SPS processing of bismuth-layer structured ferroelectric ceramics yielding highly textured microstructures

The spark plasma sintering (SPS) behaviour of nano-sized Bi₄Ti₃O₁₂ (BIT) and micron-sized CaBi₂Nb₂O₉ (CBNO) powders is described. The densification process of both powders is very rapid, i.e. the densification occurs within a very narrow time interval (2–3 min using a heating rate of 100 °C min⁻¹ and a pressure of 50 MPa). The BIT powder exhibits a lower densification onset temperature (∼650 °C) and higher maximum shrinkage rate (8.9 × 10⁻³ s⁻¹ at 780 °C) than that of the CBNO powder (∼825 °C and 4.5 × 10⁻³ s⁻¹ at 950 °C). Isothermal compaction studies revealed that fully dense nano-sized BIT compacts could be obtained within the temperature region 750 °C < T_iso < 850 °C while for T_iso > 850 °C compacts containing elongated platelet grains are formed. A new preparation route to produce highly textured compacts is described in detail. Appropriate pre-forms are prepared by spark plasma sintering (SPS) and these fully dense compacts are subject to superplastic deformation in the SPS unit to achieve a total compressive strain of ∼60%. This strain was achieved within a period of 1.5 min and with a maximum strain rates of 1.1 × 10⁻² s⁻¹ achieved at ∼840 °C and 1.3 × 10⁻² s⁻¹ at 1020 °C for the BIT and CBNO compacts, respectively. The X-ray studies showed that the Lotgering orientation factors of grains in the deformed BIT and CBNO compacts are 99% and 70%. The formation of highly textured compacts is suggested to be governed by a superplastic deformation-induced directional dynamic ripening mechanism.     

NH3-SCR activity,hydrothermal stability,sulfur resistance and regeneration of Ce0.75Zr0.25O2–PO43 −catalyst

Ce_0.75Zr_0.25O₂–PO₄^3 − catalyst with high NH₃-SCR performance was prepared by impregnating phosphates on Ce_0.75Zr_0.25O₂ synthesized by a sol–gel method. The catalysts were characterized by IR, H₂-TPR, NH₃ adsorption and activity measurements. Ce_0.75Zr_0.25O₂–PO₄^3 − catalyst shows over 80% NO_x conversion at 250–450 °C. The hydrothermal-aged catalyst at 760 °C for 48 h still presents high NH₃-SCR performance at 300–400 °C. The sulfur-aged Ce_0.75Zr_0.25O₂–PO₄^3 − catalyst can be regenerated completely by treating catalyst in air at 650 °C. Phosphates improve the ammonia adsorption and decrease the ammonia oxidation on catalyst, leading to a high NH₃-SCR activity and a high N₂ selectivity of Ce_0.75Zr_0.25O₂–PO₄^3 − catalyst.     

A remarkable promoting effect of water addition on selective hydrogenation of p-chloronitrobenzene in ethanol

Selective hydrogenation of p-chloronitrobenzene to p-chloraniline over ruthenium catalyst was found to be promoted remarkably (Selectivity: from 80.4% to 98.6%; TON: from 0.89 × 10⁻² s⁻¹ to 3.20 × 10⁻² s⁻¹) by simply adding some water into the solvent of ethanol. The optimized volume percent of water in ethanol was 30%. The promoting effect of water was also found over various supported metal catalysts, such as Fe/SiO₂, Co/SiO₂, Ni/SiO₂, Cu/SiO₂, and Ag/SiO₂.     

Reduction of N2O by NH3 on polycrystalline copper and Cu(1 1 0): A combined XPS,FT-IRRAS and kinetics investigation

