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.     

Synthesis and characterization of highly stable optically passive CeO2-ZrO2 counter electrode

Transparent and adherent CeO₂-ZrO₂ thin films having film thicknesses ∼543-598 nm were spray deposited onto the conducting (fluorine doped tin oxide coated glass) substrates from a blend of equimolar concentrations of cerium nitrate hexahydrate and zirconium nitrate having different volumetric proportions (0-6 vol.% of Zr) in methanol. CeO₂-ZrO₂ films were polycrystalline with cubic fluorite crystal structure and the crystallinity was improved with increasing ZrO₂ content. Films were highly transparent (T ∼ 92%), showing decrease in band gap energy from 3.45 eV for pristine CeO₂ to 3.08-3.14 eV for CeO₂-ZrO₂ films. The different morphological features of the film obtained at various CeO₂-ZrO₂ compositions had pronounced effect on the ion storage capacity and electrochemical stability. CeO₂-ZrO₂ film prepared at 5 vol.% Zr concentration exhibited higher ion storage capacity of 24 mC cm⁻² and electrochemical stability of 10,000 cycles in 0.5 M LiClO₄ + PC electrolyte due to its film thickness (584 nm) coupled with relatively larger porosity (8%). The optically passive behavior of such CeO₂-ZrO₂ film (with 5 vol.% Zr) is affirmed by its negligible transmission modulation irrespective of repeated Li⁺ and electron insertion/extraction. The coloration efficiency of spray deposited WO₃ thin film is found to enhance from 47 to 107 cm² C⁻¹ when CeO₂-ZrO₂ is coupled as a counter electrode with WO₃ in an electrochromic device (ECD). These films can be used as stable ‘passive’ counter electrodes in electrochromic smart windows as they retain full transparency in both the oxidized and reduced states and ever-reported longevity.     

Mixed oxides Ca2Fe2O5 and Ca2Co2O5 as anode materials for Li-ion batteries

The electrochemical performance of mixed oxides, Ca₂Fe₂O₅ and Ca₂Co₂O₅ for use in Li-ion batteries was studied with Li as the counter electrode. The compounds were prepared and characterized by X-ray diffraction and SEM. Ca₂Fe₂O₅ showed a reversible capacity of 226 mAh/g at the 14th cycle and retained 183 mAh/g at the end of 50 cycles at 60 mA/g in the voltage window 0.005-2.5 V. A reversible capacity in the range, 365-380 mAh/g, which is stable up to 50 charge-discharge cycles is exhibited by Ca₂Co₂O₅ in the voltage window, 0.005-3.0 V and at 60 mA/g. This corresponds to recycleable moles of Li of 3.9±0.1 (theoretical: 4.0). Significant improvement in the cycling performance and attainable reversible capacity were noted for Ca₂Co₂O₅ on cycling to an upper cut-off voltage of 3.0 V as compared to 2.5 V. Coulombic efficiency for both compounds is >98%. Electrochemical impedance spectroscopy (EIS) data clearly indicate the reversible formation/decomposition of polymeric surface film on the electrode surface of Ca₂Co₂O₅ in the voltage window, 0.005-3.0 V. Cyclic voltammetry results compliment the galvanostatic cycling data.     

Texture effect on the electrochemical properties of LiCoO2 thin films prepared by PLD

LiCoO₂ thin films were prepared by pulsed laser deposition (PLD) on Pt/Ti/SiO₂/Si (Pt) and Au/MgO/Si (Au) substrates, respectively. Crystal structures and surface morphologies of thin films were investigated by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The LiCoO₂ thin films deposited on the Pt substrates exhibited a preferred (0 0 3) texture with smooth surfaces while the LiCoO₂ thin films deposited on the Au substrates exhibited a preferred (1 0 4) texture with rough surfaces. The electrochemical properties of the LiCoO₂ films with different textures were compared with charge-discharge, dQ/dV, and Li diffusion measurements (PITT). Compared with the (1 0 4)-textured LiCoO₂ thin films, the (0 0 3)-textured thin films exhibited relatively lower electrochemical activity. However, the advantage of the (1 0 4)-textured film only remained for a small number of cycles due to the relatively faster capacity fade. Li diffusion measurements showed that the Li diffusivity in the (0 0 3)-textured film is one order of magnitude lower than that in the (1 0 4)-textured film. As discussed in this paper, we believe that Li diffusion through grain boundaries is comparable to or even faster than Li diffusion through the grains.     

