Textural and pseudocapacitive characteristics of sol-gel derived RuO2·xH2O: Hydrothermal annealing vs. annealing in air

Hydrous ruthenium dioxide (RuO₂·xH₂O) prepared in a modified sol-gel process was subjected to annealing in air and water at various temperatures for supercapacitor applications. The textural and pseudocapacitive characteristics of RuO₂·xH₂O annealed in air and water were systematically compared to show the benefits of annealing in water (denoted as hydrothermal annealing). An important concept that hydrothermal annealing effectively restricts condensation of hydroxyl groups within nanoparticles, inhibits crystal growth, and maintains high water content of RuO₂·xH₂O is demonstrated in this work. The unique textural characteristics of hydrothermally annealed RuO₂·xH₂O are attributable to the high-pressured, water-enriched surroundings which restrain coalescence of RuO₂·xH₂O nanocrystallites. The crystalline, hydrous nature of hydrothermally annealed RuO₂·xH₂O favors the utilization of active species in addition to a merit of minor dependence of specific capacitance on the scan rate of CV for pseudocapacitors. As a result, RuO₂·xH₂O with hydrothermal annealing at 225 °C for 24 h exhibits 16 wt.% water, an average particle size of about 7 nm, and specific capacitance of ca. 390 F g⁻¹.     

Effects of substrates on the capacitive performance of RuOx·nH2O and activated carbon-RuOx electrodes for supercapacitors

The electrochemical energy storage and delivery on the electrodes composed of hydrous ruthenium oxide (RuO_x·nH₂O) or activated carbon-hydrous ruthenium oxide (AC-RuO_x) composites are found to strongly depend on the substrate employed. The contact resistance at the active material-graphite interface is much lower than that at the active material-stainless steel (SS) mesh interface. Thin films of gold plus RuO_x·nH₂O deposited on SS meshes (RuO_x/Au/SS) are found to greatly improve the poor contact between SS meshes and electrode materials. The maximum specific capacitance (C_S,RuOx) of RuO_x·nH₂O, 1580 F g⁻¹ (measured at 1 mV s⁻¹), very close to the theoretic value, was obtained from an AC-RuO_x/RuO_x/Au/SS electrode with 10 wt.% sol-gel-derived RuO_x·nH₂O annealed in air at 200 °C for 2 h. The highly electrochemical reversibility, high-power characteristics, good stability, and improved frequency response of this AC-RuO_x/RuO_x/Au/SS electrode demonstrate its promising application potential in supercapacitors. The ultrahigh specific capacitance of RuO_x·nH₂O probably results from the uniform size distribution of RuO_x·nH₂O nanoparticles, ranged from 1.5 to 3 nm which is clearly observed from the high-resolution transmission electron microscopy (HRTEM).     

RuO2·xH2O/NiO composites as electrodes for electrochemical capacitors: Effect of the RuO2 content and the thermal treatment on the specific capacitance

RuO₂·xH₂O/NiO composites having RuO₂ contents in the range 0-100 wt.% have been prepared by a co-precipitation method. Structural, microstructural and textural transformations after heating the as-prepared composites at 200 and 600 °C have been followed by X-ray diffraction, scanning electron microscopy (SEM) and nitrogen adsorption/desorption isotherms. At 200 °C the composites are made of micrometric particles in which nanometric crystallites of the two oxides are aggregated. The composites show microporosity (0.02-0.10 cm³/g), mesoporosity (0.07-0.12 cm³/g) and relatively high specific surface area (62-309 m²/g). At 600 °C the composites are fully dehydrated and RuO₂ has crystallized and segregated. Microporosity and mesoporosity as well as specific surface area are strongly decreased. Specific capacitance and specific surface area of the composites heated at 200 and 600 °C have been measured and discussed on the basis of the RuO₂ content. For comparison the specific capacitance and specific surface area of mixtures of NiO and RuO₂·xH₂O (or RuO₂) have been taken as references. The higher specific capacitance of the 200 °C-heated composites compared to the 600 °C-heated ones is due to the higher specific surface area of the former and the higher pseudocapacitance of RuO₂·xH₂O compared to RuO₂. The discussion reported in this work can be applied to other composites such as RuO₂·xH₂O/carbon and RuO₂·xH₂O/other oxides.     

