Electrochemistry of LiMn2O4 epitaxial films deposited on various single crystal substrates

LiMn₂O₄ epitaxial thin films were synthesized on SrTiO₃:Nb(1 1 1) and Al₂O₃(0 0 1) single crystal substrates by pulsed laser deposition (PLD) method and the electrochemical properties were discussed comparing with that of amorphous LiMn₂O₄ film on polycrystalline Au substrate. LiMn₂O₄ epitaxial film showed only a single plateau in charge–discharge curves and a single redox peak at the corresponding voltage of cyclic voltammograms. This phenomenon seems to originate from the effect of the epitaxy: the film is directly connected with the substrate by the chemical bond and this connection would suppress the phase transition of Li_xMn₂O₄ film during lithium (de-)intercalation. The discharge voltage of LiMn₂O₄ epitaxial film on SrTiO₃ was lower than that of LiMn₂O₄ film on Al₂O₃. This lowered discharge voltage may be caused by the electronic interaction between LiMn₂O₄ film and SrTiO₃:Nb n-type semiconductor substrate.     

Mechanistic study on lithium intercalation using a restricted reaction field in LiNi0.5Mn0.5O2

Structure changes of LiNi_0.5Mn_0.5O₂ were detected at the electrode/electrolyte interface of lithium cell using synchrotron X-ray scattering and two-dimensional model electrodes. The electrodes were constructed by an epitaxial film of LiNi_0.5Mn_0.5O₂ synthesized by pulsed laser deposition (PLD) method. The orientation of the film depends on the substrate plane; the 2D layer of LiNi_0.5Mn_0.5O₂ is parallel to the SrTiO₃(1 1 0) substrate ((1 1 0) LiNi_0.5Mn_0.5O₂//(1 1 0) SrTiO₃), while the 2D layer is perpendicular to the SrTiO₃(1 1 1) substrate ((0 0 3) LiNi_0.5Mn_0.5O₂//(1 1 1) SrTiO₃). The in situ X-ray diffraction of LiNi_0.5Mn_0.5O₂(0 0 3) confirmed three-dimensional lithium diffusion through the two-dimensional transition meal layers. The intercalation reaction of LiNi_0.5Mn_0.5O₂ will be discussed.     

Electrochemical performance of In2O3 thin film electrode in lithium cell

Indium oxide (In₂O₃) coating on Pt, as an electrode of thin film lithium battery was carried out by using cathodic electrochemical synthesis in In₂(SO₄)₃ aqueous solution and subsequently annealing at 400 °C. The coated specimens were characterized by X-ray photoelectron spectroscopy (XPS) for chemical bonding, X-ray diffraction (XRD) for crystal structure, scanning electron microscopy (SEM) for surface morphology, cyclic voltammetry (CV) for electrochemical properties, and charging/discharging test for capacity variations. The In₂O₃ coating film composed of nano-sized particles about 40 nm revealing porous structure was used as the anode of a lithium battery. During discharging, six lithium ions were firstly reacted with In₂O₃ to form Li₂O and In, and finally the Li_4.33In phase was formed between 0.7 and 0.2 V, revealing the finer particles size about 15 nm. The reverse reaction was a removal of Li⁺ from Li_4.33In phase at different oxidative potentials, and the rates of which were controlled by the thermodynamics state initially and diffusion rate finally. Therefore, the total capacity was increased with decreasing current density. However, the cell delivering a stable and reversible capacity of 195 mAh g⁻¹ between 1.2 and 0.2 V at 50 μA cm⁻² may provide a choice of negative electrode applied in thin film lithium batteries.     

Vertically aligned nanocomposite La0.8Sr0.2MnO3−δ/Zr0.92Y0.08O1.96 thin films as electrode/electrolyte interfacial layer for solid oxide reversible fuel cells

A thin layer with a vertically aligned nanocomposite (VAN) structure of La_0.8Sr_0.2MnO_3−δ (LSM) and Zr_0.92Y_0.08O_1.96 (YSZ) between the oxygen electrode and the electrolyte has been fabricated by a pulsed laser deposition (PLD) technique for solid oxide reversible fuel cells (SORFCs). The high quality epitaxial growth of VAN structured LSM/YSZ has been achieved on single crystal SrTiO₃ substrate at high-deposition temperatures. The symmetric cells with the VAN interlayer are found to have a lower area specific resistance compared to that without the interlayer. The enhancement in performance has been demonstrated by increased oxygen electrode catalytic properties and porous oxygen electrode microstructure. The cell with the VAN interlayer shows an open circuit voltage (OCV) of 1.00 V at 650 °C and maximum power densities of 0.22, 0.32, 0.43 and 0.55 W cm⁻² at 650, 700, 750 and 800 °C, respectively. Compared with the cell without an interlayer, the cells with the interlayer have ∼2 times of the overall maximum power density at the measured temperature range, demonstrating that the VAN interlayer significantly enhances the oxygen electrode performance.     

