Anode Material For Potassium-ion Batteries Research Articles

Carbon coating engineering enhances the stability of graphite anode in potassium ion batteries

Graphite forms reversible potassium-graphite intercalation compounds electrochemically. Graphite anode possesses a high reversible specific capacity (279 mAh g−1) and an optimal low potential platform, rendering it an ideal anode material for potassium-ion batteries. However, the intercalation of K+ ions in graphite causes a bulk volume expansion of up to 61%, resulting in irreversible damage to the structure of graphite, which leads to inferior cycling stability. In this paper, surface-oxidized graphite (OG) with reduced particle size and increased defect densities was obtained by mechanical ball milling and chemical oxidation. Composites of soft carbon-coated OG (OG@PC) were prepared by soft carbon coating. The soft carbon coating can alleviate the bulk expansion caused by K+ intercalation/deintercalation in OG, thus slowing down the destruction of the crystalline structure of graphite after multiple charging/discharging cycles. OG@PC exhibits increased reversible specific capacity from 267 mAh g−1 to 314 mAh g−1 compared with pristine graphite at a current density of 0.05 A g−1. Moreover, at a high current density of 0.5 A g−1, a reversible specific capacity of 213 mAh g−1 was achieved after 200 cycles. This work investigates simple surface carbon coating strategies to improve the cycling stability of a graphite anode of potassium-ion batteries.

Self-hybridization structures of BiOBr0.5Cl0.5: An ultra-high capacity anode material for half/full potassium-ion batteries

Potassium-ion batteries (PIBs) are gaining attention among emerging technologies for their cost-effectiveness and the abundance of resources they utilize. Within this context, bismuth oxyhalides (BiOX) have emerged as exceptional candidates for anode materials in PIBs due to their unique structural and superior electrochemical properties. However, challenges such as structural instability and low electronic conductivity remain to be addressed. In this study, a flower-like BiOBr0.5Cl0.5/rGO composite anode material was synthesized, demonstrating outstanding K+ storage performance. The self-hybridized structure enhances ion adsorption and diffusion, which in turn improves charge and discharge efficiency as well as long-term stability. In situ X-ray diffraction (XRD) tests confirmed the gradual release and alloying potassium storage mechanism of Bi metal, which occurs through the intermediate KxBiOBr0.5Cl0.5 phase within the BiOBr0.5Cl0.5 anode. This composite exhibited a high specific capacity of 246.4 mAh/g at 50 A/g and maintained excellent capacity retention after 2400 cycles at 5 A/g. Additionally, in full battery tests, it showed good rate performance and long cycle life, maintaining a discharge specific capacity of 119.6 mAh/g at a high current density of 10 A/g. Comprehensive characterizations revealed insights into the structural, electrochemical, and kinetic properties, advancing high-performance PIBs.

Sulfur-doped pomegranate-like carbon microclusters designed via facile spray-drying process: A novel anode material for potassium-ion batteries

Recent research has demonstrated increasing inclination toward employing hollow carbons featuring nanoscale amorphous structures as anodes in potassium-ion batteries. However, these amorphous structures detrimentally impact the electrode’s electron and ion conductivities, leading to subpar rate performance. Additionally, integrating nanoparticles into electrodes typically yields an uneven distribution, owing to the propensity of nanomaterials to readily aggregate. To address these challenges, S-doped pomegranate-like carbon microclusters (S-PCMs) comprising S-doped primary hollow carbon spheres (HCSs) were synthesized via spray drying. The effects of self-assembly and S doping on the morphological structure and potassium storage performance of the HCS materials were systematically investigated through comprehensive analyses. PCMs mitigated volume expansion and imparted high conductivity and charge/discharge rates owing to short potassium-ion diffusion distances, while the self-assembled nanospheres improved slurry flow properties. Additionally, sulfur doping increased the pore size, interlayer spacing, and number of defect sites in the carbon lattice, improving electron mobility. The resulting S-PCMs exhibited exceptional potassium storage properties, particularly cycling performance (224 mA h g−1 at the 1000th cycle). Furthermore, various electrochemical tests attributed S-PCM’s enhanced potassium storage performance to the numerous active sites and increased resistance to charge transfer, improving the potassium diffusion coefficient.