Kinetics of N₂O decomposition and catalytic reduction of N₂O by NH₃ in the presence or absence of oxygen have been studied on polycrystalline Cu planar chip (3 cm × 3 cm × 0.1 cm) or Cu(1 1 0) single crystal, using catalytic test equipment, XPS and FT-IRRAS techniques. It has been shown that N₂O decomposes on metallic Cu, but gives then Cu₂O, which is detrimental to N₂O decomposition. The presence of a reductant, such as NH₃, allowed N₂O to react leading to its catalytic reduction to N₂; 500 °C is the best temperature for catalytic reduction alone, i.e. with low additional self-decomposition of N₂O or NH₃. The presence of oxygen, in amount less than that of NH₃, leads to more efficient NH₃ oxidation, oxygen being observed to be more reactive than N₂O on NH₃. XPS results enabled to identify the active surface as metallic Cu and Cu₃N for NH₃ oxidation and NH₂, NH, N adsorbed species as intermediates of the reaction. At room temperature, in the presence of N₂O, O₂ and NH₃, FT-IRRAS allowed to show the formation of NH₂ and NH species (bands at 1550 and 1440 cm⁻¹, respectively) and of two N₂^δ− species (bands at 2170 and 2204 cm⁻¹), the latter one corresponding to adsorbed N₂^δ− species close to adsorbed electron accepting O or OH species. This study demonstrated that N₂O decomposed to N₂ and O species during SCR reaction; it enabled to identify several adsorbed surface species (N, NH, NH₂, N₂^δ−), both by XPS after catalytic reaction at 500 °C on the polycrystalline Cu chip and by IRRAS on Cu(1 1 0) single crystal in the presence of the reactants at room temperature. In addition, it was shown that N₂ is a powerful IR probe to characterise the surrounding environment of surface sites that cannot be identified by any other way.     

Selective catalytic reduction of nitrogen oxides by ammonia on iron oxide catalysts

In this study, new Fe₂O₃ based materials are developed for the selective catalytic reduction (SCR) of NO_x by NH₃ in diesel exhaust. As a result of the catalyst screening, performed in a synthetic model exhaust, ZrO₂ is considered to be the most effective carrier for Fe₂O₃. The modification of the Fe₂O₃/ZrO₂ system with tungsten leads to drastic increase of SCR performance as well as pronounced thermal stability. These results show that tungsten acts as bifunctional component. The highest catalytic activity is observed for ZrO₂ that is coated with 1.4 mol% Fe₂O₃ and 7.0 mol% WO₃ (1.4Fe/7.0W/Zr). By the use of this catalyst quantitative conversion of NO_x is obtained between 285 and 430 °C with selective formation of N₂. Here, the turnover frequency of NO_x per Fe atom is found to be 35 × 10⁻⁵ s⁻¹ that indicates a high catalytic performance. The SCR activity of the 1.4Fe/7.0W/Zr material is decreased in the presence of H₂O and CO₂, whereas it is increased by NO₂.Temperature programmed reduction by H₂ (HTPR) analyses show that the Fe sites of the 1.4Fe/7.0W/Zr catalyst are mainly in the form of crystalline Fe₂O₃, whereby relatively small oxide entities are also present. The strongly aggregated Fe₂O₃ species are associated with the presence of the promoter tungsten. Based upon stationary catalytic examinations as well as diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) studies we postulate an Eley Rideal type mechanism for SCR on 1.4Fe/7.0W/Zr catalyst. The mechanistic model includes a redox cycle of the active Fe sites. As first reaction step, we assume dissociative adsorption of NH₃ that leads to partial reduction of the iron as well as to production of very reactive amide surface species. These amide intermediates are supposed to react with gaseous NO to form N₂ and H₂O. In the final step, the reduced Fe sites be regenerated by oxidation with O₂. As a side reaction of SCR, imide species, originated from decomposition of amide, are oxidized by NO₂ or O₂ into NO.     

Selective catalytic reduction of NO by ammonia using mesoporous Fe-containing HZSM-5 and HZSM-12 zeolite catalysts: An option for automotive applications

Mesoporous and conventional Fe-containing ZSM-5 and ZSM-12 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnation method and tested in the selective catalytic reduction (SCR) of NO with NH₃. It was found that for both Fe/HZSM-5 and Fe/HZSM-12 catalysts with similar Fe contents, the activity of the mesoporous samples in NO SCR with NH₃ is significantly higher than for conventional samples. Such a difference in the activity is probably related with the better diffusion of reactants and products in the mesopores and better dispersion of the iron particles in the mesoporous zeolite as was confirmed by SEM analysis. Moreover, the maximum activity for the mesoporous zeolites is found at higher Fe concentrations than for the conventional zeolites. This also illustrates that the mesoporous zeolites allow a better dispersion of the metal component than the conventional zeolites. Finally, the influence of different pretreatment conditions on the catalytic activity was studied and interestingly, it was found that it is possible to increase the SCR performance significantly by preactivation of the catalysts in a 1% NH₃/N₂ mixture at 500 °C for 5 h. After preactivation, the activity of mesoporous 6 wt% Fe/HZSM-5 and 6 wt% Fe/HZSM-12 catalyst is comparable with that of traditional 3 wt% V₂O₅/TiO₂ catalyst used as a reference at temperatures below 400 °C and even more active at higher temperatures.     

