Novel graphite/TiO2 electrochemical cells as a safe electric energy storage system

A graphite/TiO₂ full cell has been developed as a new safety energy storage system using a highly safety process. The crystal structures of the anatase TiO₂ electrode have been investigated with respect to the performance of the electrodes. Due to the large anion intercalation into the graphite positive electrode, the possible charging potential can be raised to around 5.3 V against the Li/Li⁺ electrode, which is a higher charging voltage than lithium-ion batteries (maximum voltage is around 4.3 V vs. Li/Li⁺). In situ XRD measurements have been carried out on both the cathode and anode electrodes of the graphite/TiO₂ cell during the charge process to elucidate the intercalation mechanism.     

Behaviour of highly crystalline graphitic materials in lithium-ion cells with propylene carbonate containing electrolytes: An in situ Raman and SEM study

The microcrystalline flaked graphites SFG6 and SFG44 were evaluated with regard to their compatibility with propylene carbonate (PC) by in situ Raman microscopy and postmortem scanning electron microscopy (SEM) study. PC is employed as electrolyte component in lithium-ion batteries. However, when used with certain types of graphitic materials, exfoliation occurs. To compare the effects of exfoliation, the first lithium insertion properties of these graphitic materials were measured with in situ Raman microscopy. Lithium half-cells containing either 1 M LiClO₄ 1:1 (w/w) ethylene carbonate (EC):dimethyl carbonate (DMC) or 1:1 (w/w) EC:PC were investigated. The commencement of the exfoliation process was detected in SFG44 EC:PC by the appearance of a shoulder band at 1597 cm⁻¹ on the G-band (1584 cm⁻¹) below 0.9 V versus Li/Li⁺. The band (assigned as the exfoliation or E-band) at higher wavenumbers (1597 cm⁻¹) corresponded to solvated lithium ions intercalated into graphite. The in situ Raman spectra of SFG6 in EC:DMC or EC:PC and SFG44 in EC:DMC did not show the E-band and instead displayed regular lithium intercalation spectra.In situ Raman microscopy and SEM were further employed to study the exfoliation process observed for SFG44 in 1:1 (w/w) EC:PC, when the potential was held under steady-state conditions at 0.8, 0.6 and 0.3 V, respectively. A blue-shift in the E-band from 1597 to 1607 cm⁻¹ was observed as the potential was lowered. SEM images showed dissimilar degrees of exfoliation at these three potentials.     

Impedance study of protecting film formation on lithium and lithiated graphite induced by bis(fluorosulfonyl) imide anion

The process of Li⁺ reduction from room temperature ionic liquids consisting of N-methyl-N-propylpyrrolidinium cation (MPPyr⁺) and bis(fluorosulfonyl) imide (FSI⁻) or bis(trifluoromethanesulfonyl) imide (TFSI⁻) anions was studied with the use of impedance spectroscopy. Reduction was carried out on both metallic lithium (Li) and graphite (G) electrodes. It has been found that the FSI anion in high amounts is able to form a protective film on both graphite and metallic lithium. The Li⁺/Li couple should rather be represented by a Li⁺/SEI/Li system. The SEI structure depends on the manner of its formation (chemical or electrochemical) and is not stable with time. The rate constant for the Li⁺ + e⁻ → Li process at the Li/SEI/Li⁺ (in MPPyrFSI) interface is k_o = 4.2 × 10⁻⁵ cm/s. In the case of carbon electrodes (G/SEI/Li⁺ interface), lithium diffusion in solid graphite is the rate determining step, reducing current by ca. two orders of magnitude, from ca. 10⁻⁴ A/cm², characteristic of the Li/SEI/Li⁺ electrode, to ca. 10⁻⁶ A/cm².     

Preparation and characterization of ramsdellite Li2Ti3O7 as an anode material for asymmetric supercapacitors

Ramsdellite Li₂Ti₃O₇ was first synthesized via sol-gel process with good crystallity of an average particle size of 0.175 μm. The product was thoroughly investigated as a lithium intercalation compound, and as an active anode material in asymmetric supercapacitors coupling with activated carbon as cathode. Lithium intercalation reactions were found occurring at 1.32 and 1.62 V versus Li/Li⁺, respectively. A reversible specific capacity of 150 mA h g⁻¹ at 1C was obtained on Li₂Ti₃O₇ electrode in a nonaqueous electrolyte. The charge current was found to strongly influence the anodic discharge capacity in the asymmetric cell. The capacity retention at 10C charge-discharge rate was found to be 75.9% in comparison with that at 1C.     

