High lithium ion conducting Li2S–GeS2–P2S5 glass–ceramic solid electrolyte with sulfur additive for all solid-state lithium secondary batteries

Glass–ceramic Li₂S–GeS₂–P₂S₅ electrolytes were prepared by a single step ball milling (SSBM) process. Various compositions of Li_4−xGe_1−xP_xS₄ from x = 0.70 to x = 1.00 were systematically investigated. Structural analysis by X-ray diffraction (XRD) showed gradual increase of the lattice constant followed by significant phase change with increasing GeS₂. All-solid-state LiCoO₂/Li cells were tested by constant-current constant-voltage (CCCV) charge–discharge cycling at a current density of 50 μA cm⁻² between 2.5 and 4.3 V (vs. Li/Li⁺). In spite of the high conductivity of the solid-state electrolyte (SSE), LiCoO₂/Li cells showed a large irreversible reaction especially during the first charging cycle. Limitation of instability of Li₂S–GeS₂–P₂S₅ in contact with Li was solved by using double layer electrolyte configuration: Li/(Li₂S-P₂S₅/Li₂S–GeS₂–P₂S₅)/LiCoO₂. LiCoO₂ with SSEs heat-treated with elemental sulfur at elevated temperature exhibited a discharge capacity of 129 mA h g⁻¹ at the second cycle and considerably improved cycling stability.     

Fabrication of all-solid-state battery using Li5La3Ta2O12 ceramic electrolyte

The chemical and electrochemical properties of Li₅La₃Ta₂O₁₂ (LLTa) solid electrolyte were extensively investigated to determine its compatibility with an all-solid-state battery. A well-sintered LLTa pellet with a garnet-like structure was obtained after sintering at 1200 °C for 24 h. Li ion conductivity of the LLTa pellet was estimated to be 1.3×10⁻⁴ S cm⁻¹. The LLTa pellet was stable when in contact with lithium metal. This indicates that Li metal anode, which is the best anode material, can be applied with the LLTa system. A full cell composed of LiCoO₂/LLTa/Li configuration was constructed, and its electrochemical properties were tested. In the resulting cyclic voltammogram, a clear redox couple of LiCoO₂ was observed, implying that the all-solid-state battery with the Li metal anode was successfully operated at room temperature. The redox peaks of the battery were still observed even after one year of storage in an Ar-filled glove-box. It can be concluded that the LLTa electrolyte is a promising candidate for the all-solid-state battery because of its relatively high Li ion conductivity and good stability when in contact with Li metal anode and LiCoO₂ cathode.     

Examinations on 2.5 V Li[Li1/3Ti5/3]O4/Li[Li0.1Al0.1Mn1.8]O4 cells at −10, 25, and 55 °C for the first-generation 12 V lead-free batteries

Electrochemical behaviors of 2.5 V Li[Li_1/3Ti_5/3]O₄ (LTO)/Li[Li_0.1Al_0.1Mn_1.8]O₄ (LAMO) cells for the first-generation 12 V lead-free battery were examined at −10, 25, and 55 °C. The LTO/LAMO cells showed the same rechargeable capacity in temperature ranging from −10 to 55 °C when the cells were examined at 0.5 mA cm⁻² in cell potential ranging from 0 to 3.0 V. Capacity fading after 250 cycles was negligibly small at −10 °C. Rechargeable capacities, however, faded 5% at 25 °C and 15% at 55 °C after 250 cycles. In the discharged LTO/LAMO cell after 250 cycles at 55 °C, the state of charge (SOC) of the positive electrode was 16% while SOC of the negative electrode was 0%, indicated that the capacity fading was due to an imbalance in SOC between the positive and negative electrodes. To understand the progress of an imbalance in SOC, the LTO/LAMO cell with a lithium auxiliary electrode was fabricated and examined at 55 °C for 400 cycles, and the possible origin of capacity fading was discussed.     

