Fluorescence improvement of Ba1.3Ca0.7SiO4:Eu,Mn phosphors via Dy addition and their color-tunable properties

A series of novel single-phase white phosphors Ba_1.3Ca_0.69−x−ySiO₄:0.01Eu²⁺,xMn²⁺, yDy³⁺ were synthesized by the solid-state method. The excitation spectra of these phosphors exhibit a broad band in the range of 260–410 nm, which can meet the application requirements for near-UV LED chips (excited at 350–410 nm). The emission spectra consist of two broad bands positioned around 455 nm and 596 nm, which are assigned to 5d→4f transition of Eu²⁺, and ⁴T₁→⁶A₁ transition of Mn²⁺, respectively. The luminescence intensity of phosphors enhances obviously by doping Dy³⁺ ions, and the intensity of two bands reaches an optimum when Dy³⁺ amounts to 2 mol%. In addition, thermoluminescence investigation of phosphor was conducted, getting two shallow trap defects with activation energy of 0.43 eV and 0.45 eV, which demonstrates the energy transfer mechanism of Dy–Eu through the process of hole and electron traps. By precisely tuning the Mn²⁺ content, an optimized white light with color rendering index (CRI) of R_a=84.3%, correlated color temperature (CCT) of T_c=8416 K and CIE chromaticity coordinates of (0.2941, 0.2937) is generated. The phosphor could be a potential white phosphors for near-UV light emitting diodes.     

Effect of sintering atmosphere and lithium ion co-doping on photoluminescence properties of NaCaPO4:Eu phosphor

This paper reports on the photoluminescence properties of Na_1−yLi_yCa_1−xPO₄:_xEu²⁺ phosphors synthesized by a solid state reaction method. The prepared phosphors have been thoroughly characterized by means of X-ray diffraction (XRD), Field-emission scanning electron microscopy (FE-SEM), Fourier transform infrared spectrum (FTIR), Raman spectrum, Thermo gravimetric and differential thermal analysis (TG–DTA) and photoluminescent spectral measurements. The structure of Na_1−yLi_yCa_1−xPO_4:xEu²⁺ phosphors were found to be orthorhombic in nature with a sphere-like morphology and having the particle size in micrometer range. The excitation spectra of NaCaPO₄:Eu²⁺ phosphors revealed a broad excitation band having its maximum intensity at 373 nm and ranging from 250 m to 450 nm. Incidentally, it matches well with the ultraviolet (UV) radiation of light-emitting diodes (LEDs). Upon 373 nm excitation, these phosphors exhibited intense bluish-green emission band centered at 505 nm. The effect of sintering atmospheres and co-doping of lithium ions on the photoluminescence properties of the NaCaPO₄:Eu²⁺ phosphors were studied and explained suitably. The obtained results indicate that the prepared NaCaPO₄:Eu²⁺ phosphors are promising bluish-green candidates for the phosphor-converted white LED applications.     

Garnet-based red emitting phosphors Li6MLa2Nb2O12: Eu (M=Ca,Sr, Ba): Photoluminescence improvement by changing crystal lattice

A series of novel red emitting phosphors Li₆M(La_1−xEu_x)₂Nb₂O₁₂ (M=Ca, Sr, Ba; 0≤x≤0.3) were synthesized by solid state reaction, and their structures and photoluminescence properties were investigated in detail. The excitation spectrum of Li₆M(La_1−xEu_x)₂Nb₂O₁₂ revealed two mainly excitation bands at 393 nm and 464 nm, which match well with the two popular emissions from near-UV and blue LED chips. Upon the 464 nm light excitation, Li₆MLa₂Nb₂O₁₂:Eu³⁺ phosphors exhibit a red emission centered at 608 nm, originated from the ⁵D₀–⁷F₂ transition of Eu³⁺ ions. The Eu³⁺ surrounding crystal lattice environment in the garnet-based host was changed by altering the c sites element with different radii alkaline earth Ba, Sr, and Ca. The evident photoluminescence enhancement was observed in Li₆M(La_1−xEu_x)₂Nb₂O₁₂ phosphors with the decreasing of the c sites ionic radius. The emission intensity of the optimized Li₆Ca(La_0.8Eu_0.2)₂Nb₂O₁₂ (λ_exc=464 nm) phosphor is about two times higher than that of Y₂O₃:Eu³⁺ (λ_exc=467 nm) under blue light excitation. In addition, the quenching mechanism and the relationship between the structure and photoluminescence property were also discussed.     

