Enhanced electrochemical performance of carbon-LiMn1−xFexPO4 nanocomposite cathode for lithium-ion batteries

4 V-class olivine C-LiMn_1−xFe_xPO₄ (x = 0 and 0.15) are synthesized by ultrasonic pyrolysis followed by ball milling with AB carbon to evaluate the doping effect of iron. The C-LiMn_0.85Fe_0.15PO₄ shows excellent rate capability having discharge capacity of 150 mAh g⁻¹ at 0.5C-rate and 121 mAh g⁻¹ at 2C-rate. The capacity retention of the C-LiMn_0.85Fe_0.15PO₄ is 91% after 50 cycles at 55 °C whereas C-LiMnPO₄ is limited to 87%. The improved electrochemical performance of the C-LiMn_0.85Fe_0.15PO₄ electrode is attributed to the enhanced electrical conductivity caused by tighter binding on the carbon particles with the LiMn_0.85Fe_0.15PO₄ primary particles as well as by the surface coating of carbon on the primary particles.     

Electrical conductivity and reaction with lithium of LiFe1−yMnyPO4 olivine-type cathode materials

Structural, electrical and electrochemical properties of Mn-substituted phospho-olivines LiFe_1−yMn_yPO₄ were investigated and compared to those of LiFePO₄. Rietvield refined XRD patterns taken in the course of delithiation process showed apparent difference between phase compositions of these cathode materials upon lithium extraction. Contrary to the LiFePO₄ and LiMnPO₄ compositions for which a two-phase mechanism of electrochemical lithium extraction/insertion is observed, in case of Mn-substituted LiFe_1−yMn_yPO₄ samples a single-phase mechanism of deintercalation was observed in the studied range of lithium concentration. Electrochemical characterization of the cathode materials were performed in Li/Li⁺/Li_xFe_1−yMn_yPO₄-type cells for y = 0.0, 0.25, 0.55, 0.75 and 1.0 compositions. Voltammery studies showed low reversibility of the lithium extraction process in the high-voltage “manganese” range, while in the “iron” range the reversibility of lithium extraction is high. Impedance measurements of the LiFe_1−yMn_yPO₄ cathode materials, which enabled separation of the ionic and electronic components of their entire electrical conductivity, showed distinct influence of Mn content on the electronic part of conductivity. EIS measurements performed at different states of cell charge revealed that the charge-transfer impedance in Li_xFe_1−yMn_yPO₄ is much lower than that of Li_xFePO₄.     

Synthesis and characterization of Li3V(2 − 2x/3)Mgx(PO4)3/C cathode material for lithium-ion batteries

Li₃V_{(2 − 2x/3)}Mg_x(PO₄)₃/C (x = 0, 0.15, 0.30, 0.45) composites have been synthesized by the sol-gel assisted solid state method, using adipic acid C₆H₁₀O₄ (hexanedioic acid) as carbon source. The particle size of the composites is ∼1 μm. During the pyrolysis process, Li₃V_{(2 − 2x/3)}Mg_x(PO₄)₃/C network structure is formed. The effect of Mg²⁺ doped on the electrochemical properties of Li₃V₂(PO₄)₃/C positive materials has been studied. Li₃V_1.8Mg_0.30(PO₄)₃/C as the cathode materials of Li-ion batteries, the retention rate of discharge capacity is 91.4% (1 C) after 100 cycles. Compared with Li₃V₂(PO₄)₃/C, Li₃V_{(2 − 2x/3)}Mg_x(PO₄)₃/C composites have shown enhanced capacity and retention rate capability. The long-term cycles and ex situ XRD tests disclose that Li₃V_1.8Mg_0.30(PO₄)₃ exhibits higher structural stability than the undoped system.     