Antimony nanoparticles encapsulated in interconnected nitrogen-doped carbon nanospheres for high performances PIBs

Antimony (Sb) has attracted significant attention as an anode material for potassium-ion batteries (PIBs) due to its high theoretical capacity and suitable working voltage. However, the severe volume variations of Sb during potassiation/depotassiation process lead to sluggish kinetics and poor cyclic stability for PIBs. In this study, Sb nanoparticles are confined within interconnected N-doped carbon nanospheres (Sb@NC) through an effective carbothermal reduction process. The potassium storage performances and mechanism are elucidated through electrochemical tests combined with ex-XRD analysis. When used as an anode for PIBs, the optimized Sb@NC-2 anode exhibits excellent cycle stability of 463.0 mAh g−1 at 200 mA g−1 over 100 cycles and superior rate capability of 113.4 mAh g−1 at a high current density of 2 A g−1. Besides, a full cell comprising an Sb@NC-2 anode and a PTCDA cathode is also tested to validate the practical feasibility of the anode. Furthermore, Density Functional Theory (DFT) calculations demonstrate that N-doped carbon can enhance the adsorption of K+ and improve the kinetics of electrochemical reactions. Therefore, the unique yolk-shell structure in this study effectively restricts volume expansion and aggregation of Sb particles while facilitating rapid electron/ion transfer. These findings provide a potential alternative anode material for advanced PIBs.

Self-Propagating Fabrication of a 3D Graphite@rGO Film Anode for High-performance Potassium-Ion Batteries.

Graphite, with abundant resources and low cost, is regarded as a promising anode material for potassium-ion batteries (PIBs). However, because of the large size of potassium ions, the intercalation/deintercalation of potassium between the interlayers of graphite results in its huge volume expansion, leading to poor cycling stability and rate performance. Herein, a self-propagating reduction strategy is adopted to fabricate a flexible, self-supporting 3D porous graphite@reduced graphene oxide (3D-G@rGO) composite film for PIBs. The 3D porous network can not only effectively mitigate the volume expansion in graphite but also provide numerous active sites for potassium storage as well as allow for electrolyte penetration and rapid ion migration. Therefore, compared to the pristine graphite anode, the flexible 3D-G@rGO film electrode exhibits greatly improved K-storage performance with a reversible capacity of 452.8 mAh g-1 at 0.1 C and a capacity retention rate of 80.4% after 100 cycles. It also presents excellent rate capability with a high specific capacity of 139.1 and 94.2 mAh g-1 maintained at 2 and 5 C, respectively. The proposed self-propagating reduction strategy to construct a three-dimensional self-supporting structure is a viable route to improve the structural stability and potassium storage performance of graphite anodes.

Porous-structured FeS2@C nanoparticles prepared from spent LiFePO4 cathodes with excellent rate performance for potassium-ion batteries

Recycling spent cathode materials is crucial for sustainably developing lithium-ion battery technology. To achieve the high-value utilization of spent LiFePO4 (LFP) cathodes, this paper proposes a method for preparing MIL-100(Fe) based on solid waste residues from spent LFP cathodes. R-FeS2@C derived from MIL-100(Fe) can serve as an anode material for potassium-ion batteries featuring a porous structure. Electrochemical tests demonstrate that the R-FeS2@C exhibits more stable cycling performance compared with the FeS2@C derived from the traditional MIL-100(Fe), reaching 525 mAh g−1 after 100 cycles at a current density of 100 mA g−1. Impressively, R-FeS2@C also showcases excellent rate performance (343 mAh g−1 specific capacity at 5 A g−1). Furthermore, full cells assembled with PI@rGO cathodes also exhibit excellent rate performance and stable cycling performance. The porous structure of R-FeS2@C provides numerous voids to accommodate volume changes and introduces sufficient channels for electrolyte penetration. The higher carbon content enhances the electrical conductivity improving the kinetics of the K+ migration reaction. These researches can provide guidance for the recycling of spent lithium-ion batteries and the design of sulfide electrodes for PIBs.

Analogous Chelation to Boost Utilization of Sb in Sb Nanoparticles and N-doped Carbon Composites for Enhancing Potassium Storage.

