High-performance Potassium-ion Batteries Research Articles

Zn Doping Strategy to Suppress the Jahn-Teller Effect to Stabilize Mn-Based Layered Oxide Cathode toward High-Performance Potassium Ion Batteries.

In the research report of cathode of potassium ion battery, Mn-based layered structural oxides have attracted the researcher's attention because of its good energy density and high specific rate capacity. However, the Jahn-Teller effect is the main limiting factor for their development. It leads to the expansion and deactivation of Mn-based layered metal oxides during cycling for a long time. Therefore, mitigation of the Jahn-Teller effect is considered a useful measure to enhance the electrochemical capability of Mn-based layered oxide. In this paper, an R3m-type K0.4Mn0.7Co0.25Zn0.05O2 cathode material is designed through a Zn doping strategy. X-ray diffraction techniques and electrochemical tests verified that the Jahn-Teller effect is effectively mitigated. High performance is achieved in the rate capacity test with 113 mAh g-1 at 50mA g-1. Comparison with similar materials in recent years has demonstrated its superiority, leading rate performance among Mn-based metal oxides reported in recent years. The practical feasibility is verified in the assembled full cell with soft carbon in anode materials and K0.4Mn0.7Co0.25Zn0.05O2 as cathode. In the full cell rate test, 104.8 mAh g-1 discharging capacity is achieved at 50mA g-1 current density.

Encapsulation of Sn Sub-Nanoclusters in Multichannel Carbon Matrix for High-Performance Potassium-Ion Batteries.

Sub-nanoclusters with ultra-small particle sizes are particularly significant to create advanced energy storage materials. Herein, Sn sub-nanoclusters encapsulated in nitrogen-doped multichannel carbon matrix (denoted as Sn-SCs@MCNF) are designed by a facile and controllable route as flexible anode for high-performance potassium ion batteries (PIBs). The uniformly dispersed Sn sub-nanoclusters in multichannel carbon matrix can be precisely identified, which ensure us to clarify the size influence on the electrochemical performance. The sub-nanoscale effect of Sn-SCs@MCNF restrains electrode pulverization and enhances the K+ diffusion kinetics, leading to the superior cycling stability and rate performance. As freestanding anode in PIBs, Sn-SCs@MCNF manifests superior K+ storage properties, such as exceptional cycling stability ( around 331 mAh g-1 after 150 cycles at 100 mA g-1) and rate capability. Especially, the Sn-SCs@MCNF||KFe[Fe(CN)6] full cell demonstrates impressive reversible capacity of around 167 mAh g-1 at 0.4 A g-1 even after 200 cycles. Theoretical calculations clarify that the ultrafine Sn sub-nanoclusters are beneficial for electron transfer and contribute to the lower energy barriers of the intermediates, thereby resulting in promising electrochemical performance. Comprehensive investigation for the intrinsic K+ storage process of Sn-SCs@MCNF is revealed by in situ analysis. This work provides vital guidance to design sub-nanoscale functional materials for high-performance energy-storage devices.

CoSe2 nanocrystals embedded in one-dimensional mesoporous carbon nanofibers as advanced anode for potassium-ion storage

High-performance potassium-ion batteries have received great attention for electrochemical energy storage owing to their low redox potential, abundant natural resources and excellent safety. As an advanced negative material, CoSe2 has been widely investigated for potassium-ion batteries. Unfortunately, the pure CoSe2 anode suffers from the fast capacity decay and sluggish kinetics, preventing its practical application. Herein, we introduce a novel strategy to fabricate the CoSe2 nanoparticles embedded in one-dimensional mesoporous carbon nanofibers (denoted as 1D-CoSe2@CNFs) with superior high-rate property and good cycle stability for the first time. In this designed material, the conductive carbon nanofibers are loaded with CoSe2 particles. The obtained 1D-CoSe2@CNFs anode shows a specific capacity of 706.3 mAh/g at 0.1 A/g and presents a high capacity retention ratio of around 96.3 % at 5 A/g over 400 cycles. Therefore, this fabricated 1D-CoSe2@CNFs nanocomposite can be employed as a novel negative electrode for potassium-ion storage.

