LiMn2O4 Research Articles

Effect of Co3+ Doping on Crystal Structure and Electrochemical Properties of Spinel LiMn2O4 Cathode Material

To inhibit the influence of structural distortion caused by the Jahn–Teller effect on LiMn2O4 (LMO), the spinel LMO doped with cobalt ions is prepared by a simple solid-state calcining method. The effects of different cobalt doping amounts on the structure and electrochemical properties of LMO are investigated. The XRD refinement results show that Co3+ successfully enters the lattice of LMO, and its spinel structure is not changed. Due to the smaller radius of Co3+ and the larger bond energy, the unit cell of the LMO material shrinks, and the spinel structure is more stable. The initial capacity of the material decreases with the increase of Co doping content, but the cycle performance is significantly improved. Impressively, when Co doped at x = 0.04, the initial discharge specific capacity of the LMO-0.04 sample is 115.5 mAh·g–1 at 0.1C, and the capacity retention rate is still 81.04% after 500 cycles. The cycle times are much higher than that of the pure LMO sample. Additionally, the diffusion coefficient of Li+ calculated by the Randles–Sevcik equation shows that the doping of Co3+ significantly improves the mobility of Li+ compared with pure LMO. Hence, Co3+ doping can effectively inhibit the structural distortion caused by the Jahn–Teller effect and improve the electrochemical performance of LMO.

Pulsed electric field controlled lithium extraction process by LMO/MXene composite electrode from brines

Low-cost and highly efficient extraction of lithium from brine is the key to solving energy and environmental problems for sustainable development. The electrochemical lithium extraction method is of high selectivity, low energy consumption and environmental friendly. In this work, two innovations were proposed for electrochemical lithium extraction technology. Firstly, the layered Ti3C2-MXene was combined with a LiMn2O4 (LMO) electrode to reduce the damage to the LMO crystal structure caused by manganese dissolution and the Jahn-Teller effect, and to greatly improve the lithium-ion transport rate and the cyclic stability of the electrode material. The good cyclic stability and high capacity were verified by XRD, SEM, and electrochemical tests before and after cycling. Secondly, the influence of four electric field controlling modes, namely constant current (CC) mode, pulse-rest(P10r2 and P10r10), pulse-rest-reverse pulse(P12r2R2), on the selectivity of lithium extraction was studied in simulated brine with an initial lithium/sodium ratio as low as 0.01. The results show that the Pulse Electric Field controlling method can effectively improve the lithium/sodium separation coefficient. Finally, an actual lithium extraction test was carried out in Atacama salt Lake brine with an initial Li/Na ratio of about 0.06. The Li/Na separation coefficient reached 1020 under the optimized electrode material structure and electric field mode. In conclusion, the application of LMO/MXene electrode under the pulse electric field mode is a highly selective method for lithium extraction with low initial lithium/sodium ratios.

A new strategy to quickly synthetize true nanoparticles of the spinel LiMn2O4 by using a microwave-assisted hydrothermal route

Based on a microwave-assisted hydrothermal reaction, a new route is proposed to prepare highly pure true nanoparticles (≤15 nm) of the single-phase spinel LiMn2O4 (LMO) at a low temperature (140 °C) and short reaction time (5 min), using exclusively water-soluble reagents. The obtention of this material was confirmed by using different techniques such as X-ray diffractometry, Rietveld crystal structure refinement, inductively coupled plasma-atomic emission spectroscopy and high-resolution transmission electron microscopy. Electrochemical evaluations were performed by using cyclic voltammetry and galvanostatic charge and discharge tests. Only electrodes prepared from spinel LMO nanoparticles with an average size of ~15 nm showed electrochemical activity. From charge and discharge tests at a constant rate of C/5, the electrodes prepared from this active material exhibited an initial specific capacity of 128 mA h g–1 with a capacity retention of 95% after the 27th cycle. The hallmark of the synthesis route here described is the saving of energy while preparing truly nanoparticulate LMO with excellent chemical, structural and promising electrochemical properties.

