Synthesis and characterization of pristine Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript> and Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript>/C cathode materials for lithium ion batteries

The cathode materials, pristine Li₂MnSiO₄ and carbon-coated Li₂MnSiO₄ (Li₂MnSiO₄/C), were synthesized by the sol–gel method. Power X-ray diffraction and scanning electron microscopy analyses show that the presence of carbon during synthesis can weaken the formation of impurities in the final product and decrease the particle size of the final product. The effects of carbon coating on electrochemical characteristics were investigated by galvanostatic cycling test and electrochemical impedance spectroscopy. The galvanostatic cycling test results indicate that Li₂MnSiO₄/C cathode exhibits better electrochemical performance with an initial discharge capacity of 134.4 mAh g⁻¹ and a capacity retention of 63.9 mAh g⁻¹ after 20 cycles. Electrochemical impedance analyses confirm that carbon coating can increase electronic conductivity, which results in good electrochemical performance of Li₂MnSiO₄/C cathode. The two semicircles and the large arc obtained in this study can be attributed to the migration of lithium ions through the solid electrolyte interphase films, the electronic properties of the material, and the charge transfer step, respectively.     

Preparation of carbon encapsulated Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode material for lithium ion battery through pre-coating method

Carbon encapsulated Li₄Ti₅O₁₂ (C/Li₄Ti₅O₁₂) anode material for lithium ion battery was prepared by using the pre-coat method of two steps, and the TiO₂ was pre coated before the reaction with Li₂CO₃. The structure and morphology of the resultant C/Li₄Ti₅O₁₂ materials were characterized by X-ray diffraction (XRD) and scanning microscopy (SEM). Electrochemical tests showed that at 0.1 C, the initial discharge capacity was 169.9 mAh g^?1, and the discharge capacity was 80 mAh g^?1 at 5 C. After 100 cycles at 2 C, the discharge specific capacity was 108.5 mAh g^?1. Compare with one step coating method, results showed the C/Li₄Ti₅O₁₂ prepared by pre-coat method can reduce the particle’s size and effectively improve the electrochemical performance.     

Improvement in rate capability of lithium-rich cathode material Li[Li<Subscript>0.2</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>Mn<Subscript>0.54</Subscript>]O<Subscript>2</Subscript> by Mo substitution

Lithium-rich cathode material Li[Li_0.2Ni_0.13Co_0.13Mn_0.54]O₂ doped with trace Mo is successfully synthesized by a sol-gel method. The X-ray diffraction patterns show that trace Mo substitution increases the inter-layer space of the material, of which is benefiting to lithium ion insertion/extraction among the electrode materials. The (CV) tests demonstrate the decrease of polarization, and on the other hand, the lithium ion diffusion coefficient (D _Li) of the modified material turns out to be larger, which indicates a faster electrochemical process. As a result, the Mo doped material possesses high rate performance and good cycling stability, and the initial discharge capacity reaches 149.3 mAh g^?1 at a current density of 5.0 °C, and the residual capacity is 144.0 mAh g^?1 after 50 cycles with capacity retention of 96.5 % in the potential range of 2.0–4.8 V at room temperature.     

Urea-assisted solvothermal synthesis of monodisperse multiporous hierarchical micro/nanostructured ZnCo<Subscript>2</Subscript>O<Subscript>4</Subscript> microspheres and their lithium storage properties

High-quality monodisperse multiporous hierarchical micro/nanostructured ZnCo₂O₄ microspheres have been fabricated by calcinating the Zn_1/3Co_2/3CO₃ precursor prepared by urea-assisted solvothermal method. The as-prepared products are characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), and Brunauer-Emmett-Teller (BET) measurement to study the crystal phase and morphology. When tested as anode material for lithium ion batteries, the multiporous ZnCo₂O₄ microspheres exhibit an initial discharge capacity of 1,369 mAh g^?1 (3,244.5 F cm^?3) and retain stable capacity of 800 mAh g^?1 (1,896 F cm^?3) after 30 cycles. It should be noted that the good electrochemical performances can be attributed to the porous structure composed of interconnected nanoscale particles, which can promote electrolyte diffusion and reduce volume change during discharge/charge processes. More importantly, this ZnCo₂O₄ 3D hierarchical structures provide a large number of active surface position for Li⁺ diffusion, which may contribute to the improved electrochemical performance towards lithium storage.     