In-situ doped and activated N, S co-doped porous carbon derived from organic salt for application in high-performance potassium-ion batteries

Owing to its abundance in nature and low cost, potassium has attracted considerable attention as a substitute for lithium in the manufacture of secondary-ion batteries. However, developing amorphous carbon materials that show fast K+ ion kinetics for application in high-performance potassium-ion battery (PIB) anodes remains challenging. In this study, we designed and synthesized a 3-D hierarchical nitrogen and sulfur co-doped porous carbon electrode via in-situ doping and activation using acesulfame potassium. Owing to its prominent structural advantages, the as-prepared N, S co-doped electrode showed a high reversible capacity (459.8 mAh g−1 at 0.05 A g−1) and long-term cycle stability (205 mAh g−1 after 1000 cycles at 0.5 A g−1). Further, the results of ex-situ Raman spectroscopy and X-ray photoelectron spectroscopy verified the advantages of N and S co-doping with respect to K+ ion intercalation and adsorption/desorption properties within the carbon matrix. Therefore, our findings enhance understanding regarding the advantages of the dual-doped system with respect to K+ ion storage and highlight an efficient strategy for developing high-performance and durable carbon anode materials for PIBs.

Three-dimensional MoS2 nanosheets embeded within NiTe nanorods forming semicoherent heterojunctions achieving high-performance potassium-ion batteries

Three-dimensional MoS2 nanosheets uniformly embedded within NiTe nanorods are synthesized via one-step hydrothermal method and subsequently coated with a carbon layer to form stable NiTe@MoS2@C heterojunctions. The heterojunctions exhibit moderate lattice mismatch (δ =20.0 %), strong electric fields, and uniform carbon shells, resulting in unique electronic configurations and abundant active sites. As an anode for potassium-ion batteries, NiTe@MoS2@C demonstrated an high reversible capacity of 258.4 mAh g−1 after 100 cycles at a rate of 200 mA g−1. Moreover, it showed a stable reversible capacity of 177.5 mAh g−1 at a high rate of 5000 mA g−1, indicating excellent rate performance. Notably, even in the NiTe@MoS2@C//perylene tetracarboxylic dianhydride full battery configuration, a significant reversible capacity of 87.4 mAh g−1 was maintained after 100 cycles at a rate of 200 mA g−1, manifesting its remarkable potential for practical applications in potassium-ion batteries. Theoretical calculations further revealed that the well-designed NiTe@MoS2 heterojunction significantly enhances K+ ion diffusion.

KxFeO2 As Electrode Material for K-Ion Batteries

To meet future energy demands, developing beyond-lithium energy storage technologies have become a major part of global research activities. Potassium-ion batteries (KIBs) represent a promising technology thanks to their chemical and economic advantages1–3. The majority of the work on layered transition oxide was done on the KxMnO2 family4,5 due to their safety and price advantage.Interestingly, KFeO2 structure is not a layered structure as for LiFeO2 or NaFeO2; this structure is defined as FeO4 tetrahedral linked by their corners. In electrochemistry, a reversible capacity of 60 mAh/g (for 0.3K+) was delivers6.In our presentation, we will detail the electrochemical behaviour of KFeO2 and discuss the structure/properties relationship of this family of materials, showing the interest in the exploration of such a system. Xu, Y. et al. 2023 roadmap for potassium-ion batteries. J. Phys. Energy 5, 021502 (2023).Tian, Y. et al. Promises and Challenges of Next-Generation “Beyond Li-ion” Batteries for Electric Vehicles and Grid Decarbonization. Chem. Rev. 121, 1623–1669 (2021).Zhang, W., Liu, Y. & Guo, Z. Approaching high-performance potassium-ion batteries via advanced design strategies and engineering. Sci. Adv. 5, eaav7412 (2019).Kim, H. et al. Investigation of Potassium Storage in Layered P3-Type K0.5MnO2 Cathode. Adv. Mater. 29, 1702480 (2017).Liu, C., Luo, S., Huang, H., Zhai, Y. & Wang, Z. Layered potassium-deficient P2- and P3-type cathode materials KxMnO2 for K-ion batteries. Chem. Eng. J. 356, 53–59 (2019).Han, S. C., Park, W. B., Sohn, K.-S. & Pyo, M. KFeO2 with corner-shared FeO4 frameworks as a new type of cathode material in potassium-ion batteries. J. Solid State Electrochem. 23, 3135–3143 (2019).

