Cathode Material For Batteries Research Articles

The effect of copper doping in α-MnO2 as cathode material for aqueous Zinc-ion batteries

Copper-doped Manganese Dioxide has been synthesised through a simple hydrothermal method at different doping levels. The synthesised materials have been characterized by X-ray diffraction (XRD), and scanning electron microscopy (SEM) to determine the composition, structure, and morphology. All the Cu doped MnO2 are found to be single phased. Their electrochemical properties as cathode for Zinc-ion batteries are studied by cyclic voltammetry (CV), galvano-static charge / discharge (GCD) and electrochemical impedance spectroscopy (EIS), using 3 M ZnSO4 + 0.3 MnSO4 solution as the electrolyte. 3.8% Cu doped MnO2 has shown the highest initial capacity of 379.5 mAh g−1 at 0.02 A·g−1, and 304.4 mA h g−1 at 0.5 A g−1, but experienced fast fading with a poor capacity retention of 56.8% after 100 cycles. 7.4% Cu doping gives lower capacity, while 5.9% doping shows a higher discharging capacity (320.0 mAh·g−1 at 0.02 A·g−1 and 269.3 mAh·g−1 at 0.5 A·g−1) and improved stability (85.8% capacity retention after 100 cycles), better than non-doped MnO2 electrode (284.4 mAh g−1 at 0.02 A g−1 and 252.1 mAh·g−1 at 0.5 A g−1, capacity retention 76.7%). The samples show satisfactory capacity and rate capability while the cycling stability is not ideal, which may relate to the needle like morphology and nanoscale particle size. CV tests revealed that the electrochemical process is mainly diffusion controlled. The zinc ion diffusion coefficient is tested to be in the range of 10−12 cm2·s−1 from both CV and EIS tests and showed the same trend in their electrochemical capacity. Doping of Copper in MnO2 reduced the polarization on electrode, improved the electrochemical reversibility, as evidenced by the reduction of the redox peak potential difference from 0.31 to 0.24 V at 1.1 mV·s−1, and from 0.45 V to 0.31 V at 5 mV·s−1. Whilst the cell resistance of non-doped MnO2 increased from 1.78 Ω to 7.39 Ω after cycling, the cell resistances of all Cu-doped cathodes reduced, indicating improved electronic conductivities after cycling. These results indicate that Cu-doping is effective to increase the conductivity of the materials, reduce the polarization during charge and discharge, and improve the cycling stability of MnO2 cathode.

High mass loading potassium ion stabilized manganese dioxide nanowire forests for rechargeable Zn batteries

Manganese dioxide (MnO2) represents an ideal cathode material for rechargeable aqueous Zn batteries due to its high theoretical capacity (308 mAh g−1), suitable potential (1.4 V vs. Zn2+/Zn), natural abundance, and negligible toxicity. However, the capacity and rate capability of MnO2 deteriorate significantly in thick electrodes owing to its low electrical and ionic conductivities. Herein, we report the design of high mass loading potassium ion stabilized α-MnO2 (K0.133MnO2) nanowire forests on carbon cloth through a seed-assisted hydrothermal method for Zn batteries. The vertically aligned K0.133MnO2 nanowire forests with uninterrupted charge transport afford a high area capacity of 3.54 mAh cm−2 and a capacity retention of 79.2% over 1000 cycles in aqueous electrolyte. Moreover, the high area capacity and cyclability can be readily transferred to quasi-solid-state devices.

Enhancing the Electrochemical Performances of Disordered Li1.23Ni0.3Nb0.3Fe0.16O0.85F0.15 Cathode Material for Lithium-Ion Batteries by LiNbOx Coating.

