Discharge properties of all-solid sodium–sulfur battery using poly (ethylene oxide) electrolyte

An all-solid sodium/sulfur battery using poly (ethylene oxide) (PEO) polymer electrolyte are prepared and tested at 90 °C. Each battery is composed of a solid sulfur electrode, a sodium metal electrode, and a solid PEO polymer electrolyte. During the first discharge, the battery shows plateau potentials at 2.27 and at 1.76 V. The first discharge capacity is 505 mAh g⁻¹ sulfur at 90 °C. The capacity drastically decreases by repeated on charge–discharge cycling but remains at 166 mAh g⁻¹ sulfur after 10 cycles. The latter value is higher than that reported for a Na/poly (vinylidene difluoride)/S battery at room temperature.     

Low temperature behaviour of TiO2 rutile as negative electrode material for lithium-ion batteries

High surface nanosized rutile TiO₂ is prepared via a sol-gel method from an ethylene glycol-based titanium-precursor in the presence of a non-ionic surfactant, at pH 0. Its electrochemical behaviour has been investigated at low temperature using two different potential windows. Typically, the potential window of the rutile system is 1-3 V but the use of an enlarged potential window (0.1-3 V), leads to an excellent reversible capacity of 341 mAh g⁻¹ which is comparable to graphite anodes. The electrochemical performance was investigated by cyclic voltammetry and galvanostatic techniques at temperatures ranging from −40 to 20 °C. Nanosized TiO₂ exhibits excellent rate capability (341 mAh g⁻¹ at 20 °C, 197 mAh g⁻¹ at −10 °C, 138 mAh g⁻¹ at −20 °C, and 77 mAh g⁻¹ at −40 °C at a C/5 rate) and good cycling stability. The superior low-temperature electrochemical performance of nanosized rutile TiO₂ may make it a promising candidate as lithium-ion battery material.     

Synthesis and electrochemical performance of the high voltage cathode material Li[Li0.2Mn0.56Ni0.16Co0.08]O2 with improved rate capability

The high voltage layered Li[Li_0.2Mn_0.56Ni_0.16Co_0.08]O₂ cathode material, which is a solid solution between Li₂MnO₃ and LiMn_0.4Ni_0.4Co_0.2O₂, has been synthesized by co-precipitation method followed by high temperature annealing at 900 °C. XRD and SEM characterizations proved that the as prepared powder is constituted of small and homogenous particles (100-300 nm), which are seen to enhance the material rate capability. After the initial decay, no obvious capacity fading was observed when cycling the material at different rates. Steady-state reversible capacities of 220 mAh g⁻¹ at 0.2C, 190 mAh g⁻¹ at 1C, 155 mAh g⁻¹ at 5C and 110 mAh g⁻¹ at 20C were achieved in long-term cycle tests within the voltage cutoff limits of 2.5 and 4.8 V at 20 °C.     

Effects of roasting temperature and modification on properties of Li2FeSiO4/C cathode

Li₂FeSiO₄/C cathodes were synthesized by combination of wet-process method and solid-state reaction at high temperature, and effects of roasting temperature and modification on properties of the Li₂FeSiO₄/C cathode were investigated. The XRD patterns of the Li₂FeSiO₄/C samples indicate that all the samples are of good crystallinity, and a little Fe₃O₄ impurity was observed in them. The primary particle size rises as the roasting temperature increases from 600 to 750 °C. The Li₂FeSiO₄/C sample synthesized at 650 °C has good electrochemical performances with an initial discharge capacity of 144.9 mAh g⁻¹ and the discharge capacity remains 136.5 mAh g⁻¹ after 10 cycles. The performance of Li₂FeSiO₄/C cathode is further improved by modification of Ni substitution. The Li₂Fe_0.9Ni_0.1SiO₄/C composite cathode has an initial discharge capacity of 160.1 mAh g⁻¹, and the discharge capacity remains 153.9 mAh g⁻¹ after 10 cycles. The diffusion coefficient of lithium in Li₂FeSiO₄/C is 1.38 × 10⁻¹² cm² s⁻¹ while that in Li₂Fe_0.9Ni_0.1SiO₄/C reaches 3.34 × 10⁻¹² cm² s⁻¹.     

