PVA-assisted spray deposited porous Li4Ti5O12 thin film as high-rate and long-cycle anode for lithium-ion thin-film batteries.

Spinel Li4Ti5O12 (LTO), a zero-strain material, is a promising anode material for solid-state thin-film lithium-ion batteries (TFB). However, the preparation of high-performance Li4Ti5O12 thin-film electrodes through facile methods remains a significant challenge. Herein, we present a novel approach to prepare a binder- and conductor-free porous Li4Ti5O12 (P-LTO) thin-film. This approach polyvinyl alcohol (PVA)-assisted spray deposition and does not require the use of complex or expensive methods. Adding PVA to the precursor solution effectively prevents thin-film cracking during high-temperature annealing, enhances adhesion, and forms a highly interconnected porous structure. This unique structure shortens the lithium-ion diffusion pathways and facilitates electron transport. Therefore, P-LTO thin film electrodes demonstrate exceptional rate capacity of 104.1 mAh/g at a current density of 100C. In addition, the electrodes exhibit ultra-long cycle stability, retaining 80.9 % capacity after 10,000 cycles at 10C. This work offers a novel approach for the preparation of high-performance thin-film electrodes for TFBs.

Unlocking the Use of LiCl as an Inexpensive Salt for Lithium-Ion Batteries with a Novel Anion Receptor.

Lithium chloride (LiCl) is an inexpensive and environmentally friendly salt abundant in the ocean. However, the insolubility of LiCl in conventional electrolyte solvents prevents the practical use of LiCl for lithium-ion batteries. Here, we report a novel method to increase the solubility of LiCl in a conventional electrolyte. The solubility of LiCl in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1/1, v/v) is about quadrupled by adding a small amount of anion receptor with two urea moieties as recognition sites connecting with an ether chain. Anion receptor is an organic molecule that can associate with anions. Our anion receptor is able to associate with chloride anion. The ionic conductivity of LiCl in EC/DMC increased from 0.023 mS cm-1 (without an anion receptor) to 0.075 mS cm-1 (with a 0.05 M anion receptor). The electrolyte in the presence of a 0.05 M receptor exhibits higher ionic conductivity, rate capability, and cyclability than the electrolyte without the receptor.

Electrochemical Lithium Deposition on LixTi5O12.

Lithium metal batteries (LMBs) have been regarded as one of the most promising next-generation high-energy-density storage devices. However, uncontrolled lithium dendrite growth leads to low Coulombic efficiencies and severe safety issues, hindering the commercialization of LMBs. Reducing the diffusion barrier of lithium is beneficial for uniform lithium deposition. Herein, a composite is constructed with Li4Ti5O12 as the skeleton of metallic lithium (Li@LixTi5O12) because Li4Ti5O12 is a "zero-strain" material and exhibits a low lithium diffusion barrier. It was found that the symmetric cells of Li@LixTi5O12 can stably cycle for over 400 h at 1 mA cm-2 in the carbonate electrolyte, significantly exceeding the usual lifespan (∼170 h) of the symmetric cell using a lithium metal electrode. In a full cell with Li@LixTi5O12 as the anode, the cathode LiFePO4 delivers a capacity retention of 78.2% after 550 cycles at 3.6C rate and an N/P ratio = 8.0. This study provides new insights for designing a practical lithium anode.

High-Performance Li-Ion and Na-Ion Capacitors Based on a Spinel Li4Ti5O12 Anode and Carbonaceous Cathodes.

Lithium-ion hybrid capacitors (LICs) have become promising electrochemical energy storage systems that overcome the limitations of lithium-ion batteries and electrical double-layer capacitors. The asymmetric combination of these devices enhances the overall electrochemical performance by delivering simultaneous energy and power capabilities. Lithium titanate (Li4Ti5O12, LTO), a spinel zero-strain material, has been studied extensively as an anode material for LIC applications because of its high-rate capability, negligible volume change, and enhanced cycling performance. Here, the different synthetic methods and modifications of the intercalation-type LTO to enhance the overall electrochemical performance of LICs are mainly focused. Moreover, the cathodic part (i.e., the activated carbon derived from various sources, including natural products, polymers, and inorganic materials) is also dealt with as it contributes substantially to the overall performance of the LIC. Not only do the anode and cathode, but also the electrolytes have a substantial influence on LIC performance. The electrolytes used in LTO-based LICs as well as in flexible and bendable configurations are also mentioned. Overall, the previous work along with other available reports on LTO-based LICs in a simplified way is analyzed.

