Ion Storage Research Articles

Battery-Type Desalination Behavior Confined Within Capsules for Efficient Capacitive Deionization.

Battery-type faradaic materials are considered a class of promising electrodes for capacitive deionization (CDI) due to their superior ability to store ions through redox reactions. However, the desalination potential of such electrode materials has not been fully explored subject to the accessibility, conductivity, stability, etc. Herein, embedded battery material Ag nanoparticles is designed in capsule-structural units composed of graphene and constructed freestanding composite electrodes for CDI. Particularly, these Ag nanoparticles confined in interconnected graphene capsules can be both efficiently accessed by the electrolyte and rationally protected by the capsule networks, significantly unlocking their potential as desalination materials. Impressively, the optimized Ag-involved anodes can achieve an ultrahigh NaCl desalination capacity of ≈360 mg g-1 (≈218 mg g-1 for Cl-) at 1.4 V and exhibit good cycling stability. Moreover, the as-designed anodes also have very competitive desalination capacities for other anions, such as SO2- 4 (≈90 mg g-1) and CrO2- 4 (≈77 mg g-1), suggesting the broad applicability of such Ag-involved electrodes. This work shows that the ingenious introduction of space-confined structures is an effective means of unlocking the desalination potential of Ag-based materials, opening up alternative avenues for the development of other high-performance battery-type desalination electrodes.

Realizing Dual-Mode Zinc-Ion Storage of Generic Vanadium-Based Cathodes via Organic Molecule Intercalation.

Intercalation engineering is a promising strategy to promote zinc-ion storage of layered cathodes; however, is impeded by the complex fabrication routes and inert electrochemical behaviors of intercalators. Herein, an organic imidazole intercalation strategy is proposed, where V2O5 and NH4V3O8 (NVO) model materials are adopted to verify the feasibility of the imidazole intercalator in improving the zinc storage capabilities of vanadium-based cathodes. The intercalated imidazole molecules could not only expand interlayer spacing and strengthen structural stability by serving as extra "pillars" but also provide extra coordination sites for zinc storage via the coordination reaction between Zn2+ and the C═N group. This gives rise to a dual-mode ion storage mechanism and favorable electrochemical performances. As a result, imidazole-intercalated V2O5 delivers a capacity of 179.9 mAh g-1 after 5000 cycles at 20 A g-1, while the imidazole-intercalated NVO harvests a high capacity output of 170.2 mAh g-1 after 700 cycles at 2 A g-1. This work is anticipated to boost the application potentials of vanadium-based cathodes in aqueous zinc-ion batteries.

The Development and Prospect of Stable Polyanion Compound Cathodes in LIBs and Promising Complementers.

Cathode materials are usually the key to determining battery capacity, suitable cathode materials are an important prerequisite to meet the needs of large-scale energy storage systems in the future. Polyanionic compounds have significant advantages in metal ion storage, such as high operating voltage, excellent structural stability, safety, low cost, and environmental friendliness, and can be excellent cathode options for rechargeable metal-ion batteries. Although some polyanionic compounds have been commercialized, there are still some shortcomings in electronic conductivity, reversible specific capacity, and rate performance, which obviously limits the development of polyanionic compound cathodes in large-scale energy storage systems. Up to now, many strategies including structural design, ion doping, surface coating, and electrolyte optimization have been explored to improve the above defects. Based on the above contents, this paper briefly reviews the research progress and optimization strategies of typical polyanionic compound cathodes in the fields of lithium-ion batteries (LIBs) and other promising metal ion batteries (sodium ion batteries (SIBs), potassium ion batteries (PIBs), magnesium ion batteries (MIBs), calcium ion batteries (CIBs), zinc ion batteries (ZIBs), aluminum ion batteries (AIBs), etc.), aiming to provide a valuable reference for accelerating the commercial application of polyanionic compound cathodes in rechargeable battery systems.

Combination Displacement/Intercalation Reaction of Ag0.11V2O5 Cathode Realizes Efficient Manganese Ion Storage Properties.

