Sodium Layer Research Articles

Regulating local chemical environment in O3-type layered sodium oxides by dual-site Mg2+/B3+ substitution achieves durable and high-rate cathode

The O3-Na0.85Ni0.2Fe0.4Mn0.4O2 layered oxide cathode material possesses the advantages of high specific capacity, low cost, and simple synthesis. However, sluggish kinetics and complicated phase transition caused by the large size difference between Na+ and tetrahedral gaps lead to poor rate and cycling performance. Therefore, a scalable and feasible strategy was proposed to modulate local chemical environment by introducing Mg2+ and B3+ into O3-Na0.85Ni0.2Fe0.4Mn0.4O2, which can distinctly improve kinetic transport rate as well as electrochemical performance. The capacity retention of O3-(Na0.82Mg0.04)(Ni0.2Fe0.4Mn0.4)B0.02O2 (NFMB) increases from 43.3% and 12.4% to 89.5% and 89.0% at 1 C and 3 C after 200 cycles, respectively. Moreover, the electrode still delivers high rate capacity of 93.9 mAh/g when current density increases to 10 C. Mg2+ ions riveted on Na layer act as a “pillar” to stabilize crystal structure and inhibit structural change during the desodiumization process. B3+ ions entering tetrahedral interstice of the TM layer strengthen the TM-O bond, lower Na+ diffusion energy barrier and inhibits the slip of TM layer. Furthermore, the assembled full batteries with the modified cathode material deliver a high energy density of 278.2 Wh/kg with commercial hard carbon as anode. This work provides a strategy for the modification of high-performance SIB layered oxide materials to develop the next-generation cost-effective energy storage grid systems.

Slow-Released Cationic Redox Activity Promoted Stable Anionic Redox and Suppressed Jahn-Teller Distortion in Layered Sodium Manganese Oxides.

Manganese-based layered oxides are considered promising cathodes for sodium ion batteries due to their high capacity and low-cost manganese and sodium resources. Triggering the anionic redox reaction (ARR) can exceed the capacity limitation determined by conventional cationic redox. However, the unstable ARR charge compensation and Jahn-Teller distortion of Mn3+ ions readily result in structural degradation and rapid capacity fade. Here, we report a P2-type Na0.8Li0.2Mn0.7Cu0.1O2 cathode that shows a capacity retention of 84.5% at 200 mA/g after 200 cycles. Combining in situ X-ray diffraction and multi other ex situ characterizations, we reveal that the enhanced cycling stability is ascribed to a slow release of cationic redox activity which can well suppress the Jahn-Teller distortion and favor the ARR reversibility. Furthermore, density-functional theory calculations demonstrate that the inhibited interlayer migration and reduced band gap facilitate the stability and kinetic behavior of ARR. These findings provide a perspective for designing high-energy-density cathode materials with ARR activity.

Competition between dual alkali metal ions fuels high-performance sodium-ion batteries

Dual alkali metal ion battery is expected to apply in future high-efficiency energy storage applications as it can skillfully combine the advantages of Li+ and Na+. However, the specific insertion and extraction processes of the two ions are not well explained. Herein, a layered sodium transition metal oxide electrode with ordered mixing of Na/Li ions is prepared by ion exchange method. The ion behavior is explained in terms of activation energy of chemical reaction and Gibbs free energy. Based on thermodynamic analysis and material characterizations, the priorities of Na+ and Li+ deblock reactions are determined. The competition mechanism of alkali metal ions and the double gain effect of Li are revealed by electrochemical experiments. This work is expected to provide a positive impact on the future design of multifunctional cathodes for advanced rechargeable batteries.

Multi-element doped hexagonal sheet Ni/Mn-based layered oxide with ZrO2 surface modification for sodium ion batteries cathode with high capacity and good cycle/air stability