Relationship between glass network structure and conductivity of Li2O-B2O3-P2O5 solid electrolyte

Solid state glass electrolyte, xLi₂O-(1 − x)(yB₂O₃-(1 − y)P₂O₅) glasses were prepared with wide range of composition, i.e. x = 0.35 - 0.5 and y = 0.17 - 0.67. This material system is one of the parent compositions for chemically and electrochemically stable solid-state electrolyte applicable to thin film battery. Lithium ion conductivity of Li₂O-B₂O₃-P₂O₅ glasses was studied in the correlation to the structural variation of glass network by using FTIR and Raman spectroscopy. The measured ionic conductivity of the electrolyte at room temperature increased with x and y. The maximum conductivity of this glass system was 1.6 × 10⁻⁷ Ω⁻¹ cm⁻¹ for 0.45Li₂O-0.275B₂O₃-0.275P₂O₅ at room temperature. It was shown that the addition of P₂O₅ reduces the tendency of devitrification and increases the maximum amount of Li₂O added into glass former without devitrification. As Li₂O and B₂O₃ contents increased, the conductivity of glass electrolyte increased due to the increase of three-coordinated [BO₃] with a non-bridging oxygen (NBO).     

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.     

Tunable luminescence properties and efficient energy transfer in Eu,Mn co-doped Ba2MgP4O13

A series of Ba₂Mg_1−xMn_xP₄O₁₃ (x = 0-1.0) and Ba_1.94Eu_0.06Mg_1−xMn_xP₄O₁₃ (x = 0-0.15) phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), the photoluminescence spectra, and the decay curves are investigated. XRD analysis shows that the maximum tolerable substitution of Mn²⁺ for Mg is about 50 mol% in Ba₂MgP₄O₁₃. Mn²⁺-singly doped Ba₂MgP₄O₁₃ shows weak red-luminescence peaked at about 615 nm. The Eu²⁺/Mn²⁺ co-doped phosphor emits two distinctive luminescence bands: a blue one centered at 430 nm originating from Eu²⁺ and a broad red-emitting one peaked at 615 nm from Mn²⁺ ions. The luminescence of Mn²⁺ ions can be greatly enhanced with the co-doping of Eu²⁺ in Ba₂MgP₄O₁₃. The efficient energy transfer from Eu²⁺ to Mn²⁺ is verified by the excitation and emission spectra together with the luminescence decay curves. The emission colors could be tuned from the blue to the red-purple and eventually to the deep red. The resonance-type energy transfer via a dipole-quadrupole interaction mechanism is supported by the decay lifetime data. The energy transfer efficiency and the critical distance are calculated and discussed. The temperature dependent luminescence spectra of the Eu²⁺/Mn²⁺ co-doped phosphor show a good thermal stability on quenching effect.     

Synthesis and emission analysis of RE (Eu or Dy):Li2TiO3 ceramics

The development and photoluminescence analysis of Eu³⁺or Dy³⁺ ions in the matrix of lithium titanate (Li₂TiO₃) ceramics by using a solid state reaction method are reported. Emission spectra of Eu³⁺:Li₂TiO₃ ceramics have shown strong red emission at 611 nm (⁵D₀ → ⁷F₂) with λ_exci = 392 nm (⁷F₀ → ⁵L₆) and from the Dy³⁺:Li₂TiO₃, a blue emission at 493 nm (⁴F_9/2 → ⁶H_15/2) and also an yellow emission at 582 nm (⁴F_9/2 → ⁶H_13/2) have been observed with λ_exci = 366 nm (⁶H_15/2 → ⁶P_5/2). Both the rare-earth ions containing ceramics have displayed their brighter emission performance from their measured spectral results. In addition, X-ray diffraction (XRD), Fourier transform infra red (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) have been used to characterize the structural properties of (Eu³⁺ or Dy³⁺):Li₂TiO₃ ceramics.     

