Anode For Batteries Research Articles

Research Progress and Future Expectations in Anode of Secondary Zinc-Air Batteries: A Review

Research Progress and Future Expectations in Anode of Secondary Zinc-Air Batteries: A Review

Extended Plateau Capacity of Hard Carbon Anode for High Energy Lithium-Ion Batteries.

Hard carbon materials have shown promising potential for sodium-ion storage due to accommodating larger sodium ions. However, as for lithium-ion storage, the challenge lies in tuning the high lithiation plateau capacities, which impacts the overall energy density. Here, hard carbon microspheres (HCM) are prepared by tailoring the cross-linked polysaccharide, establishing a comprehensive methodology to obtain high-performance lithium-ion batteries (LIBs) with long plateau capacities. The "adsorption-intercalation mechanism" for lithium storage is revealed combining in situ Raman characterization and ex situ nuclear magnetic resonance spectroscopy. The optimized HCM possesses reduced defect content, enriched graphitic microcrystalline, and low specific surface area, which is beneficial for fast lithium storage. Therefore, HCM demonstrates a high reversible capacity of 537mAhg-1 with a significant low-voltage plateau capacity ratio of 55%, high initial Coulombic efficiency, and outstanding rate performance (152mAhg-1 at 10Ag-1). Moreover, the full cell (HCM||LiCoO2) delivers outstanding fast-charging capability (4min charge to 80% at 10C) and impressive energy density of 393Whkg-1. Additionally, 80% reversible capacity can be delivered under -40°C with competitive cycling stability. This work provides in-depth insights into the rational design of hard carbon structures with extended low-voltage plateau capacity for high energy LIBs.

Double-layer carbon coated on the micrometer bismuth by photothermal effect as anode for high-rate sodium-ion batteries

Bismuth (Bi) is considered a promising anode material for high-rate sodium-ion batteries (SIBs) due to its unique layered crystal structure which can easily insert/extract sodium-ion (Na+). However, the cycle stability of micrometer Bi with great commercial potential needs to be improved. Because the large volume change occurs during alloying/dealloying of Bi and sodium (Na) resulting in the crack of Bi, which reduces the stability of the battery. Herein, we design a Bi/Bi2O3@C composite where a double-layer carbon coated commercial micrometer Bi/Bi2O3 particles. The heat generated by Bi/Bi2O3 particles under ultraviolet (UV) exposure (called photothermal effect) accelerates the decomposition rate of photoinitiator, which in turn improves the polymerization rate of the monomer on the surface of Bi/Bi2O3 particles. So that, the surface of Bi/Bi2O3 particles is coated with a dense polymer, while the polymer away from the particle is relatively loose, thus forming a dense-loose double-layer carbon during the annealing process. The dense carbon layer can effectively protect against the volume effect of Bi/Bi2O3, and the loose carbon layer can provide channels for the transport of Na+. As a result, Bi/Bi2O3@C exhibits excellent cycling stability with a capacity retention rate of 94.5 % after 1600 cycles at 10 A g−1.

Cost-effective preparation of high-performance Si@C anode for lithium-ion batteries

Cost-effective preparation of high-performance Si@C anode for lithium-ion batteries

Amorphous GeSnSe nanoparticles as a Li-Ion battery anode with High-Capacity and long cycle performance

A new ternary amorphous GeSnSe (GSS) nanopowder was effectively synthesized by using ball milling under inert atmosphere. Its topographical, microstructural and elemental characterizations revealed the formation of nanoparticles with undefined shape, short-range order and the tailored stoichiometry. Remarkably, this novel amorphous material demonstrates its competences as a promising Li-ion host anode, exhibiting a high cycle performance with a specific charge capacity of 963 mAh g−1 at an applied C-rate of 0.2C with a coulombic efficiency > 99.4 % after 300 cycles. Its high specific capacity, large rate capability, acceptable capacity retention and long cycle life could be attributed to a dual Li-ion storage mechanism that consists mostly of multiple reversible electrochemical processes as conversion and alloying reactions and capacitive processes. Moreover, its stable volume expansion (34 %), moderate electrode polarization (248.9 mV), reasonable charge transfer resistance (83 Ω) and apparent Li-ion diffusion coefficients between 10–9 – 10–14 cm2 s−1 could be promoted by a synergistic effect between Ge (capacity), Sn (conductivity) and Se (stability), which plays an important role on the stability and high cycle performance of the promising GSS-based anode.