In situ X-ray diffraction study of different graphites in a propylene carbonate based electrolyte at very positive potentials

Synchrotron based in situ X-ray powder diffraction was applied for the investigation of the PF₆⁻ intercalation behaviour into graphite of different particle size and various crystallinity at very positive potentials above 5 V vs. Li/Li⁺. In a propylene carbonate based electrolyte, small particles with low crystallinity show almost no anion intercalation and the particle structure remains intact. In graphite particles with increased particle size and/or higher crystallinity PF₆⁻ intercalation up to a stage 4 phase occurs but the reversibility is poor and exfoliation of graphene layers takes place as it was proven by post-mortem scanning electron microscopy. Thus, graphites with small particles and less crystallinity are preferred as conductive additive in positive “high voltage” cathodes in terms of structural integrity.     

Spray-drying synthesized lithium-excess Li4+xTi5−xO12−δ and its electrochemical property as negative electrode material for Li-ion batteries

Li₄Ti₅O₁₂ (Fd-3m space group) materials were synthesized by controlling the lithium and titanium ratios (Li/Ti) in the range of 0.800-0.900 by using a spray-drying method, followed by calcination at several temperatures between 700 and 900 °C for large-scale production. Chemical and structure studies of the final products were done by X-ray diffraction (XRD), neutron diffraction (ND), X-ray photon electron spectroscopy (XPS), scanning electron microscopy (SEM) and inductively coupled plasma mass spectrometry (ICP-MS). The optimum synthesis condition was examined in relation to the electrochemical characteristics including charge-discharge cycling and ac impedance spectroscopy. It was found that when the spray-drying precursors at the Li/Ti ratio of 0.860 were calcined at 700-900 °C for 12 h in air, a pure Li_4+xTi_5−xO_12−δ (x = 0.06-0.08) phase with a lithium-excess composition was obtained. Based on the structural studies, it was found that the excess lithium is located at the lithium and titanium layer of the 16d site in the spinel structure (Fd-3m). These pure Li_4+xTi_5−xO_12−δ (x = 0.06-0.08) phase materials showed a higher discharge capacity of ∼164 mAh g⁻¹ at 1.55 V (vs. Li/Li⁺), between the cut-off voltage of 1.2-3.0, with an excellent cyclability and superior rate performance in comparison with the Li₄Ti₅O₁₂ phase containing impurity phases.     

High lithium conductivities in weakly-ionophilic low-dimensional block copolymer electrolytes

The structure of amphiphilic low-dimensional copolymer electrolytes I of similar overall composition but prepared by different synthetic procedures X and Y are described. I are copolymers of poly[2,5,8,11,14-pentaoxapentadecamethylene(5-alkyloxy-1,3-phenylene)] (CmO5) and poly[2,-oxatrimethylene(5-alkyloxy-1,3-phenylene)] (CmO1) where the alkyl side chains having m carbons are hexadecyl or mixed dodecyl/octadecyl (50/50). ¹H NMR shows that the copolymers have 50% (m = 16) or only 18 and 13% of CmO5 units and DSC indicates that the copolymers have ‘block’ sequencing of CmO1 and CmO5 segments. Molecular dynamics modelling indicates that in CmO5 Li⁺ and BF₄⁻ ions are separated by Li⁺ encapsulation in tetraethoxy segments but in ionophobic CmO1 units the salt is mostly present as neutral aggregates decoupled from the polymer. Conductivities of these microphase-separated mixtures with salt-bridge amphiphilic polyethers II and III of each system are similar. They have low temperature dependence over the range 20 °C to 110 °C at ∼10⁻³ S cm⁻¹. ⁷Li NMR linewidth measurements confirm high lithium mobilities at −20 °C. A conduction mechanism is proposed whereby Li⁺ hopping takes place along rows of decoupled aggregates (dimers/quadrupoles) within an essentially block copolymer structure. Subambient measurements to −10 °C gave a conductivity of 4 × 10⁻⁵ S cm⁻¹.     