Oxalic acid-assisted preparation of LTO-carbon composite anode material for lithium-ion batteries.

This study presents an oxalic acid-assisted method for synthesizing spinel-structured lithium titanate (Li4Ti5O12; LTO)/carbon composite materials. The Ag-doped LTO nanoparticles (NPs) are synthesized via flame spray pyrolysis (FSP). The synthesized material is used as a precursor for synthesizing the LTO-NP/C composite material with chitosan as a carbon source and oxalic acid as an additive. Oxalic acid improves the dissolution of chitosan in water as well as changes the composition and physical and chemical properties of the synthesized LTO-NP/C composite material. The oxalic acid/chitosan ratio can be optimized to improve the electrochemical performance of the LTO-NP/C composite material, and the electrode synthesized with a high mass loading ratio (5.44 mg cm-2) exhibits specific discharge capacities of 156.5 and 136 mAh g-1at 0.05 C- and 10 C-rate currents, respectively. Moreover, the synthesized composite LTO-NP/C composite material exhibits good cycling stability, and only 1.7% decrease in its specific capacity was observed after 200 charging-discharging cycles at 10 C-rate discharging current.

Spray fabrication of additive-free electrodes for advanced Lithium-Ion storage technologies.

Polymer binders and carbon conductivity enhancers are inevitably required to make improvements in structural durability and electrochemical performance of lithium-ion battery (LIB) electrodes, although these additive constituents incur weight and volume penalties on the overall battery capacity. Here, additive-free electrode architectures were successfully fabricated over 20 × 20 cm2 electrode areas using a layer-by-layer spray coating approach, with the ultimate goal to boost gravimetric/volumetric electrode capacity and to reduce the total cost of LIB cells. Initially, the binder fraction of spray-coated Li4Ti5O12 (LTO) electrodes was reduced progressively, from 40 to 0 wt%. The electrochemical behavior of electrodes was then re-optimized as a proportion of conductivity enhancers within the binder-free electrode decreased to zero. Further, the otherwise identical spray coating process was applied to manufacture LiFePO4 (LFP) positive electrodes, leading to all-additive-free full-cell LIB configurations with attractive energy density of âˆ¼310 Wh/kg and power performance of âˆ¼1500 W/kg.

Two-Dimensional Films Based on Graphene/Li4Ti5O12 and Carbon Nanotube/Li4Ti5O12 Nanocomposites as a Prospective Material for Lithium-Ion Batteries: Insight from Ab Initio Modeling.

The combination of spinel Li4Ti5O12 (LTO) with carbon nanostructures, such as graphene (G) and carbon nanotubes (CNTs), provides all of the required properties for modern chemical power sources such as Li-ion batteries (LIBs) and supercapacitors (SCs). G/LTO and CNT/LTO composites demonstrate a superior reversible capacity, cycling stability, and good rate performances. In this paper, an ab initio attempt to estimate the electronic and capacitive properties of such composites was made for the first time. It was found that the interaction between LTO particles and CNTs was higher than that with graphene due to the larger amount of transfer charge. Increasing the graphene concentration raised the Fermi level and enhanced the conductive properties of G/LTO composites. For CNT/LTO samples, the radius of CNT did not affect the Fermi level. For both G/LTO and CNT/LTO composites, an increase in the carbon ratio resulted in a similar reduction in quantum capacitance (QC). It was observed that during the charge cycle in the real experiment, the non-Faradaic process prevailed during the charge cycle, while the Faradaic process prevailed during the discharge cycle. The obtained results confirm and explain the experimental data and improve the understanding of the processes occurring in G/LTO and CNT/LTO composites for their usages in LIBs and SCs.

Enhanced Electrochemical Performance of Rare-Earth Metal-Ion-Doped Nanocrystalline Li4Ti5O12 Electrodes in High-Power Li-Ion Batteries.