Aqueous manganese-ion batteries (AMIBs) are becoming more noticeable because of their excellent theoretical capacity, outstanding safety profile, and cost-effectiveness. However, there aren't many studies on cathode materials appropriate for AMIBs, and the manganese-ion storage mechanisms within these materials have not been thoroughly investigated. Furthermore, the electrochemical performance of existing cathode materials remains suboptimal. Here, Ag0.11V2O5 is designed and synthesized as the cathode material and introduces the combination displacement/intercalation reaction mechanism to the manganese ion storage for the first time. Ag0.11V2O5 demonstrates a capacity retention of 90.3% after 1200 cycles at 5 A g⁻¹ and achieves a high rate performance of 100.01 mAh g⁻¹ at 20 A g⁻¹. This impressive electrochemical performance is attributed to the reaction, which provides more Mn2+ storage sites and generates highly conductive Ag within the electrode. This study presents a novel approach to achieving high-capacity AMIBs.

Facilitating Ion Storage and Transport Pathways by In Situ Constructing 1D Carbon Nanotube Electric Bridges between 2D MXene Interlayers.

Multiple van der Waals (vdW) gaps invoke abundant opportunities for contriving artificial architectures and tailoring desired properties via the intercalation route beyond the reach of conventional concepts. Intriguingly, the electrochemical intercalation strategy can precisely and reversibly tune the intercalation stage of charged functional species. This study presents a valid structural editing protocol facilitated by electrochemical intercalation to engineer MXene interlayers, ultimately incorporating in situ constructed carbon nanotube (CNT) electric bridges for enhanced ion storage and transport pathways. The method allows for the precise modulation of electrochemical forces to tailor materials for specific applications. Deep intercalation and in situ growth processes establish robust anchoring sites and connectivity hubs between MXenes and CNTs, ensuring structural homogeneity and stability in advanced electrode materials. The results demonstrate the effectiveness of electrochemistry-mediated interlayer nanoengineering in MXenes, offering a versatile approach to design vdW heterostructures with tailored functionalities for energy storage and conversion applications. This work highlights the potential of electrochemical modulation in advancing materials engineering strategies for next-generation energy storage technologies.

N, S-Codoped 3D Carbon Protected Nanoporous MnS With Record High Sodium Ion Storage Performance for Potential Industry Applications.

With a high theoretical capacity, the MnS anode, however, exhibits a rather complex sodium diffusion kinetics and poor mechanical stability that hinder its application in sodium-ion batteries (SIBs). In this work, a simple, economical, and scalable strategy is developed to inherently coat nanoporous MnS with a 3D N, S co-doped thin carbon layer by using commercially available MnCO3 as precursors. Specifically, the strategy involves a two-step annealing process, which converts the MnCO3 microparticles into nanoporous Mn2O3 and MnS step by step. The 3D N, S codoped carbon layer is in situ formed during the second annealing process by first coating the nanoporous Mn2O3 with a polyaniline layer. Due to the inherent 3D carbon protection and the strong electronic interaction between N, S dopants and MnS, the N, S codoped carbon protected MnS obtained at 900 °C (NS-C@MnS-900) anode displays a high specific capacity of 845mAhg-1 at 0.1Ag-1, which is higher than all reported MnS-based SIB anodes. It also shows an outstanding cyclability and rate performance, maintaining a stable capacity of ≈493mAhg-1 after 1300 cycles at 10Ag-1, which is also the best according to knowledge. These exceptional electrochemical performances and the scalable/simple/low-cost synthesis make the NS-C@MnS-900 attractive for industry application.

Regulating the Pore Structure and Heteroatom Doping of Soybean Straw Carbon Based on a Bifunctional Template Method for the High-Performance Carbon Supercapacitor.