Deformation behavior and joining of a MgF2 optical ceramic

Compressive deformation behavior of a polycrystalline magnesium fluoride (MgF₂) ceramic was investigated at temperatures ranging from 760 to 830 °C in an argon atmosphere at strain rates between 2 × 10⁻⁶ and 4 × 10⁻⁵ s⁻¹. Steady-state flow stresses increased with increasing strain rates and ranged between 2 and 38 MPa. Stress exponents of ≈1.4 ± 0.2 were determined at temperatures >760 °C, indicative of a viscous diffusion-controlled deformation mechanism. Activation energy, determined from flow stress as a function of temperature, at a constant strain rate, was ≈476 ± 60 kJ/mol. Self-joining by plastic deformation of MgF₂ was demonstrated at 830 °C at a strain rate of 5 × 10⁻⁶ s⁻¹. The joined samples were characterized by optical transmission measurements and their transmittivity was ≈80% of the unjoined sample in the 2.5–8 μm wavelength range.     

Thermal cycling induced capacity enhancement of graphite anodes in lithium-ion cells

Graphite electrodes were electrochemically cycled in Li-ion cells at 50 and 60 °C in order to determine the changes in their surface properties in comparison to the electrodes tested at 25 °C. A 17% drop in planar capacity occurred during the first cycle at 60 °C compared to a 40% at 25 °C and reduced the amount of damage that occurred to graphite due to a rapidly formed solid electrolyte interphase (SEI). During the following cycles, a planar capacity of 3.11 ± 0.12 mAh cm⁻² was attained at 60 °C rather than 0.53 ± 0.03 mAh cm⁻² at 25 °C. The SEI layer formed at 60 °C predominantly consisted of Li₂CO₃ and was devoid of residual LiClO₄ detected at 25 °C. At 25 °C, the diffusion coefficient of Li⁺ (D_Li⁺) was calculated as 1.07 × 10⁻⁸ cm² s⁻¹, whereas at 60 °C, D_Li⁺ increased to 3.25 × 10⁻⁸ cm² s⁻¹. A pre-treatment conducted at 60 °C enhanced the cyclic performance of graphite subsequently cycled at 25 °C; a Li₂CO₃-enriched SEI, generated during the 60 °C pre-treatment, covered the graphite surface uniformly and resulted in a 28% increase in battery capacity at 25 °C.     

Effect of Nd-doping on structural,thermal and electrochemical properties of LaFe0.5Cr0.5O3 perovskites

The structural, thermal and electrochemical properties of the perovskite-type compound La_1−xNd_xFe_0.5Cr_0.5O₃ (x=0.10, 0.15, 0.20) are investigated by X-ray diffraction, thermal expansion, thermal diffusion, thermal conductivity and impedance spectroscopy measurements. Rietveld refinement shows that the compounds crystallize with orthorhombic symmetry in the space group Pbnm. The average thermal expansion coefficient decreases as the content of Nd increases. The average coefficient of thermal expansion in the temperature range of 30–850 °C is 10.12×10⁻⁶, 9.48×10⁻⁶ and 7.51×10⁻⁶ °C⁻¹ for samples with x=0.1, 0.15 and 0.2, respectively. Thermogravimetric analyses show small weight gain at high temperatures which correspond to filling up of oxygen vacancies as well as the valence change of the transition metals. The electrical conductivity measured by four-probe method shows that the conductivity increases with the content of Nd; the electrical conductivity at 520 °C is about 4.71×10⁻³, 6.59×10⁻³ and 9.62×10⁻³ S cm⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. The thermal diffusivity of the samples decreases monotonically as temperature increases. At 600 °C, the thermal diffusivity is 0.00425, 0.00455 and 0.00485 cm² s⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. Impedance measurements in symmetrical cell arrangement in air reveal that the polarization resistance decreases from 55 Ω cm⁻² to 22.5 Ω cm⁻² for increasing temperature from 800 °C to 900 °C, respectively.     