Effects of surface modification by MgO on interfacial reactions of lithium cobalt oxide thin film electrode

Magnesium oxide (MgO)-modified lithium cobalt oxide (LiCoO₂) thin film electrodes were prepared by pulsed laser deposition (PLD) and effects of surface modification by MgO on interfacial reactions of LiCoO₂ were studied. The modification by MgO was carried out by PLD on LiCoO₂ thin film electrode successively after the deposition of LiCoO₂ thin film by PLD. Auger electron spectroscopy suggested that Mg dispersed uniformly in nano-scale on the film electrode. Cyclic voltammetry measurements clearly showed that MgO modification suppresses the increase of resistances caused by repetition of lithium-ion insertion–extraction reaction charged up to 4.2 V versus Li/Li⁺. Moreover, MgO modification decreased the activation energy of lithium-ion transfer reaction at LiCoO₂ thin film electrode–electrolyte interface, indicating that the modification by MgO affects the kinetics of lithium-ion transfer reaction at LiCoO₂–electrolyte interface.     

Structural and electrical properties of thin films of Pr0.8Sr0.2Fe0.8Ni0.2O3−δ

Pr_0.8Sr_0.2Fe_0.8Ni_0.2O_3−δ (PN22) films have been deposited at different temperatures on yttria-stabilized zirconia (YSZ) substrates by pulsed laser deposition (PLD) for application to thin film solid oxide fuel cell cathodes. The structure of the films was analysed by X-ray diffraction (XRD) and atomic force microscopy (AFM). A marked influence in the structural properties of the substrate temperature has been found but not of the composition. Samples deposited at temperatures below 700 °C are amorphous, with granular aspect, and with decreasing roughness with the temperature. Meanwhile, the films at 700 °C are polycrystalline and exhibit a needle-shaped surface, with the highest roughness observed. Additionally, the conducting behaviour of the films has been studied by electrochemical impedance spectroscopy (EIS) and their cathodic area specific resistance (ASR) was determined. The main part of the impedance of the testing cells is due to the electrode. The ASR values of the films of PN22 are lower than those of Pr_0.9Sr_0.1Fe_0.8Ni_0.2O_3−δ (PN12), being the lowest 0.5 Ω cm² at 850 °C for the sample PN22 deposited at room temperature.     

Electrochemical properties of Li2ZrO3-coated silicon/graphite/carbon composite as anode material for lithium ion batteries

Silicon/graphite/disordered carbon (Si/G/DC) is coated by Li₂ZrO₃ using Zr(NO₃)₄·5H₂O and CH₃COOLi·2H₂O as coating reagents. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are used to characterize Li₂ZrO₃-coated Si/G/DC composite. The Li₂ZrO₃-coated Si/G/DC composite exhibits a high reversible capacity with no capacity fading from 2nd to 70th cycle, indicating its excellent cycleability when used as anode materials for lithium ion batteries. A compact and stable solid-electrolyte interphase (SEI) layer is formed on the surface of Li₂ZrO₃-coated Si/G/DC electrode. Analysis of electrochemical impedance spectra (EIS) shows that the resistance of the coated material exhibits less variation during cycling, which indicates the integrity of electrode structure is kept during cycling. XPS shows that F and P elements do not appear in the SEI layers of Li₂ZrO₃-coated Si/G/DC electrode, while they have a relatively high content in SEI layers of Si/G/DC electrode. The improvement of Li₂ZrO₃-coated Si/G/DC is attributed to the decrease of lithium insertion depth and the formation of stable SEI film.     

Cycle test and degradation analysis of WO3/PC+LiClO4/CeO2·TiO2 electrochromic device

We fabricated an electrochromic full cell device adopting WO₃ as a working electrode, and 1 M LiClO₄ in PC with 3% water addition as an electrolyte and CeO₂·TiO₂ with various thicknesses as an ion storage layer. CeO₂·TiO₂ with less than 100 nm shows large charge density but the long-term cyclability is not good due to lithium ion diffusion into ITO thin film. Therefore, the thickness of CeO₂·TiO₂ ion storage layer should be coated at more than 200 mm/min. Long-term cycle test results show that CeO₂·TiO₂ ion storage layer with more than 150 nm thickness and two time coating enhance the long-term stability. SIMS analysis results show that the degradation is due to the remaining lithium ion in the working electrode, WO₃.     