Achieving the Interface Stability of LiMn2O4 Cathode Using Aqueous Polyacrylic Acid/acrylate Copolymer and Nanoscale CaCO3 to Improve the High‐Temperature Cycling and Storage Performance of Lithium‐Ion Batteries

Based on a strategy of stabilizing the LiMn2O4 (LMO) cathode interface, the high‐temperature cycling and storage performance of 18 650‐type LMO/graphite lithium‐ion batteries (LIBs) is effectively improved. The LMO cathode is prepared using lithium carboxymethyl cellulose (CMCLi)–polyacrylic acid/acrylate copolymer composite binder and nanoscale CaCO3 functional component (marked as binder C). Compared with the traditional oily binder, the dissolution of Mn2+ from LMO cathode into the electrolyte can effectively decrease, and the structure stability of LMO cathode can increase. The batteries exhibit retention capacity of 80.3% at 1 C after 600 cycles at room temperature and 76.7% at 1 C after 200 cycles at temperature of 45 °C. The high‐temperature storage performance is also improved and there are 81.1% and 73.5% residual capacities when the fully charged batteries are stored in 60 °C for 14 and 28 days. The enhanced performance is mainly attributed to the interfacial stability of LMO cathode due to the bonding ability of composite binders and the elimination of HF by CaCO3. These results reveal the application prospect of as‐developed aqueous binders and provide a way to improve the performance of LMO‐based LIBs through stable interface strategy.

Aging effect delays overcharge-induced thermal runaway of lithium-ion batteries

This research focuses on the effect of overcharging on aged batteries, and the experiments aim to show the thermal runaway (TR) behavior of batteries with different degrees of aging. In order to clarify the typical behavioral characteristics of overcharge-induced battery thermal runaway, commercial 18,650 type LiMn2O4 (LMO)/graphite batteries with different capacity retention rates (CRRs) were applied for overcharge testing operation. The changes of external characteristics, such as surface temperature, voltage and fire explosion phenomena of aged batteries during the whole process of thermal runaway under overcharge conditions were investigated. The results showed that the battery TR trigger time was negatively correlated with the CRR. The batteries having CRR of 86.7%, 80.8%, and 75.2% took 28.2%, 32.5%, and 52.0% longer than fresh battery to reach the TR triggering temperature. Besides, they took 54.1%, 91.8% and 115.1% longer than fresh battery to reach the lithium plating time point. The deposition of manganese oxide on the cathode surface and the phenomenon of lithium plating on the anode surface together lead to the reduction of reversible lithium. With the deepening of aging, the amount of reversible lithium inside the battery decreases, which is the main reason why the TR trigger time is delayed.

Elastic Lattice Enabling Reversible Tetrahedral Li Storage Sites in a High-Capacity Manganese Oxide Cathode.

The key to breaking through the capacity limitation imposed by intercalation chemistry lies in the ability to harness more active sites that can reversibly accommodate more ions (e.g., Li+ ) and electrons within a finite space. However, excessive Li-ion insertion into the Li layer of layered cathodes results in fast performance decay due to the huge lattice change and irreversible phase transformation. In this study, an ultrahigh reversible capacity is demonstrated by a layered oxide cathode purely based on manganese. Through a wealth of characterizations, it is clarified that the presence of low-content Li2 MnO3 domains not only reduces the amount of irreversible O loss; but also regulates Mn migration in LiMnO2 domains, enabling elastic lattice with high reversibility for tetrahedral sites Li-ion storage in Li layers. This work utilizes bulk cation disorder to create stable Li-ion-storage tetrahedral sites and an elastic lattice for layered materials, with a reversible capacity of 600mA h g-1 , demonstrated in th range 0.6-4.9V versus Li/Li+ at 10mA g-1 . Admittedly, discharging to 0.6V might be too low for practical use, but this exploration is still of great importance as it conceptually demonstrates the limit of Li-ions insertion into layered oxide materials.

Coulometric ion sensing with Li+-selective LiMn2O4 electrodes

A coulometric signal readout method, which was originally developed for solid-contact ion-selective electrodes, was investigated in this work using LiMn2O4 (LMO) as a combined ion-recognition and signal-transduction layer. The redox process of LMO, which is associated with reversible intercalation/expulsion of Li+ ions, allowed coulometric sensing of Li+ ions in aqueous solutions. On increasing the active area (mass loading) of LMO, the coulometric signal increased for a given change in Li+ ion activity. The excellent redox reversibility of LMO and its relatively low resistance were instrumental in achieving a high signal amplification together with a relatively fast response. Coating the LMO layer with a conventional Li+-selective plasticized PVC membrane was found to dramatically lower the coulometric response. Hence, the application of LMO as a combined Li+-selective electrode material and ion-to-electron transducer was found to be highly compatible with the coulometric signal readout method, especially for detecting small Li+ activity changes at high Li+ concentrations.

