Multifunctional Electrode Design Consisting of 3D Porous Separator Modulated with Patterned Anode for High‐Performance Dual‐Ion Batteries

Searching for low‐cost and high‐capacity electrode materials such as metal anodes is of important significance for the development of new generation rechargeable batteries. However, metal anodes always suffer from severe volume expansion/contraction during a repeated electrochemical alloying/dealloying process. In this study, a novel concept about modifying metal‐anodes‐based battery construction with a multifunctional electrode (ME) design is provided. The ME consists of a 3D porous separator that is modulated with a patterned aluminum anode, which simultaneously works as a current collector, anode material, and separator in a dual‐ion battery (DIB). The 3D porous separator not only enables the ME to possess significantly improved electrolyte uptake and retention capabilities, but also acts as a protecting layer to restrict the surface pulverization of the Al anode. The ME‐DIB displays remarkably enhanced cell performances, including excellent cycling stability with 92.4% capacity retention after 1000 cycles at a current density of 2 C, and superior rate performance with 80.7% capacity retention at 10 C.     

Fast,Scalable Synthesis of Micronized Ge3N4@C with a High Tap Density for Excellent Lithium Storage

Nanostructuring has significantly contributed to alleviating the huge volume expansion problem of the Ge anodes. However, the practical use of nanostructured Ge anodes has been hindered due to several problems including a low tap density, poor scalability, and severe side reactions. Therefore, micrometer-sized Ge is desirable for practical use of Ge-based anode materials. Here, micronized Ge₃N₄ with a high tap density of 1.1 mg cm⁻² has been successfully developed via a scalable wet oxidation and a subsequent nitridation process of commercially available micrometer-sized Ge as the starting material. The micronized Ge₃N₄ shows much-suppressed volume expansion compared to micrometer-sized Ge. After the carbon coating process, a thin carbon layer (≈3 nm) is uniformly coated on the micronized Ge₃N₄, which significantly improves electrical conductivity. As a result, micronized Ge₃N₄@C shows high reversible capacity of 924 mAh g⁻¹ (2.1 mAh cm⁻²) with high mass loading of 3.5 mg cm⁻² and retains 91% of initial capacity after 300 cycles at a rate of 0.5 C. Additionally, the effectiveness of Ge₃N₄@C as practical anodes is comprehensively demonstrated for the full cell, showing stable cycle retention and especially excellent rate capability, retaining 47% of its initial capacity at 0.2 C for 12 min discharge/charge condition.     

Dendrite‐Free Lithium Plating Induced by In Situ Transferring Protection Layer from Separator

Lithium (Li) metal anodes are regarded as a promising pathway to meet the rapidly growing requirements on high energy density cells, owing to their highest gravimetric capacity (3840 mAh g^?1) and their lowest redox potential. The application of Li metal anodes, however, is still hindered by undesired dendrites formation and endless consumption of liquid electrolyte due to a continuous reaction on interface of electrolyte/Li‐metal without a stable solid–electrolyte–interface (SEI) layer. A stable protection layer is formed on Li metal anode by in situ transferring the coating layer from polymer separator. The Li anode protection strategy is developed with an in situ formed protection layer transferred through the reduction of a coating layer on polymer separator. A PbZr_0.52Ti_0.48O₃ (PZT) coating layer on polypropylene (PP) separator is reduced by Li metal anode to produce a Pb metal containing composite layer, which could form Pb–Li alloy and adhere to the surface of Li metal anode after the reaction and improves the Li plating/stripping efficiency owing to the formation of a more homogenized electric field. Both the Li/Li symmetric cells and LiFePO₄/Li cells with this PZT precoated PP separators exhibit significantly improved Coulombic efficiency and cycling life.     

