Acidity-Aided Surface Modification Strategy to Enhance In Situ MnO2 Deposition for High Performance Zn-MnO2 Battery Prototypes.

Zn-MnO2 batteries offer cost-effective, eco-friendly, and efficient solutions for large-scale energy storage applications. However, challenges, like irreversible cathode reactions, prolonged cyclability, and electrolyte stability during high-voltage operations limit their broader application. This study provides insight into the charge-discharge process through in situ deposition of active ß-MnO2 nanoflakes on a carbon-based current collector. The study elucidates the effect of pH and electrolyte concentration on chemical conversion reactions with Zn, in particular focus on their impact on the two-electron MnO2/Mn2+ reaction crucial for high voltage operation. The electrolyte, characterized by being relatively lean in Mn2+ and with a targeted low pH, enables extended cycling. This research achieves greater cycling durability by integrating a carbon-based cathode current collector with high density of structural defects in combination with cell architectures suitable for large-scale energy storage. A flooded stack-type Zn-MnO2 battery prototype employing the optimized electrolyte demonstrates a high discharge voltage (≈2 V) at a substantial discharge current rate of 10 mA cm-2. The battery exhibits an impressive areal capacity of ≈2 mAh cm-2, maintaining ≈100% capacity retention over 400 cycles. This research establishes a promising practical, and cost-effective cathode-free design for Zn-MnO2 batteries, that minimizes additional processing and assembly costs.

Structural Design of 3D Current Collectors for Lithium Metal Anodes: A Review.

Due to the ultrahigh theoretical specific capacity (3860 mAh g-1) and low redox potential (-3.04 V vs. standard hydrogen electrode), Lithium (Li) metal anode (LMA) received increasing attentions. However, notorious dendrite and volume expansion during the cycling process seriously hinder the development of high energy density Li metal batteries. Constructing three-dimensional (3D) current collectors for Li can fundamentally solve the intrinsic drawback of hostless for Li. Therefore, this review systematically introduces the design and synthesis engineering and the current development status of different 3D collectors in recent years (the current collectors are divided into two major parts: metal-based current collectors and carbon-based current collectors). In the end, some perspectives of the future promotion for LMA application are also presented.

Constructing High-Performance Cobalt-Based Environmental Catalysts from Spent Lithium-Ion Batteries: Unveiling Overlooked Roles of Copper and Aluminum from Current Collectors.

Converting spent lithium-ion batteries (LIBs) cathode materials into environmental catalysts has drawn more and more attention. Herein, we fabricated a Co3O4-based catalyst from spent LiCoO2 LIBs (Co3O4-LIBs) and found that the role of Al and Cu from current collectors on its performance is nonnegligible. The density functional theory calculations confirmed that the doping of Al and/or Cu upshifts the d-band center of Co. A Fenton-like reaction based on peroxymonosulfate (PMS) activation was adopted to evaluate its activity. Interestingly, Al doping strengthened chemisorption for PMS (from -2.615 eV to -2.623 eV) and shortened Co-O bond length (from 2.540 Što 2.344 Å) between them, whereas Cu doping reduced interfacial charge-transfer resistance (from 28.347 kΩ to 6.689 kΩ) excepting for the enhancement of the above characteristics. As expected, the degradation activity toward bisphenol A of Co3O4-LIBs (0.523 min-1) was superior to that of Co3O4 prepared from commercial CoC2O4 (0.287 min-1). Simultaneously, the reasons for improved activity were further verified by comparing activity with catalysts doped Al and/or Cu into Co3O4. This work reveals the role of elements from current collectors on the performance of functional materials from spent LIBs, which is beneficial to the sustainable utilization of spent LIBs.

Cu Current Collector with Binder-Free Lithiophilic Nanowire Coating for High Energy Density Lithium Metal Batteries.