Enhanced thermoelectric properties induced by chemical pressure in Ca3Co4O9

We report the investigation of boron substitution on structural, electrical, thermal, and thermoelectric properties of Ca_3−xB_xCo₄O₉ (x=0, 0.5, 0.75, and 1) in the temperature range between 300 K and 5 K. X-ray diffraction studies show that the Ca₃Co₄O₉ phase is successfully preserved as the majority phase in the x=0.5 sample despite the small size of boron ions. Electrical transport measurements confirm that B³⁺ substitution for Ca²⁺ causes an increase in resistivity due to the decrease in carrier concentration. x=0.5 sample is found to have a Seebeck coefficient of 181 μV/K at room temperature which is ~1.5 times higher than that of the pure Ca₃Co₄O₉. Our results indicate that the chemical pressure due to the large ionic radii difference between B³⁺ (0.27 Å) and Ca²⁺ (1 Å) enhances the thermoelectric properties as long as the unique crystal structure of Ca₃Co₄O₉ is preserved.     

Preparation and cycling performance of Aland F co-substituted compounds Li4AlxTi5−xFyO12−y

Li₄Al_xTi_5−xF_yO_12−y compounds were prepared by a solid-state reaction method. Phase analyses demonstrated that both Al³⁺ and F⁻ ions entered the structure of spinel-type Li₄Ti₅O₁₂. Charge-discharge cycling results at a constant current density of 0.15 mA cm⁻² between the cut-off voltages of 2.5 and 0.5 V showed that the Al³⁺ and F⁻ substitutions improved the first total discharge capacity of Li₄Ti₅O₁₂. However, Al³⁺ substitution greatly increased the reversible capacity and cycling stability of Li₄Ti₅O₁₂ while F⁻ substitution decreased its reversible capacity and cycling stability slightly. The electrochemical performance of the Al³⁺-F⁻-co-substituted specimen was better than the F⁻-substituted one but worse than the Al³⁺-substituted one.     

Preparation and electrochemical properties of LiCoO2-LiNi0.5Mn0.5O2-Li2MnO3 solid solutions with high Mn contents

The solid solutions LiCoO₂-LiNi_1/2Mn_1/2O₂-Li₂MnO₃ with higher Mn content have been prepared by a spray drying method between 750 and 950 °C and their electrochemical performances have also been characterized. The effects of the Li content on the structure and electrochemical performance of the samples have been studied. It was found that their lattice parameters a, c and V increase with the increase in Ni content and the decrease in Co content. The solid solutions xLiCoO₂-yLiNi_1/2Mn_1/2O₂-(1−x−y)Li₂MnO₃ with x = 0.18, 0.27 and y = 0.2 have the largest discharge capacity, which is more than 200 mAh/g in the voltages of 3.0-4.6 V. It is believed that the optimum Co content x in xLiCoO₂-yLiNi_1/2Mn_1/2O₂-(1−x−y)Li₂MnO₃ is between 0.2 and 0.3 in the charge-discharge voltage range of 3.0-4.6 V. The solid solutions xLiCoO₂-yLiNi_1/2Mn_1/2O₂-(1−x−y)Li₂MnO₃ with x = 0.18-0.36 and y = 0.2 have the excellent cycling performance and the capacity retention attains to almost 100% after 50 cycles. Moreover, it is found that the discharge capacity gradually increases with the increment of cycle number especially in the initial 10 cycles. XRD showed that the layered structure has been kept all the time in 20 cycles, which is perhaps the reason why the sample has the excellent cycling performance.     

