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Solid-state batteries based on Li7La3Zr2O12 (LLZO) garnet electrolyte are a robust and safe alternative to conventional lithium-ion batteries. However, the large-scale implementation of ceramic composite cathodes is still challenging due to a complex multistep manufacturing process. A new one-step route for the direct synthesis of LLZO during the manufacturing of LLZO/LiCoO2 (LCO) composite cathodes based on cheap precursors and utilizing the industrially established tape casting process is presented. It is shown that Al, Ta:LLZO can be formed directly in the presence of LCO from metal oxide precursors (LiOH, La2O3, ZrO2, Al2O3, and Ta2O5) by heating to 1050 °C, eliminating the time- and energy-consuming synthesis of preformed LLZO powders. In addition, performance-optimized gradient microstructures can be produced by sequential casting of slurries with different compositions, resulting in dense and flat phase-pure cathodes without unwanted ion interdiffusion or secondary phase formation. Freestanding cathodes with a thickness of 85 µm, a relative density of 95%, and an industrial relevant LCO loading of 15 mg show an initial capacity of 82 mAh g-1 (63% of the theoretical capacity of LCO) in a solid-state cell with Li metal anodes, which is comparable to conventional LCO/LLZO cathodes and can be further improved in the future.
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All-solid-state potassium metal batteries have caught increasing interest owing to their abundance, cost-effectiveness, and high energy/power density. However, their development is generally constrained by the lack of suitable solid-state electrolytes. Herein, we report a new complex KCB9H10·2C3H4N2, synthesized by grinding and heating the mixture of potassium decahydrido-monocarba-closo-decaborate (KCB9H10) and imidazole (C3H4N2) under mild conditions, to achieve the K-ion superionic solid-state electrolyte. The crystal structure was revealed as an orthorhombic lattice with the space group of Pna21 by FOX software. The diffusion properties for K+ in the crystal structure were calculated using the climbing image nudged elastic band (CI-NEB) method. KCB9H10·2C3H4N2 exhibited a high ionic conductivity of 1.3 × 10-4 S cm-1 at 30 °C, four orders of magnitude higher than that of KCB9H10. This ionic conductivity is also the highest value of hydridoborate-based K+ conductors reported. Moreover, KCB9H10·2C3H4N2 demonstrated a K+ transference number of 0.96, an electrochemical stability window of 1.2 to 3.2 V vs. K/K+, and good stability against the K metal coated by a layer of potassium imidazolate (KIm). These great performances make KCB9H10·2C3H4N2 a promising K-ion solid-state electrolyte.
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Herein, we report halide nanocomposite solid electrolytes (HNSEs) that integrate diverse oxides with alterations that allow tuning of their ionic conductivity, (electro)chemical stability, and specific density. A two-step mechanochemical process enabled the synthesis of multimetal (or nonmetal) HNSEs, MO2-2Li2ZrCl6, as verified by pair distribution function and X-ray diffraction analyses. The multimetal (or nonmetal) HNSE strategy increases the ionic conductivity of Li2ZrCl6 from 0.40 to 0.82 mS cm-1. Additionally, cyclic voltammetry test findings corroborated the enhanced passivating properties of the HNSEs. Notably, incorporating SiO2 into HNSEs leads to a substantial reduction in the specific density of HNSEs, demonstrating their strong potential for achieving a high energy density and lowering costs. Fluorinated SiO2-2Li2ZrCl5F HNSEs exhibited enhanced interfacial compatibility with Li6PS5Cl and LiCoO2 electrodes. Cells employing SiO2-2Li2ZrCl5F with LiCoO2 exhibit superior electrochemical performance delivering the initial discharge capacity of 162 mA h g-1 with 93.7% capacity retention at the 100th cycle at 60 °C.
