High-performance Lithium-ion Battery Anodes Research Articles

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.

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.

A novel embedded KVO3/NC anode for high-performance lithium-ion batteries

Vanadium-based metallic salts, characterized by intrinsic low electronic conductivity, are impeded their advancement as anode materials in the realm of lithium-ion battery technology. This study presents a novel embedded anode material KVO3/NC(KVO/NC) synthesized via a sol–gel method, with KVO3(KVO) particles in situ growing on N-doped carbon, thereby ameliorating conductivity and electrochemical performance. The findings reveal that KVO/NC composite has three lithium-ion storage sites, ultra-high cycling stability (289 mA h/g@5000 cycles@10C@100 %), and superior rate performance (249 mA h/g@15C; 221 mA h/g@20C). Coupled with LiFePO4 cathode, it achieves a competitive energy density (391 W h kg−1@0.1C; 1–3.9 V). This work reveals the practical potential of KVO/NC as a new type of lithium-ion battery anode material with high energy density and long cycle life through a series of ex situ/in situ characterizations.

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

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.

Nanoflake Ni-MOF anchored octahedral nickel-porphyrins as a high-performance anode for lithium-ion batteries

Metal-organic framework materials (MOFs) have great potential as organic electrode materials for lithium-ion batteries due to their amiable porous structure and property tunability. However, the structure instability and poor electrochemical durability of MOFs hinders their application. An interesting metal–organic composite composed of Ni-MOF and Nickel (II)meso-Tetraphenylporphyin (NiTPP) is strategically proposed and configured in this study. The synergic integration of Ni-MOF and NiTPP presents a stable electrochemical cycling performance with a high retention capacity up to 840 mAh/g after 200 cycles, ascribed to the facilitation of the charge transfer capability and the diffusion kinetics. The configured metal–organic composites provide an explorative approach for organic alternatives for nonaqueous metal-ion batteries.

Modulating porous silicon-carbon anode stability: Carbon/silicon carbide semipermeable layer mitigates silicon-fluorine reaction and enhances lithium-ion transport

Modulating porous silicon-carbon anode stability: Carbon/silicon carbide semipermeable layer mitigates silicon-fluorine reaction and enhances lithium-ion transport

Tailoring nanoscale primary silicon in laser powder bed fusion for high-performance lithium-ion battery anodes

Silicon-based anodes, utilizing nanosized silicon materials, hold great promise for the next-generation of lithium-ion batteries due to their high capacity and stable expansion. This study aims to address challenges in traditional slurry-coated anodes, such as agglomeration and low adhesive strength, through the application of laser powder bed fusion (LPBF). The process involves fabricating an Al-Si-Cu alloy layer on a Cu foil current collector, followed by dealloying to create a porous Si-Cu anode. Simulated and experimental results demonstrate successful alloy layer formation through optimized laser spot (55 μm) and powder sizes (1-5 μm). Controlled cooling produces primary Si particles ranging from 150 nm to 1 μm. The resulting microstructure enhances electrochemical performance, particularly by tailoring the size of primary Si. The resultant porous Si-Cu anode, featuring uniformly distributed primary Si (200 nm) metallurgically bonded with Cu networks, exhibits an initial coulombic efficiency of 83% and a remarkable capacity retention of 80% after 300 cycles at 2 C. In-situ and ex-situ observations confirm the crucial role of anode architecture in performance enhancement. This study elucidates the influence of the LPBF microstructure on anode performance and broadens the potential application of laser powder bed fusion in battery manufacturing.

N-doped C encapsulated Li2TiSiO5 nanoparticles for high-rate highly stable lithium storage

Achieving high charging rates (≤ 15 min) in lithium-ion batteries (LIBs) is imperative for their widespread implementation in all-electric vehicles. However, the pursuit of elevated charging rates often leads to compromises in capacity and cycling stability. In this manuscript, we present a groundbreaking approach utilizing a composite material composed of nitrogen-doped carbon-encapsulated Li2TiSiO5 nanoparticles (LTSO@C-N) as the anode material for LIBs, offering rapid and exceptionally stable lithium storage. The encapsulation of Li2TiSiO5 nanoparticles by nitrogen-doped carbon is realized via a facile liquid-phase polymerization and the following pyrolysis route. The uniformly deposited nitrogen-doped carbon layer on the surface of Li2TiSiO5 nanoparticles within LTSO@C-N serves a dual purpose: enhancing the conductive properties of Li2TiSiO5 to ensure efficient charge transfer and Li+ transport, while concurrently inhibiting grain pulverization over extended cycling periods. The deliberate incorporation of nitrogen-doped carbon optimizes Li2TiSiO5 anode electrochemical performance, simultaneously reducing structural degradation during prolonged cycling. This enhances the lithium-ion battery system's long-term stability and reliability. While exhibiting an average operational potential of approximately 0.28 V in comparison to Li+/Li, the LTSO@C-N electrode manifests a commendable specific capacity of 345 mAh g-1 at a current density of 0.1 A g-1. Notably, it attains a robust lithium storage capability even under high-rate conditions, exemplified by a sustained capacity of 205 mAh g-1 over 1000 cycles at 2 A g-1, devoid of any discernible decay. The electrode's impressive electrochemical performance highlights its potential as an advanced anode for high-performance lithium-ion batteries, ensuring stability.