Despite significant efforts to fabricate high energy density (ED) lithium (Li) metal anodes, problems such as dendrite formation and the need for excess Li (leading to low N/P ratios) have hampered Li metal battery (LMB) development. Here, the use of germanium (Ge) nanowires (NWs) directly grown on copper (Cu) substrates (Cu-Ge) to induce lithiophilicity and subsequently guide Li ions for uniform Li metal deposition/stripping during electrochemical cycling is reported. The NW morphology along with the formation of the Li15 Ge4 phase promotes uniform Li-ion flux and fast charge kinetic, resulting in the Cu-Ge substrate demonstrating low nucleation overpotentials of 10 mV (four times lower than planar Cu) and high Columbic efficiency (CE) efficiency during Li plating/stripping. Within a full-cell configuration, the Cu-Ge@Li - NMC cell delivered a 63.6% weight reduction at the anode level compared to a standard graphite-based anode, with impressive capacity retention and average CE of over 86.5% and 99.2% respectively. The Cu-Ge anodes are also paired with high specific capacity sulfur (S) cathodes, further demonstrating the benefits of developing surface-modified lithiophilic Cu current collectors, which can easily be integrated at the industrial scale.

A Gradient Lithiophilic Structure for Stable Lithium Metal Anodes with Ultrahigh Rate and Ultradeep Capacity.

Using three-dimensional current collectors (3DCC) as frameworks for lithium metal anodes (LMAs) is a promising approach to inhibit dendrite growth. However, the intrinsically accumulated current density on the top surface and limited Li-ion transfer in the interior of 3DCC still lead to the formation of lithium dendrites, which can pose safety risks. In this study, it reports that gradient lithiophilic structures can induce uniform lithium deposition within the interior of the 3DCC, greatly suppressing dendrite formation, as confirmed by COMSOL simulations and experimental results. With this concept, a gradient-structured zinc oxide-loaded copper foam (GSZO-CF) is synthesized via an easy solution-combustion method at low cost. The resulting Li@GSZO-CF symmetric cells demonstrate stable cycling performance for over 800 cycles, with an ultra-deep capacity of 10 mAh cm-2 even under an ultra-high current density of 50 mA cm-2 , the top results reported in the literature. Moreover, when combined with a LiFePO4 (LFP) cathode under a low negative/positive (N/P) capacity ratio of 2.9, the Li@GSZO-CF||LFP full cells exhibit stable performance for 200 cycles, with a discharge capacity of 130 mAh g-1 and retention of 85.5% at a charging/discharging rate of 1C. These findings suggest a promising strategy for the development of new-generation LMAs.

3D Lithiophilic CuZrAg Metallic Glass Based-Current Collector for High-Performance Lithium Metal Anode.

Lithium metal anodes face several challenges in practical applications, such as dendrite growth, poor cycle efficiency, and volume variation. 3D hosts with lithiophilic surfaces have emerged as a promising design strategy for anodes. In this study, inspiration from the intrinsic isotropy, chemical heterogeneity, and wide tunability of metallic glass (MG) is drew to develop a 3D mesoporous host with a lithiophilic surface. The CuZrAg MG is prepared using the scalable melt-spinning technique and subsequently treated with a simple one-step chemical dealloying method. This resultes in the creation of a host with a homogeneously distributed abundance of lithium affinity sites on the surface. The excellent lithiophilic property and capability for uniform lithium deposition of the 3D CuZrAg electrode have been confirmed through theoretical calculations. Therefore, the 3D CuZrAg electrode displays excellent cyclic stability for over 400 cycles with 96% coulomb efficiency, and ultra-low overpotentials of 5 mV for over 2000 h at 1.0 mA cm-2 and 1.0 mAh cm-2 . Additionally, the full cells partied with either LiFePO4 or LiNi0.8 Co0.1 Mn0.1 O2 cathode deliver exceptional long-term cyclability and rate capability. This work demonstrates the great potential of metallic glass in lithium metal anode application.

The Mechanism of Li Deposition on the Cu Substrates in the Anode-Free Li Metal Batteries.