Highly Reversible Zn Anode Enabled by Controllable Formation of Nucleation Sites for Zn‐Based Batteries

Aqueous Zn batteries have drawn tremendous attention for their several advantages. However, the challenges of Zn anodes such as the corrosion and ZnO densification have compromised their application in rechargeable Zn‐based batteries. In this paper, a straightforward strategy is employed to facilitate the uniform Zn stripping/plating of the Zn anode through using a ZrO₂ coating layer, which contributes to the controllable nucleation sites for Zn²⁺ and fast Zn²⁺ transportation through the favorable Maxwell–Wagner polarization. As a result, the low polarization (24 mV at 0.25 mA cm^?2), high Coulombic efficiency (99.36% at 20 mA cm^?2), and long cycle life (over 3800 h at 0.25 mA cm^?2) can be obtained for the ZrO₂‐coated Zn anode. It is believed that the ZrO₂ coating layer can also act as an inert physical barrier to decrease the contact of the anode and electrolyte, thus reducing both the Zn corrosion and formation of ZnO densification, and then improve the reversibility of Zn anode. The results demonstrated in this work provide an appealing strategy for the future development of rechargeable Zn‐based batteries.     

Nanoflake Arrays of Lithiophilic Metal Oxides for the Ultra‐Stable Anodes of Lithium‐Metal Batteries

A molten lithium infusion strategy has been proposed to prepare stable Li‐metal anodes to overcome the serious issues associated with dendrite formation and infinite volume change during cycling of lithium‐metal batteries. Stable host materials with superior wettability of molten Li are the prerequisite. Here, it is demonstrated that a series of strong oxidizing metal oxides, including MnO₂, Co₃O₄, and SnO₂, show superior lithiophilicity due to their high chemical reactivity with Li. Composite lithium‐metal anodes fabricated via melt infusion of lithium into graphene foams decorated by these metal oxide nanoflake arrays successfully control the formation and growth of Li dendrites and alleviate volume change during cycling. A resulting Li‐Mn/graphene composite anode demonstrates a super‐long and stable lifetime for repeated Li plating/stripping of 800 cycles at 1 mA cm^?2 without voltage fluctuation, which is eight times longer than the normal lifespan of a bare Li foil under the same conditions. Furthermore, excellent rate capability and cyclability are realized in full‐cell batteries with Li‐Mn/graphene composite anodes and LiCoO₂ cathodes. These results show a major advancement in developing a stable Li anode for lithium‐metal batteries.     

Interlamellar Lithium-Ion Conductor Reformed Interface for High Performance Lithium Metal Anode

Lithium metal anodes are promising for application in new-type secondary batteries. Unfortunately, low cycle life and safety peril induced by uncontrollable dendrites growth and weak solid electrolyte interface (SEI) have blocked their utilization. In this work, an interlamellar lithium-ion conductor of lithium-montmorillonite (Li-MMT) is applied to enhance the SEI properties, inhibit dendrites-germination, and thus significantly enhance electrochemical performance. Such a well-designed Li-MMT SEI not only possesses inherent fast lithium-ion channels, but also works as a reservoir to supply adequate lithium-ions in the interlaminations and periphery of Li-MMT nanosheets, offering fast lithium-ion transfer in interlaminations and sheet-to-sheet. Furthermore, the strong trend of lithium-ion absorption of Li-MMT is confirmed by density functional theory calculations and stable lithium deposition under Li-MMT SEI layer at 10 mA cm⁻² is verified via finite element modeling. As a result, a steady lithium deposition process without dendrites is achieved. Coulombic efficiency of the half-cell accomplishes a mean value of 99.1% over 400 cycles at 1 mA cm⁻², while Li-LiFePO₄ full cells show a stable capacity up to 120 mAh g⁻¹ and steady circulation over 400 loops at 1C. This work offers a novel strategy to design a high-performance SEI layer and suppress dendrite growth.     

