Li-ion diffusion kinetics in LiCoPO4 thin films deposited on NASICON-type glass ceramic electrolytes by magnetron sputtering

LiCoPO₄ thin films were deposited on Li_1+x+yAl_xTi_2−xSi_yP_3−yO₁₂ (LATSP) solid electrolyte by radio frequency magnetron sputtering and were characterized by X-ray diffraction and scanning electron microscope. The films show a (1 1 1) preferred orientation upon annealing and are chemically stable with LATSP up to 600 °C in air. An all-solid-state Li/PEO₁₈-Li(CF₃SO₂)₂N/LATSP/LiCoPO₄/Au cell was fabricated to investigate the electrochemical performance and Li-ion chemical diffusion coefficients, , of the LiCoPO₄ thin films. The potential dependence of values of the LiCoPO₄ thin film was investigated by potentiostatic intermittent titration technique and was compared with those of the LiFePO₄ thin film. These results showed that the intercalation mechanism of Li-ion in LiCoPO₄ is different from that in LiFePO₄.     

Electrochemical performance of all-solid-state Li batteries based LiMn0.5Ni0.5O2 cathode and NASICON-type electrolyte

LiNi_0.5Mn_0.5O₂ thin films have been deposited on the NASICON-type glass ceramics, Li_1+x+yAl_xTi_2−xSi_yP_3−yO₁₂ (LATSP), by radio frequency (RF) magnetron sputtering followed by annealing. The films have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. All-solid-state Li/PEO₁₈-Li(CF₃SO₂)₂N/LATSP/LiNi_0.5Mn_0.5O₂/Au cells are fabricated using the LiNi_0.5Mn_0.5O₂ thin films and the LATSP electrolyte. The electrochemical performance of the cells is investigated by galvanostatic cycling, cyclic voltammetry (CV), potentiostatic intermittent titration technique (PITT) and electrochemical impedance spectroscopy (EIS). Interfacial reactions between LiNi_0.5Mn_0.5O₂ and LATSP occur at a temperature as low as 300 °C with the formation of Mn₃O₄, resulting in an increased obstacle for Li-ion diffusion across the LiNi_0.5Mn_0.5O₂/LATSP interface. The electrochemical performance of the cells is limited by the interfacial resistance between LATSP and LiNi_0.5Mn_0.5O₂ as well as the Li-ion diffusion kinetics in LiNi_0.5Mn_0.5O₂ bulk.     

Electrochemical performance of all-solid-state lithium secondary batteries improved by the coating of Li2O-TiO2 films on LiCoO2 electrode

All-solid-state lithium secondary batteries using LiCoO₂ particles coated with amorphous Li₂O-TiO₂ films as an active material and Li₂S-P₂S₅ glass-ceramics as a solid electrolyte were fabricated; the electrochemical performance of the batteries was investigated. The interfacial resistance between LiCoO₂ and solid electrolyte was decreased by the coating of Li₂O-TiO₂ films on LiCoO₂ particles. The rate capability of the batteries using the LiCoO₂ coated with Li₂Ti₂O₅ (Li₂O·2TiO₂) film was improved because of the decrease of the interfacial resistance of the batteries. The cycle performance of the all-solid-state batteries under a high cutoff voltage of 4.6 V vs. Li was highly improved by using LiCoO₂ coated with Li₂Ti₂O₅ film. The oxide coatings are effective in suppressing the resistance increase between LiCoO₂ and the solid electrolyte during cycling. The battery with the LiCoO₂ coated with Li₂Ti₂O₅ film showed a large initial discharge capacity of 130 mAh/g and good capacity retention without resistance increase after 50 cycles at the current density of 0.13 mA/cm².     