The previous research addressed the waste problem of agriculture and forestry residues by exploring the efficient utilization of liquefied soybean straw in supercapacitor. The structures of the liquefied soybean straw were controlled by coupling microwave hydrothermal treatment with carbonization under the influence of a C3N4 bifunctional template. What's more, C3N4 could effectively regulate the pore structures and provide an effective N active site of carbon materials C3N4. The obtained N-SLR Carbon-700 possess a specific surface area of up to 1593.7 m2 g -1, and the pore size is mainly concentrated in the range of 1.8-2.5 nm, providing efficient ions transmission channels and storage space. Its specific capacitance is up to 261.5 F g-1 (current density of 0.5 A g-1), and the capacity retention is 74.04 % when the current density is expanded by 20 times. In the two-electrode system, the energy density of N-SLR Carbon-700 could reach to 31.3 W h kg-1 at a power density of 360 W kg-1, as well as the energy surface density is maintained at 69 % when the power density is increased by a factor of 20. This work enhances effectively the charging and discharging stability and capacitance value of carbon-based supercapacitor.

High-Performance Sodium-Ion Batteries with Graphene: An Overview of Recent Developments and Design.

Due to their low production cost, sodium-ion batteries (SIBs) are considered attractive alternatives to lithium-ion batteries (LIBs) for next generation sustainable and large-scale energy storage systems. However, during the charge/discharge cycle, a large volume strain is resulted due to the presence of a large radius of sodium ions and high molar compared to lithium ions, which further leads to poor cyclic stability and lower reversible capacity. In the past, researchers have devoted significant efforts to explore various anode materials to achieve SIBs with high energy density. Hence, as a promising anode material for SIBs, the two-dimensional (2D) materials including graphene and its derivatives and metal oxides have attracted remarkable attention due to their layered structure and superior physical and chemical properties. The inclusion of graphene and metal oxides with other nanomaterials in electrodes have led to the significant enhancements in electrical conductivity, reaction kinetics, capacity, rate performance and accommodating the large volume change respectively. Moreover, these 2D materials facilitated large surface areas and shorter paths for sodium ion adsorption and transportation respectively. In this review article, the fabrication techniques, structural configuration, sodium ion storage mechanism and its electrochemical performances will be introduced. Subsequently, an insight into the recent advancements in SIBs associated with 2D anode materials (graphene, graphene oxide (GO), transition metal oxides etc.) and other graphene-like elementary analogues (germanene, stanine etc.) as anode materials respectively will be discussed. Finally, the key challenges and future perspectives of SIBs towards enhancing the sodium storage performance of graphene-based electrode materials are discussed. In summary, we believe that this review will shed light on the path towards achieving long-cycling life, low operation cost and safe SIBs with high energy density using 2D anode materials and to be suitably commercialized for large-scale energy storage applications in the future.

A simplified coaxial ion trap mass analyzer: Characterization of the simplified toroidal ion trap with a rectilinear ion guide

A new miniature coaxial ion trap mass analyzer with a rectilinear ion guide has been constructed using a combination of planar and cylindrical electrodes. The results reported here focus on characterizing the performance of the rectilinear ion guide and simplified toroidal ion trap components. The simplified toroidal ion trap was found to have an ion capacity in excess of 105 ions and mass spectral resolution of 0.5–0.6 when used as a mass analyzer. The ion storage efficiency within the toroidal trapping region was evaluated and found the stored ion population decreased exponentially with storage time. Ion losses depended slightly on the stored βz condition. Ion losses within the toroidal region are attributed primarily to field instabilities at the intersection point of the two components while charge exchange reactions were observed but considered a minor loss mechanism. The ability to mass selectively ejection ions of a specific mass from the toroidal trapping region was characterized and found to approach 100 % efficiency under appropriate ejection conditions.

Tuning Crystalline Preferred Orientation of SnSe2 Anode by Co-doping to Enhance Pseudocapacitive Behaviors for High-Performance Sodium Storage.