Improved electrochemical performance of Li<Subscript>1.2</Subscript>Ni<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>O<Subscript>2</Subscript> cathode material with fast ionic conductor Li<Subscript>3</Subscript>VO<Subscript>4</Subscript> coating

Layered lithium-enriched nickel manganese oxides Li_1.2Ni_0.2Mn_0.6O₂ have been synthesized and coated by fast ionic conductor Li₃VO₄ with varying amounts (1, 3, and 5 wt%) in this paper. The effect of Li₃VO₄ on the physical and electrochemical properties of Li_1.2Ni_0.2Mn_0.6O₂ has been discussed through the characterizations of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), discharge, cyclic performance, rate capability, and electrochemical impedance spectroscopy (EIS). The discharge capacity and coulomb efficiency of Li_1.2Ni_0.2Mn_0.6O₂ in the first cycle have been improved after Li₃VO₄ coating. And, the 3 wt% Li₃VO₄-coated Li_1.2Ni_0.2Mn_0.6O₂ shows the best discharge capacity (246.8 mAh g^?1), capacity retention (97.3 % for 50 cycles), and rate capability (90.4 mAh g^?1 at 10 C). Electrochemical impedance spectroscopy (EIS) results show that the R _ct of Li_1.2Ni_0.2Mn_0.6O₂ electrode decreases after Li₃VO₄ coating, which is due to high lithium ion diffusion coefficient of Li₃VO₄, is responsible for superior rate capability.     

A novel approach to employ Li<Subscript>2</Subscript>MnSiO<Subscript>4</Subscript> as anode active material for lithium batteries

In the present paper, we describe utilization of cathode active material as anode active material, for example, Li₂MnSiO₄. The lithium manganese silicate has been successfully synthesized by solid-state reaction method. The X-ray diffraction pattern confirms the orthorhombic structure with Pmn2 ₁ space group. The Li/Li₂MnSiO₄ cell delivered the initial discharge capacity of 420 mA h g⁻¹, which is 110 mA h g⁻¹ higher than graphitic anodes. The electrochemical reversibility and solid electrolyte interface formation of the Li₂MnSiO₄ electrode was emphasized by cyclic voltammetry.     

Fabrication and electrochemical investigation of Li<Subscript>0.5</Subscript>TiO<Subscript>2</Subscript> as anode materials for lithium ion batteries

Hexagonal and cubic Li_0.5TiO₂ particles have been fabricated through magnesiothermic reduction of Li₂TiO₃ particles in a temperature range of 600 to 640 °C. The prolonged reduction time results in lattice transition from hexagonal to cubic structure of Li_0.5TiO₂. Their microstructures, valance state, chemical composition, as well as electrochemical performance as anode candidates for lithium ion batteries have been characterized and evaluated. The hexagonal Li_0.5TiO₂ exhibits better electrochemical activity compared with the cubic one. Further, the carbon-coated hexagonal Li_0.5TiO₂ displays improved electrochemical performance with initial reversible capacity of 176.6 mAh g^?1 and excellent cyclic behavior except capacity fading in the initial 10 cycles, which demonstrate a novel anode candidate for long lifetime lithium ion batteries.     

Preparation and electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/Ti<Subscript>4</Subscript>O<Subscript>7</Subscript> composite for lithium-ion batteries

In order to improve the rate capability of Li₄Ti₅O₁₂, Ti₄O₇ powder was successfully fabricated by improved hydrogen reduction method, then a dual-phase composite Li₄Ti₅O₁₂/Ti₄O₇ has been synthesized as anode material for lithium-ion batteries. It is found that the Li₄Ti₅O₁₂/Ti₄O₇ composite shows higher reversible capacity and better rate capability compared to Li₄Ti₅O₁₂. According to the charge-discharge tests, the Li₄Ti₅O₁₂/Ti₄O₇ composite exhibits excellent rate capability of 172.3 mAh g^?1 at 0.2 C, which is close to the theoretical value of the spinel Li₄Ti₅O₁₂. More impressively, the reversible capacity of Li₄Ti₅O₁₂/Ti₄O₇ composite is 103.1 mAh g^?1 at the current density of 20 C after 100th cycles, and it maintains 84.8% of the initial discharge capacity, whereas that of the bare spinel Li₄Ti₅O₁₂ is only 22.3 mAh g^?1 with a capacity retention of 31.1%. The results indicate that Li₄Ti₅O₁₂/Ti₄O₇ composite could be a promising anode material with relative high capacity and good rate capability for lithium-ion batteries.     

