Polyanionic Cathode Research Articles

Constructing Multi-Electron Reactions by Doping Mn2+ to Increase Capacity and Stability in K3.2V2.8Mn0.2(PO4)4/C of Phosphate Cathodes for Potassium-Ion Batteries.

Vanadium-based phosphate cathode materials (e.g., K3V2(PO4)3) have attracted widespread concentration in cathode materials in potassium-ion batteries owing to their stable structure but suffer from low capacity and poor conductivity. In this work, an element doping strategy is applied to promote its electrochemical performance so that K3.2V2.8Mn0.2(PO4)4/C is prepared via a simple sol-gel method. The heterovalent Mn2+ is introduced to stimulated multiple electron reactions to improve conductivity and capacity, as well as interlayer spacing. Galvanostatic intermittent titration technique (GITT) and in situ X-ray diffraction results further confirm that Mn-doping in the original electrode can obtain superior electrode process kinetics and structural stability. The prepared K3.2V2.8Mn0.2(PO4)4/C exhibits a high-capacity retention of 80.8% after 1500 cycles at 2 C and an impressive rate capability, with discharge capacities of 87.6 at 0.2 C and 45.4mA h g-1 at 5 C, which is superior to the majority of reported vanadium-based phosphate cathode materials. When coupled K3.2V2.8Mn0.2(PO4)4/C cathode with commercial porous carbon (PC) anode as the full cell, a prominent energy density of 175Wh kg-1 is achieved based on the total active mass. Overall, this study provides an effective strategy for meliorating the cycling stability and capacity of the polyanion cathodes for KIB.

Achieving a Rapid Na+ Migration and Highly Reversible Phase Transition of NASICON for Sodium-Ion Batteries with Suppressed Voltage Hysteresis and Ultralong Lifespan.

Sodium ion batteries have attracted great attention for large scale energy storage devices to replace lithium-ion batteries. As a promising polyanionic cathode material of sodium-ion batteries, Na3V2(PO4)2F3 (NVPF) belonging to NASICON exhibits large gap space and excellent structural stability, leading to a high energy density and ultralong cycle lifespan. To improve its stability and Na ion mobility, K+ cations are introduced into NVPF crystal as in situ partial substitution for Na+. The influence of K+ in situ substitution on crystal structure, electronic properties, kinetic properties, and electrochemical performance of NVPF are investigated. Through ex situ examination, it turns out that K+ occupied Na1 ion, in which the K+ does not participate in the charge-discharge process and plays a pillar role in improving the mobility of Na+. Moreover, the doping of K+ cation can reduce the bandgap energy and improve the electronic conductivity. Besides, the optimal K+ doping concentration in N0.92K0.08VPF/C is found so as to achieve rapid Na+ migration and reversible phase transition. The specific capacity of N0.92K0.08VPF/C is as high as 128.8 mAh g-1 at 0.2 C, and at 10 C its rate performance is excellent, which shows a capacity of 113.3 mAh g-1.

From Lab to Application: Challenges and Opportunities in Achieving Fast Charging with Polyanionic Cathodes for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs), recognized for balanced energy density and cost-effectiveness, are positioned as a promising complement to lithium-ion batteries (LIBs) and a substitute for lead-acid batteries, particularly in low-speed electric vehicles and large-scale energy storage. Despite their extensive potential, concerns about range anxiety due to lower energy density underscore the importance of fast-charging technologies, which drives the exploration of high-rate electrode materials. Polyanionic cathode materials are emerging as promising candidates in this regard. However, their intrinsic limitation in electronic conductivity poses challenges for synchronized electron and ion transport, hindering their suitability for fast-charging applications. This review provides a comprehensive analysis of sodium ion migration during charging/discharging, highlighting it as a critical rate-limiting step for fast charging. By delving into intrinsic dynamics, key factors that constrain fast-charging characteristics are identified and summarized. Innovative modification routes are then introduced, with a focus on shortening migration paths and increasing diffusion coefficients, providing detailed insights into feasible strategies. Moreover, the discussion extends beyond half cells to full cells, addressing challenges and opportunities in transitioning polyanionic materials from the laboratory to practical applications. This review aims to offer valuable insights into the development of high-rate polyanionic cathodes, acknowledging their pivotal role in advancing fast-charging SIBs.