Antimony (Sb) is an attractive anode material for potassium-ion batteries (PIBs), but it suffers from aggregation during the charging-discharging process, thus causing embedded active sites and collapsed structure. The analogous chelation refers to the reaction in which the central nanoparticle is linked to the matrix through multiple coordination bonds to form a stable composite. This strategy can inhibit aggregation and maintain the nanosized structure of Sb, thus activating the utilization of Sb active sites and structural stability. Given the special position of nitrogen (N) in the periodic table of elements and the strong bond energy of Sb-N, the N element can serve as an intermediate to connect Sb nanoparticles and an intrinsic N-doped carbon network via strong Sb-N-C/Sb-N═C covalent bonds using analogous chelation. Herein, a hybrid material of Sb@CTF-NC is fabricated via analogous chelation. The Sb atoms exposed on the surface of Sb nanoparticles are used to chelate with the N-doped carbon for high-performance PIBs. The mechanism underwent ex situ characterizations. The calculation of density functional theory reveals that the increase of adsorption energy and reduction of the K+ diffusion barrier accelerate the electrochemical reaction kinetics.

Construction of Bi/Bi2O3 particles embedded in carbon sheets for boosting the storage capacity of potassium-ion batteries

Bismuth-based materials have attracted interest in potassium-ion batteries (PIBs). However, the large volume expansion prevents further use of bismuth-based materials for potassium storage. This work employs a two-step synthesis method to innovatively synthesize of Bi/Bi2O3 nanoparticles assembled on N-doped porous carbon sheets (Bi/Bi2O3@CN). The layered structures with uniformly shaped and N-doped porous carbon skeleton buffer the expansion of Bi and the Bi/Bi2O3 particles increase the capacity of potassium storage. In brief, the Bi/Bi2O3@CN served as anode in half-cell of PIBs have a good rate capacity of more than 234.7 mAh/g at 20 A/g. The specific capacity retention was 73 % compared with 322.16 mAh/g at 1 A/g, demonstrating good holding capacity for diverse current densities. The cycle also displays 163 mAh/g after 1500 cycles at 2 A/g in the KPF6 metal salt solution, showing its potential as one of the anode materials in PIBs.

Construction of High-Performance Anode of Potassium-Ion Batteries by Stripping Covalent Triazine Frameworks with Molten Salt.

Covalent triazine frameworks (CTFs) are promising battery electrodes owing to their designable functional groups, tunable pore sizes, and exceptional stability. However, their practical use is limited because of the difficulty in establishing stable ion adsorption/desorption sites. In this study, a melt-salt-stripping process utilizing molten trichloro iron (FeCl3) is used to delaminate the layer-stacked structure of fluorinated covalent triazine framework (FCTF) and generate iron-based ion storage active sites. This process increases the interlayer spacing and uniformly deposits iron-containing materials, enhancing electron and ion transport. The resultant melt-FeCl3-stripped FCTF (Fe@FCTF) shows excellent performance as a potassium ion battery with a high capacity of 447 mAh g-1 at 0.1 A g-1 and 257 mAh g-1 at 1.6 A g-1 and good cycling stability. Notably, molten-salt stripping is also effective in improving the CTF's Na+ and Li+ storage properties. A stepwise reaction mechanism of K/Na/Li chelation with C═N functional groups is proposed and verified by in situ X-ray diffraction testing (XRD), ex-situ X-ray photoelectron spectroscopy (XPS), and theoretical calculations, illustrating that pyrazines and iron coordination groups play the main roles in reacting with K+/Na+/Li+ cations. These results conclude that the Fe@FCTF is a suitable anode material for potassium-ion batteries (PIBs), sodium-ion batteries (SIBs), and lithium-ion batteries (LIBs).

Effects of cation substitution effects of dicarboxylic acid for energy storage applications