Electrochemical performance of Li3V2(PO4)3/C cathode materials using stearic acid as a carbon source

The Li₃V₂(PO₄)₃/C cathode materials are synthesized by a simple solid-state reaction process using stearic acid as both reduction agent and carbon source. Scanning electron microscopy and transmission electron microscopy observations show that the Li₃V₂(PO₄)₃/C composite synthesized at 700 °C has uniform particle size distribution and fine carbon coating. The Li₃V₂(PO₄)₃/C shows a high initial discharge capacity of 130.6 and 124.4 mAh g⁻¹ between 3.0 and 4.3 V, and 185.9 and 140.9 mAh g⁻¹ between 3.0 and 4.8 V at 0.1 and 5 C, respectively. Even at a charge–discharge rate of 15 C, the Li₃V₂(PO₄)₃/C still can deliver a discharge capacity of 103.3 and 112.1 mAh g⁻¹ in the potential region of 3.0–4.3 V and 3.0–4.8 V, respectively. Based on the analysis of cyclic voltammograms and electrochemical impedance spectra, the apparent diffusion coefficients of Li ions in the composites are in the region of 1.09 × 10⁻⁹ and 4.95 × 10⁻⁸ cm² s⁻¹.     

Electrochemical properties of bare and Ta-substituted Nb2O5 nanostructures

In this work, bare and Ta-substituted Nb₂O₅ nanofibers are prepared by electrospinning followed by sintering at temperatures in the 800–1100 °C range for 1 h in air. Obtained bare and Ta-substituted Nb₂O₅ polymorphs are characterized by X-ray diffraction, scanning electron microscopy, density measurement, and Brunauer, Emmett and Teller surface area. Electrochemical properties are evaluated by cyclic voltammetry and galvanostatic techniques. Cycling performance of Nb₂O₅ structures prepared at temperature 800 °C, 900 °C, and 1100 °C shows following discharge capacity at the end of 10th cycle: 123, 140, and 164 (±3) mAh g⁻¹, respectively, in the voltage range 1.2–3.0 V and at current rate of 150 mA g⁻¹ (1.5 C rate). Heat treated composite electrode based on M-Nb₂O₅ (1100 °C) in argon atmosphere at 220 °C, shows an improved discharge capacity of 192 (±3) mAh g⁻¹ at the end of 10th cycle. The discharge capacity of Ta-substituted Nb₂O₅ prepared at 900 °C and 1100 °C showed a reversible capacity of 150, 202 (±3) mAh g⁻¹, respectively, in the voltage range 1.2–3.0 V and at current rate of 150 mA g⁻¹. Anodic electrochemical properties of M-Nb₂O₅ deliver a reversible capacity of 382 (±5) mAh g⁻¹ at the end of 25th cycle and Ta-substituted Nb₂O₅ prepared at 900 °C, 1000 °C and 1100 °C shows a reversible capacity of 205, 130 and 200 (±3) mAh g⁻¹ (at 25th cycle) in the range, 0.005–2.6 V, at current rate of 100 mA g⁻¹.     

Enhanced high rate capability of dual-phase Li4Ti5O12–TiO2 induced by pseudocapacitive effect

The dual-phase Li₄Ti₅O₁₂–TiO₂ nanocomposite is successfully synthesized by a hydrothermal route with adding thiourea. The electrochemical performance of the dual-phase nanocomposite as anode for lithium-ion batteries is investigated by the galvanostatic method, cyclic voltammetry and electrochemical impedance spectra. It is demonstrated that the dual-phase Li₄Ti₅O₁₂–TiO₂ nanocomposite presents the improved electrochemical performance over individual single phase Li₄Ti₅O₁₂ and anatase TiO₂ samples. After 300 cycles at 1 C, the dual-phase Li₄Ti₅O₁₂–TiO₂ nanocomposite can still maintain the large discharge capacity of 116 mAh g⁻¹. It indicates that the as-prepared nanocomposite can endure great changes of various discharge current densities to retain a good stability. The large discharge capacity of 132 mAh g⁻¹ is also obtained at the large current density of 1600 mA g⁻¹ upon cycling. In particular, as verified by the cyclic voltammetry, the pseudocapacitive effect is induced due to the presence of abundant phase interfaces in the dual-phase Li₄Ti₅O₁₂–TiO₂ nanocomposite, which is beneficial to the enhanced high rate capability and good cycle stability.     