Sustainable Upcycling of Spent Lithium‐Ion Batteries Cathode Materials: Stabilization by In Situ Li/Mn Disorder

AbstractThe non‐destructive repair of spent lithium‐ion batteries cathode materials has been the holy grail in the field of waste‐to‐resource research due to the potential for optimal environmental and economic benefits. Here, Mn deficiency and cationic disorder in degraded materials are discovered for the first time and the degraded crystal structure is repaired by the in situ upcycling process using a low‐carbon and economical technique. The repaired disordered LiMn2O4 (LMO) material can contribute higher capacity and greater stability than ordered LMO materials. This unexpected behavior is attributed to the in‐situ upcycling process that enhances the Li/Mn atomic disorder, thereby altering the electrochemical activity as well as the structural stability of the cathode material. Specifically, the Li/Mn disorder can effectively suppress the Jahn–Teller distortion and two‐phase phase transition and activate the activity of disordered Li, contributing to a stable high discharge capacity of upcycled material. The discovery of the Mn‐deficiency mechanism solves many doubts as to the conventional repair technology and can provide a more adequate theoretical guidance of the development of recycling technology together with the Li‐deficiency mechanism. The atomic disorder structure also provides guidance for the design of battery materials and promotes the sustainable development of future green lithium‐ion batteries.

Tailoring structure, nonlinear/linear optical, and dielectric properties of PVA/PVP film by spinel LiMn2O4 nanoparticles

LiMn2O4 (LMO) nanoparticles have received significant attention owing to their role in energy storage and power supply applications. Here, the facile low-temperature synthesis of new hybrid freestanding films incorporated with different LMO nanoparticle concentrations (0, 0.037, 0.37, and 3.7 wt.%) was preceded to tunable the optical and electrical properties of the PVA-PVP blend. The formation of the nanoparticles and polymeric nanocomposite (PNC) films was confirmed using various techniques, including HRTEM, SEM, FTIR, and XRD. The relationship between the optical and dielectric properties of the films with the bandgap was tuned using the doping ratio. Two models were used to estimate the precision of the optical transition bandgap. Our results revealed that the calculated extinction coefficient, Urbach energy, optical conductivity, and refractive index of PVA-PVP were enhanced. The nonlinear optical parameters, including the third-order susceptibility (χ(3)) and refractive index (n2), also improved with a reduction in the bandgap. In addition, a hybrid film with 3.7 wt.% LMO exhibited excellent optical shielding. However, the electrical properties of the PNC films are not only affected by the applied frequency but can also be tuned by the LMO ratio. The AC conductivity and dielectric constant of the hybrid/PNC films were enhanced by the addition of LMO, and the highest values were achieved for the semi-transparent PNC with 0.37 wt.% LMO. For the oblique film with 3.7 wt.% LMO, most nanoparticles cover the significant portions of the polymer surface, which decreases the electrical properties. The dominant mechanism in all PNC films is related to barrier hopping (CBH) and follows Jonscher's power (JP) performance. The investigated hybrid films are promising for environmental optoelectronics, photosensors, optical shielding, and Li+ ion-based battery devices.

Inhibiting Mn Migration by Sb-Pinning Transition Metal Layers in Lithium-Rich Cathode Material for Stable High-Capacity Properties.

Owing to the interacted anion and cation redox dynamics in Li2 MnO3 , the high energy density can be obtained for lithium-rich manganese-based layered transition metal (TM) oxide [Li1.2 Ni0.2 Mn0.6 O2 , LNMO]. However, irreversible migration of Mn ions and oxygen release during highly de-lithiation can destroy its layered structure, leading to voltage and capacity decline. Herein, non-TM antimony (Sb) is pinned to the TM layer of LNMO by a facile sol-gel method. High-resolution ex and in situ characterization technologies manifest that the introduction of trace Sb inhibits the migration of Mn ions, forming a more stable structure. Sb can impressively adjust the Mn-O interaction between anions and cations, beneficial to decrease the energy level of Mn 3d and O 2p orbitals and expand their band gap according to the theoretical calculation results. As a result, the discharge specific capacity and the energy density for SbLi1.2 [Ni0.2 Mn0.6 ]O2 (SLNMO) reaches as high as 301 mAh g-1 and 1019.6Wh kg-1 at 0.1 C, respectively. Moreover, the voltage decay is reduced by 419.8mV compared with LNMO. The regulative interaction between Mn 3d and isolated O 2p bands provides an accurate guidance for solving electrochemical performance deficiencies of lithium-rich manganese-based cathode oxide.