Ice template-induced assembly coupled with carbonization strategy for preparation of sulfur-doped porous carbon nanosheets from lignite as high-capacity anode for lithium-ion batteries

Two-dimensional (2D) porous carbon nanosheets with heteroatom doping are promising anode materials for lithium-ion batteries (LIBs) due to their distinctive sheet-like structure and excellent electrical conductivity. Limited by high preparation costs and cumbersome preparation processes, the large-scale production of carbon nanosheets remains a major challenge. Herein, a series of sulfur-doped porous carbon nanosheets (SCNSs) are successfully synthesized through ice template-induced assembly coupled with a carbonization approach using aromatic ring fragments exfoliating from lignite as the precursor and K2SO4 as the sulfur source. The prepared SCNSs exhibit well-defined sheet-like structures, abundant hierarchical nanopores, large specific surface areas (∼1761 m2·g−1), and high sulfur doping contents (∼7.72 at%). Such unique microstructure characteristics of SCNSs not only provide favorable and efficient channels for the lithium-ions/electrons transportation but also offer sufficient available space or active sites for lithium-ions storage. When used as anode materials for LIBs, the SCNS-3 shows high reversible capacity (1620 mAh·g−1 at 0.05 A·g−1), excellent rate performance (315 mAh·g−1 at 2 A·g−1), and superior cycling stability (901 mAh·g−1 at 1 A·g−1 after 500 cycles). Lithium storage behavior analysis indicated that the capacitance enhancement in SCNSs anodes is primarily due to improved capacitive behavior. This study provides a novel and effective route for the large-scale production of sulfur-doped carbon nanosheets using aromatic ring fragments exfoliated from lignite, which demonstrates promising industrial application potential in LIBs anode materials.

Lithium Hydride in the Solid Electrolyte Interphase of Lithium‐Ion Batteries as a Pulverization Accelerator of Silicon

As a highly promising next‐generation high‐specific capacity anode, the industrial‐scale utilization of micron silicon has been hindered by the issue of pulverization during cycling. Although numerous studies have demonstrated the effectiveness of regulating the inorganic components of the solid electrolyte interphase (SEI) in improving pulverization, the evolution of most key inorganic components in the SEI and their correlation with silicon failure mechanisms remain ambiguous. This study provides a clear and direct correlation between the lithium hydride (LiH) in the SEI and the degree of micron silicon pulverization in the battery system. The reverse lithiation behavior of LiH on micron silicon during de‐lithiation exacerbates the localized stress in silicon particles and contributes to particle pulverization. This work successfully proposes a novel approach to decouple the SEI from electrochemical performance, which can be significant to decipher the evolution of critical SEI components at varied battery anode interfaces and analyze their corresponding failure mechanisms.

Recent Progress in Using Covalent Organic Frameworks to Stabilize Metal Anodes for Highly-Efficient Rechargeable Batteries.

Alkali metals (Li, Na, and K) and multivalent metals (Zn, Mg, Ca, and Al) have become star anodes for developing high-energy-density rechargeable batteries due to their high theoretical capacity and excellent conductivity. However, the inevitable dendrites and unstable interfaces of metal anodes pose challenges to the safety and stability of batteries. To address these issues, covalent organic frameworks (COFs), as emerging materials, have been widely investigated due to their regular porous structure, flexible molecular design, and high specific surface area. In this minireview, we summarize the research progress of COFs in stabilizing metal anodes. First, we present the research origins of metal anodes and delve into their advantages and challenges as anodes based on the physical/chemical properties of alkali and multivalent metals. Then, special attention has been paid to the application of COFs in the host design of metal anodes, artificial solid electrolyte interfaces, electrolyte additives, solid-state electrolytes, and separator modifications. Finally, a new perspective is provided for the research of metal anodes from the molecular design, pore modulation, and synthesis of COFs.

A gradient-distributed binder with high energy dissipation for stable silicon anode

Silicon is considered as a promising alternative to traditional graphite anode for lithium-ion batteries. Due to the dramatic volume expansion of silicon anode generated from the insertion of Li+ ions, the binder which can suppress the severe volume change and repeated massive stress impact during cycling is required greatly. Herein, we design a gradient-distributed two-component binder (GE-PAA) to achieve excellent cyclic stability, and reveal the mechanism of high energy dissipative binder stabilized silicon electrodes. The inner layer of the electrode is the polyacrylic acid polymer (PAA) with high Young’s modulus, which is used as the skeleton binder to stabilize the silicon particle interface and the electrode structure. The outer layer is the gel electrolyte polymer (GE) with lower Young’s modulus, which releases the stress generated during the lithiation and de-lithiation process effectively, achieving the high structural stability at the molecular level and silicon particles. Due to the synergistic effect of the gradient binder design, the silicon electrode retains a reversible capacity of 1557.4 mAh g-1 after 200 cycles at the current density of 0.5 C and 1539.2 mAh g-1 at a high rate of 1.8 C. This work provides a novel binder design strategy for Si anode with long cycle stability.

