3Ga-EGaSn anode displays the much better Li storage performance (specific capacity, rate performance and cycling stability) than the untreated EGaSn anode. More importantly, operando XRD measurement clearly clarified the electrochemical reaction mechanism of Ag3Ga-EGaSn in LIBs. This work indicates a potential strategy to directly use liquid Ga-based electrode with regulated wettability for LIBs.

Construction of Porous Aromatic Frameworks with Specifically Designed Motifs for Charge Storage and Transport.

ConspectusPorous frameworks possess high porosity and adjustable functions. The two features conjointly create sufficient interfaces for matter exchange and energy transfer within the skeletons. For crystalline porous frameworks, including metal organic frameworks (MOFs) and covalent organic frameworks (COFs), their long-range ordered structures indeed play an important role in managing versatile physicochemical behaviors such as electron transfer or band gap engineering. It is now feasible to predict their functions based on the unveiled structures and structure-performance relationships. In contrast, porous organic frameworks (POFs) represent a member of the porous solid family with no long-range regularity. For the case of POFs, the randomly packed building units and their disordered connections hinder the electronic structural consistency throughout the entire networks. However, many investigations have demonstrated that the functions of POFs could also be designed and originated from their local motifs.In this Account, we will first provide an overview of the design and synthesis principles for porous aromatic frameworks (PAFs), which are a typical family of POFs with high porosity and exceptional stability. Specifically, the functions achieved by the specific design and synthesis of in-framework motifs will be demonstrated. This strategy is particularly intuitive to introduce desired functions to PAFs, owing to the exceptional tolerance of PAFs to harsh chemical treatments and synthetic conditions. The local structures can be either obtained by selecting suitable building units, sometimes with the aid of computational screening, or emerge as the product of coupling reactions during the synthetic process. Radical PAFs can be obtained by incorporating a persistent radical molecule as a building unit, and the rigid and porous framework may facilitate the formation of radical species by trapping spins in the organic network, which could avoid the delocalizing and recombining processes. Alternatively, radical motifs can also be formed during the formation of the framework linkages. The coupling reaction plays an important role in the construction of functional motifs like diacetylene. The highly porous, radical PAFs showed significant performance as anodes of lithium-ion batteries. To improve the charge transport within the framework, the building units and their connecting manner were cohesively considered, and the framework with a fully conjugated backbone was built up. In another case, the explicit product of the cross-coupling reaction ensured the precise assembly of two building units with electron donating and accepting abilities; therefore, the moving direction of photogenerated electrons was rationally controlled. Constructing a fully conjugated backbone or rationally designing a D-A system for charge transfer in porous frameworks introduced exciting properties for photovoltaic and photocatalysis, and their highly porous, stable frameworks improved their functional applications for perovskite solar cells and chemical productions. These investigations shed light on the designable combination of intrinsic functional motifs with highly porous organic frameworks for effective energy storage and conversion.

Effect of asphaltene content in petroleum residues on carbon layer properties and the electrochemical performance of SiOx as an anode in lithium-ion batteries

Effect of asphaltene content in petroleum residues on carbon layer properties and the electrochemical performance of SiOx as an anode in lithium-ion batteries

An Effective Strategy on Synthesizing a Stable SiOx-Based Anode for High Density Lithium-Ion Batteries.

Silicon oxides (SiOx) have received extensive attention as an promising anode candidate for next-generation lithium-ion batteries (LIBs). However, their commerical applications have been seriously hindered by low conductivity,largevolume expansion and unstable soild-electrolyte interface (SEI) layer, which result in low intial coulombic efficiency, poor rate performance and short cycling lifepan. In this work, we demonstrate a simple way to prepare a series of SiOxmaterials with lithiumfluoride(LiF) modified by hydrothermal method and carbothermalmodification. When the mass ratio of SiOxand LiF equals 1:0.15, the long-term cycling capacity retention can be greatly improve form 30.2% to 76.7% after 200 cycles. The result is primarilybecause the enhancementof electrons andLi+-ionstransport andthe stability of SEI layer due to LiF addition. However, excess LiF addition can hinder the diffusion of Li+-ions. This study presents the great potential of LiF modified on SiOxanode materials for LIBs.