LiFexMn1−xPO4: A cathode for lithium-ion batteries

The high redox potential of LiMnPO₄, ∼4.0 vs. (Li⁺/Li), and its high theoretical capacity of 170 mAh g⁻¹ makes it a promising candidate to replace LiCoO₂ as the cathode in Li-ion batteries. However, it has attracted little attention because of its severe kinetic problems during cycling. Introducing iron into crystalline LiMnPO₄ generates a solid solution of LiFe_xMn_1−xPO₄ and increases kinetics; hence, there is much interest in determining the Fe-to-Mn ratio that will optimize electrochemical performance. To this end, we synthesized a series of nanoporous LiFe_xMn_1−xPO₄ compounds (with x = 0, 0.05, 0.1, 0.15, and 0.2), using an inexpensive solid-state reaction. The electrodes were characterized using X-ray diffraction and energy-dispersive spectroscopy to examine their crystal structure and elemental distribution. Scanning-, tunneling-, and transmission-electron microscopy (viz., SEM, STEM, and TEM) were employed to characterize the micromorphology of these materials; the carbon content was analyzed by thermogravimetric analyses (TGAs). We demonstrate that the electrochemical performance of LiFe_xMn_1−xPO₄ rises continuously with increasing iron content. In situ synchrotron studies during cycling revealed a reversible structural change when lithium is inserted and extracted from the crystal structure. Further, introducing 20% iron (e.g., LiFe_0.2Mn_0.8PO₄) resulted in a promising capacity (138 mAh g⁻¹ at C/10), comparable to that previously reported for nano-LiMnPO₄.     

A novel high-performance cylindrical hybrid supercapacitor with Li4−xNaxTi5O12/activated carbon electrodes

A cylindrical hybrid supercapacitor was fabricated using Li_4−xNa_xTi₅O₁₂ as an anode and activated carbon as a cathode. Li_4−xNa_xTi₅O₁₂ (0 ≤ x ≤ 0.6) powder was successfully crystallized, and the grain size of Li_4−xNa_xTi₅O₁₂ decreased with increasing Na content. This indicated that Na can enhance the electrochemical performance due to smaller grain size and ionic conductivity. However, excessive Na content causes a distortion of the original Li₄Ti₅O₁₂ structure during cycling. The hybrid supercapacitor with the Li_3.7Na_0.3Ti₅O₁₂ anode shows similar electrochemical performance to Li_3.4Na_0.6Ti₅O₁₂, and approximately 92% of the maximum cycle performance is retained, even after 5000 cycles at 2.5 Ag⁻¹.     

Li1+xFePO4 (0 ≤ x ≤ 3) as anode material for lithium ion batteries: From ab initio studies

Li_1+xFePO₄ (0 ≤ x ≤ 3) as anode material for lithium ion batteries has been studied using ab initio calculations. Results show that large amount of lithium ions can be intercalated into LiFePO₄ host. The structure changes continuously when the first two Moles of lithium ions (x ≤ 2) are intercalated into the LiFePO₄ host, accompanied by large volume expansion (37.4% and 25.4% for the first and second Mole). The final product of Li₃FePO₄ possesses a stable chained structure, which is favorable for storing even more lithium. In the same time, lithium ion diffuses in a three-dimension pathway within the chained structure. The unit cell volume increases only by 4.9% from Li₃FePO₄ to Li₄FePO₄, and the chained structure keeps unchanged.     

Electrochemical properties of LiFe0.9Mn0.1PO4/Fe2P cathode material by mechanical alloying

LiFePO₄, olivine-type LiFe_0.9Mn_0.1PO₄/Fe₂P composite was synthesized by mechanical alloying of carbon (acetylene back), M₂O₃ (M = Fe, Mn) and LiOH·H₂O for 2 h followed by a short-time firing at 900 °C for only 30 min. By varying the carbon excess different amounts of Fe₂P second phase was achieved. The short firing time prevented grain growth, improving the high-rate charge/discharge capacity. The electrochemical performance was tested at various C/x-rate. The discharge capacity at 1C rate was increased up to 120 mAh g⁻¹ for the LiFe_0.9Mn_0.1PO₄/Fe₂P composite, while that of the unsubstituted LiFePO₄/Fe₂P and LiFePO₄ showed only 110 and 60 mAh g⁻¹, respectively. Electronic conductivity and ionic diffusion constant were measured. The LiFe_0.9Mn_0.1PO₄/Fe₂P composite showed higher conductivity and the highest diffusion coefficient (3.90 × 10⁻¹⁴ cm² s⁻¹). Thus the improvement of the electrochemical performance can be attributed to (1) higher electronic conductivity by the formation of conductive Fe₂P together with (2) an increase of Li⁺ ion mobility obtained by the substitution of Mn²⁺ for Fe²⁺.     