Due to the rapid growth in the demand for high-energy-density Lithium (Li) batteries and insufficient global Li reserves, the anode-free Li metal batteries are receiving increasing attention. Various strategies, such as surface modification and structural design of copper (Cu) current collectors, have been proposed to stabilize the anode-free Li metal batteries. Unfortunately, the mechanism of Li deposition on the Cu surfaces with the different Miller indices is poorly understood, especially on the atomic scale. Here, the large-scale molecular dynamics simulations of Li deposition on the Cu substrates are performed in the anode-free Li metal batteries. The results show that the surface properties of the Li panel can be altered through the different Cu substrate surfaces. Through surface similarity analysis, potential energy distributions,and inhomogeneous deposition simulations, it is found that the Li atoms exhibit different potential energy variances and kinetic characteristics on the different Cu surfaces. Furthermore, a proposal to reduce the fraction of the (110) facet in commercial Cu foils is made to improve the reversibility and stability of Li plating/stripping in the anode-free Li metal batteries.

Electrochemically Dealloyed 3D Porous Copper Nanostructure as Anode Current Collector of Li-Metal Batteries.

The commercialization of high-energy Li-metal batteries is impeded by Li dendrites formed during electrochemical cycling and the safety hazards it causes. Here, a novel porous copper current collector that can effectively mitigate the dendritic growth of Li is reported. This porous Cu foil is fabricated via a simple two-step electrochemical process, where Cu-Zn alloy is electrodeposited on commercial copper foil and then Zn is electrochemically dissolved to form a 3D porous structure of Cu. The 3D porous Cu layers on average have a thickness of ≈14 um and porosity of ≈72%. This current collector can effectively suppress Li dendrites in cells cycled with a high areal capacity of 10 mAh cm-2 and under a high current density of 10 mA cm-2 . This electrochemical fabrication method is facile and scalable for mass production. Results of advanced in situ synchrotron X-ray diffraction reveal the phase evolution of the electrochemical deposition and dealloying processes.

Polyimide Compounds For Post-Lithium Energy Storage Applications.

The exploration of cathode and anode materials that enable reversible storage of mono and multivalent cations has driven extensive research on organic compounds. In this regard, polyimide (PI)-based electrodes have emerged as a promising avenue for the development of post-lithium energy storage systems. This review article provides a comprehensive summary of the syntheses, characterizations, and applications of PI compounds as electrode materials capable of hosting a wide range of cations. Furthermore, the review also delves into the advancements in PI based solid state batteries, PI-based separators, current collectors, and their effectiveness as polymeric binders. By highlighting the key findings in these areas, this review aims at contributing to the understanding and advancement of PI-based structures paving the way for the next generation of energy storage systems.

Integrated Porous Cu Host Induced High-Stable Bidirectional Li Plating/Stripping Behavior for Practical Li Metal Batteries.

The double-sided electrodes with active materials are widely used for commercial lithium (Li) ion batteries with a higher energy density. Accordingly, developing an anode current collector that can accommodate the stable and homogeneous Li plating/stripping on both sides will be highly desired for practical Li metal batteries (LMBs). Herein, an integrated bidirectional porous Cu (IBP-Cu) film with a through-pore structure is fabricated as Li metal hosts using the powder sintering method. The resultant IBP-Cu current collector with tunable pore volume and size exhibits high mechanical flexibility and stability. The bidirectional and through-pore structure enables the IBP-Cu host to achieve homogeneous Li deposition and effectively suppresses the dendritic Li growth. Impressively, the as-fabricated Li/IBP-Cu anode exhibits a remarkable capacity of up to 7.0 mAh cm-2 for deep plating/stripping, outstanding rate performance, and ultralong cycling ability with high Coulombic efficiency of ≈100% for 1000 cycles. More practicably, a designed pouch cell coupled with one Li/IBP-Cu anode and two LiFePO4 cathodes exhibits a highly elevated energy density (≈187.5%) compared with a pouch cell with one anode and one cathode. Such design of a bidirectional porous Cu current collector with stable Li plating/stripping behaviors suggests its promising practical applications for next-generation Li metal batteries.