Electrochemical performance of mesoporous TiO2 anatase

Mesoporous TiO₂ was prepared via a sol–gel method from an ethylene glycol-based titanium-precursor in the presence of a non-ionic surfactant at pH 2. Only the anatase structure was detected after annealing, while the BET specific surface area was measured as being 90 m² g⁻¹ with a rather monomodal pore diameter close to 5 nm. Electrochemical performances were investigated by cyclic voltammetry and galvanostatic techniques. Mesoporous TiO₂ exhibits excellent rate capability (184 mAh g⁻¹ at C/5, 158 mAh g⁻¹ at 2C, 127 mAh g⁻¹ at 6C, and 95 mAh g⁻¹ at 30C) and good cycling stability.     

Effect of nano-silica filler in polymer electrolyte on Li dendrite formation in Li/poly(ethylene oxide)-Li(CF3SO2)2N/Li

Lithium dendrite growth in Li/poly(ethylene oxide) (PEO)-Li(CF₃SO₂)₂N (LiTFSI)-nano-SiO₂/Li was examined using direct in situ observation under galvanostatic conditions at 60 °C. Both the onset time of dendrite formation and the short-circuit time of the cells were extended by the addition of nano-SiO₂ filler into the polymer electrolyte, of which an acid-modified nano-SiO₂ filler was the most effective. The onset time was dependent on the current density in the range from 0.1 to 1.0 mA cm⁻². Li dendrite growth in Li/PEO₁₈LiTFSI/Li at 60 °C for current densities of 0.1 and 0.5 mA cm⁻² started at 125 and 15 h, respectively. PEO₁₈ LiTFSI with addition of 10 wt% acid-modified 50 nm SiO₂ showed extended dendrite formation onset times of 250 h at 0.1 mA cm⁻² and 32 h at 0.5 mA cm⁻². The suppression of dendrite formation at the Li/PEO₁₈ LiTFSI interface could be explained by enhancement of the conductivity and suppression of the interface resistance between lithium and the polymer electrolyte by addition of the nano-SiO₂ filler. The electrical conductivity of 4.1 × 10⁻⁴ S cm⁻¹ and interface resistance of 405 Ω cm² for PEO₁₈ LiTFSI at 60 °C were respectively increased to 7.2 × 10⁻⁴ S cm⁻¹ and decreased to 77 Ω cm² by the addition of 10 wt% acid-modified nano-SiO₂.     

High voltage spinel cathode materials for high energy density and high rate capability Li ion rechargeable batteries

We have synthesized LiMn_1.5Ni_0.4Cr_0.1O₄ cathode material for high energy density Li ion rechargeable batteries using sol-gel method. The synthesized materials were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy, cyclic voltammetry and charge-discharge characteristics. It was found that phase pure materials were obtained an annealing temperature of 875 °C for 15 h. The maximum discharge capacity at a constant charge-discharge current rate 1C, 0.5C, and 0.2C were found to be about 99 mAh g⁻¹, 110 mAh g⁻¹, and 131 mAh g⁻¹, respectively. The capacity retentions after 50 charge-discharge cycles were found to be about 99%, 97%, and 97.3% at discharge current rates of 0.2C, 0.5C, and 1C. The stable electrochemical behavior of the above cathode material even at high C rate, showed that it could be used for high energy density and high rate capability Li ion rechargeable batteries.     