Characterization of all-solid-state secondary batteries with LiCoO2 thin films prepared by ECR sputtering as positive electrodes

We fabricated all-solid-state lithium secondary batteries consisting of LiCoO₂ thin films prepared by electron cyclotron resonance (ECR) sputtering LiPON and metallic lithium films, and investigated the influence of the sputtering target composition on the performance of the batteries and LiCoO₂ films. We found that the LiCoO₂ film sputtered with a stoichiometric LiCoO₂ target included many impurities (mainly Co₃O₄) and these impurities were eliminated by adding an excess of Li source to the sputtering target to achieve a Li/Co atomic ratio of 2.0 elsewhere. The LiCoO₂ film sputtered with a Li2.0 target exhibited a larger discharge capacity and a high performance level for large current operation. However, the capacity of a battery employing LiCoO₂ film sputtered with a Li2.0 target decreased more rapidly than that with a Li1.0 or Li1.7 target in a charge–discharge cycle test. We also investigated the cycle performance of LiCoO₂ films in an ordinary liquid electrolyte by using beaker type cells. We found that the decrease in capacity during the cycle tests was caused by the deterioration of the LiCoO₂ film, because the dependence of the target composition on the cycle performance in the beaker type cells was similar to that in the all-solid-state cells. We consider the capacity decrease to be caused by the deterioration in the crystallinity of the LiCoO₂ film when using the Li2.0 target and caused by the formation of a Co₃O₄ layer on the surface of the LiCoO₂ film when using a Li1.7 target on basis of the results of X-ray diffraction analysis and Raman spectroscopy.     

High-rate performance of all-solid-state lithium secondary batteries using Li4Ti5O12 electrode

The all-solid-state Li–In/Li₄Ti₅O₁₂ cell using the 80Li₂S·20P₂S₅ (mol%) solid electrolyte was assembled to investigate rate performances. It was difficult to obtain the stable performance at the charge current density of 3.8 mA cm⁻² in the all-solid-state cell. In order to improve the rate performance, the pulverized Li₄Ti₅O₁₂ particles were applied to the all-solid-state cell, which retained the reversible capacity of about 90 mAh g⁻¹ at 3.8 mA cm⁻². The 70Li₂S·27P₂S₅·3P₂O₅ glass–ceramic, which exhibits the higher lithium ion conductivity than the 80Li₂S·20P₂S₅ solid electrolyte, was also used. The Li–In/70Li₂S·27P₂S₅·3P₂O₅ glass–ceramic/pulverized Li₄Ti₅O₁₂ cell was charged at a current density higher than 3.8 mA cm⁻² and showed the reversible capacity of about 30 mAh g⁻¹ even at 10 mA cm⁻² at room temperature.     

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.     

An amorphous LiCo1/3Mn1/3Ni1/3O2 thin film deposited on NASICON-type electrolyte for all-solid-state Li-ion batteries

Amorphous LiCo_1/3Mn_1/3Ni_1/3O₂ thin films were deposited on the NASICON-type Li-ion conducting glass ceramics, Li_1+x+yAl_xTi_2−xSi_yP_3−yO₁₂ (LATSP), by radio frequency (RF) magnetron sputtering below 130 °C. The amorphous films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The Li/PEO₁₈-Li(CF₃SO₂)₂N/LATSP/LiCo_1/3Mn_1/3Ni_1/3O₂/Au all-solid-state cells were fabricated to investigate the electrochemical performance of the amorphous films. It was found that the low-temperature deposited amorphous cathode film shows a high discharge voltage and a high discharge capacity of around 130 mAh g⁻¹.     

Synthesis and electrochemical performance of doped LiCoO2 materials

Layered intercalation compounds LiM_0.02Co_0.98O₂ (M = Mo⁶⁺, V⁵⁺, Zr⁴⁺) have been prepared using a simple solid-state method. Morphological and structural characterization of the synthesized powders is reported along with their electrochemical performance when used as the active material in a lithium half-cell. Synchrotron X-ray diffraction patterns suggest a single phase HT-LiCoO₂ that is isostructural to α-NaFeO₂ cannot be formed by aliovalent doping with Mo, V, and Zr. Scanning electron images show that particles are well-crystallized with a size distribution in the range of 1–5 μm. Charge–discharge cycling of the cells indicated first cycle irreversible capacity loss in order of increasing magnitude was Zr (15 mAh g⁻¹), Mo (22 mAh g⁻¹), and V (45 mAh g⁻¹). Prolonged cycling the Mo-doped cell produced the best performance of all dopants with a stable reversible capacity of 120 mAh g⁻¹ after 30 cycles, but was inferior to that of pure LiCoO₂.     