The effect of concentration of Dy ions on luminescence properties of Y2O2S:Dy,Mg, Ti phosphors

Y₂O₂S:Dy³⁺, Mg²⁺, Ti⁴⁺ white-light long-lasting phosphors were synthesized by the sol–gel method. The effect of Dy³⁺ doping concentration on the luminescence properties was investigated. The samples were characterized by X-ray diffraction, photoluminescence spectroscopy and thermally stimulated spectrometry. The samples doped with different concentrations of Dy³⁺ ions were composed of the pure Y₂O₂S phase. Under 359 nm UV excitation, the phosphor presented white luminescence due to mixing of the dominating emissions centered at 488 nm (blue) and 579 nm (yellow), corresponding to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions of Dy³⁺, respectively. When Dy³⁺ concentration was 1 mol%, the CIE chromaticity diagram was (0.375,0.374), and the decay time could last for over 65 min (≥1 mcd/m²).     

Insignificant impact of designed oxygen release from high capacity Li[(Ni1/2Mn1/2)xCoy(Li1/3Mn2/3)1/3]O2 (x + y = 2/3) positive electrodes during the cycling of Li-ion cells

The properties of graphite/Li[(Ni_0.5Mn_0.5)_xCo_y(Li_1/3Mn_2/3)_1/3]O₂ (x + y = 2/3, y = 1/12 and 1/6) Li-ion cells are reported. There is an extended plateau near 4.5 V during the first charging of the cells that corresponds to the simultaneous removal of Li and oxygen from the Li[(Ni_0.5Mn_0.5)_xCo_y(Li_1/3Mn_2/3)_1/3]O₂ (x + y = 2/3, y = 1/12 and 1/6) electrodes. The release of this oxygen directly within a Li-ion cell has been a cause for concern. However, it was found that subsequent to O₂ release, Li-ion cells delivered a high reversible positive electrode specific capacity near 250 mAh/g at C/30 between 2.5 and 4.8 V, the cells did not display increased irreversible capacity relative to counterparts having Li metal negative electrodes and the cells retained 85% of their initial capacity after 70 cycles at C/6 between 2.5 and 4.6 V. Therefore, the O₂ released during the first charge does not significantly impact the electrochemical properties of graphite/Li[(Ni_0.5Mn_0.5)_xCo_y(Li_1/3Mn_2/3)_1/3]O₂ (x + y = 2/3) lithium-ion cells.     

A reddish orange stoichiometric phosphor LiEu(PO3)4 for white light-emitting diodes

Stoichiometric phosphors LiGd_1−xEu_x(PO₃)₄(x=0, 0.2, 0.4, 0.6, 0.8, 1.0) were synthesized via traditional solid state reactions. The X-ray powder diffraction measurements show that all prepared samples are isostructural with LiNd(PO₃)₄. Eu³⁺ doped phosphors can emit intense reddish orange light under the excitation of near ultraviolet light from 370 to 410 nm. The strongest two at 591 and 613 nm can be attributed to the transitions from excited state ⁵D₀ to ground states ⁷F₁ and ⁷F₂, respectively. The typical chromaticity coordinates (x=0.620, y=0.368) of Eu³⁺ doped phosphors are in red area. The recorded absorbance spectra indicate that there is effective absorbance in the near UV region for all Eu³⁺ doped samples. Present research indicates that LiGd_1–xEu_x(PO₃)₄ is a promising phosphor for white light-emitting diodes.     

Preparation and characterization of novel spinel Li4Ti5O12−xBrx anode materials

Br-doped Li₄Ti₅O₁₂ in the form of Li₄Ti₅O_12−xBr_x (0 ≤ x ≤ 0.3) compounds were successfully synthesized via solid state reaction. The structure and electrochemical properties of the spinel Li₄Ti₅O_12−xBr_x (0 ≤ x ≤ 0.3) materials were investigated. The Li₄Ti₅O_12−xBr_x (x = 0.2) presents the best discharge capacity among all the samples, and shows better reversibility and higher cyclic stability compared with pristine Li₄Ti₅O₁₂, especially at high current rates. When the discharge rate was 0.5 C, the Li₄Ti₅O_12−xBr_x (x = 0.2) sample presented the excellent discharge capacity of 172 mAh g⁻¹, which was very close to its theoretical capacity (175 mAh g⁻¹), while that of the pristine Li₄Ti₅O₁₂ was 123.2 mAh g⁻¹ only.     