Synthesis and electrochemical properties of Co-doped Li3V2(PO4)3 cathode materials for lithium-ion batteries

Co-doped Li₃V_2−xCo_x(PO₄)₃/C (x = 0.00, 0.03, 0.05, 0.10, 0.13 or 0.15) compounds were prepared via a solid-state reaction. The Rietveld refinement results indicated that single-phase Li₃V_2−xCo_x(PO₄)₃/C (0 ≤ x ≤ 0.15) with a monoclinic structure was obtained. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the cobalt is present in the +2 oxidation state in Li₃V_2−xCo_x(PO₄)₃. XPS studies also revealed that V⁴⁺ and V³⁺ ions were present in the Co²⁺-doped system. The initial specific capacity decreased as the Co-doping content increased, increasing monotonically with Co content for x > 0.10. Differential capacity curves of Li₃V_2−xCo_x(PO₄)₃/C compounds showed that the voltage peaks associated with the extraction of three Li⁺ ions shifted to higher voltages with an increase in Co content, and when the Co²⁺-doping content reached 0.15, the peak positions returned to those of the unsubstituted Li₃V₂(PO₄)₃ phase. For the Li₃V_1.85Co_0.15(PO₄)₃/C compound, the initial capacity was 163.3 mAh/g (109.4% of the initial capacity of the undoped Li₃V₂(PO₄)₃) and 73.4% capacity retention was observed after 50 cycles at a 0.1 C charge/discharge rate. The doping of Co²⁺into V sites should be favorable for the structural stability of Li₃V_2−xCo_x(PO₄)₃/C compounds and so moderate the volume changes (expansion/contraction) seen during the reversible Li⁺ extraction/insertion, thus resulting in the improvement of cell cycling ability.     

Electrochemical behavior of LiCoO2 in a saturated aqueous Li2SO4 solution

The electrochemical behavior of a commercial LiCoO₂ with spherical shape in a saturated Li₂SO₄ aqueous solution was investigated with cyclic voltammetry and electrochemical impedance spectroscopy. Three redox couples at E_SCE = 0.87/0.71, 0.95/0.90 and 1.06/1.01 V corresponding to those found at ELi/Li⁺=4.08/3.83, 4.13/4.03 and 4.21/4.14 V in organic electrolyte solutions were observed. The diffusion coefficient of lithium ions is 1.649 × 10⁻¹⁰ cm² s⁻¹, close to the value in organic electrolyte solutions. The results indicate that the intercalation and deintercalation behavior of lithium ions in the Li₂SO₄ solution is similar to that in the organic electrolyte solutions. However, due to the higher ionic conductivity of the aqueous solution, current response and reversibility of redox behavior in the aqueous solution are better than in the organic electrolyte solutions, suggesting that the aqueous solution is favorable for high rate capability. The charge transfer resistance, the exchange current and the capacitance of the double layer vary with the charge voltage during the deintercalation process. At the peak of the oxidation (0.87 V), the charge transfer resistance is the lowest. These fundamental results provide a good base for exploring new safe power sources for large scale energy storage.     

Electrochemical characterization of amorphous LiFe(WO4)2 thin films as positive electrodes for rechargeable lithium batteries

Amorphous LiFe(WO₄)₂ thin films have been fabricated by radio-frequency (R.F.) sputtering deposition at room temperature. The as-deposited and electrochemically cycled thin films are, respectively, characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectra techniques. An initial discharge capacity of 198 mAh/g in Li/LiFe(WO₄)₂ cells is obtained, and the electrochemical behavior is mostly preserved in the following cycling. These results identified the electrochemical reactivity of two redox couples, Fe³⁺/Fe²⁺ and W⁶⁺/W^x+ (x = 4 or 5). The kinetic parameters and chemical diffusion coefficients of Li intercalation/deintercalation are estimated by cyclic voltammetry and alternate-current (AC) impedance measurements. All-solid-state thin film lithium batteries with Li/LiPON/LiFe(WO₄)₂ layers are fabricated and show high capacity of 104 μAh/cm² μm in the first discharge. As-deposited LiFe(WO₄)₂ thin film is expected to be a promising positive electrode material for future rechargeable thin film batteries due to its large volumetric rate capacity, low-temperature fabrication and good electrode/electrolyte interface.     