SnSe2 has attracted great attention due to its unique 2D-layered structure, which makes it capable of sodium ion storage and higher theoretical capacities compared to traditional anode materials like hard carbon for sodium ion batteries (SIBs). However, SnSe2-based materials will cause structural damage due to volume expansion during ion storage, leading to poor cycle stability and rate capacity. In this work, Co-doped SnSe2 (Co-SnSe2) with preferred crystal orientation was fabricated by a one-step solvothermal method. It has been found that after doping Co, the lower (001) crystal plane located at 14.4° replaced the higher (101) plane at 30.7° as the dominant crystal plane in Co-SnSe2, which significantly promoted ion diffusion and enhanced the pseudocapacitance behavior. Therefore, this Co-SnSe2 anode achieves a high capacity of 504 mAh g-1 at 1 A g-1, and a high-rate cycle stability, delivering a reversible capacity of 302 mAh g-1 at 5 A g-1 after 1800 cycles with a retained capacity rate of 94%. Moreover, the Na3V2(PO4)3||Co-SnSe2 full cell exhibits a stable cycle performance of over 300 cycles at 1 A g-1, demonstrating great promise for practical applications. This work provides an effective reference for the exploration of high-performance sodium storage anode materials.

Progress in aluminum-ion battery technology: innovations in cathode materials, electrolyte chemistry, and performance enhancement

The review explores recent advancements in aluminum-ion battery technology, focusing on innovations in cathode materials, electrolyte chemistry, and performance enhancement. Notable developments include new cathode materials like activated carbon and graphene composites, which improve surface area, conductivity, and overall battery performance. Advances in electrolyte formulations, particularly AlCl3-based ionic liquids, have optimized ion transport and stabilized electrochemical processes, extending cycle life and reliability. Studies on ion intercalation mechanisms using density functional theory and molecular dynamics have provided insights into electrode transformations during charge-discharge cycles, aiding in the design of cathode materials with higher ion storage capacities and improved cyclability. These advancements highlight AIBs' potential as a promising alternative for large-scale energy storage applications.

Unraveling the Ionic Storage Mechanism of Flexible Nitrogen-Doped MXene Films for High-Performance Aqueous Hybrid Supercapacitors.

2D MXene nanomaterials have excellent potential for application in novel electrochemical energy storage technologies such as supercapacitors and batteries, but the existing pure MXene is difficult to meet the practical needs. Although the electrochemical properties of modified MXene have been improved, the unclear ion storage mechanism still hinders the development of MXene-based electrode materials. Herein, the study develops flexible self-supported nitrogen-doped Ti3C2 (Py-Ti3C2) films by the highly mobile, high nitrogen content, oxygen-free pyridine-assisted solvothermal method, and then deeply investigates the energy storage mechanism of hybrid supercapacitors in four aqueous electrolytes (H2SO4, Li2SO4, Na2SO4, and MgSO4). The experimental results suggest that the Py-Ti3C2 film electrode exhibits a pseudocapacitance-dominated energy storage mechanism. Particularly, the specific capacity of the Py-Ti3C2 in 1M H2SO4 (506 F g-1 at 0.1 A g-1) is 4-5 times higher than other electrolytes (≈110 F g-1), which could be attributed to the substantially higher ionic diffusion coefficient of H+ than those of Li+, Na+, Mg2+ with small ionic size, high ionic conductivity, and fast pseudocapacitance response. Theoretical analysis further confirms that Py-Ti3C2 has strengthened conductivity and electrical double-layer capacitance performance. Meanwhile, it has lower free energy for protonation and deprotonation of functional groups, which gives excellent pseudocapacitance performance.

Fluoride Ion Storage and Conduction Mechanism in Fluoride Ion Battery Positive Electrode, Ruddlesden-Popper-Type Layered Perovskite La1.2Sr1.8Mn2O7 Crystal.