CNT-Strung LiMn2 O4 for Lithium Extraction with High Selectivity and Stability.

LiMn2 O4 is of great potential for selectively extracting Li+ from brines and seawater, yet its application is hindered by its poor cycle stability and conductivity. Herein a two-step strategy to fabricate highly conductive and stable CNT-strung LiMn2 O4 (CNT-s-LMO) is reported, by first stringing Mn3 O4 particles with multiwalled carbon nanotube (CNT), then converting the hybrids into CNT-s-LMO through hydrothermal lithiation. The as-synthesized CNT-s-LMO materials have a net-like structure with CNTs threading through LMO particles. This unique structure has endowed the CNT-s-LMO electrode with excellent conductivity, high specific capacitance, and enhanced rate performance. Because of this, the CNT-s-LMO electrode in the hybrid capacitive deionization cell (HCDI) can deliver a high Li+ extraction percentage (≈84%) in brine and an outstanding lithium selectivity with a separation factor of ≈181 at the Mg2+ /Li+ molar ratio of 60. Significantly, the CNT-s-LMO-based HCDI cell has a high stability, evidenced by 90% capacity retention and negligible Mn loss in 100 cycles. This method has paved a new way to fabricate carbon-enabled LMO-based absorbents with tuned structure and superior capacity for electrochemical lithium extraction with high Li+ selectivity and exceptional cycling stability, which may help to tackle the shortage in supply of Li-ion batteries in industry in the future.

A Valence-Engineered Self-Cascading Antioxidant Nanozyme for the Therapy of Inflammatory Bowel Disease.

Antioxidant treatment strategy by scavenging reactive oxygen species (ROS) is a highly effective disease treatment option. Nanozymes with multiple antioxidant activities can cope with the diverse ROS environment. However, lack of design strategies and limitation of negative correlation for nanozymes with multiple antioxidant activities hindered their development. To overcome these difficulties, here we used ZnMn2 O4 as a model to explore the role of Mn valency at the octahedral site via a valence-engineered strategy, and found that its multiple antioxidant activities are positively correlated with the content of Mn4+ . Therefore, through this strategy, a self-cascading antioxidant nanozyme LiMn2 O4 was constructed, and its efficacy was verified at the cellular level and in an inflammatory bowel disease model. This work not only provides guidance for the design of multiple antioxidant nanozymes, but also broadens the biomedical application potential of multiple antioxidant nanozymes.

Beneficial impact of incorporating spinel lithium manganate and samarium oxide into high performance positive materials through ultrasonic cavitation strategy

Spinel LiMn2O4 (LMO) positive material has the advantage of a robust structure with a three-dimensional network of channels for fast Li+ conduction, which is one of the hot topics in the zero-cobalt electrodes field of new energy technology. Nonetheless, the spinel LiMn2O4 has serious transition metal dissolution as well as phase/surface stability problems, resulting in unsatisfactory cycle performance which hinders large scale applications in the field of lithium-ion batteries. In this study, Sm2O3 surface modified LiMn2O4 positive material is obtained by a facile ultrasonic cavitation combined with sol-gel strategy. The structural and surface morphological are analyses by X-ray diffraction, X-ray photoelectron spectroscopy and high resolution transmission electron microscopy illuminate the formation of the Sm2O3-coated LiMn2O4. Electrochemical analysis revealed that the LMO particles coated by the 1 wt% Sm2O3 is exhibited the best electrochemical performance among other coated and non-coated samples, with an initial capacity of 110.92 mAh g−1 and a capacity retention of 94.79% after 200 cycles. Furthermore, ICP analysis is showed that the manganese dissolution of the modified material in organic electrolyte is much lower than that of pristine sample. This work may provoke wide interests in surface modification areas and motivate the further improvement of the electrochemical performance for other commercialized spinel lithium ion batteries (LIBs).