K3MnO4 a New Cathode Material for K-Ion Batteries

To meet future energy demands, developing beyond-lithium energy storage technologies have become a major part of global research activities. Potassium-ion batteries (KIBs) represent a promising technology thanks to their chemical and economic advantages1–3. To succeed in developing commercial KIBs, it is necessary to develop new cathode materials4 which must be non-toxic, inexpensive, easy to prepare and have a reasonable K+ diffusion pathway to improve their electrochemical performance. Here we have chosen to explore the inexpensive and non-toxic K-Mn-O system, where only two-dimensional materials of the KxMnO2 type have been studied so far for their electrochemical properties5,6.In this system, a composition attracted our attention: K3MnO4. In principle, up to two potassium ions can be removed from the structure, leading to KMnO4 with a theoretical capacity of 227 mAh/g.Hagenmuller and co-workers succeeded in preparing two polymorphs of K3MnO4 as single crystals7. The high temperature polymorph γ-K3MnO4 has a cubic symmetry (P213) with a disordered distribution of K and Mn in similar tetrahedral sites. The low temperature polymorph β-K3MnO4, can be prepared by annealing γ-K3MnO4 under argon. This polymorph has a tetragonal symmetry (I-42m) with ordered MnO4 tetrahedra. Mn is reported at the edge and at the center of the tetragonal unit cell, surrounded by four oxygens. These phases could be described as a 0D-type structure built of isolated MnO4 tetrahedra surround by potassium ions.We recently succeed in the synthesis of a new polymorph of K3MnO4, labelled α-K3MnO4,8 prepared by a conventional solid-state route by annealing a mixture of KO2 and MnO under vacuum at 500°C in a Al2O3 boat. The structure of this polymorph could be described with a “zig-zag” distribution of the MnO4 tetrahedra (Fig. 1a) and is isostructural to the iron-based K3FeO4 9,10 with an orthorhombic symmetry (Pnma). The blue colour of the powder is classically associated to the Mn+V oxidation state, as confirmed by magnetic and EDS analyses. K3MnO4 exhibits a reversible capacity of 70 mAh/g in the 1.6-3.5 V vs. K+/K potential window at C/20 (Fig. 1b).In our presentation, we will detail the electrochemical behaviour of K3MnO4 and discuss the structure/properties relationship of this family of materials, showing the interest in the exploration of such a system. Xu, Y. et al. 2023 roadmap for potassium-ion batteries. J. Phys. Energy 5, 021502 (2023).Tian, Y. et al. Promises and Challenges of Next-Generation “Beyond Li-ion” Batteries for Electric Vehicles and Grid Decarbonization. Chem. Rev. 121, 1623–1669 (2021).Zhang, W., Liu, Y. & Guo, Z. Approaching high-performance potassium-ion batteries via advanced design strategies and engineering. Sci. Adv. 5, eaav7412 (2019).Nathan, M. G. T. et al. Recent Advances in Layered Metal-Oxide Cathodes for Application in Potassium-Ion Batteries. Adv. Sci. n/a, 2105882.Liu, T. et al. Insight of K-deficient layered KxMnO2 cathode for potassium-ions batteries. J. Energy Chem. 64, 335–343 (2022).Liu, C., Luo, S., Huang, H., Zhai, Y. & Wang, Z. Layered potassium-deficient P2- and P3-type cathode materials KxMnO2 for K-ion batteries. Chem. Eng. J. 356, 53–59 (2019).Olazcuaga, R., Reau, J.-M., Leflem, G. & Hagenmuller, P. Préparation, Proprietés Cristallographiques et Magnétiques des Phases K3XO4 (X=V, Cr, Mn). Z. Für Anorg. Allg. Chem. 412, 271–280 (1975).Sagot, A., Stievano, L. & Pralong, V. K3MnO4: A New Cathode Material for K-Ion Batteries. ACS Appl. Energy Mater. 6, 7785–7789 (2023).Kokarovtseva, I. G., Belyaev, I. N. & Semenyakova, L. V. Oxygen Compounds of Iron(VI, V, IV). Russ. Chem. Rev. 41, 929–937 (1972).Hoppe, R. & Mader, K. Zur Konstitution von K3[FeO4]. Z. F ür Anorg. Allg. Chem. 586, 115–124 (1990). Figure 1