Investigations on the synthesis and electrochemical performance of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C by different methods

Li₃V₂(PO₄)₃/C samples were synthesized by two different synthesis methods. Their influence on electrochemical performances of Li₃V₂(PO₄)₃/C as cathode materials for lithium-ion batteries was investigated. The structure and morphology of Li₃V₂(PO₄)₃/C samples were characterized by X-ray diffraction and scanning electron microscopy. Electrochemical performance was characterized by charge/discharge, cyclic voltammetry, and alternating current (AC) impedance measurements. Li₃V₂(PO₄)₃/C with smaller grain size showed better performances in terms of the discharge capacity and cycle stability. The improved electrochemical properties of the Li₃V₂(PO₄)₃/C were attributed to the decreasing grain size and enhanced electrical conductivity produced via low temperature route. AC impedance measurements also showed that the Li₃V₂(PO₄)₃/C synthesized by low temperature route significantly decreased the charge-transfer resistance and shortened the migration distance of lithium ion.     

Preparation and characterization of LiTi<Subscript>2</Subscript>O<Subscript>4</Subscript> anode material synthesized by one-step solid-state reaction

LiTi₂O₄ anode material for lithium-ion battery has been prepared by a novel one-step solid-state reaction method using Li₂CO₃, TiO₂, and carbon black as raw materials. X-ray diffraction, scanning electron microscopy, energy-dispersive spectrometry, and the determination of electrochemical properties show that the single phase of LiTi₂O₄ with spinel crystal structure is formed at 850?°C by this new method, and the lattice parameter is about 8.392?Å. The primary particle size of the LiTi₂O₄ powder is about 0.5–1.0 μm and its morphology is similar to a sphere. The lithium ion insertion voltage of LiTi₂O₄ anode material is about 1.50 V versus lithium metal, the initial discharge capacity is about 133.6 mAh g^-1, the charge–discharge voltage plateau is very flat, and no solid electrolyte interface film is formed when working potential is more than 1.0 V. The reaction reversibility and the cycling stability are excellent, and the high rate performance is good.     

Synthesis of spinel LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> as advanced cathode via a modified oxalate co-precipitation method

Spinel-type LiNi_0.5Mn_1.5O₄ (LNMO) cathode materials for lithium ion batteries have been synthesized via a modified oxalate co-precipitation method. By virtue of the co-precipitation of Li⁺ with transition metal ions, the target materials can be obtained through one-pot reaction without subsequent mixing with lithium salts. What’s more, a uniform distribution between the lithium and transition metal ions at molecular level could be realized, which is beneficial for final electrochemical performances. The physical and electrochemical properties of the material are characterized by XRD, TGA, EDS, FT-IR, SEM, CV, EIS, and charge/discharge tests. The results prove that the as-prepared material owns a cubic spinel structure with a space group of Fd-3m, high crystallinity, uniform particle size, and excellent electrochemical performances. A higher initial capacity and superior rate performance are delivered compared with that of material by conventional co-precipitation method. High capacities of 131.7 and 104.0 mAh g^?1 could be displayed at 0.5 and 10 C, respectively. Excellent cycle stability is also demonstrated with more than 98.5 % capacity retention after 100 cycles at 1 C.     

Electrochemical comparison of LiFe<Subscript>0.4</Subscript>Mn<Subscript>0.595</Subscript>Cr<Subscript>0.005</Subscript>PO<Subscript>4</Subscript>/C and LiMnPO<Subscript>4</Subscript>/C cathode materials

A comparison of electrochemical performance between LiFe_0.4Mn_0.595Cr_0.005PO₄/C and LiMnPO₄/C cathode materials was conducted in this paper. The cathode samples were synthesized by a nano-milling-assisted solid-state process using caramel as carbon sources. The prepared samples were investigated by XRD, SEM, TEM, energy-dispersive X-ray spectroscopy (EDAX), powder conductivity test (PCT), carbon-sulfur analysis, electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge cycling. The results showed that LiFe_0.4Mn_0.595Cr_0.005PO₄/C exhibited high specific capacity and high energy density. The initial discharge capacity of LiFe_0.4Mn_0.595Cr_0.005PO₄/C was 163.6 mAh g^?1 at 0.1C (1C = 160 mA g^?1), compared to 112.3 mAh g^?1 for LiMnPO₄/C. Moreover, the Fe/Cr-substituted sample showed good cycle stability and rate performance. The capacity retention of LiFe_0.4Mn_0.595Cr_0.005PO₄/C was 98.84 % over 100 charge-discharge cycles, while it was only 86.64 % for the pristine LiMnPO₄/C. These results indicated that Fe/Cr substitution enhanced the electronic conductivity for the prepared sample and facilitated the Li⁺ diffusion in the structure. Furthermore, LiFe_0.4Mn_0.595Cr_0.005PO₄/C composite presented high energy density (606 Wh kg^?1) and high power density (574 W kg^?1), thus suggested great potential application in lithium ion batteries (LIBs).     