Performance of electrochemically generated Li21Si5 phase for lithium-ion batteries

The nature of Li-Si alloy phases that are generated in electrochemical lithiation is examined as a function of temperature. The electrochemical lithiation is performed at 0.0 V (vs. Li/Li⁺) by short-circuiting an amorphous Si thin-film electrode with a Li metal counter electrode. At 25-85 °C, the well-known Li₁₅Si₄ phase (theoretical specific capacity = 3580 mA h g⁻¹) forms. At 100-120 °C, however, Li₂₁Si₅ (4008 mA h g⁻¹) that is known to be the most Li-rich phase in Li-Si system is generated. The crystallization into Li₂₁Si₅ is, however, so kinetically slow that it does not appear in the transient cycling experiment. The Li₂₁Si₅ phase is converted to amorphous Si upon de-lithiation, but the restoration back to the initial phase is only observed at 100-120 °C after a prolonged lithiation at 0.0 V. The cycleability of this phase is poor due to a successive Li trapping inside the Si matrix, which is caused by the formation of electrically isolated Si islands.     

Hollow CuFe2O4 spheres encapsulated in carbon shells as an anode material for rechargeable lithium-ion batteries

We report here a polymer-templated hydrothermal growth method and subsequent calcination to achieve carbon coated hollow CuFe₂O₄ spheres (H–CuFe₂O₄@C). This material, when used as anode for Li-ion battery, retains a high specific capacity of 550 mAh g⁻¹ even after the 70th cycle, which is much higher than those of both CuFe₂O₄@C (∼300 mAh g⁻¹) and H–CuFe₂O₄ (∼120 mAh g⁻¹). And galvanostatic cycling at different current densities reveals that a capacity of 480 mAh g⁻¹, 91% recovery of the specific capacity cycling at 100 mA g⁻¹, can be obtained even after 50 cycles running from 100 to 1600 mA g⁻¹. The significantly enhanced electrochemical performances of H–CuFe₂O₄@C with regard to Li-ion storage are ascribed to the following factors: (1) the hollow void, which could mitigate the pulverization of electrode and facilitate the lithium-ion, electron and electrolyte transport; (2) the conductive carbon coating, which could enhance the conductivity, alleviate the agglomeration problem, prevent the formation of an overly thick SEI film and buffer the electrode. Such a structural motif of H–CuFe₂O₄@C is promising, for electrode materials of LIBs, and points out a general strategy for creating other hollow-shell electrode materials with improved electrochemical performances.     

Carbon-coated Li2S cathode for improving the electrochemical properties of an all-solid-state lithium-sulfur battery using Li2S-P2S5 solid electrolyte

Li₂S is coated with carbon to improve the electrical conductivity of the composite cathode in all-solid-state lithium-sulfur batteries. Carbon is applied by thermal evaporation from a polyacrylonitrile (PAN) source at 600 °C for 5 h. It is shown that the carbon coating is impurity free, and the crystallinity of Li₂S is well maintained. The electronic conductivity of Li₂S is dramatically improved from 9.21 × 10^?9 S cm^?1 to 2.39 × 10^?2 S cm^?1 upon carbon coating. An all-solid-state battery prepared with the carbon-coated Li₂S shows a high initial capacity of 585 mAh g^?1 (g of Li₂S) that increases up to 730 mAh g^?1 (g of carbon-coated Li₂S) by the 10th cycle. This high capacity is stable throughout the 25 cycles tested, with an excellent coulombic efficiency of 99%. Carbon-coated Li₂S is advantageous for all-solid-state batteries due to the increased electrical conductivity, while allowing a reduction of the total carbon content present in the composite cathode.     