Ni/Mn-based layered oxides have been widely studied for sodium ion battery cathode because of high capacity and simple preparation. However, its application has been restricted owing to unstable structure and poor cycling performance. Herein, the multi-element doped hexagonal sheet Ni/Mn-based layered oxide with ZrO2 surface modification O3-NaNi0.3Mn0.5-xFe0.1Cu0.1ZrxO2@ZrO2 (NFMCZ-x) cathode materials have been successfully synthesize by high temperature calcination method accompanied by ball milling activation. XRD refinement results show Zr4+ substitution of Mn3+ can increase interlayer distance of sodium layer. Benefiting from the synergetic effect of multi-element doping and ZrO2 surface modification, the optimized NFMCZ-0.03 sample exhibits a higher discharge capacity of 178 mAh/g at 0.1C and good capacity retention (77 % after 50 cycles at 2C). Furthermore, NFMCZ-0.03 has an excellent air stability with a capacity retention rate of 86 % during 50 cycles at 1C after being exposed in the air for 20 days. The ex-situ XRD results of NMFC at different charge/discharge voltages show Zr4+ doping can suppress O3 + P3′'–O3′-O3 + P3′' phase transition during charge/discharge process. These results confirm that synergistic effect of multi-doping combined with surface modification can improve electrochemical performance of layered oxides cathodes, which provides a research idea for development of Ni/Mn-based layered oxides cathodes for sodium-ion batteries.

A dual strategy of Na+/vacancy disorder and high Na to construct a P2-type cathode for high-stability sodium-ion batteries.

P2-type layered oxides are widely regarded as highly promising contenders for cathode materials in sodium-ion batteries. However, the occurrence of severe reactive phase transitions hinders satisfactory cycling stability and rate performance, thereby imposing limitations on their practical application. Here we prepared P2-type Na0.75Ni0.23Mg0.1Mn0.67O2 cathode materials using the agar gel approach. The use of agar reduces the synthesis time significantly, and the high Na content enhances the stability of the structure and contributes to its capacity. Meanwhile, the introduction of electrochemically inactive Mg ions into sodium layers not only disrupts the Na+/vacancy ordering, but also increases the spacing between sodium layers, thus reducing the diffusion barrier for sodium ions. The dual modification strategy led to excellent stability of Na0.75Ni0.23Mg0.1Mn0.67O2 with 94% capacity retention after 100 cycles at 1C. This work provides new insights into the design of sodium-ion cathode materials.

The low-latitude sodium layer: comparative data from lidar observations at Hainan, China and São Paulo, Brazil

The low-latitude sodium layer: comparative data from lidar observations at Hainan, China and São Paulo, Brazil

Enhanced conduction and phase transition reversibility of O3-type NaNi1/3Fe1/3Mn1/3O2 cathode via Ta doping for high-performance sodium-ion battery

The complex phase transition that occurs during the charge/discharge process leads to poor rate and cycling performance of O3-type NaNi1/3Fe1/3Mn1/3O2 (NFM). In this paper, we propose a novel modification strategy for NFM that involves doping its transition metal layer with Ta5+ ions of higher valence and stronger binding energy to oxygen than the transition metal. The effects of Ta doping on the crystal structure, transition metal valence states, activation barrier energy, and bandgap of NFM were investigated, and the modification mechanisms were explored. The capacity retention of NFM-Ta0.01 (80.15 %) was higher than that of NFM (35.44 %) after 200 cycles. This improvement is attributable to the strong bonding energy effect of TaO, which stabilized the crystal structure of NFM, delayed the transition of the material from the hexagonal O3 phase to the hexagonal P3 phase beyond 3.2 V, and enhanced the phase transition reversibility of NFM. Moreover, Ta introduction increased the sodium layer spacing and reduced the Na+ activation barrier energy of the material from 0.773 to 0.692 eV, and the band gap from 1.7416 to 1.5951 eV, leading to a significant improvement in electronic conductivity. Owing to the synergistic effect of these factors, the discharge capacity of NFM-Ta0.01 at a 5C rate (100.6 mAh g−1) was considerably higher than that of NFM (79.3 mAh g−1). This work presents a proven modification strategy for achieving structurally stable and improved rate performance for NFM.