Dielectric and thermal properties of AlN ceramics

The effects of slow-cooling and annealing conditions on dielectric loss, thermal conductivity and microstructure of AlN ceramics were investigated. Y₂O₃ from 0.5 to 1.25 mol% at 0.25% increments was added as a sintering additive to AlN powder and pressureless sintering was carried out at 1900 °C for 2 h in a nitrogen flowing atmosphere. To improve the properties, AlN samples were slow-cooled at a rate of 1 °C min⁻¹ from 1900 to 1750 °C, subsequently cooled to 970 °C at a rate of 10 °C min⁻¹ and then annealed at the same temperature for 4 h. AlN and YAG (5Al₂O₃/3Y₂O₃) were the only identified phases from XRD. AlN doped with 0.5 and 0.75 mol% Y₂O₃ had a low loss of <2.0 × 10⁻³ and a high thermal conductivity of >160 W m⁻¹ °C⁻¹.     

Effect of Cu doping on the SCR activity of CeO2 catalyst prepared by citric acid method

CeO₂–CuO catalyst prepared by citric acid method was investigated for selective catalytic reduction of NO with NH₃. The activity of the CeO₂ catalyst was enhanced about 8–27% in the temperature range of 125–225 °C at a space velocity of 28,000 h⁻¹ by the addition of Cu. It was found that the state of Cu species had great impact on the SCR performance of CeO₂–CuO catalyst. Cu²⁺ can enhance the low temperature activity of SCR reaction, while CuO would promote NH₃ oxidation before SCR reaction at high temperature, which would cause the decrease of its high temperature SCR activity.     

Size controlled ZSM-5 on the structure and performance of Fe catalyst in the selective catalytic reduction of NOx with NH3

Fe/ZSM-5 catalysts with various morphologies and sizes were prepared and the catalytic properties in NH₃-SCR were also investigated. The different ZSM-5 morphologies and sizes indeed influence the dispersion of Fe species. The Fe/ZSM-5 catalyst, which was cauliflower-like morphology of ZSM-5 support aggregated by small nano-crystal zeolite with crystallite size of about 50 nm, exhibited the best NH₃-SCR activity (T_≥ 90% = 280–650 °C). This specific morphology and size of ZSM-5 support were considered to benefit the distribution of isolated Fe^3 + species, which was proved to be the main active sites in SCR reaction.     

Influence of sintering aids and excess Lithium on the conductivity of perovskite-type Li3/8Sr7/16Zr1/4Nb3/4O3 solid electrolyte

Perovskite-structured Li_3/8Sr_7/16Zr_1/4Nb_3/4O₃ solid-state Lithium-conductors were prepared by conventional solid-state reaction method. Influence of sintering aids (Al₂O₃, B₂O₃) and excess Lithium on structure and electrical properties of Li_3/8Sr_7/16Zr_1/4Nb_3/4O₃ (LSNZ) has been investigated. Their crystal structure and microstructure were characterized by X-ray diffraction analysis and scanning electron microscope, respectively. The conductivity and electronic conductivity were evaluated by AC-impedance spectra and potentiostatic polarization experiment. All sintered compounds are cubic perovskite structure. Optimal amount of excess Li₂CO₃ was chosen as 20 wt% because of the total conductivity of LSNZ-20% was as high as 1.6×10⁻⁵ S cm⁻¹ at 30 °C and 1.1×10⁻⁴ S cm⁻¹ at 100 °C, respectively. Electronic conductivity of LSNZ-20% is 2.93×10⁻⁸ S cm⁻¹, nearly 3 orders of magnitude lower than ionic conductivity. The density of solid electrolytes appears to be increased by the addition of sintering aids. The addition of B₂O₃ leads to a considerable increase of the total conductivity and the enhancement of conductivity is attributed to the decrease of grain-boundary resistance. Among these compounds, LSNZ-1 wt%B₂O₃ has lower activation energy of 0.34 eV and the highest conductivity of 1.98×10⁻⁵ S cm⁻¹ at 30 °C.     

SO42−–Mn–Co–Ce supported on TiO2/SiO2 with high sulfur durability for low-temperature SCR of NO with NH3

The catalysts SO₄^2 − Mn–Co–Ce/TiO₂/SiO₂ were investigated for the low-temperature SCR of NO with NH₃ in the presence of SO₂. An excellent SO₂ durability at low temperature was obtained with the catalyst used TiO₂/SiO₂ as support and modified with SO₄^2 −. The catalyst sulfated with 0.1 mol/L H₂SO₄ solution and then calcined at 300 °C exhibited the best NO_x conversion efficiency of 99.5% at 250 °C in the presence of 50 ppm SO₂. The conversion efficiency did not decrease after repeatedly used for 8 times.     