RESUMEN
In all-solid-state batteries, a solid electrolyte with high ionic conductivity is required for fast charging, uniform lithium deposition, and increased cathode capacity. Lithium argyrodite with BH4 - substitution has promising potential due to its higher ionic conductivity compared to argyrodites substituted with halides. In this study, Li5.25PS4.25(BH4)1.75, characterized by a high ionic conductivity of 13.8 mS cm-1 at 25 °C, is synthesized via wet ball-milling employing o-xylene. The investigation focused on optimizing wet ball-milling parameters such as ball size, xylene content, drying temperature, as well as the amount of BH4 - substitution in argyrodite. An all-solid-state battery prepared using Li5.25PS4.25(BH4)1.75 as the electrolyte and LiNbO3 coated NCM811 as the cathode exhibits an initial coulombic efficiency of 90.2% and maintains 93.9% of its initial capacity after 100 cycles at fast charging rate (5C). It is anticipated that the application of this wet mechanochemical synthesis will contribute further to the commercialization of all-solid-state batteries using BH4-substituted argyrodites.
RESUMEN
The high interface resistance at the cathode-sulfide electrolyte interface is still a crucial drawback in an all-solid-state battery, unlike the initial expectation that the all-solid-state interface would enhance electrochemical stability by reducing side reactions at the interface. In this study, we examined the fundamental mechanism of unexpected reactions at the interface of LiNi0.8Co0.1Mn0.1O2 (NCM811) and argyrodite (Li6PS5Br0.5Cl0.5, LPSBC) sulfide solid electrolytes based on the combined method of multiscale simulations and electrochemical experiments. The high interface resistance originates from the formation of a passivating layer at the interface combined with irregular atomic and electronic structures, Li depletion, mutual element exchange, and mechanical contact loss between the oxide cathode and sulfide solid electrolyte. We also confirmed that these side reactions were suppressed by O substitutions to sulfide solid electrolyte (LPSOBC), and then the chemo-mechanical stability of the all-solid battery was enhanced by alleviating the side reactions at the interface. This study provides rational insights into the design of an interface for all-solid-state batteries.
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All-solid-state lithium sulfide-based batteries (ASSLSBs) have drawn much attention due to their intrinsic safety and excellent performance in overcoming the polysulfide shuttle effect. However, the sluggish kinetics of Li2S cathode severely impede commercial utilization. Here, a Cu+, I- co-doping strategy is employed to activate the kinetics of Li2S to construct high-performance ASSLSBs. The electronic conductivity and Li-ion diffusion coefficient of the co-doped Li2S are increased by five and two orders of magnitude, respectively. Cu+ as a redox medium greatly improves the reaction kinetics, which is supported by ex situ X-ray photoelectron spectroscopy. Density functional theory calculation (DFT) shows that Cu+, I- co-doping reduces the Li-ions diffusion energy barrier. The co-doped Li2S exhibits a remarkable improvement in capacity (1165.23 mAh g-1 (6.65 times that of pristine Li2S) at 0.02 C and 592.75 mAh g-1 at 2 C), and excellent cycling stability (84.58% capacity retention after 6200 cycles at 2 C) at room temperature. Moreover, an ASSLSB, fabricated with a lithium-free (SiâC) anode, obtains a high specific capacity of 1082.7 mAh g-1 at 0.05 C and 97% capacity retention after 400 cycles at 0.5 C. This work provides a broad prospect for the development of ASSLSBs with practical energy density exceeding that of traditional lithium-ion batteries.
RESUMEN
Pure sulfur (S8 and Li2S) all solid-state batteries inherently suffer from low electronic conductivities, requiring the use of carbon additives, resulting in decreased active material loading at the expense of increased loading of the passive components. In this work, a transition metal sulfide in combination with lithium disulfide is employed as a dual cation-anion redox conversion composite cathode system. The transition metal sulfide undergoes cation redox, enhancing the electronic conductivity, whereas the lithium disulfide undergoes anion redox, enabling high-voltage redox conducive to achieving high energy densities. Carbon-free cathode composites with active material loadings above 6.0 mg cm-2 attaining areal capacities of â¼4 mAh cm-2 are demonstrated with the possibility to further increase the active mass loading above 10 mg cm-2 achieving cathode areal capacities above 6 mAh cm-2, albeit with less cycle stability. In addition, the effective partial transport and thermal properties of the composites are investigated to better understand FeS:Li2S cathode properties at the composite level. The work introduced here provides an alternative route and blueprint toward designing new dual conversion cathode systems, which can operate without carbon additives enabling higher active material loadings and areal capacities.