Insights into P-Type Iron- and Manganese-Based Layered Sodium Cathodes

Sodium-ion batteries are a low-cost alternative to lithium-ion batteries in large-scale electric energy storage applications due to the natural-abundant sodium resources and similar working principle to LIBs during cycling [1]. Until now, many different cathodes for SIBs have been studied, including layered transition metal oxides (NaxTMO2, x<1), Prussian blue-type compounds, polyanionic and organic compounds [2]. Among them, NaxTMO2 has been extensively reported, due to its layered structure, easy synthesis, promising electrochemical properties, and feasibility for commercial production [3]. According to the occupation of Na ions and oxygen stacking, NaxTMO2 can be classified into P2 and O3 types, where P2 structure contasins trigonal prismatic sites of sodium ions and ABBA oxygen stacking sequence and O3 structure represents octahedral sites of sodium ions and ABCABC oxygen stacking sequence [4]. At low potentials (<2.0V), there is a phase transition P2-P2’ connected with the manganese redox activity and the Jahn-Teller distortion [5]. Compared with O3-type structure, P2-type NaxTMO2 provides higher specific capacity and better structural stability due to the lower diffusion barriers through Na-ion prismatic sites [6].Iron- and manganese-based layered oxides for sodium-ion batteries have attracted renewed interest due to their low cost and environmental friendliness. However, the phase change at high voltage and the Jahn-Teller effect lead to shortening cycle life and poor rate capability. We design a structure optimization of the Na2/3Mn1/2Fe1/2O2 cathode through a partial substitution of Fe3+ to explore the mechanism of redox activity of P2-type Mn/Fe-based layered cathodes. We present the investigation of the effect of simultaneous cationic substitution on the electrochemical performance and structural stability of P2-Na2/3Mn1/2Fe1/2O2. The obtained material exhibits a solid solution mechanism during desodiation/resodiation process and delivers an initial discharge capacity of 168 mA h g-1 at 0.1C and a capacity retention of 80% after 50 cycles. The modified P2 composition has stable cycle performance in the potential window from 1.5V to 4.5V. The main focus here is to understand the fundamental electrochemical mechanism of this layered cathode material by exploring the redox processes of transition metal cations and oxygen anions upon cycling. In situ X-ray synchrotron radiation diffraction is used to explore the structural changes during cycling. In situ X-ray Absorption Near Edge Spectroscopy is used to elucidate the local electronic structure of Fe and Mn atoms as it evolves throughout this electrochemical process. 23Na solid-state nuclear magnetic resonance spectroscopy is used to investigate Na coordination environments during desodiation/resodiation. Ex situ soft X-ray absorption spectroscopy results reveal the participation of oxygen anions in the electrochemical reactions. Thus, we explore the redox reactions of transition metals and oxygen to explain the mechanism and the electrochemical performance for the P2-type Mn/Fe-based layered cathodes.

Engineering Transition Metal Layers for Long Lasting Anionic Redox in Layered Sodium Manganese Oxide

Oxygen-redox-based layered cathode materials are of great importance in realizing high-energy-density sodium-ion batteries (SIBs) that can satisfy the demands of next-generation energy storage technologies. However, Mn-based layered materials (P2-type Na-poor Nay[AxMn1−x]O2, where A=alkali ions) still suffer from poor reversibility during oxygen-redox reactions and low conductivity. Herein, we introduce P2-Na0.75[Li0.15Ni0.15Mn0.7]O2 and P2-Na0.6[Li0.15Co0.15Mn0.7]O2, an oxygen-redox-based layered oxide cathode materials for SIBs. The effect of Ni and Co doping on the electrochemical performance was investigated by comparison with Ni-free and Co-free P2-Na0.67[Li0.22Mn0.78]O2 material. Combined experiments (galvanostatic cycling, neutron powder diffraction (NPD), X-ray absorption spectroscopy (XANES), X-ray photoelectron spectroscopy (XPS), and nuclear magnetic resonance (7Li NMR)) and theoretical studies (density functional theory, DFT calculations) confirmed that Ni substitution not only increases the operating voltage and decreases voltage hysteresis but also improves the cycling stability by reducing Li migration from transition metal (TM) to Na layers. It is also anticipated that having Na–O–Li configuration in a Mn4+-based layered material is important to active oxygen redox and that Co doping is crucial for improving the electrical conductivity. This research demonstrates the effect of Ni and Co doping in P2-type layered materials and suggests a new strategy of using Mn-rich cathode materials via oxygen redox with optimization of doping elements for SIBs.