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.

Scaly MoS2/rGO Composite as an Anode Material for High-Performance Potassium-Ion Battery.

Potassium-ion batteries (PIBs) have been widely studied owing to the abundant reserves, widespread distribution, and easy extraction of potassium (K) resources. Molybdenum disulfide (MoS2) has received a great deal of attention as a key anode material for PIBs owing to its two-dimensional diffusion channels for K+ ions. However, due to its poor electronic conductivity and the huge influence of embedded K+ ions (with a large ionic radius of 3.6 Å) on MoS2 layer, MoS2 anodes exhibit a poor rate performance and easily collapsed structure. To address these issues, the common strategies are enlarging the interlayer spacing to reduce the mechanical strain and increasing the electronic conductivity by adding conductive agents. However, simultaneous implementation of the above strategies by simple methods is currently still a challenge. Herein, MoS2 anodes on reduced graphene oxide (MoS2/rGO) composite were prepared using one-step hydrothermal methods. Owing to the presence of rGO in the synthesis process, MoS2 possesses a unique scaled structure with large layer spacing, and the intrinsic conductivity of MoS2 is proved. As a result, MoS2/rGO composite anodes exhibit a larger rate performance and better cycle stability than that of anodes based on pure MoS2, and the direct mixtures of MoS2 and graphene oxide (MoS2-GO). This work suggests that the composite material of MoS2/rGO has infinite possibilities as a high-quality anode material for PIBs.

Tailoring Stress-Relieved Structure for SnSe Toward High Performance Potassium Ion Batteries.

Metal chalcogenides as an ideal family of anode materials demonstrate a high theoretical specific capacity for potassium ion batteries (PIBs), but the huge volume variance and poor cyclic stability hinder their practical applications. In this study, a design of a stress self-adaptive structure with ultrafine SnSe nanoparticles embedded in carbon nanofiber (SnSe@CNF) via the electrospinning technology is presented. Such an architecture delivers a record high specific capacity (272 mAh g-1 at 50mA g-1) and high-rate performance (125 mAh g-1 at 1 A g-1) as a PIB anode. It is decoded that the fundamental understanding for this great performance is that the ultrafine SnSe particles enhance the full utilization of the active material and achieve stress relief as the stored strain energy from cycling is insufficient to drive crack propagation and thus alleviates the intrinsic chemo-mechanical degradation of metal chalcogenides.

Nonflammable Phosphate-Based Electrolyte for Safe and Stable Potassium Batteries Enabled by Optimized Solvation Effect.