Thermal,mechanical and electrical properties of hard B4C,BCN, ZrBC and ZrBCN ceramics

We study the thermal, mechanical and electrical properties of B₄C, BCN, ZrBC and ZrBCN ceramics prepared in the form of thin films by magnetron sputtering. We focus on the effect of Zr_x(B₄C)_1−x sputter target composition, the N₂+Ar discharge gas mixture composition, the deposition temperature and the annealing temperature after the deposition. The thermal properties of interest include thermal conductivity (observed in the range 1.3–7.3 W m⁻¹ K⁻¹), heat capacity (0.37–1.6×10³ J kg⁻¹ K⁻¹ or 1.9–4.1×10⁶ Jm⁻³ K⁻¹), thermal effusivity (1.6–4.5×10³ J m⁻² s^−1/2 K⁻¹) and thermal diffusivity (0.38–2.6×10⁻⁶ m² s⁻¹). We discuss the relationships between materials composition, preparation conditions, structure, thermal properties, temperature dependence of the thermal properties and other (mechanical and electrical) properties. We find that the materials structure (amorphous×crystalline hexagonal ZrB₂-like×nanocrystalline cubic ZrN-like), more than the composition, is the crucial factor determining the thermal conductivity and other properties. The results are particularly important for the design of future ceramic materials combining tailored thermal properties, mechanical properties, electrical conductivity and oxidation resistance.     

Selective esterification of tert-butanol by acetic acid anhydride over clay supported InCl3, GaCl3, FeCl3 and InCl2 catalysts

Clay (kaolin, mont-K10 and mont-KSF) supported InCl₃, GaCl₃, FeCl₃ and ZnCl₂ catalysts (metal chloride loading=1.1 mmol g⁻¹) show high selectivity (⩾98%) at high conversion in the esterification of tert-butanol by acetic anhydride to tert-butyl acetate (t-BA) and very low activity for the dehydration of tert-butanol at ⩽50°C. For all the catalysts, mont-K10 is the best support and the order of their esterification activity (at 26°C) is: InCl₃/mont-K10 (TOF=0.025 s⁻¹) > GaCl₃/mont-K10 (0.023 s⁻¹) > FeCl₃/mont-K10 (0.02 s⁻¹) ⩾ ZnCl₂/mont-K10 (0.019 s⁻¹). InCl₃/mont-K10 is highly active, selective and reusable catalyst for the esterification.     

Application of BaO–CaO–Al2O3–B2O3–SiO2 glass–ceramic seals in large size planar IT-SOFC

BaO–CaO–Al₂O₃–B₂O₃–SiO₂ (BCAS) glass–ceramics can be used as sealant for large size planar anode-supported solid oxide fuel cells (SOFCs). BCAS glass–ceramics after heat treatment for different times were characterized by means of thermal dilatometer, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the coefficients of thermal expansion (CTE) of BCAS glass–ceramics are 11.4×10⁻⁶ K⁻¹, 11.3×10⁻⁶ K⁻¹ and 11.2×10⁻⁶ K⁻¹ after heated at 750 °C for 0 h, 50 h, and 100 h, respectively. The CTE of BCAS matches that of YSZ, Ni–YSZ and the interconnection of SOFC. Needle-like barium silicate, barium calcium silicate and hexacelsian are crystallized in the BCAS glass after heat-treatment for above 50 h at 750 °C. The glass–ceramics green tape prepared by aqueous tape casting can be directly applied in sealing the cell of SOFCs with 10 cm×10 cm. The open circuit voltage (OCV) of the cell keeps 1.19 V after running for 280 h at 750 °C and thermal cycling 10 times from 750 °C to room temperature. The maximum power density is 0.42 W/cm² using pure H₂ as fuel and air as oxidation gas. SEM images show no cracks or pores exist in the interface of BCAS glass–ceramics and the cell.     

