An Antiaging Electrolyte Additive for High‐Energy‐Density Lithium‐Ion Batteries

High‐capacity Li‐rich layered oxide cathodes along with Si‐incorporated graphite anodes have high reversible capacity, outperforming the electrode materials used in existing commercial products. Hence, they are potential candidates for the development of high‐energy‐density lithium‐ion batteries (LIBs). However, structural degradation induced by loss of interfacial stability is a roadblock to their practical use. Here, the use of malonic acid‐decorated fullerene (MA‐C₆₀) with superoxide dismutase activity and water scavenging capability as an electrolyte additive to overcome the structural instability of high‐capacity electrodes that hampers the battery quality is reported. Deactivation of PF₅ by water scavenging leads to the long‐term stability of the interfacial structures of electrodes. Moreover, an MA‐C₆₀‐added electrolyte deactivates the reactive oxygen species and constructs an electrochemically robust cathode‐electrolyte interface for Li‐rich cathodes. This work paves the way for new possibilities in the design of electrolyte additives by eliminating undesirable reactive substances and tuning the interfacial structures of high‐capacity electrodes in LIBs.     

Flexible Composite Solid Electrolyte Facilitating Highly Stable “Soft Contacting” Li–Electrolyte Interface for Solid State Lithium‐Ion Batteries

A flexible composite solid electrolyte membrane consisting of inorganic solid particles (Li_1.3Al_0.3Ti_1.7(PO₄)₃), polyethylene oxide (PEO), and boronized polyethylene glycol (BPEG) is prepared and investigated. This membrane exhibits good stability against lithium dendrite, which can be attributed to its well‐designed combination components: the compact inorganic lithium ion conducting layer provides the membrane with good mechanical strength and physically barricades the free growth of lithium dendrite; while the addition of planar BPEG oligomers not only disorganizes the crystallinity of the PEO domain, leading to good ionic conductivity, but also facilitates a “soft contact” between interfaces, which not only chemically enables homogeneous lithium plating/stripping on the lithium metal anode, but also reduces the polarization effects. In addition, by employing this membrane to a LiFePO₄/Li cell and testing its galvanostatic cycling performances at 60 °C, capacities of 158.2 and 94.2 mA h g^?1 are delivered at 0.1 C and 2 C, respectively.     

High‐Capacity Concentration Gradient Li[Ni0.865Co0.120Al0.015]O2 Cathode for Lithium‐Ion Batteries

A Ni‐rich concentration‐gradient Li[Ni_0.865Co_0.120Al_0.015]O₂ (NCA) cathode is prepared with a Ni‐rich core to maximize the discharge capacity and a Co‐rich particle surface to provide structural and chemical stability. Compared to the conventional NCA cathode with a uniform composition, the gradient NCA cathode exhibits improved capacity retention and better thermal stability. Even more remarkably, the gradient NCA cathode maintains 90% of its initial capacity after 100 cycles when cycled at 60 °C, whereas the conventional cathode exhibits poor capacity retention and suffers severe structural deterioration. The superior cycling stability of the gradient NCA cathode largely stemmed from the gradient structure combines with the Co‐rich surface, which provides chemical stability against electrolyte attack and reduces the inherent internal strain observed in all Ni‐rich layered cathodes in their charged state, thus providing structural stability against the repeated anisotropic volume changes during cycling. The high discharge capacity of the proposed gradient NCA cathode extends the driving range of electric vehicles and reduces battery costs. Furthermore, its excellent capacity retention guarantees a long battery life. Therefore, gradient NCA cathodes represent one of the best classes of cathode materials for electric vehicle applications that should satisfy the demands of future electric vehicles.     

Ni‐Rich/Co‐Poor Layered Cathode for Automotive Li‐Ion Batteries: Promises and Challenges

To pursue a higher energy density (>300 Wh kg^?1 at the cell level) and a lower cost (<$125 kWh^?1 expected at 2022) of Li‐ion batteries for making electric vehicles (EVs) long range and cost‐competitive with internal combustion engine vehicles, developing Ni‐rich/Co‐poor layered cathode (LiNi_1?x?yCo_xMn_yO₂, x+y ≤ 0.2) is currently one of the most promising strategies because high Ni content is beneficial to high capacity (>200 mAh g^?1) while low Co content is favorable to minimize battery cost. Unfortunately, Ni‐rich cathodes suffer from limited structure stability and electrode/electrolyte interface stability in the charged state, leading to electrode degradation and poor cycling performance. To address these problems, various strategies have been employed such as doping, structural optimization design (e.g., core–shell structure, concentration‐gradient structure, etc.), and surface coating. In this review, five key aspects of Ni‐rich/Co‐poor layered cathode materials are explored: energy density, fast charge capability, service life including cycling life and calendar life, cost and element resources, and safety. This enables a comprehensive analysis of current research advances and challenges from the perspective of both academy and industry to help facilitate practical applications for EVs in the future.     