Built-In Stable Lithiophilic Sites in 3D Current Collectors for Dendrite Free Li Metal Electrode.

Stable lithiophilic sites in 3D current collectors are the key to guiding the uniform Li deposition and thus suppressing the Li dendrite growth, but such sites created by the conventional surface decoration method are easy to be consumed along with cycling. In this work, carbon fiber (CF)-based 3D porous networks with built-in lithiophilic sites that are stable upon cycling are demonstrated. Such heterostructured architecture is constructed by the introduction of zeolitic imidazolate framework-8-based nanoparticles during the formation of the 3D fibrous carbonaceous network and the following annealing. The introduced Zn species are found to be re-distributed along the entire individual CF in the 3D network, and function as lithiophilic sites that favor the homogenous lithium nucleation and growth. The 3D network also presents a multi-scale porous structure that improves the space utilization of the host. The corresponding symmetric cells adopting such 3D anode demonstrate excellent cycling performance, especially at a high rate (300 cycles at 10 mA cm-2 with a capacity of 5 mA h cm-2 ). A full cell with LiFePO4 cathode shows a capacity retention of 98% after cycling at 1C for 300 cycles. This method provides an effective design strategy for 3D hosting electrodes in dendrite-free alkali metal anode applications.

A Novel Dendrite-Free Lithium Metal Anode via Oxygen and Boron Codoped Honeycomb Carbon Skeleton.

Lithium (Li) metal is an excellent anode of Li ion batteries because of its high theoretical capacity and the low redox potential compared to other anodes. However, the uncontrollable growth of Li dendrites still incurs serious safety issues and poor electrochemical performances, leading to its limited practical application. An oxygen and boron codoped honeycomb carbon skeleton (OBHcCs) is reported and a stable Li metal-based anode is realized. It can be coated on a copper foil substrate to be used as a current collector for a dendrite-free Li metal anode. OBHcCs effectively reduces the local current density owing to the high surface area and inhibits Li dendrite growth, which is explored by scanning electron microscopy and an X-ray photoelectron spectra depth profile. The abundant lithiophilic oxygen and boron-containing functional groups reduce the potential barrier of nucleation and lead to the homogeneous Li ions flux as confirmed by the density functional theories. Therefore, the Li metal anode based on OBHcCs (OBHcCs@Li) stably runs for 700 h in a symmetric cell with a Li stripping capacity of 1 mAh cm-2 at 1 mA cm-2 . Furthermore, the OBHcCs@Li|LiFePO4 full cell shows a good capacity retention of 84.6% with a high coulombic efficiency of 99.6% at 0.5 C for 500 cycles.

Controllable 3D Porous Ni Current Collector Coupled with Surface Phosphorization Enhances Na Storage of Ni3 S2 Nanosheet Arrays.

3D porous Ni is fabricated via an easily scalable electroless plating method using a dynamic template formed through in-situ hydrogen bubbles. The pore size in the range of several micrometers is controllable through adjusting the Ni2+ depositing rate and hydrogen bubbles releasing rate. The Ni3 S2 nanosheet arrays anode is then grown on the unique 3D porous Ni current collector followed by subsequent surface phosphorization. The tremendous interconnected pores and rich voids between the Ni3 S2 nanosheet arrays cannot only provide rapid transferring channels for Na+ , but also accommodate volumetric changes of the Ni3 S2 electrode during cycling, guaranteeing the integrity of the active material. In addition, the surface phosphorized layer enhances the electronic conductivity through providing an electron transport highway along the 3D Ni3 S2 , NiP2 layer, and 3D porous Ni current collector, and simultaneously stabilizes the electrode/electrolyte interphase as a protecting layer. Because of these merits, the phosphorized 3D porous Ni3 S2 (3D P-Ni3 S2 ) electrode is capable of delivering an ultra-stable capacity of 387.5 mAh g-1 at 0.1 A g-1 , and a high capacity retention of 85.3% even at a high current density of 1.6 A g-1 .