Semiconducting properties of cold sintered V2O5 ceramics and Co-sintered V2O5-PEDOT:PSS composites

Recently we established a sintering approach, namely Cold Sintering Process (CSP), to densify ceramics and ceramic-polymer composites at extraordinarily low temperatures. In this work, the microstructures and semiconducting properties of V₂O₅ ceramic and (1-x)V₂O₅-xPEDOT:PSS composites cold sintered at 120 °C were investigated. The electrical conductivity (25 °C), activation energy (25 °C), and Seebeck coefficient (50 °C) of V₂O₅ are 4.8 × 10⁻⁴ S/cm, 0.25 eV, and −990 μV/K, respectively. The conduction mechanism was studied using a hopping model. A reversible metal-insulator transition (MIT) was observed with V₂O₅ samples exposed to a N₂ atmosphere, whereas in a vacuum atmosphere, no obvious MIT could be detected. With the addition of 1–2 Vol% PEDOT:PSS, the electrical conductivity (50 °C) dramatically increases from 10⁻⁴ to 10⁻³ ∼ 10⁻² S/cm, and the Seebeck coefficient (50 °C) shifts from −990 to −(600 ∼ 250) μV/K. All the results indicate that CSP may offer a new processing route for the semiconductor electroceramic development without a compromise to the all-important electrical properties.     

Oxygen ionic transport in SrFe1−yAlyO3−δ and Sr1−xCaxFe0.5Al0.5O3−δ ceramics

The oxygen permeability of mixed-conducting Sr_1−xCa_xFe_1−yAl_yO_3−δ (x=0–1.0; y=0.3–0.5) ceramics at 850–1000 °C, with an apparent activation energy of 120–206 kJ/mol, is mainly limited by the bulk ionic conduction. When the membrane thickness is 1.0 mm, the oxygen permeation fluxes under pO₂ gradient of 0.21/0.021 atm vary from 3.7×10⁻¹⁰ mol s⁻¹ cm⁻² to 1.5×10⁻⁷ mol s⁻¹ cm⁻² at 950 °C. The maximum solubility of Al³⁺ cations in the perovskite lattice of SrFe_1−yAl_yO_3−δ is approximately 40%, whilst the brownmillerite-type solid solution formation range in Sr_1−xCa_xFe_0.5Al_0.5O_3−δ system corresponds to x>0.75. The oxygen ionic conductivity of SrFeO₃-based perovskites decreases moderately on Al doping, but is 100–300 times higher than that of brownmillerites derived from CaFe_0.5Al_0.5O_2.5+δ. Temperature-activated character and relatively low values of hole mobility in SrFe_0.7Al_0.3O_3−δ, estimated from the total conductivity and Seebeck coefficient data, suggest a small-polaron mechanism of p-type electronic conduction under oxidising conditions. Reducing oxygen partial pressure results in increasing ionic conductivity and in the transition from dominant p- to n-type electronic transport, followed by decomposition. The low-pO₂ stability limits of Sr_1−xCa_xFe_1−yAl_yO_3−δ seem essentially independent of composition, varying between that of LaFeO_3−δ and the Fe/Fe_1−γO boundary. Thermal expansion coefficients of Sr_1−xCa_xFe_1−yAl_yO_3−δ ceramics in air are 9×10⁻⁶ K⁻¹ to 16×10⁻⁶ K⁻¹ at 100–650 °C and 12×10⁻⁶ K⁻¹ to 24×10⁻⁶ K⁻¹ at 650–950 °C. Doping of SrFe_1−yAl_yO_3−δ with aluminum decreases thermal expansion due to decreasing oxygen nonstoichiometry variations.     

Enhanced electrochemical properties of LiFePO4–silicon composites as positive electrode materials fabricated using a solid-state method

LiFePO₄–silicon composites were fabricated by using a solid-state method for applying positive electrodes in lithium ion batteries. The LiFePO₄–silicon composites were characterized with X-ray diffraction and field emission scanning electron microscopy. Their electrochemical properties were investigated with cyclic voltammetry, electrochemical impedance spectroscopy, and charge–discharge tests. The added silicon not only suppressed the surface corrosion caused by the decreasing H⁺ concentration in the electrolyte, but it also acted as a barrier between the LiFePO₄ particles and LiPF₆ electrolyte, thereby preventing the dissolution of Fe²⁺ in the electrode and enhancing the electrolyte/active material interactions. This resulted in improved lithium-ion transfer kinetics and excellent positive electrode performance, especially at high current densities and different operating temperatures (0, 25, and 50 °C). At 25 °C, the LiFePO₄ composite containing 2 wt% of silicon delivered the best electrochemical performance with a lithium-ion diffusion coefficient of 1.81×10⁻⁹ cm² s⁻¹, a specific discharge capacity of 143 mA h g⁻¹ for the initial cycle, and a capacity retention of 98% after 100 cycles. In contrast, the corresponding values for the pure LiFePO₄ were 1.19×10⁻¹¹ cm² s⁻¹, 115 mA h g⁻¹, and a capacity retention of 76% after 100 cycles, respectively.