Effect of FePO4 coating on electrochemical and safety performance of LiCoO2 as cathode material for Li-ion batteries

LiCoO₂ was surface modified by a coprecipitation method followed by a high-temperature treatment in air. FePO₄-coated LiCoO₂ was characterized with various techniques such as X-ray diffraction (XRD), auger electron spectroscopy (AES), field emission scanning electron microscope (FE-SEM), energy dispersive spectroscopy (EDS), transmission electron microscope (TEM), electrochemical impedance spectroscopy (EIS), 3 C overcharge and hot-box safety experiments. For the 14500R-type cell, under a high charge cutoff voltage of 4.3 and 4.4 V, 3 wt.% FePO₄-coated LiCoO₂ exhibits good electrochemical properties with initial discharge specific capacities of 146 and 155 mAh g⁻¹ and capacity retention ratios of 88.7 and 82.5% after 400 cycles, respectively. Moreover, the anti-overcharge and thermal safety performance of LiCoO₂ is greatly enhanced. These improvements are attributed to the FePO₄ coating layer that hinders interaction between LiCoO₂ and electrolyte and stabilizes the structure of LiCoO₂. The FePO₄-coated LiCoO₂ could be a high performance cathode material for lithium-ion battery.     

A novel and efficient water-based composite binder for LiCoO2 cathodes in lithium-ion batteries

The dispersion, adhesion strength, electrical, and electrochemical properties of LiCoO₂ cathodes in lithium-ion batteries with the addition of a new composite binder composed of two acrylic emulsions, poly(butyl acrylate)-based (PBA) and polyacrylonitrile-based (PA) latex in a ratio of 3:7, were evaluated. PBA binder has a low-glass transition temperature of 10 °C, which can improve the flexibility of the electrode. This new composite binder has a very good binding ability as same as the typical organic solvent-based binder, poly(vinylidene fluoride). The dispersions of the water-based cathode slurries with the composite binder were measured by analyzing the viscosity and sedimentation behaviors. The results show that the new composite binder can well disperse the LiCoO₂. Moreover, using the new composite binder could greatly improve the rate capabilities and the cycle stability of water-based LiCoO₂ cathodes.     

Amorphous Si film anode coupled with LiCoO2 cathode in Li-ion cell

An amorphous silicon film with an average thickness of up to 2 μm was deposited on copper foil by direct-circuit (dc) magnetron sputtering and coupled with commercial LiCoO₂ cathode to fabricate cells. Their cycle performance and high rate capability at room temperature have been investigated. In the voltage range 2.5–3.9 V at the current density of 0.2C (0.11 mA cm⁻²), the lithiation and delithiation capacity of this cell was first increased to 0.55 mAh cm⁻² within 80 cycles and maintained stable during the following cycles. After 300 cycles its capacity still retained 0.54 mAh cm⁻². High-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) image indicated that the sputtered film could keep an amorphous structure although the volume expansion ratio during the lithiation and delithiation was still up to 300% after 300 cycles observed from scanning electron microscopy (SEM) image. This recovered amorphous structure was believed to be beneficial for the improvement of the cycle life of the cell. Rate performance showed that the cells had a promising high rate capability. At 30C, its lithiation/delithiation capacity remained 25% of that at 0.2C.     

All-solid-state lithium secondary batteries using LiCoO2 particles with pulsed laser deposition coatings of Li2S-P2S5 solid electrolytes

Electrode-electrolyte composite materials were prepared by coating a highly conductive Li₂S-P₂S₅ solid electrolyte onto LiCoO₂ electrode particles using pulsed laser deposition (PLD). Cross-sections of the composite electrode layers of the all-solid-state cells were observed using a transmission electron microscope to investigate the packing morphology of the LiCoO₂ particles and the distribution of solid electrolyte in the composite electrode. All-solid-state cells based on a composite electrode composed entirely of solid-electrolyte-coated LiCoO₂ were fabricated, and their performance was investigated. The coating amounts of Li₂S-P₂S₅ solid electrolytes on LiCoO₂ particles and the conductivity of the coating material were controlled to increase the capacity of the resulting all-solid-state cells. All-solid-state cells using LiCoO₂ with thick solid electrolyte coatings, grown over 120 min, had a capacity of 65 mAh g⁻¹, without any addition of Li₂S-P₂S₅ solid electrolyte particles to the composite electrode. The capacity of the all-solid-state cell increased further after increasing the conductivity of the Li₂S-P₂S₅ solid electrolyte coating by heat treatment at 200 °C. Furthermore, an all-solid-state cell based on a composite electrode using both a solid electrolyte coating and added solid electrolyte particles was fabricated, and the capacity of the resulting all-solid-state cell increased to 95 mAh g⁻¹.     

