Li Sites Research Articles

Revealing Dynamic Evolution of the Anode‐Electrolyte Interphase in All‐Solid‐State Batteries with Excellent Cyclability

AbstractAll‐solid‐state‐batteries (ASSBs) based on a halide solid electrolyte (SE) and a lithium‐metal based anode typically have poor cyclability without a buffer layer (such as Li3PS4 or Li6PS5Cl) to prevent the degradation reactions. Here excellent cycling stability of ASSB consisting of an uncoated single‐crystal LiNi0.8Co0.1Mn0.1O2 cathode and a Li3YCl6 (LYC) SE separator in direct contact with a Li‐In anode are demonstrated. Through a combination of electrochemical measurements, synchrotron micro‐X‐ray absorption and diffraction analyses, and density functional theory calculations, reveal for the first time that along with the standard Li+ transport during charge/discharge, indium in the Li‐In anode also participates in the redox reactions. The in‐situ generated In3+ preferentially occupies the vacant Li sites in the trigonal LYC lattice, leading to the formation, growth, and eventual stabilization of an anode‐electrolyte interphase (AEI) layer consisting of an In‐doped Li3‐xInxYCl6 (x = ≈0.2) phase. It is discussed how the presence of such an AEI layer prevents LYC decomposition and suppresses dendrite formation and propagation, enabling stable cycling of ASSB with ≈90% capacity retention over 1000 cycles. This work sheds light on the dynamic evolution of the halide SE and alloy anode interphase, and opens new avenues in the future design of long‐lasting high‐energy all‐solid‐state‐batteries.

Can large lattice volume always facilitate ion diffusion in solids?

Large lattice volume is usually expected to expand the bottleneck size and enlarge free volume for fast Li ion transport in solids. But the universality of lattice expansion decreasing activation energy barrier for Li ion migration is still debatable. Herein, our molecular dynamics simulations and density functional theory calculations detect the unconventional phenomenon of lattice expansion increasing activation energy barrier for Li ion migration in β-Li3PS4, Li4SnS4 and Li4GeS4 sulfides with the hcp-type anion sublattice, and discover the underlying mechanism. On one hand, lattice expansion enlarges the relative energies between the octahedral and tetrahedral Li sites, and correspondingly increase activation energy barrier for tetrahedral Li ions migration along the Tet-Oct-Tet migration paths in β-Li3PS4, Li4SnS4 and Li4GeS4. On the other hand, the lattice dynamics calculations show Li energy landscapes of β-Li3PS4, Li4SnS4 and Li4GeS4 are anharmonic and enlarging lattice volume make the local minimum of Li potential energy surface flatter, simultaneously reduce the relative energy of Li occupation site, eventually resulting in the higher activation energy barrier for Li ion migration. Thus, understanding the effect of lattice volume on ion migration in solids should not only consider the factor of bottleneck size and free volume, but also combine the aspects of Li ion occupation type, Li ion migration path and anion sublattice type. These new understandings of the lattice expansion increasing activation energy barrier for ion migration would further promote the further optimization and rational design of superionic conductors by element doping or strain engineering.

Theoretical Study of the Magnetic and Optical Properties of Ion-Doped LiMPO4 (M = Fe, Ni, Co, Mn).

Using a microscopic model and Green's function theory, we calculated the magnetization and band-gap energy in ion-doped LiMPO4 (LMPO), where M = Fe, Ni, Co, Mn. Ion doping, such as with Nb, Ti, or Al ions at the Li site, induces weak ferromagnetism in LiFePO4. Substituting Li with ions of a smaller radius, such as Nb, Ti, or Al, creates compressive strain, resulting in increased exchange interaction constants and a decreased band-gap energy, Eg, in the doped material. Notably, Nb ion doping at the Fe site leads to a more pronounced decrease in Eg compared to doping at the Li site, potentially enhancing conductivity. Similar trends in Eg reduction are observed across other LMPO4 compounds. Conversely, substituting ions with a larger ionic radius than Fe, such as Zn and Cd, causes an increase in Eg.