Synthesis and performance of Li3(V1−xMgx)2(PO4)3 cathode materials

In order to search for cathode materials with better performance, Li₃(V_1−xMg_x)₂(PO₄)₃ (0, 0.04, 0.07, 0.10 and 0.13) is prepared via a carbothermal reduction (CTR) process with LiOH·H₂O, V₂O₅, Mg(CH₃COO)₂·4H₂O, NH₄H₂PO₄, and sucrose as raw materials and investigated by X-ray diffraction (XRD), scanning electron microscopic (SEM) and electrochemical impedance spectrum (EIS). XRD shows that Li₃(V_1−xMg_x)₂(PO₄)₃ (x = 0.04, 0.07, 0.10 and 0.13) has the same monoclinic structure as undoped Li₃V₂(PO₄)₃ while the particle size of Li₃(V_1−xMg_x)₂(PO₄)₃ is smaller than that of Li₃V₂(PO₄)₃ according to SEM images. EIS reveals that the charge transfer resistance of as-prepared materials is reduced and its reversibility is enhanced proved by the cyclic votammograms. The Mg²⁺-doped Li₃V₂(PO₄)₃ has a better high rate discharge performance. At a discharge rate of 20 C, the discharge capacity of Li₃(V_0.9Mg_0.1)₂(PO₄)₃ is 107 mAh g⁻¹ and the capacity retention is 98% after 80 cycles. Li₃(V_0.9Mg_0.1)₂(PO₄)₃//graphite full cells (085580-type) have good discharge performance and the modified cathode material has very good compatibility with graphite.     

Electrochemical performances of LiFe1−xMnxPO4 with high Mn content

A series of LiFe_1−xMn_xPO₄/C materials with high Mn content (0.7 ≤ x ≤ 0.9) are synthesized by solid state reaction. The samples have mesoporous structure with an average pore size of 25 nm, particle size around 200-300 nm, crystalline size around 30 nm and specific areas around 50 m² g⁻¹. Their electrochemical performances are studied and the reversible capacity and rate performance decrease with the increase of Mn content. The redox potential of the Fe²⁺/Fe³⁺ and Mn²⁺/Mn³⁺ redox couple also shift accordingly. The overpotential value of the Mn²⁺/Mn³⁺ redox couple (80 mV) is close to that of the Fe²⁺/Fe³⁺ couple (60 mV) in all three compositions and shows a maximum (∼300 mV) in the regions of voltage transition.     

Pillared layered Li1−2xCaxCoO2 cathode materials obtained by cationic exchange under hydrothermal conditions

A simple method has been employed to prepare pillared layered Li_1−2xCa_xCoO₂ cathode materials by cationic exchange under hydrothermal conditions. The synthesized materials were characterized by means of X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), field emission scanning electron microscope (FE-SEM) and galvanostatic charge–discharge cycling. The XRD data of the products show that they are single phases and retain the layered α-NaFeO₂ type structure. The FE-SEM images of the materials prepared by hydrothermal method show uniform small particles, and the particle size of the materials is about 200 nm. The initial discharge specific capacities of layered LiCoO₂ and pillared layered Li_0.946Ca_0.027CoO₂ cathode materials calcined at 800 °C for 5 h within the potential range of 3.0–4.3 V (vs. Li⁺/Li) are 144.6 and 142.3 mAh g⁻¹, respectively, and both materials retain good charge–discharge cycling performance. However, with increasing upper cutoff voltage, the pillar effect of Ca²⁺ in Li_1−2xCa_xCoO₂ becomes more significant. The pillared layered Li_0.946Ca_0.027CoO₂ has a higher capacity with an initial discharge specific capacity of 177.9 and 215.8 mAh g⁻¹ within the potential range of 3.0–4.5 and 4.7 V (vs. Li⁺/Li), respectively, and retains good charge–discharge cycling performance.     

