Anode For Lithium-ion Batteries Research Articles

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.

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.

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

The timescale identification and quantification of complicated kinetic processes in lithium-ion batteries based on micro-reference electrodes

The lack of reliable methods for acquiring accurate and stable electrochemical impedance spectroscopy (EIS) data at both the cathode and anode makes overlapping kinetic processes in commercial lithium-ion batteries (LIBs) with enhanced capacity and size indistinguishable. Micro-reference electrodes offer an elegant solution for obtaining accurate and stable EIS data for both the cathode and anode. The proposed selection model ensures that the mean absolute percentage error between the EIS of the combined cathode and anode and the battery remains below 3.5 % under varying temperatures and states of charge (SOCs). Different SOCs, temperatures, and pressures are utilized on the timescale to identify and quantify the kinetic processes of the cathode and anode. The results indicate that under varying temperature conditions, the process of Li+ traversing the solid electrolyte interphase dominates the total impedance of the battery, contributing over 75 %. At −10 °C, polarization resistance from this process exceeds a 2500 % increase compared to 20 °C. Moreover, the variations in the kinetic processes of LIB cathodes and anodes with temperature are revealed on the timescale, with potential reasons for the overlap of kinetic processes provided. This study offers new insights into LIB electrode kinetics and lays a theoretical groundwork for enhancing battery design and performance.

Dual-Function Alloying Nitrate Additives Stabilize Fast-Charging Lithium Metal Batteries.

Lithium metal is regarded as the "holy grail" of lithium-ion battery anodes due to its exceptionally high theoretical capacity (3800 mAh g-1) and lowest possible electrochemical potential (-3.04 V vs Li/Li+); however, lithium suffers from the dendritic formation that leads to parasitic reactions and cell failure. In this work, we stabilize fast-charging lithium metal plating/stripping with dual-function alloying M-nitrate additives (M: Ag, Bi, Ga, In, and Zn). First, lithium metal reduces M, forming lithiophilic alloys for dense Li nucleation. Additionally, nitrates form ionically conductive and mechanically stable Li3N and LiNxOy, enhancing Li-ion diffusion through the passivation layer. Notably, Zn-protected cells demonstrate electrochemically stable Li||Li cycling for 750+ cycles (2.0 mA cm-2) and 140 cycles (10.0 mA cm-2). Moreover, Zn-protected Li||Lithium Iron Phosphate full-cells achieve 134 mAh g-1 (89.2% capacity retention) after 400 cycles (C/2). This work investigates a promising solution to stabilize lithium metal plating/stripping for fast-charging lithium metal batteries.

Recycled micro-sized silicon anode for high-voltage lithium-ion batteries

Recycled micro-sized silicon anode for high-voltage lithium-ion batteries

Theoretical prediction on Irida-graphene monolayer as promising anode material for lithium-ion batteries

With the growing interest in energy storage technologies, the demand for alternative rechargeable batteries has become increasingly urgent. We evaluate the feasibility of a two-dimensional (2D) material, Irida-graphene (IG) monolayer, as an anode for lithium-ion batteries (LIBs) through first-principles calculations. IG monolayer, after Li adsorption, exhibits metallic property, suggesting the good electrical conductivity. Additionally, in comparison with IG bilayer, IG monolayer possesses low diffusion barriers (0.19–0.24 eV), high theoretical capacity (1115.8mA h/g), and low average open circuit voltage (0.317 V). Furthermore, under the influence of solvent effects, the adsorption performance becomes even more stable, and the theoretical capacity increases. These intriguing findings make IG monolayer great potentials for the anode of LIBs.

Lithiation Depth Regulation of Silicon Anodes toward Excellent Stability.

Silicon (Si) is an appealing choice of anode for next-generation lithium ion batteries with high energy density, but its dramatic volume expansion makes it a tremendous challenge to achieve acceptable stability. Herein, we demonstrate that no capacity decay is observed during the testing period when the lithiation depth of Si nanoparticles is regulated at 2000 mAh g-1 or below, the fracture of Si anode films is well mitigated under suitable regulation of lithiation depth, and the cycled Si remains particulate without turning flocculent as under full lithiation. In addition, the solid electrolyte interphase (SEI) with a LiF-dominated outer region produced under lithiation regulation could better passivate the Si anodes and prevent further electrolyte decomposition than the mosaic-type SEI formed under full lithiation. Regulating lithiation depth proved to be a feasible solution to the pressing volume issues, and optimization of capacity utilization should be considered as much as materials-level optimization.

Enabling stable high lithium storage of Si anode via synergistic effects of nanosized Fe3C and partially graphitized porous carbon

Si is considered as a promising anode for high-energy lithium-ion batteries (LIBs) because of its ultrahigh theoretical specific capacity and desired working potential. However, the main problems of Si as an anode are still faced with low conductivity and inevitable structure damage caused by large volume change during cycle. Although design of Si/C composites effectively mitigates the above problems, their preparation usually involves complex methods. This work demonstrates a very simple ball milling and subsequent carbonization approach for the preparation of high-performance Si NPs@Fe3C@PC anode, which integrates partially hollow Fe3C nanoparticles (Fe3C) and partially graphitized porous carbon (PC) into Si nanoparticles (Si NPs)-based composite. It is found that Fe3C with catalysis is favorable not only to formation of a graphitized porous carbon during material preparation but also to formation of a stable solid electrolyte interfaces (SEI) on electrode surface during cycle. With Fe3C, the Si NPs@Fe3C@PC shows smaller Li+ adsorption energy, lower activation energy, higher electric conductivity, larger Li+ diffusion coefficient and a thinner SEI film than Si NPs and Si NPs@PC counterparts. The findings verify that the synergistic effects of the Fe3C and PC provide fast kinetics, high capacitive contribution, improved structure stability and a stable LiF-rich SEI film for Si NPs@Fe3C@PC during cycle. Therefore, Si NPs@Fe3C@PC shows excellent electrochemical performance, gaining 1786, 1211.4 and 411.5 mAh/g after 210, 650 and 840 cycles at 100, 1000 and 5000 mA g−1, respectively. Finally, this contribution proposes a simple and effective strategy for improving Si NPs performance and hence obtaining a high-performance of Si-based anode for LIBs.

