The formation of stable interphases on the electrodes is crucial for rechargeable lithium (Li) batteries. However, next-generation high-energy batteries face challenges in controlling interphase formation due to the high reactivity and structural changes of electrodes, leading to reduced stability and slow ion transport, which accelerate battery degradation. Here, we report an approach to address these issues by introducing multicomponent grain-boundary-rich interphase that boosts the rapid transport of ions and enhances passivation toward prolonged lifespan. This is guided by fundamental principles of solid-state ionics and geological crystallization differentiation theory, achieved through improved solvation chemistry. Demonstrations showcase how the introduction of the interphase substantially impacts the Li-ion transport across the interphase and the electrode-electrolyte compatibility in cost-effective electrolyte solutions optimized with multiple Li salts. The resulting interphases feature microstructures rich in inorganic grain boundaries with a diverse array of nanosized grains, presenting enhanced Li-ion transport. Comprehensive analyses revealed that this realizes remarkable electrochemical stability over extended cycling periods by inhibiting electrode corrosion, thus holding promise for high-capacity thin-Li-metal, Si-based anodes, and even Li-free anodes when paired with high-capacity oxide cathodes. This work opens new avenues to customize protective interphases on high-capacity electrodes, promoting the development of batteries with the highest energy density using cost-effective electrolytes.

Ordered layered structures serve as essential components in lithium (Li)-ion cathodes^1–3. However, on charging, the inherently delicate Li-deficient frameworks become vulnerable to lattice strain and structural and/or chemo-mechanical degradation, resulting in rapid capacity deterioration and thus short battery life^2,4. Here we report an approach that addresses these issues using the integration of chemical short-range disorder (CSRD) into oxide cathodes, which involves the localized distribution of elements in a crystalline lattice over spatial dimensions, spanning a few nearest-neighbour spacings. This is guided by fundamental principles of structural chemistry and achieved through an improved ceramic synthesis process. To demonstrate its viability, we showcase how the introduction of CSRD substantially affects the crystal structure of layered Li cobalt oxide cathodes. This is manifested in the transition metal environment and its interactions with oxygen, effectively preventing detrimental sliding of crystal slabs and structural deterioration during Li removal. Meanwhile, it affects the electronic structure, leading to improved electronic conductivity. These attributes are highly beneficial for Li-ion storage capabilities, markedly improving cycle life and rate capability. Moreover, we find that CSRD can be introduced in additional layered oxide materials through improved chemical co-doping, further illustrating its potential to enhance structural and electrochemical stability. These findings open up new avenues for the design of oxide cathodes, offering insights into the effects of CSRD on the crystal and electronic structure of advanced functional materials.

The original version of this article contained errors in Figure 3a and Figure 3f. In Figure 3a, the activation energies (Ea) were calculated using a log scale instead of a logarithm ln scale. In Figure 3f, the y-axis interval was not properly selected. The correct y-axis interval in Figure 3f and the numerical values of the activation energy are now provided in Figure 3a and the main text. These errors have been corrected in the HTML and PDF versions of the article.

Improving the reversibility of lithium metal batteries is one of the challenges in current battery research. This requires better fundamental understanding of the evolution of the lithium deposition morphology, which is very complex due to the various parameters involved in different systems. Here, we clarify the fundamental origins of lithium deposition coverage in achieving highly reversible and compact lithium deposits, providing a comprehensive picture in the relationship between the lithium microstructure and solid electrolyte interphase (SEI) for lithium metal batteries. Systematic variation of the salt concentration offers a framework that brings forward the different aspects that play a role in cycling reversibility. Higher nucleation densities are formed in lower concentration electrolytes, which have the advantage of higher lithium deposition coverage; however, it goes along with the formation of an organic-rich instable SEI which is unfavorable for the reversibility during (dis)charging. On the other hand, the growth of large deposits benefiting from the formation of an inorganic-rich stable SEI is observed in higher concentration electrolytes, but the initial small nucleation density prevents full coverage of the current collector, thus compromising the plated lithium metal density. Taking advantages of the paradox, a nanostructured substrate is rationally applied, which increases the nucleation density realizing a higher deposition coverage and thus more compact plating at intermediate concentration (∼1.0 M) electrolytes, leading to extended reversible cycling of batteries.

A key challenge for solid-state-batteries development is to design electrode-electrolyte interfaces that combine (electro)chemical and mechanical stability with facile Li-ion transport. However, while the solid-electrolyte/electrode interfacial area should be maximized to facilitate the transport of high electrical currents on the one hand, on the other hand, this area should be minimized to reduce the parasitic interfacial reactions and promote the overall cell stability. To improve these aspects simultaneously, we report the use of an interfacial inorganic coating and the study of its impact on the local Li-ion transport over the grain boundaries. Via exchange-NMR measurements, we quantify the equilibrium between the various phases present at the interface between an S-based positive electrode and an inorganic solid-electrolyte. We also demonstrate the beneficial effect of the LiI coating on the all-solid-state cell performances, which leads to efficient sulfur activation and prevention of solid-electrolyte decomposition. Finally, we report 200 cycles with a stable capacity of around 600 mAh g⁻¹ at 0.264 mA cm⁻² for a full lab-scale cell comprising of LiI-coated Li₂S-based cathode, Li-In alloy anode and Li₆PS₅Cl solid electrolyte.