Overcoming Kinetic Limitations of Polyanionic Cathode toward High-Performance Na-Ion Batteries.

Polyanionic cathodes have attracted extensive research interest for Na-ion batteries (NIBs) due to their moderate energy density and desirable cycling stability. However, these compounds suffer from visible capacity fading and significant voltage decay upon the rapid sodium storage process, even if modified through nanoengineering or carbon-coating routes, leading to limited applications in NIBs. Herein, the Na3(VOPO4)2F cathode material with dominantly exposed {001} active facets is demonstrated by a topochemical synthesis route. Owing to the rational geometrical structure design and thereby directly shortening Na diffusion distance, the electrode delivers a reversible capacity of ∼129 mA h g-1 even at a high rate of 10 C, which is very close to the theoretical capacity of 132 mA h g-1, achieving a high energy density of ∼452 W h kg-1 coupled with a high-power density of 4660 W kg-1. When further served as a cathode for nonaqueous, aqueous-based, and solid-state full NIBs, respectively, our designed Na3(VOPO4)2F always enables superior electrochemical performance due to favorable kinetics.

Partial cationic exchange boosting sodium storage of NaVP2O7

Sodium vanadium pyrophosphate (NaVP2O7 or NVP) with KAlP2O7-type structure exhibits an elevated redox potential (3.9 V vs. Na/Na+) compared to other vanadium-based polyanion cathodes, which enhances its superiority for high-energy sodium-ion batteries (SIBs), but encounters with the low Na+ conduction. Herein, we propose a cation exchange strategy to generate a skeleton-expanded Na1-xKxVP2O7 (x ≈ 0.25, denoted as NKVP) cathode stemming from its pyrophosphate counterpart KVP2O7. Different from previous entire ion-exchange method, the partial retained K skeleton in NKVP expanded the Na-ion conduction bottleneck to facilitate the Na-ions to across, lowered the Na-ion diffusion barriers (0.33 to 0.27 eV), which directly boosted Na-ion diffusion kinetics. As a result, the NKVP exhibited much higher specific capacity than NVP (73.8 vs. 25.2 mAh g−1), and it remained 55.7 % even at 40C (4.1 A g−1), surpassing most of pyrophosphate cathode. This was also verified at high-rate NKVP//NaTi2(PO4)3 and NKVP//hard‑carbon full cells. Moreover, the expanded bottleneck also reinforced the structure stability, enabling the NKVP cycle at 10C over 2200 cycles. This research opens new avenues for the design of high-rate and long-cycling polyanionic materials.

Cetyltrimethylammonium bromide induced generation of highly (200) planes-exposed LiMnPO4 nanosheets coated by nitrogen-doped carbon for high-performance batteries

A simple solvothermal method is designed to synthesize LiMnPO4/N-doped C composites with core-shell structure using cetyltrimethylammonium bromide (CTAB) as surfactant and nitrogen source. The effectively growth of (200) planes and nitrogen-doped carbon layer coated LiMnPO4 nanosheets are obtained. The doped nitrogen induces the generation of active defect sites, which changes the cell electronic layer structure, and improve the electronic conductivity and diffusion rate of lithium ions. Thus, the electrochemical performance is beneficial from the synergistic effect of specific planar exposure and particular interfacial modifications. The optimal sample shows the supreme electrochemical performance at 0.1C, 1C and 5C with capacities of 159.1, 122.6 and 83.1 mAh g−1, respectively. The capacity retention can achieve 98 % even after 200 cycles at 1C. This work provides a simple but effective strategy to design polyanion cathode materials with enhanced electrochemical performance.