Electrochemical performance of the carbon coated Li3V2(PO4)3 cathode material synthesized by a sol-gel method

A carbon coated Li₃V₂(PO₄)₃ cathode material for lithium ion batteries was synthesized by a sol-gel method using V₂O₅, H₂O₂, NH₄H₂PO₄, LiOH and citric acid as starting materials, and its physicochemical properties were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX), transmission electron microscope (TEM), and electrochemical methods. The sample prepared displays a monoclinic structure with a space group of P2₁/n, and its surface is covered with a rough and porous carbon layer. In the voltage range of 3.0-4.3 V, the Li₃V₂(PO₄)₃ electrode displays a large reversible capacity, good rate capability and excellent cyclic stability at both 25 and 55 °C. The largest reversible capacity of 130 mAh g⁻¹ was obtained at 0.1C and 55 °C, nearly equivalent to the reversible cycling of two lithium ions per Li₃V₂(PO₄)₃ formula unit (133 mAh g⁻¹). It was found that the increase in total carbon content can improve the discharge performance of the Li₃V₂(PO₄)₃ electrode. In the voltage range of 3.0-4.8 V, the extraction and reinsertion of the third lithium ion in the carbon coated Li₃V₂(PO₄)₃ host are almost reversible, exhibiting a reversible capacity of 177 mAh g⁻¹ and good cyclic performance. The reasons for the excellent electrochemical performance of the carbon coated Li₃V₂(PO₄)₃ cathode material were also discussed.     

Effect of fluorine in the preparation of Li(Ni1/3Co1/3Mn1/3)O2 via hydroxide co-precipitation

Uniform and spherical Li(Ni_1/3Co_1/3Mn_1/3)O_(2−δ)F_δ powders were synthesized via NH₃ and F⁻ coordination hydroxide co-precipitation. The effect of F⁻ coordination agent on the morphology, structure and electrochemical properties of the Li(Ni_1/3Co_1/3Mn_1/3)O_(2−δ)F_δ were studied. The morphology, size, and distribution of (Ni_1/3Co_1/3Mn_1/3)(OH)_(2−δ)F_δ particle diameter were improved in a shorter reaction time through the addition of F⁻. The study suggested that the added F improves the layered characteristics of the lattice and the cyclic performance of Li(Ni_1/3Co_1/3Mn_1/3)O₂ in the voltage range of 2.8-4.6 V. The initial capacity of the Li(Ni_1/3Co_1/3Mn_1/3)O_1.96F_0.04 was 178 mAh g⁻¹, the maximum capacity was 186 mAh g⁻¹ and the capacity after 50 cycles was 179 mAh g⁻¹ in the voltage range of 2.8-4.6 V.     

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%.     

Nanocomposite Fe2O3-Se as a new lithium storage material

The electrochemical properties of nanocomposite Fe₂O₃-Se thin film prepared by pulsed laser deposition (PLD) method have been investigated by cyclic voltammetry and charge/discharge measurements. A large reversible capacity of nanocomposite Fe₂O₃-Se thin film was found to be around 650 mAh g⁻¹. A new couple of reduction and oxidation peaks at 1.4 and 1.8 V were observed from cyclic voltammogram for the first time. Our data demonstrated that nanocomposite Fe₂O₃-Se exhibit larger capacity and better cycle performance than pure Fe₂O₃. The electrochemical reaction mechanisms of Fe₂O₃-Se with lithium were examined by X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM) and selected-area electron diffraction (SAED). The reversible conversions reaction of nanosized metal Fe with Li₂Se and Li₂O formed after initial discharge process into FeSe and Fe₂O₃ respectively were revealed.     