Structural characteristics on fluoride ion storage and conduction mechanism in La1.2Sr1.8Mn2O7, and its fluoridated materials, La1.2Sr1.8Mn2O7F and La1.2Sr1.8Mn2O7F2, for an all-solid-state fluoride ion battery positive electrode with a high volumetric capacity surpassing those of lithium-ion ones have been revealed using the Rietveld method and maximum entropy method. In La1.2Sr1.8Mn2O7, once the F- ions are taken into the NaCl slabs in its crystal through the charging process, it forms two stable fluoride compounds, La1.2Sr1.8Mn2O7F and La1.2Sr1.8Mn2O7F2, with the help of the Mn oxidation reaction. In these oxyfluorides, thermal vibrations of the F- ions inserted are much larger, especially in the a-b plane, than along the c axis. When surplus energy, such as an electric field for charging, is applied to these crystals at near room temperature or higher, the anions immediately begin to jump to their neighboring lattice sites, resulting in sufficiently rapid and large ionic conduction. The MEM analyses and density functional theory (DFT) calculations have revealed that the F- ions enable to easily travel along the ⟨110⟩ directions in the NaCl slabs of these crystals. These structural features thus make La1.2Sr1.8Mn2O7 and its fluorides possess both of two features incompatible with each other, ion storage and conduction, indispensable for rechargeable batteries.

Porous Metal Phosphonate Frameworks: Construction and Physical Properties.

ConspectusPorous metal phosphonate frameworks (PMPFs) as a subclass of metal-organic frameworks (MOFs) have promising applications in the fields of gas adsorption and separation, ion exchange and storage, catalysis, sensing, etc. Compared to the typical carboxylate-based MOFs, PMPFs exhibit higher thermal and water stability due to the strong coordination ability of the phosphonate ligands. Despite their robust frameworks, PMPFs account for less than 0.51% of the porous MOFs reported so far. This is because metal phosphonates are highly susceptible to the formation of dense layered or pillared-layered structures, and they precipitate easily and are difficult to crystallize. There is a tendency to use phosphonate ligands containing multiple phosphonate groups and large organic spacers to prevent the formation of dense structures and generate open frameworks with permanent porosity. Thus, many PMPFs are composed of chains or clusters of inorganic metal phosphonates interconnected by organic spacers. Using this feature, a wide range of metal ions and organic components can be selected, and their physical properties can be modulated. However, limited by the small number of PMPFs, there are still relatively few studies on the physical properties of PMPFs, some of which merely remain in the description of the phenomena and lack in-depth elaboration of the structure-property relationship. In this Account, we review the strategies for constructing PMPFs and their physical properties, primarily based on our own research. The construction strategies are categorized according to the number (n = 1-4) of phosphonate groups in the ligand. The physical properties include proton conduction, electrical conduction, magnetism, and photoluminescence properties. Proton conductivity of PMPFs can be enhanced by increasing the proton carrier concentration and mobility. The former can be achieved by adding acidic groups such as -POH and/or introducing acidic guests in the hydrophilic channels. The latter can be attained by introducing conjugate acid-base pairs or elevating the temperature. Semiconducting PMPFs, on the other hand, can be obtained by constructing highly conjugated networks of coordination bonds or introducing large conjugated organic linkers π-π stacked in the lattice. In the case of magnetic PMPFs, long-range magnetic ordering occurs at very low temperatures due to very weak magnetic exchange couplings propagated via O-P-O and/or O(P) units. However, lanthanide compounds may be interesting candidates for single-molecule magnets because of the strong single-ion magnetic anisotropy arising from the spin-orbit coupling and large magnetic moments of lanthanide ions. The luminescent properties of PMPFs depend on the metal ions and/or organic ligands. Emissive PMPFs containing lanthanides and/or uranyl ions are promising for sensing and photonic applications. We conclude with an outlook on the opportunities and challenges for the future development of this promising field.

Hydrogen-Bonded Ionic Co-Crystals for Fast Solid-State Zinc Ion Storage.