A High‐Throughput Search for Functionally Stable Interfaces in Sulfide Solid‐State Lithium Ion Conductors

Interfacial reactions between ceramic‐sulfide solid‐electrolytes and common electrodes have remained a major impediment to the development of solid‐state lithium‐ion batteries. In practice, this means that ceramic‐sulfide batteries require a suitable coating material to isolate the electrolyte from the electrode materials. In this work, the interfacial stability of Li₁₀SiP₂S₁₂ with over 67 000 materials is computationally evaluated. Over 2000 materials that are predicted to form stable interfaces in the cathode voltage range and over 1000 materials for the anode range are reported on and cataloged. LiCoO₂ is chosen as an example cathode material to identify coating compounds that are stable with both Li₁₀SiP₂S₁₂ and a common cathode. The correlation between elemental composition and multiple instability metrics (e.g., chemical/electrochemical) is analyzed, revealing key trends in, amongst others, the role of anion selection. A new binary‐search algorithm is introduced for evaluating the pseudo‐phase with improved speed and accuracy. Computational challenges posed by high‐throughput interfacial phase‐diagram calculations are highlighted as well as pragmatic computational methods to make such calculations routinely feasible. In addition to the over 3000 materials cataloged, representative materials from the anionic classes of oxides, fluorides, and sulfides are chosen to experimentally demonstrate chemical stability when in contact with Li₁₀SiP₂S₁₂.     

A Comprehensive Analysis of the Interphasial and Structural Evolution over Long‐Term Cycling of Ultrahigh‐Nickel Cathodes in Lithium‐Ion Batteries

Ultrahigh‐Ni layered oxides hold great promise as high‐energy‐density cathodes at an affordable cost for lithium‐ion batteries, yet their practical application is greatly hampered by the poor cyclability. Herein, by employing LiNi_0.94Co_0.06O₂ as a model cathode in a full‐cell configuration, the interphasial and structural evolution processes of ultrahigh‐Ni layered oxides are systematically investigated over the course of their service life (1500 cycles). By applying advanced analytic techniques (e.g., Li‐isotope labeling, region‐of‐interest method), the dynamic chemical evolution on the cathode surface is revealed with spatial resolution, and the correlation between lattice distortion and cathode surface reactivity is established. Benefiting from in situ X‐ray diffraction (XRD) analysis, the ultrahigh‐Ni layered oxide is demonstrated to undergo dual‐phase reaction mechanisms with huge lattice variation, which leads to a decrease in crystallinity and secondary particle pulverization. Furthermore, the critical impact of cathode surface reaction on the graphite anode–electrolyte interphase (AEI) is revealed at nanometer scale, and a universal chemical/physical evolution process of the AEI is illustrated, for the first time. Finally, the practical viability of ultrahigh‐Ni layered oxides is demonstrated through Al‐doping strategy. This work presents a comprehensive understanding of the structural and interphasial degradation of ultrahigh‐Ni layered oxide cathodes for developing high‐energy‐density lithium‐ion batteries.     

Mesoporous Hybrid Electrolyte for Simultaneously Inhibiting Lithium Dendrites and Polysulfide Shuttle in Li–S Batteries

A bifunctional hybrid electrolyte composed of mesoporous silica nanosheets and liquid electrolyte is achieved for lithium–sulfur (Li–S) batteries. This hybrid electrolyte possesses abundant mesopores (2.8 nm), thin feature (20 µm), and high ionic conductivity (1.17 × 10^?1 mS cm^?1) as well as a low interfacial resistance with electrodes. Such unique features not only enable the efficient inhibition of the growth of lithium dendrites, but also significantly prevents polysulfide shuttling. Consequently, a Li–S battery with this hybrid electrolyte exhibits a relatively high reversible capacity and good capacity retention.     