Investigation of positive electrodes after cycle testing of high-power Li-ion battery cells: I. An approach to the power fading mechanism using XANES

Cylindrical lithium-ion (Li-ion) cells with a nickel-cobalt oxide (LiNi_0.73Co_0.17Al_0.10O₂) positive electrode and a non-graphitizable carbon (hard carbon) negative electrode were degraded using cycle tests. The degraded cells were disassembled and examined; most attention was paid to the positive electrodes in order to clarify the origin of the power fade of the cells. X-ray absorption near-edge structure (XANES) analysis demonstrated that the crystal structure of the electrode at the surface changed from rhombohedral to cubic symmetry. Furthermore, a film of lithium carbonate (Li₂CO₃) covered the surface of the positive electrode after the cycle tests. Using a combination of X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), and glow discharge optical emission spectrometry (GD-OES) measurements, a schematic model of the changes occurring in the surface structure of the positive electrode during the cycle tests was constructed. The appearance of both an electrochemically inactive cubic phase and lithium carbonate films at the surface of the positive electrode are important factors giving rise to power fade of the positive electrode.     

Li3V2(PO4)3/C composite as an intercalation-type anode material for lithium-ion batteries

The carbon coated monoclinic Li₃V₂(PO₄)₃ (LVP/C) powder is successfully synthesized by a carbothermal reduction method using crystal sugar as the carbon source. Its structure and physicochemical properties are investigated using X-ray diffraction (XRD), scanning electron microscopy, high-resolution transmission electron microscopy and electrochemical methods. The LVP/C electrode exhibits stable reversible capacities of 203 and 102 mAh g⁻¹ in the potential ranges of 3.0-0.0 V and 3.0-1.0 V versus Li⁺/Li, respectively. It is identified that the insertion/extraction of Li⁺ undergoes a series of two-phase transition processes between 3.0 and 1.6 V and a single phase process between 1.6 and 0.0 V. The ex situ XRD patterns of the electrodes at various lithiated states indicate that the monoclinic structure can still be retained during charge-discharge process and the insertion/deinsertion of lithium ions occur reversibly, which provides an excellent cycling stability with high energy efficiency.     

Electrochromic properties of nanocomposite WO3 films

A new nanocomposite WO₃ (NWO) film-based electrochromic layer was fabricated by a spray and electroplating technique in sequence. An indium–tin oxide (ITO) nanoparticle layer was employed as a permanent template to generate the particular nanostructure. The structure and morphology of the NWO film were characterized. The optical and electrochromic properties of the NWO films under lithium intercalation are described and compared to the regular WO₃ film. The NWO films showed an improved cycling life and an improved contrast with compatible bleach-coloration transition time, owing to the larger reactive surface area. The nanocomposite WO₃ film-based electrochromic device (NWO-ECD) was also successfully fabricated. Most importantly, the NWO film can be prepared on a large scale directly onto a transparent conductive substrate, which demonstrates its potential for many electrochromic applications, especially, smart windows, sunroof and displays.     

Influence of polymeric binder on the stability and intercalation/de-intercalation behaviour of graphite electrodes in non-aqueous solvents

Cyclic voltammetric and scanning electron microscopic investigations on a highly-packed, crystalline, graphite electrode (HPC) and on a polypropylene composite graphite electrode (CPP) containing 20 wt.% polypropylene binder indicate that the latter has higher mechanical stability and higher electrochemical intercalation/de-intercalation activity. This holds for the intercalation of lithium (Li⁺) and tetrabutyl ammonium (TBA⁺) cations from dimethyl sulfoxide (DMSO) and dimethyl formamide (DMF), as well as for the intercalation of perchlorate (Cl0₄⁻) and fluoroborate (Bf₄⁻) anions from propylene carbonate (PC) and acetonitrile (AN). There is a linear correlation between the threshold potential for the beginning of intercalation (E_th) and the intercalation/de-intercalation efficiency (IDE) for cationic intercalation. In the case of anionic intercalation, two distinct linear relationships for HPC and CPP electrodes are observed. Competitive oxidation processes reduce the IDE on the HPC electrode.     

