Layered transition metal oxide P2‐Na2/3Ni1/3Mn2/3O2 usually suffers from large‐volume phase transitions and different Na‐vacancy ordering during sodium (de)intercalation, incurring rapid capacity ...decline and poor rate capability. Herein, an effective strategy based on synergetic effect of selected multiple metal ions is designed for P2‐type cathodes with improved performance. The role of tetravalent titanium provides high redox potential, inactive divalent magnesium stabilizes the structure, and the monovalent lithium smooths the electrochemical curves. The combined analysis of in operando X‐ray diffraction, in operando X‐ray absorption spectroscopy and density functional theory calculations demonstrates the contribution of multi‐metal ions converts the unfavorable and large‐volume P2 to O2 transition into a moderate “Z”‐intergrowth structure by increasing the energy barrier of transition metal slab gliding. As a consequence, the resultant P2‐Na0.7Li0.03Mg0.03Ni0.27Mn0.6Ti0.07O2 electrode delivers a reversible capacity of 134 mAh g−1, a working voltage of 3.57 V, excellent cycling stability (82% of capacity retention after 200 cycles), and superior rate performance (110 mAh g−1 at 4 C). Full cells fabricated with a hard carbon anode achieve an energy density of 296 Wh kg−1. This study presents a route to rationally design cathode materials with this functionalization to improve the cell performance for sodium‐ion batteries.
Herein, a co‐substitution strategy is proposed for P2‐Na2/3Ni1/3Mn2/3O2 to realize high‐energy sodium‐ion batteries. On account of the synergetic effects of Li+ (suppressing Na‐vacancy ordering), Ti4+ (increasing redox potential), and Mg2+ (stabilizing structure), the as‐obtained Na0.7Li0.03Mg0.03Ni0.27Mn0.6Ti0.07O2 electrode demonstrates moderate phase transition behavior and superior electrochemical performance.
Sodium‐ion batteries have gained much attention for their potential application in large‐scale stationary energy storage due to the low cost and abundant sodium sources in the earth. However, the ...electrochemical performance of sodium‐ion full cells (SIFCs) suffers severely from the irreversible consumption of sodium ions of cathode during the solid electrolyte interphase (SEI) formation of hard carbon anode. Here, a high‐efficiency cathode sodiation compensation reagent, sodium oxalate (Na2C2O4), which possesses both a high theoretical capacity of 400 mA h g−1 and a capacity utilization as high as 99%, is proposed. The implementation of Na2C2O4 as sacrificial sodium species is successfully realized by decreasing its oxidation potential from 4.41 to 3.97 V through tuning conductive additives with different physicochemical features, and the corresponding mechanism of oxidation potential manipulation is analyzed. Electrochemical results show that in the full cell based on a hard carbon anode and a P2‐Na2/3Ni1/3Mn1/3Ti1/3O2 cathode with Na2C2O4 as a sodium reservoir to compensate for sodium loss during SEI formation, the capacity retention is increased from 63% to 85% after 200 cycles and the energy density is improved from 129.2 to 172.6 W h kg−1. This work can provide a new avenue for accelerating the development of SIFCs.
The development of sodium‐ion batteries has been hindered so far by the irreversible consumption of sodium ions of the cathode during the solid electrolyte interphase formation. Therefore, in search of a safe, cost‐effective, and highly efficient cathode sodiation reagent, the feasibility of Na2C2O4 as a sodium reservoir source for enhancing the performance of sodium‐ion batteries is investigated.
Chemical modification of electrode materials by heteroatom dopants is crucial for improving storage performance in rechargeable batteries. Electron configurations of different dopants significantly ...influence the chemical interactions inbetween and the chemical bonding with the host material, yet the underlying mechanism remains unclear. We revealed competitive doping chemistry of Group IIIA elements (boron and aluminum) taking nickel‐rich cathode materials as a model. A notable difference between the atomic radii of B and Al accounts for different spatial configurations of the hybridized orbital in bonding with lattice oxygen. Density functional theory calculations reveal, Al is preferentially bonded to oxygen and vice versa, and shows a much lower diffusion barrier than BIII. In the case of Al‐preoccupation, the bulk diffusion of BIII is hindered. In this way, a B‐rich surface and Al‐rich bulk is formed, which helps to synergistically stabilize the structural evolution and surface chemistry of the cathode.
A model study has been performed on Group IIIA element (boron and aluminum) co‐doped high‐nickel layered oxide cathode materials to understand competitive doping chemistry. A notable difference between the atomic radii of B and Al accounts for different spatial configurations of the hybridized orbital in bonding with lattice oxygen, resulting in the formation of a B‐rich surface and an Al‐rich bulk.