Possibility of defective monolayer graphene as potential anode material of metal-ion batteries

The necessitates exploration in the field of rechargeable metal ion batteries demands safe, cost-efficient, and face significant challenges in their development. Defect engineering may be helpful for the ion storage and diffusion in the battery anodes. In this paper, we use density functional theory to investigate the adsorption and diffusion behavior of Li, Mg, and Al atom on single vacancy (SV), Stone-Wales vacancy (SWV), double vacancy (DV) and quadruple vacancy (QV) defective monolayer graphene. It is evident that metal exhibits the strongest adsorption strengthen at the defect center. The DV and QV defective graphene shows the ideal diffusion energy barrier for three metals. Importantly, the QV structure exhibit maximum storage capacities of the 775 mAh/g for Li, 911 mAh/g for Mg, and 1543.4 mAh/g for Al respectively. Additionally, their open-circuit voltages are all in a very safe range. This study can support a strong basis for the experimental research for metal-ion battery anodes.

Regeneration of photovoltaic industry silicon waste toward high-performance lithium-ion battery anode

Regeneration of photovoltaic industry silicon waste toward high-performance lithium-ion battery anode

The Burgeoning Zinc Powder Anode for Aqueous Zinc Metal Batteries: from Electrode Preparation to Performance Enhancement

AbstractAqueous zinc metal batteries (AZMBs) have emerged as a focal point of interest in academic research and industrial strategic planning. Zinc powder (ZP) is poised to assume a prominent position in both future research and practical applications due to its high Zn utilization rate and processability. However, critical challenges need to be addressed before realizing substantial progress. Notably, severe voltage polarization and gas production of ZP electrodes stand out as the primary causes of battery failure, differing with zinc foil where short circuits caused by zinc dendrites contribute to battery failure. While numerous comprehensive reviews have offered effective strategies for zinc foil, a systematic summary of ZP electrodes is still lacking. For ZP, electrode preparation dictates the performance. This review summarizes the criteria for optimal ZP electrodes, covering electrode components, preparation methods, and technique parameters. It emphatically introduces the underlying causes and strategies of water‐related side reactions and briefly analyzes the stripping/plating behaviors of ZP electrodes. The status quo of ZP‐based batteries is then discussed in categories of ZP, current collector, conductive scaffold, binder, and electrolytes. Finally, potential avenues for future research are proposed from three aspects to enhance the focus on ZP electrodes and facilitate the practical application of AZMBs.

Monolithic Layered Silicon Composed of a Crystalline-Amorphous Network for Sustainable Lithium-Ion Battery Anodes.

While nanostructural engineering holds promise for improving the stability of high-capacity silicon (Si) anodes in lithium-ion batteries (LIBs), challenges like complex synthesis and the high cost of nano-Si impede its commercial application. In this study, we present a local reduction technique to synthesize micron-scale monolithic layered Si (10-20 μm) with a high tap density of 0.9-1.0 g cm-3 from cost-effective montmorillonite, a natural layered silicate mineral. The created mesoporous structure within each layer, combined with the void spaces between interlayers, effectively mitigates both lateral and vertical expansion throughout repeated lithiation/delithiation cycles. Furthermore, the remaining SiO2 network fortifies the layered structure, preventing it from collapsing during cycling. Half-cell tests reveal a capacity retention of 92% with a reversible capacity of 1130 mAh g-1 over 500 cycles. Moreover, the pouch cell integrated with this Si anode (with a mass loading of 3.0 mg cm-2) and a commercial NCM811 cathode delivers a high energy density of 655 Wh kg-1 (based on the total mass of the cathode and anode) and maintains 82% capacity after 200 cycles. This work demonstrates a cost-efficient and scalable strategy to manufacture high-performance micron Si anodes for the ever-growing demand for high-energy LIBs.

