Superior Lithium Storage Capability Research Articles

Iron-based bimetallic oxide carbon composites with superior lithium storage capabilities serve as anode in lithium-ion batteries

Transition metal oxides (TMOs) have emerged as highly promising electrode materials for lithium-ion batteries (LIBs) owing to their versatile valence states and distinctive morphological attributes. Bimetallic oxides, in particular, exhibit the ability to mitigate the volume expansion associated with lithium alloying and de-alloying processes. Despite these advantages, metal oxides often suffer from drawbacks such as poor conductivity, limited cycle stability, and a propensity for lithiation. Addressing the challenges of low electronic conductivity, significant volume expansion, and inadequate uniformity, we synthesized two bimetallic oxide-based carbon composites via a “one-pot” solvothermal approach: ZnFe2O4@C and MnFe2O4@C. These composites are enveloped in a carbon shell derived from anhydrous ethanol. Notably, the specific discharge capacities of ZnFe2O4@C and MnFe2O4@C surpass those of their respective single metal oxide counterparts. Following nearly 300 cycles of charge and discharge operations at a current density of 100 mA g−1, ZnFe2O4@C exhibited a specific discharge capacity of 1528 mAh g−1, while MnFe2O4@C demonstrated a capacity of 1283 mAh g−1. The synthesis method offers simplicity, high yield, and uniform morphology, making it a promising avenue for enhancing the performance of LIBs electrode materials.

Reasonable Design and Deep Insight of Efficient Integrated Photorechargeable Li-Ion Batteries by Using a Cu/CuO/Cu2S Electrode.

Herein, Cu-foam-supported CuO nanowire arrays covered with Cu2S nanosheet substrates (Cu/CuO/Cu2S) are adopted as efficient photoelectrodes for photorechargeable lithium-ion batteries (PR-LIBs). The assembled PR-LIB exhibits remarkable solar energy conversion efficiency alongside superior lithium storage capabilities. Without an electrical power supply, the photocharged PR-LIB sustained a discharge process for 63.0 h under a constant current density of 0.05 mA cm-2. The corresponding solar-to-electrical energy conversion efficiency is 4.50%, which is an impressive achievement among recently reported contemporary technologies. Mechanism investigation shows that the Cu/CuO/Cu2S photogenerated carriers augment the extraction and insertion of Li+ according to different oxidation and reduction reactions in the charging and discharging reactions. This research delineates a refined model system and proposes innovative directions for developing efficient heterojunction photoelectrodes, significantly propelling the development of PR-LIB technology.

Facile and efficient fabrication of Cu1.04Mn0.96O2 nanosheet anodes with superior electrochemical lithium storage capability

In this work, Cu1.04Mn0.96O2 nanosheets were synthesized via a simple hydrothermal method, and their electrochemical lithium storage properties and reaction mechanisms were investigated. The nanosheet structure effectively promotes electron transfer and shortens the transport path. Additionally, the partial substitution of Cu for Mn decreases the Jahn-Teller distortion of the MnO6 octahedron. Employing as an anode for Li-ion batteries, the specific capacity reached 610.91 mAh g−1 after 100 cycles at a current density of 100 mA g−1.

Enhancing lithium storage rate and durability in sphalerite GeP by engineering configurational entropy

High-entropy sphalerite-structured compounds, derived from cubic GeP, demonstrate remarkable metallic conductivity and superior lithium-storage capabilities when compared to the parent phases of monoclinic layered GeP or SiP.

Efficient and stable lithium storage of porous carbon fiber composite bimetallic sulfides (FeS-ZnS) anode

To enhance the utilization of lithium-ion battery anodes, it is crucial to improve both the lithium storage stability and kinetics of transition metal sulfides. This optimization is critical for the development of battery technologies that are more efficient, durable, and environmentally sustainable. In this study, a facile electrospinning technique followed by a thermal treatment was used to fabricate a bimetallic sulfide/porous carbon fiber composite (FeS-ZnS/PCFs). Its stability was largely improved due to the buffered ability derived from its porous structure. The presence of FeS-ZnS grain boundaries fosters the generation of extra redox active sites, ultimately boosting the kinetics of lithium storage. The optimized composite material exhibits excellent stability and efficient lithium storage performance. Density functional theory calculations and kinetics analysis further clarify superior lithium storage capabilities of this material.