Electrochemical capacitance of nanoporous hydrous RuO2 templated by anionic surfactant

The nanoporous RuO₂·3.38H₂O was synthesized with a surfactant template using sodium dodecyl sulfate. The surface area of the material amounted to 220 m² g⁻¹ while the maximum specific capacitance obtained was 870 Fg⁻¹ at a scan rate of 10 mV s⁻¹. The specific capacitance of nanoporous RuO₂·3.38H₂O electrode exhibits enhancement, compared with other porous RuO₂ materials synthesized by different methods. The nanoporous RuO₂·3.38H₂O is a very promising material for high performance capacitance.     

Two-step hydrothermal synthesis of Ru-Sn oxide composites for electrochemical supercapacitors

A two-step hydrothermal process was developed to synthesize hydrous 30RuO₂-70SnO₂ composites with much better capacitive performances than those fabricated through the normal hydrothermal process, co-annealing method, or modified sol-gel procedure. A very high specific capacitance of RuO₂ (C_S,Ru), ca. 1150 F g⁻¹, was obtained when this composite was synthesized via this two-step hydrothermal process with annealing in air at 150 °C for 2 h. The voltammetric currents of this annealed composite were found to be quasi-linearly proportional to the scan rate of CV (up to 500 mV s⁻¹), demonstrating its excellent power property. From Raman, UV-vis spectroscopic and TEM analyses, the reduction in mean particulate size is clearly found for this two-step oxide composite, attributable to the co-precipitation of (Ru_δSn_1−δ)O₂·xH₂O onto partially dissolved SnO₂·xH₂O and the formation of (Ru_δSn_1−δ)O₂·xH₂O crystallites in the second step. This effect significantly promotes the utilization of RuO₂ (i.e., very high C_S,Ru). The excellent capacitive performances, very similar to that of RuO₂·xH₂O, suggest the deposition of RuO₂-enriched (Ru_δSn_1−δ)O₂·xH₂O onto SnO₂·xH₂O seeds as well as the individual formation of (Ru_δSn_1−δ)O₂·xH₂O crystallites in the second hydrothermal step.     

Soft template synthesis of mesoporous Co3O4/RuO2·xH2O composites for electrochemical capacitors

Co₃O₄/RuO₂·xH₂O composites with various Ru content (molar content of Ru = 5%, 10%, 20%, 50%) were synthesized by one-step co-precipitation method. The precursors were prepared via adjusting pH of the mixed aqueous solutions of Co(NO₃)₂·6H₂O and RuCl₃·0.5H₂O by using Pluronic123 as a soft template. For the composite with molar ratio of Co:Ru = 1:1 annealed at 200 °C, Brunauer-Emmet-Teller (BET) results indicated that the composite showed mesoporous structure, and the specific surface area of the composite was as high as 107 m² g⁻¹. The electrochemical performances of these composites were measured in 1 M KOH electrolyte. Compared with the composite prepared without template, the composite with P123 exhibited a higher specific capacitance. When the molar content of Ru was rising, the specific capacitance of the composites increased significantly. It was also observed that the crystalline structures as well as the electrochemical activities were strongly dependent on the annealing temperature. A capacitance of 642 F/g was obtained for the composite (Co:Ru = 1:1) annealed at 150 °C. Meanwhile, the composites also exhibited good cycle stability. Besides, the morphologies and textural characteristic of the samples were also investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM).     

Synthesis and characterization of ZnxMg1 − xGa2O4:Co fabricated by low-temperature burning method

A series of Zn_xMg_1 − xGa₂O₄:Co²⁺ spinels (x = 0, 0.25, 0.5, 0.75, and 1.0) was successfully produced through low-temperature burning method by using Mg(NO₃)₂·4H₂O, Zn(NO₃)₂·6H₂O, Ga(NO₃)₃·6H₂O, CO(NH₂)₂, NH₄NO₃, and Co(NO₃)₂·6H₂O as raw materials. The product was characterized by X-ray diffraction, transmission electron microscopy, and photoluminescence spectroscopy. The product was not merely a simple mixture of MgGa₂O₄ and ZnGa₂O₄; rather, it formed a solid solution. The lattice constant of Zn_xMg_1 − xGa₂O₄:Co²⁺ (0 ≤ x ≤ 1.0) crystals has a good linear relationship with the doping density, x. The synthesized products have high crystallinities with neat arrays. Based on an analysis of the form and position of the emission spectrum, the strong emission peak around the visible region (670 nm) can be attributed to the energy level transition [⁴T₁(⁴P) → ⁴A₂(⁴F)] of Co²⁺ in the tetrahedron. The weak emission peak in the near-infrared region can be attributed to the energy level transition [⁴T₁(⁴P) → ⁴T₂(⁴F)] of Co²⁺ in the tetrahedron.     