Abstract
Na-ion cathode materials operating at high voltage with a stable cycling behavior are needed to develop future high-energy Na-ion cells. However, the irreversible oxygen redox reaction at ...the high-voltage region in sodium layered cathode materials generates structural instability and poor capacity retention upon cycling. Here, we report a doping strategy by incorporating light-weight boron into the cathode active material lattice to decrease the irreversible oxygen oxidation at high voltages (i.e., >4.0 V vs. Na
+
/Na). The presence of covalent B–O bonds and the negative charges of the oxygen atoms ensures a robust ligand framework for the NaLi
1/9
Ni
2/9
Fe
2/9
Mn
4/9
O
2
cathode material while mitigating the excessive oxidation of oxygen for charge compensation and avoiding irreversible structural changes during cell operation. The B-doped cathode material promotes reversible transition metal redox reaction enabling a room-temperature capacity of 160.5 mAh g
−1
at 25 mA g
−1
and capacity retention of 82.8% after 200 cycles at 250 mA g
−1
. A 71.28 mAh single-coated lab-scale Na-ion pouch cell comprising a pre-sodiated hard carbon-based anode and B-doped cathode material is also reported as proof of concept.
As one of the fascinating high capacity cathodes, O3‐type layered oxides usually suffer from their intrinsic air sensitivity and sluggish kinetics originating from the spontaneous lattice Na ...extraction during air exposure and high tetrahedral site energy of Na+ diffusion transition state. What is worse, the improvement on the two handicaps is hard to simultaneously realize because of the contradiction between Na containment suggested in air stability mechanism and enhanced Na diffusion mentioned in kinetics strategy. Herein, it is shown that a simple strategy of introducing proper Na vacancies into lattice can simultaneously realize a dual performance improvement. Na vacancies decrease the charge density on transitional metal ions and enhance the antioxidative capability of material, ensuring a stable lattice Na containment for Na0.93Li0.12Ni0.25Fe0.15Mn0.48O2 when exposed to air. Additionally, more Na+ diffusional sites and enlarged Na layer spacing are obtained and result in a significantly decreased energy barrier from ≈1000 to 300 meV and a high rate capability of 70.8% retention at 2000 mA g−1. Remarkably, such a strategy can be easily realized by either pre‐ or post‐treating, which exhibits excellent universality for various O3 materials, implying its enormous potential to promote the commercial application of O3‐type cathodes.
A universal strategy of introducing proper Na vacancies into a crystal lattice is proposed to simultaneously improve air‐stability and kinetics of O3‐type layered oxide cathodes. The dual improvement benefits from the multiple effects of Na vacancies on crystalline and electronic structure, namely, decreased charge density on transition metal ions, enhanced antioxidative capability, decreased Na+ diffusion barrier, and optimized migration path.
Layered oxide cathodes usually exhibit high compositional diversity, thus providing controllable electrochemical performance for Na‐ion batteries. These abundant components lead to complicated ...structural chemistry, closely affecting the stacking preference, phase transition and Na+ kinetics. With this perspective, we explore the thermodynamically stable phase diagram of various P2/O3 composites based on a rational biphasic tailoring strategy. Then a specific P2/O3 composite is investigated and compared with its monophasic counterparts. A highly reversible structural evolution of P2/O3–P2/O3/P3–P2/P3–P2/Z/O3′–Z/O3′ based on the Ni2+/Ni3.5+, Fe3+/Fe4+ and Mn3.8+/Mn4+ redox couples upon sequential Na extraction/insertion is revealed. The reduced structural strain at the phase boundary alleviates the phase transition and decreases the lattice mismatch during cycling, endowing the biphasic electrode a large reversible capacity of 144 mAh g−1 with the energy density approaching 514 Wh kg−1.
A rational biphasic tailoring strategy to prepare layered composite cathodes with the desired phase ratio is proposed. Benefiting from the reversible phase transition within transition metal slabs and the decreased structure strain at the phase boundary of the intergrowth structure during Na extraction and insertion, the Com‐NaNMFT composite material demonstrates excellent electrochemical performance.
Low‐cost and stable sodium‐layered oxides (such as P2‐ and O3‐phases) are suggested as highly promising cathode materials for Na‐ion batteries (NIBs). Biphasic hybridization, mainly involving P2/O3 ...and P2/P3 biphases, is typically used to boost their electrochemical performances. Herein, a P3/O3 intergrown layered oxide (Na2/3Ni1/3Mn1/3Ti1/3O2) as high‐rate and long‐life cathode for NIBs via tuning the amounts of Ti substitution in Na2/3Ni1/3Mn2/3−xTixO2 (x = 0, 1/6, 1/3, 2/3) is demonstrated. The X‐ray diffraction (XRD) Rietveld refinement and aberration‐corrected scanning transmission electron microscopy show the co‐existence of P3 and O3 phases, and density functional theory calculation corroborates the appearance of the anomalous O3 phase at the Ti substitution amount of 1/3. The P3/O3 biphasic cathode delivers an unexpected rate capability (≈88.7% of the initial capacity at a high rate of 5 C) and cycling stability (≈68.7% capacity retention after 2000 cycles at 1 C), superior to those of the sing phases P3‐Na2/3Ni1/3Mn2/3O2, P3‐Na2/3Ni1/3Mn1/2Ti1/6O2, and O3‐Na2/3Ni1/3Ti2/3O2. The highly reversible structural evolution of the P3/O3 integrated cathode observed by ex situ XRD, ex situ X‐ray absorption spectra, and the rapid Na+ diffusion kinetics, underpin the enhancement. These results show the important role of P3/O3 biphasic hybridization in designing and engineering layered oxide cathodes for NIBs.