Cobalt ion doping and morphology tailoring enable superior zinc-ion storage in sodium vanadate nanoflowers

Layered sodium vanadium materials have aroused increasing interest owing to their open layered structures and high theoretical capacity. Nevertheless, the strong electrostatic interactions between vanadium oxide layers and intercalated Zn2+ and the weak electronic conductivity severely limit their further development. Here, we design a series of cobalt ion-doped sodium vanadium electrode materials with nanoflower-like morphologies. Due to the open interlayer space and improved electron transfer enabled by cobalt ion preintercalation and sufficient contact area between the electrode and electrolyte provided by the three-dimensional (3D) flower-like morphology, the cobalt ion-doped sodium vanadate (CNVO-2) cathode exhibits excellent electrochemical performance, including an exceptional specific capacity (411 mA h g−1 at 0.5 A g−1) and ultrahigh structural stability (90.4 % capacity retention after 3000 cycles at 10 A g−1), outperforming many advanced ZIBs cathode materials. In addition, through various ex situ characterization techniques, an ionic exchange and multiple ion cointercalation mechanism is first revealed in sodium vanadate cathode material.

Trace Ti/Mg co-doped O3-type layered oxide cathodes with enhanced kinetics and stability for sodium-ion batteries

O3-type layered oxide cathodes are identified as a promising cathode material for sodium-ion batteries (SIBs) due to their high specific capacity and moderate operating voltage, yet it usually suffers from sluggish Na-ion diffusion and structure instability. Herein, we demonstrate the synthesis of a trace Ti/Mg co-doped NaNi1/3Fe1/3Mn1/3O2 (TiMg-NFM) cathode, in which Ti-ion is distributed in transition metal layers and Mg-ion is doped into sodium layers. The co-doping can enlarge the Na-layer spacing inside the layered structure to reduce Na-ion diffusion barrier. Meanwhile, the structural stability is effectively reinforced via the stronger Ti-O bond and the pillar effect of Mg-ions, further reducing surface side reaction with electrolyte. These merits endow a high reversible capacity of the TiMg-NFM cathode with 144.5 mAh g−1 at 0.1C, and much higher capacity retention of 111.4 mAh g−1 at 5C versus the pristine NFM (62.1 mAh g−1). More impressively, 80.1% of initial capacity can be maintained after 300 cycles at 2C. This work presents a feasible strategy to enhance the reaction kinetics and structure stability for developing advanced O3-type layered oxide cathodes.

Deposition of Sodium Metal at the Copper‐NaSICON Interface for Reservoir‐Free Solid‐State Sodium Batteries

Abstract“Anode‐free” solid‐state battery concepts are explored extensively as they promise a higher energy density with less material consumption and simple anode processing. Here, the homogeneous and uniform electrochemical deposition of alkali metal at the interface between current collector and solid electrolyte plays the central role to form a metal anode within the first cycle. While the cathodic deposition of lithium has been studied intensively, knowledge on sodium deposition is scarce. In this work, dense and uniform sodium layers of several microns thickness are deposited at the Cu|Na3.4Zr2Si2.4P0.6O12 interface with high reproducibility. At current densities of ≈1 mA∙cm−2, relatively uniform coverage is achieved underneath the current collector, as shown by electrochemical impedance spectroscopy and 3D confocal microscopy. In contrast, only slight variations of the coverage are observed at different stack pressures. Early stages of the sodium metal growth are analyzed by in situ transmission electron microscopy revealing oriented growth of sodium. The results demonstrate that reservoir‐free (“anode‐free”) sodium‐based batteries are feasible and may stimulate further research efforts in sodium‐based solid‐state batteries.

Superstructure and Correlated Na+ Hopping in a Layered Mg-Substituted Sodium Manganate Battery Cathode are Driven by Local Electroneutrality.

In this work, we present a variable-temperature 23Na NMR and variable-temperature and variable-frequency electron paramagnetic resonance (EPR) analysis of the local structure of a layered P2 Na-ion battery cathode material, Na0.67[Mg0.28Mn0.72]O2 (NMMO). For the first time, we elucidate the superstructure in this material by using synchrotron X-ray diffraction and total neutron scattering and show that this superstructure is consistent with NMR and EPR spectra. To complement our experimental data, we carry out ab initio calculations of the quadrupolar and hyperfine 23Na NMR shifts, the Na+ ion hopping energy barriers, and the EPR g-tensors. We also describe an in-house simulation script for modeling the effects of ionic mobility on variable-temperature NMR spectra and use our simulations to interpret the experimental spectra, available upon request. We find long-zigzag-type Na ordering with two different types of Na sites, one with high mobility and the other with low mobility, and reconcile the tendency toward Na+/vacancy ordering to the preservation of local electroneutrality. The combined magnetic resonance methodology for studying local paramagnetic environments from the perspective of electron and nuclear spins will be useful for examining the local structures of materials for devices.