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Polyethylene oxide (PEO)-based all solid-state lithium metal batteries (ASSLMBs) are strongly hindered by the fast dendrite growth at the Li metal/electrolyte interface, especially under large rates. The above issue stems from the suboptimal interfacial chemistry and poor Li+ transport kinetics during cycling. Herein, a SnF2-catalyzed lithiophilic-lithiophobic gradient solid electrolyte interphase (SCG-SEI) of LixSny/LiF-Li2O is in-situ formed. The superior ionic LiF-Li2O rich upper layer (17.1 nm) possesses high interfacial energy and fast Li+ diffusion channels, wherein lithiophilic LixSny alloy layer (8.4 nm) could highly reduce the nucleation overpotential with lower diffusion barrier and promote rapid electron transportation for reversible Li+ plating/stripping. Simultaneously, the insoluble SnF2-coordinated PEO promotes the rapid Li+ ion transport in the bulk phase. As a result, an over 46.7 and 3.5 times improvements for lifespan and critical current density of symmetrical cells are achieved, respectively. Furthermore, LiFePO4-based ASSLMBs deliver a recorded cycling performance at 5 C (over 1000 cycles with a capacity retention of 80.0%). More importantly, impressive electrochemical performances and safety tests with LiNi0.8Mn0.1Co0.1O2 and pouch cell with LiFePO4, even under extreme conditions (i.e., 100 â), are also demonstrated, reconfirmed the importance of lithiophilic-lithiophobic gradient interfacial chemistry in the design of high-rate ASSLMBs for safety applications.
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The silicon-based anodes are one of the promising anodes to achieve the high energy density of all-solid-state batteries (ASSBs). Nano silicon (nSi) is considered as a suitable anode material for assembling sheet-type sulfide ASSBs using thin free-standing Li6PS5Cl (LPSC) membrane without causing short circuit. However, nSi anodes face a significant challenge in terms of rapid capacity degradation during cycling. To address this issue, dual-function Li4.4Si modified nSi anode sheets are developed, in which Li4.4Si serves a dual role by not only providing additional Li+ but also stabilizing the anode structure with its low Young's modulus upon cycling. Sheet-type ASSBs equipped with the Li4.4Si modified nSi anode, thin LPSC membrane, and LiNi0.83Co0.11Mn0.06O2 (NCM811) cathode demonstrate exceptional cycle stability, with a capacity retention of 96.16% at 0.5 C (1.18 mA cm-2) after 100 cycles and maintain stability for 400 cycles. Furthermore, a remarkable cell-level energy density of 303.9 Wh kg-1 is achieved at a high loading of 5.22 mAh cm-2, representing a leading level of sulfide ASSBs using electrolyte membranes at room temperature. Consequently, the chemically stable slurry process implemented in the fabrication of Li4.4Si-modified nSi anode sheet paves the way for scalable applications of high-performance sulfide ASSBs.
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All-solid-state lithium batteries, including sulfide electrolytes and nickel-rich layered oxide cathode materials, promise safer electrochemical energy storage with high gravimetric and volumetric densities. However, the poor electrical conductivity of the active material results in the requirement for additional conducive additives, which tend to react negatively with the sulfide electrolyte. The fundamental scientific principle uncovered through this work is simple and suggests that the electrical network benefits associated with the introduction of short-length carbons will eventually be overpowered by the increase in bulk resistance associated with their instability in the sulfide electrolyte. However, applying just the right amount of short carbon fibres minimizes degradation of the sulfide solid electrolyte and maximizes the electron movement. Therefore, we propose the application of a low-weight-percent carbon nanotubes (CNTs) coating on the nickel-rich cathode LiNi0.8Co0.1Mn0.1O2 (NCM811) along with large-aspect-ratio carbon nanofibers (CNFs) as the primary conductive additive. When only 0.3 wt % CNTs was utilized with 4.7 wt % CNFs, an initial Coulombic efficiency of 83.55% at 0.05C and a notably excellent capacity retention of 90.1% over 50 cycles at 0.5C were achieved along with a low ionic resistance. This work helps to confirm the validity of applying short carbon pathways in sulfide-electrolyte-based cathode composites and proposes their combination with a larger primary carbon additive as a solution to the ongoing all-solid-state battery rate and instability issues.