Properties of Li-graphite and LiFePO4 electrodes in LiPF6–sulfolane electrolyte

Sulfolane (also referred to as tetramethylene sulfone, TMS) containing LiPF₆ and vinylene carbonate (VC) was tested as a non-flammable electrolyte for a graphite |LiFePO₄ lithium-ion battery. Charging/discharging capacity of the LiFePO₄ electrode was ca. 150 mAh g⁻¹ (VC content 5 wt%). The capacity of the graphite electrode after 10 cycles establishes at the level of ca. 350 mAh g⁻¹ (C/10 rate). In the case of the full graphite |1 M LiPF₆ + TMS + VC 10 wt% |LiFePO₄ cell, both charging and discharging capacity (referred to cathode mass) stabilized at a value of ca. 120 mAh g⁻¹. Exchange current density for Li⁺ reduction on metallic lithium, estimated from electrochemical impedance spectroscopy (EIS) experiments, was j_o(Li/Li⁺) = 8.15 × 10⁻⁴ A cm⁻². Moreover, EIS suggests formation of the solid electrolyte interface (SEI) on lithium, lithiated graphite and LiFePO₄ electrodes, protecting them from further corrosion in contact with the liquid electrolyte. Scanning electron microscopy (SEM) images of pristine electrodes and those taken after electrochemical cycling showed changes which may be interpreted as a result of SEI formation. No graphite exfoliation was observed. The main decomposition peak of the LiPF₆ + TMS + VC electrolyte (TG/DTA experiment) was present at ca. 275 °C. The LiFePO₄(solid) + 1 M LiPF₆ + TMS + 10 wt% VC system shows a flash point of ca. 150 °C. This was much higher in comparison to that characteristic of a classical LiFePO₄ (solid) + 1 M LiPF₆ + 50 wt% EC + 50 wt% DMC system (T_f ≈ 37 °C).     

X-ray photoelectron spectroscopy and electrochemical behaviour of 4 V cathode, Li(Ni1/2Mn1/2)O2

Layered Li(Ni_1/2Mn_1/2)O₂ was prepared by the solution and mixed hydroxide methods, characterised by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and studied by cyclic voltammetry (CV) and charge discharge cycling in CC and CCCV modes at room temperature (r.t.) and at 50 °C. The XPS studies show about 8% of Ni³⁺ and Mn³⁺ ions are present in Li(Ni²⁺_1/2Mn_1/2⁴⁺)O₂ due to valency-degeneracy. The compound prepared at 950 °C, 12 h, solution method gives a second cycle discharge capacity of 150 mA h g⁻¹ (2.5-4.4 V) at a specific current of 30 mA g⁻¹ and retains 137 mA h g⁻¹ at the end of 40 cycles. CV shows that the redox process at 3.7-4.0 V corresponds to Ni²⁺↔Ni⁴⁺ and clear indication of Mn^3+/4+ couple was noted at 4.2-4.5 V. The observed capacity-fading (2.5-4.4 V) is shown to be contributed by the polarisation at the end of charging. The cathodic capacity is stable up to 40 cycles in the voltage window, 2.5-4.2 V both at room temperature and 50 °C.     

Preparation and Characterization of LiNi<Subscript>0.8</Subscript>Co<Subscript>0.2</Subscript>O<Subscript>2</Subscript> Synthesized by an Emulsion Drying Method

A layered LiNi_0.8Co_0.2O₂ solid solution, which is a promising cathode material for secondary lithium batteries, was successfully synthesized by an emulsion drying method. Because electrochemical properties significantly depend on the conditions of the synthesis, the calcination temperature was carefully determined on the basis of X-ray diffraction and TG studies. The prepared cathodes were characterized by means of SEM, BET, X-ray diffraction, Rietveld refinement, cyclic voltammetry and a charge-discharge experiment. From the Rietveld analysis, it was found that powder calcined at 800 °C for 12 h exhibits a well ordered and lower cation mixed layered structure than the others. The cyclic voltammetry experiment shows that phase transformation can be suppressed considerably by increasing the calcination temperature to 800 °C. The highest discharge capacity of 188.4 mA h g⁻¹ was obtained from the sample prepared at 800 °C. Furthermore, a high capacity retention ratio of 88.1% was found for the initial value after 50 cycles at a constant current density of 40 mA g⁻¹ between 2.7 V_Li/Li⁺ and 4.3 V_Li/Li⁺. In the rate capability test, the cathode delivered a higher discharge capacity of 153.1 mA h g⁻¹ at a 4 C (800 mA g⁻¹) rate.     