For the next generation of lithium-ion batteries (LIBs), it is primary to seek high capacity and long-lifetime electrode materials. Li-excess disordered rock-salt structure (DRS) cathodes have gained much attention due to their high specific capacity. However, Li-excess can lead to a decrease in the structural stability of an electrode material. A new Li-rich DRS oxyfluorides, Li1.23Ni0.3Nb0.3Fe0.16O0.85F0.15 (F0.15) with a series amounts of LiNbOx (LN) coating (0, 5, 10, and 15 wt % denoted as F0.15-LN0, F0.15-LN5, F0.15-LN10, and F0.15-LN15, respectively), are successfully synthesized and evaluated as cathode materials in LIBs. Among them, F0.15-LN10 exhibits the highest initial discharge specific capacity of 296.1 mAh g-1 (at a current density of 20 mA g-1) with the capacity retention rate of 14% higher than that of the uncoated F0.15 after 80 cycles. Even at 300 mA g-1, F0.15-LN10 still delivers the highest discharge specific capacity of 130 mAh g-1. After 20 cycles, the charge-transfer impedance of F0.15-LN10 remained the smallest. The characterizations indicate that LN coating reduces the surface polarization of the cathode materials, slows the interfacial side reactions between the electrolyte and the electrode, and speeds up the Li+ diffusion. These results demonstrate that LN coating is an effective strategy to improve the electrochemical performance.

Electrochemical and transport properties of nickel hexacyanoferrate (KNi[Fe(CN)6]) as potential cathode material for aqueous potassium-ion batteries

Electronic transport properties of the material can give insight into the inherent charge transport mechanism in the material. Here, we report the transport properties and electrochemical performance of potassium-based nickel hexacyanoferrate (KNiHCF) Prussian Blue Analogue (PBA) synthesized via sonochemical assisted co-precipitation method. The transport properties of the compound were studied from 1 Hz to 10 MHz over 223 K to 423 K. The compound exhibited a specific capacity of 88.5 mAh/g at a current density of 2 A/g, making it a good candidate for potassium-ion batteries.

Homogenous coating of Li+ conductive Li5AlO4 on single-crystalline nonstoichiometric Li1.04Ni0.92Al0.04O2 for rechargeable lithium-ion batteries

Cobalt-free, nickel-rich LiNi1-xAlxO2 (x ≤ 0.1) is an attractive cathode material because of high energy density and low cost but suffers from severe structural degradation and poor rate performance. In this study, we propose a molten salt-assisted synthesis in combination with a Li-refeeding induced aluminum segregation strategy to prepare Li5AlO4-coated single-crystalline slightly Li-rich Li1.04Ni0.92Al0.04O2. The symbiotic formation of Li5AlO4 from reaction between molten lithium hydroxide and doped aluminum in the bulk ensures a high lattice matching between the Ni-rich oxide and the homogenous conductive Li5AlO4 that permits high Li+ conductivity. Benefiting from mitigated undesirable side reactions and phase evolution, the Li5AlO4-coated single-crystalline Li1.04Ni0.92Al0.04O2 delivers a high specific capacity of 220.2 mA h g−1 at 0.1 C and considerable rate capability (182.5 mA h g−1 at 10 C). Besides, superior capacity retention of 90.8% is obtained at 1/3 C after 100 cycles in a 498.1 mA h pouch full cell. Furthermore, the particulate morphology of Li1.04Ni0.92Al0.04O2 remains intact after cycling at a cutoff voltage of 4.3 V, whereas slightly Li-deficient Li0.98Ni0.97Al0.05O2 features intragranular cracks and irreversible lattice distortion. The results highlight the value of molten salt-assisted synthesis and Li-refeeding induced elemental segregation strategy to upgrade Ni-based layered oxide cathode materials for advanced Li-ion batteries.