Single crystal nanobelts of V3O7·H2O: A lithium intercalation host with a large capacity

In this study, single crystal V₃O₇·H₂O nanobelts were successfully synthesized using a simple hydrothermal route, in which templates or catalysts were absent. The synthesized V₃O₇·H₂O nanobelts are highly crystalline and have lengths up to several tens of micrometers. The width and thickness of the nanobelts are found to be about 30-50 and 30 nm, respectively. A lithium battery using V₃O₇·H₂O nanobelts as the positive electrode exhibits a high initial discharge capacity of 409 mAh g⁻¹, corresponding to the formation of Li_xV₃O₇·H₂O (x = 4.32). Such a high degree of electrochemical performance is attributed to the intrinsic properties of the single-crystalline V₃O₇·H₂O nanobelts.     

Anodic deposition of hydrous ruthenium oxide for supercapaciors: Effects of the AcO concentration, plating temperature, and oxide loading

Effects of the sodium acetate (NaCH₃COO, denoted as NaAcO) concentration, plating temperature, and oxide loading on the pseudocapacitive characteristics of hydrous ruthenium oxide (denoted as RuO₂·xH₂O) films anodically plated from aqueous RuCl₃·xH₂O media were systematically investigated in this work. The electrochemical behavior of RuO₂·xH₂O with annealing in air at 200 °C for 2 h is approximately independent of the NaAcO concentration and plating temperature although a negative shift in the onset and peak potentials of deposition with rising the plating temperature is found. The morphologies and adhesion of RuO₂·xH₂O deposits strongly depend on the deposition rate which is obviously influenced by varying the above two deposition variables. The specific capacitance of RuO₂·xH₂O is monotonously decreased from 760 to 505 F g⁻¹ when the oxide loading is gradually increased from 0.34 to 1.0 mg cm⁻², due to the longer pathways of both electrons and protons during the redox transitions. The XRD and Raman spectroscopic analyses reveal the extremely localized crystalline nature of as-deposited RuO₂·xH₂O. All RuO₂·xH₂O deposits show the ideal pseudocapacitive characteristics, definitely illustrating the merits of RuO₂·xH₂O prepared by anodic deposition without considering the advantages of its simplicity, one-step, reliability, low cost, and versatility for electrode preparation.     

Hydrothermal synthesis of binary Ru-Ti oxides with excellent performances for supercapacitors

Hydrous, crystalline, binary (Ru-Ti)O₂·nH₂O with compositions equal to the ratios of metallic ions in the precursor solutions are successfully synthesized by a mild hydrothermal process. The maximum utilization of RuO₂·nH₂O (ca. 793 F/g) occurs at the composition of 60 M% TiO₂·nH₂O although phase separation is clearly found for this TiO₂-enriched binary oxides. The nano-structured architecture with a high BET surface area (ca. 253 m²/g) of the hydrothermal-derived (Ru-Ti)O₂·nH₂O with annealing at 200 °C favors the physical adsorption of water and maintains a high water content which is novel and never found before. Due to this novel nanostructure, the annealed (Ru-Ti)O₂·nH₂O synthesized by means of the hydrothermal process exhibits excellent performances (i.e., high utilization of RuO₂, high power property, and long cycle life) for supercapacitors.     