Enhancement of electrochemical performance of lithium dry polymer battery with LiFePO4/carbon composite cathode

LiFePO₄/carbon composite electrode was prepared and applied to the dry polymer electrolyte. Enhanced low-temperature performance of LiFePO₄ was achieved by modifying the interface between LiFePO₄ and polymer electrolyte. The molecular weight of the polymer and the salt concentration as the Li/O ratio were optimized at 3 × 10⁵ and 1/10, respectively. Impedance analysis revealed that a small resistive component occurred in the frequency range of the charge transfer process. The reversible capacity of the laminate cell was 140 mAh g⁻¹ (C/20) and 110 mAh g⁻¹ (C/2) at 40 °C, which is comparable to the performance in the liquid electrolyte system.     

High capacity and high rate capability of nanostructured CuFeO2 anode materials for lithium-ion batteries

Non-toxic, cheap, nanostructured ternary transition metal oxide CuFeO₂ was synthesised using a simple sol-gel method at different temperatures. The effects of the processing temperature on the particle size and electrochemical performance of the nanostructured CuFeO₂ were investigated. The electrochemical results show that the sample synthesised at 650 °C shows the best cycling performance, retaining a specific capacity of 475 mAh g⁻¹ beyond 100 cycles, with a capacity fading of less than 0.33% per cycle. The electrode also exhibits good rate capability in the range of 0.5C-4C. At the high rate of 4C, the reversible capacity of CuFeO₂ is around 170 mAh g⁻¹. It is believed that the ternary transition metal oxide CuFeO₂ is quite acceptable compared with other high performance nanostructured anode materials.     

Preparation of manganese oxide with high density by decomposition of MnCO3 and its application to synthesis of LiMn2O4

Manganese oxide with high tap density was prepared by decomposition of spherical manganese carbonate, and then LiMn₂O₄ cathode materials were synthesized by solid-state reaction between the manganese oxide and lithium carbonate. Structure and properties of the samples were determined by X-ray diffraction, Brunauer–Emmer–Teller surface area analysis, scanning electron microscope and electrochemical measurements. With increase of the decomposition temperature from 350 °C to 900 °C, the tap density of the manganese oxide rises from 0.91 g cm⁻³ to 2.06 g cm⁻³. Compared with the LiMn₂O₄ cathode made from chemical manganese dioxide or electrolytic manganese dioxide, the LiMn₂O₄ made from manganese oxide of this work has a larger tap density (2.53 g cm⁻³), and better electrochemical performances with an initial discharge capacity of 117 mAh g⁻¹, a capacity retention of 93.5% at the 15th cycle and an irreversible capacity loss of 2.24% after storage at room temperature for 28 days.     

Basic molten salt process—A new route for synthesis of nanocrystalline Li4Ti5O12-TiO2 anode material for Li-ion batteries using eutectic mixture of LiNO3-LiOH-Li2O2

A nanocrystalline Li₄Ti₅O₁₂-TiO₂ duplex phase has been synthesized by a simple basic molten salt process (BMSP) using an eutectic mixture of LiNO₃-LiOH-Li₂O₂ at 400-500 °C. The microstructure and morphology of the Li₄Ti₅O₁₂-TiO₂ product are characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The sample prepared by heat-treating at 300 °C for 3 h (S-1) reveals dense agglomerates of ultra-fine nanocrystalline Li₄Ti₅O₁₂; with heat treatment at 400 °C for 3 h (S-2), there is a duplex crystallite size (fine < 10 nm, and coarse > 20 nm) of Li₄Ti₅O₁₂-TiO₂; at 500 °C for 3 h (S-3), a much coarser and less-dense distribution of lithium titanate (crystallite size ∼15-30 nm) is observed. According to the results of electrochemical testing, the S-2 sample shows initial discharge capacities of 193 mAh g⁻¹ at 0.2 C, 168 mAh g⁻¹ at 0.5 C, 146 mAh g⁻¹ at 1 C, 135 mAh g⁻¹ at 2 C, and 117 mAh g⁻¹ at 5 C. After 100 cycles, the discharge capacity is 138 mAh g⁻¹ at 1 C with a capacity retention of 95%. The S-2 sample yields the best electrochemical performance in terms of charge-discharge capacity and rate capability compared with other samples. Its superior electrochemical performance can be mainly attributed to the duplex crystallite structure, composed of fine (<10 nm) and coarse (>20) nm nanoparticles, where lithium ions can be stored within the grain boundary interfaces between the spinel Li₄Ti₅O₁₂ and the anatase TiO₂.     