Novel multiphase nano Ni3Bi2S2/NiS anchored on graphite nanosheet for high-capacity sodium-ion battery anodes

In the context of scalable electrode production via ball-milling, achieving high cycling stability and electrochemical performance in bifunctional anodes for sodium ion batteries (SIBs) is crucial yet remains a significant challenge. To address these objectives, we have developed a unique hybrid anode nanocomposite characterized by its local multiphase nature. This composite involves the incorporation of novel ternary-Ni-Bi-S/binary-Ni-S nanomaterials onto exfoliated graphite nanosheets (Ni3Bi2S2/NiS-G) through a facile ball-milling process. Our combined experimental and theoretical investigations suggest that the interactions between graphite nanosheets and the layered structure of Ni3Bi2S2/NiS, along with the discharge products of Na2S, play pivotal roles in enhancing the Na+ diffusion rate and stability of the hierarchical configuration anode. Upon testing, the novel Ni3Bi2S2/NiS-G shows overwhelmingly higher electrochemical performance compared to the Ni3Bi2S2/NiS counterpart, the Ni3Bi2S2/NiS-G delivered a reversible capacity of 489.9 mAh/g at 0.2 A/g after 400 cycles, and displayed a high capacity of 387.3 and 339.6 mAh/g after 500 cycles at 1 A/g and 2 A/g, respectively, yielding a high capacity retention ratio of 84.8 % and 82.8 % of the 1st cycle. This work provided a novel approach for developing new bifunctional anode electrodes with high capacity and rate performance as well as superior cycling stability.

On the Dendrite‐Suppressing Effect of Laser‐Processed Polylactic Acid‐Derived Carbon Coated Zinc Anode in Aqueous Zinc Ion Batteries

AbstractA major bottleneck limiting the commercialization of aqueous zinc ion batteries (AZIBs) is dendrite formation on the zinc (Zn) anode during the plating/stripping process, which leads to rapid deterioration in performance and, consequently to the device failure. In this regard, researchers are trying to design more stable anodes toward suppressing dendrite formation. One possible solution to tackle this problem and to extend the cycling life of AZIBs is to modify the zinc anode surface by coating carbonaceous materials, enabling more controlled charge flux and uniform ion distribution. This work reports sustainable and bio‐derived polylactic acid (PLA) as a coating layer on the zinc anode. Carbonizing this polymer under ambient conditions using a high‐power nanosecond laser forms a carbon‐coated zinc foil, which was directly utilized as the anode in aqueous zinc ion batteries. The fabricated laser‐processed PLA‐derived carbon‐coated zinc anode demonstrated an extended cycling life of almost 1600 hours, significantly outperforming the bare zinc anode. A full aqueous zinc ion battery assembled from as‐modified anode and as‐prepared V2O5 nanofibers as cathode was able to deliver a specific capacity of 238 mAh g−1 at 1.0 A g−1 with a capacity retention of 70 % after 1000 cycles.

On the Dendrite-Suppressing Effect of Laser-Processed Polylactic Acid-Derived Carbon Coated Zinc Anode in Aqueous Zinc Ion Batteries.

A major bottleneck limiting the commercialization of aqueous zinc ion batteries (AZIBs) is dendrite formation on the zinc (Zn) anode during the plating/stripping process, which leads to rapid deterioration in performance and, consequently to the device failure. In this regard, researchers are trying to design more stable anodes toward suppressing dendrite formation. One possible solution to tackle this problem and to extend the cycling life of AZIBs is to modify the zinc anode surface by coating carbonaceous materials, enabling more controlled charge flux and uniform ion distribution. This work reports sustainable and bio-derived polylactic acid (PLA) as a coating layer on the zinc anode. Carbonizing this polymer under ambient conditions using a high-power nanosecond laser forms a carbon-coated zinc foil, which was directly utilized as the anode in aqueous zinc ion batteries. The fabricated laser-processed PLA-derived carbon-coated zinc anode demonstrated an extended cycling life of almost 1600 hours, significantly outperforming the bare zinc anode. A full aqueous zinc ion battery assembled from as-modified anode and as-prepared V2O5 nanofibers as cathode was able to deliver a specific capacity of 238 mAh g-1 at 1.0 A g-1 with a capacity retention of 70 % after 1000 cycles.