Current potassium-ion batteries (PIBs) are limited in safety and lifetime owing to the lack of suitable electrolyte solutions. To address these issues, herein, we report an innovative non-flammable electrolyte design strategy that leverages an optimal moderate solvation phosphate-based solvent which strikes a balance between solvation capability and salt dissociation ability, leading to superior electrochemical performance. The formulated electrolyte simultaneously exhibits the advantages of low salt concentration (only 0.6 M), low viscosity, high ionic conductivity, high oxidative stability, and safety. Our electrolyte also promotes the formation of self-limiting inorganic-rich interphases at the anode surface, alongside robust cathode-electrolyte interphase on iron-based Prussian blue analogues, mitigating electrode/electrolyte side reactions and preventing Fe dissolution. Notably, the PIBs employing our electrolyte exhibit exceptional durability, with 80 % capacity retention after 2,000 cycles at high-voltage of 4.2 V in a coin cell. Impressively, in a larger scale pouch cell, it maintains over 81 % of its initial capacity after 1,400 cycles at 1 C-rate with high average Coulombic efficiency of 99.6 %. This work represents a significant advancement toward the realization of safe, sustainable, and high-performance PIBs.

Restructuring Electrolyte Solvation by a Partially and Weakly Solvating Cosolvent toward High-Performance Potassium-Ion Batteries.

Ether-based electrolytes are among the most important electrolytes for potassium-ion batteries (PIBs) due to their low polarization voltage and notable compatibility with potassium metal. However, their development is hindered by the strong binding between K+ and ether solvents, leading to [K+-solvent] cointercalation on graphite anodes. Herein, we propose a partially and weakly solvating electrolyte (PWSE) wherein the local solvation environment of the conventional 1,2-dimethoxyethane (DME)-based electrolyte is efficiently reconfigured by a partially and weakly solvating diethoxy methane (DEM) cosolvent. For the PWSE in particular, DEM partially participates in the solvation shell and weakens the chelation between K+ and DME, facilitating desolvation and suppressing cointercalation behavior. Notably, the solvation structure of the DME-based electrolyte is transformed into a more cation-anion-cluster-dominated structure, consequently promoting thin and stable solid-electrolyte interphase (SEI) generation. Benefiting from optimized solvation and SEI generation, the PWSE enables a graphite electrode with reversible K+ (de)intercalation (for over 1000 cycles) and K with reversible plating/stripping (the K||Cu cell with an average Coulombic efficiency of 98.72% over 400 cycles) and dendrite-free properties (the K||K cell operates over 1800 h). We demonstrate that rational PWSE design provides an approach to tailoring electrolytes toward stable PIBs.

Fluorine-doped porous carbon coating on Sn/SnOx as anode materials for high-performance potassium ion batteries

Potassium-ion batteries (PIBs) are considered alternatives to lithium-ion batteries because of their comparatively cheaper manufacturing costs and lower potential (2.936 V compared to standard hydrogen electrodes). However, their large ionic radii and unstable structures hindered their satisfactory electrochemical performance. In this study, F–Sn/SnOx@C, a novel porous layered composite material, was prepared using NaCl as a template for in situ etching to obtain a promising negative electrode material for PIBs. The significant specific surface area of the composite material and the uniform embedding of tin nanoparticles within the layered porous carbon shell, contributed to its excellent potassium intercalation/deintercalation performance. Fluorine doping enhanced electron transfer, prevented nanoparticle aggregation, and improved electrolyte penetration and potassium ion migration. The PIBs prepared from this electrode showed high potassium storage capacity, outstanding cycle stability (retaining 263 mAh g−1 after 200 cycles at 100 mA g−1), and remarkable rate capability (505.6, 288.4, 193.5, 134.1, and 83.3 mAh g−1 at 0.1, 0.2, 0.3, 0.5, and 1.0 A g−1, respectively). These results provide a straightforward solution for improving the electrochemical performance of PIBs.

Carbon quantum dots/carbon-coated SnS2 as a high-performance potassium-ion battery cathode material

Carbon quantum dots/carbon-coated SnS2 as a high-performance potassium-ion battery cathode material

Lignite-based hard carbon for high-performance potassium-ion battery anode

Lignite-based hard carbon for high-performance potassium-ion battery anode

Flower-like CoSe2/N, P-doped carbon microspheres accommodated on carbon nanosheets for high-performance potassium-ion batteries