Co-doped Sr2FeNbO6 as cathode materials for intermediate-temperature solid oxide fuel cells

Sr₂Fe_1−xCo_xNbO₆ (0.1 ≤ x ≤ 0.9) (SFCN) oxides with perovskite structure have been developed as the cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). These materials are synthesized via solid-state reaction and characterized by XRD, SEM, electrical conductivity, AC impedance spectroscopy and DC polarization measurements. The reactivity tests show that the Sr₂Fe_1−xCo_xNbO₆ electrodes are chemically compatible with the Zr_0.85Y_0.15O_1.925 (YSZ) and Ce_1.9Gd_0.1O_1.95 (CGO) electrolytes at 1200 °C, and the electrode forms a good contact with the electrolyte after sintering at 1200 °C for 12 h. The total electrical conductivity that has a considerable effect on the electrode properties is determined in a temperature range from 200 °C to 800 °C. The highest conductivity of 5.7 S cm⁻¹ is found for Sr₂Fe_0.1Co_0.9NbO₆ at 800 °C in air. The electrochemical performances of these cathode materials are studied using impedance spectroscopy at various temperatures and oxygen partial pressures. Two different kinds of reaction rate-limiting steps exist on the Sr₂Fe_0.1Co_0.9NbO₆ electrode, depending on the temperature. The Sr₂Fe_0.1Co_0.9NbO₆ electrode on CGO electrolyte exhibits a polarization resistance of 0.74 Ω cm² at 750 °C in air, which indicates that the Sr₂Fe_0.1Co_0.9NbO₆ electrode is a promising cathode material for IT-SOFCs.     

Synthesis and electrochemical properties of Li1−xFe0.8Ni0.2O2–LixMnO2 (Mn/(Fe + Ni + Mn) = 0.8) material

A new type of Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ (Mn/(Fe + Ni + Mn) = 0.8) material was synthesized at 350 °C in air atmosphere using a solid-state reaction. The material had an XRD pattern that closely resembled that of the original Li_1−xFeO₂–Li_xMnO₂ (Mn/(Fe + Mn) = 0.8) with much reduced impurity peaks. The Li/Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ cell showed a high initial discharge capacity above 192 mAh g⁻¹, which was higher than that of the parent Li/Li_1−xFeO₂–Li_xMnO₂ (186 mAh g⁻¹). We expected that the increase of initial discharge capacity and the change of shape of discharge curve for the Li/Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ cell is the result from the redox reaction from Ni²⁺ to Ni³⁺ during charge/discharge process. This cell exhibited not only a typical voltage plateau in the 2.8 V region, but also an excellent cycle retention rate (96%) up to 45 cycles.     

Electrochemical performance of a solid oxide fuel cell based on Ce0.8Sm0.2O2−δ electrolyte synthesized by a polymer assisted combustion method

A polyvinyl alcohol assisted combustion synthesis method was used to prepare Ce_0.8Sm_0.2O_2−δ (SDC) powders for an intermediate temperature solid oxide fuel cell (IT-SOFC). The XRD results showed that this combustion synthesis route could yield phase-pure SDC powders at a relatively low calcination temperature. A thin SDC electrolyte film with thickness control was produced by a dry pressing method at a lower sintering temperature of 1250 °C. With Sm_0.5Sr_0.5Co₃-SDC as the composite cathode, a single cell based on this thin SDC electrolyte was tested from 550 to 650 °C. The maximum power density of 936 mW cm⁻² was achieved at 650 °C using humidified hydrogen as the fuel and stationary air as the oxidant.     