Investigation on the charging process of Li2O2-based air electrodes in Li-O2 batteries with organic carbonate electrolytes

The charging process of Li₂O₂-based air electrodes in Li-O₂ batteries with organic carbonate electrolytes was investigated using in situ gas chromatography/mass spectroscopy (GC/MS) to analyze gas evolution. A mixture of Li₂O₂/Fe₃O₄/Super P carbon/polyvinylidene fluoride (PVDF) was used as the starting air electrode material, and 1-M lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) in carbonate-based solvents was used as the electrolyte. We found that Li₂O₂ was actively reactive to 1-methyl-2-pyrrolidinone and PVDF that were used to prepare the electrode. During the first charging (up to 4.6 V), O₂ was the main component in the gases released. The amount of O₂ measured by GC/MS was consistent with the amount of Li₂O₂ that decomposed during the electrochemical process as measured by the charge capacity, which is indicative of the good chargeability of Li₂O₂. However, after the cell was discharged to 2.0 V in an O₂ atmosphere and then recharged to ∼4.6 V, CO₂ was dominant in the released gases. Further analysis of the discharged air electrodes by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy indicated that lithium-containing carbonate species (lithium alkyl carbonates and/or Li₂CO₃) were the main discharge products. Therefore, compatible electrolytes and electrodes, as well as the electrode-preparation procedures, need to be developed for rechargeable Li-air batteries for long term operation.     

Fabrication of all-solid-state lithium battery with lithium metal anode using Al2O3-added Li7La3Zr2O12 solid electrolyte

Li₇La₃Zr₂O₁₂ (LLZ) solid electrolyte is one of the promising electrolytes for all-solid-state battery due to its high Li ion conductivity and stability against Li metal anode. However, high calcination temperature for LLZ preparation promotes formation of La₂Zr₂O₇ impurity phase. In this paper, an effect of Al₂O₃ addition as sintering additive on LLZ solid electrolyte preparation and electrochemical properties of Al₂O₃-added LLZ were examined. By the Al₂O₃ addition, sintered LLZ pellet could be obtained after 1000 °C calcination, which is 230 °C lower than that without Al₂O₃ addition. Chemical and electrochemical properties of the Al₂O₃-added LLZ, such as stability against Li metal and ion conductivity, were comparable with the LLZ without Al₂O₃ addition, i.e. σ_bulk and σ_total were 2.4 × 10⁻⁴ and 1.4 × 10⁻⁴ S cm⁻¹ at 30 °C, respectively. All-solid-state battery with Li/Al₂O₃-added LLZ/LiCoO₂ configuration was fabricated and its electrochemical properties were tested. In cyclic voltammogram, clear redox peaks were observed, indicating that the all-solid-state battery with Li metal anode was successfully operated. The redox peaks were still observed even after one year storage of the all-solid-state battery in the Ar-filled globe-box. It can be inferred that the Al₂O₃-added LLZ electrolyte would be a promising candidate for all-solid-state battery because of facile preparation by the Al₂O₃ addition, relatively high Li ion conductivity, and good stability against Li metal and LiCoO₂ cathode.     