Organic materials (OMs) can accept alkali ions and function as energy storage systems, displaying several advantages such as low cost, ease of synthesis, and utilization of recyclable materials. Owing to their higher theoretical capacity, OMs exhibit a higher energy density, cheaper price, and easy recover than those of inorganic materials such as graphite, silicon, and metal oxides, respectively. This study reports the use of potassium 4-oxo-4H-pyran-2,6-dicarboxylic acid (K2CDA) and potassium 4-oxo-4H-pyran-2,6-dicarboxylic acid (K2CDO) as anode materials for potassium-ion batteries (KIBs) and lithium-ion batteries (LIBs). Although they share similar lightweight, carbonyl, and carboxylate functional groups, both materials display distinct reaction behaviors owing to differences in electronegative heteroatoms N and O. In this study, two alkaline salts (KFSI and LiFSI) have been discussed on the substitution effect of doping/ de-doping processes. K2CDA and K2CDO. Consequently, after 200 cycles, the K2CDA anodes deliver capacities of 310 (KFSI) and 485 (LiFSI) mAh g−1, respectively, at 0.1 C. The larger size of K+ compared with Li+ negatively impacts the performance of K2CDA. A similar trend is observed in the case of K2CDO in capacities of 220 (KFSI) and 405 mAh g‒1 (LiFSI), with 1.5 and 2.86 K+ ions participated in the corresponding redox reactions on the Fourier-transfer infrared spectroscopy analysis. The presence of N‒H in the K2CDA structure contributes to its superior performance and rate capability compared with K2CDO. In addition to the cation effect, the structural differences between K2CDA and K2CDO also influence their electrochemical activity.

Structure-modulation of flower-like VS2 via ammonium ion intercalation for high performance potassium-ion batteries

Transition vanadium sulfide is a promising anode material for potassium-ion batteries (PIBs), but the volume variation during charge-discharge cycling and low electric conductivity seriously hinder its applications. Herein, we designed a multilayer lamellar self-assembled flower-like vanadium sulfide with ammonium ion intercalation (VS2–NF) by a facile and inexpensive hydrothermal method to improve its electrochemical potassium ion storage performance. By introducing ammonia during the hydrothermal synthesis process, the structures of vanadium sulfide transformed to nanoflowers composed by ultrathin nanosheets from the initial nanosphere structures. The intercalation of ammonium ion enlarges the lattice fringes and induces anisotropic growth of vanadium sulfide, resulting in a large number of mesopores and increased specific surface area as well as the reactive sites of vanadium sulfide, which contribute to the enhanced potassium ion storage performance. Consequently, the structure-modulated VS2–NF exhibits a high specific capacity of 507 mAh g−1 after 50 cycles at a current density of 100 mA g−1. This approach provides a new routine for the modification of other transition metal disulfides as anode materials for PIBs.

Novel NASICON-type Mn0.5Ti2(PO4)3@F-doped carbon composite with high electrochemical performance as anode materials for potassium-ion batteries

Mn0.5Ti2(PO4)3 with a NASICON structural is used as an anode material in potassium-ion batteries due to its abundance of vacancies that can hold potassium ions. This characteristic not only contributes to its excellent stability but also results in a high specific capacity. However, the poor electrical conductivity of the polyanionic type structure limits the material's ability to fully utilize its capacity. In this paper, the conductivity and electrochemical stability of the Mn0.5Ti2(PO4)3 anode material are enhanced through composite formation with an F-doped carbon layer. The introduction of F into the carbon matrix creates a large number of vacancy defects and F active sites. The vacancies enhance the transport of potassium ions on the Mn0.5Ti2(PO4)3 material's surface, while the active sites exhibit strong electronegativity, improving the absorption of potassium ions. Therefore, the diffusion impedance of potassium ions is significantly reduced, leading to an increased diffusion rate of potassium ions. Attributing to the improved reaction kinetics, the Mn0.5Ti2(PO4)3@F-doped carbon composite demonstrates a high specific capacity of 86 mA h g−1 at 10,000 mA g−1 when used as the anode for potassium-ion batteries. Even more, the specific capacity remains a capacity of 136 mA g−1 after 3000 cycles at 1000 mA h g−1. This study enhances our comprehension of material design by investigating the alteration of carbon matrix to promote the electrochemical characteristics of materials.

Enhanced potassium-ion battery performance with Bi Nanoparticle-Infused 3D porous carbon composites

Bismuth (Bi) based materials are widely utilized in potassium-ion batteries (PIBs) due to their high theoretical capacity; however, they undergo severe volume changes during electrochemical processes. To develop Bi-based anode with extended lifespan, Bi nanoparticles and porous carbon materials were composited by a template method in this study. N-doped three-dimensional porous carbon coated Bi nanoparticles (Bi@3DNC) composites were successfully synthesized by using sodium chloride as a template and anchoring Bi nanoparticles on a porous carbon skeleton. Bi@3DNC exhibits excellent electrochemical performance as an anode material for PIBs, retaining a capacity of 273 mAh/g after 700 cycles at 1 A/g. We elucidate that the 3D porous carbon mesh serves to confine the alloying particles and buffer the volume expansion of the metal during continuous K+ de-intercalation, while also enhancing the availability of active sites. This strategy offers promising prospects for the development of advanced metal based anodes for PIBs.