Recent Development of Phosphate Based Polyanion Cathode Materials for Sodium‐Ion Batteries

AbstractSodium‐ion batteries (SIBs) are regarded as next‐generation secondary batteries and complement to lithium‐ion batteries (LIBs) for large‐scale electrochemical energy storage applications due to the abundant availability, even distribution, and cost‐effectiveness of raw sodium resources. The phosphate‐based polyanions stand out of various cathode material owing to their high operation voltage, stable structure, superior safety, and excellent sodium‐storage properties. The undesirable electric conductivities and specific capacities limit their large‐scale industrialization. Herein, a recent research development of phosphate‐based polyanion cathodes including orthophosphate, oxyphosphate, pyrophosphate, and mixed phosphates is thoroughly reviewed. Subsequently, the effect of modification strategies including element doping, surface coating, morphology control, and electrode design toward high‐performance cathode materials for SIBs are systematically explored. Finally, the future research directions of phosphate‐based polyanion cathodes based on electrochemical performance including reversible capacity, voltage, energy density, rate capacity, cycling stability, and commercial applications are comprehensively concluded. It is believed that current review will present instructive perspectives into developing practicable phosphate‐based polyanion cathode materials for SIBs.

Sustainable upcycling of mixed spent cathodes to a high-voltage polyanionic cathode material

Sustainable battery recycling is essential for achieving resource conservation and alleviating environmental issues. Many open/closed-loop strategies for critical metal recycling or direct recovery aim at a single component, and the reuse of mixed cathode materials is a significant challenge. To address this barrier, here we propose an upcycling strategy for spent LiFePO4 and Mn-rich cathodes by structural design and transition metal replacement, for which uses a green deep eutectic solvent to regenerate a high-voltage polyanionic cathode material. This process ensures the complete recycling of all the elements in mixed cathodes and the deep eutectic solvent can be reused. The regenerated LiFe0.5Mn0.5PO4 has an increased mean voltage (3.68 V versus Li/Li+) and energy density (559 Wh kg–1) compared with a commercial LiFePO4 (3.38 V and 524 Wh kg–1). The proposed upcycling strategy can expand at a gram-grade scale and was also applicable for LiFe0.5Mn0.5PO4 recovery, thus achieving a closed-loop recycling between the mixed spent cathodes and the next generation cathode materials. Techno-economic analysis shows that this strategy has potentially high environmental and economic benefits, while providing a sustainable approach for the value-added utilization of waste battery materials.

Exceeding Three-Electron Reactions in Polyanionic Cathode To Achieve High-Energy Density for Sodium-Ion Batteries.

Activating multielectron reactions of sodium superionic conductor (NASICON)-type cathodes toward higher energy density remains imperative to boost their application feasibility. However, multisodium storage with high stability is difficult to achieve due to the sluggish reaction kinetics, irreversible phase transitions, and negative structural degradation. Herein, a kind of NASICON-type Na2.5V1.5Ti0.5(PO4)3/C (NVTP-0.5) hierarchical microsphere consisting of abundant primary nanoparticles is designed, realizing a reversible 3.2-electron reaction with high stability. The optimized NVTP-0.5 cathode demonstrates an ultrahigh discharge capacity of 192.42 mAh g-1, energy density of up to 497.3 Wh kg-1 at 20 mA g-1, and capacity retention ratio of 94.1% after 1000 cycles at 1 A g-1. Additionally, the NVTP-0.5 cathode delivers excellent tolerance to extreme temperatures while also achieving a high-energy density of 400 Wh kg-1 (based on the cathode mass) in a full-cell configuration. Systematic in situ/ex situ analysis results confirm the multisodium storage processes of NVTP-0.5 involving successive redox reactions (V2+/V3+, Ti3+/Ti4+, and V3+/V4+ redox couples) and reversible structure evolution (solid-solution and biphasic mechanisms), which contribute to the high capacity and excellent cycling stability. This work indicates that the rational regulation of components with different functions can unlock more possibilities for the development of NASICON-type cathodes.

Microwave-Assisted Hydrothermal Synthesis of Na3V2(PO4)2F3 Nanocuboid@Reduced Graphene Oxide as an Ultrahigh-Rate and Superlong-Lifespan Cathode for Fast-Charging Sodium-Ion Batteries.