Effect of CO2 on layered Li1+zNi1−x−yCoxMyO2 (M = Al,Mn) cathode materials for lithium ion batteries

We investigated the effect of CO₂ on layered Li_1+zNi_1−x−yCo_xM_yO₂ (M = Al, Mn) cathode materials for lithium ion batteries which were prepared by solid-state reactions. Li_1+zNi_(1−x)/2Co_xMn_(1−x)/2O₂ (Ni/Mn mole ratio = 1) singularly exhibited high storage stability. On the other hand, Li_1+zNi_0.80Co_0.15Al_0.05O₂ samples were very unstable due to CO₂ absorption. XPS and XRD measurements showed the reduction of Ni³⁺ to Ni²⁺ and the formation of Li₂CO₃ for Li_1+zNi_0.80Co_0.15Al_0.05O₂ samples after CO₂ exposure. SEM images also indicated that the surfaces of CO₂-treated samples were covered with passivation films, which may contain Li₂CO₃. The relationship between CO₂-exposure time and CO₃²⁻ content suggests that there are two steps in the carbonation reactions; the first step occurs with the excess Li components, Li₂O for example, and the second with LiNi_0.80Co_0.15Al_0.05O₂ itself. It is well consistent with the fact that the discharge capacity was not decreased and the capacity retention was improved until the excess lithium is consumed and then fast deterioration occurred.     

The effect of carbon coating thickness on the capacity of LiFePO4/C composite cathodes

Two types of carbon source and precursor mixing pellets were employed simultaneously to prepare the LiFePO₄/C composite materials: Type I using the LiFePO₄ precursor with 20 wt.% polystyrene (PS) as a primary carbon source, and Type II using the LiFePO₄ precursor with 50 wt.% malonic acid as a secondary carbon vapor source. During final sintering, a Type I pellet was placed down-stream and Type II precursor pellet(s) was(were) placed upstream next to a Type I precursor pellet in a quartz-tube furnace. The carbon-coated product of the sintered Type I precursor pellet was obtained by using both PS and malonic acid as carbon sources. When two Type II pellets were used as a carbon vapor source (defined as Product-2), a more uniform film between 4 and 8 nm was formed, as shown in the TEM images. In the absence of a secondary carbon source (defined as Product-0), the discharge capacity of Product-0 was 137 mAh g⁻¹ with 100 cycles at a 0.2C-rate, but Product-2 demonstrated a high capacity of 151 mAh g⁻¹ with 400 cycles. Our results indicate that electrochemical properties of LiFePO₄ are correlated to the amount of carbon and its coating thickness and uniformity.     

Electrochemical characteristics of Li2−xVTiO4 rock salt phase in Li-ion batteries

Li_2−xVTiO₄/C sample with a disordered rock salt structure was successfully prepared by annealing at a temperature of 850 °C. The electrochemical oxidation in the first cycle occurs at voltages above 4 V vs. metallic lithium, while the shapes of the electrochemical curves in consequent reduction-oxidation processes show a monotonous change of the potential between the selected cut-off voltages. A linear combination fit of individual XANES spectra was used for the determination of the oxidation states of as prepared sample and intermediate states during oxidation and reduction. In the as-prepared sample, vanadium was found to be in the average oxidation state of V^3.5+ and was additionally oxidized to V^3.8+ by the electrochemical charging. During the discharge process, the vanadium oxidation state was reduced to V^3.0+. In situ X-ray diffraction patterns and EXAFS analysis suggest good structural stability during oxidation and reduction, which is also reflected in the cycling stability if batteries were cycled in the voltage window between 2.0 V and 4.4 V. Extension of the lower cut-off voltage to 1.0 V doubles the capacity retention with the improved capacity stability if compared with several high capacity vanadium based materials.     