Tailoring the Size of Reduced Graphene Oxide Sheets to Fabricate Silicon Composite Anodes for Lithium-Ion Batteries.

The integration of a silicon (Si) anode into lithium-ion batteries (LIBs) holds great promise for energy storage, but challenges arise from unstable electrochemical reactions and volume changes during cycling. This study investigates the influence of reduced graphene oxide (rGO) size on the performance of rGO-protected Si composite (Si@rGO) anodes. Two sizes of graphene oxide (GO(L) and GO(S)) are used to synthesize Si@rGO composites with a core-shell structure by spray drying and thermal reduction. Electrochemical evaluations show the advantages of the Si@rGO(S) anode with improved cycle life and cycling efficiency over Si@rGO(L) and pure Si. The Si@rGO(S) anode facilitates the formation of a stable LiF-rich solid electrolyte interface (SEI) after cycling, ensuring enhanced capacity retention and swelling control. Rate capability tests also demonstrate the superior high-power performance of Si@rGO(S) with low and stable resistances in Si@rGO(S) over extended cycles. This study provides critical insights into the tailoring of graphene-protected Si composites, highlighting the critical role of rGO size in shaping structural and electrochemical properties. The Si material wrapped by graphene with an optimal lateral size of graphene emerges as a promising candidate for high-performance LIB anodes, thereby advancing electrochemical energy storage technologies.

A study on molecular weight controlled conducting polymer-based binder for high-performance lithium-ion battery anodes

A study on molecular weight controlled conducting polymer-based binder for high-performance lithium-ion battery anodes

Simple hydrothermal synthesis of HCNFs@CoNiO2 composite material for high-performance anode of lithium-ion batteries

In this study, a novel helical carbon nanofibers@CoNiO2 (HCNFs@CoNiO2) composite was first successfully synthesized by the simple hydrothermal method and utilized as anode materials of lithium-ion batteries (LIBs). CoNiO2 nanoparticles with a particle size of about 6 nm were distributed on the surface of HCNFs matrix. The HCNFs@CoNiO2 anode shows the excellent reversible specific capacity of 808.5 mAh/g after 100 cycles at 200 mA/g, which is about four and twenty times larger than that of HCNFs (193.5 mAh/g) and CoNiO2 (35.4 mAh/g), respectively. The electrochemical performance of HCNFs@CoNiO2 was improved due to the synergistic contribution of HCNFs and CoNiO2. In particular, HCNFs with the unique three-dimensional helical structure improve the conductivity and also provide a strong supporting network space during the volume expansion of CoNiO2 nanoparticles. The present study provides a useful reference for the development of the novel high-performance anode material for LIBs.

One-pot synthesis of interconnected carbon-coated silicon nanosheets from clay minerals for high-performance lithium-ion battery anodes

The silicon nanosheet/carbon composite emerges as a promising anode material for the next-generation commercial lithium-ion batteries. However, complex, costly, and energy-intensive synthesis procedures impede its practical application. Herein, the carbon-coated silicon nanosheets (Si/C) have been successfully synthesized via a one-pot strategy, involving a modified magnesiothermic reduction of talc followed by a reaction with CO2. The distinct chemical composition and layered nanostructure of talc enable the retention of Si nanosheets during exothermic reactions without additional templates or heat absorbents. The method shows significant potential for the scalable production of Si/C owing to the abundant silicon source, sustainable carbon source, and straightforward protocol. The resulting Si/C displays a hierarchical porous structure, with both macropores and mesopores, and an interconnected network of carbon-coated Si nanosheets. These structural characteristics facilitate rapid Li+ diffusion and enable the material to accommodate the lithiation-induced mechanical strains. As a result, the Si/C electrode exhibits outstanding electrochemical performance, including a remarkable rate capability (with a specific capacity of 1220 mAh g−1 at 10.0 A g−1) and a high initial Coulombic efficiency of 88%. The work opens a new avenue for the development of Si/C composites from natural clay minerals through an economical and scalable strategy, which would contribute to the practical application of advanced Si-based anodes in lithium-ion batteries.