A comprehensive and comparative exploration research performed, aiming to elucidate the fundamental mechanisms of rare-earth (RE) metal-ion doping into Li4Ti5O12 (LTO), reveals the enhanced electrochemical performance of the nanocrystalline RE-LTO electrodes in high-power Li-ion batteries. Pristi ne Li4Ti5O12 (LTO) and rare-earth metal-doped Li4-x/3Ti5-2x/3LnxO12 (RE-LTO with RE = Dy, Ce, Nd, Sm, and Eu; x ≈ 0.1) nanocrystalline anode materials were synthesized using a simple mechanochemical method and subsequent calcination at 850 °C. The X-ray diffraction (XRD) patterns of pristine and RE-LTO samples exhibit predominant (111) orientation along with other characteristic peaks corresponding to cubic spinel lattice. No evidence of RE-doping-induced changes was seen in the crystal structure and phase. The average crystallite size for pristine and RE-LTO samples varies in the range of 50-40 nm, confirming the formation of nanoscale crystalline materials and revealing the good efficiency of the ball-milling-assisted process adopted to synthesize nanoscale particles. Raman spectroscopic analyses of the chemical bonding indicate and further validate the phase structural quality in addition to corroborating with XRD data for the cubic spinel structure formation. Transmission electron microscopy (TEM) reveals that both pristine and RE-LTO particles have a similar cubic shape, but RE-LTO particles are better interconnected, which provide a high specific surface area for enhanced Li+-ion storage. The detailed electrochemical characterization confirms that the RE-LTO electrodes constitute promising anode materials for high-power Li-ion batteries. The RE-LTO electrodes deliver better discharge capacities (in the range of 172-198 mAh g-1 at 1C rate) than virgin LTO (168 mAh g-1). Among them, Eu-LTO provides the best discharge capacity of 198 mAh g-1 at a 1C rate. When cycled at a high current rate of 50C, all RE-LTO electrodes show nearly 70% of their initial discharge capacities, resulting in higher rate capability than virgin LTO (63%). The results discussed in this work unfold the fundamental mechanisms of RE doping into LTO and demonstrate the enhanced electrochemical performance derived via chemical composition tailoring in RE-LTO compounds for application in high-power Li-ion batteries.

Application of Thermally Fluorinated Multi-Wall Carbon Nanotubes as an Additive to an Li4Ti5O12 Lithium Ion Battery.

In this study, multi-walled carbon nanotubes (MWCNTs) were modified by thermal fluorination to improve dispersibility between MWCNTs and Li4Ti5O12 (LTO) and were used as additives to compensate for the disadvantages of LTO anode materials with low electronic conductivity. The degree of fluorination of the MWCNTs was controlled by modifying the reaction time at constant fluorination temperature; the clear structure and surface functional group changes in the MWCNTs due to the degree of fluorination were determined. In addition, the homogeneous dispersion in the LTO was improved due to the strong electronegativity of fluorine. The F-MWCNT conductive additive was shown to exhibit an excellent electrochemical performance as an anode for lithium ion batteries (LIBs). In particular, the optimized LTO with added fluorinated MWCNTs not only exhibited a high specific capacity of 104.8 mAh g-1 at 15.0 C but also maintained a capacity of ~116.8 mAh g-1 at a high rate of 10.0 C, showing a capacity almost 1.4 times higher than that of LTO with the addition of pristine MWCNTs and an improvement in the electrical conductivity. These results can be ascribed to the fact that the semi-ionic C-F bond of the fluorinated MWCNTs reacts with the Li metal during the charge/discharge process to form LiF, and the fluorinated MWCNTs are converted into MWCNTs to increase the conductivity due to the bridge effect of the conductive additive, carbon black, with LTO.

Ti3C2 MXene-derived Li4Ti5O12 nanoplates with in-situ formed carbon quantum dots for metal-ion battery anodes.

Two-dimensional (2D) material Ti3C2 MXenes have recently been used in electrode composites for lithium-ion batteries (LIBs) for their excellent electrical conductivity and accordion-like nanosheet morphology. However, Ti3C2 has low specific capacity and fast degradation rate upon cycling after inevitably coupling with surface species during synthesis. In this work, Ti3C2 is used as Ti-source for Li4Ti5O12 (LTO) and C-source for carbon quantum dots (CQDs) in a one-step hydrothermal process. The resultant LTO product (M-LTO) inherits the nanosheet morphology of Ti3C2 with uniformly anchored CQDs. The highly electronic conductive CQDs optimize the transmission path of ions which reduces the diffusion barrier of ions, and they further increase the density of states of the material which effectively improving the conductivity of M-LTO. Remarkable electrochemical performances including high initial specific capacity, long lifetime and excellent low temperature capacity are demonstrated for this type of electrode in LIBs, sodium ion batteries (SIBs) and lithium-magnesium ion hybrid batteries (LMIHBs). This paper offers a new strategy to the rapidly expanding research on the application of transition metal MXenes in electrodes for metal-ion batteries.