Surface amorphous coating for an economical and high-stability current collector for rechargeable aluminum-ion batteries.

Rechargeable aluminum-ion batteries (AIBs) are regarded as the next-generation energy storage devices due to their low flammability, low cost and high power density as well as abundant aluminum (Al) reserves. However, these popular ionic liquid electrolytes contain highly corrosive acid, which always corrodes the most used positive current collector, thus hindering the commercialization of AIBs. This study proposes an efficient and economical method of coating amorphous Ni3S2compound on a nickel metal current collector (Ni-S/Ni). The conductivity and the onset oxidation potential of amorphous Ni3S2coating can be up to 2.3 × 106S m-1and 2.7 V respectively. A Ni-S/Ni current collector can provide excellent cycling stability with no electrochemical corrosion in the AIBs. The AIBs fabricated using a Ni-S/Ni current collector exhibits a specific capacity of 65 mAh/g at 1 A g-1, high coulombic efficiency of 99% and cyclability of at least 2000 cycles. Moreover, the total cost of the Ni-S/Ni current collector can be limited to less than 3.3 USD/m2. The comprehensive performances of these AIBs are better than most reported results so far, which indicates that this method can advance the commercialization of AIBs.

Application of electrodeposited Cu-metal nanoflake structures as 3D current collector in lithium-metal batteries.

Since uncontrolled lithium (Li) dendrite growth and dendrite-induced dead Li severely limit the development of Li metal batteries, 3D Cu current collectors can effectively alleviate these problems during Li plating/stripping. Herein, one-step galvanostatic electrodeposition method is employed to fabricate a new current collector on Cu foam decorated with large-scale and uniform 3D porous Cu-based nanoflake (NF) structures (abbreviated as 3D Cu NF@Cu foam). This 3D structure with large internal surface areas not only generates lithophilic surface copper oxides and hydroxides as charge centers and nucleation sites for Li insertion/extraction, but also endows abundant space with interlinked NFs for buffering the cell volume expansion and increasing battery performance. As a result, Li-deposited 3D Cu NF@Cu foam current collector can realize stable cycling over 455 cycles with an average Coulombic efficiency of 98.8% at a current density of 1.0 mA cm-2, as well as a prolonged lifespan of >380 cycles in symmetrical cell without short-circuit, which are superior to those of blank Cu foam current collector. This work realizes Li metal anode stabilization by constructing 3D porous Cu NFs current collectors, which can advance the development of Li metal anode for battery industries.

Dynamic Intelligent Cu Current Collectors for Ultrastable Lithium Metal Anodes.

Three-dimensional (3D) current collectors have shown great potential in realizing dendrite-free lithium (Li) metal anodes. However, the rigid 3D current collectors could not simultaneously suppress Li dendrite growth and allow Li plating/stripping under high capacities and large current densities. Here, we report a dynamic intelligent Cu (DICu) current collector that dynamically accommodates the volume change by changing the packing density of the assembled particles. The Li/DICu electrode achieves a high Coulombic efficiency of 99.6% after 800 cycles. The symmetrical cell shows exceptional cycling stability under the high current density of 10 mA cm-2. Notably, when assembled in full-cell batteries, the Li/DICu|LiFePO4 battery maintains a specific capacity of 139.5 mAh g-1 at 1 C for 500 cycles, and the Li/DICu|S battery delivers a specific capacity of 804 mAh g-1 after 500 cycles at 0.5 C, corresponding to the best performance among Li metal batteries with Cu-based current collectors to date.

Nanomanufacturing of RGO-CNT Hybrid Film for Flexible Aqueous Al-Ion Batteries.