Simultaneously promoting the surface/bulk structural stability of Fe/Mn-based layered cathode for sodium ion batteries

Layered sodium iron manganese oxide cathodes have attracted great interest owing to their high specific capacity and cost-effective metal resources, while the detrimental phase transitions and surface structural degradation severely limit their commercial applications. In this work, the bulk and surface structure stability of a P2-Na0.67Fe0.5Mn0.5O2 cathode can be synergically enhanced by a one-step Li/Nb co-doping strategy. Structural characterizations reveal that Li doping promotes the formation of P2/O3 biphasic structure and makes the unfavorable P2-OP4 phase transition convert into a smooth solid-solution reaction. Nb doping enhances the mobility of sodium ions and forms strong Nb-O bonds, thereby enhancing the stability of the TMO2 layer structure. In particular, the Nb element induces the surface reorganization of an atomic-scale NaNbO3 coating layer, which could effectively prevent the dissolution of metals and surface side reactions. The synergistic mechanism of enhanced electrochemical performance is proved by multiple characterizations during cycling. As a result, the as-prepared Na0.67Li0.1Fe0.5Mn0.38Nb0.02O2 exhibits improved capacity retention of 85.4 % than raw material (45.7 %) after 100 cycles at 0.5C (1C = 174 mA g−1) within 2.0–4.0 V. This co-regulating strategy provides a promising approach to designing highly stable sodium-ion battery cathodes. Furthermore, a full cell of Na0.67Li0.1Fe0.5Mn0.38Nb0.02O2 with hard carbon displays excellent cycling stability (85.1 % capacity retention after 100 cycles), making its commercial operation possible. This synergistic strategy of biphasic structure and surface reorganization is a critical route to accelerate the application of layer oxide cathodes.

Efficient Hybrid Capacitive Deionization Device with High Operating Voltage Based on Layered Sodium Manganese Oxide

Efficient Hybrid Capacitive Deionization Device with High Operating Voltage Based on Layered Sodium Manganese Oxide

Structure and evolution of disordered deep-charge phases in NaxCrO2 Na-ion battery electrodes

Layered sodium chromium oxide, O3–NaCrO2, is a promising electrode material for Na-ion batteries due to the high thermal stability, high rate-capability, and good coulombic efficiency of the material. However, it is well-known that the material loses crystallinity and the ability to store Na-ions reversibly when taken to high states of charge. While the structural identity of the disordered state has been investigated, a bulk structural model has so far been lacking, as has the mechanism for the order-disorder transition from the P′3-NaxCrO2 (the last crystalline phase observed during charge) to the disordered state. In this work, we combine pair distribution function analysis from total X-ray scattering and powder X-ray diffraction to obtain a complete structural model for the disordered O3-like NaxCrO2 forming at high states-of-charge, and from operando pair distribution function analysis and X-ray absorption spectroscopy, we elucidate the structural evolution of the order-disorder transition and shed new light on the Cr-migration in the disordered state, which is the cause of the irreversibility of the Na-ion storage.

Preparation of high strength, self-healing conductive hydrogel based on polysaccharide and its application in sensor

The development of cost-effective, eco-friendly conductive hydrogels with excellent mechanical properties, self-healing capabilities, and non-toxicity holds immense significance in the realm of biosensors. The biosensors demonstrate promising applications in the fields of biomedical engineering and human motion detection. A unique double-network hydrogel was prepared through physical-chemical crosslinking using chitosan (CS), polyacrylic acid (AA), and sodium alginate (SA) as raw materials. The prepared double-network hydrogels exhibited exceptional mechanical properties, as well as self-healing and conductive capabilities. Polyacrylic acid as the first layer network, while chitosan and sodium alginate were incorporated to establish the second layer network through electrostatic interactions, thereby imparting self-healing and self-recovery properties. The hydrogel was subsequently immersed in the salt solution to induce network winding. The mechanical robustness of the hydrogel was significantly enhanced through synergistic coordination of covalent and non-covalent interactions. When the concentration of sodium alginate was 20 g/L, the double-network hydrogel exhibits enhanced mechanical properties, with a tensile fracture stress of up to 1.31 MPa and a strength of 4.17 MPa under 80% compressive deformation. Furthermore, the recovery rate of this double-network hydrogel reached an impressive 89.63% within a span of 30 min. After 24 h without any external forces, the self-healing rate reached 26.11%, demonstrating remarkable capabilities in terms of self-recovery and self-healing. Furthermore, this hydrogel exhibited consistent conductivity properties and was capable of detecting human finger movements. Hence, this study presents a novel approach for designing and synthesizing environmentally friendly conductive hydrogels for biosensors.