Structural and electrochemical behaviors of metastable Li2/3[Ni1/3Mn2/3]O2 modified by metal element substitution

Layered metastable lithium manganese oxides, Li_2/3[Ni_1/3−xMn_2/3−yM_x+y]O₂ (x = y = 1/36 for M = Al, Co, and Fe and x = 2/36, y = 0 for M = Mg) were prepared by the ion exchange of Li for Na in P2-Na_2/3[Ni_1/3−xMn_2/3−yM_x+y]O₂ precursors. The Al and Co doping produced the T^#2 structure with the space group Cmca. On the other hand, the Fe and Mg doped samples had the O6 structure with space group R-3m. Electron diffraction revealed the 1:2 type ordering within the Ni_1/3−xMn_2/3−yM_x+yO₂ slab. It was found that the stacking sequence and electrochemical performance of the Li cells containing T^#2-Li_2/3[Ni_1/3Mn_2/3]O₂ were affected by the doping with small amounts of Al, Co, Fe, and Mg. The discharge capacity of the Al doped sample was around 200 mAh g⁻¹ in the voltage range between 2.0 and 4.7 V at the current density of 14.4 mA g⁻¹ along with a good capacity retention. Moreover, for the Al and Co doped and undoped oxides, the irreversible phase transition of the T^#2 into the O2 structure was observed during the initial lithium deintercalation.     

Effect of Ti substitution for Nb in double perovskite-type Ba3CaNb2O9 on chemical stability and electrical conductivity

This paper reports the synthesis, structure, chemical stability and electrical transport properties of Ti substituted Ba₃CaNb₂O₉ (BCN) to develop electrolytes for proton conducting solid oxide fuel cells (H-SOFCs). The powder X-ray diffraction (PXRD) of Ba₃CaNb_2−xTi_xO_9−δ (x = 0.1, 0.15, 0.2, 0.25 and 0.3) and Ba₃Ca_1.18Nb_1.82−xTi_xO_9−δ (x = 0.15 and 0.25) showed formation of double perovskite-like structure with lattice constant comparable to that of Ba₃Ca_1.18Nb_1.82O_9−δ (BCN18). Scanning electron microscopy (SEM) showed dense and pore-free microstructure for Ba₃CaNb_1.75Ti_0.25O_8.875. PXRD and Fourier transform infrared (FTIR) spectroscopy data confirmed long-term stability of Ba₃CaNb_2−xTi_xO_9−δ and Ba₃Ca_1.18Nb_1.82−xTi_xO_9−δ in boiling H₂O and in CO₂ at elevated temperatures. The AC impedance investigation showed contribution due to bulk, grain-boundary and electrode effect at low temperatures. The electrical conductivity of studied materials were measured in different medium including dry air, dry H₂, wet H₂, wet N₂ and D₂O. Increase in conductivity in wet N₂ and decrease in conductivity in D₂O confirmed the proton conduction in Ba₃CaNb_1.75Ti_0.25O_9-δ. Among Ti-substituted compounds investigated in this study, Ba₃Ca_1.18Nb_1.57Ti_0.25O_8.605 showed the highest conductivity of 3.5 × 10⁻⁴ S cm⁻¹ at 400 °C in wet N₂ (3%H₂O), which is comparable to reported values of Ba₂Ca_0.79Nb_0.66Ta_0.55O_6−δ and BCN18.     

Preparation, characterization and electrical conductivity studies of NdYb1−xGdxZr2O7 (0 ≤ x ≤ 1.0) ceramics

Several compositions of NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 1.0) ceramics were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, microstructure and electrical conductivity of NdYb_1−xGd_xZr₂O₇ ceramics were analyzed by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance plots measurements. NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 0.3) ceramics have a single phase of defect fluorite-type structure, and NdYb_1−xGd_xZr₂O₇ (0.7 ≤ x ≤ 1.0) ceramics exhibit a single phase of pyrochlore-type structure; however, the NdYb_0.5Gd_0.5Zr₂O₇ composition shows mixed phases of both defect fluorite-type and pyrochlore-type structures. The measured values of the grain conductivity obey the Arrhenius relation. The grain conductivity of each composition in NdYb_1−xGd_xZr₂O₇ ceramics gradually increases with increasing temperature from 673 to 1173 K. NdYb_1−xGd_xZr₂O₇ ceramics are oxide-ion conductor in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The highest grain conductivity value obtained in this work is 1.79 × 10⁻² S cm⁻¹ at 1173 K for NdYb_0.3Gd_0.7Zr₂O₇ composition.     