Kinetics and thermodynamic behavior of WO3 and WO3:P thin films

 There is a considerable interest in the research and development of materials and devices, that can be used for optical switching of large-scale glazings. Several potential switching technologies are available for glazings, including those based on electrochromic, thermochromic and photochromic phenomena. One of the most promising technologies for optical switching devices is electrochromism (EC). In order to improve the electrochromic properties of tungsten oxide, we have investigated the effect of phosphorous insertion on the electrochromic behavior of oxide films prepared by the sol–gel process.The kinetics and thermodynamics of electrochemical intercalation of lithium into Li_xWO₃ and Li_xWO₃:P films prepared by the sol–gel process were investigated. The standard Gibbs energy for lithium intercalation was calculated. The chemical diffusion coefficients, D, of lithium intercalation into oxide, were measured by galvanostatic intermittent titration technique (GITT), as functions of the depth of lithium intercalation.     

Co-deposition of TiO2/CdS films electrode for photo-electrochemical cells

A densely packed TiO₂ thin film onto an indium doped–tin oxide (ITO) substrate was synthesized at room temperature by chemical deposition and a CdS thin film was deposited onto the pre-deposited TiO₂ film by a doctor blade route (powder of CdS was obtained from chemical deposition). TiO₂/CdS film was annealed at 300 °C for 1 h in air for crystallinity improvement. The first grown TiO₂ film was nanocrystalline, whereas the CdS film was polycrystalline as evidenced by X-ray diffraction (XRD) and selected area electron diffraction (SAED). Scanning electron microscopy (SEM) images show formation of mono-dispersed CdS spherical grains onto compact, densely packed spherical nanocrystalline grains of TiO₂. The TiO₂/CdS bilayer film was used in a photo-electrochemical cell as a working electrode, and a platinum electrode as a counter electrode (0.1 M lithium iodide electrolyte) under 80 mW/cm² light illumination intensity.     

The electrochemical behaviour of the carbon-coated Ni0.5TiOPO4 electrode material

Ni_0.5TiOPO₄ oxyphosphate exhibits good electrochemical properties as an anode material in lithium ion batteries but suffers from its low conductivity. We present here the electrochemical performances of the synthesized Ni_0.5TiOPO₄/carbon composite by using sucrose as the carbon source. X-ray diffraction study confirms that this phosphate crystallizes in the monoclinic system (S.G. P2₁/c). The use of the Ni_0.5TiOPO₄/C composite in lithium batteries shows enhanced electrochemical performances compared with the uncoated material. Capacities up to 200 mAh g⁻¹ could be reached during cycling of this electrode. Furthermore, an acceptable rate capability was obtained with very low capacity fading even at 0.5C rate. Nevertheless, a considerable irreversible capacity was evidenced during the first discharge. In situ synchrotron X-ray radiation was utilized to study the structural change during the first discharge in order to evidence the origin of this irreversible capacity. Lithium insertion during the first discharge induces an amorphization of the crystal structure of the parent material accompanied by an irreversible formation of a new phase.     

Electrochemical intercalation of cationic and anionic species from a lithium perchlorate–propylene carbonate system—a rocking-chair type of dual-intercalation system

The reductive and oxidative intercalation of ionic species of lithium perchlorate (LiClO₄) in propylene carbonate (PC) medium are carried out to develop a dual-intercalation battery system. Cyclic voltammetry (CV), potentiostatic transients (i-t), galvanostatic charging, thermogravimetry (TG) and differential thermal analysis (DTA) are performed to establish the intercalation behaviour of both lithium and perchlorate ionic species. A polypropylene graphite composite electrode material containing 20 wt.% polypropylene as a binder is found to be a suitable host material for dual intercalation studies. The intercalation/de-intercalation efficiency (IDE) increases with increasing sweep rate and reaches up to 90% for Li⁺ and 65% for ClO₄⁻ ions at a sweep rate of 40 mV s⁻¹. The formation of a passive film decreases the IDE during the first intercalation/de-intercalation cycle. The open-circuit potential for a battery assembly involving these two electrodes is in the range 3.8 to 4.0 V.     