P3/O3 biphasic Na2/3Ni1/3Mn1/3Ti1/3O2 cathode material is prepared for Na‐ion batteries by tuning the Ti amounts. This P3/O3 intergrown cathode delivers superior rate capability and cycling stability to those of the pristine P3 and O3 phases, which are underpinned by the observed highly reversible structural transition of P3/O3 biphase and the rapid Na+ diffusion kinetics.
Electrochemical energy storage devices with a high energy density are an important technology in modern society, especially for electric vehicles. The most effective approach to improve the energy ...density of batteries is to search for high‐capacity electrode materials. According to the concept of energy quality, a high‐voltage battery delivers a highly useful energy, thus providing a new insight to improve energy density. Based on this concept, a novel and successful strategy to increase the energy density and energy quality by increasing the discharge voltage of cathode materials and preserving high capacity is proposed. The proposal is realized in high‐capacity Li‐rich cathode materials. The average discharge voltage is increased from 3.5 to 3.8 V by increasing the nickel content and applying a simple after‐treatment, and the specific energy is improved from 912 to 1033 Wh kg−1. The current work provides an insightful universal principle for developing, designing, and screening electrode materials for high energy density and energy quality.
Li‐ion batteries with high energy quality require a high capacity coupled with high operating voltage. This requires the electrode materials to not only have a high specific capacity but also a high discharge voltage for cathode materials and low charge voltage for anode materials.
Lithium–sulfur (Li–S) batteries are one of the most promising next‐generation battery types for their high energy density and low cost. On the other hand, safety issues and poor cyclability strongly ...limit practical application. Solid‐state electrolytes (SSEs) can present as high ionic conductivity as aprotic electrolytes and eventually avoid the shuttle effect, which provides an ultimate solution for safe Li–S batteries with good cyclability. In this review, the recent achievements in all‐solid‐state Li–S batteries based on inorganic SSEs are summarized. Furthermore, the main attentions are paid to the interfaces, including metallic lithium|SSEs, SSEs|SSEs, and composite sulfur cathode|SSEs. The potential approaches to deal with these interfacial issues are proposed as well, such as composite SSEs with an asymmetric structure to enhance their compatibility with lithium anodes and sulfur cathodes, adding Li2O or LiF and increasing the densification to reduce the grain boundary resistance, and nanomaterials used to improve the kinetic process in cathode.
The interfaces in all‐solid‐state Li–S batteries including metallic lithium| solid‐state electrolytes (SSEs), SSEs|SSEs, and composite sulfur cathode|SSEs are surveyed and the corresponding approaches to handle the interface issues are proposed toward better electrochemical performance.
The increasing demand for replacing conventional fossil fuels with clean energy or economical and sustainable energy storage drives better battery research today. Sodium‐ion batteries (SIBs) are ...considered as a promising alternative for grid‐scale storage applications due to their similar “rocking‐chair” sodium storage mechanism to lithium‐ion batteries, the natural abundance, and the low cost of Na resources. Searching for appropriate electrode materials with acceptable electrochemical performance is the key point for development of SIBs. Layered transition metal oxides represent one of the most fascinating electrode materials owing to their superior specific capacity, environmental benignity, and facile synthesis. However, three major challenges (irreversible phase transition, storage instability, and insufficient battery performance) are known for cathodes in SIBs. Herein, a comprehensive review on the latest advances and progresses in the exploration of layered oxides for SIBs is presented, and a detailed and deep understanding of the relationship of phase transition, air stability, and electrochemical performance in layered oxide cathodes is provided in terms of refining the structure–function–property relationship to design improved battery materials. Layered oxides will be a competitive and attractive choice as cathodes for SIBs in next‐generation energy storage devices.
The recent progress in layered oxide cathodes for sodium‐ion batteries is comprehensively reviewed. Some new perspectives concentrating on phase transition, air stability, and electrochemical performance in layered cathodes are provided, in terms of refining the structure–function–property relationship to rationally design better electrode materials.
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