A Li2S‐TiS2‐Electrolyte Composite for Stable Li2S‐Based Lithium–Sulfur Batteries

Li₂S is a fully lithiated sulfur‐based cathode with a high theoretical capacity of 1166 mAh g^?1 that can be coupled with lithium‐free anodes to develop high‐energy‐density lithium–sulfur batteries. Although various approaches have been pursued to obtain a high‐performance Li₂S cathode, there are still formidable challenges with it (e.g., low conductivity, high overpotential, and irreversible polysulfide diffusion) and associated fabrication processes (e.g., insufficient Li₂S, excess electrolyte, and low reversible capacity), which have prevented the realization of high electrochemical utilization and stability. Here, a new cathode design composed of a homogeneous Li₂S‐TiS₂‐electrolyte composite that is prepared by a simple two‐step dry/wet‐mixing process is demonstrated, allowing the liquid electrolyte to wet the powder mixture consisting of insulating Li₂S and conductive TiS₂. The close‐contact, three‐phase boundary of this system improves the Li₂S‐activation efficiency and provides fast redox‐reaction kinetics, enabling the Li₂S‐TiS₂‐electrolyte cathode to attain stable cyclability at C/7 to C/3 rates, superior long‐term cyclability over 500 cycles, and promising high‐rate performance up to 1C rate. More importantly, this improved performance results from a cell design attaining a high Li₂S loading of 6 mg cm^?2, a high Li₂S content of 75 wt%, and a low electrolyte/Li₂S ratio of 6.     

High‐Fluorinated Electrolytes for Li–S Batteries

Rechargeable Li–S batteries are regarded as one of the most promising next‐generation energy‐storage systems. However, the inevitable formation of Li dendrites and the shuttle effect of lithium polysulfides significantly weakens electrochemical performance, preventing its practical application. Herein, a new class of localized high‐concentration electrolyte (LHCE) enabled by adding inert fluoroalkyl ether of 1H,1H,5H‐octafluoropentyl‐1,1,2,2‐tetrafluoroethyl ether into highly‐concentrated electrolytes (HCE) lithium bis(fluorosulfonyl) imide/dimethoxyether (DME) system is reported to suppress Li dendrite formation and minimize the solubility of the high‐order polysulfides in electrolytes, thus reducing the amount of electrolyte in cells. Such a unique LHCE can achieve a high coulombic efficiency of Li plating/stripping up to 99.3% and completely suppressing the shuttling effect, thus maintaining a S cathode capacity of 775 mAh g^?1 for 150 cycles with a lean electrolyte of 4.56 g A^?1 h^?1. The LHCE reduces the solubility of lithium polysulfides, allowing the Li/S cell to achieve super performance in a lean electrolyte. This conception of using inert diluents in a highly concentrated electrolyte can accelerate commercialization of Li–S battery technology.     

An Efficient Separator with Low Li‐Ion Diffusion Energy Barrier Resolving Feeble Conductivity for Practical Lithium–Sulfur Batteries

Due to unprecedented features including high‐energy density, low cost, and light weight, lithium–sulfur batteries have been proposed as a promising successor of lithium‐ion batteries. However, unresolved detrimental low Li‐ion transport rates in traditional carbon materials lead to large energy barrier in high sulfur loading batteries, which prevents the lithium–sulfur batteries from commercialization. In this report, to overcome the challenge of increasing both the cycling stability and areal capacity, a metallic oxide composite (NiCo₂O₄@rGO) is designed to enable a robust separator with low energy barrier for Li‐ion diffusion and simultaneously provide abundant active sites for the catalytic conversion of the polar polysulfides. With a high sulfur‐loading of 6 mg cm^?2 and low sulfur/electrolyte ratio of 10, the assembled batteries deliver an initial capacity of 5.04 mAh cm^?2 as well as capacity retention of 92% after 400 cycles. The metallic oxide composite NiCo₂O₄@rGO/PP separator with low Li‐ion diffusion energy barrier opens up the opportunity for lithium–sulfur batteries to achieve long‐cycle, cost‐effective operation toward wide applications in electric vehicles and electronic devices.     