Transition metal selenides (TMSs) have emerged as promising electrode materials for potassium-ion batteries (PIBs), whereas the large volume expansion and sluggish reaction kinetics have seriously hindered the cycle life and rate performance. Herein, a hierarchical composite of flower-like CoSe2/N, P-doped carbon microspheres accommodated on carbon nanosheets (CoSe2-NPC@CNS) was rationally fabricated as the anode for PIBs through a one-pot hydrothermal and subsequent selenization method. The intimate hybridization of CoSe2/N, P-doped carbon microspheres can effectively alleviate the volume expansion of CoSe2 during charge-discharge cycles, and the ultrathin carbon nanosheets derived from fluid catalytic cracking (FCC) slurry serves as a highly conductive and buffered substrate. By robustly merging them together, the interconnected hierarchical nanoarchitecture with exposed active sites achieves promoted potassium storage capacity, electrochemical reaction kinetics, and structural stability. As a result, the PIBs with CoSe2-NPC@CNS anode deliver high reversible capacities of 320.8 mAh g−1 after 100 cycles at 0.1 A g−1 and 213.9 mAh g−1 after 850 cycles at 1.0 A g−1, excellent rate capability (188.8 mAh g−1 at 5 A g−1), and enhanced pseudo-capacitive contribution rate of 88.7 %. This work offers valuable insight into the rational design and development of hierarchical anode materials with high performance for PIBs and beyond.

Efficient Polytelluride Anchoring for Ultralong-Life Potassium Storage: Combined Physical Barrier and Chemisorption in Nanogrid-in-Nanofiber

HighlightsThe hierarchical nanogrid-in-nanofiber-structured dual-type carbon-confined CoTe2 nanodots (CoTe2@NC@NSPCNFs) were synthesized via facile templates and an electrospinning approach.Hierarchical nanogrid-in-nanofiber structure effectively suppresses the volume change of CoTe2 and the shuttle of potassium polytelluride (K-pTex) through robust physical restraint and strong chemisorption.CoTe2@NC@NSPCNFs hybrid achieves ultralong lifespan potassium-storage performance over 3500 cycles, and the deep mechanisms underlying the evolution, dissolution, and shuttle of K-pTex have been clearly revealed.

Selective phosphorylation of MOF to construct KTP/KTOP/C heterojunction for high-performance potassium-ion batteries

Polyanion compounds are considered as promising electrodes for potassium-ion batteries (PIBs) due to their structural diversity and chemical versatility. However, the cycling performance of previously reported electrodes at high current densities still suffers from their relatively sluggish electron and ion transport kinetics. Here, by combining K2Ti2(PO4)3 (KTP) framework with KTiOPO4 (KTOP) composition, we construct a series of KTP/KTOP/C heterojunctions (denoted as KTP/KTOP/C-n) via selectively phosphorylatiny from metal-organic framework (MOF) precuror, and demonstrate the successful synergistic cooperation of both electron and ion transport kinetics by carefully controlling the structure and composition. Comparative analysis and density functional theoretical calculations confirm the reaction kinetics and pseudocapacitive behaviors can be dramatically promoted by synergistically structural, electronic and ionic modulations. Consequently, the optimized KTP/KTOP/C-2 delivers an impressive specific capacity of 140 mAh/g after 150 cycles at 100 mA g−1 and superior cycling stability with 79 mAh/g for 2000 cycles at a high current of 1000 mA g−1. Furthermore, it displays outstanding rate performance, achieving 87 mAh/g at 2000 mA g−1.

Highly crystalline graphite nanofibers as an anode for high-performance potassium-ion batteries

Graphite nanofibres with high crystallinity and low defect levels for potassium-ion batteries with high initial Coulombic efficiency and long cycling stability are reported in this study.

In situ built nanoconfined Nb2O5 particles in a 3D interconnected Nb2C MXene@rGO conductive framework for high-performance potassium-ion batteries

A 3D Nb2C/rGO conductive framework with in situ generated Nb2O5 nanoparticles (Nb2O5/Nb2C/rGO) is synthesized, exhibiting high capacity and excellent cycling stability. The synergetic charge–discharge mechanism is revealed explicitly.