Layered Siloxene Microparticles: Unveiling Long-Term Stability and High Volumetric Capacity for Advanced Lithium-Ion Batteries

Two-dimensional (2D) Si π materials, a silicon counterpart of graphene, are particularly interesting because they exhibit intrinsic electrochemical and mechanical behavior combined with structural anisotropy. This work aims to improve the Li-storage performance of 2D siloxene (2DSi) microparticles by co-imidization with polymer binder. The proposed method combines 2DSi with poly(amic acid) to form a covalently bound poly(imide) (PI) layer upon thermal dehydration. Electrochemical evaluations reveal that the resulting 2DSi-PI electrode exhibits a unique electrochemical behavior toward Li+ based on intercalation, with additional reversible (de-)lithiation attributed to carbonyl oxygens of PI. Without suffering volume expansion, the 2DSi-PI electrodes display a highly stable capacity generation of 585 mAh g−1 at 250 mA g−1 with a capacity loss of 0.13 % per cycle at the 200th cycle. In addition, the full-cell of the 2DSi-PI electrode combined with the LiNi0.8Co0.1Mn0.1O2 cathode achieves an energy density of 426 Wh kg−1 at a power density of 1,155 W kg−1. Ex-situ and theoretical analyses of the (de-)lithiated 2DSi-PI electrodes demonstrate that the surface-bound PI suppresses solvent reduction, increases the amount of LiF in the SEI layer, and improves the binding affinity of 2DSi to LiF. As a result, the cycle stability of 2DSi-PI electrodes is significantly improved in comparison to 2DSi-polyvinylidene fluoride electrodes. Co-imidization with PI emerges as a promising strategy for advancing the electrochemical properties of 2DSi electrodes, offering insights for the design of high-performance lithium-ion battery anodes.

Bio-synthesized TiO2 nanoparticles and the aqueous binder-based anode derived thereof for lithium-ion cells.

Titanium dioxide nanoparticles (TiO2-NPs) are a promising anode material for Lithium-ion batteries (LIBs) due to their good rate capability, low cost, non-toxicity, excellent structural stability, extended cycle life, and low volumetric change (∼4%) during the Li+insertion/de-insertion process. In the present paper, anatase TiO2-NPs with an average particle size of ~ 12nm were synthesized via a green synthesis route using Beta vulgaris (Beetroot) extract, and the synthesized TiO2-NPs were evaluated as anode material in LIBs. Furthermore, we employed an aqueous binder (1:1 mixture of carboxy methyl cellulose and styrene butadiene) for electrode processing, making the process cost-effective and environmentally friendly. The results revealed that the Li/TiO2 half-cells delivered an initial discharge capacity of 209.7 mAh g-1 and exhibited superior rate capability (149 mAh g-1 at 20 C) and cycling performances. Even at the 5C rate, the material retained a capacity of 82.2% at the end of 100 cycles. The synthesis route of TiO2-NPs and the aqueous binder-based electrode processing described in the present work are facile, green, and low-cost and are thus practically beneficial for producing low-cost and high-performance anodes for advanced LIBs.

Fe2O3 nanoparticles encapsulated in the inner walls of integrated 3D carbon tube grid as high-performance anode for lithium-ion batteries

Ferric oxide (Fe2O3) holds huge potential as a promising anode material for lithium-ion batteries (LIBs) due to its high theoretical capacity and low cost, however, its battery performance is still limited by the intrinsic poor conductivity and huge volume variation during lithiation and de-lithiation processes. Herein, we developed a self-standing 3D interconnected vertical and lateral carbon tube (3D-CT) grid with Fe2O3 nanoparticles (NPs) encapsulated in the wall of CT (denoted as 3D-CT@Fe2O3-NPs@C), as structurally-integrated anode without any inactive components. The 3D-interconnected vertical and lateral CTs with open channels not only provide plenty of attachment sites for the Fe2O3 NPs and accommodate the strain generated by the volume variation of Fe2O3, but also facilitate the fast ions and electrons transfer. Therefore, the self-supported 3D-CT@Fe2O3-NPs@C electrode delivers superior cycling and high-rate performance with a high stable specific capacity of 896.2 mAh g−1 at the current density of 1.0 A g−1 after 700 cycles. Even at the high current density of 4.0 A g−1, a reversible capacity of 488.1 mAh g−1 can be reached based on the mass of the electrode. This study provides a facile and efficient strategy to improve the electrochemical performance of LIBs through the design of structurally-integrated grid electrode.