The development of new ionic conductors meeting the requirements of current solid-state devices is imminent but still challenging. Hydrogen-bonded ionic co-crystals (HICs) are multi-component crystals based on hydrogen bonding and Coulombic interactions. Due to the hydrogen bond network and unique features of ionic crystals, HICs have flexible skeletons. More importantly, anion vacancies on their surface can potentially help dissociate and adsorb excess anions, forming cation transport channels at grain boundaries. Here, it is demonstrated that a HIC optimized by adjusting the ratio of zinc salt and imidazole can construct grain boundary-based fast Zn2+ transport channels. The as-obtained HIC solid electrolyte possesses an unprecedentedly high ionic conductivity at room and low temperatures (≈11.2 mScm-1 at 25°C and ≈2.78mScm-1 at -40°C) with ultra-low activation energy (≈0.12eV), while restraining dendrite growth and exhibiting low overpotential even at a high current density (<200mV at 5.0mAcm-2) during Zn symmetric cell cycling. This HIC also allows solid-state Zn||covalent organic framework full cells to work at low temperatures, providing superior stability. More importantly, the HIC can even support zinc-ion hybrid supercapacitors to work, achieving extraordinary rate capability and a power density comparable to aqueous solution-based supercapacitors. This work provides a path for designing facilely prepared, low-cost, and environmentally friendly ionic conductors with extremely high ionic conductivity and excellent interface compatibility.

Experimental and computational insights into oxygen vacancy-rich MoO2-x/N-doped carbon nanowires as high-performance cathode for magnesium batteries and magnesium-lithium hybrid batteries

This work aims to develop efficient cathode materials for magnesium based batteries, which are considered promising next-generation energy storage and conversion devices. One major challenge in magnesium based batteries is the strong Coulomb interaction between magnesium ions and cathode materials, which hinders ion storage and diffusion. To overcome this, we designed and synthesized oxygen vacancy-rich MoO2-x/N-doped carbon nanowires (MoO2-x-NC-NWS). The materials were prepared through a controlled synthesis process, ensuring the incorporation of N-doped carbon and oxygen vacancies, which play crucial roles in improving magnesium ion diffusion and storage. The prepared MoO2-x-NC-NWS demonstrated superior energy storage performance, achieving a capacity of 64 mAh/g in magnesium batteries and 263 mAh/g in magnesium-lithium hybrid batteries at a current density of 50 mA/g. Theoretical calculations further confirmed that oxygen vacancies enhance the diffusion capabilities of magnesium and lithium ions, thereby improving the overall energy storage performance. Therefore, the controllable synthesis of defects such as oxygen vacancies and the development of composite cathode materials are clearly effective strategies for enhancing the performance of magnesium-based battery cathodes. Meanwhile, this rational design of MoO2-based nanostructures provides valuable insights into the development of high-performance cathode materials for magnesium-based energy storage systems.

Modified structure of vanadium oxide via cadmium doping and in-situ activation for high-performance aqueous zinc ion storage

Vanadium oxides are promising cathode materials for aqueous zinc-ion batteries, but they suffer from severe crystal collapse and poor electrical/ionic conductivity. Herein, we successfully synthesized the designed cadmium-doped, carbon-coated vanadium oxide precursor with abundant oxygen vacancies (Cd0.015V2O3-x@C) using a straightforward one-pot thermal reduction method, followed by in-situ activation to form a high-performance cathode material, Cd0.004V2O5-y·nH2O@C. We find that the interlayered water dramatically reduces the electrostatic force between zinc ions and V2O5-y layers, meanwhile, abundant oxygen vacancies and cadmium doping alter the material’s band structure, resulting in enhanced electronic and ionic conductivities. Leveraging these advantages, the phase transitioned Cd0.004V2O5-y·nH2O@C cathode delivers a remarkably high capacity of 420 mAh/g (0.2 A/g), an excellent rate capability of 198 mAh/g (20.0 A/g), and an outstanding capacity retention of 78.5 % after 3500 cycles (20 A/g). This synergistic structure modification strategy of elemental doping and in-situ activation offers a novel approach to design high-performance vanadium oxide-based cathodes for advanced aqueous batteries.