Minimization of the cation mixing in Li1+x(NMC)1−xO2 as cathode material

Li_1+x(Ni_1/3Mn_1/3Co_1/3)_1−xO₂ layered materials were synthesized by the co-precipitation method with different Li/M molar ratios (M = Ni + Mn + Co). Elemental titration evaluated by inductively coupled plasma spectrometry (ICP), structural properties studied by X-ray diffraction (XRD), Rietveld analysis of XRD data, scanning electron microscopy (SEM) and magnetic measurements carried out by superconducting quantum interference devices (SQUID) showed the well-defined α-NaFeO₂ structure with cationic distribution close to the nominal formula. The Li/Ni cation mixing on the 3b Wyckoff site of the interlayer space was consistent with the structural model [Li_1−yNi_y]_3b[Li_x+yNi_{(1−x)/3−y}Mn_(1−x)/3Co_(1−x)/3]_3aO₂ (x = 0.02, 0.04) and was very small. Both Rietveld refinements and magnetic measurements revealed a concentration of Ni²⁺-3b ions lower than 2%; moreover, for the optimized sample synthesized at Li/M = 1.10, only 1.43% of nickel ions were located into the Li sublattice. Electrochemical properties were investigated by galvanostatic charge-discharge cycling. Data obtained with Li_1+x(Ni_1/3Mn_1/3Co_1/3)_1−xO₂ reflected the high degree of sample optimization. An initial discharge capacity of 150 mAh g⁻¹ was delivered at 1 C-rate in the cut-off voltage of 3.0-4.3 V. More than 95% of its initial capacity was retained after 30 cycles at 1 C-rate. Finally, it is demonstrated that a cation mixing below 2% is considered as the threshold for which the electrochemical performance does not change for Li_1+x(Ni_1/3Mn_1/3Co_1/3)_1−xO₂.     

Effect of Bi oxide surface treatment on 5 V spinel LiNi0.5Mn1.5−xTixO4

The effect of Bi surface treatment on LiNi_0.5Mn_1.5−xTi_xO₄ was examined. As a result, Bi surface film around 20 nm thick was confirmed to be fabricated on the surface of 5 V spinel LiNi_0.5Mn_1.5−xTi_xO₄ by transmission electron microscopy (TEM) and energy dispersion X-ray spectrometer (EDX) analysis. The Bi compound was confirmed to be Bi₂O₃ by X-ray diffraction analysis. Cycle behavior was also found to be improved by Bi treatment. A retention capacity of up to around 85% was achieved after 500 cycles at 20 °C, while a retention capacity as high as 70% was obtained after 500 cycles, even at 45 °C. Storage performance was also improved with Bi treatment. Recovery capacity of more than 90% was obtained with Bi treatment after storage for 1 week at 60 °C. The increased resistance in storage was also suppressed with Bi treatment, which would be due to the suppression of electrolyte decomposition by the Bi coating film. It was found that Bi treatment had the effect of decreasing the dissolution of Mn, Ni and Ti of the elements of the cathode active material, due to inductively coupled plasma (ICP) analysis. Based on these results, the Bi surface coating was found to have a remarkable effect on the improvement of the cells with 5 V spinel.     