A metal-organic framework-derived engineering of carbon-encapsulated monodispersed CoP/Co2P@N[sbnd]C electroactive nanoparticles toward highly efficient lithium storage

Attracted due to their potentially high theoretical capacities, storage redox activities, and diverse shape, cobalt phosphides (Co2P, CoP etc.) are thought to be the promising anodes for lithium-ion batteries (LIBs). Nevertheless, there still remain challenging bottlenecks of their low intrinsic conductivity and severe volume expansion when subjected to repeated electrochemical cycles, which unavoidably bring about structural collapse, active particle aggregation and rapid capacity degradation, and thereby poor long-term lifespan. Herein, we present a distinctively facile route and adopt metal-organic frameworks (MOFs) as the self-sacrificing hosts to construct carbon-encapsulated CoP/Co2P@NC composites which are composed of monodispersed electroactive CoxP (CoP/Co2P) nanoparticles encapsulated in carbon nanotubes (CNTs) based on N-doped carbon substrates. Remarkably, one exemplary CoP/Co2P@NC-600 electrode among them, when serves as anode for LIBs, exhibits high reversible capacity (977.9 mAh g−1, 100 cycles at 0.1 A g−1) and superior rate capability (639.7 mAh g−1 at 4 A g−1). Furthermore, an assembled LFP//CoP/Co2P@NC-600 full cell displays remarkable cycling performance. The more advantageous synergistic interaction of distinctive carbon-encapsulated architectures, robust N-doped carbon frameworks and electroactive components provides the fundamental foundation for superior lithium storage capabilities, where the synergistic interaction contributes towards enhancing electronic conductivity, offering extra electrochemical active sites, shortening the Li+/e− transport channels and alleviating volumetric variation. This contribution emphasizes the value of rationally designing MOF-derived carbon-encapsulated metal phosphide-based anodes for advanced LIBs.

An Effective Way to Prepare Submicron MoO2 Anodes for High-Stable Lithium-Ion Batteries

Herein, MoO2-based submicrons (named MoO2@C) are synthesized through an effective one-step hydrothermal process. The prepared MoO2 submicrons wrapped in carbonouse layer are uniformly produced and can be applied to the anodes in lithium-ion batteries (LIBs). The novel MoO2@C electrodes demonstrate attractive lithium storage ability. Moreover, compared with the commercial pure MoO2, the MoO2@C delivers a superior electrochemical capacity (e.g, 760.83 mAh g-1 capacity in long-life test at high rate of 1 A g-1) with outstanding capacity retention ratio and stability as well as rate capability. The superior lithium storage capabilities result from plenty of the Li+ sites and adequate electrolyte infiltration effect, which allows the fast transport of electrons and ions, and well-dispersed MoO2 submicrons in carbon-based layers that effectively prevents aggregation of nano size particles.

In-situ synthesized carbon-coated Sn–SnO2 nanoparticles embedded in carbon nanotubes on Cu foam as anode material for lithium-ion batteries

Sn-based materials are considered as a prospective anode for lithium-ion batteries because of their high theoretical lithium storage capacity and large reserves. But the application of Sn-based materials is still hampered by their significant capacity decay owing to volume changes during lithiation and delithiation. To address this problem, we propose the in-situ synthesis of amorphous carbon-coated (thickness: ∼3 nm) Sn–SnO2 nanoparticles (size: ∼20–50 nm) embedded in helical carbon nanotubes (diameter: ∼30 nm) grown on Cu foam (C@Sn–SnO2/CNT) via hydrothermal and subsequent chemical vapor deposition process. The 3D hierarchical framework decorated by C@Sn–SnO2 nanoparticles provides enhanced contact between the electrode and electrolyte, and guarantees an efficient reversible conversion reaction. Moreover, the introduction of the carbon layer and carbon nanotubes inhibits large volume changes of Sn and SnO2 during cycling. In comparison with pure SnO2, C@Sn–SnO2/CNT displays superior lithium storage capability, rate performance, and cycle stability. The discharge capacity for C@Sn–SnO2/CNT at 0.2 A g−1 is 1772 mAh g−1 in the first cycle and 856 mAh g−1 after 300 cycles, as well as 480 mAh g−1 at 1 A g−1. Consequently, C@Sn–SnO2/CNT possesses enormous potentiality for practical application in high-performance lithium-ion batteries.