Recent Advances in Cost‐Effective ZnO‐Based Electrode Material for Lithium‐Ion Batteries

AbstractFuel cell and lithium ion battery (LIB) technologies are increasingly recognized as cutting‐edge power sources that are gradually displacing various versions of older systems. High‐performance electrode materials must be developed for enhanced next‐generation LIBs. Because of their low cost, high theoretical specific capacity, and environmental friendliness, nanoparticles based on zinc oxide (ZnO) have been regarded as promising alternatives. However, significant problems including intrinsic poor conductivity and significant volume expansion have made ZnO‐based nanomaterials for less viable. In this review we discussed about the mechanism of lithium ion battery and how strategies to overcome intrinsic poor conductivity and significant volume expansion of ZnO‐based nanomaterials. Followed by the best methods for improving the lithium ion storage capacity of ZnO‐based materials as cathode and anode separately reviewed. And summarized the challenges and potential lines of inquiry for Zn‐based nanomaterials in the future.

Lithium-ion comb—artificial self-regulating lithium-storage film on aluminum anode enabling long cycles of batteries

Al anode can increase battery energy density, but its non-wettability and high Li nucleation hindrance cause uneven Li nucleation to deteriorate the anode structure. Herein, we present a novel in-situ synthesis method for the deposition of molybdenum oxide nanospheres (NMO) onto the surface of Al foil, that is, molybdenum oxide/aluminum (M-Al), which demonstrates a two-stage propulsion effect on Li-ion migration to address the issue at hand. The high wettability and low Li nucleation hindrance of the NMO layer drive the first stage of Li-ion migration. NMO acted as a comb to deliver Li ions uniformly with minor volume expansion. Subsequently, the formation of Li2O-rich solid electrolyte interphase (SEI) film with exceptional desolvation capability, facilitated by the NMO layer and electrochemically activated M-Al to Li molybdate/aluminum (Li-M-Al), represents the second stage in the advancement of Li−ion migration. The embedding of lithium ions makes molybdenum oxide evolve into lithium molybdate, thereby enabling Mo to regulate the storage of Li ions through the valence state. Hence, the Li nucleation overpotential of M-Al is decreased by 0.32 V, leading to a significant enhancement in the cycling performance of the Li-M-Al||LiFePO4 (LFP) battery, with a capacity retention rate of 78.5 % after 400 cycles at 1C.

High temperature induced abundant closed nanopores for hard carbon as high-performance sodium-ion batteries anodes

Hard carbon (HC) stands out as the preeminent anode material for sodium-ion batteries (SIBs) which are deployed in expansive energy storage infrastructures. Herein, the large enough graphene nanosheets interlayer and abundant nanopores with a diameter of ∼2.1 nm induced by adjusting the pyrolysis temperature in the thermosetting phenolic resin-derived hard carbon matrix to augment the performance of the sodium ion storage. The presence of sufficiently large carbon interlayers has been proven to provide active sites for reversible adsorption, enabling effective storage of sodium ions in the high-voltage slope region, while also promoting rapid Na+ transport. Meanwhile, forming abundant closed nanopores with larger sizes helps sodium ion storage in the low-voltage plateau region. In the optimized samples, the formation of sufficient long graphene nanosheets with a perfect crystal lattice, which further shrinks to form enclosed nanopores, effectively reduces defective sites and specific surface area. Additionally, the appropriate content of C-O and C=O functional groups contributes to an exceptional initial Coulombic efficiency (ICE) of up to 93%. Simultaneously, the optimized sample HC-1500 contributes to a remarkable plateau capacity of 294 mAh g-1 during the charging process (high reversible capacity of 403 mAh g-1 at 0.1 C). Moreover, based on the microstructure evolution and Na storage behavior of hard carbon, an “adsorption (27%) – filling (73%)” sodium storage mechanism that the sodium storage as a quasi-metallic sodium state is demonstrated. Consequently, this study will offer valuable insights for the development of hard carbon anodes tailored for high-energy practical SIBs, while also advancing the understanding of sodium storage mechanisms.