High-performance PrBaCo2O5+δ-Ce0.8Sm0.2O1.9 composite cathodes for intermediate temperature solid oxide fuel cell

PrBaCo₂O_5+δ-Ce_0.8Sm_0.2O_1.9 (PBCO-SDC) composite material are prepared and characterized as cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). The powder X-ray diffraction result proves that there are no obvious reaction between the PBCO and SDC after calcination at 1100 °C for 3 h. AC impedance spectra based on SDC electrolyte measured at intermediate temperatures shows that the addition of SDC to PBCO improved remarkably the electrochemical performance of a PBCO cathode, and that a PBCO-30SDC cathode exhibits the best electrochemical performance in the PBCO-xSDC system. The total interfacial resistances R_p is the smallest when the content of SDC is 30 wt%, where the value is 0.035 Ω cm² at 750 °C, 0.072 Ω cm² at 700 °C, and 0.148 Ω cm² at 650 °C, much lower than the corresponding interfacial resistance for pure PBCO. The maximum power density of an anode-supported single cell with PBCO-30SDC cathode, Ni-SDC anode, and dense thin SDC/LSGM (La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ)/SDC tri-layer electrolyte are 364, 521 and 741 mW cm⁻² at 700, 750 and 800 °C, respectively.     

Ba0.5Sr0.5Co0.8Fe0.2O3 − δ + LaCoO3 composite cathode for Sm0.2Ce0.8O1.9-electrolyte based intermediate-temperature solid-oxide fuel cells

A novel Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ + LaCoO₃ (BSCF + LC) composite oxide was investigated for the potential application as a cathode for intermediate-temperature solid-oxide fuel cells based on a Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte. The LC oxide was added to BSCF cathode in order to improve its electrical conductivity. X-ray diffraction examination demonstrated that the solid-state reaction between LC and BSCF phases occurred at temperatures above 950 °C and formed the final product with the composition: La_0.316Ba_0.342Sr_0.342Co_0.863Fe_0.137O_3 − δ at 1100 °C. The inter-diffusion between BSCF and LC was identified by the environmental scanning electron microscopy and energy dispersive X-ray examination. The electrical conductivity of the BSCF + LC composite oxide increased with increasing calcination temperature, and reached a maximum value of ∼300 S cm⁻¹ at a calcination temperature of 1050 °C, while the electrical conductivity of the pure BSCF was only ∼40 S cm⁻¹. The improved conductivity resulted in attractive cathode performance. An area-specific resistance as low as 0.21 Ω cm² was achieved at 600 °C for the BSCF (70 vol.%) + LC (30 vol.%) composite cathode calcined at 950 °C for 5 h. Peak power densities as high as ∼700 mW cm⁻² at 650 °C and ∼525 mW cm⁻² at 600 °C were reached for the thin-film fuel cells with the optimized cathode composition and calcination temperatures.     

A new anode material for intermediate solid oxide fuel cells

A new anode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) with a composite of La_0.7Sr_0.3Cr_1−xNi_xO₃ (LSCN), CeO₂ and Ni has been synthesized. EDX analysis showed that 1.19 at% Ni was doped into the perovskite-type La_0.7Sr_0.3CrO₃ and Ce could not be detected in the perovskite phases. Results showed that the fine CeO₂ and Ni were highly dispersed on the La_0.7Sr_0.3Cr_1−xNi_xO₃ substrates after calcining at 1450 °C and reducing at 900 °C. The thermal expansion coefficient (TEC) of the as-prepared anode material is 11.8 × 10⁻⁶ K⁻¹ in the range of 30–800 °C. At 800 °C, the electrical conductivity of the as-prepared anode material calcined at 1450 °C for 5 h is 1.84 S cm⁻¹ in air and 5.03 S cm⁻¹ in an H₂ + 3% H₂O atmosphere. A single cell with yttria-stabilized zirconia (YSZ, 8 mol% Y₂O₃) electrolyte and the new materials as anodes and La_0.8Sr_0.2MnO₃ (LSM)/YSZ as cathodes was assembled and tested. At 800 °C, the peak power densities of the single cell was 135 mW cm⁻² in an H₂ + 3% H₂O atmosphere.     