Physical and electrochemical properties of spherical Li1+x(Ni1/3Co1/3Mn1/3)1−xO2 cathode materials

A (Ni_1/3Co_1/3Mn_1/3)CO₃ precursor with an uniform, spherical morphology was prepared by coprecipitation using a continuously stirred tank reactor method. The as-prepared spherical (Ni_1/3Co_1/3Mn_1/3)CO₃ precursor served to produce dense, spherical Li_1+x(Ni_1/3Co_1/3Mn_1/3)_1−xO₂ (0 ≤ x ≤ 0.15) cathode materials. These Li-rich cathodes were also prepared by a second synthesis route that involved the use of an M₃O₄ (M = Ni_1/3Co_1/3Mn_1/3) spinel compound, itself obtained from the carbonate (Ni_1/3Co_1/3Mn_1/3)CO₃ precursor. In both cases, the final Li_1+x(Ni_1/3Co_1/3Mn_1/3)_1−xO₂ products were highly uniform, having a narrow particle size distribution (10-μm average particle size) as a result of the homogeneity and spherical morphology of the starting mixed-metal carbonate precursor. The rate capability of the Li_1+x(Ni_1/3Co_1/3Mn_1/3)_1−xO₂ electrode materials, which was significantly improved with increased lithium content, was found to be better in the case of the denser materials made from the spinel precursor compound. This result suggests that spherical morphology, high density, and increased lithium content were key factors in enabling the high rate capabilities, and hence the power performances, of the Li-rich Li_1+x(Ni_1/3Co_1/3Mn_1/3)_1−xO₂ cathodes.     

Electrochemical activity of Li2FeTiO4 and Li2MnTiO4 as potential active materials for Li ion batteries: A comparison with Li2NiTiO4

We demonstrate, for the first time, a considerable electrochemical activity of two members of lithium transition element titanates: Li₂FeTiO₄ and Li₂MnTiO₄. Both materials consist of 10–20 nm particles embedded in a conductive carbon coating. We show that not the coating but the small particle size is decisive for materials’ activity. Li₂FeTiO₄ shows a stable reversible capacity of up to 123 mA hg⁻¹ at C/20 and 60 °C which is 83% of the theoretical value for exchange of 1 electron (148 mA hg⁻¹). Li₂MnTiO₄ could only be prepared in a nanosized form that contained about 30% of impurities. The capacity of the whole material (including impurities) is comparable to that of Li₂FeTiO₄ but the cycling stability is much poorer. In contrast to the Fe and Mn analogues, the third member of the titanate family, Li₂NiTiO₄, shows a good electrochemistry even when the particle size is much larger (about 100 nm). During initial cycles at C/10 and 60 °C, exchange of more than 1 electron per compound formula has been observed. The cycling stability at high temperatures, however, is poor.     

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.     

Synthesis and photoelectrochemical study of BiWxV1−xO4+x/2 films by a polymer-assisted method

A series of BiW_xV_1−xO_4+x/2 films were coated on fluorine-doped tin oxide (FTO) glass by a polymer-assisted method and examined as photoelectrodes for photoelectrochemical measurements under Xe lamp light irradiation in a 0.5 M Na₂SO₄ solution. The compositions, structural, optical and morphologic properties of the films were characterized by XPS, XRD, UV–vis and SEM. The results showed the successfully synthesized films and their photoelectrochemical activities, revealing that the amount of tungsten had an important effect on the photoelectrochemical activities of BiW_xV_1−xO_4+x/2 films and the highest incident photon to current conversion efficiency (IPCE) was obtained when x equaled 0.1.     

Thermal stability of Li1−yNixMn(1−x)/2Co(1−x)/2O2 layer-structured cathode materials used in Li-Ion batteries

In order to develop safe lithium-ion batteries using Ni-based cathode active materials, such as LiNi_xMn_(1−x)/2Co_(1−x)/2O₂, thermal stability is one of the most important requirements. We used XRD and TDS-MS in the first step of our study to elucidate the thermal stability and to improve it under anomalous high temperature conditions. We investigated the relationship between the thermal stability and cathode composition, especially for that of the nickel and lithium content. The XRD indicated that the crystal structure of electrochemically delithiated materials changed from a layered into a spinel structure followed by a rock-salt structure as the temperature rose. The TDS-MS indicated that these changes coincided with the release of oxygen from the cathode materials. We found that decreasing the lithium content and increasing the nickel content made the temperature of the crystal structure change and oxygen release lower, and thus, influenced the cathode composition.