Preparation,structural and luminescent properties of YAl3(BO3)4:Dy phosphor for white light-emission under UV excitation

A series of YAl₃(BO₃)₄ phosphors doped with different concentrations of Dy₂O₃ (0.1≤x≤5 mol%) were prepared by solid-state reaction method. The crystallization process of the precursor has been examined by differential thermal analysis (DTA) measurements. The phase purity and surface morphological features were characterized by X-ray diffraction (XRD) and scanning electron microscopic (SEM) investigations. The YAl₃(BO₃)₄ nanocrystals obtained were found to be about 45 nm in size and have the trigonal structure with some agglomeration. Fourier transform infrared (FTIR) and energy dispersive X-ray spectra (EDS) measurements were carried out to understand the compositional and elemental analysis. The characteristics emission peaks of Dy³⁺ ion corresponding to the transitions of ⁴F_9/2→⁶H_15/2 at 485 nm and ⁴F_9/2→⁶H_13/2 at 576 nm were observed in the emission spectra. The luminescence quenching noticed at higher Dy₂O₃ concentrations is due to the exchange interaction among the excited Dy³⁺ ions.     

White emitting Dy3+ activated perovskite titanates and energy transfer by Eu3+ codoping

Perovskite type titanate phosphors Sr_0.97−xDy_0.03Li_xTi_1−xNb_xO₃, Sr_0.9−xDy_xLi_0.1Ti_0.9Nb_0.1O₃ and Sr_0.87−yDy_0.03Eu_yLi_0.1Ti_0.9Nb_0.1O₃ were prepared by conventional solid state method. Herein, white light emission from Sr_0.9−xDy_xLi_0.1Ti_0.9Nb_0.1O₃ phosphors and the lowering of its color temperature through codoping with Eu³⁺ ions are reported. Raman measurements have shown that the incorporation of dopants alters the vibrational properties of these phosphors significantly, indicating the reduction of the local symmetry in the crystal lattice. The addition of LiNbO₃ in SrTiO₃:Dy³⁺ phosphor enhances the luminescence intensity and the yellow to blue ratio resulting in emission of high quality white light with color coordinates corresponding to that of standard white. Life time measurements and data fits of Sr_0.9−xDy_xLi_0.1Ti_0.9Nb_0.1O₃ phosphors revealed the biexponential behaviour of luminescence decay profiles. From Judd-Ofelt analysis it is found that the intensity parameter Ω₂ increases with Dy³⁺ concentration and a quantum efficiency of 90.4% was obtained for optimum concentration. In the case of Dy³⁺ and Eu³⁺ codoped phosphors, the color coordinates are found to be sensitive to the Eu³⁺ concentration and the highest energy transfer efficiency of 92% was obtained for the phosphor doped with 10 mol% Eu³⁺. The emission color changes from cold white to reddish orange when the wavelength of excitation alters from 452 to 388 nm, since the energy transfer mechanism alone take place under 452 nm excitation and both direct absorption and the energy transfer mechanism occurs under 388 nm excitation.     

Synthesis and electrochemical properties of Co-doped Li3V2(PO4)3 cathode materials for lithium-ion batteries

Co-doped Li₃V_2−xCo_x(PO₄)₃/C (x = 0.00, 0.03, 0.05, 0.10, 0.13 or 0.15) compounds were prepared via a solid-state reaction. The Rietveld refinement results indicated that single-phase Li₃V_2−xCo_x(PO₄)₃/C (0 ≤ x ≤ 0.15) with a monoclinic structure was obtained. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the cobalt is present in the +2 oxidation state in Li₃V_2−xCo_x(PO₄)₃. XPS studies also revealed that V⁴⁺ and V³⁺ ions were present in the Co²⁺-doped system. The initial specific capacity decreased as the Co-doping content increased, increasing monotonically with Co content for x > 0.10. Differential capacity curves of Li₃V_2−xCo_x(PO₄)₃/C compounds showed that the voltage peaks associated with the extraction of three Li⁺ ions shifted to higher voltages with an increase in Co content, and when the Co²⁺-doping content reached 0.15, the peak positions returned to those of the unsubstituted Li₃V₂(PO₄)₃ phase. For the Li₃V_1.85Co_0.15(PO₄)₃/C compound, the initial capacity was 163.3 mAh/g (109.4% of the initial capacity of the undoped Li₃V₂(PO₄)₃) and 73.4% capacity retention was observed after 50 cycles at a 0.1 C charge/discharge rate. The doping of Co²⁺into V sites should be favorable for the structural stability of Li₃V_2−xCo_x(PO₄)₃/C compounds and so moderate the volume changes (expansion/contraction) seen during the reversible Li⁺ extraction/insertion, thus resulting in the improvement of cell cycling ability.     