Na3V2(PO4)2F3 (NVPF) has been regarded as a favorable cathode for sodium-ion batteries (SIBs) due to its high voltage and stable structure. However, the limited electronic conductivity restricts its rate performance. NVPF@reduced graphene oxide (rGO) was synthesized by a facile microwave-assisted hydrothermal approach with subsequent calcination to shorten the hydrothermal time. NVPF nanocuboids with sizes of 50-150 nm distributed on rGO can be obtained, delivering excellent electrochemical performance such as a longevity life (a high capacity retention of 85.6% after 7000 cycles at 10 C) and distinguished rate capability (116 mAh g-1 at 50 C with a short discharging/charging time of 1.2 min). The full battery with a Cu2Se anode represents a capacity of 116 mAh g-1 at 0.2 A g-1. The introduction of rGO can augment the electronic conductivity and advance the Na+ diffusion speed, boosting the cycling and rate capability. Besides, the small lattice change (3.3%) and high structural reversibility during the phase transition process between Na3V2(PO4)2F3 and NaV2(PO4)2F3 testified by in situ X-ray diffraction are also advantageous for Na storage behavior. This work furnishes a simple method to synthesize polyanionic cathodes with ultrahigh rate and ultralong lifespan for fast-charging SIBs.

Boosting the capacity and stability of Na3V2(PO4)2F3-2xO2x microspheres, using atomic layer deposition of artificial CEI

Phosphate-based materials [e.g. Na3V2(PO4)2F3-2xO2x; (NVPFO2x;0 < x < 1)] are regarded as a promising intercalation cathodes for Sodium-ion batteries (SIBs) due to their high reversible specific capacity and stability. However, so far only 2 Na ion were demonstrated to be active in these polyanionic cathodes, which limit their capacity. Herein we provide a strategic approach towards electrochemical activation of a 3rd Na ion, which leads to higher capacity, and preserves structural integrity. We synthesize and study a series of NVPFO2x (0 < x < 1) with well-controlled surface morphology and vanadium oxidation state, and study the dependence of the electrochemical behavior on the various composition and morphology. The optimized NVPFO cathode exhibited highest initial specific discharge capacity (131 mA h g−1) indicating the activation of 3rd Na ion. Nevertheless, the material suffers rapid capacity fading within ~50 cycles. We demonstrate how this instability is suppressed profoundly through the formation of a thin artificial cathode electrolyte interface (CEI) layer of TiO2 (ca. 2 nm) on the surface of NVPFO by atomic layer deposition (ALD). This TiO2 coating enabled even further extraction of sodium through higher voltage domain, but more importantly, it facilitated excellent long-term stability over 200 cycles. The structural stability of the cathode material was revealed by post cycling HRSEM, XPS, and XRD study. All these studies demonstrate that the thin TiO2 layer effectively contributes to formation of a robust CEI layer, diminishes the parasitic reaction on the electrode surface, reduces carbonate formation, and restricts the electrolyte decomposition.

Boosting Multielectron Reaction Stability of Sodium Vanadium Phosphate by High-Entropy Substitution.

Na3V2(PO4)3 (NVP) based on the multielectron reactions between V2+ and V5+ has been considered a promising cathode for sodium-ion batteries (SIBs). However, it still suffers from unsatisfactory stability, caused by the poor reversibility of the V5+/V4+ redox couple and structure evolution. Herein, we propos a strategy that combines high-entropy substitution and electrolyte optimization to boost the reversible multielectron reactions of NVP. The high reversibility of the V5+/V4+ redox couple and crystalline structure evolution are disclosed by in situ X-ray absorption near-edge structure spectra and in situ X-ray diffraction. Meanwhile, the electrochemical reaction kinetics of high-entropy substitution NVP (HE-NVP) can be further improved in the diglyme-based electrolyte. These enable HE-NVP to deliver a superior electrochemical performance (capacity retention of 93.1% after 2000 cycles; a large reversible capacity of 120 mAh g-1 even at 5.0 A g-1). Besides, the long cycle life and high power density of the HE-NVP∥natural graphite full-cell configuration demonstrated the superiority of HE-NVP cathode in SIBs. This work highlights that the synergism of high-entropy substitution and electrolyte optimization is a powerful strategy to enhance the sodium-storage performance of polyanionic cathodes for SIBs.