Microwave dielectric properties of the (1 − x)Mg2TiO4-xCaTiO3-y wt.% ZnNb2O6 ceramics system

Composite ceramics based on (1 − x)Mg₂TiO₄-xCaTiO₃-y wt.% ZnNb₂O₆ (x = 0.12-0.16, y = 0-8) were prepared by a conventional mixed-oxide route. Zn²⁺ partially replaced Mg²⁺ in Mg₂TiO₄ and formed the spinel-structured (Mg_1−δZn_δ)₂TiO₄ phase. Nb²⁺, is known to be solid soluble in CaTiO₃, was found to change its shape from cubic to pliable. A bi-phase system (Mg_1−δZn_δ)₂TiO₄ and CaTiO₃ exhibited in all samples, where a small amount of second phase Mg_1−δZn_δTiO₃ was also detected. The microwave dielectric properties of specimens were strongly related to ZnNb₂O₆ and CaTiO₃ content. As y increased, ?_r and τ_f decreased, however, Q × f decreased to a minimum value and started to increase thereafter. It was also found that ?_r and τ_f increased and Q × f decreased with increasing x. The optimized microwave dielectric properties with ?_r = 18.37, Q × f = 31,027 GHz (at 6 GHz), and τ_f = 0.51 ppm/°C were achieved for (1 − x)Mg₂TiO₄-xCaTiO₃-y wt.% ZnNb₂O₆ (x = 0.12, y = 4) sintered at 1360 °C for 6 h.     

Amorphous Ru1−yCryO2 loaded on TiO2 nanotubes for electrochemical capacitors

Amorphous Ru_1−yCr_yO₂/TiO₂ nanotube composites were synthesized by loading different amount of Ru_1−yCr_yO₂ on TiO₂ nanotubes via a reduction reaction of K₂Cr₂O₇ with RuCl₃·nH₂O at pH 8, followed by drying in air at 150 °C. Cyclic voltammetry and galvanostatic charge/discharge tests were applied to investigate the performance of the Ru_1−yCr_yO₂/TiO₂ nanotube composite electrodes. For comparison, the performance of amorphous Ru_1−yCr_yO₂ was also studied. The results demonstrated that the three dimensional nanotube network of TiO₂ offered a solid support structure for active materials Ru_1−yCr_yO₂, allowed the active material to be readily available for electrochemical reactions, and increased the utilization of active materials. A maximum specific capacitance 1272.5 F/g was obtained with the proper amount of Ru_1−yCr_yO₂ loaded on the TiO₂ nanotubes.     

Synthesis and tunable thermal expansion properties of Sc2−xYxW3O12 solid solutions

A new series of rare earth solid solutions Sc_2−xY_xW₃O₁₂ was successfully synthesized by the conventional solid-state method. Effects of doping ion yttrium on the crystal structure, morphology and thermal expansion property of as-prepared Sc_2−xY_xW₃O₁₂ ceramics were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TG), field emission scanning electron microscope (FE-SEM) and thermal mechanical analyzer (TMA). Results indicate that the obtained Sc_2−xY_xW₃O₁₂ samples with Y doping of 0≤x≤0.5 are in the form of orthorhombic Sc₂W₃O₁₂-structure and show negative thermal expansion (NTE) from room temperature to 600 °C; while as-synthesized materials with Y doping of 1.5≤x≤2 take hygroscopic Y₂W₃O₁₂·nH₂O-structure at room temperature and exhibit NTE only after losing water molecules. It is suggested that the obvious difference in crystal structure leads to different thermal expansion behaviors in Sc_2−xY_xW₃O₁₂. Thus it is proposed that thermal expansion properties of Sc_2−xY_xW₃O₁₂ can be adjusted by the employment of Y dopant; the obtained Sc_1.5Y_0.5W₃O₁₂ ceramic shows almost zero thermal expansion and its average linear thermal expansion coefficient is −0.00683×10⁻⁶ °C⁻¹ in the 25–250 °C range.     

Study on the rapid synthesis of LiNi1−xCoxO2 cathode material for lithium secondary battery

LiNi_1−xCo_xO₂ (x = 0, 0.1, 0.2) cathode materials were successfully synthesized by a rheological phase reaction method with calcination time of 0.5 h at 800 °C. All obtained powders are pure phase with α-NaFeO₂ structure (R-3m space group). The samples deliver an initial discharge capacity of 182, 199 and 189 mAh g⁻¹ (25 mA g⁻¹, 4.35-3.0 V), respectively. The reaction mechanism was also discussed, which consists of a series of defect reactions. As a result of these defect reactions, the reaction of forming LiNi_1−xCo_xO₂ takes place in high speed.     