A highly electrically conductive film-type current collector is an essential part of batteries. Apart from the metal-based current collectors, lightweight and highly conductive carbon materials such as reduced graphene oxide (RGO) and carbon nanotubes (CNTs) show great potential as current collectors. However, traditional RGO manufacturing usually requires a long time and high energy, which decreases the product yielding rate and manufacturing efficiency. Moreover, the performance of the manufactured RGO needs to be further improved. In this work, CNT and GO are evenly mixed into GO-CNT, which can be directly reduced into RGO-CNT by Joule heating at 2936 K within less than 1 min. The fabricated RGO-CNT achieves a high electrical conductivity of 2750 S cm-1 , and realizes a 106 -fold increase. The assembled flexible aqueous Al-ion battery with RGO-CNT as the current collector exhibits impressive electrochemical performance in terms of superior cycling stability and exceptional rate capability, and excellent mechanical ability regarding the tolerance to mechanical damage such as bending, folding, piercing, and cutting without detrimental consequences.

Aqueous Rechargeable Li+ /Na+ Hybrid Ion Battery with High Energy Density and Long Cycle Life.

The practical application of aqueous rechargeable batteries is hampered by the low energy density and poor cycle stability, which mostly arises from the corrosion of cathode current collector, exfoliation of active material, and narrow electrochemical stability window of aqueous electrolyte. A light-weight and low-cost cathode current collector composed of graphite and carbon nanotube coated on nylon membrane exhibiting corrosion resistance and strong adhesion is developed. Also, a modified aqueous electrolyte with the addition of urea whose window is expanded to ≈3.2 V is developed that contributes to the formation of solid-electrolyte interphase on surfaces of electrodes. LiMn2 O4 /NaTi2 (PO4 )3 Li+ /Na+ hybrid ion battery using such aqueous electrolyte and current collector is demonstrated to cycle up to 10 000 times with low cost (60 dollars per kWh) and high energy density (100 Wh kg-1 ) for stationary energy storage and electronic vehicles applications.

Chemical Energy Release Driven Lithiophilic Layer on 1 m2 Commercial Brass Mesh toward Highly Stable Lithium Metal Batteries.

It is imperative to explore practical methods and materials to drive the development of high energy density lithium metal batteries. The constuciton of nanostructure electrodes and surface engineering on the current collectors are the two most effective strategies to regulate the homogeneous Li plating/stripping to relieve the Li dendrites and infinite volume change problems. Based on the low stacking fault energy of the Cu-Zn alloy, we present a novel chemical energy release induced surface atom diffusion strategy, which is achieved by the negative Gibbs free energy from the surface oxidation reaction and subsequent replacement reaction under thermal treatment in air, to realize a uniform upper ZnO nanoparticles coating. Furthermore, we apply the modified brass mesh as a lithiophilic current collector to decrease the Li deposition nucleation overpotential and effectively restrain the Li dendrite growth. The modified brass current collector achieves a long-term cycling stability of 500 cycles at 2.0 mA cm-2. We have verified the effectiveness of our chemical energy release modification strategy on a 1 m2 brass mesh and other Cu alloy (Tin bronze mesh), which demonstrates its great opportunities for scalable and safe lithium metal batteries.

Solution-Processed Metal Coating to Nonwoven Fabrics for Wearable Rechargeable Batteries.

Wearable rechargeable batteries require electrode platforms that can withstand various physical motions, such as bending, folding, and twisting. To this end, conductive textiles and paper have been highlighted, as their porous structures can accommodate the stress built during various physical motions. However, fabrics with plain weaves or knit structures have been mostly adopted without exploration of nonwoven counterparts. Also, the integration of conductive materials, such as carbon or metal nanomaterials, to achieve sufficient conductivity as current collectors is not well-aligned with large-scale processing in terms of cost and quality control. Here, the superiority of nonwoven fabrics is reported in electrochemical performance and bending capability compared to currently dominant woven counterparts, due to smooth morphology near the fiber intersections and the homogeneous distribution of fibers. Moreover, solution-processed electroless deposition of aluminum and nickel-copper composite is adopted for cathodes and anodes, respectively, demonstrating the large-scale feasibility of conductive nonwoven platforms for wearable rechargeable batteries.