Regulation of Ionic Distribution and Desolvation Activation Energy Enabled by In Situ Zinc Phosphate Protective Layer toward Highly Reversible Zinc Metal Anodes

Despite the merits of high specific capacity, low cost, and high safety, the practical application of aqueous Zn metal batteries (AZMBs) is plagued by the dendritic growth and corrosion reaction of Zn metal anodes. To solve these issues, a Zn₃(PO₄)₂·4H₂O protective layer is in-situ constructed on Zn foil (Zn@ZnPO) by a simple hydrothermal method, avoiding the traditional slurry-casting process. The insulating and conformable ZnPO layer improves the wettability of Zn@ZnPO and aqueous electrolyte via decreasing the contact angle to 11.7^o. Compared with bare Zn, the Zn@ZnPO possesses a lower desolvation activation energy of 35.25 kJ mol^-1, indicating that the ZnPO fasters the desolvation of hydrated Zn²⁺ ions and thereby ameliorates their transport dynamics. Micro-morphology and structural characterization show that there are no dendrites forming on the post-cycling Zn@ZnPO anodes, and the interfacial ZnPO layer remains almost identical before and after cycles. It can be explained that the electrochemically stable ZnPO layer acts as an ionic modulator to enable the homogeneous distribution of Zn²⁺ ions, inhibiting the growth of Zn dendrites. Benefiting from these advantages, the Zn@ZnPO based symmetric and full cells deliver highly reversible Zn plating/stripping behavior and long cycling lifespans.     

Lithiation MXene Derivative Skeletons for Wide-Temperature Lithium Metal Anodes

Lithium (Li) metal, as an appealing candidate for the next-generation of high-energy-density batteries, is plagued by its safety issue mainly caused by uncontrolled dendrite growth and infinite volume expansion. Developing new materials that can improve the performance of Li-metal anode is one of the urgent tasks. Herein, a new MXene derivative containing pure rutile TiO₂ and N-doped carbon prepared by heat-treating MXene under a mixing gas, exhibiting high chemical activity in molten Li, is reported. The lithiation MXene derivative with a hybrid of LiTiO₂-Li₃N-C and Li offers outstanding electrochemical properties. The symmetrical cell assembling lithiation MXene derivative hybrid anode exhibits an ultra-long cycle lifespan of 2000 h with an overpotential of ≈30 mV at 1 mA cm⁻², which overwhelms Li-based anodes reported so far. Additionally, long-term operations of 34, 350, and 500 h at 10 mA cm⁻² can be achieved in symmetrical cells at temperatures of −10, 25, and 50 °C, respectively. Both experimental tests and density functional theory calculations confirm that the LiTiO₂-Li₃N-C skeleton serves as a promising host for Li infusion by alleviating volume variation. Simultaneously, the superlithiophilic interphase of Li₃N guides Li deposition along the LiTiO₂-Li₃N-C skeleton to avoid dendrite growth.     

A Robust Ion‐Conductive Biopolymer as a Binder for Si Anodes of Lithium‐Ion Batteries

Binders have been reported to play a key role in improving the cycle performance of Si anode materials of lithium‐ion batteries. In this study, the biopolymer guar gum (GG) is applied as the binder for a silicon nano­particle (SiNP) anode of a lithium‐ion battery for the first time. Due to the large number of polar hydroxyl groups in the GG molecule, a robust interaction between the GG binder and the SiNPs is achieved, resulting in a stable Si anode during cycling. More specifically, the GG binder can effectively transfer lithium ions to the Si surface, similarly to polyethylene oxide solid electrolytes. When GG is used as a binder, the SiNP anode can deliver an initial discharge capacity as high as 3364 mAh g^?1, with a Coulombic efficiency of 88.3% at the current density of 2100 mA g^?1, and maintain a capacity of 1561 mAh g^?1 after 300 cycles. The study shows that the electrochemical performance of the SiNP anode with GG binder is significantly improved compared to that of a SiNP anode with a sodium alginate binder, and it demonstrates that GG is a promising binder for Si anodes of lithium‐ion batteries.