Modification of LiMn2O4 surfaces by controlling the Acid–Base surface chemistry of atomic layer deposition

In this combined theoretical and experimental study, we report the effects of Al precursor selection on the growth chemistry, interfacial structure, and electrochemistry of Al2O3 coatings on spinel LiMn2O4 (LMO) surfaces by atomic layer deposition (ALD). Five Al precursors, exhibiting a range of Lewis acid–base properties, were used to establish trends in the ALD Al2O3 growth chemistry on LMO powders in comparison to redox-inactive planar silicon substrates. We show that the Lewis acid–base properties of the Al precursor ligands can be used to tune both the Mn oxidation states and the Al2O3 coverage on the LMO surface. Density functional theory calculations are used to examine the reaction mechanism of each precursor on LMO surfaces, elucidating a correlation between the Lewis acidity of the ligands and the decomposition thermochemistry. In-depth X-ray photoelectron spectroscopy and in situ Fourier transform infrared spectroscopy measurements support these theoretical predictions and further reveal how different Al precursors modify the atomic and electronic structure near the LMO surface during ALD. While the Mn oxidation state is strongly influenced by the Lewis acidity of the precursor ligand, the surface coverage and thickness of the Al2O3 coating are a more representative descriptor of the electrochemical performance measured in coin cell experiments. We show how the ligand acid–base properties of ALD precursors can be used to rationally tailor atomic layer growth mechanisms, which may enable atomic level control over the structure of functionalized interfaces for various applications related to catalysis, semiconductors, and energy storage.

Electrode design and performance of flow-type electrochemical lithium recovery (ELR) systems

Due to increasing interests in carbon neutral engineering, global market demand for lithium compounds is steadily growing, which serve as key compounds in the battery production. As a sustainable alternative for lithium compound production, electrochemical lithium recovery (ELR) is being studied extensively in recent years. However, research efforts for ELR have been mainly devoted to the synthesis of electrode materials, leaving an open problem of comprehensively understanding the effects of multiple electrode design parameters on the system performances. In this study, to address such a problem systematically, the ELR system with λ-MnO2/LiMn2O4 (LMO) electrodes is numerically investigated at a low current density of 62.5 μA/cm2. Three electrode design parameters are selected, which are known as key parameters in the literature: effective radius of LMO particles (rp), volume fraction of LMO particles in electrodes (εs), and electrode thickness (δ). Under the parameter range considered, the specific mass of Li+ recovered (qLi+) took the value ranging from 35.71 mg/g to 37.66 mg/g, while the range covered by the net energy consumption (Wnet) was from 0.17 Wh/mol to 5.44 Wh/mol. Sensitivity analysis showed that, with increasing rp, qLi+ decreases and Wnet increases, while opposite correlations were observed for εs and δ. It was also shown that the maximum of qLi+ and the minimum of Wnet can be achieved only with small rp (regardless of εs and δ), making it the most important parameter.

Promoting the electrochemical performance of commercial LiMn2O4 by hydrothermal modification with poly (vinylidene fluoride)

The fast capacity decay and poor rate performance hinder the application of commercial LiMn2O4 (LMO) cathode in Li-ion batteries despite the low cost and environmental friendliness. Herein, commercial LMO was hydrothermally modified with poly (vinylidene fluoride) (PVDF). The PVDF-modified LMO with 1.0 wt% PVDF exhibits excellent rate performance (delivering discharge capacities of 128.2, 121.7, 112.4, 99.9, 85.5, 62.4 mAh g−1 at current densities of 20, 50, 100, 200, 400, 800 mA g−1, respectively) and superior cyclability (attaining capacity retention above 90% after 150 cycles at 100 mA g−1). The enhanced performance associates with the uniform PVDF coating on the surface of LMO particles (which suppresses the dissolution of Mn-ions in electrolyte to maintain the structural stability of LMO) and F-doing in LMO (which improves Li+ conductivity and reversible capacity). The PVDF-modification may push the application of the commercial LMO cathode forward.

Boosting the cycling performance of spinel LiMn2O4 by in situ MnBO3 coating

Spinel LiMn2O4 (LMO) is a promising cathode material for lithium-ion batteries (LIBs) due to its low cost, high safety, and high energy density. However, surface dissolution of manganese and irreversible phase transitions reduce its long-term cycling performance. Although surface coating is a promising strategy for improving the structural stability of LMO, the commonly used coating process is tedious and complicated. In this work, a one-step sintering process is developed to prepare LMO materials coated in situ with MnBO3. It is found that the MnBO3 layer formed in this way is uniformly coated on the surface of LMO, and effectively suppresses Mn dissolution and undesirable phase transition during repeated charge/discharge cycles. Furthermore, the MnBO3-coated LMO has improved electrode kinetics, demonstrating significantly improved rate performance compared to the pristine LMO. As a result, the optimized LMO sample exhibits 85.2% capacity retention after 1000 cycles at 1 C and still can deliver 96 mAh g−1, even at 5 C. This work proposes a facile and efficient coating strategy for improving the electrochemical performance of LMO as a cathode material for LIBs.