Preparing Li6V3(PO4)5 Cathode with Boron‐Doped Carbon Layer as a Cathode Material for Lithium‐Ion Batteries

Polyanionic cathode materials are increasingly used in research because of their good cycling performance, high theoretical capacity, and high operating voltage. However, it exhibits poor performance due to its structure, which prevents it from reaching its full theoretical capacity. In this study, carbon‐coated Li6V3(PO4)5@C cathode materials are constructed under Li3V2(PO4)3 research conditions using the sol–gel process and anhydrous citric acid as the carbon source. Several boron doping concentrations are investigated to create Li6V3(PO4)5@BC cathode materials. The electrochemical measurements demonstrate that during the first cycle, at a current density of 0.5 C and a B doping quantity of 2 wt%, the specific discharge capacity of Li6V3(PO4)5@BC reaches 167.43 mAh g−1. The steady discharge specific capacity following 80 cycles of constant‐current charging and discharging is 136.84 mAh g−1. Li6V3(PO4)5@BC‐2 has a specific discharge capacity of 131.1 mAh g−1 at 2 C. The material's electrochemical performance greatly improves following the right quantity of B doping, which is primarily attributed to the increase in carbon layer defects brought on by B's entrance. This can increase the rate of lithium‐ion migration and hold more lithium ions.

Modification of Layered Cathodes of Sodium-Ion Batteries with Conducting Polymers

Layered oxides exhibit interesting performance as positive electrodes for commercial sodium-ion batteries. Nevertheless, the replacement of low-sustainable nickel with more abundant iron would be desirable. Although it can be achieved in P2-Na2/3Ni2/9Fe2/9Mn5/9O2, its performance still requires further improvement. Many imaginative strategies such as surface modification have been proposed to minimize undesirable interactions at the cathode–electrolyte interface while facilitating sodium insertion in different materials. Here, we examine four different approaches based on the use of the electron-conductive polymer poly(3,4-ethylene dioxythiophene) (PEDOT) as an additive: (i) electrochemical in situ polymerization of the monomer, (ii) manual mixing with the active material, (iii) coating the current collector, and (iv) a combination of the latter two methods. As compared with pristine layered oxide, the electrochemical performance shows a particularly effective way of increasing cycling stability by using electropolymerization. Contrarily, the mixtures show less improvement, probably due to the heterogeneous distribution of oxide and polymer in the samples. In contrast with less conductive polyanionic cathode materials such as phosphates, the beneficial effects of PEDOT on oxide cathodes are not as much in rate performance as in inhibiting cycling degradation, due to the compactness of the electrodes without loss of electrical contact between active particles.

Novel high-voltage cathode for aqueous zinc ion batteries: Porous K0.5VOPO4·1.5H2O with reversible solid-solution intercalation and conversion storage mechanism

Cathode materials that possess high output voltage, as well as those that can be mass-produced using facile techniques, are crucial for the advancement of aqueous zinc-ion battery (ZIBs) applications. Herein, we present for the first time a new porous K0.5VOPO4·1.5H2O polyanionic cathode (P-KVP) with high output voltage (above 1.2 V) that can be manufactured at room temperature using straightforward coprecipitation and etching techniques. The P-KVP cathode experiences anisotropic crystal plane expansion via a sequential solid-solution intercalation and phase conversion pathway throughout the Zn2+ storage process, as confirmed by in-situ synchrotron X-ray diffraction and ex-situ X-ray photoelectron spectroscopy. Similar to other layered vanadium-based polyanionic materials, the P-KVP cathode experiences a progressive decline in voltage during the cycle, which is demonstrated to be caused by the irreversible conversion into amorphous VOx. By introducing a new electrolyte containing Zn(OTF)2 to a mixed triethyl phosphate and water solution, it is possible to impede this irreversible conversion and obtain a high output voltage and longer cycle life by forming a P-rich cathode electrolyte interface layer. As a proof-of-concept, the flexible fiber-shaped ZIBs based on modified electrolyte woven into a fabric watch band can power an electronic watch, highlighting the application potential of P-KVP cathode.

Polyanionic Cathode Materials: A Comparison Between Na‐Ion and K‐Ion Batteries

AbstractSodium‐ion batteries (SIBs) and potassium‐ion batteries (PIBs) are considered the next‐generation candidates for future energy storage systems to partially substitute commercial lithium‐ion batteries because of their abundant sodium/potassium reserves, cost‐effectiveness, and high safety. Polyanionic cathode materials are widely used in alkali ion batteries due to their stable structural framework, high thermal stability, excellent alkali ion diffusion kinetics, and adjustable working voltage. Generally, the polyanionic cathodes used for SIBs surpass PIBs in the aspect of energy density and cycle life in most cases, however, the PIBs also have their unique advantages that are seldom reported. To this end, the polyanionic materials are classified by the valence states of active metal sites, the storage mechanism of Na+ and K+ in different crystal structures is summarized, and the electrochemical performance between SIBs and PIBs is compared. Particularly, some unique advantages of polyanionic cathodes in PIBs, such as high working voltage, superior rate capability, and excellent capacity retention are revealed, and the possible reasons are discussed in detail. Finally, various viable solutions are proposed to improve the battery performance of polyanionic compounds for future development.