Long-Cycle Stability of In Situ Ultraviolet Curable Organic/Inorganic Composite Electrolyte for Solid-State Batteries.

Lithium-ion solid-state batteries with spinel Li4Ti5O12 (LTO) electrodes have significant advantages, such as stability, long life, and good multiplication performance. In this work, the LTO electrode was obtained by the atmospheric plasma spraying method, and a composite solid electrolyte was prepared by in situ ultraviolet (UV) curing on the LTO electrode. The composite solid electrolyte was designed using a soft-hard combination strategy, and the electrolyte was prepared into a composite of a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) flexible structure and high-conductivity Li1.3Al0.3Ti1.7(PO4)3 (LATP) hard particles. The composite electrolyte exhibited a good ionic conductivity up to 0.35 mS cm-1 at 30 °C and an electrochemical window above 4.0 V. In situ and ex situ electrolytes were assembled into LTO//electrolyte//Li solid-state batteries to investigate their impact on the electrochemical performance of the batteries. As a result, the assembled Li4Ti5O12//in situ electrolytes//Li batteries exhibited excellent rate of performance, and their capacity retention rate was 90% at 0.2 mA/cm2 after 300 cycles. This work provides a new method for the fabrication of novel advanced solid-state electrolytes and electrodes for applications in solid-state batteries.

Important Impact of the Slurry Mixing Speed on Water-Processed Li4Ti5O12 Lithium-Ion Anodes in the Presence of H3PO4 as the Processing Additive.

The aqueous processing of lithium transition metal oxides into battery electrodes is attracting a lot of attention as it would allow for avoiding the use of harmful N-methyl-2-pyrrolidone (NMP) from the cell fabrication process and, thus, render it more sustainable. The addition of slurry additives, for instance phosphoric acid (PA), has been proven to be highly effective for overcoming the corresponding challenges such as aluminum current collector corrosion and stabilization of the active material particle. Herein, a comprehensive investigation of the effect of the ball-milling speed on the effectiveness of PA as a slurry additive is reported using Li4Ti5O12 (LTO) as an exemplary lithium transition metal oxide. Interestingly, at elevated ball-milling speeds, rod-shaped lithium phosphate particles are formed, which remain absent at lower ball-milling speeds. A detailed surface characterization by means of SEM, EDX, HRTEM, STEM-EDX, XPS, and EIS revealed that in the latter case, a thin protective phosphate layer is formed on the LTO particles, leading to an improved electrochemical performance. As a result, the corresponding lithium-ion cells comprising LTO anodes and LiNi0.5Mn0.3Co0.2O2 (NMC532) cathodes reveal greater long-term cycling stability and higher capacity retention after more than 800 cycles. This superior performance originates from the less resistive electrode-electrolyte interphase evolving upon cycling, owing to the interface-stabilizing effect of the lithium phosphate coating formed during electrode preparation. The results highlight the importance of commonly neglected─frequently not even reported─electrode preparation parameters.

Transport and Electrochemical Properties of Li4Ti5O12-Li2TiO3 and Li4Ti5O12-TiO2 Composites.

The study demonstrates that the introduction of the electrochemically inactive dielectric additive Li2TiO3 to LTO results in a strong decrease in the grain boundary resistance of LTO-Li2TiO3 (LTC) composites at a low concentration of Li2TiO3. With the increase in the concentration of Li2TiO3 in LTC composites, the grain boundary resistance goes through a minimum and increases again due to the growth of the insulation layer of small Li2TiO3 particles around LTO grains. For LTO-TiO2 (LTT) composites, a similar effect was observed, albeit not as strong. It was found that LTC composites at low concentration of Li2TiO3 have unusually high charge-discharge capacity exceeding the theoretical value for pure LTO. This effect is likely to be caused by the occurrence of the electrochemical activity of Li2TiO3 in the vicinity of the interfaces between LTO and Li2TiO3. The increase in the capacity may be qualitatively described in terms of the model of two-phase composite in which there is the interface layer with a high capacity. Contrasting with LTC composites, in LTT composites, no capacity enhancement was observed, which was likely due to a noticeable difference in crystal structures of LTO and TiO2 preventing the formation of coherent interfaces.

Extraordinarily Stable Aqueous Electrochromic Battery Based on Li4Ti5O12 and Hybrid Al3+/Zn2+ Electrolyte.