The doping concentration dependent tunable yellow luminescence of Sr5(PO4)2(SiO4):Eu

Color tunable yellow-emitting phosphors of Sr_5−5xEu_5x(PO₄)₂SiO₄ (x = 0.05-0.15) were prepared by conventional solid-state reaction method. The X-ray powder diffraction patterns, the photoluminescence excitation and emission spectra were measured. The main excitation bands of the phosphors locate at a broad band extending from 300 to 500 nm, which can match the emission of ultraviolet- and blue-emitting diode chips. The tunable luminescence color was realized by the changing Eu²⁺ doping in Sr₅(PO₄)₂SiO₄. The structure and luminescence properties were investigated. Sr_5−5x(PO₄)₂SiO₄:Eu_5x displays two typical luminescence centers, which originate from two different Sr²⁺ (Eu²⁺) sites in the host. The site-occupation, the luminescence intensity and energy transfer between the Eu²⁺ ions occupying two different crystallographic Sr²⁺ sites were discussed on the base of the luminescence spectra and crystal structure. This is helpful to improve this phosphor for a potential application as a white light emitting diode phosphor.     

Influence of the tetravalent cation on the high-voltage electrochemical activity of LiNi0.5M1.5O4 spinel cathode materials

The electrochemical properties of substituted LiNi_0.5Mn_1.5−xM_xO₄ spinels at high potential (>4 V vs Li⁺/Li) have been investigated for M = Ti and Ru, in order to determine the role of the tetravalent cation in such systems where nickel is a priori the only electroactive species. These systems are found to form extended solid solutions (up to x = 1.3 and x = 1.0 for Ti and Ru, respectively) that were characterized by X-ray diffraction and Raman spectroscopy. Titanium substitution induces a drastic decrease in high potential electrochemical capacity, whereas the capacity is maintained and the kinetics are even improved in the presence of ruthenium. These results are completed by new results on the Li_4−2xNi_3xTi_5−xO₁₂ spinel system, which shows not any high potential activity in spite of the presence of up to 0.5 Ni²⁺ per spinel formula unit on the octahedral site. Taking into account previous data on LiNi_0.5Ge_1.5O₄, we clearly show that even if the tetravalent cation does not participate in the overall redox reaction, electrochemical activity is only possible when nickel is surrounded by tetravalent cations able to accept a local variation of valence (Mn, Ru), whereas full-shell cations such as Ti⁴⁺ and Ge⁴⁺ block the necessary electron transfer pathways in the spinel oxide electrode.     

Relationship between electrochemical behavior and Li/vacancy arrangement in ramsdellite type Li2+xTi3O7

The changes of Li⁺/vacancy arrangement in Li_2+xTi₃O₇ with a ramsdellite-type structure upon topo-electrochemical Li⁺ insertion were investigated by the entropy measurement of reaction combined with the Monte Carlo simulation. The experimental entropy measurement was conducted by potentiometric and calorimetrical methods. The obtained experimental data were in good accordance with simulated results.The results indicated that the ordered Li⁺/vacancy arrangement appeared at the compositions of x ∼ 0.45 and ∼1.20, where the observed entropy of reaction humped. The ordering of Li/vacancy were also indicated at the composition x ∼ 0.24 and 1.16 in Li_2+xTi₃O₇ by the Monte Carlo simulation which considers the most stable Li/vacancy arrangement in terms of Coulombic interaction. This substantial agreement between electrochemical behaviors and computational results confirmed that the formation of superstructure arising from Li/vacancy arrangement during the electrochemical reaction deeply related to the atomic level Coulombic interactions.