In situ X-ray diffraction of the intercalation of (C2H5)4N and BF4 into graphite from acetonitrile and propylene carbonate based supercapacitor electrolytes

The intercalation of (C₂H₅)₄N⁺ and BF₄⁻ from acetonitrile (AN) and propylene carbonate (PC) solutions into bound graphite electrodes during cyclic voltammetry was investigated by in situ X-ray diffraction (XRD) using synchrotron radiation. The disappearance of the 0 0 2 reflection of graphite in the XRD patterns upon intercalation of (C₂H₅)₄N⁺ indicates that the cations are accumulated between the graphene layers. For the intercalation of BF₄⁻, the appearance of 0 0 l reflexes in the intercalated state provides clear evidence of staging. In both cases, the in-plane periodicity was not significantly altered by the intercalation process apart from slight changes in the CC bond length. The intercalation of BF₄⁻ from the PC-based electrolyte was found to have the least destructive effect on the periodicity of the graphite structure during initial cycling in the anodic potential range along with the highest charge/discharge efficiency.     

Synthesis and characterization of high-density non-spherical Li(Ni1/3Co1/3Mn1/3)O2 cathode material for lithium ion batteries by two-step drying method

Non-spherical Li(Ni_1/3Co_1/3Mn_1/3)O₂ powders have been synthesized using a two-step drying method with 5% excess LiOH at 800 °C for 20 h. The tap-density of the powder obtained is 2.95 g cm⁻³. This value is remarkably higher than that of the Li(Ni_1/3Co_1/3Mn_1/3)O₂ powders obtained by other methods, which range from 1.50 g cm⁻³ to 2.40 g cm⁻³. The precursor and Li(Ni_1/3Co_1/3Mn_1/3)O₂ are characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscope (SEM). XPS studies show that the predominant oxidation states of Ni, Co and Mn in the precursor are 2⁺, 3⁺ and 4⁺, respectively. XRD results show that the Li(Ni_1/3Co_1/3Mn_1/3)O₂ material obtained by the two-step drying method has a well-layered structure with a small amount of cation mixing. SEM confirms that the Li(Ni_1/3Co_1/3Mn_1/3)O₂ particles obtained by this method are uniform. The initial discharge capacity of 167 mAh g⁻¹ is obtained between 3 V and 4.3 V at a current of 0.2 C rate. The capacity of 159 mAh g⁻¹ is retained at the end of 30 charge-discharge cycle with a capacity retention of 95%.     

Preparation and cycling performance of Aland F co-substituted compounds Li4AlxTi5−xFyO12−y

Li₄Al_xTi_5−xF_yO_12−y compounds were prepared by a solid-state reaction method. Phase analyses demonstrated that both Al³⁺ and F⁻ ions entered the structure of spinel-type Li₄Ti₅O₁₂. Charge-discharge cycling results at a constant current density of 0.15 mA cm⁻² between the cut-off voltages of 2.5 and 0.5 V showed that the Al³⁺ and F⁻ substitutions improved the first total discharge capacity of Li₄Ti₅O₁₂. However, Al³⁺ substitution greatly increased the reversible capacity and cycling stability of Li₄Ti₅O₁₂ while F⁻ substitution decreased its reversible capacity and cycling stability slightly. The electrochemical performance of the Al³⁺-F⁻-co-substituted specimen was better than the F⁻-substituted one but worse than the Al³⁺-substituted one.     