C3N4-digested intercalation MoS2 nano-flowers with expanded interlayer spacing towards high-performance rechargeable zinc-ion batteries

Molybdenum disulfide (MoS2) materials are very competitive cathode materials for aqueous zinc-ion batteries (AZIBs) due to their sandwich structure, large surface area and low cost. Also, the inherent low capacity and high energy barrier limit its further development. Here, the C3N4-digested intercalation MoS2 (MSCN) has been achieved via a hydrothermal strategy by using g-C3N4 nanosheets as a self-sacrificial template. The introduction of g-C3N4 greatly improves the MoS2 conductivity, which further enhances the Zn2+ diffusion dynamics, and succeeds in increasing the spacing between the layers. With a discharge capacity of 168 mAh g−1 at 5 A g−1, Zn-ion batteries based on the MSCN cathode assembly exhibit good cycle stability and excellent rate performance, under the same current density circulation capacity remain a rate of 92.9 % after 1000 cycles. And beyond that, flexible quasi-solid ZIBs with MSCN cathodes which have good Zn2+ storage properties and promising for future applications. The research in this article is of great significance for the design and development of AZIBs layered transition metal sulfide cathodes.

Improving Zinc-Ion Batteries’ Performance: The Role of Nitrogen Doping in V2O3/C Cathodes

This study presents the synthesis and electrochemical evaluation of nitrogen-doped vanadium oxide (N−V2O3/C) as a cathode material for aqueous zinc-ion batteries (AZIBs), using a hydrothermal method. Compared to undoped V2O3/C, N−V2O3/C exhibits enhanced electrical conductivity, capacity, and electrochemical kinetics, attributed to the incorporation of pyridinic and pyrrolic nitrogen. The initial charge–discharge cycles indicate phase transitions to amorphous vanadium oxides, enhancing conductivity. N−V2O3/C shows a high specific capacity of 168.4 mAh g−1 at 10 A g−1 and remarkable reversibility, highlighted by the transient existence of intermediate species during cycling. Optimal electrochemical performance is achieved with a vanadium-to-nitrogen molar ratio of 2:3, indicating the significant impact of the nitrogen doping concentration on the material’s efficiency. This work underscores the potential of N−V2O3/C as a superior cathode material for AZIBs.

High-capacity dilithium hydroquinone cathode material for lithium-ion batteries.

Lithiated organic cathode materials show great promise for practical applications in lithium-ion batteries owing to their Li-reservoir characteristics. However, the reported lithiated organic cathode materials still suffer from strict synthesis conditions and low capacity. Here we report a thermal intermolecular rearrangement method without organic solvents to prepare dilithium hydroquinone (Li2Q), which delivers a high capacity of 323 mAh g-1 with an average discharge voltage of 2.8V. The reversible conversion between orthorhombic Li2Q and monoclinic benzoquinone during charge/discharge processes is revealed by in situ X-ray diffraction. Theoretical calculations show that the unique Li-O channels in Li2Q are beneficial for Li+ ion diffusion. In situ ultraviolet-visible spectra demonstrate that the dissolution issue of Li2Q electrodes during charge/discharge processes can be handled by separator modification, resulting in enhanced cycling stability. This work sheds light on the synthesis and battery application of high-capacity lithiated organic cathode materials.

Bifunctional low molecular weight polyacrylic acid as aqueous binder and coating agent enables high performance LiMn2O4 cathode for lithium-ion batteries

LiMn2O4 is considered to be a promising cathode material for lithium-ion batteries due to its decent energy density, low price and environmental benignity. However, the problems of Mn dissolution, migration and deposition during the cycle, seriously affect its lifespan, especially at high temperature. In this study, we developed a strategy by which we killed two birds with one stone. A low molecular weight polyacrylic acid (PAA) mixed with sodium carboxymethyl cellulose (CMC) is applied as binder and coating agent for cathode particles at the same time. The conventional and environmental unfriendly polyvinylidene difluoride (PVDF)-N-methylpyrrolidone (NMP) system is replaced by the cheap and green aqueous binder with improved adhesive effect. Furthermore, the binder-based surface coating layer not only alleviates the side reaction between the electrolyte and the cathode particles, but also chelates the dissolved Mn2+ by the large amount of carboxyl groups in PAA molecules and so prevents the following migration and deposition of Mn2+. In the button half-cell with low molecular weight PAA based binder, the capacity retention reaches 94.1 % after 1000 cycles at room temperature and 92.0 % after 200 cycles at 60 degrees centigrade. Meanwhile, 18650-type cylindrical cells were prepared with this binder, which shows a great high temperature storage performance. After the cell was held at 60 degrees centigrade for 25 days at full charged state, the internal resistance increased by only 1.25mΩ, the voltage decreased by only 0.1 V, the residual capacity retention and recovery capacity retention reaches 85.6 % and 92.2 %. This work shows the great potential of the aqueous binder in dealing with the problem of Mn dissolution during the cycling of manganese-based cathode materials for lithium-ion batteries.