RESUMEN
Recently emerging lithium ternary chlorides have attracted increasing attention for solid-state electrolytes (SSEs) due to their favorable combination between ionic conductivity and electrochemical stability. However, a noticeable discrepancy in Li-ion conductivity persists between chloride SSEs and organic liquid electrolytes, underscoring the need for designing novel chloride SSEs with enhanced Li-ion conductivity. Herein, an intriguing trigonal structure (i.e., Li3SmCl6 with space group P3112) is identified using the global structure searching method in conjunction with first-principles calculations, and its potential for SSEs is systematically evaluated. Importantly, the structure of Li3SmCl6 exhibits a high ionic conductivity of 15.46 mS cm-1 at room temperature due to the 3D lithium percolation framework distinct from previous proposals, associated with the unique in-plane cation ordering and stacking sequences. Furthermore, it is unveiled that Li3SmCl6 possesses a wide electrochemical window of 0.73-4.30 V vs Li+/Li and excellent chemical interface stability with high-voltage cathodes. Several other Li3MCl6 (M = Er, and In) materials with isomorphic structures to Li3SmCl6 are also found to be potential chloride SSEs, suggesting the broader applicability of this structure. This work reveals a new class of ternary chloride SSEs and sheds light on strategy for structure searching in the design of high-performance SSEs.
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The development of all-solid-state lithium-sulfur batteries (ASSLSBs) toward large-scale electrochemical energy storage is driven by the higher specific energies and lower cost in comparison with the state-of-the-art Li-ion batteries. Yet, insufficient mechanistic understanding and quantitative parameters of the key components in sulfur-based cathode hinders the advancement of the ASSLSB technologies. This review offers a comprehensive analysis of electrode parameters, including specific capacity, voltage, S mass loading and S content toward establishing the specific energy (Wh kg-1) and energy density (Wh L-1) of the ASSLSBs. Additionally, this work critically evaluates the progress in enhancing lithium ion and electron percolation and mitigating electrochemical-mechanical degradation in sulfur-based cathodes. Last, a critical outlook on potential future research directions is provided to guide the rational design of high-performance sulfur-based cathodes toward practical ASSLSBs.
RESUMEN
Superionic halides have attracted widespread attention as solid electrolytes due to their excellent ionic conductivity, soft texture, and stability toward high-voltage electrode materials. Among them, Li3InCl6 has aroused interest since it can be easily synthesized in water or ethanol. However, investigations into the influence of solvents on both the crystal structure and properties remain unexplored. In this work, Li3InCl6 is synthesized by three different solvents: water, ethanol, and water-ethanol mixture, and the difference in properties has been studied. The results show that the product obtained by the ethanol solvent demonstrates the largest unit cell parameters with more vacancies, which tend to crystallize on the (131) plane and provide the 3D isotropic network migration for lithium-ions. Thus, it exhibits the highest ionic conductivity (1.06 mS cm-1) at room temperature and the lowest binding energy (0.272 eV). The assembled all-solid-state lithium metal batteries (ASSLMBs) employing Li3InCl6 electrolytes demonstrate a high initial discharge capacity of 153.9 mA h g-1 at 0.1 C (1 C = 170 mA h g-1) and the reversible capacity retention rate can reach 82.83% after 50 cycles. This work studies the difference in ionic conductivity between Li3InCl6 electrolytes synthesized by different solvents, which can provide a reference for the future synthesis of halide electrolytes and enable their practical application in halide-based ASSLMBs with a high energy density.