Polymer Tetrabenzimidazole Aluminum Phthalocyanine Complex with Carbon Nanotubes: A Promising Approach for Boosting Lithium-Ion Battery Anode Performance

Polymer Tetrabenzimidazole Aluminum Phthalocyanine Complex with Carbon Nanotubes: A Promising Approach for Boosting Lithium-Ion Battery Anode Performance

Formation of nanosized copper silicides in a high-speed electric discharge plasma jet

Relevance. The search for suitable materials for creating a new generation of anodes in lithium-ion batteries that have not only high capacity, but also high electrical conductivity. For this purpose, the attempts have been made to use silicon Si, which has a high specific capacitance, instead of graphite C, but this material does not have high electrical conductivity. Copper silicides, in addition to high specific capacity, have high electrical conductivity values, since they do not react with lithium during operation, and therefore can be used to solve problems in the development of the above-mentioned lithium-ion anodes. Aim. To obtain dispersed materials in a high-speed jet of electric discharge plasma in the Cu-Si-C system. Objects. Dispersed materials obtained in the Cu-Si-C system. Methods. Plasma dynamic synthesis, X-ray diffractometry (X-ray phase analysis), scanning electron microscopy, transmission electron microscopy. Results. The authors have carried out the experimental studies to obtain dispersed materials of the Cu-Si-C system in a high-speed electric-discharge plasma jet and studied the microstructure and composition of the synthesized materials. It was revealed that the product consists of nanodispersed particles, which is confirmed by the results of scanning and electron microscopy. According to the results of X-ray diffractometry, crystalline phases of copper of the cubic system and copper silicides Cu3Si and Cu7Si of the hexagonal system are identified in the composition of the synthesized material.

Novel Three-Dimensional Skeleton Structure Li-B Alloys as Anode for Solid-State Lithium Batteries

Novel Three-Dimensional Skeleton Structure Li-B Alloys as Anode for Solid-State Lithium Batteries

Dual carbon protected ultrafine SnO2 nanoparticles with Sn–C interface for robust lithium storage

Stannic oxide (SnO2)-based lithium-ion batteries (LIBs) have garnered tremendous attention due to their high theoretical capacity and suitable lithium ion insertion potential. However, their widespread applications have been hindered by severe electrode degradation caused by substantial volume expansion of SnO2. In this study, we embedded amorphous carbon encapsulated ultrafine SnO2 nanoparticles on hollow macroporous carbon (AC@SnO2/HMC) as a superior anode material for LIBs. The unique Sn–C interface and dual carbon protection layers effectively mitigated SnO2 nanoparticle agglomeration and volume expansion, reinforcing the cycling stability. Additionally, the capacitive contribution from amorphous carbon significantly improved the reversible capacity and rate capability. As such, the resulting AC@SnO2/HMC electrode exhibited high capacity (1828 mAh g−1 after 200 cycles at 0.1 A g−1), excellent rate capability (1017.6 mAh g−1 at 1 A g−1), and outstanding cycling performance (792.1 mAh g−1 after 880 cycles at 2 A g−1), surpassing previously reported SnO2-based anodes. Furthermore, the AC@SnO2/HMC-based Li-ion full cell demonstrated a remarkable capacity of 566.3 mAh g−1 at 0.2 A g−1 after 200 cycles. This study offers valuable insights into the development of advanced SnO2-based anodes for LIBs and beyond, highlighting their potential for future advancements in battery technology.