Phytic Acid Customized Hydrogel Polymer Electrolyte and Prussian Blue Analogue Cathode Material for Rechargeable Zinc Metal Hydrogel Batteries.

Zinc anode deterioration in aqueous electrolytes, and Zn dendrite growth is a major concern in the operation of aqueous rechargeable Zn metal batteries (AZMBs). To tackle this,the replacement of aqueous electrolytes with a zinc hydrogel polymer electrolyte (ZHPE) is presented in this study. This method involves structural modifications of the ZHPE by phytic acid through an ultraviolet (UV) light-induced photopolymerization process. The high membrane flexibility, high ionic conductivity (0.085Scm-1), improved zinc corrosion overpotential, and enhanced electrochemical stability value of ≈2.3V versus Zn|Zn2+ show the great potential of ZHPE as an ideal gel electrolyte for rechargeable zinc metal hydrogel batteries (ZMHBs). This is the first time that the dominating effect of chelation of phytic acid with M2+ center over H-bonding with water is described to tune the gel electrolyte properties for battery applications. The ZHPE shows ultra-high stability over 360h with a capacity of 0.50mAhcm-2 with dendrite-free plating/stripping in Zn||Zn symmetric cell. The fabrication of the ZMHB with a high-voltage zinc hexacyanoferrate (ZHF) cathode shows a high-average voltage of ≈1.6V and a comparable capacity output of 63mAhg-1 at 0.10Ag-1 of the current rate validating the potential application of ZHPE.

Polyoxovanadate Li7[V15O36(CO3)] and its derivative γ-LiV2O5 as superior performance cathode materials for aqueous zinc-ion batteries

Recently, many reports have been published about polyoxovanadates (POVs) with multiple electrons redox activity for energy storage. However, they are easily transformed into solid-state oxides after calcination. We noted that although dehydrated Li7[V15O36(CO3)] (Li7V15) exhibited a high capacity for lithium-ion batteries (LIBs), it was reported that the electrochemical behavior of the dehydrated sample same as γ-LiV2O5 (γ-LVO) which prepared by annealing the cluster and undehydrated Li7V15 was not redox-active. Interestingly, we were surprised to find that undehydrated Li7V15 and its derivative γ-LVO showed better electrochemical performance than LIBs when first proposed as the cathode to store Zn2+. Both Li7V15 and γ-LVO electrodes provided excellent rate performance and satisfied cyclability (135.0 and 214.1 mAh g−1 at 3 A g−1 after 1000 cycles, respectively). The fast kinetics of Li7V15 and γ-LVO were verified by pseudocapacitive analysis, GITT and EIS tests. Moreover, the Zn2+ storage mechanism and redox behavior of Li7V15 and γ-LVO were examined by ex-situ measurements. First-principles calculations revealed that the Zn2+ was chemisorbed on the clusters and physisorbed between the clusters. This work enriches the POVs cathode chemistry in aqueous energy storage.