Ionic liquid-based electrolyte with dual-functional LiDFOB additive toward high-performance LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> batteries

Manganese oxide-based cathodes are one of the most promising lithium-ion battery (LIB) cathode materials due to their cost-effectiveness, high discharge voltage plateau (above 4.0 V vs. Li/Li⁺), superior rate capability, and environmental benignity. However, these batteries using conventional LiPF₆-based electrolytes suffer from Mn dissolution and poor cyclic capability at elevated temperature. In this paper, the ionic liquid (IL)-based electrolytes, consisting of 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfon)imidate (PYR_1,4-TFSI), propylene carbonate (PC), lithium bis(trifluoromethanesulfon)imide (LiTFSI), and lithium oxalyldifluoroborate (LiDFOB) additive, were explored for improving the high temperature performance of the LiMn₂O₄ batteries. It was demonstrated that LiTFSI-ILs/PC electrolyte associated with LiDFOB addition possessed less Mn dissolution and Al corrosion at the elevated temperature in LiMn₂O₄/Li batteries. Cyclic voltammetry and electrochemical impedance spectroscopy implied that this kind of electrolyte also contributed to the formation of a highly stable solid electrolyte interface (SEI), which was in accordance with the polarization measurement and the Li deposition morphology of the symmetric lithium metal cell, thus beneficial for improving the cycling performance of the LiMn₂O₄ batteries at the elevated temperature. Cyclic voltammetry and electrochemical impedance spectroscopy implied that the cells using this kind of electrolyte exhibited better interfacial stability, which was further verified by the polarization measurement and the Li deposition morphology of the symmetric lithium metal cell, thus beneficial for improving the cycling performance of the LiMn₂O₄ batteries at the elevated temperature. These unique characteristics would endow this kind of electrolyte a very promising candidate for the manganese oxide-based batteries.     

A lithium salt additive Li<Subscript>2</Subscript>ZrF<Subscript>6</Subscript> for enhancing the electrochemical performance of high-voltage LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> cathode

In this work, Li₂ZrF₆, a lithium salt additive, is reported to improve the interface stability of LiNi_0.5Mn_1.5O₄ (LNMO)/electrolyte interface under high voltage (4.9 V vs Li/Li⁺). Li₂ZrF₆ is an effective additive to serve as an in situ surface coating material for high-voltage LNMO half cells. A protective SEI layer is formed on the electrode surface due to the involvement of Li₂ZrF₆ during the formation of SEI layer. Charge/discharge tests show that 0.15 mol L^?1 Li₂ZrF₆ is the optimal concentration for the LiNi_0.5Mn_1.5O₄ electrode and it can improve the cycling performance and rate property of LNMO/Li half cells. The results obtained by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) demonstrate that Li₂ZrF₆ can facilitate the formation of a thin, uniform, and stable solid electrolyte interface (SEI) layer. This layer inhibits the oxidation decomposition of the electrolyte and suppresses the dissolution of the cathode materials, resulting in improved electrochemical performances.     

Nano Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> as sulfur host for high-performance Li-S battery

S/Li₄Ti₅O₁₂ cathode with high lithium ionic conductivity was prepared for Li-S battery. Herein, nano Li₄Ti₅O₁₂ is used as sulfur host and fast Li⁺ conductor, which can adsorb effectively polysulfides and improve remarkably Li⁺ diffusion coefficient in sulfur cathode. At 0.5 C, S/Li₄Ti₅O₁₂ cathode has a stable discharge capacity of 616 mAh g^?1 at the 700th cycle and a capacity loss per cycle of 0.0196% from the second to the 700th cycle, but the corresponding values of S/C cathode are 437 mAh g^?1 and 0.0598%. Even at 2 C, the capacity loss per cycle of S/Li₄Ti₅O₁₂ cathode is only 0.0273% from the second to the 700th cycle. The results indicate that Li₄Ti₅O₁₂ as the sulfur host plays a key role on the high performance of Li-S battery due to reducing the shuttle effect and enhancing lithium ionic conductivity.     

Electrochemical properties of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C cathode materials synthesized via ethylene glycol-assisted solvothermal method

The Li₃V₂(PO₄)₃/C (LVP/C) cathode materials for lithium-ion batteries were synthesized via ethylene glycol-assisted solvothermal method. The phase composition, phase transition temperature, morphology, and fined microstructure were studied using X-ray diffraction (XRD), differential thermal analyzer (DTA), scanning electron microscope (SEM), and transmission electron microscope (TEM), respectively. The electrochemical properties, impedance, and electrical conductivity of LVP/C cathode materials were tested by channel battery analyzer, the electrochemical workstation, and the Hall test system, respectively. The results shown that the appropriate amount of water added to ethylene glycol solvent contributes to the synthesis of pure phase LVP. The LVP₁₀/C cathode material can exhibit discharge capacities of 128, 126, 126, 123, 124, and 114 mAh g^?1 at 0.1, 0.5, 2, 5, 10, and 20 C in the voltage range of 3.0–4.3 V, respectively. Meanwhile, it shows also a stable cycling performance with the capacity retention of 89.6% after 180 cycles at 20 C.     

LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.5</Subscript>O<Subscript>4</Subscript> hollow nano-micro hierarchical microspheres as advanced cathode for lithium ion batteries

The high-voltage spinel-type LiNi_0.5Mn_1.5O₄ (LNMO) is a promising cathode material for next-generation lithium ion batteries. In this study, hollow LNMO microspheres have been synthesized via co-precipitation method accompanied with high-temperature calcinations. The physical and electrochemical properties of the materials are characterized by x-ray diffraction (XRD), TGA, RAMAN, CV, scanning electron microscope (SEM), transmission electon microscopy (TEM), electrochemical impendence spectroscopy (EIS), and charge-discharge tests. The results prove that the microspheres combine hollow structures inward and own a cubic spinel structure with space group of Fd-3m, high crystallinity, and excellent electrochemical performances. With the short Li⁺ diffusion length and hollow structure, the hierarchical LNMO microspheres exhibit 138.2 and 108.5 mAh g^?1 at 0.5 and 10 C, respectively. Excellent cycle stability is also demonstrated with more than 98.8 and 88.2 % capacity retention after 100 cycles at 1 and 10 C, respectively.     

Spectral properties of a Nd<Superscript>3+</Superscript>-doped Li<Subscript>3</Subscript>Ba<Subscript>2</Subscript>Gd<Subscript>3</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>8</Subscript> crystal

The spectral properties of a promising laser material, ternary molybdate Li₃Ba₂Gd₃(MoO₄)₈:Nd³⁺, are studied (i.e., its optical absorption spectra, luminescence spectra, kinetic of luminescence decay, and temperature dependence of luminescence). Luminescence of the crystalline matrix is detected, and the temperature dependence of its intensity and reabsorption by neodymium are investigated.     

V<Subscript>2</Subscript>O<Subscript>5</Subscript>-SiO<Subscript>2</Subscript> hybrid as anode material for aqueous rechargeable lithium batteries

V₂O₅-SiO₂ hybrid material was fabricated by heat-treating a mixture of H₂SiO₃ and V₂O₅. SEM, TEM, XRD, and N₂ isotherm analyses were performed to characterize the morphology and structure details of the as-prepared V₂O₅-SiO₂. The possibility of using the as-prepared V₂O₅-SiO₂ as anode material for aqueous lithium-ion batteries was investigated. Potentiostatic and galvanostatic results indicated that the intercalation/de-intercalation of Li⁺ in this material in aqueous electrolyte was quasi-reversible. It was also found that a discharge capacity of up to 199.1 mAh g^?1 was obtained at a current density of 50 mA g^?1 in aqueous solution of 1 M Li₂SO₄, a value which is much higher than the available reported capacities of vanadium (+5) oxides in aqueous electrolytes.     

Electrospinning preparation of one-dimensional Co<Superscript>2+</Superscript>-doped Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> nanofibers for high-performance lithium ion battery

One-dimensional Co²⁺-doped Li₄Ti₅O₁₂ nanofibers with a diameter of approximately 500 nm have been synthesized via a one-step controllable electrospinning method. The Co²⁺-doped Li₄Ti₅O₁₂ nanofibers were systematically characterized by XRD, ICP, TEM, SEM, BET, EDS mapping, and XPS. Based on the cubic spinel structure and one-dimensional effect of Li₄Ti₅O₁₂, Co²⁺-doped Li₄Ti₅O₁₂ nanofibers exhibit the enlarged lattice volume, reduced particle size and enhanced electrical conductivity. More importantly, Co²⁺-doped Li₄Ti₅O₁₂ nanofibers as a lithium ion battery anode electrode performs superior electrochemical performance than undoped Li₄Ti₅O₁₂ electrode in terms of electrochemical measurements. Particularly, the reversible capacity of Co²⁺-doped Li₄Ti₅O₁₂ electrode reaches up to 140.1 mAh g^?1 and still maintains 136.5 mAh g^?1 after 200 cycles at a current rate of 5 C. Therefore, one-dimensional Co²⁺-doped Li₄Ti₅O₁₂ nanofiber electrodes, showing high reversible capacity and remarkable recycling property, could be a potential candidate as an anode material.