Dependence of Initial Capacity Irreversibility on Oxygen Framework Chemistry in Li‐Rich Layered Cathode Oxides

The undesirable capacity loss after first cycle is universal among layered cathode materials, which results in the capacity and energy decay. The key to resolving this obstacle lies in understanding the effect and origin of specific active Li sites during discharge process. In this study, focusing on Ah‐level pouch cells for reliability, an ultrahigh initial Coulombic efficiency (96.1%) is achieved in an archetypical Li‐rich layered oxide material. Combining the structure and electrochemistry analysis, we demonstrate that the achievement of high‐capacity reversibility is a kinetic effect, primarily related to the sluggish Li mobility during oxygen reduction. Activating oxygen reduction through small density would induce the oxygen framework contraction, which, according to Pauli repulsion, imposes a great repulsive force to hinder the transport of tetrahedral Li. The tetrahedral Li storage upon deep oxygen reduction is experimentally visualized and, more importantly, contributes to 6% Coulombic efficiency enhancement as well as 10% energy density improvement for pouch cells, which shows great potentials breaking through the capacity and energy limitation imposed by intercalation chemistry.

Enhancement of microstructure and electrochemical properties of LLZTO solid state electrolyte by co-doping with Ga and Y

Recently, there has been strong interest in inorganic solid-state electrolytes for all-solid-state batteries, among which the garnet electrolyte LLZO has attracted much attention due to its excellent properties, such as high ionic conductivity and broad electrochemical stability. The aim of our study was to improve the performance of Ta-doped LLZO (LLZTO) by co-doping Ga and Y at the Li and La sites using conventional solid-phase synthesis methods. We thoroughly investigated how Ga and Y affect the microstructure and electrochemical properties of LLZTO. The results show that the relative density of Ga- and Y-doped LLZTO increases significantly up to 94% under the same sintering conditions. This doping resulted in a significant increase in ionic conductivity from 2.0 × 10−4 S·cm−1 to 1.05 × 10−3 S·cm−1 and a decrease in electronic conductivity from 2.16 × 10−7 S·cm−1 to 9.18 × 10−8 S·cm−1. Subsequently, the symmetric cells were assembled and tested, and it was found that the interfaces of the doped solid-state electrolytes were much more stable and that the cycling time was longer. Thus, our study successfully coordinated the co-doping of Ga, Y, and Ta, providing valuable insights for the subsequent production of LLZO materials with higher densities and better performance. This study is a promising step toward the realization of safer all-solid-state batteries with higher energy densities.

Synthesis and Comprehensive Analytical Study of β-Li3PS4 Stabilization by Ca- and Ba-Codoped Li3PS4.

Sulfide-based solid electrolytes with high Li+ conductivity, such as Li3PS4, are key materials for the realization of all-solid-state Li+ batteries. One approach to achieving high Li+ conductivity is to combine crystalline-phase stabilization at high temperatures with the introduction of defects at room temperature. In this work, this approach was verified by codoping Li3PS4 with two kinds of divalent cations. The resulting structural changes were comprehensively investigated both experimentally and computationally. The high-temperature β-Li3PS4 phase of Li3PS4 could be stabilized at room temperature by adjusting the amount of Ca or Ba doping. The synthesized samples doped with divalent cations were found to have conductivities about 2 orders of magnitude higher than that of the γ-Li3PS4 phase at room temperature. The resultant Li+ conductivity at room temperature was also higher than that expected from interpolation of results for nondoped β-Li3PS4. It is believed that the structural changes produced by the divalent cation doping contribute to this increase in conductivity. The stability of the β-Li3PS4 phase with divalent cation doping was also demonstrated using density-functional-theory calculations for models with equivalent compositions to the synthesized samples. The Li+ positions obtained by structural optimization calculations showed the presence of diverse and disordered Li sites in the Ca-doped lattice. Such structural changes can contribute to cascade processes involving Li+ collisions, referred to as the "billiard-ball" mechanism, which cannot occur in nondoped β-Li3PS4. This series of experiments involving the synthesis and analyses of β-Li3PS4 with divalent cation doping provides a way to enhance Li+ conductivity through structural modification and optimization.