Deciphering the structural and kinetic factors in lithium titanate for enhanced performance in Li+/Na+ dual-cation electrolyte

The widespread application of Li4Ti5O12 (LTO) anode in lithium-ion batteries has been hindered by its relatively low energy density. In this study, we investigated the capacity enhancement mechanism of LTO anode through the incorporation of Na+ cations in an Li+-based electrolyte (dual-cation electrolyte). LTO thin film electrodes were prepared as conductive additive-free and binder-free model electrodes. Electrochemical performance assessments revealed that the dual-cation electrolyte boosts the reversible capacity of the LTO thin film electrode, attributable to the additional pseudocapacitance and intercalation of Na+ into the LTO lattice. Operando Raman spectroscopy validated the insertion of Li+/Na+ cations into the LTO thin film electrode, and the cation migration kinetics were confirmed by ab initio molecular dynamic (AIMD) simulation and electrochemical impedance spectroscopy, which revealed that the incorporation of Na+ reduces the activation energy of cation diffusion within the LTO lattice and improves the rate performance of LTO thin film electrodes in the dual-cation electrolyte. Furthermore, the interfacial charge transfer resistance in the dual-cation electrolyte, associated with ion de-solvation processes and traversal of the cations in the solid-electrolyte interphase (SEI) layer, are evaluated using the distribution of relaxation time, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Our approach of performance enhancement using dual-cation electrolytes can be extrapolated to other battery electrodes with sodium/lithium storage capabilities, presenting a novel avenue for the performance enhancement of lithium/sodium-ion batteries.

A Novel Spinel High-Entropy Oxide (Cr0.2Mn0.2Co0.2Ni0.2Zn0.2)3O4 as Anode Material for Lithium-Ion Batteries

In this study, we synthesized spinel high-entropy oxide (HEO) (Cr0.2Mn0.2Co0.2Ni0.2Zn0.2)3O4 nanoparticles by a simple solution combustion method. These particles were investigated for their performance as anodes in lithium-ion batteries. The reversible capacity is 132 mAh·g−1 after 100 cycles at a current density of 100 mA·g−1, 107 mAh·g−1 after 1000 cycles at a current density of 1 A g−1, and 96 mAh·g−1 rate capacity at a high current density of 2 A g−1. The outstanding cycle stability under high current densities and remarkable rate performance can be attributed to the stable structure originating from the high entropy of the material.

Tailored synthesis of a unique two-dimensional pretzel-like core-shell SnO2/C composite for improved lithium storage performance

In this research, a unique two-dimensional (2D) core-shell SnO2/C composite with a distinctive pretzel-like morphology was successfully synthesized using the tin-citrate complex as the tin source, and glucose as the carbon source through a hydrothermal synthesis, and followed by a high-temperature carbonization process. When assessed as an anode for lithium-ion batteries (LIBs), the composite demonstrated a significant specific capacity of 529 mAh g−1 at a current density of 200 mA g−1 after 100 cycles. Furthermore, it maintained ca. 200 mAh g−1 at a high current density of 1.6 A g−1, indicating excellent cycling stability and rate capability. The remarkable electrochemical performance can be ascribed to the well-dispersed nanoscale SnO2 particles within the amorphous carbon matrix, the distinctive core-shell structure and 2D pretzel-like conductive network. The prepared SnO2/C composite can be a promising alternative anode for future LIBs, offering higher energy density, prolonged cycle life, and faster charging capability compared to traditional graphite-based anodes.

The role of carbon component on the electrochemical performances of Ti0.95Nb0.95O4/C composites as anode of lithium-ion batteries

The role of carbon component on the electrochemical performances of Ti0.95Nb0.95O4/C composites as anode of lithium-ion batteries

A Novel Gelatin Binder with Helical Crosslinked Network for High-Performance Si Anodes in Lithium-Ion Batteries.