Ageing of V2O5 thin films induced by Li intercalation multi-cycling

Cyclic voltammetry, XPS, RBS and AFM have been combined to study the ageing mechanism of Li intercalation in V₂O₅ thin films prepared by thermal oxidation of vanadium metal. Multi-cycling tests were performed in 1 M LiClO₄-PC in the potential range E ∈ [3.8, 2.8 V] versus Li/Li⁺, corresponding to the α-to-δ phase transition. XPS and AFM were performed using direct anaerobic and anhydrous transfer. Capacity fading remains inferior to 20% during ∼2500 cycles. XPS shows slight modifications of the oxide composition with a V⁴⁺ concentration increasing from ∼5% prior to cycling to ∼16–27% after cycling, due to Li trapped in the oxide film and to the loss of V₂O₅ active material. The presence of lithium carbonate and lithium-alkyl carbonate species evidences the formation of the so-called SEI layer. AFM evidences the loss of crystalline material by grain exfoliation from the outer V₂O₅ layer of the oxide film. By further exfoliation, the inner VO₂ layer of the oxide film is reached and pits are formed, occupying ∼9–13% of the surface. This de-cohesion at grain boundaries is attributed to the strain generated by repeated lattice distortions. After 3300 cycles, the disappearance of lithium carbonates, whereas Li-alkyl carbonates and/or Li-alkoxides remain on the surface, indicates the dissolution and/or conversion of the SEI layer. After 4500 cycles, the oxide film became very labile and could be stripped away by rinsing to reveal the vanadium metal substrate.     

Characterization of the interface between LiCoO2 and Li7La3Zr2O12 in an all-solid-state rechargeable lithium battery

The interfacial layer formed between a lithium-ion conducting solid electrolyte, Li₇La₃Zr₂O₁₂ (LLZ), and LiCoO₂ during thin film deposition was characterized using a combination of microscopy and electrochemical measurement techniques. Cyclic voltammetry confirmed that lithium extraction occurs across the interface on the first cycle, although the nonsymmetrical redox peaks indicate poor electrochemical performance. Using analytical transmission electron microscopy, the reaction layer (∼50 nm) was analyzed. Energy dispersive X-ray spectroscopy revealed that the concentrations of some of the elements (Co, La, and Zr) varied gradually across the layer. Nano-beam electron diffraction of this layer revealed that the layer contained neither LiCoO₂ nor LLZ, but some spots corresponded to the crystal structure of La₂CoO₄. It was also demonstrated that reaction phases due to mutual diffusion are easily formed between LLZ and LiCoO₂ at the interface. The reaction layer formed during high temperature processing is likely one of the major reasons for the poor lithium insertion/extraction at LLZ/LiCoO₂ interfaces.     

Electrochemical intercalation of lithium ions into LiV3O8 in an aqueous electrolyte

Electrochemical intercalation of lithium ions from a saturated LiNO₃ aqueous electrolyte solution into LiV₃O₈ prepared by a solid-state reaction at 680 °C was studied with cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Results show that there are three steps of intercalation in the presence of an aqueous electrolyte, in agreement with those previously observed with organic liquid electrolytes. In addition, variations of several parameters including the charge transfer resistance (R_ct), the capacitance of the double layer (C_DL), the Warburg diffusion impedance (Z_w), and diffusion coefficient of lithium ions (DLi₊$D_{\text{L}{\text{i}}^{+}}$) during the intercalation process are reported.     

AlF3-coated LiCoO2 and Li[Ni1/3Co1/3Mn1/3]O2 blend composite cathode for lithium ion batteries

Surface modifications of electrode materials can improve the electrochemical and thermal properties of cathodes for use in lithium batteries. In this study, AlF₃-coated LiCoO₂ and AlF₃-coated Li[Ni_1/3Co_1/3Mn_1/3]O₂ cathode materials are blended, as both have the same crystal structure and exhibit similar electrochemical properties. The composite electrodes exhibit high discharge capacities of 180-188 mAh g⁻¹ in a voltage range of 3.0-4.5 V at room temperature. The capacity retention of the composite electrode is greater than 95% of the initial capacity after 50 cycles. The thermal stability of these composite electrodes is greatly improved because of the superior thermal stability of AlF₃-coated Li[Ni_1/3Co_1/3Mn_1/3]O₂. The blended AlF₃-coated LiCoO₂ and AlF₃-coated Li[Ni_1/3Co_1/3Mn_1/3]O₂ electrode shows two exothermic peaks, one at 227 °C from AlF₃-coated LiCoO₂ and another at 277 °C from AlF₃-coated Li[Ni_1/3Co_1/3Mn_1/3]O₂, accompanied by significantly reduced exothermic heat generation.