Optimum synthesis of Li2Fe1−xMnxSiO4/C cathode for lithium ion batteries

Li₂Fe_1−xMn_xSi0₄/C cathode materials were synthesized by mechanical activation-solid-state reaction. The effects of Mn-doping content, roasting temperature, soaking time and Li/Si molar ratio on the physical properties and electrochemical performance of the Li₂Fe_1−xMn_xSi0₄/C composites were investigated. The materials were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM), charge-discharge tests and AC impedance measurements. SEM images suggest that the morphology of the Li₂Fe_1−xMn_xSi0₄/C composite is sensitive to the reaction temperature. Samples synthesized at different temperatures have different extent of agglomeration. Being charged-discharged at C/32 between 1.5 and 4.8 V, the Li₂Fe_0.9Mn_0.1Si0₄/C synthesized at the optimum conditions shows good electrochemical performances with an initial discharge capacity of 158.1 mAh g⁻¹ and a capacity retention ratio of 94.3% after 30 cycles. AC impendence investigation shows Li₂Fe_0.9Mn_0.1SiO₄/C have much lower resistance of electrode/electrolyte interface than Li₂FeSiO₄/C.     

LiCoO2 thin film cathode fabrication by rapid thermal annealing for micro power sources

The rapid thermal annealing (RTA) process was employed to obtain crystalline LiCoO₂ thin films. XRD analyses of the LiCoO₂ thin film show increased crystallinity with an increase in the RTA time. The Auger electron spectroscopic analysis of the LiCoO₂ film strongly suggests that the RTA process is more advantageous to obtain a stable inter layer between the substrate and the deposited film and between each deposited layer than the conventional annealing process. All-solid-state thin film cells composed of Li/lithium phosphorous oxynitride (Lipon)/LiCoO₂ systems were fabricated using the LiCoO₂ cathode treated with RTA. The optimum condition of RTA would be 900 s at 650 °C, which exhibited a good rate capability for high power applications. Two cells were connected in parallel to obtain a higher discharge current, and they showed a specific capacity of 38.4 μAh cm⁻² μm⁻¹ even at a 25C rate (current density: 7.96 mA cm⁻²).     

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.     

Synthesis of compounds, Li(MMn11/6)O4 (M = Mn1/6, Co1/6, (Co1/12Cr1/12), (Co1/12Al1/12), (Cr1/12Al1/12)) by polymer precursor method and its electrochemical performance for lithium-ion batteries

The compounds, Li(MMn_11/6)O₄ (M = Mn_1/6, Co_1/6, (Co_1/12Cr_1/12), (Co_1/12Al_1/12), (Cr_1/12Al_1/12)) are synthesised by the polymer precursor method. The structure and the morphology of the compounds are studied by the Rietveld refined X-ray diffraction (XRD), and transmission electron microscopy (TEM) techniques, respectively. Density and the Brunauer, Emmet and Teller surface area (BET) of the compounds are also studied. The cobalt doped compound, Li(Co_1/6Mn_11/6)O₄ is found to be nanosized particles in the range of 60-100 nm, when compared to the other compounds in our present study. The oxidation state and the local structure of the compounds are analysed by the X-ray absorption spectroscopy (XAS) technique. Cyclic voltammetry (CV) and the galvanostatic charge-discharge cycling (30 mA g⁻¹) studies are made in the voltage range of 3.5-4.3 V at room temperature for all the compounds under study. The bare and (Co_1/6), and (Co_1/12Cr_1/12) substituted spinels are cycled at high current rates of 1, 2 and 5C (assuming 1C∼120 mA g⁻¹). Cycling results of Co-substituted spinels show better and long-term capacity retention at all the current rates. At the end of the second cycle, Li(Co_1/6Mn_11/6)O₄ compound delivers a discharge capacity value of 100 (±3) and 87 (±3) mAh g⁻¹ for the current rate of 2 and 5C, respectively. An excellent capacity retention value of 94% is observed at the end of the 1000 cycles for both 2 and 5C rates.     

Effect of TiO2 supporting layer on Fe2O3 photoanode for efficient water splitting

For an electrochemical water splitting system, titanate nanotubular particles with a thickness of ∼700 nm produced by a hydrothermal process were repetitively coated on fluorine-doped tin oxide (FTO) glass via layer-by-layer self-assembly method. The obtained titanate/FTO films were dipped in aqueous Fe solution, followed by heat treatment for crystallization at 500 °C for 10 min in air. The UV–vis absorbance of the Fe-oxide/titanate/FTO film showed a red-shifted spectrum compared with the TiO₂/FTO coated film; this red shift was achieved by the formation of thin hematite-Fe₂O₃ and anatase-TiO₂ phases verified using X-ray diffraction and Raman results. The cyclic voltammetry results of the Fe₂O₃/TiO₂/FTO films showed distinct reversible cycle characteristics with large oxidation–reduction peaks with low onset voltage of I–V characteristics under UV–vis light illumination. The prepared Fe₂O₃/TiO₂/FTO film showed much higher photocurrent densities for more efficient water splitting under UV–vis light illumination than did the Fe₂O₃/FTO film. Its maximum photocurrent was almost 3.5 times higher than that obtained with Fe₂O₃/FTO film because of the easy electron collection in the current collector. The large current collection was due to the existence of a TiO₂ base layer beneath the Fe₂O₃ layer.     