Improving the high-voltage behavior of LiNiO2 through electrochemical property regulation by Mg doping

In this study, high-temperature solid-phase techniques are used to prepare pristine and Mg-modified LiNiO2 cathode materials. Various characterizations are performed to analyze the morphology, structure, and electrical state of the two materials. Electrochemical tests show that Mg doping effectively improves the electrochemical properties of the materials. In particular, the modified sample exhibits a higher specific discharge capacity of 244.5 mA h g−1 than the pristine sample. Moreover, its maximum capacity retention after 304 cycles at 1 C is 54.1%. In situ X-ray powder diffraction imaging reveals that the modified material has better phase-transition reversibility than the pristine material. Density functional theory calculations indicate that Mg-doped Li sites can accelerate Li+ transport. Atomic force microscopy results demonstrate that Mg-doped Li sites act as supportive skeletons that enhance the mechanical properties of the material. Therefore, the proposed strategy for the Mg doping of Li sites can improve the architecture of LiNiO2 cathode materials.

Mg/Fe site-specific dual-doping to boost the performance of cobalt-free nickle-rich layered oxide cathode for high-energy lithium-ion batteries

Layer-type LiNi0.9Mn0.1O2 is promising to be the primary cathode material for lithium-ion batteries (LIBs) due to its excellent electrochemical performance. Unfortunately, the cathode with high nickel content suffers from severely detrimental structural transformation that causes rapid capacity attenuation. Herein, site-specific dual-doping with Fe and Mg ions is proposed to enhance the structural stability of LiNi0.9Mn0.1O2. The Fe3+ dopants are inserted into transition metal sites (3b) and can favorably provide additional redox potential to compensate for charge and enhance the reversibility of anionic redox. The Mg ions are doped into the Li sites (3a) and serve as O2−-Mg2+-O2− pillar to reinforce the electrostatic cohesion between the two adjacent transition-metal layers, which further suppress the cracking and the generation of harmful phase transitions, ultimately improving the cyclability. The theoretical calculations, including Bader charge and crystal orbital Hamilton populations (COHP) analyses, confirm that the doped Fe and Mg can form stable bonds with oxygen and the electrostatic repulsion of O2−-O2−can be effectively suppressed, which effectively mitigates oxygen anion loss at the high delithiation state. This dual-site doping strategy offers new avenues for understanding and regulating the crystalline oxygen redox and demonstrates significant potential for designing high-performance cobalt-free nickel-rich cathodes.

First-principles evaluation of dopant impact on structural deformability and processability of Li7La3Zr2O12.

Li7La3Zr2O12 (LLZO) and related ceramic solid electrolytes feature excellent stability and reasonable ionic conductivity, but processing remains challenging. High-temperature co-sintering is required for successful integration with the electrode, which is energetically costly and can lead to unacceptable cathode degradation. The introduction of dopants can promote lower-temperature processing by improving deformability and disrupting lattice integrity; however, an unbiased, systematic study correlating these properties to the dopant chemistry and composition is lacking. Here, we rely on a set of static and dynamic metrics derived from first-principles simulations to estimate the impact of doping on LLZO processability by quantifying LLZO structural deformability. We considered three distinct dopants (Al, Ba, and Ta) as representatives of substitutional incorporation on Li, La, and Zr sites. Our descriptors indicate that doping in general positively impacts lattice deformability, although significant sensitivities to dopant identity and concentration are observed. Amongst the tested dopants, Al doping (on the Li site) appears to have the greatest impact, as signaled across nearly the entire set of computed features. We suggest that these proxy descriptors, once properly calibrated against well-controlled experiments, could enable the use of first-principles simulations to computationally screen new ceramic electrolyte compositions with improved processability.

Stabilization of the cubic, fast-ion conducting phase of Li7La3Sn2O12 garnet by gallium doping.

All-solid-state batteries present promising high-energy-density alternatives to conventional Li-ion chemistries, and Li-stuffed garnets based on Li7La3Zr2O12 (LLZO) remain a forerunner for candidate solid-electrolytes. One route to access fast-ion conduction in LLZO phases is to stabilize the cubic LLZO phase by doping on the Li sites with aliovalent ions such as Al3+ or Ga3+. Despite prior attempts, the stabilization of the cubic phase of isostructural Li7La3Sn2O12 (LLSO) by doping on the Li sites has up to now not been realised. Here, we report a novel cubic fast-ion conducting Li7La3Sn2O12-type phase stabilized by doping Ga3+ in place of Li. 0.3 mole of gallium per formula unit of LLSO were needed to fully stabilize the cubic garnet, allowing structural and electrochemical characterizations of the new material. A modified sol-gel synthesis approach is introduced in this study to realise Ga-doping in LLSO, which offers a viable route to preparing new Sn-based candidate solid-electrolytes for all-solid-state battery applications.