Effects of synthetic route on structure and electrochemical performance of Li3V2(PO4)3/C cathode materials

Three different synthetic routes, including solid-state reaction, sol–gel and hydrothermal methods are successfully used for preparation of Li₃V₂(PO₄)₃/C. Ascorbic acid is used as a reducing agent and/or as a chelating agent. The Li₃V₂(PO₄)₃/C synthesized by hydrothermal method with fine particles exhibits lower impedance and smaller potential difference values between oxidation and reduction peaks than those by solid-state reaction and sol–gel methods. Thus as cathode material for Li-ion batteries, the Li₃V₂(PO₄)₃/C synthesized by hydrothermal method shows higher discharge capacity, better rate capability and cyclic performance. Even at a high charge–discharge rate of 10 C, it still can deliver a discharge capacity of 101.4 mAh g⁻¹ and 106.6 mAh g⁻¹ in the potential range of 3.0–4.3 V and 3.0–4.8 V, respectively. The hydrothermal synthesis has been considered to be a competitive process to prepare Li₃V₂(PO₄)₃/C cathode materials with excellent electrochemical performances.     

Electrochemical properties and structural characterization of layered Li[Ni0.5Mn0.5]O2 cathode materials

Layered Li[Ni_0.5Mn_0.5]O₂ materials with high homogeneity and crystallinity were prepared using high speed ball milling. The Li[Ni_0.5Mn_0.5]O₂ electrode delivered a high discharge capacity of 152 mA h g⁻¹ between 2.8 and 4.3 V with excellent cycleability. The TEM analysis showed that the Li[Ni_0.5Mn_0.5]O₂ electrode went through a considerable morphological change without altering its initial layered structure while the electrode retained its initial discharge capacity even after 50 cycles.     

Synthesis and electrochemical performance of Li2FeSiO4/carbon/carbon nano-tubes for lithium ion battery

Li₂FeSiO₄/carbon/carbon nano-tubes (Li₂FeSiO₄/C/CNTs) and Li₂FeSiO₄/carbon (Li₂FeSiO₄/C) composites were synthesized by a traditional solid-state reaction method and characterized comparatively by X-ray diffraction, scanning electron microscopy, BET surface area measurement, galvanostatic charge-discharge and AC impedance spectroscopy, respectively. The results revealed that the Li₂FeSiO₄/C/CNT composite exhibited much better rate performance in comparison with the Li₂FeSiO₄/C composite. At 0.2 C, 5 C and 10 C, the former composite electrode delivered a discharge capacity of 142 mAh g⁻¹, 95 mAh g⁻¹, 80 mAh g⁻¹, respectively, and after 100 cycles at 1 C, the discharge capacity remained 95.1% of its initial value.     

High capacity ZnFe2O4 anode material for lithium ion batteries

A nanostructured ternary transition metal oxide, ZnFe₂O₄, is synthesized via the simple polymer pyrolysis method. The characteristics of the material are examined by thermogravimetry, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The electrochemical test results show that this method of ZnFe₂O₄ synthesis produces high specific capacities and good cycling performance, with an initial specific capacity as high as 1419.6 mAh g⁻¹ at first discharge that is maintained at over 800 mAh g⁻¹ even after 50 charge–discharge cycles. The electrode also presents a good rate capability, with a high rate of 4C (1C = 928 mA g⁻¹), a reversible specific capacity that can be as high as 400 mAh g⁻¹. ZnFe₂O₄ is a potential alternative to high-performance nanostructured anode material in lithium ion batteries.     