Carbon nanotube enables high-performance thiophene-containing organic anodes for lithium ion batteries

Poly(thiophene)-based organic compounds with reversible n-type redox behavior can be employed as anode materials for lithium ion batteries (LIBs). However, their inherent problems such as low redox activity, poor rate performance and processing difficultly limit the practical application in LIBs. Herein, a one-dimensional structure-design is reported for a poly(thiophene) derivative (i.e. poly(3-butylthiophene), briefly denoted as P3BT) with a superior lithium storage capability in LIBs. The experimental study and DFT calculation reveal that carbon nanotubes (CNTs) play a critical role in this structure design to promote the electrochemical performances of P3BT. CNTs act as a highly conductive nano-skeleton, which can facilitate the electron transfer, enlarge the electroactive surface area and shorten the ions diffusion path. Besides, the strong π-π interation between P3BT and CNT not only stabilizes the charged and discharged states of P3BT for enhancing the cycling stability, but also compensates the negative effect of introducing of butyl side chains on the energy gap and electron affinity. To the best of our knowledge, the designed one-dimensional P3BT@CNT nanocomposite exhibits a better electrochemical performance compared with the reported thiophene-containing anode materials. This work provides a new insight for the application of thiophene-containing anode materials for LIBs.

Conjugated cyclized-polyacrylonitrile encapsulated carbon nanotubes as core–sheath heterostructured anodes with favorable lithium storage

Conjugated cyclized-polyacrylonitrile encapsulated conductive carbon nanotubes to form highly redox-active sheath–core heterostructured anodes with superior lithium storage capability.

In-situ grown flower-like C@SnO2/Cu2O nanosheet clusters on Cu foam as high performance anode for lithium-ion batteries

Tin dioxide (SnO2) is considered as one of promising anode materials in lithium-ion batteries due to its high specific discharge capacity, low cost and environmental friendliness. However, practical application of SnO2 is still hindered by severe capacity fading, poor cycling stability and inferior rate performance due to volume expansion during charge/discharge processes. To overcome this problem, composites of flower-like carbon layer (thickness: ~1.5 nm) enwrapped SnO2/Cu2O (thickness: ~20 nm; length: ~ 200 nm) anchored on Cu foam were in-situ synthesized by facile hydrothermal method and subsequent annealing. Compared with pure SnO2, such novel hierarchical structure effectively enhancs the conductivity and structural stability of the composites as integrated electrode for lithium-ion batteries. Electrochemical studies reveal superior lithium storage capability, cycle stability, and rate performance for C@SnO2/Cu2O nanosheet clusters with discharge capacity of 1726 mAh g−1 in first cycle and 814 mAh g−1 after 300 cycles at 0.5 C, as well as 425 mAh g−1 at 2 A g−1. Therefore, C@SnO2/Cu2O nanosheet clusters possess great potential for scientific research and future application in lithium-ion batteries.

Fabrication of cactus-like CNT/SiO2/MoO3 ternary composites for superior lithium storage

Advanced electrode materials with high rate capability and long cycling stability are highly pursued for high-performance lithium-ion batteries (LIBs). In this study, cactus-like CNT/SiO2/MoO3composites are synthesized via self-assembly followed by in-situ carbonization, wherein the CNT, SiO2, and MoO3 are uniformed distributed. Such unique structure can effectively alleviate the strain during cycling, reduce the Li+ diffusion time, and provide more active sites for the interaction of ions, thus allowing much better rate capability. Specifically, CNTs act as the cactus veins to rapidly transport the electrons, while the SiO2 and MoO3 particles located in the cactus leaf-like region are used to store lithium. In addition, the MoO3 can play as a supporter to minimize the change of the whole structure and further stabilize the electrode because of the lower strain during lithiation. As a consequence, the CNT/SiO2/MoO3electrode delivers a high specific capacity (700 mAh g−1at 1000 mA g−1over 500 cycles) and long cycle life (320 mAh g−1at 5000 mA g−1within 800 cycles). It is possible that this research could provide new insights for developing novel anode materials with superior lithium storage capability.

Stable Lithium Storage at Subzero Temperatures for High‐capacity Co3O4@graphene Composite Anodes

AbstractAchieving high energy density and long‐term stability at subzero temperatures remains one of the main challenges for the development of lithium‐ion batteries. Shortcomings in energy density and stability mainly highlight on the increase in internal resistance and electrode polarization at subzero temperatures, which greatly affect the reversible capacities of lithium‐ion batteries. In this work, a conversion type Co3O4@graphene (Co3O4@G) composite is prepared via a simple hydrothermal method and first evaluated at subzero temperatures. Benefitting from the especially suitable lithiation/delithiation potentials of Co3O4, ingenious nanostructure and high conductivity of graphene, the Co3O4@G anode exhibits much higher capacity retentions than intercalation‐ and alloying‐type anodes at subzero temperatures, with 58.4% of room‐temperature capacity retention at −30 °C for initial cycle and a highly stable reversible capacity of 605.0 mAh g−1 (0.5 A g−1) for 600 cycles at −10 °C. Furthermore, very high capacities of ∼920.4 mAh g−1 (0.2 A g−1) can be maintained at 30 °C, and ∼450.2 mAh g−1 (0.5 A g−1) can be remained at −20 °C during alternating cycling. This work demonstrates that conversion‐type Co3O4@G composites have superior extreme temperature lithium storage capabilities and can be viable Li‐ion anode materials with fast and highly efficient ion/electron transport capacity at subzero operating temperatures.