Understanding the electrochemical properties of Mg-doped Li2MnO3: first-principles calculations.

Non-transition metal doping, especially for Mg, has been gradually employed to optimize the electrochemical performance of Li-rich cathode material Li2MnO3. However, the effects of Mg doping on the electrochemical behavior of Li2MnO3 have not been studied extensively. In this work, we investigate the effect of Mg doping at both the 2b (in the Li/Mn mixed layer) and 4h (in the Li layer) Li sites on the electrochemical properties of Li2MnO3 through first-principles calculations and ab initio molecular dynamics simulations. The local lattice structure, electronic density of states, Bader charge, delithiation voltage, lattice oxygen stability and Li diffusion kinetics are examined. Electronic structure analysis shows that Mg can activate the electrochemical activity of surrounding Mn by charge transfer, making Mn participate in charge compensation at the initial delithiation stage. Mg doping can also cause an increase in the average oxygen vacancy formation energy and hence depress the oxygen release during the delithiation process. Molecular dynamics simulations show that the diffusion kinetics of Li ions in Mg2b-Li2MnO3 is enhanced with respect to the undoped one, whereas Mg doped at the 4h site cannot improve the diffusion kinetics of Li ions. Further studies found that Mg doped at the 2b site results in a decrease in the energy barrier for the intra-layer diffusion and an increase in the energy barrier for the inter-layer diffusion of the nearby Li vacancies.

Li vacancy-induced ionic conductivity enhancement in Li4B7O12Cl for all-solid-state Li-ion battery application

Doping Mg into the Li sites of Li4B7O12Cl contributes to the generation of Li vacancies and the enhancement of ionic conductivity.

Lattice Engineering on Li2CO3-Based Sacrificial Cathode Prelithiation Agent for Improving the Energy Density of Li-Ion Battery Full-Cell.

Developing sacrificial cathode prelithiation technology to compensate for active lithium loss is vital for improving the energy density of lithium-ion battery full-cells. Li2CO3 owns high theoretical specific capacity, superior air stability, but poor conductivity as an insulator, acting as a promising but challenging prelithiation agent candidate. Herein, extracting a trace amount of Co from LiCoO2 (LCO), a lattice engineering is developed through substituting Li sites with Co and inducing Li defects to obtain a composite structure consisting of (Li0.906Co0.043▫0.051)2CO2.934 and ball milled LiCoO2 (Co-Li2CO3@LCO). Notably,both the bandgap and Li─O bond strength have essentially declined in this structure. Benefiting from the synergistic effect of Li defects and bulk phase catalytic regulation of Co, the potential of Li2CO3 deep decomposition significantly decreases from typical >4.7 to ≈4.25V versus Li/Li+, presenting >600 mAh g-1 compensation capacity. Impressively, coupling 5 wt% Co-Li2CO3@LCO within NCM-811 cathode, 235Wh kg-1 pouch-type full-cell is achieved, performing 88% capacity retention after 1000 cycles.

Implanting Transition Metal into Li2O‐Based Cathode Prelithiation Agent for High‐Energy‐Density and Long‐Life Li‐Ion Batteries

AbstractCompensating the irreversible loss of limited active lithium (Li) is essentially important for improving the energy‐density and cycle‐life of practical Li‐ion battery full‐cell, especially after employing high‐capacity but low initial coulombic efficiency anode candidates. Introducing prelithiation agent can provide additional Li source for such compensation. Herein, we precisely implant trace Co (extracted from transition metal oxide) into the Li site of Li2O, obtaining (Li0.66Co0.11□0.23)2O (CLO) cathode prelithiation agent. The synergistic formation of Li vacancies and Co‐derived catalysis efficiently enhance the inherent conductivity and weaken the Li−O interaction of Li2O, which facilitates its anionic oxidation to peroxo/superoxo species and gaseous O2, achieving 1642.7 mAh/g~Li2O prelithiation capacity (≈980 mAh/g for prelithiation agent). Coupled 6.5 wt % CLO‐based prelithiation agent with LiCoO2 cathode, substantial additional Li source stored within CLO is efficiently released to compensate the Li consumption on the SiO/C anode, achieving 270 Wh/kg pouch‐type full‐cell with 92 % capacity retention after 1000 cycles.