Carbon coated Li3V2(PO4)3 cathode material prepared by a PVA assisted sol-gel method

Carbon coated Li₃V₂(PO₄)₃ cathode material was prepared by a poly(vinyl alcohol) (PVA) assisted sol-gel method. PVA was used both as the gelating agent and the carbon source. XRD analysis showed that the material was well crystallized. The particle size of the material was ranged between 200 and 500 nm. HRTEM revealed that the material was covered by a uniform surface carbon layer with a thickness of 80 Å. The existence of surface carbon layer was further confirmed by Raman scattering. The electrochemical properties of the material were investigated by charge-discharge cycling, CV and EIS techniques. The material showed good cycling performance, which had a reversible discharge capacity of 100 mAh g⁻¹ when cycled at 1 C rate. The apparent Li⁺ diffusion coefficients of the material ranged between 9.5 × 10⁻¹⁰ and 0.9 × 10⁻¹⁰ cm² s⁻¹, which were larger than those of olivine LiFePO₄. The large lithium diffusion coefficient of Li₃V₂(PO₄)₃ has been attributed to its special NASICON-type structure.     

Preparation of micro-dot electrodes of LiCoO2 and Li4Ti5O12 for lithium micro-batteries

Fabrications of micro-dot electrodes of LiCoO₂ and Li₄Ti₅O₁₂ on Au substrates were demonstrated using a sol-gel process combined with a micro-injection technology. A typical size of prepared dots was about 100 μm in diameter, and the dot population on the substrate was 2400 dots cm⁻². The prepared LiCoO₂ and Li₄Ti₅O₁₂ micro-dot electrodes were characterized with scanning electron microscopy, X-ray diffraction, micro-Raman spectroscopy, and cyclic voltammetry. The prepared LiCoO₂ and Li₄Ti₅O₁₂ micro-dot electrodes were evaluated in an organic electrolyte as cathode and anode for lithium micro-battery, respectively. The LiCoO₂ micro-dot electrode exhibited reversible electrochemical behavior in a potential range from 3.8 to 4.2 V versus Li/Li⁺, and the Li₄Ti₅O₁₂ micro-dot electrode showed sharp redox peaks at 1.5 V.     

Structural and electrochemical behaviors of metastable Li2/3[Ni1/3Mn2/3]O2 modified by metal element substitution

Layered metastable lithium manganese oxides, Li_2/3[Ni_1/3−xMn_2/3−yM_x+y]O₂ (x = y = 1/36 for M = Al, Co, and Fe and x = 2/36, y = 0 for M = Mg) were prepared by the ion exchange of Li for Na in P2-Na_2/3[Ni_1/3−xMn_2/3−yM_x+y]O₂ precursors. The Al and Co doping produced the T^#2 structure with the space group Cmca. On the other hand, the Fe and Mg doped samples had the O6 structure with space group R-3m. Electron diffraction revealed the 1:2 type ordering within the Ni_1/3−xMn_2/3−yM_x+yO₂ slab. It was found that the stacking sequence and electrochemical performance of the Li cells containing T^#2-Li_2/3[Ni_1/3Mn_2/3]O₂ were affected by the doping with small amounts of Al, Co, Fe, and Mg. The discharge capacity of the Al doped sample was around 200 mAh g⁻¹ in the voltage range between 2.0 and 4.7 V at the current density of 14.4 mA g⁻¹ along with a good capacity retention. Moreover, for the Al and Co doped and undoped oxides, the irreversible phase transition of the T^#2 into the O2 structure was observed during the initial lithium deintercalation.     

In situ transmission FTIR spectroelectrochemistry: A new technique for studying lithium batteries

In situ transmission FTIR spectra are measured during the electrochemical insertion of lithium into phospho-olivine FePO₄. The spectroelectrochemical cell consists of a composite FePO₄ cathode, a lithium metal anode, and an electrolyte of 1 M LiPF₆ in a 1:1 mixture of ethylene carbonate and diethyl carbonate (EC-DEC). Bands belonging to the electrolyte and cathode are identified in the infrared spectra of the in situ cells. The antisymmetric PO₄³⁻ bending vibrations (ν₄) are used to monitor Li⁺ insertion into FePO₄. Discharging produces spectral changes that are consistent with the formation of phospho-olivine LiFePO₄, yet the electrolyte bands are not affected by the discharging process. The in situ infrared experiments confirm the two-phase mechanism for lithium insertion into FePO₄. Moreover, the experiments demonstrate the ability to collect in situ transmission FTIR spectra of functioning electrode materials in lithium batteries. Unfortunately, lithium plating occurs on the optical window when the Li//FePO₄ half-cells are charged. The use of an intercalation anode such as graphite could alleviate this problem; however, this avenue of research is not explored in this study.     