As-deposited LiCoO2 thin film cathodes prepared by rf magnetron sputtering

LiCoO₂ thin films were deposited using radio frequency (rf) magnetron sputtering system on stainless steel substrates. Different rf powers, up to 150 W, were applied during deposition. The as-deposited films exhibited (1 0 1) and (1 0 4) preferred orientation and the nanocrystalline film structure was enhanced with increasing rf power. The film crystallinity was examined using X-ray diffraction, Raman scattering spectroscopy and transmission electron microscopy. The compositions of the films were determined by inductively coupled plasma-mass spectroscopy. The average discharge capacity of as-deposited films is about 59 μAh/(cm² μm) for cut-off voltage range of 4.2 and 3.0 V. From the electrochemical cycling data, it is suggested that as-deposited LiCoO₂ films with a nanocrystalline structure and a favorable preferred orientation, e.g. (1 0 1) or (1 0 4) texture, can be used without post-annealing at high temperatures for solid-state thin film batteries.     

Hydrothermal synthesis of Li(Ni1/3Co1/3Mn1/3)O2 for lithium rechargeable batteries

Ultrafine powders of Li(Ni_1/3Co_1/3Mn_1/3)O₂ cathode materials for lithium-ion secondary batteries were prepared under mild hydrothermal conditions. The influence of the molar ratio of Li/(Ni + Co + Mn) was studied. The products were investigated by XRD, TEM and EDS. The final products were found to be well crystallized Li(Ni_1/3Co_1/3Mn_1/3)O₂ with an average particle size of about 10 nm.     

Characterization of high tap density Li[Ni1/3Co1/3Mn1/3]O2 cathode material synthesized via hydroxide co-precipitation

Li[Ni_1/3Co_1/3Mn_1/3]O₂ cathode material for lithium ion batteries was prepared by mixing metal hydroxide, (Ni_1/3Co_1/3Mn_1/3)(OH)₂, with 6% excess LiOH followed by calcinations. The (Ni_1/3Co_1/3Mn_1/3)(OH)₂ with secondary particle of about 12 μm was prepared by hydroxide co-precipitation. The tap density of the obtained Li[Ni_1/3Co_1/3Mn_1/3]O₂ powder was 2.56 ± 0.21 g cm⁻³. The powder was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), particle size distribution (PSD) and galvanostatic charge-discharge cycling. The XRD pattern of Li[Ni_1/3Co_1/3Mn_1/3]O₂ revealed a well ordered hexagonal layered structure with low cation mixing. Secondary particles with size of 13-14 μm and primary particles with size of about 1 μm can be identified from the SEM observations. In the voltage range of 2.8-4.3 V, the initial discharge capacity of the Li[Ni_1/3Co_1/3Mn_1/3]O₂ electrode was 166.6 mAh g⁻¹, and 96.5% of the initial capacity was retained after 50 charge-discharge cycling.     

Comparison of AlPO4- and Co3(PO4)2-coated LiNi0.8Co0.2O2 cathode materials for Li-ion battery

Electrochemical and thermal properties of Co₃(PO₄)₂- and AlPO₄-coated LiNi_0.8Co_0.2O₂ cathode materials were compared. AlPO₄-coated LiNi_0.8Co_0.2O₂ cathodes exhibited an original specific capacity of 170.8 mAh g⁻¹ and had a capacity retention (89.1% of its initial capacity) between 4.35 and 3.0 V after 60 cycles at 150 mA g⁻¹. Co₃(PO₄)₂-coated LiNi_0.8Co_0.2O₂ cathodes exhibited an original specific capacity of 177.6 mAh g⁻¹ and excellent capacity retention (91.8% of its initial capacity), which was attributed to a lithium-reactive Co₃(PO₄)₂ coating. The Co₃(PO₄)₂ coating material could react with LiOH and Li₂CO₃ impurities during annealing to form an olivine Li_xCoPO₄ phase on the bulk surface, which minimized any side reactions with electrolytes and the dissolution of Ni⁴⁺ ions compared to the AlPO₄-coated cathode. Differential scanning calorimetry results showed Co₃(PO₄)₂-coated LiNi_0.8Co_0.2O₂ cathode material had a much improved onset temperature of the oxygen evolution of about 218 °C, and a much lower amount of exothermic-heat release compared to the AlPO₄-coated sample.     