Implanting Transition Metal into Li2 O-Based Cathode Prelithiation Agent for High-Energy-Density and Long-Life Li-Ion Batteries.

Compensating the irreversible loss of limited active lithium (Li) is essentially important for improving the energy-density and cycle-life of practical Li-ion battery full-cell, especially after employing high-capacity but low initial coulombic efficiency anode candidates. Introducing prelithiation agent can provide additional Li source for such compensation. Herein, we precisely implant trace Co (extracted from transition metal oxide) into the Li site of Li2 O, obtaining (Li0.66 Co0.11 □0.23 )2 O (CLO) cathode prelithiation agent. The synergistic formation of Li vacancies and Co-derived catalysis efficiently enhance the inherent conductivity and weaken the Li-O interaction of Li2 O, which facilitates its anionic oxidation to peroxo/superoxo species and gaseous O2 , achieving 1642.7 mAh/g~Li2O prelithiation capacity (≈980 mAh/g for prelithiation agent). Coupled 6.5 wt % CLO-based prelithiation agent with LiCoO2 cathode, substantial additional Li source stored within CLO is efficiently released to compensate the Li consumption on the SiO/C anode, achieving 270 Wh/kg pouch-type full-cell with 92 % capacity retention after 1000 cycles.

Na/W co-doping enhances the electrochemical performance of Li-rich Mn-based cathode through improved electronic conductivity and promoted cationic migration

The study aimed to improve the performance of a cathode material (Li1.16Na0.01Mn0.5Ni0.15Co0.15Al0.025W0.01O2) by co-doping with Na and W. The X-ray diffraction and scanning electron microscopy results indicate that both Na+ and W6+ cations are introduced into the lattice, and further investigation with scanning transmission electron microscopy reveals that Na + occupy the original Li sites while W6+ are placed in the transition metal layer. First principle calculations suggest that the band structure of the cathode material is primarily influenced by the incorporation of W6+ in the lattice, which decreases the bandgap and increases the electronic conductivity of the cathode powder. The Rietveld refinements suggest that the introduction of Na+ increases the thickness of the Li slab, thereby promoting the diffusion of Li+ within the layer. Based on the synergistic effect of Na and W co-doping, the electrochemical performance of LNCMA-Na/W cathode is significantly improved. The sample LNCMA displays an initial capacity of 277.7 mAh·g−1 at 0.1C and a capacity retention of 86.3 % after 100 cycles at 0.5C. By comparison, the initial capacity of sample LNCMA-Na/W increases to 326 mAh·g−1 at 0.1C, and the capacity retention reaches 93.4 % after 100 cycles at 0.5C, LNCMA-Na/W cathode exhibits a higher specific capacity of 167.3 mAh·g−1 at 5C compared to the undoped cathode (110.8 mAh·g−1).

Redox Mechanisms, Structural Changes, and Electrochemistry of the Wadsley-Roth LixTiNb2O7 Electrode Material.

The TiNb2O7 Wadsley-Roth phase is a promising anode material for Li-ion batteries, enabling fast cycling and high capacities. While already used in commercial batteries, many fundamental electronic and thermodynamic properties of LixTiNb2O7 remain poorly understood. We report on an in-depth first-principles study of the redox mechanisms, structural changes, and electrochemical properties of LixTiNb2O7 as a function of Li concentration. First-principles electronic structure calculations reveal an unconventional redox mechanism upon Li insertion that results in the formation of metal-metal bonds. This metal dimer redox mechanism has important structural consequences as it results in a shortening of cation-pair distances, which in turn affects lattice parameters of the host and thereby alters Li site preferences as the Li concentration is varied. The new insights about redox mechanisms in TiNb2O7 and their effect on the structure and Li site preferences provide guidance on how the electrochemical properties of a promising class of anode materials can be tailored by exploiting the tremendous structural and chemical diversity of Wadsley-Roth phases.