Aqueous electrochromic battery (ECB) is a multifunctional technology that shows great potential in various applications including energy-saving buildings and wearable batteries with visible energy levels. However, owing to the mismatch between traditional electrochromic materials and the electrolyte, aqueous ECBs generally exhibit poor cycling stability which bottlenecks their practical commercialization. Herein, we present an ultrastable electrochromic system composed of lithium titanate (Li4Ti5O12, LTO) electrode and Al3+/Zn2+ hybrid electrolyte. The fully compatible system exhibits excellent redox reaction reversibility, thus leading to extremely high cycling stabilities in optical contrast (12 500 cycles with unnoticeable degradation) and energy storage (4000 cycles with 82.6% retention of capacity), superior electrochromic performances including high optical contrast (∼74.73%) and fast responses (4.35 s/7.65 s for bleaching/coloring), as well as excellent discharge areal capacity of 151.94 mAh m-2. The extraordinary cycling stability can be attributed to the robust [TiO6] octahedral frameworks which remain chemically active even upon the gradual substitution of Li+ with Al3+ in LTO over multiple operation cycles. The high-performance electrochromic system demonstrated here not only makes the commercialization of low-cost, high-safety aqueous-based electrochromic devices possible but also provides potential design guidance for LTO-related materials used in aqueous-based energy storage devices.

High Lithium Storage Performance of Co Ion-Doped Li4Ti5O12 Induced by Fast Charge Transport.

In this study, Co3O4-doped Li4Ti5O12 (LTO) composite was designed and synthesized by the hydrothermal reduction method and metal doping modification method. The microstructure and electrochemical performance of the Co3O4-doped Li4Ti5O12 composite were characterized by XRD, SEM, TEM, electrochemical impedance spectroscopy, and galvanostatic tests. The results showed that Li4Ti5O12 particles attached to lamellar Co3O4 constituted a heterostructure and Co ion doped into Li4Ti5O12 lattice. This Co ion-doped microstructure improved the charge transportability of Li4Ti5O12 and inhibited the gas evolution behavior of Li4Ti5O12, which enhanced the lithium storage performance. After 20 cycles, the discharge specific capacity reached stability, and the capacity retention maintained 99% after 1,000 cycles at 0.1 A/g (compared to the capacity at the 20th cycle). It had an excellent rate performance and long cycle stability, in which the capacity reached 174.6 mA h/g, 2.2 times higher than that of Li4Ti5O12 at 5 A/g.

Photo-Charging of Li(Ni0.65Co0.15Mn0.20)O2 Lithium-Ion Battery Using Silicon Solar Cells.

This study reports an integrated device in which a lithium-ion battery (LIB) and Si solar cells are interconnected. The LIB is fabricated using the Li(Ni0.65Co0.15Mn0.20)O2 (NCM622) cathode and the Li4Ti5O12 (LTO) anode. The surface and shape morphologies of the NCM and LTO powders were investigated by field emission scanning electron microscopy (FE-SEM). In addition, the structural properties were thoroughly examined by X-ray diffraction (XRD). Further, their electrochemical characterization was carried out on a potentiostat. The specific discharge capacity of the NCM cathode (half-cell) was 188.09 mAh/g at 0.1 C current density. In further experiments, the NCM-LTO full-cell has also shown an excellent specific capacity of 160 mAh/g at a high current density of 1 C. Additionally, the capacity retention was outstanding, with 99.63% at 1 C after 50 cycles. Moreover, to meet the charging voltage requirements of the NCM-LTO full-cell, six Si solar cells were connected in series. The open-circuit voltage (VOC) and the short-circuit photocurrent density (JSC) for the Si solar cells were 3.37 V and 5.42 mA/cm2. The calculated fill factor (FF) and efficiency for the Si solar cells were 0.796 and 14.54%, respectively. Lastly, the integrated device has delivered a very high-power conversion-storage efficiency of 7.95%.

TiO2(B) nanosheets modified Li4Ti5O12microsphere anode for high-rate lithium-ion batteries.

With the increasing applications of Lithium-ion batteries in heavy equipment and engineering machinery, the requirements of rate capability are continuously growing. The high-rate performance of Li4Ti5O12(LTO) needs to be further improved. In this paper, we synthesized LTO microsphere-TiO2(B) nanosheets (LTO-TOB) composite by using a solvothermal method and subsequent calcination. LTO-TOB composite combines the merits of TiO2(B) and LTO, resulting in excellent high-rate capability (144.8, 139.3 and 124.4 mAh g-1at 20 C, 30 C and 50 C) and superior cycling stability (98.9% capability retention after 500 cycles at 5 C). Its excellent electrochemical properties root in the large surface area, high grain-boundary density and pseudocapacitive effect of LTO-TOB. This work reveals that LTO-TOB composite can be a potential anode for high power and energy density lithium-ion batteries.