A modification engineering to form two kinds of truncated octahedrons by in situ LaBO3 coating for high-performance LiMn2O4 cathode material

Rapid capacity fade of spinel LiMn2O4 cathode material limits the application of lithium-ion batteries. Herein, the introduction of La/B elements achieves the dual-modification of surface coating and single-crystal truncated morphology, ensuring the compatibility of rate capability and cycling stability. The La and B introduction enables the in situ formation of LaBO3 coating layer. Both the LaBO3 coating and truncated morphology prevent the direct exposure of the cathode to the electrolyte, decreasing the Mn dissolution and providing the additional Li+ diffusion channels. The increase of La and B modification partially restrains the development of {110} crystal planes. The refinement manifests that the La3+/B3+ doping partially replaces Mn3+ of the LiMn2O4, inhibiting the Jahn-Teller effect and stabilizing the [MnO6] skeleton. Consequently, the optimized LiMn2O4@0.04LaBO3 with the favorable LaBO3 coating thickness and two truncated octahedrons exhibits the excellent electrochemical properties at high current rate. The first discharge capacities of 109.1, 104.2 and 96.9 mAh⋅g−1 are obtained, whilst the capacity retentions of 64.8 % (after 2000 cycles), 65.8 % (after 2000 cycles) and 80.5 % (after 1000 cycles) can be maintained at 5 C, 10 C and 20 C, respectively. Even at 5 C and 55 °C, the high initial discharge capacity of 113.6 mAh⋅g−1 and good cycling lifespans can be achieved. This modification strategy provides valuable insight for preparing the advanced LiMn2O4 cathode materials for lithium-ion batteries.

Synthesis and Properties of the LiMn2O4 Cathode Material for Lithium-ion Batteries

Spinel LiMn2O4 was synthesized by high-temperature solid-state method with lithium salt and manganese salt as raw materials, which were mixing with anhydrous ethanol as solvent under stirring, and calcining at high temperature in in the oxygen atmosphere. X-ray diffraction (XRD) and scanning electron microscope (SEM) showed that the size of lithium manganese particles with spinel structure was 80 to 200 nm, and the particle size distribution was uniform. The results showed that the prepared LiMn2O4 sample sintered at 700°C exhibited superior electrochemical performance when used as a cathode material for lithium-ion batteries with a voltage window of 2.5–4.8 V. The first charge-discharge specific capacity and first discharge capacity can reach 158.0 mAh‧g-1 and 138.4 mAh‧g-1, respectively, at 0.1 A‧g-1 current density, and the first Coulomb retention efficiency is 87.6%. The discharge specific capacity of the LiMn2O4 material can be maintained at 114 mAh‧g-1 when the test current density was returned to 0.1 A‧g-1 after 60 cycles.

Co-free and low strain cathode materials for sodium-ion batteries: Machine learning-based materials discovery

Sodium-ion batteries (SIBs) are promising alternatives to lithium-ion batteries (LIBs) owing to their cost-effectiveness and similar intercalation mechanisms. Layered transition metal oxides (LTMOs) are the promising cathode candidates for SIBs owing to their high voltages and ease of synthesis. However, O3-type LTMOs undergo structural deformation and performance degradation during de-/intercalation. Owing to the limitations of single-element compounds, doping them with various elements can enhance their stability and performance. In this study, machine learning (ML) algorithms are used to predict the structural stability of O3-type materials without phase transitions to facilitate efficient material selection. ML classification models assess the phase stability of cathodes in the pristine and desodiated states. Data sampling and feature engineering enhanced the accuracy of the pristine model from 0.886 to 0.962 and desodiated model from 0.642 to 0.954. Furthermore, a novel database in the form of NaxNi0.5MayMbzO2 (0.5 ≤ x ≤ 1, y + z = 0.5; M = transition metal) was constructed using density functional theory (DFT) calculations. Out of 1,451 LTMOs candidates, we present 128 cathode candidates that satisfy the following conditions: (1) O3 phase is maintained during dis-/charging processes, (2) average voltage ≥ 3 V, (3) theoretical capacity ≥ 200 mAh/g, and (4) -5 % ≤ volume change ≤ 5 %. Among them, 125 materials showed the possibility of stable Co-free cathodes, and 13 materials exhibited -0.5 % < volume change < 0.5 %. This study suggests optimal LTMO candidates that satisfy both the high energy density and electrochemical stability and provides a reliable battery material screening platform.