Cathode performance of LiMnPO4/C nanocomposites prepared by a combination of spray pyrolysis and wet ball-milling followed by heat treatment

LiMnPO₄/C nanocomposites could be prepared by a combination of spray pyrolysis and wet ball-milling followed by heat treatment in the range of spray pyrolysis temperature from 200 to 500 °C. The ordered LiMnPO₄ olivine structure without any impurity phase could be identified by X-ray diffraction analysis for all samples. It could be also confirmed from scanning electron microscopy and transmission electron microscopy observations that the final samples were the LiMnPO₄/C nanocomposites with approximately 100 nm in primary particles size. The LiMnPO₄/C nanocomposite samples were used as cathode active materials for lithium batteries, and the electrochemical tests were carried out for the cell Li|1 M LiPF₆ in EC:DMC = 1:1|LiMnPO₄/C at various charge/discharge rates in three charge modes. As a result, the final sample which was synthesized at 300 °C by spray pyrolysis showed the best electrochemical performance due to the largest specific surface area, the smallest primary particle size and a well distribution of carbon. At galvanostatic charge/discharge rates of 0.05 C, the cell delivered first discharge capacities of 123 and 165 mAh g⁻¹ in correspondence to charge cutoff voltages of 4.4 and 5.0 V, respectively. Furthermore, in a constant current-constant voltage charge mode at 4.4 V, the cells also exhibited initial discharge capacities of 147 mAh g⁻¹ at 0.05 C, 145 mAh g⁻¹ at 0.1 C, 123 mAh g⁻¹ at 1 C and 65 mAh g⁻¹ at 10 C. Moreover, the cells showed fair good cycleability over 100 cycles.     

All-solid-state lithium secondary batteries with oxide-coated LiCoO2 electrode and Li2S–P2S5 electrolyte

All-solid-state lithium secondary batteries using LiCoO₂ active materials coated with Li₂SiO₃ and SiO₂ oxide films and Li₂S–P₂S₅ solid electrolytes were fabricated and their electrochemical performance was investigated. The electrochemical performace of the all-solid-state cells at a high voltage region was highly improved by using oxide-coated LiCoO₂. The oxide coatings are effective in suppressing the formation of an interfacial resistance between LiCoO₂ and the solid electrolyte at a high cutoff voltage of 4.6 V (vs. Li). As a result, charge–discharge capacities and cycle performance at the cutoff voltage were improved. The cell with Li₂SiO₃-coated LiCoO₂ showed a large initial discharge capacity of 130 mAh g⁻¹ and a good capacity retention of 110 mAh g⁻¹ after 50th cycles at the cutoff voltage of 4.6 V (vs. Li).     

Optimized solid-state synthesis of LiFePO4 cathode materials using ball-milling

Olivine-type LiFePO₄ cathode materials were synthesized by a solid-state reaction method and ball-milling. The ball-milling time, heating time and heating temperature are optimized. A heating temperature higher than 700 °C resulted in the appearance of impurity phase Fe₂P and growth of large particle, which was shown by high resolution X-ray diffraction and field emission scanning electron microscopy. The impurity phase Fe₂P exhibited a considerable capacity loss at the 1st cycle and a gradual increase in discharge capacity upon cycling. Moreover, it exhibited an excellent high-rate capacity of 104 mAh g⁻¹ at 3 C in spite of the large particle size. The optimum synthesis conditions for LiFePO₄ were ball-milling for 24 h and heat-treatment at 600 °C for 3 h. LiFePO₄/Li cells showed an enhanced cycling performance and a high discharge capacity of 160 mAh g⁻¹ at 0.1 C.