Electrochemical properties of nanostructured Li1.2V3O8 in aqueous LiNO3 solution

The amorphous hydrated precursor of Li_1.2V₃O₈ was synthesized by soft chemistry method, and then heat-treated in air at several temperatures within the range 200–400 °C. The heat-treatment changed its morphological, structural and charging/discharging performance. The product obtained upon the treatment at 300 °C, consisting of uniform, rod-shaped particles, 100–150 nm in diameter and 300–800 nm in length, displayed the best electrochemical performance in aqueous LiNO₃ solution. Its initial discharge capacity amounted to 136.8 mAh g⁻¹ at a rate of C/5, which upon 50 charging/discharging cycles decreased for only 12%.     

Preparation,structural and thermo-mechanical properties of lithium aluminum silicate glass–ceramics

Lithium aluminum silicate glasses of composition (wt%) 12.6Li₂O–71.7SiO₂–5.1Al₂O₃–4.9K₂O–3.2B₂O₃–2.5P₂O₅ were prepared by the melt quench technique. These glasses were converted to glass–ceramics based on DTA data. X-ray diffraction (XRD) and Fourier transform infra-red spectroscopy (FTIR) were used to discern the phases evolved in the glass–ceramics. Phase morphology was studied using scanning electron microscopy (SEM). Thermal expansion coefficient (TEC) and glass transition temperature (T_g) of all samples were measured using thermo-mechanical analyzer (TMA). It was found that 3 h dwell time at crystallization temperature yielded samples with good crystallinity with a TEC of 9.461 × 10⁻⁶ °C⁻¹. Glass–ceramic-to-metal compressive seal with SS-304 was fabricated using LAS glass–ceramic. The presence of metal housing and compressive stresses at the glass–ceramic-to-metal interface reduced average grain size and changed the overall microstructure.     

Rapid preparation and electrochemical behavior of carbon-coated Li3V2(PO4)3 from wet coordination

An improved solid-state coordination method namely wet coordination has been developed to synthesize carbon-coated monoclinic Li₃V₂(PO₄)₃ rapidly at a low temperature of 600 °C in 1 h. The structure of the sample was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and energy dispersive analysis of X-rays (EDAX). The diffusion coefficient of the lithium ions was measured by cyclic voltammetry (CV). The electrochemical behavior of the sample exhibits a high initial discharge capacity of 130 mAh g⁻¹, which is very close to its theoretical capacity of 132 mAh g⁻¹ under 95 mA g⁻¹ (0.67 C) in the range of 3.3-4.3 V (vs. Li/Li⁺). These results suggest that wet coordination is a promising method for large-scale production of carbon-coated Li₃V₂(PO₄)₃.     

Heat-treated metal phthalocyanine complex as an oxygen reduction catalyst for non-aqueous electrolyte Li/air batteries

In this work we study heat-treated FeCu-phthalocyanine (FeCuPc) complexes as the catalyst for oxygen reduction in non-aqueous electrolyte Li/air cells by supporting the catalyst on a high surface area Ketjenblack EC-600JD carbon black. It is shown that the resultant FeCu/C catalyst not only accelerates the two-electron reduction of oxygen as “O₂ + 2Li⁺ + 2e → Li₂O₂”, but also catalyzes the chemical disproportionation of Li₂O₂ as “2Li₂O₂ → 2Li₂O + O₂”. In Li/air cells, the catalyst reduces polarization on discharge while simultaneously reducing the fraction of Li₂O₂ in the final discharged products. In a 0.2 mol kg⁻¹ LiSO₃CF₃ 7:3 (wt.) propylene carbonate (PC)/tris(2,2,2-trifluoroethyl) phosphate (TFP) electrolyte, the Li/air cells with FeCu/C show at least 0.2 V higher discharge voltage at 0.2 mA cm⁻² than those with pristine carbon. By measuring the charge-transfer resistance (R_ct) of Li/air cells at temperatures ranging between −30 °C and 30 °C, we determine the apparent activation energy of the discharge of Li/air cells and discuss the effect of FeCu/C catalyst on the oxygen reduction in Li/air cells.