Ammonolyzed MoO3 Nanobelts as Novel Cathode Material of Rechargeable Li‐Ion Batteries

Through a moderate ammonolysis method, nanobelts of α‐MoO₃ can be modified to H_xMo(O, N)_3. When reaction temperatures are kept between 200–300 °C, gaseous NH₃ diffuses in‐between the oxide layers and reacts with terminal oxygen sites of MoO₃. As a consequence, hydrogen is introduced into the layers and bonded to terminal oxygen, and together with the effect of nitradation, the unit cell volume significantly shrinks mostly along the b axis. The modified compound H_xMo(O, N)₃ exhibits not only better electronic conductivity, but also faster lithium ion mobility than regular MoO₃. In addition, this ammonolyzed MoO₃ exhibits enhanced electrochemical performance beyond MoO₃. In the potential window 1.5–3.5 V, the specific capacity of H_xMo(O, N)₃ can reach more than 250 A h kg^?1 and was cycled 300 times without fading. It can be considered as a novel candidate cathode material with high specific charge for rechargeable Li‐ion batteries.     

Vanadate‐Based Materials for Li‐Ion Batteries: The Search for Anodes for Practical Applications

While the practical application of electrode materials depends intensively on the Li⁺ ion storage mechanisms correlating ultimately with the coulombic efficiency, reversible capacity, and morphology variation of electrode material upon cycling, only intercalation‐type electrode materials have proven viable for commercialization up to now. This paper reviews the promising anode materials of metal vanadates (M_xV_yO_z, M = Co, Cu, Mn, Fe, Zn, Ni, Li) that have high capacity, low cost, and abundant resource, and also discusses the related Li⁺ ion storage mechanism. It is concluded that most of these (M_xV_yO_z, M = Co, Cu, Mn, Fe, Zn, Ni) exhibit irreversible redox reactions upon lithiation/delithiation accompanied by large volume expansion, which is not favorable for industrial applications. In particular, Li₃VO₄ with specific intercalation Li⁺ ion storage mechanism and compatible merits of safety and energy density exhibits great potential for practical application. This review systematically summarizes the latest progress in Li₃VO₄ research, including the representative fabrication approaches for advanced morphology and state‐of‐the‐art technologies to boost performance and the morphology variation associated with Li⁺ ion storage mechanisms. Furthermore, an outlook on where breakthroughs for Li₃VO₄ may be most likely achieved will be provided.     

A Hollow‐Shell Structured V2O5 Electrode‐Based Symmetric Full Li‐Ion Battery with Highest Capacity

The symmetric batteries with an electrode material possessing dual cathodic and anodic properties are regarded as an ideal battery configuration because of their distinctive advantages over the asymmetric batteries in terms of fabrication process, cost, and safety concerns. However, the development of high‐performance symmetric batteries is highly challenging due to the limited availability of suitable symmetric electrode materials with such properties of highly reversible capacity. Herein, a triple‐hollow‐shell structured V₂O₅ (THS‐V₂O₅) symmetric electrode material with a reversible capacity of >400 mAh g^?1 between 1.5 and 4.0 V and >600 mAh g^?1 between 0.1 and 3.0 V, respectively, when used as the cathode and anode, is reported. The THS‐V₂O₅ electrodes assembled symmetric full lithium‐ion battery (LIB) exhibits a reversible capacity of ≈290 mAh g^?1 between 2 and 4.0 V, the best performed symmetric energy storage systems reported to date. The unique triple‐shell structured electrode makes the symmetric LIB possessing very high initial coulombic efficiency (94.2%), outstanding cycling stability (with 94% capacity retained after 1000 cycles), and excellent rate performance (over 140 mAh g^?1 at 1000 mA g^?1). The demonstrated approach in this work leaps forward the symmetric LIB performance and paves a way to develop high‐performance symmetric battery electrode materials.     

From Surface ZrO2 Coating to Bulk Zr Doping by High Temperature Annealing of Nickel‐Rich Lithiated Oxides and Their Enhanced Electrochemical Performance in Lithium Ion Batteries