The C-BixSnSb composite toward fast-charging and long-life sodium-ion batteries

Sodium ion batteries (SIBs) fitted with high-rate and high-capacity anodes are attractive for their higher energy density and faster charging capability. However, it is still a challenge to develop high-energy SIBs with high power and long life, due to the sluggish kinetic and limited Na+ insertion in electrode materials. The inherent crystal structure and constituent element are two important factors to resolve the critical issues faced above. Taking the merits of layer-structure and middle-entropy, herein, we proposed and designed a high ion-conductive composite combing with ternary alloy and layered BixSnSb@C nanofibers, which eliminate ion migration barriers while maintaining the structural framework for superior rate property and cycle stability. Used as anode for SIBs, the multiphase BixSnSb@C with adjustable Bi content exhibits excellent Na storage capability as compared to their single phase counterpart. Specially, up to a rate of 132C (50 A g−1), the capacity is still as high as 400 mAh g−1, meanwhile, after 5000 charge and discharge cycles at a current density of 12C, the capacity still maintains 85 % of its initial capacity, which outperform the individual Bi- or SnSb-based materials. The superior electrochemical performances originate from the middle-entropy nature and layer structure of BiSnSb alloy, which can provide more channels for fast Na+ transport, and accommodate large volume changes. Besides, the activity energy and ions transport resistance of Na+ in different composites were evaluated. Furthermore, the full-cell coupled with NaNi1/3Fe1/3Mn1/3O2 as cathode was formed and a capacity retention of ∼80 % is realized in 100 cycles. The results show that the BixSnSb@C is a potential anode for fast-charging Na-ion batteries and could be used to guide the design of multi-component alloy-base anodes.

Facile synthesis of SiOx/C as high-performance anodes for lithium-ion batteries

Despite its high capacity (∼2615 mAh·g−1), silicon oxide (SiOx) suffers from low electrical conductivity and volume expansion during cycling, leading to capacity fading. In this work, a SiOx/C composite was synthesized by magnesium thermal reduction using co-assembled mesoporous SiO2 and graphitic carbon nitride (g-C3N4) as precursors. The SiOx/C composite displays a sheet-like nanostructure with highly dispersed SiOx. The presence of carbon enhances the conductivity and structural stability of the composite, leading to a low charge resistance (94.0 Ω), fast lithium diffusion (DLi+ = 5.15 × 10−14 cm2·s−1), and excellent cycling capability (863 mAh·g−1 after 160 cycles).

Construction of sub micro-nano-structured silicon based anode for lithium-ion batteries

The significant volume change experienced by silicon (Si) anodes during lithiation/delithiation cycles often triggers mechanical-electrochemical failures, undermining their utility in high-energy-density lithium-ion batteries (LIBs). Herein, we propose a sub micro-nano-structured Si based material to address the persistent challenge of mechanic-electrochemical coupling issue during cycling. The mesoporous Si-based composite submicrospheres (M-Si/SiO2/CS) with a high Si/SiO2 content of 84.6 wt.% is prepared by magnesiothermic reduction of mesoporous SiO2 submicrospheres followed by carbon coating process. M-Si/SiO2/CS anode can maintain a high specific capacity of 740 mAh g−1 at 0.5 A g−1 after 100 cycles with a lower electrode thickness swelling rate of 63%, and exhibits a good long-term cycling stability of 570 mAh g−1 at 1 A g−1 after 250 cycles. This remarkable Li-storage performance can be attributed to the synergistic effects of the hierarchical structure and SiO2 frameworks. The spherical structure mitigates stress/strain caused by the lithiation/delithiation, while the internal mesopores provide buffer space for Si expansion and obviously shorten the diffusion path for electrolyte/ions. Additionally, the amorphous SiO2 matrix not only servers as support for structure stability, but also facilitates the rapid formation of a stable solid electrolyte interphase layer. This unique architecture offers a potential model for designing high-performance Si-based anode for LIBs.

Shell Modulation of Hollow Metal Sulfide Nanocomposite for Stable Potassium Storage at Room and High Temperature.

The large size of K-ion makes the pursuit of stable high-capacity anodes for K-ion batteries (KIBs) a formidable challenge, particularly for high temperature KIBs as the electrode instability becomes more aggravated with temperature climbing. Herein, we demonstrate that a hollow ZnS@C nanocomposite (h-ZnS@C) with a precise shell modulation can resist electrode disintegration to enable stable high-capacity potassium storage at room and high temperature. Based on a model electrode, we identify an interesting structure-function correlation of the h-ZnS@C: with an increase in the shell thickness, the cyclability increases while the rate and capacity decrease, shedding light on the design of high-performance h-ZnS@C anodes via engineering the shell thickness. Typically, the h-ZnS@C anode with a shell thickness of 60 nm can deliver an impressive comprehensive performance at room temperature; the h-ZnS@C with shell thickness increasing to 75 nm can achieve an extraordinary stability (88.6 % capacity retention over 450 cycles) with a high capacity (450 mAh g-1) and a superb rate even at an extreme temperature of 60 °C, which is much superior than those reported anodes. This contribution envisions new perspectives on rational design of functional metal sulfides composite toward high-performance KIBs with insights into the significant structure-function correlation.