RESUMEN
Traditional trial-error approach severely limits and restricts rapid development of high-performance anode and electrolytes materials, searching huge parameters space of various anode-solid electrolyte interfaces in an effective and efficient way is the key issue. Here, a novel computational strategy combining machine learning and first-principles is proposed to achieve efficient high-throughput screening of oxides and sulfides electrolytes for highly stable silicon oxycarbide all-solid-state batteries. First-principles calculations demonstrate significant compact of material type and elemental doping on interfacial compatibility between silicon oxycarbide and various electrolytes. By proposing several novel descriptors including interfacial adhesion and formation energies of frozen system with low computation cost, the amounts of demanded trainings data are significantly reduced. Gradient-boosted regression tree model shows low mean absolute errors of 0.09 and high R2 value of 0.99 for the prediction of interface formation energy, demonstrating ultrahigh accuracy and reliability of the algorithm. The present work discovers a series of uninvestigated stable anode-solid electrolytes interfacial couples for further experimental preparation.
RESUMEN
All-solid-state batteries (ASSBs) possess the advantage of ensuring safety while simultaneously maximizing energy density, making them suitable for next-generation battery models. In particular, sulfide solid electrolytes (SSEs) are viewed as promising candidates for ASSB electrolytes due to their excellent ionic conductivity. However, a limitation exists in the form of interfacial side reactions occurring between the SSEs and cathode active materials (CAMs), as well as the generation of sulfide-based gases within the SSE. These issues lead to a reduction in the capacity of CAMs and an increase in internal resistance within the cell. To address these challenges, cathode composite materials incorporating zinc oxide (ZnO) are fabricated, effectively reducing various side reactions occurring in CAMs. Acting as a semiconductor, ZnO helps mitigate the rapid oxidation of the solid electrolyte facilitated by an electronic pathway, thereby minimizing side reactions, while maintaining electron pathways to the active material. Additionally, it absorbs sulfide-based gases, thus protecting the lithium ions within CAMs. In this study, the mass spectrometer is employed to observe gas generation phenomena within the ASSB cell. Furthermore, a clear elucidation of the side reactions occurring at the cathode and the causes of capacity reduction in ASSB are provided through density functional theory calculations.
RESUMEN
All-solid-state batteries (ASSBs) have garnered considerable attention as promising candidates for next-generation energy storage systems due to their potentially simultaneously enhanced safety capacities and improved energy densities. However, the solid future still calls for materials with high ionic conductivity, electrochemical stability, and favorable interfacial compatibility. In this study, we present a series of halide solid-state electrolytes (SSEs) utilizing a doping strategy with highly valent elements, demonstrating an outstanding combination of enhanced ionic conductivity and oxidation stability. Among these, Li2.6In0.8Ta0.2Cl6 emerges as the standout performer, displaying a superionic conductivity of up to 4.47 mS cm-1 at 30 °C, along with a low activation energy barrier of 0.321 eV for Li+ migration. Additionally, it showcases an extensive oxidation onset of up to 5.13 V (vs Li+/Li), enabling high-voltage ASSBs with promising cycling performance. Particularly noteworthy are the ASSBs employing LiCoO2 cathode materials, which exhibit an extended cyclability of over 1400 cycles, with 70% capacity retention under 4.6 V (vs Li+/Li), and a capacity of up to 135 mA h g-1 at a 4 C rate, with the loading of active materials at 7.52 mg cm-2. This study demonstrates a feasible approach to designing desirable SSEs for energy-dense, highly stable ASSBs.
RESUMEN
It is unclear, which role space charge layers (SCLs) play within an all-solid-state battery during operation with high current densities, and to which extent they form. Herein, we use a solid electrolyte with a known SCL formation and investigate it in a symmetric cell under non-blocking conditions with Li metal electrodes. Since the used LICGC™ electrolyte is known for its instability against lithium, it is protected from rapid degradation by nanometer-thin layers of TiOx deployed by atomic layer deposition. Close attention is given to the interfacial properties, as now additional Li+ can traverse through the interface depending on the applied bias potential. The interlayer's impedance response shows efficient lithium-ion conduction for low bias potentials and a diffusion-limiting effect towards high positive and negative potentials. SCLs grow up to a thickness of 5.1 µm. Additionally, estimating the apparent rate constant of the charge transfer across the interface indicates that the potentials where kinetics are hindered coincide with the widest SCLs. In conclusion, the investigation under higher steady-state currents was only possible because of the improved stability due to the interlayer. No chemo-physical failure could be observed after 800+ hours of cycling. However, SEM study shows a new phase at the interface.