One of the major hurdles of Ni‐rich cathode materials Li_1+x(Ni_xCo_zMn_z)_wO₂, y > 0.5 for lithium‐ion batteries is their low cycling stability especially for compositions with Ni ≥ 60%, which suffer from severe capacity fading and impedance increase during cycling at elevated temperatures (e.g., 45 °C). Two promising surface and structural modifications of these materials to alleviate the above drawback are (1) coatings by electrochemically inert inorganic compounds (e.g., ZrO₂) or (2) lattice doping by cations like Zr⁴⁺, Al³⁺, Mg²⁺, etc. This paper demonstrates the enhanced electrochemical behavior of Ni‐rich material LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) coated with a thin ZrO₂ layer. The coating is produced by an easy and scalable wet chemical approach followed by annealing the material at ≥700 °C under oxygen that results in Zr doping. It is established that some ZrO₂ remains even after annealing at ≥800 °C as a surface layer on NCM811. The main finding of this work is the enhanced cycling stability and lower impedance of the coated/doped NCM811 that can be attributed to a synergetic effect of the ZrO₂ coating in combination with a zirconium doping.     

Best Practices for Mitigating Irreversible Capacity Loss of Negative Electrodes in Li‐Ion Batteries

Development of high performance lithium‐ion (Li‐ion) power packs is a topic receiving significant attention in research today. Future development of the Li‐ion power packs relies on the development of high capacity and high rate anodes. More specifically, materials undergo either conversion or an alloying mechanism with Li. However, irreversible capacity loss (ICL) is one of the prime issues for this type of negative electrode. Traditional insertion‐type materials also experience ICL, but it is considered negligible. Therefore, eliminating ICL is crucial before the fabrication of practical Li‐ion cells with conventional cathodes such as LiFePO₄, LiMn₂O₄, etc. There are numerous methods for eliminating ICL such as pre‐treating the electrode, usage of stabilized Li metal powder, chemical and electrochemical lithiation, sacrificial salts for both anode and cathode, etc. The research strategies that have been explored are reviewed here in regards to the elimination of ICL from the high capacity anodes as described. Additionally, mitigating ICL observed from the carbonaceous anodes is discussed and compared.     

Lithium Polyacrylate (LiPAA) as an Advanced Binder and a Passivating Agent for High‐Voltage Li‐Ion Batteries

Intensive studies of an advanced energy material are reported and lithium polyacrylate (LiPAA) is proven to be a surprisingly unique, multifunctional binder for high‐voltage Li‐ion batteries. The absence of effective passivation at the interface of high‐voltage cathodes in Li‐ion batteries may negatively affect their electrochemical performance, due to detrimental phenomena such as electrolyte solution oxidation and dissolution of transition metal cations. A strategy is introduced to build a stable cathode–electrolyte solution interphase for LiNi_0.5Mn_1.5O₄ (LNMO) spinel high‐voltage cathodes during the electrode fabrication process by simply using LiPAA as the cathode binder. LiPAA is a superb binder due to unique adhesion, cohesion, and wetting properties. It forms a uniform thin passivating film on LNMO and conducting carbon particles in composite cathodes and also compensates Li‐ion loss in full Li‐ion batteries by acting as an extra Li source. It is shown that these positive roles of LiPAA lead to a significant improvement in the electrochemical performance (e.g., cycle life, cell impedance, and rate capability) of LNMO/graphite battery prototypes, compared with that obtained using traditional polyvinylidene fluoride (PVdF) binder for LNMO cathodes. In addition, replacing PVdF with LiPAA binder for LNMO cathodes offers better adhesion, lower cost, and clear environmental advantages.     

Electrospun LiFe1−yMnyPO4/C Nanofiber Composites as Self‐Supporting Cathodes in Li‐Ion Batteries

LiFe_1?yMn_yPO₄/C nanofiber composites are applied as cathode materials in Li‐ion batteries and their electrochemical properties are explored. Nanofiber meshes are synthesized via electrospinning of commercially available precursors (LiOH·H₂O, FeSO₄·7H₂O, MnSO₄·H₂O, H₃PO₄, and polyvinylpyrrolidone). Nanofibers calcined at 850 °C under Ar/H₂ (95/5 vol%) atmosphere are directly used as self‐supporting electrodes in Swagelok half cells without the need for any conductive additive or polymer binder. The morphology, phase, and chemical composition of as‐prepared and heat‐treated samples are analyzed by means of X‐ray powder diffraction, thermogravimetric analysis, and electron and scanning microscopy techniques. Brunauer–Emmett–Teller gas adsorption–desorption measurements show a high specific surface area (111m² g^?1) for LiFe_0.5Mn_0.5PO₄. The influence of different Fe/Mn ratios on the morphology, electrical, and electrochemical performances are analyzed.