Nanostructured LiTi2(PO4)3 anode with superior lithium and sodium storage capability aqueous electrolytes

Aqueous alkali metal ion batteries show great promise as the next generation secondary batteries with low cost, high power density and better safety. However, they suffer from inferior cycle stability at a higher current density and displays poor coulombic efficiency. In this work, LiTi2(PO4)3@C/CNTs (LTP@C/CNTs) with three-dimensional mesoporous nanostructure was investigated in both aqueous lithium-ion batteries (ALIBs) and aqueous sodium-ion battery (ASIBs). Improved rate and cycling performance at high current densities were demonstrated in contrast to LiTi2(PO4)3@C (LTP@C). Typically, the LTP@C/CNTs electrode achieves a discharge capacity of 97.37 mAhg−1 and 90.88 mAhg−1 in ALIBs and ASIBs half cells at 3 A g-1 current density. LTP@C/CNTs//LiMn2O4 and LTP@C/CNTs//Na0.44MnO2 full cells show the capacity retention of 72.9% and 79.4% after 500 cycles. Besides, new electrochemical behavior is reported for the first time, that the anode materials present a two-step sodium ion insertion/extraction in ASIBs. After cycling, LTP anode converts into (NaTi2(PO4)3) NTP phase with maintained crystallinity. LTP@C/CNTs composite anode thus shows a great potential application in next-generation aqueous energy storage systems.

Highly dispersed SnO2 nanoparticles confined on xylem fiber-derived carbon frameworks as anodes for lithium-ion batteries

Abstract Tin oxide (SnO2) has been considered as a promising alternative material for lithium-ion batteries (LIBs) anodes owing to its high specific capacity, low operation potential and high natural abundance. However, its practical performance is hampered by the poor rate capability and fast capacity fading. In this work, we synthesized the highly dispersed SnO2 nanoparticles confined on the xylem fiber-derived carbon frameworks (SnO2@XFC@C) by a facile solvothermal method. The synergy of using open XFs-derived carbon as conductive framework and glucose-derived carbon as matrix enables the superior lithium storage capability of SnO2 materials. Using aqueous electrode proceeding, the SnO2@XFC@C delivers a high discharge capacity of 1810 mAh g−1 with an initial Coulombic efficiency of 85.4%, and excellent high-rate cycling stability (505 mAh g−1 at 1.0 C after 1000 cycles). This structure design offers significant advantages in terms of realization of low cost, high energy and sustainable lithium-ion batteries, and is extendable to other battery systems.

Dual-metal-organic frameworks derived manganese and zinc oxides nanohybrids as high performance anodes for lithium-ion batteries

Metal-organic framework (MOF) derivatives are attracting increasing interests for next-generation lithium-ion battery anode materials. Here, a novel approach has been applied to synthesize binary Mn–Zn oxides nanohybrids embedded in porous carbon matrix by pyrolysis of dual-metal-organic frameworks. The as-fabricated MnO/ZnO@C nanohybrids exhibit superior lithium storage capabilities, reaching a reversible capacity of 1396 mAh g−1 at 0.2 A g−1 with an initial coulombic efficiency of higher than 75%. When cycled at 2 A g−1, the electrode maintained at 636 mAh g−1 after 1000 cycles, indicating the outstanding high-rate capability and cycling stability. The improved electrochemical performance can be attributed to the interconnected porous structure of carbon frameworks and uniform heterostructure nanohybrids, which efficiently improve the charge transfer and buffer the volume expansion during repeated lithiation process. These findings demonstrate an efficient strategy of using dual-MOF-derived bi-metal oxide nanostructures as high performance anodes for lithium-ion batteries.