Effects of lithium content on the electrochemical performance of Li1+xV3O8 cathode materials for lithium-ion batteries

Lithium trivanadate (LiV3O8) is of great interest due to its large capacity, low cost and easy preparation. However, it still suffers from an inferior cyclability and rate capability. To solve these shortcomings of LiV3O8, a small extra amount of lithium was introduced into Li sites of LiV3O8. Herein, Li-doped LiV3O8 (Li1+xV3O8) materials were prepared and the electrochemical performance of Li1+xV3O8 changes with x from 0 to 0.1, 0.2 and 0.3. The discharge capacity of Li1+xV3O8 increases from x = 0 to 0.2 and then decreases, and the change trend of cycle performance is the same as that of discharge capacity. The optimal Li-doped LiV3O8 sample, Li1.2V3O8, exhibits much higher capacity and better cyclability and rate capability than LiV3O8. Galvanostatically discharged and charged between 2.0 and 4.0 V, Li1.2V3O8 and LiV3O8 present the initial discharge capacities of 305 and 268 mAh g−1 at 0.1 C (30 mA g−1), respectively, and the corresponding capacity retentions are 87% and 80% after 50 cycles. Even at a high current rate of 2 C, Li1.2V3O8 exhibits high discharge capacity of 173 mAh g−1, much higher than the discharge capacity of 133.6 mAh g−1 for LiV3O8. The better electrochemical performance of Li1.2V3O8 can be ascribed to the doping of appropriate amount of Li+ in LiV3O8 and the resulted higher diffusion coefficients of Li+ in Li1.2V3O8.

Enhanced electrochemical properties of Li2MgCl4 by Zn substitution for all-solid-state batteries

Halides have currently been discovered to be ideal electrolytes for all-solid-state Li batteries (ASSLBs) due to their variability, splendid electrochemical stability, and high Li+ conductivities. Here, we studied the electrochemical properties of Li2-2xZnxMgCl4 (x = 0–0.3) and their application in ASSLBs. By Zn substitution into the Li site of Li2MgCl4, the Li + conductivities of Li1.6Zn0.2MgCl4 (1.2 × 10−5 S/cm) at room temperature is two orders higher than that of Li2MgCl4 (1.9 × 10−7 S/cm). The activation energy is reduced to 0.28 eV for Li1.6Zn0.2MgCl4 (Li2MgCl4 is 0.47 eV). We attributed the enhanced electrochemical performance to Li vacancies generated from the Zn substitution. In addition, we fabricated a Li | Li1.6Zn0.2MgCl4 | Li cell to appraise the electrochemical performance in the lithiation and stripping. It is demonstrated that Li1.6Zn0.2MgCl4 can cycle for 100 h under a current density of 0.07 mA/cm2. This study demonstrates that introducing Li vacancy into Li2MgCl4 may be a valid way to promote the electrochemical properties of the halides.

Restraining formation of Fe-Li anti-site defects via in-situ surface construction on single-crystal LiFePO4 cathode for extending fast charging lifespan

The widespread utilization of olivine LiFePO4 is impeded by its inadequate electrochemical characteristics, primarily caused by the inherently low diffusion coefficient of Li+ ions. This deficiency is further exacerbated by the presence of Fe-Li anti-site defects, which significantly deteriorate the diffusion coefficient during prolonged cycling periods. Herein, a highly efficient and cost-effective method is employed to fabricate single-crystal LiFePO4 possessing minimal Fe-Li anti-site defects. The Fe-O bond is reinforced by the formation of a uniform and stable carbon layer through the introduction of acetylene. This reinforcement effectively hinders the migration of Fe ions to the 4a site, which is associated with the Li site (known as LiFe defects). The validity of this phenomenon has been confirmed through theoretical calculations. The uniform carbon layer on LiFePO4 surface not only facilitates the migration of Li+ ions without obstruction but also significantly enhances the pseudo-capacitance, leading to remarkable preservation of capacity even at a high discharge rate of 10 C, with a retention rate of 80.86 % after undergoing 1500 cycles. The present study signifies a notable advancement in the acquisition of uniformly carbon-coated single-crystal cathode materials, thereby presenting a novel methodology for augmenting their electrochemical efficacy.