Dynamic magnesiothermic reduction of various silica to porous silicon structures for lithium battery anodes

A dynamic magnesiothermic reduction (DMR) of various silica having different size and porosity is conducted to study the effects of silica properties on the ⅰ) DMR reaction kinetics, ⅱ) properties of resulting porous silicon (pSi) microparticles, and ⅲ) performances of pSi/C composites as anodes in lithium batteries. A DMR kinetic study using the Ginstling–Brounstein diffusion model shows that the smaller the silica particle size, the higher the reduction rate and the lower the apparent activation energy. Irrespective of silica properties, all the resulting pSi particles have mesoporous structures. The pSi particles comprise interconnected small primary silicon nanoparticles (approximately 30–40 nm in diameter) to render similar particle morphologies to those of the parent silica. Owing to these appealing features of pSi particles, pSi/C composites exhibit excellent cycling performance for over 200 cycles and high rate capabilities, whereas SiMP/C (prepared with a non-porous silicon microparticles) loses most of its capacity in early cycles owing to high resistance build-up during cycling. Overall, the DMR of silica precursors of several micrometers or less in size (preferably porous precursors) are desirable for the production of high-purity pSi microparticles for use in high-capacity and stable anodes for advanced lithium batteries.

SnS nanoflowers as an efficient anode for next generation lithium-ion batteries

Tin (II) Sulfide (SnS) nanoflowers are synthesized by hydrothermal method. The electrochemical performance of SnS nanoflower versus Li/Li+ is studied. X-ray diffraction and X-ray photoelectron spectroscopy results confirms the formation of SnS. Scanning electron microscope images validate the existence of nanoflowers. SnS vs. Li/Li+ half-cell delivers the first charge/discharge capacity of 847.2/853 mAh g−1 at 0.1 C-rate, with a columbic efficiency of 99 %. Differential capacity versus voltage plot reveals intercalation and deintercalation of lithium ions during cycling and also delves the conversion and alloying reaction of SnS anodes. The better electrochemical result could be ascribed to the flower like morphology, which improves lithium diffusion and reaction kinetics.

Densification of Alloying Anodes for High Energy Lithium-Ion Batteries: Critical Perspective on Inter- Versus Intra-Particle Porosity.

High Li-storage-capacity particles such as alloying-based anodes (Si, Sn, Ge, etc.) are core components for next-generation Li-ion batteries (LIBs) but are crippled by their intrinsic volume expansion issues. While pore pre-plantation represents a mainstream solution, seldom do this strategy fully satisfy the requirements in practical LIBs. One prominent issue is that porous particles reduce electrode density and negate volumetric performance (WhL-1) despite aggressive electrode densification strategies. Moreover, the additional liquid electrolyte dosage resulting from porosity increase is rarely noticed, which has a significant negative impact on cell gravimetric energy density (Whkg-1). Here, the concept of judicious porosity control is introduced to recalibrate existing particle design principles in order to concurrently boost gravimetric and volumetric performance, while also maintaining the battery's cycle life. The critical is emphasized but often neglected role that intraparticle pores play in dictating battery performance, and also highlight the superiority of closed pores over the open pores that are more commonly referred to in the literature. While the analysis and case studies focus on silicon-carbon composites, the overall conclusions apply to the broad class of alloying anode chemistries.

ZIF-derived "cocoon"-like in-situ Zn/N-doped carbon as high-capacity anodes for Li/Na-ion batteries

Owing to the unique structure and physicochemical properties, including high specific surface area, self-doped N atoms, open pore structure and good chemical stability, zeolitic imidazolate frameworks (ZIFs) and their derivatives have been widely used in the field of energy storage. Here, a new type of "cocoon"-like Zn/N doped ZIF-derived porous carbon (Zn@N-C-800) is synthesized as an anode for lithium-ion batteries (LIBs) and sodium ion batteries (SIBs) through a one-step carbonization process using a novel Zn-ZIF as the precursor. In Zn@N-C-800, the "cocoon"-like disordered carbon skeleton is conducive to electrolyte infiltration, while the Zn/N doping can provide additional active sites for ion storage. Benefiting from these unique structural characteristics, Zn@N-C-800 achieves excellent electrochemical performances as anode for both LIBs and SIBs: an ultrahigh rate capability of 352 mAh g−1 can be delivered at 12.8 A g−1 for LIBs; an outstanding long-term cycling stability (312 mAh g−1 at 1 A g−1 after 2000 cycles) can be achieved for SIBs. This paper provides new ideas for the design and preparation of high-performance anodes for LIBs and SIBs.

High-stable and High-capacity Sn/SnO2@C as Anode of Lithium-ion Batteries

High-stable and High-capacity Sn/SnO2@C as Anode of Lithium-ion Batteries