Li diffusion in LiNi0.5Mn0.5O2 thin film electrodes prepared by pulsed laser deposition

Kinetic and transport parameters of Li ion during its extraction/insertion into thin film LiNi_0.5Mn_0.5O₂ free of binder and conductive additive were provided in this work. LiNi_0.5Mn_0.5O₂ thin film electrodes were grown on Au substrates by pulsed laser deposition (PLD) and post-annealed. The annealed films exhibit a pure layered phase with a high degree of crystallinity. Surface morphology and thin film thickness were investigated by field emission scanning electron microscopy (FESEM). The charge/discharge behavior and rate capability of the thin film electrodes were investigated on Li/LiNi_0.5Mn_0.5O₂ cells at different current densities. The kinetics of Li diffusion in these thin film electrodes were investigated by cyclic voltammetry (CV) and galvanostatic intermittent titration technique (GITT). CV was measured between 2.5 and 4.5 V at different scan rates from 0.1 to 2 mV/s. The apparent chemical diffusion coefficients of Li in the thin film electrode were calculated to be 3.13 × 10⁻¹³ cm²/s for Li intercalation and 7.44 × 10⁻¹⁴ cm²/s for Li deintercalation. The chemical diffusion coefficients of Li in the thin film electrode were determined to be in the range of 10⁻¹²-10⁻¹⁶ cm²/s at different cell potentials by GITT. It is found that the Li diffusivity is highly dependent on the cell potential.     

Electrochemical and thermal studies of Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 (x = 1/12, 1/4, 5/12, and 1/2)

Samples of the layered cathode materials, Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ (x = 1/12, 1/4, 5/12, and 1/2), were synthesized at 900 °C. Electrodes of these samples were charged in Li-ion coin cells to remove lithium. The charged electrode materials were rinsed to remove the electrolyte salt and then added, along with EC/DEC solvent or 1 M LiPF₆ EC/DEC, to stainless steel accelerating rate calorimetry (ARC) sample holders that were then welded closed. The reactivity of the samples with electrolyte was probed at two states of charge. First, for samples charged to near 4.45 V and second, for samples charged to 4.8 V, corresponding to removal of all mobile lithium from the samples and also concomitant release of oxygen in a plateau near 4.5 V. Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples with x = 1/4, 5/12 and 1/2 charged to 4.45 V do not react appreciably till 190 °C in EC/DEC. Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples charged to 4.8 V versus Li, across the oxygen release plateau, start to significantly react with EC/DEC at about 130 °C. However, their high reactivity is similar to that of Li_0.5CoO₂ (4.2 V) with 1 μm particle size. Therefore, Li[Ni_xLi_(1/3−2x/3)Mn_(2/3−x/3)]O₂ samples showing specific capacity of up to 225 mAh/g may be acceptable for replacing LiCoO₂ (145 mAh/g to 4.2 V) from a safety point of view, if their particle size is increased.     

Electrochemical study of the interaction between Eu and ciliate Euplotes octocarinatus centrin

A new species was formed when protein P₂₃ (one segment of ciliate Euplotes octocarinatus centrin) was added to a solution of Eu³⁺. The interaction between P₂₃ and Eu³⁺ was investigated by cyclic voltammetry, pulse voltammetry and electrochemical impedance spectroscopy in 10 mM N-2-hydroxyethylpiperazine-N-2-ethanesulfonic acid (HEPES) buffer (pH 7.4) using a pyrolytic graphite electrode. The formal potential (E^o′) of Eu³⁺ shifted from −0.61 to −0.84 V (versus saturated calomel electrode) after P₂₃ was added to the Eu³⁺ solution. The diffusion coefficient (D), the charge-transfer coefficient (α) and the electron transfer standard rate constant (k_s) were obtained in the absence and the presence of P₂₃. The affinity constant of Eu³⁺ and P₂₃ was determined to be (1.89 ± 0.51) × 10⁴ M⁻¹. The electrochemical investigation of europium bound to the protein provided useful data for the studies of calcium-binding proteins.