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The construction of a continuous ionic/electronic pathway is critical for Si-based sulfide all-solid-state batteries (ASSBs) with the advantages of high-energy density and high-cycle stability. However, a significant impediment arises from the parasitic reaction occurring between the ionic sulfide solid-state electrolyte and electronic carbon additive, posing a formidable challenge. Additionally, the fabrication of electrodes necessitates stringent operational conditions, further limiting practical applicability. Herein, an ionic-electronic dual conductive binder for the fabrication of robust silicon anode under ambient air conditions in the absence of high-cost and air-sensitive sulfide solid-state electrolyte for ASSBs is reported. This binder incorporates in situ reduced silver nanoparticles into a high-strength polymer rich in ether bonds, establishing a conductive pathway for lithium ions and electrons. With the binder-composited Si anode, the half-cell exhibits a remarkable capacity of 1906.9 mAh g-1 and stable cycling for 500 cycles at a current density of 2 C (4.4 mA cm-2) under a low stack pressure of 5 MPa. The full cell using Ni0.9Co0.075Mn0.025O2 (NCM90) exhibits a remark cycling stability within 2000 cycles at 5 C (8 mA cm-2). This work presents an inspired design of functional binders for large-scale manufacture and mild operation in a low-cost way for Si anodes in ASSBs.
RESUMEN
Solid electrolytes may be the answer to overcome many obstacles in developing the next generation of renewable batteries. A novel composite solid electrolyte (CSE) composed of a poly(vinylidene fluoride) (PVDF) base with an active nanofiber filler of aluminum-doped garnet Li ceramic, Li salt lithium bis-(trifluoromethanesulfonyl)imide (LiTFSI), Li fluoride (LiF) stabilizing additive, and plasticizer sulfolane was fabricated. In a Li|CSE|LFP cell with this CSE, a high capacity of 168 mAh g-1 with a retention of 98% after 200 cycles was obtained, representing the best performance to date of a solid electrolyte with a PVDF base and a garnet inorganic filler. In a Li metal cell with Si and Li, it yielded a discharge capacity of 2867 mAh g-1 and was cycled 60 times at a current density of 100 mAh g-1, a significant step forward in utilizing a solid electrolyte of any kind with the desirable Si anode. In producing this CSE, the components and fabrication process were chosen to have a lower cost and improved safety and environmental impact compared with the current state-of-the-art Li-ion battery.
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The interfacial instability of the poly(ethylene oxide) (PEO)-based electrolytes impedes the long-term cycling and further application of all-solid-state lithium metal batteries. In this work, we have shown an effective additive 1-adamantanecarbonitrile, which contributes to the excellent performance of the poly(ethylene oxide)-based electrolytes. Owing to the strong interaction of the 1-Adamantanecarbonitrile to the polymer matrix and anions, the coordination of the Li+-EO is weakened, and the binding effect of anions is strengthened, thereby improving the Li+ conductivity and the electrochemical stability. The diamond building block on the surface of the lithium anode can suppress the growth of lithium dendrites. Importantly, the 1-Adamantanecarbonitrile also regulates the formation of LiF in the solid electrolyte interface and cathode electrolyte interface, which contributes to the interfacial stability (especially at high voltages) and protects the electrodes, enabling all-solid-state batteries to cycle at high voltages for long periods of time. Therefore, the Li/Li symmetric cell undergoes long-term lithium plating/stripping for more than 2000 h. 1-Adamantanecarbonitrile-poly(ethylene oxide)-based LFP/Li and 4.3 V Ni0.8Mn0.1Co0.1O2/Li all-solid-state batteries achieved stable cycles for 1000 times, with capacity retention rates reaching 85% and 80%, respectively.