Conductive copper ion-reinforced sodium alginate aerogel based free-standing Si anode for Li-ion storage

Biomass materials with great advantages of wide accessibility, low cost and environmental benignity have favorable application prospects as Si anodes for lithium-ion batteries (LIBs). In order to alleviate the volume effect and improve the conductance of Si, we fabricated a conductive copper ion-reinforced sodium alginate (SA) aerogel based free-standing Si anode (Si@CNTs/Alg-Cu-II) containing silicon nanoparticles, sodium alginate aerogel, carbon nanotubes and Cu nanoparticles, via a simple, low-cost and sustainable process (under 1 × 10−1 Pa, 1 °C/min to 200 °C holding for 1 h). In the irregular lamellar porous aerogel, silicon particles with good dispersion are bound by macromolecular chains of SA via dynamic hydrogen bonds and subsequently restrained in the porous aerogel to release volume stress. The in situ generated Cu particles and well-dispersed carbon nanotubes (CNTs) construct the conductive network around Si particles to improve the electrical conductivity of the electrode. This unique structure delivers a capacity of 835.6 mAh/g after 100 cycles at 0.1 A/g based on the total mass of Si@CNTs/Alg-Cu-II composite (Si content of 25.62%). Moreover, it also shows outstanding stability under high current density (a capacity retention of 84.1% after 100 cycles at 0.5 A/g). The sustainable preparation method and excellent electrochemical performance of Si@CNTs/Alg-Cu-II provide a new strategy to develop high-performance free-standing Si-based anodes for LIBs.

Mechanically robust and conductive Ti5Te4/P@C composite materials as promising lithium-ion battery anodes

An urgent need has emerged to develop lithium-ion battery anodes that exhibit high reversible capacity and rate performance surpassing carbonaceous materials. Si-based composites have been investigated extensively. However, in this study, we explored another potential alloy anode consisting of Te and phosphorus without Si. Herein, we present a novel composite material, Ti5Te4/P@C, as an anode for lithium-ion batteries (LIBs). Tellurium, which exhibits good electrical conductivity and high volumetric capacity, and red phosphorus, which exhibits high theoretical capacity, were selected as potential anode materials. To overcome the common drawbacks of the two materials, including the vigorous expansion of volume, electrochemically inactive materials, such as titanium and carbon, were introduced as matrix buffers. Te, Ti, red phosphorus, and C were synthesized using a three-step high energy ball milling (HEBM) technique, that is, stepwise synthesis of (1) Ti and Te, (2) red phosphorus, and (3) carbon. The developed Ti5Te4/P@C composites revealed that the introduction of red P led to the generation of additional pure Te in the Ti5Te4/P@C composites, which was owing to the different binding interactions between Ti, Te, and red P, as confirmed by DFT calculations. Among the developed Ti5Te4/P@C anodes, Ti5Te4/P(30 wt%)@C exhibited outstanding cyclability and high rate performance (440 mAh g−1 at 300 mA g−1 after 500 cycles). To confirm the electrochemical responses and Li+ ion diffusion mechanisms, CV and GITT analyses were performed. Based on the electrochemical characteristics, the superior electrochemical performance of the Ti5Te4/P@C anodes can be ascribed to the well-defined composite structure, including the high electrical conductivity of Te, high theoretical capacity of red P, and effective buffering agents of Ti as a mechanical supporter and conductive C, which enable a pseudocapacitive response, providing better reversibility. Therefore, the Ti5Te4/P@C composite materials are viable anodes for high-performance LIBs.

Boron-doped three-dimensional porous carbon framework/carbon shell encapsulated silicon composites for high-performance lithium-ion battery anodes

Deleterious volumetric expansion and poor electrical conductivity seriously hinder the application of Si-based anode materials in lithium-ion batteries (LIBs). Herein, boron-doped three-dimensional (3D) porous carbon framework/carbon shell encapsulated silicon (B-3DCF/Si@C) hybrid composites are successfully prepared by two coating and thermal treatment processes. The presence of 3D porous carbon skeleton and carbon shell effectively improves the mechanical properties of the B-3DCF/Si@C electrode during the cycling process, ensures the stability of the electrical contacts of the silicon particles and stabilizes the solid electrolyte interface (SEI) layer, thus enhancing the electronic conductivity and ion migration efficiency of the anode. The developed B-3DCF/Si@C anode has a high reversible capacity, excellent cycling stability and outstanding rate performance. A reversible capacity of 1288.5 mAh/g is maintained after 600 cycles at a current density of 400 mA g−1. The improved electrochemical performance is demonstrated in a full cell using a LiFePO4-based cathode. This study presents a novel approach that not only mitigates the large volume expansion effects in LIB anode materials, but also provides a reference model for the preparation of porous composites with various functionalities.