Two-Dimensional TOD-Graphene in a Honeycomb–Kagome Lattice: A High-Performance Anode Material for Potassium-Ion Batteries

Two-Dimensional TOD-Graphene in a Honeycomb–Kagome Lattice: A High-Performance Anode Material for Potassium-Ion Batteries

Pyrolysis fuel oil-derived hollow carbon nanocages as high-stability anode materials for potassium ion storage

The use of graphite to make anode materials for potassium-ion batteries (KIBs) results in diminished electrochemical performance, largely due to significant interlayer expansion caused by potassation/depotassiation. To address this limitation, novel hollow carbon nanocages (HCNCs) are prepared from pyrolysis fuel oil (PFO), a cost-effective byproduct. The HCNCs heat-treated at 1500 °C has a graphitic structure with high porosities and numerous closed pores and exhibits a notable potassium-ion storage capacity of 307.2 mAh/g at a current density of 50 mA g−1. Moreover, structurally stable HCNCs withstand the substantial volume expansion associated with potassium-ion intercalation. The stability of the material is attributed to a hybrid adsorption/insertion mechanism, which results from synergistic interplay between the unique morphologies of the HCNCs and the developed carbon layers. This configuration delivers a specific capacity of 131.6 mAh/g and 98.9 % capacity retention over 1000 cycles at a high current density of 2000 mA g−1. Consequently, these proposed HCNCs present a significant advance in developing efficient carbon materials for KIBs, and addressing the critical challenges of graphite such as unstable cycling stability.

Electrolyte solvent composition regulating endows CoSe2 hollow nanocage anode with stable potassium ion storage

Metal selenides are ideal anode materials for potassium-ion batteries (PIBs) due to their significant merits of favorable conductivity and ion transport property. However, the inevitable volume changes of metal selenides electrode during potassiation/depotassiation processes result in the fracture and reconstruction of the solid electrolyte interphase (SEI) layer, causing capacity decay and significantly limiting their practical applications. Reasonable morphology control accompanied by uniform and rigid SEI layer formation are key factors in improving the electrochemical cycling stability of metal selenides. In this paper, nano-hollow CoSe2 (CoSe2@CNC) anode materials are prepared using ZIF-67 as the precursor. The differences of electrochemical performances for CoSe2@CNC anode material in ester-based and ether-based electrolytes have been investigated in detail. Results demonstrate that the SEI layer formed in the ester-based electrolyte is loose and thick, leading to electrode pulverization and material detachment after several cycles, resulting in rapid degradation of cycle performance. In contrast, a thin and inorganic-rich SEI layer containing more inorganic components is formed in the ether-based electrolyte, effectively protecting the electrode from damage, facilitating electronic transfer at the electrode electrolyte interphase, and optimizing potassium ions storage performance.

Nanomesh NiO-modified carbon cloth for highly efficient self-supporting potassium metal anodes

Potassium metal is one of the most promising anode materials for potassium-ion batteries owing to its low cost and ability to withstand high current density and relatively low operating potential. However, it is restricted from being used in practical implementations because of its high reactivity and disordered dendrite growth. To circumvent these issues, we stabilize potassium metal anodes by growing NiO with high potassium affinity and interconnected network porous structure on carbon cloth fibers (CC-NiO). A symmetric cell assembled from a composite material formed by infiltrating molten K into CC-NiO (K@CC-NiO) can cycle stably for 1840 h at a low overpotential of 33 mV. Furthermore, the first-cycle discharge capacities of the full batteries with carbon nanotubes-interwoven KFeSO4F microspheres (KFSF@CNTs) and perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) as the cathodes are 101.4 and 105.1 mAh g−1, respectively. The capacity retention of KFSF@CNTs||K@CC-NiO full battery after 1000 cycles is 79.3 %, and the capacity retention of PTCDA||K@CC-NiO full battery after 800 cycles is 70.2 %. The strategy of utilizing NiO as an efficient potassium metal nucleation anchor opens up a new direction for the development of high-energy and long-cycle-life potassium metal batteries.