Bio-Phenolic Resin Derived Porous Carbon Materials for High-Performance Lithium-Ion Capacitor.

In this article, hierarchical porous carbon (HPC) with high surface area of 1604.9 m2/g is prepared by the pyrolysis of rubberwood sawdust using CaCO3 as a hard template. The bio-oil pyrolyzed from the rubber sawdust, followed by the polymerization reaction to form resole phenolic resin, can be used as a carbon source to prepare HPC. The biomass-derived HPC shows a three-dimensionally interconnected morphology which can offer a continuous pathway for ionic transport. The symmetrical supercapacitors based on the as-prepared HPC were tested in 1.0 M tetraethylammonium tetrafluoroborate/propylene carbonate electrolyte. The results of electrochemical analysis show that the HPC-based supercapacitor exhibits a high specific capacitance of 113.3 F/g at 0.5 A/g with superior rate capability and cycling stability up to 5000 cycles. Hybrid lithium-ion capacitors (LICs) based on the HPC and Li4Ti5O12 (LTO) were also fabricated. The LICs have a maximum energy density of 113.3 Wh/kg at a power density of 281 W/kg. Moreover, the LIC also displays a remarkable cycling performance with a retention of 92.8% after 3000 cycles at a large current density of 0.75 A/g, suggesting great potential application in the energy storage of the LIC.

Slow-Moving Phase Boundary in Li4/3+ x Ti5/3 O4.

Lithium titanate is one of the most promising anode materials for high-power demands but such applications desire a complete understanding of the kinetics of lithium transport. The poor diffusivity of lithium in the completely lithiated and delithiated (pseudo spinel) phases challenges to explain the high-rate performance. This study aims at clearing the kinetics of lithium transport using an innovative technique that employs optical microscopy in a constrained region of sputter-deposited thin-film samples. It enables the in situ observation of the transport of lithium through the electrode. Furthermore, with a thermostatically controlled cell, the Arrhenius-like temperature dependence is revealed. The quantitative findings demonstrate that indeed the end phases have poor diffusivity which is, however, accelerated at intermediate Li concentrations in the spinel structured Li4/3+ δ Ti5/3 O4 phase. Surprisingly, the slow migration of the phase boundary hinders the formation of the Li-rich (rock-salt) phase in the initial stages. Such kinetic control by the phase boundary stands in obvious contrast to a prior (theoretical) study postulating almost "liquid" behavior of the interface. Only after the Li diffusion into the Li-poor (spinel) phase has faded, when approaching the solubility limit, the further growth of the rock-salt phase becomes diffusion controlled.

Impact of Li3BO3 Addition on Solid Electrode-Solid Electrolyte Interface in All-Solid-State Batteries.

All-solid-state lithium-ion batteries raise the issue of high resistance at the interface between solid electrolyte and electrode materials that needs to be addressed. The article investigates the effect of a low-melting Li3BO3 additive introduced into LiCoO2- and Li4Ti5O12-based composite electrodes on the interface resistance with a Li7La3Zr2O12 solid electrolyte. According to DSC analysis, interaction in the studied mixtures with Li3BO3 begins at 768 and 725 °C for LiCoO2 and Li4Ti5O12, respectively. The resistance of half-cells with different contents of Li3BO3 additive after heating at 700 and 720 °C was studied by impedance spectroscopy in the temperature range of 25-340 °C. It was established that the introduction of 5 wt% Li3BO3 into LiCoO2 and heat treatment at 720 °C led to the greatest decrease in the interface resistance from 260 to 40 Ω cm2 at 300 °C in comparison with pure LiCoO2. An SEM study demonstrated that the addition of the low-melting component to electrode mass gave better contact with ceramics. It was shown that an increase in the annealing temperature of unmodified cells with Li4Ti5O12 led to a decrease in the interface resistance. It was found that the interface resistance between composite anodes and solid electrolyte had lower values compared to Li4Ti5O12|Li7La3Zr2O12 half-cells. It was established that the resistance of cells with the Li4Ti5O12/Li3BO3 composite anode annealed at 720 °C decreased from 97.2 (x = 0) to 7.0 kΩ cm2 (x = 5 wt% Li3BO3) at 150 °C.