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.     

Recent advances on the use of active anodes in environmental electrochemistry

Active anodes, especially those consisting of metal mixed oxides (MMOs) containing Ru and/or Ir oxides, have been applied in the treatment of wastewater, especially when chloride ions are present. Their characteristics continuously drive the study of applications of these materials, be they in the degradation of different organic molecules, the preparation of new electrode materials and in the association of various processes to increase pollutant removal. Thus, this brief review aims to present some of the recent advances in the application of active anode materials in environmental electrochemistry. Focussing on the 2018–2020 period, it is possible to note many applied studies, using commercially available materials, covering a wide range of target pollutants. Still other studies aim to modify the catalyst surfaces to increase the mineralization capacity, and the use of these anodes in the production of free chlorine species to mediate indirect organic reduction is observed.     

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在四阳极直流放电装置上,测量并分析了辉光放电的电流-电压和发光特征随气压的变化关系。结果表明,采用稳流放电模式比稳压放电具有更宽的稳定放电气压和电流范围,能在从1～800Pa的较宽气压范围内实现氦气辉光放电,放电电流可达到500mA左右。随着电极表面亮斑的变化,对于同一气压,在低电流区,放电电压几乎成指数增长;随电流增大,电压的增长速度变缓;对于高的气压,碰撞频率的增大使得电压随电流升高的速率变小。分析表明,放电处于异常辉光区。从放电管的CCD图像可以看出,对于同一放电电流,随气压的升高,等离子体往阴极收缩。     

Metal Oxide Film Anodes in the Electrolysis of Water or Brine

Metal (M) oxide (M: Ir, Os, Pd, Pt, Rh, Ru) together with MaO₂ and MnO₂ alone, were coated on SnO₂ films and the anode behavior was examined in 1.0 N H₂SO₄, 1.0 N NaOH and 1.0, N NaCl aqueous solutions at 25°. The results are compared with those of DSA and of metallic Pt.     

Amorphization Boost Multi-Ions Storage for High-Performance Aqueous Batteries

Regarding the complex properties of various cations, the design of aqueous batteries that can simultaneously store multi-ions with high capacity and satisfactory rate performance is a great challenge. Here an amorphization strategy to boost cation-ion storage capacities of anode materials is reported. In monovalent (H⁺, Li⁺, K⁺), divalent (Mg²⁺, Ca²⁺, Zn²⁺) and even trivalent (Al³⁺) aqueous electrolytes, the capacity of the resulting amorphous MoO_x is more than quadruple than that of crystalline MoO_x and exceeds those of other reported multiple-ion storage materials. Both experimental and theoretical calculations reveal the generation of ample active sites and isotropic ions in the amorphous phase, which accelerates cation migration within the electrode bulk. Amorphous MoO_x can be coupled with multi-ion storage cathodes to realize electrochemical energy storage devices with different carriers, promising high energy and power densities. The power density exceeded 15000 W kg⁻¹, demonstrating the great potential of amorphous MoO_x in advanced aqueous batteries.     

In Situ Artificial Hybrid SEI Layer Enabled High-Performance Prelithiated SiOx Anode for Lithium-Ion Batteries

Considered the promising anode material for next-generation high-energy lithium-ion batteries, SiO_x has been slow to commercialize due to its low initial Coulombic efficiency (ICE) and unstable solid electrolyte interface (SEI) layer, which leads to reduced full-cell energy density, short cycling lives, and poor rate performance. Herein, a novel strategy is proposed to in situ construct an artificial hybrid SEI layer consisting of LiF and Li₃Sb on a prelithiated SiO_x anode via spontaneous chemical reaction with SbF₃. In addition to the increasing ICE (94.5%), the preformed artificial SEI layer with long-term cycle stability and enhanced Li⁺ transport capability enables a remarkable improvement in capacity retention and rate capability for modified SiO_x. Furthermore, the full cell using Li(Ni_0.8Co_0.1Mn_0.1)O₂ and a pre-treated anode exhibits high ICE (86.0%) and capacity retention (86.6%) after 100 cycles at 0.5 C. This study provides a fresh insight into how to obtain stable interface on a prelithiated SiO_x anode for high energy and long lifespan lithium-ion batteries.     

Electrocatalysis of Fe-N-C Bonds Driving Reliable Interphase and Fast Kinetics for Phosphorus Anode in Sodium-Ion Batteries

Phosphorus exhibits high capacity and low redox potential, making it a promising anode material for future sodium-ion batteries. However, its practical applications are confined by poor durability and sluggish kinetics. Herein, an innovative in-situ electrochemically self-driven strategy is presented to embed phosphorus nanocrystal (≈10 nm) into a Fe-N-C-rich 3D carbon framework (P/Fe-N-C). This strategy enables rapid and high-capacity sodium ion storage. Through a combination of experimental assistance and theoretical calculations, a novel synergistic catalytic mechanism of Fe-N-C is reasonably proposed. In detail, the electrochemical formation of Fe-N-C catalytic sites facilitates the release of fluorine in ester-based electrolyte, inducing Na⁺-conducting-enhanced solid-electrolyte interphase. Furthermore, it also effectively induces the dissociation energy of the P-P bond and promotes the reaction kinetics of P anode. As a result, the unconventional P/Fe-N-C anode demonstrates outstanding rate-capability (267 mAh g⁻¹ at 100 A g⁻¹) and cycling stability (72%, 10 000 cycles). Notably, the assembled pouch cell achieves high-energy density of 220 Wh kg⁻¹.     