A diffusion kinetics study of Li-ion in LiV3O8 thin film electrode

The kinetic behaviors of Li-ion insertion/extraction in LiV₃O₈ thin film have been investigated using cyclic voltammetry (CV), potentiostatic intermittent titration (PITT) and electrochemical impedance spectroscopy (EIS) method. This LiV₃O₈ thin film with a mixed amorphous-nanocrystalline microstructure was fabricated by RF sputtering. For the first time, the intrinsic kinetics of LiV₃O₈ thin film electrode is obtained. The DLi+ value is about 10⁻¹³ cm²/s in mixed amorphous-nanocrystalline microstructure LiV₃O₈ thin film. Different to crystalline LiV₃O₈ thin film, the DLi+ values do not change a lot with the increase of cell potential which is due to the absence of structural phase transition behavior in mixed microstructure LiV₃O₈ thin film during Li⁺ insertion/extraction process. This is also the reason for excellent capacity retention performance of LiV₃O₈ film with a mixed microstructure.     

Film thickness dependence of the dielectric properties of SrTiO3/BaTiO3 multilayer thin films deposited by double target RF magnetron sputtering

Four-layer SrTiO₃/BaTiO₃ thin films ((ST/BT)₄) with various thicknesses deposited on Pt/Ti/SiO₂/Si substrates at 500 °C by double target RF magnetron sputtering have been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), profilometry, capacitance-voltage and current-voltage measurements. The XRD patterns reveal the frame formation of the sputter deposited (ST/BT)₄ with controlled modulation. The adhesion between the Pt bottom electrode layer and the BT layer is excellent. The dielectric constant of the (ST/BT)₄ multilayer thin film increases with increasing film thickness. The effects of temperature, frequency, and bias voltage on the dielectric constant of the (ST/BT)₄ multilayer thin films are discussed in detail. The leakage current density of the (ST/BT)₄ multilayer with a thickness of 450.0 nm is lower than 1.0 × 10⁻⁸ A/cm² for the applied voltage of less than 5 V, showing that the multilayer thin films with such a characteristic could be applied for use in dynamic random access memory (DRAMs) capacitors.     

All-solid-state lithium battery with a three-dimensionally ordered Li1.5Al0.5Ti1.5(PO4)3 electrode

To fabricate all-solid-state Li batteries using three-dimensionally ordered macroporous Li_1.5Al_0.5Ti_1.5(PO₄)₃ (3DOM LATP) electrodes, the compatibilities of two anode materials (Li₄Mn₅O₁₂ and Li₄Ti₅O₁₂) with a LATP solid electrolyte were tested. Pure Li₄Ti₅O₁₂ with high crystallinity was not obtained because of the formation of a TiO₂ impurity phase. Li₄Mn₅O₁₂ with high crystallinity was produced without an impurity phase, suggesting that Li₄Mn₅O₁₂ is a better anode material for the LATP system. A Li₄Mn₅O₁₂/3DOM LATP composite anode was fabricated by the colloidal crystal templating method and a sol-gel process. Reversible Li insertion into the fabricated Li₄Mn₅O₁₂/3DOM LATP anode was observed, and its discharge capacity was measured to be 27 mA h g⁻¹. An all-solid-state battery composed of LiMn₂O₄/3DOM LATP cathode, Li₄Mn₅O₁₂/3DOM LATP anode, and a polymer electrolyte was fabricated and shown to operate successfully. It had a potential plateau that corresponds to the potential difference expected from the intrinsic redox potentials of LiMn₂O₄ and Li₄Mn₅O₁₂. The discharge capacity of the all-solid-state battery was 480 μA h cm⁻².