Electrochemical and thermal studies of Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 (x = 1/12, 1/4, 5/12, and 1/2)

Samples of the layered cathode materials, Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (x = 1/12, 1/4, 5/12, and 1/2), were synthesized at 900 °C. Electrodes of these samples were charged in Li-ion coin cells to remove lithium. The charged electrode materials were rinsed to remove the electrolyte salt and then added, along with EC/DEC solvent or 1 M LiPF₆ EC/DEC, to stainless steel accelerating rate calorimetry (ARC) sample holders that were then welded closed. The reactivity of the samples with electrolyte was probed at two states of charge. First, for samples charged to near 4.45 V and second, for samples charged to 4.8 V, corresponding to removal of all mobile lithium from the samples and also concomitant release of oxygen in a plateau near 4.5 V. Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples with x = 1/4, 5/12 and 1/2 charged to 4.45 V do not react appreciably till 190 °C in EC/DEC. Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples charged to 4.8 V versus Li, across the oxygen release plateau, start to significantly react with EC/DEC at about 130 °C. However, their high reactivity is similar to that of Li_0.5CoO₂ (4.2 V) with 1 μm particle size. Therefore, Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples showing specific capacity of up to 225 mAh/g may be acceptable for replacing LiCoO₂ (145 mAh/g to 4.2 V) from a safety point of view, if their particle size is increased.     

Microwave-polyol synthesis of nanocrystalline ruthenium oxide nanoparticles on carbon nanotubes for electrochemical capacitors

The ruthenium oxide nanoparticles dispersed on multi-wall carbon nanotubes (CNTs) were successfully synthesized via microwave-polyol process combined with forced hydrolysis without additional thermal oxidation or electrochemical oxidation treatment. The HRTEM, Raman spectra and TGA curve indicate that CNTs were uniformly coated with crystalline and partially hydrous RuO₂·0.64H₂O nanoparticles of 2 nm diameter and the loading amount of ruthenium oxide in the composite could be controlled up to 70 wt.%. The specific capacitance was 450 Fg⁻¹ of ruthenium oxide/CNT composite electrode with 70 wt.% ruthenium oxide at the potential scan rate of 10 mV s⁻¹ and it decreased to 362 Fg⁻¹ by 18% at 500 mV s⁻¹. The specific capacitance of ruthenium oxide in the composite was 620 Fg⁻¹ of ruthenium oxide at 10 mV s⁻¹. The ruthenium oxide nanoparticles in ruthenium oxide/CNT nanocomposite electrode had a high ratio of outer charge to total charge of 0.81, which confirmed its high-rate capability of the composite through the preparation of the nano-sized ruthenium oxide particles on the external surface of CNTs.     

Evolution of the local structure and electrochemical properties of spinel LiNixMn2−xO4 (0 ≤ x ≤ 0.5)

A series of Ni substituted spinel LiNi_xMn_2−xO₄ (0 ≤ x ≤ 0.5) have been synthesized to study the evolution of the local structure and their electrochemical properties. X-ray diffraction showed a few Ni cations moved to the 8a sites in heavily substituted LiNi_xMn_2−xO₄ (x ≥ 0.3). X-ray photoelectron spectroscopy confirmed Ni²⁺ cations were partially oxidized to Ni³⁺. The local structures of LiNi_xMn_2−xO₄ were studied by analyzing the and A_1g Raman bands. The most compact [Mn(Ni)O₆] octahedron with the highest bond energy of Mn(Ni)O was found for LiNi_0.2Mn_1.8O₄, which showed a Mn(Ni)O average bond length of 1.790 Å, and a force constant of 2.966 N cm⁻¹. Electrolyte decomposition during the electrochemical charging processes increased with Ni substitution. The discharge capacities at the 4.1 and 4.7 V plateaus obeyed the linear relationships with respect to the Ni substitution with the slopes of −1.9 and +1.9, which were smaller than the theoretical values of −2 and +2, respectively. The smaller slopes could be attributed to the electrochemical hysteresis and the presence of Ni³⁺ in the materials.