Concerted Effect of Ion- and Electron-Conductive Additives on the Electrochemical and Thermal Performances of the LiNi0.8Co0.1Mn0.1O2 Cathode Material Synthesized by a Taylor-Flow Reactor for Lithium-Ion Batteries.

To address the issue that a single coating agent cannot simultaneously enhance Li+-ion transport and electronic conductivity of Ni-rich cathode materials with surface modification, in the present study, we first successfully synthesized a LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material by a Taylor-flow reactor followed by surface coating with Li-BTJ and dispersion of vapor-grown carbon fibers treated with polydopamine (PDA-VGCF) filler in the composite slurry. The Li-BTJ hybrid oligomer coating can suppress side reactions and enhance ionic conductivity, and the PDA-VGCFs filler can increase electronic conductivity. As a result of the synergistic effect of the dual conducting agents, the cells based on the modified NCM811 electrodes deliver superior cycling stability and rate capability, as compared to the bare NCM811 electrode. The CR2032 coin-type cells with the NCM811@Li-BTJ + PDA-VGCF electrode retain a discharge specific capacity of ∼92.2% at 1C after 200 cycles between 2.8 and 4.3 V (vs Li/Li+), while bare NCM811 retains only 84.0%. Moreover, the NCM811@Li-BTJ + PDA-VGCF electrode-based cells reduced the total heat (Qt) by ca. 7.0% at 35 °C over the bare electrode. Remarkably, the Li-BTJ hybrid oligomer coating on the surface of the NCM811 active particles acts as an artificial cathode electrolyte interphase (ACEI) layer, mitigating irreversible surface phase transformation of the layered NCM811 cathode and facilitating Li+ ion transport. Meanwhile, the fiber-shaped PDA-VGCF filler significantly reduced microcrack propagation during cycling and promoted the electronic conductance of the NCM811-based electrode. Generally, enlightened with the current experimental findings, the concerted ion and electron conductive agents significantly enhanced the Ni-rich cathode-based cell performance, which is a promising strategy to apply to other Ni-rich cathode materials for lithium-ion batteries.

Stable surface lattice for prolonged cycle life of single-crystal lithium-rich layered oxide cathodes

Lithium-rich layered oxides (LLOs) have garnered significant attention due to their outstanding capacity. However, the severe capacity fading resulting from lattice deterioration initiated at the surface constrains the further advancement of LLOs. Here, we present a method to stabilize the surface lattice to enhance the capacity stability of LLOs. Specifically, we have engineered a nanometer-thin Gd-doped NiO rock-salt epitaxial layer on the surface of single-crystal LLOs, along with an atomic-level thickness LiGdO2coating layer. The dual-nanolayer protection strategy has successfully stabilized the surface structure of LLOs and suppressed electrode–electrolyte interface side reactions. As a result, the modified sample achieves a capacity retention rate of 93.4% after 500 cycles at 1C and 94.2% after 200 cycles at 0.2C. Our study underscores the importance of surface structure in achieving high cyclic stability in LLOs and provides an important approach for designing stable lithium-ion battery cathode materials.

A document-level information extraction pipeline for layered cathode materials for sodium-ion batteries

Natural language processing techniques enable extraction of valuable information from large amounts of published literature for the application of data science and technology, i.e. machine learning in the field of materials science. Nevertheless, the automated extraction of data from full-text documents remains a complex task. We propose a document-level natural language processing pipeline for literature extraction of comprehensive information on layered cathode materials for sodium-ion batteries. The pipeline enhances entity recognition with contextual supplementary information while capturing the article structure. Finally, a heuristic multi-level relationship extraction algorithm is employed in relation extraction to extract experimental parameters and complex performance relationships respectively. We successfully extracted a comprehensive dataset containing 5265 records from 1747 documents, encompassing essential information such as chemical composition, synthesis parameters, and electrochemical properties. By implementing our pipeline, we have made significant progress in overcoming the challenges associated with data scarcity in battery informatics. The extracted datasets provide a valuable resource for further research and development in the field of layered cathode materials.