Zn/Co-ZIF-derived bi-metal embedded N-doped porous carbon as anodes for lithium-ion batteries

In this work, the unique Zn-Co nitrogen-doped porous carbon (Zn-Co/NPC) polyhedrons have been successfully synthesized via pyrolysis of bimetallic zeolitic imidazolate frameworks (ZIFs) precursor under N2, wherein the metallic Co and Zn particles are dispersed in the porous carbon matrix. The obtained porous carbons show a high surface area (315.67 m2 g−1) and contain plenty of mesopores. The unique mesoporous structure benefits from either the carbonization of organic ligands and the catalytic effect of metallic Co in calcination process or the elimination of a certain amount of metal species in acid dissolution. As an anode material for lithium-ion batteries, the Zn-Co/NPC particles exhibit superior lithium storage capabilities with excellent cycling properties. It demonstrates a high discharge capacity of 970 mA h g−1 at 0.1 A g−1. Besides, a reversible capacity of 813.5 mA h g−1 was retained at a much higher current density of 0.5 A g−1 after 500 cycles. The enhanced electrochemical performance was attributed to the unique microstructure, nitrogen doping, and the synergistic effect of Zn and Co embedded in carbon matrix.

In-situ electrolytic synthesis and superior lithium storage capability of Ni–NiO/C nanocomposite by sacrificial nickel anode in molten carbonates

Abstract Herein, we demonstrate a facile electrolytic strategy to synthesize a kind of Ni–NiO/C nanocomposite via electroreduction of molten Li–Na–K carbonates synchronously combined with sacrificial nickel anode. Benefiting from its unique in situ synthesis mechanism, the Ni–NiO/C nanocomposite exhibits well-interconnected architecture with fine Ni–NiO nanoparticles embedded into electrolytic carbon matrix. The as-fabricated electrode shows ultra-long cycle stability (achieving a high capacity of 455 mA h g−1 at 1 A g−1 after 1500 cycles, average coulombic efficiency 99.88%) and impressively improved rate capability, comparing with the reported Ni–NiO/C nanocomposites. Such a superior lithium storage properties originates from the in situ formed nanoarchitecture of Ni–NiO/C. This research offers a distinctive pathway for constructing novel composite materials for advanced lithium storage.

A novel itaconic acid-graphite composite anode for enhanced lithium storage in lithium ion batteries

An itaconic acid-graphite composite anode is prepared for lithium ion batteries. The composite anode exhibits much improved electrochemical performances compared to the traditional graphite anode. A high specific capacity of 571 mAh g−1 can be obtained at 25 mA g−1 in the voltage range of 0.01–3.0 V vs. Li/Li+, and retained 96.8% at 10 A g−1. After cycled 200 cycles at 100 mA g−1 charge/200 mA g−1 discharge, a reversible capacity of 693 mAh g−1 still can be achieved. At 0.01–1.5 V vs. Li/Li+, it still delivers a specific capacity of 460 mAh g−1, higher than the theoretical capacity of graphite (372 mAh g−1). The reversible lithiation/delithiation process of both itaconic acid and graphite contribute the high capacity. The excellent rate performances are related to the buffering of the itaconic acid matrix combining its superior lithium storage capability. And the stable solid electrolyte interphase formed on the electrode during electrochemical cycling is the main factor for the stable cycle.

A Robust Route to Co2(OH)2CO3 Ultrathin Nanosheets with Superior Lithium Storage Capability Templated by Aspartic Acid‐Functionalized Graphene Oxide

AbstractTwo‐dimensional (2D) nanomaterials are widely recognized as an important class of functional materials possessing superior electrochemical reaction kinetics. Herein, an L‐aspartic acid (AA)‐modified graphene oxide (GO) templating strategy is developed to in situ yield ultrathin (i.e., ≈5 nm) cobalt carbonate hydroxide (Co2(OH)2CO3) nanosheets as advanced anode materials of lithium ion batteries. Notably, the covalent tethering of AA on the GO surface renders a high density of carboxyl groups that impart effective loading of Co‐containing precursors and subsequent growth into Co2(OH)2CO3 nanosheets bridging adjacent GO layers. The lasagna‐like Co2(OH)2CO3‐GO nanocomposites exhibit an ultrahigh lithium storage capacity of 1770 mAh g−1 after 500 cycles at 100 mA g−1. It is noteworthy that the cycled Co2(OH)2CO3 phase separates into homogeneously dispersed Co(OH)2 and CoCO3 phases with two different charge plateaus at ≈1.2 and 2.0 V, respectively, which effectively inhibit large‐scale homophase coarsening of Co, Li2CO3, and LiOH. The much shortened Li+/e− transfer distance enabled by individual ultrathin Co2(OH)2CO3 nanosheet together with robust layer‐by‐layer assembled nanostructure of Co2(OH)2CO3‐GO confers the superior electrochemical reactivity and mechanical stability. As such, the amino acid‐modified GO templating strategy may represent a simple yet robust means of crafting a variety of 2D nanostructured composites of interest for energy storage applications.