Electronic States Tailoring and Pinning Effect Boost High-Power Sodium-Ion Storage of Oriented Hollow P2-Type Cathode Materials.

Fierce phase transformation and limited sodium ion diffusion dynamics are critical obstacles that hinder the practical energy storage applications of P2-type layered sodium transition metal oxides (NaxTMO2). Herein, a synergistic strategy of electronic state tailoring and pillar effect was carefully implemented by substituting divalent Mg2+ into Na0.67Ni0.33Mn0.67O2 material with unique oriented hollow rodlike structures. Mg2+substitution can not only facilitate the anionic oxygen redox reactions and electronic conductivity through increasing the electronic states at Femi energy but also act as pillars within TMO2 layers to alleviate the severe phase transformation to improve structure stability. Moreover, the oriented hollow structure incorporating sufficient buffer spaces and rationally exposed electrochemically active facets effectively alleviates the stresses induced by low volume changes of 8% and provides more open channels for Na+ ion diffusion without crossing multiple grain boundaries. Hence, the Na0.67Mg0.08Ni0.25Mn0.67O2 cathode showed a superior rate capability with high energy density and cycling stability for sodium-ion storage. The underlying mechanisms of these achievements were deciphered through diversified dynamic analysis and the first principle calculations, providing new insights into P2-type NaxTMO2 cathodes for the infinite prospect as an alternative to lithium-ion batteries.

Extending phase-variation voltage zones in P2-type sodium cathodes through high-entropy doping for enhanced cycling stability and rate capability

P2-type layered sodium oxides hold great promise for grid-scale energy storage applications owing to their low-cost merit, while their detrimental structural and chemical transition lead to low reversible capacities and poor cycling stability. Herein, we leverage a high-entropy (HE) doping strategy to stabilize the P2-type Na0.667Mn0.667Ni0.167Co0.167O2 (NMNC) cathode. A novel Na0.667Mn0.667Ni0.167Co0.117Ti0.01Mg0.01Cu0.01Mo0.01Nb0.01O2 (HE-NMNC) composite, with five equal content (1 at %) of cation substitution and exhibiting a pure P63/mmc space group structure, is proposed. Interestingly, a reversible P2-type phase variation is identified for HE-NMNC at high degrees of charge, but such phase variation occurs in a wider voltage region and is much slower than that in the NMNC baseline. It is demonstrated that the HE-NMNC delivers outstanding rate capability and cycling stability under a charging cutoff voltage of 4.5 V, achieving a reversible capacity of 111 mAh/g at 5 C and retaining around 130 mAh/g after 100 cycles at 1 C. Apart from the charge compensation of main transition metals (Ni, Co, and Mn), the reversible redox of lattice oxygen also contributes to the capacity of HE-NMNC upon cycling. The proposed high-entropy doping strategy and reaction mechanism may provide new insights for developing advanced cathode materials.

Stabilizing the Deep Sodiation Process in Layered Sodium Manganese Cathodes by Anchoring Boron Ions.

Advanced high-energy-density sodium-ion batteries (SIBs) are inseparable from cathode materials with high specific capacities. Layered manganese-rich oxides (NaxMnO2, 0.6≤x≤1) are promising cathode materials owing to their ease of intercalation and extraction of a considerable amount of sodium ions. However, lattice interactions, especially electrostatic repulsive forces and anisotropic stresses, are usually caused by deep desodiatin/sodiation process, resulting in intragranular cracks and capacity degradation in SIBs. Here, boron ions are introduced into the layered structure to build up B─O─Mn bonds. The regulated electronic structure in Na0.637B0.038MnO2 (B-NMO) materials inhibits the deformation of MnO6 octahedra, which finally achieves a gentle structural transition during the deep sodiation process. B-NMO electrode exhibits a high capacity (141mAhg-1) at 1C with a capacity retention of 81% after 100 cycles. Therefore, anchoring boron to manganese-rich materials inhibits the detrimental structural evolution of deep sodiation and can be used to obtain excellent cathode materials for SIBs.