Silicon(Si) is a promising anode material for lithium-ion batteries, but its large volume expansion during cycling poses a challenge for the binder design. In this study, a novel gelatin binder is designed and prepared with a helical crosslinked network structure. This gelatin binder is prepared by enzymatic crosslinking and immersion in Hofmeister salt solution, which induces the formation of network and helical secondary structures. The helical crosslinked network structure can be analogous to a spring group system to effectively dissipate the stress and strain caused by the Si expansion. The gelatin binder is further partially carbonized by low-temperature pyrolysis, which improves its conductivity and stability. The Sianode with the optimized gelatin binder exhibits high initial coulombic efficiency, excellent rate performance, and long-term cycling stability. This study provides an innovative approach for the preparation of high-performance Si anodes, namely by controlling the molecular configuration of the binder to significantly improve the cycle stability, which can also be applied to other high-capacity anode materials that suffer from large volume changes during cycling.

A Triple Crosslinked Binder with Hierarchical Stress Dissipation and High Ionic Conductivity for Advanced Silicon Anodes in Lithium-ion Batteries.

Silicon (Si) is a promising anode material for high-energy-density lithium-ion batteries, but the significant volume change of Si particles during alloying/dealloying with lithium (Li) undermines the mechanical integrity of Si anode, causing electrode fracture, delamination and rapid capacity decay. Herein, a robust triple crosslinked network (TCN) binder with high ionic conductivity and hierarchical stress dissipation is reported for Si anodes, which is prepared by in situ chemical crosslinking polyacrylic acid (PAA) and melamine (MA). The triple interactions of hydrogen bonds, electrostatic interactions, and covalent amide bonds enhance the adhesion of binder to Si and synergistically promote stress dissipation within Si anodes, thus strengthening the dynamic structural stability of Si anodes during cycling. Moreover, the rapid coupling/decoupling of Li+ with the TCN binder enables an impressive Li+ transference number of 0.63 and high ionic conductivity of 1.2 × 10-4 Scm-1. Consequently, the Si-TCN anode delivers specific capacity of 2268 mAhg-1 with a high mass loading of 2mgcm-2, high-rate performance of 1673 mAhg-1 at 5 Ag-1, and stable cycling for 250 cycles at 1 Ag-1, thus showing great prospects for high-energy-density Si-based batteries.

Hierarchical Nanoporous N-Doped Carbon for Enhanced Rate Performance of Lithium-Ion Battery Anodes

Hierarchical Nanoporous N-Doped Carbon for Enhanced Rate Performance of Lithium-Ion Battery Anodes

Coaxial electrospinning synthesis free-standing Sn/TiO2 flexible carbon fibers with sheath/core structure for advanced flexible lithium/potassium-ion batteries

Flexible Sn/TiO2 carbon nanofiber (ST-NCF) composites were constructed by doping TiO2 into tin-based carbon nanofibers via coaxial electrospinning. Sn/TiO2 carbon nanofiber was directly used as an anode for Lithium-ion Batteries (LIBs) and Potassium-ion Batteries (PIBs), which show exceptional electrochemical performances. The layered sheath/core structure of the material lead to its good electrochemical properties, where the core Sn carbon nanofiber was encapsulated by the sheath layer of TiO2 nanoparticles. In addition to enhancing its electrical conductivity, the outer TiO2 and N-doped carbon fiber matrix also provide a buffer zone for volumetric strain during charging and discharging. The fiber core Sn and sheath TiO2 form a heterojunction interface on the two-dimensional tube surface, which increases the diffusion rate of ions and electrons. After 100 cycles, TiO2-NCF and ST-NCF-40%TBT (40% TBT indicates the percentage of TiO2 in shell solution to the total composition of shell spinning solution) show capacities of 386.6 mAh g−1 and 1336 mAh g-1, respectively, at 0.5A g-1. After 2000 cycles, ST-NCF-40%TBT in LIBs displayed a high capacity of 299 mAh g-1 at 10 A g-1. After 350 cycles at 1A g-1, the capacity of ST-NCF-40%TBT in PIBs is reserved at 307 mA h g-1. Due to the superior mechanical flexibility of ST-NCF-40%TBT films, it will be a promising anode candidate for flexible LIBs and PIBs.