Suppressing the dendrite formation and managing the volume change of lithium (Li) metal anode have been global challenges in the lithium batteries community. Herein, a duplex copper (Cu) foil with an ant-nest-like network and a dense substrate is reported for an ultrastable Li metal anode. The duplex Cu is fabricated by sulfurization of thick Cu foil with a subsequent skeleton self-welding procedure. Uniform Li deposition is achieved by the 3D interconnected architecture and lithiophilic surface of self-welded Cu skeleton. The sufficient space in the porous layer enables a large areal capacity for Li and significantly improves the electrode–electrolyte interface. Simulations reveal that the structure allows proper electric field penetration into the connected tunnels. The assembled Li anodes exhibit high coulombic efficiency (97.3% over 300 cycles) and long lifespan (>880 h) at a current density of 1 mA cm⁻² with a capacity of 1 mAh cm⁻². Stable and deep cycling can be maintained up to 50 times at a high capacity of 10 mAh cm⁻².

It is a huge challenge for high-tap-density electrodes to achieve high volumetric energy density but without compromising the ionic transportation. Herein, we prepared compact Li₄Ti₅O₁₂ (LTO) microspheres consisting of densely packed primary nanoparticles. The real space distribution of lithium ions inside the compact LTO was revealed by using scanning transmission electron microscopy with electron energy loss spectroscopy (STEM-EELS) to identify the function of grain boundaries for lithium ion transportation during lithiation. The as-prepared LTO microspheres possess a high tap density (1.23 g cm^-3) and an ultra-small specific surface area (2.40 m² g^-1). Impressively, the compact LTO microspheres present excellent electrochemical performance. At high rates of 5C, 10C and 20C, the LTO microspheres show a specific capacity of 146.6, 138.2 and 111 mA h g^-1, respectively. The capacity retention remains at 97.8% at 5C after 500 cycles. The STEM-EELS results indicate that the lithiation reaction of LTO is firstly initiated at grain boundaries during the high rate lithiation process and then diffuses to the bulk area. The abundant grain boundaries in compact LTO microspheres can form a highly efficient conductive network to preferentially transport the ions, which contributes to high volumetric and gravimetric energy density simultaneously.

Surface degradation is a common challenge for many electrode materials. The active surface usually reacts with the molecules in the surrounding environment to form byproducts that hinder the diffusion channels for Li ions and electrons, increase the energy barrier for (de)lithiation reactions, and ultimately shorten the cycle life. Herein, the growth of surface Li ₂ CO ₃ on LiNi _x Co _y Mn _y O ₂ (x = 0.33, 0.6, 0.7, 0.8, x + 2y = 1) cathodes upon storage has been systematically investigated. Ni-rich surfaces are found to result in more Li ₂ CO ₃ growth, based on which three discrete degradation models for layered oxides are proposed. The increase and discretization of the energy barrier for individual particles also explain the State-of-Charge heterogeneity phenomena observed by in situ XRD and the change of cyclic voltammetry curves. By providing a comprehensive picture of surface deterioration of the NCM cathode family, this study enhances the understanding of the degradation mechanism that determines the cycle life of electrode materials.

Nanosized Li₄Ti₅O₁₂ (LTO) materials enabling high rate performance suffer from a large specific surface area and low tap density lowering the cycle life and practical energy density. Microsized LTO materials have high density which generally compromises their rate capability. Aiming at combining the favorable nano and micro size properties, a facile method to synthesize LTO microbars with micropores created by ammonium bicarbonate (NH₄HCO₃) as a template is presented. The compact LTO microbars are in situ grown by spinel LTO nanocrystals. The as-prepared LTO microbars have a very small specific surface area (6.11 m² g⁻¹) combined with a high ionic conductivity (5.53 × 10⁻¹² cm⁻² s⁻¹) and large tap densities (1.20 g cm⁻³), responsible for their exceptionally stable long-term cyclic performance and superior rate properties. The specific capacity reaches 141.0 and 129.3 mAh g⁻¹ at the current rate of 10 and 30 C, respectively. The capacity retention is as high as 94.0% and 83.3% after 500 and 1000 cycles at 10 C. This work demonstrates that, in situ creating micropores in microsized LTO using NH₄HCO₃ not only facilitates a high LTO tap density, to enhance the volumetric energy density, but also provides abundant Li-ion transportation channels enabling high rate performance.

Through a facile sodium sulfide (Na₂S)-assisted hydrothermal treatment, clean and nondefective surfaces are constructed on micrometer-sized Li₄Ti₅O₁₂ particles. The remarkable improvement of surface quality shows a higher first cycle Coulombic efficiency (≈95%), a significantly enhanced cycling performance, and a better rate capability in electrochemical measurements. A combined study of Raman spectroscopy and inductive coupled plasma emission spectroscopy reveals that the evolution of Li₄Ti₅O₁₂ surface in a water-based hydrothermal environment is a hydrolysis–recrystallization process, which can introduce a new phase of anatase-TiO₂. While, with a small amount of Na₂S (0.004 mol L⁻¹ at least), the spinel-Li₄Ti₅O₁₂ phase is maintained without a second phase. During this process, the alkaline environment created by Na₂S and the surface adsorption of the sulfur-containing group (HS⁻ or S²⁻) can suppress the recrystallization of anatase-TiO₂ and renew the particle surfaces. This finding gives a better understanding of the surface–property relationship on Li₄Ti₅O₁₂ and guidance on preparation and modification of electrode material other than coating or doping.