Cellulose nanocrystal-derived carbon electrodes for sustainable potassium-ion charge storage systems

We have here produced carbon electrode materials derived from Crystalline NanoCellulose (CNC) for low-cost potassium-ion based energy storage systems through conventional annealing as well as through a fast and energy efficient microwave assisted carbonization process. A two-step 4-minute synthesis with ZnCl2 activation in a domestic microwave leads to a micro/mesoporous carbon with high surface area (SBET∼1800 m2 g−1). These CNC-derived carbons, if assessed in symmetric supercapacitor C/C cells cycled with 0.5 M K2SO4 aqueous electrolyte, show reversible capacitance values up to 66 F g−1 at current densities of 5 A g−1, retaining 83% of its initial capacitance after 10.000 cycles without any conducting additive. Due to its large electrochemical window of 1.7 V, a competitive energy density for an aqueous system of 20.9 W h kg−1 is achieved. A hybrid aqueous capacitor built with this carbon as negative electrode and coupled with a Prussian White as positive results in cell capacitance values up to 135 F g−1 under a voltage operation window of 1.8 V in 0.5 M K2SO4. On the other hand, non-activated carbons produced through a 2.25 hour thermal annealing at 900 °C, present much lower surface area (SBET∼450 m2 g−1), most of it due to its high micropore volume. This low external and mesoporous surface area carbon is a competitive anode material for potassium-ion batteries with a reversible capacity of ∼200 mA h g−1 cycled at 28 mA g−1 using 3.9 M KFSI in DME electrolyte (favourably most of it below 1 V vs K+/K) in a potassium half-cell with >80% retention in 100 cycles. The present research shows that sustainable CNC derived carbons produced through energy efficient methods are competitive electrode materials in low-cost K based energy storge systems.

Bimetallic alloy nanoparticles embedded in N-doped carbon-based as an anode for potassium-ion storage material

Metal-organic frameworks (MOFs) have great potential as anode materials for potassium-ion batteries (PIBs) due to their hierarchical porous structures, large number of reaction sites, and adjustable chemistry. However, the larger size of potassium ions adversely impacts the electrochemical performance and specific capacity. Therefore, it is imperative to develop novel electrode materials featuring distinctive structures for PIBs. This study achieved bimetal introduction by adding Ammonium ferric citrate during ZIF-67 growth. The resulting metal–organic skeleton of the bimetallic alloy nanoparticle (FeCo@PAZ-C) exhibits a core–shell structure and adorned with numerous microspheres on its surface, thereby offering an abundance of active sites for K+ storage. This architecture effectively reduces the diffusion path length for potassium ions and enhances electron transport pathways, ultimately contributing to improved performance. At 100 mA g−1 and after 500 cycles, the FeCo@PAZ-C electrode material demonstrated a stable specific capacity of 328 mAh/g with 95 % capacity retention. This self-sacrificing template method for MOFs offers a new approach to developing high-capacity and cycling-stable potassium-ion battery materials, broadening their potential applications.

Liquid phase oxidation enables stable soft carbon anodes for potassium-ion batteries

Soft carbon has been recognized as a promising anode material for potassium-ion batteries (PIBs), due to low cost, high conductivity and low voltage platform. However, their practical application is hampered by slow storage kinetics and unsatisfactory cycle life. In this work, pitch-derived needle coke, a typical soft carbon, was incorporated with oxygenated functional groups through liquid phase oxidation by using H2O2 oxidant. When used as anode materials for PIBs, the oxidized needle coke delivers a high reversible capacity of 322.7 mAh g−1, significantly superior to that of the needle coke (237.9 mAh g−1). The enhanced electrochemical performance can be attributed to the abundant oxygenated functional groups and resultant defects on the surface of oxidized needle coke, which not only serve as extra active sites for potassium storage, but also provide sufficient pathways for K+ migration across the adjacent carbon layers. Moreover, the expanded interlayer spacing derived from H2O2 oxidation facilitates rapid K+ intercalation and deintercalation. This work offers an effective modification strategy for the fabrication of high-performance pitch-based soft carbon anodes for PIBs.Graphical