Sulfolane as a co-solvent for carbonate-electrolytes in lithium-ion batteries using a LiMn2O4 cathode

In this study, we aimed to evaluate the effect of sulfolane (SL) as a co-solvent in conventional carbonate-based electrolytes and its compatibility with a LiMn2O4 (LMO) cathode. The amount of SL was varied from 10 to 50 vol.% in an EC-DMC mixture (1:1 vol. ratio) within a 1.0-M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. The thermal properties of the electrolytes were studied using thermogravimetric analysis (TGA). Solvent flammability was measured via self-extinguishing time (SET) and ignition time indexes while viscosity was gauged by the Ostwald method. Ionic conductivity was evaluated by electrochemical impedance spectroscopy (EIS). Electrochemical techniques such as cyclic voltammetry (CV) and galvanostatic cycling with potential limitation (GCPL) were carried out to evaluate battery performance with the selected electrolytes. The results indicated that an increasing proportion of SL leads to an enhancement of the thermal and oxidation stability of the electrolytes. At 20-vol.% SL and below, the as-synthesized electrolytes exhibited a high ionic conductivity of 7.45 mS.cm-1 (25oC) and enabled LMO to deliver a specific capacity of 103 mAh.g-1 with a capacity retention of 92% after 20 cycles at C/10 rate. Due to such favourable properties, SL can be used as a co-solvent in EC-DMC systems to enhance the safety of lithium-ion batteries under high voltage conditions.

Analysis of gas release during the process of thermal runaway of lithium-ion batteries with three different cathode materials

The process of thermal runaway (TR) of lithium-ion batteries (LIBs) is often accompanied by a large amount of heat generation and gas release. However, the gas release behavior during the process of TR remains unclear. Three types of 26700 LIBs with LiFePO4 (LFP), LiMn2O4 (LMO) and LiNi0.5Co0.2Mn0.3O2 (NCM) as cathodes are triggered to TR, respectively. Subsequently, the gas releases behavior of fully charged batteries during the TR process is obtained. Before the battery temperature approaches the uncontrollable temperature, the electrolyte volatilization and gas releasing are decoupled, the gas release of LFP, LMO and NCM batteries are 0.094 mol, 0.042 mol and 0.058 mol, respectively. These gases account for 29.1, 75.2 and 55.4% of the gas volume that cause the safety valve to open in the LFP, LMO, NCM batteries, respectively. After battery temperature approaches the uncontrollable temperature, the reasons for the rapid increase in total pressure are qualitatively analyzed by investigating the structural changes of the cathode materials before and after TR. For the LFP battery, the gas release is found to be the main cause of the structural change, and for the LMO and NCM batteries, the impact force is the dominant cause.

3D LiMn2 O4 Thin Film Deposited by ALD: A Road toward High-Capacity Electrode for 3D Li-Ion Microbatteries.

Miniaturized electronics suffer from a lack of energy autonomy. In that context, the fabrication of lithium-ion solid-state microbatteries with high performance is mandatory for powering the next generation of portable electronic devices. Here, the fabrication of a thin film positive electrode for 3D Li-ion microbatteries made by the atomic layer deposition (ALD) method and in situ lithiation step is demonstrated. The 3D electrodes based on spinel LiMn2 O4 films operate at high working potential (4.1 V vs Li/Li+ ) and are capable of delivering a remarkable surface capacity (≈180 μAh cm-2 ) at low C-rate while maintaining more than 40 μAh cm-2 at C/2 (time constant = 2 h). Both the thickness of the electrode material and the 3D gain of the template are carefully tuned to maximize the electrode performance. Advanced characterization techniques such as transmission electron and X-ray transmission microscopies are proposed as perfect tools to study the conformality of the deposited films and the interfaces between each layer: no interdiffusion or segregation are observed. This work represents a major issue towards the fabrication of 3D-lithiated electrode by ALD-without any prelithiation step by electrochemical technique-making it an attractive solution for the fabrication of 3D Li-ion solid-state microbatteries with semiconductor processing methods.