Dynamic behavior of surface film on LiCoO2 thin film electrode

Electrochemical oxidation behavior of non-aqueous electrolytes on LiCoO₂ thin film electrodes were investigated by in situ polarization modulation Fourier transform infrared (PM-FTIR) spectroscopy, atomic force microscopy and X-ray photoelectron spectroscopy (XPS). LiCoO₂ thin film electrode on gold substrate was prepared by rf-sputtering method. In situ PM-FTIR spectra were obtained at various electrode potentials during cyclic voltammetry measurement between 3.5 V vs. Li/Li⁺ and 4.2 V vs. Li/Li⁺. During anodic polarization, oxidation of non-aqueous electrolyte was observed, and oxidized products remained on the electrode at the potential higher than 3.75 V vs. Li/Li⁺ as a surface film. During cathodic polarization, the stripping of the surface film was observed at the potential lower than 3.9 V vs. Li/Li⁺. Depth profile of XPS also showed that more organic surface film remained on charged LiCoO₂ than that on discharged one. AFM images of charged and discharged electrodes showed that some decomposed products deposited on charged electrode and disappeared from the surface of discharged one. These results indicate that the surface film on LiCoO₂ is not so stable.     

Expanding performance limit of lithium-ion batteries simply by mixing Al(OH)3 powder with LiCoO2

Mixing a small amount of Al(OH)₃ powder with a LiCoO₂ cathode material is demonstrated to improve markedly the cycle performance and thermal stability of commercial grade LiCoO₂/graphite lithium-ion batteries. Al(OH)₃-mixed LiCoO₂/graphite prismatic cells exhibit excellent capacity retention as high as 95% after 400 cycles with negligible polarization build-up. Moreover, the thermal stability of the cells is greatly improved by Al(OH)₃ mixing, which is confirmed by higher residual and recovery capacity ratios after storage at 90 °C compared with a pristine cell. The beneficial effects of Al(OH)₃ are found to be related mainly to an improvement of the cathode side, which is ascribed to reduced unwanted side-reactions with the electrolyte.     

Characterization of LiCoO2 coated Li1.05Ni0.35Co0.25Mn0.4O2 cathode material for lithium secondary cells

In this study, nano-crystalline LiCoO₂ was coated onto the surface of Li_1.05Ni_0.35Co_0.25Mn_0.4O₂ powders via sol–gel method. The influence of the coating on the electrochemical behavior of Li_1.05Ni_0.35Co_0.25Mn_0.4O₂ is discussed. The surface morphology was characterized by transmission electron microscopy (TEM). Nano-crystallized LiCoO₂ was clearly observed on the surfaces of Li_1.05Ni_0.35Co_0.25Mn_0.4O₂. The phase and structural changes of the cathode materials before and after coating were revealed by X-ray diffraction spectroscopy (XRD). It was found that LiCoO₂ coated Li_1.05Ni_0.35Co_0.25Mn_0.4O₂ cathode material exhibited distinct surface morphology and lattice constants. Cyclic voltammetry (2.8–4.6 V versus Li/Li⁺) shows that the characteristic voltage transitions on cycling exhibited by the uncoated material are suppressed by the 7 wt.% LiCoO₂ coating. This behavior implies that LiCoO₂ inhibits structural change of Li_1.05Ni_0.35Co_0.25Mn_0.4O₂ or reaction with the electrolyte on cycling. In addition, the LiCoO₂ coating on Li_1.05Ni_0.35Co_0.25Mn_0.4O₂ significantly improves the rate capability over the range 0.1–4.0C. Comparative data for the coated and uncoated materials are presented and discussed.     

Electrochemical performance of LiCoO2 cathodes by surface modification using lanthanum aluminum garnet

LiCoO₂ particles were coated with various wt.% of lanthanum aluminum garnets (3LaAlO₃:Al₂O₃) by an in situ sol–gel process, followed by calcination at 1123 K for 12 h in air. X-ray diffraction (XRD) patterns confirmed the formation of a 3LaAlO₃:Al₂O₃ compound and the in situ sol–gel process synthesized 3LaAlO₃:Al₂O₃-coated LiCoO₂ was a single-phase hexagonal α-NaFeO₂-type structure of the core material without any modification. Scanning electron microscope (SEM) images revealed a modification of the surface of the cathode particles. Transmission electron microscope (TEM) images exposed that the surface of the core material was coated with a uniform compact layer of 3LaAlO₃:Al₂O₃, which had an average thickness of 40 nm. Galvanostatic cycling studies demonstrated that the 1.0 wt.% 3LaAlO₃:Al₂O₃-coated LiCoO₂ cathode showed excellent cycle stability of 182 cycles, which was much higher than the 38 cycles sustained by the pristine LiCoO₂ cathode material when it was charged at 4.4 V.