A Rhombic 2D Conjugated Metal-Organic Framework as Cathode for High-Performance Sodium-Ion Battery.

2D conjugated metal-organic frameworks (2D c-MOFs) have garnered significant attention as promising electroactive materials for energy storage. However, their further applications are hindered by low capacity, limited cycling life, and underutilization of the active sites. Herein, Cu-TBA (TBA=octahydroxyltetrabenzoanthracene) with large conjugation units (narrow energy gap) and a unique rhombus topology is introduced as the cathode material for sodium-ion batteries (SIBs). Notably, Cu-TBA with a rhombus topology exhibits a high specific surface area (613m2g-1) and metallic band structure. Additionally, Cu-TBA outperforms its hexagonal counterpart, Cu-HHTP (HHTP=2,3,6,7,10,11-hexahydroxyltriphenylene), demonstrating superior reversible capacity (153.6mAhg-1 at 50mAg-1) and outstanding cyclability with minimal capacity decay even after 3000 cycles at 1Ag-1. This work elucidates a new strategy to enhance the electrochemical performance of 2D c-MOFs cathode materials by narrowing the energy gap of organic linkers, effectively expanding the utilization of 2D c-MOFs for SIBs.

First-principles study of the titanium-doping effects on the properties of O3-type NaNi0.25Fe0.25Mn0.5O2 cathode material for sodium-ion batteries

We carried out first-principles calculations on titanium-doped O3-type NaNi0.25Fe0.25Mn0.5O2 oxide material for titanium substitution at 0.02, 0.04, 0.06, 0.08, and 0.1. The results obtained show that materials doped with titanium have higher structural stability than undoped material. Also after doping, the conductivity of the materials increases greatly but Na(Ni0.25Fe0.25Mn0.5)0.98Ti0.02O2 is slightly more conductive (ΔEg = 0.017 eV). Na(Ni0.25Fe0.25Mn0.5)1-xTixO2 (NNFM-Tix) (x = 0.02, 0.04, 0.06, 0.08, and 0.1) indicates a larger sodium layer, which allows easy migration of sodium ions during charge/discharge processes than NNFM. Sodium ions diffuse faster in NNFM-Ti0.06 and NNFM-Ti0.08 compared to other doped-NNFMs. In addition, the Pugh index value of NNFM (1.8222) is lower than that of NNFM-Ti0.02, NNFM-Ti0.04, NNFM-Ti0.06, NNFM-Ti0.08, and NNFM-Ti0.1 (2.1376), demonstrating enhancement of elastic ductility after doping. Titanium-doped materials exhibited improved stability under temperature effects between −20 and 60 °C, which represent the operating temperature range of sodium-ion batteries, although this effect did not vary much with the doping rate. The improved thermodynamic stability indicates that the doped materials can better resist degradation, have high efficiency, and a long cycle life. These Na(Ni0.25Fe0.25Mn0.5)1-xTixO2 materials, particularly those with the titanium rate at 0.06 and 0.08 are therefore powerful materials for the accomplishment of efficient sodium-ion batteries cathodes.

Determining effects of doping lithium nickel oxide with tungsten using Compton scattering

X-ray Compton scattering experiments along with parallel first-principles computations were carried out on LiNiO2 to understand the effects of W doping on this cathode material for Li-ion batteries. By employing high-energy x rays exceeding 100 keV, an insight is gained into the fate of the W valence electrons, which are adduced to undergo transfer to empty O 2p energy bands within the active oxide matrix of the cathode. The substitution of W for Ni is shown to increase the electronic conductivity and to enhance the total magnetization per Ni atom. Our study demonstrates that an analysis of line shapes of Compton scattered x rays in combination with theoretical modeling can provide a precise method for an atomic level understanding of the nature of the doping process.