A Configuration Entropy Enabled High‐Performance Polyanionic Cathode for Sodium‐Ion Batteries

AbstractPolyanionic sodium ion cathodes have attracted lots of concern because of their excellent structural stability. However, the low specific capacity is still a pressing issue hampering their practical application. In this work, a medium‐entropy NASICON‐structure cathode Na3.5V0.5Mn0.5Fe0.5Ti0.5(PO4)3 (Me‐NVMP) is proposed. The Me‐NVMP achieves a highly reversible specific capacity of 165.8 mAh g−1 (1.8–4.4 V vs Na+/Na) at 0.1 C via the stepwise redox reactions of Ti3+/Ti4+‐Fe2+/Fe3+, V3+/V4+‐Mn2+/Mn3+, and V4+/V5+‐Mn3+/Mn4+. More impressively, the Me‐NVMP yields super rate capability and cycling stability via the regulation of configuration entropy in NASICON. Specifically, the Me‐NVMP cathode can preserve a capacity retention of 83.5% after 10,000 cycles at 100 C (17 A g−1). Furthermore, excellent cycling performance even at the temperature of 0 °C (capacity retention of 93.45% at 20 C after 1000 cycles) is also demonstrated. In situ X‐ray diffraction analysis reveals that the enhanced performance can be mainly attributed to the solid–solution‐type Na+ storage behavior in Me‐NVMP. Moreover, issues such as Jahn‐Teller distortion of Mn3+ and irreversible structural change at high voltage (&gt;4.0 V vs Na+/Na) are effectively mitigated. This work inspires a new strategy to design high‐performance polyanionic electrode materials.

Advanced polyanionic cathode materials for aqueous zinc-ion batteries: from crystal structures, reaction mechanisms, design strategies to future perspectives

This review summarizes the latest research progress in polyanionic cathodes for aqueous Zn-ion batteries from the perspectives of crystal structure, reaction mechanism, and design strategy, finally highlights potential challenges and future outlook.

Boosting the interfacial dynamics and thermodynamics in polyanion cathode by carbon dots for ultrafast-charging sodium ion batteries.

Ultrafast-charging is the focus of next-generation rechargeable batteries for widespread economic success by reducing the time cost. However, the poor ion diffusion rate, intrinsic electronic conductivity and structural stability of cathode materials seriously hinder the development of ultrafast-charging technology. To overcome these challenges, an interfacial dynamics and thermodynamics synergistic strategy is proposed to synchronously enhance the fast-charging capability and structural stability of polyanion cathode materials. As a case study, a Na3V2(PO4)3 composite (NVP/NSC) is successfully obtained by introducing an interface layer derived from N/S co-doped carbon dots. Density functional theory calculations validate that the interfacial bonding effect of V-N/S-C significantly reduces the Na+ transport energy barrier. D-band center theory analysis confirms the downward shift of the V d-band center enhances the strength of the V-O bond and considerably inhibits irreversible phase transformation. Benefitting from this interfacial synergistic strategy, NVP/NSC achieves a high capability and excellent cycling stability with a surprisingly low carbon content (2.23%) at an extremely high rate of 100C for 10 000 cycles (87.2 mA h g-1, 0.0028% capacity decay per cycle). Furthermore, a superior performance at 5C (115.3 mA h g-1, 92.1% capacity retention after 800 cycles) is exhibited by the NVP/NSC‖HC full cell. These findings provide timely new insights for the systematic design of ultrafast-charging cathode materials.

Research Progress of Iron-based Polyanionic Cathode Materials for Sodium-Ion Batteries

Research Progress of Iron-based Polyanionic Cathode Materials for Sodium-Ion Batteries