Fast Li+ Transport via Silica Network-Driven Nanochannels in Ionomer-in-Framework for Lithium Metal Batteries

For the development of all-solid-state lithium metal batteries (LMBs), a high-porous silica aerogel (SA)-reinforced single-Li⁺ conducting nanocomposite polymer electrolyte (NPE) is prepared via two-step selective functionalization. The mesoporous SA is introduced as a mechanical framework for NPE as well as a channel for fast lithium cation migration. Two types of monomers containing weak-binding imide anions and Li⁺ cations are synthesized and used to prepare NPEs, where these monomers are grafted in SA to produce SA-based NPEs (SANPEs) as ionomer-in-framework. This hybrid SANPE exhibits high ionic conductivities (≈10⁻³ S cm⁻¹), high modulus (≈10⁵ Pa), high lithium transference number (0.84), and wide electrochemical window (>4.8 V). The resultant SANPE in the lithium symmetric cell possesses long-term cyclic stability without short-circuiting over 800 h under 0.2 mA cm⁻². Furthermore, the LiFePO₄|SANPE|Li solid-state batteries present a high discharge capacity of 167 mAh g⁻¹ at 0.1 C, good rate capability up to 1 C, wide operating temperatures (from −10 to 40 °C), and a stable cycling performance with 97% capacity retention and 100% coulombic efficiency after 75 cycles at 1 C and 25 °C. The SANPE demonstrates a new design principle for solid-state electrolytes, allowing for a perfect complex between inorganic silica and organic polymer, for high-energy-density LMBs.     

Regulating the Water Molecular in the Solvation Structure for Stable Zinc Metal Batteries

Rechargeable aqueous zinc batteries are promising energy storage devices because of their low cost, high safety, and high energy density. However, their performance is plagued by the unsatisfied cyclability due to the dendrite growth and hydrogen evolution reaction (HER) at the Zn anode. Herein, it is demonstrated that the concentrated hybrid aqueous/non-aqueous ZnCl₂ electrolytes constitute a peculiar chemical environment for not only the Zn-ions but also water molecules. The high concentration of chloride ions substitutes the H₂O molecular in the solvation structure of Zn²⁺, while the acetonitrile further interacts with H₂O to decrease its activity. The hybrid electrolytes both inhibit the dendrite formation and HER, enabling an ultrahigh average Coulombic efficiency of 99.9% in the Zn||Cu half-cell and a highly reversible Zn plating/stripping with a low overpotential of 21 mV. Using this hybrid electrolyte, the Zn||polytriphenylamine (PTPAn) full cell deliveres a high discharge capacity of 110 mAh g⁻¹, a high power density of 9200 W kg⁻¹ at 100 °C and maintains 85% of the capacity for over 6000 cycles at 10 °C. This study provides a deep understanding between the solvation structure and columbic efficiency of Zn anode, thus inspiring the development for stable Zn batteries.     

A Stable Polymer-based Solid-State Lithium Metal Battery and its Interfacial Characteristics Revealed by Cryogenic Transmission Electron Microscopy

Solid-state lithium metal batteries (SSLMBs) are a promising candidate for next-generation energy storage systems due to their intrinsic safety and high energy density. However, they still suffer from poor interfacial stability, which can incur high interfacial resistance and insufficient cycle lifespan. Herein, a novel poly(vinylidene fluoride‑hexafuoropropylene)-based polymer electrolyte (PPE) with LiBF₄ and propylene carbonate plasticizer is developed, which has a high room-temperature ionic conductivity up to 1.15 × 10⁻³ S cm⁻¹ and excellent interfacial stability. Benefitting from the stable interphase, the PPE-based symmetric cell can operate for over 1000 h. By virtue of cryogenic transmission electron microscopy (Cryo-TEM) characterization, the high interfacial compatibility between Li metal anode and PPE is revealed. The solid electrolyte interphase is made up of an amorphous outer layer that can keep intimate contact with PPE and an inner Li₂O-dominated layer that can protect Li from continuous side reactions during battery cycling. A LiF-rich transition layer is also discovered in the region of PPE close to Li metal anode. The feasibility of investigating interphases in polymer-based solid-state batteries via Cryo-TEM techniques is demonstrated, which can be widely employed in future to rationalize the correlation between solid-state electrolytes and battery performance from ultrafine interfacial structures.