Revisiting aluminum current collector in lithium-ion batteries:Corrosion and countermeasures

With the large-scale service of lithium-ion batteries(LIBs),their failures have attracted significant attentions.While the decay of active materials is the primary cause for LIB failures,the degradation of auxiliary materials,such as current collector corrosion,should not be disregarded.Therefore,it is necessary to conduct a comprehensive review in this field.In this review,from the perspectives of electrochemistry and materials,we systematically summarize the corrosion behavior of aluminum cathode current collector and propose corresponding countermeasures.Firstly,the corrosion type is clarified based on the properties of passivation layers in different organic electrolyte components.Furthermore,a thoroughgoing analysis is presented to examine the impact of various factors on aluminum corrosion,including lithium salts,organic solvents,water impurities,and operating conditions.Subsequently,strategies for electrolyte and protection layer employed to suppress corrosion are discussed in detail.Lastly and most importantly,we provide insights and recommendations to prevent corrosion of current collectors,facilitate the development of advanced current collectors and the implementation of next-generation high-voltage stable LIBs.

The Effects of the Geometry of a Current Collector with an Equal Open Ratio on Output Power of a Direct Methanol Fuel Cell

The open ratio of a current collector has a great impact on direct methanol fuel cell(DMFC)performance.Although a number of studies have investigated the influence of the open ratio of DMFC current collectors,far too little attention has been given to how geometry(including the shape and feature size of the flow field)affects a current collector with an equal open ratio.In this paper,perforated and parallel current collectors with an equal open ratio of 50%and different feature sizes are designed,and the corresponding experimental results are shown to explain the geometry effects on the output power of the DMFC.The results indicate that the optimal feature sizes are between 2 and 2.5 mm for both perforated and parallel flow field in the current collectors with an equal open ratio of 50%.This means that for passive methanol fuel cells,to achieve the highest output power,the optimal feature size of the flow field in both anode and cathode current collectors is between 2 and 2.5 mm under the operating mode of this experiment.The effects of rib and channel position are also investigated,and the results indicate that the optimum pattern depends on the feature sizes of the flow field.

Recent Advances in Structural Optimization and Surface Modification on Current Collectors for High‑Performance Zinc Anode:Principles,Strategies,and Challenges

The last several years have witnessed the prosperous development of zinc-ion batteries(ZIBs),which are considered as a promising competitor of energy storage systems thanks to their low cost and high safety.However,the reversibility and availability of this system are blighted by problems such as uncontrollable dendritic growth,hydrogen evolution,and corrosion passivation on anode side.A functionally and structurally well-designed anode current collectors(CCs)is believed as a viable solution for those problems,with a lack of summarization according to its working mechanisms.Herein,this review focuses on the challenges of zinc anode and the mechanisms of modified anode CCs,which can be divided into zincophilic modification,structural design,and steering the preferred crystal facet orientation.The possible prospects and directions on zinc anode research and design are proposed at the end to hopefully promote the practical application of ZIBs.

Status and Opportunities of Zinc Ion Hybrid Capacitors: Focus on Carbon Materials, Current Collectors, and Separators

Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.

A pre-strain strategy of current collectors for suppressing electrode debonding in lithium-ion batteries

The interfacial debonding between the active layer and the current collector has been recognized as a critical mechanism for battery fading,and thus has attracted great efforts focused on the related analyses.However,much still remains to be studied regarding practical methods for suppressing electrode debonding,especially from the perspective of mechanics.In this paper,a pre-strain strategy of current collectors to alleviate electrode debonding is proposed.An analytical model for a symmetric electrode with a deformable and limited-thickness current collector is developed to analyze the debonding behavior involving both a pre-strain of the current collector and an eigen-strain of the active layers.The results reveal that the well-designed pre-strain can significantly delay the debonding onset(by up to 100%)and considerably reduce the debonding size.The critical values of the pre-strain are identified,and the pre-strain design principles are also provided.Based on these findings,this work sheds light on the mechanical design to suppress electrode degradation.

Spontaneous local redox reaction to passivate CNTs as lightweight current collector for high energy density lithium ion batteries

Extensive usage of highly conductive carbon materials with large specific surface area(e.g.,carbon nanotubes,CNTs)in lithium ion batteries(LIBs),especially as current collector of anodes,suffers from low initial coulombic efficiency(ICE),large interfacial resistance,and severe embrittlement,as the large specific surface area often results in severe interfacial decomposition of the electrolyte and the formation of thick and fluffy solid electrolyte interphase(SEI)during cycling of LIBs.Herein,we demonstrate that when the CNT-based current collector and Na foil(which are being stacked intimately upon each other)are being placed in Na+-based organic electrolyte,local redox reaction between the Na foil and the electrolyte would occur spontaneously,generating a thin and homogeneous NaF-based passivating layer on the CNTs.More importantly,we found that owing to the weak solvation behaviors of Na+in the organic electrolyte,the resulting passivation layer,which is rich in NaF,is thin and dense;when used as the anode current collector in LIBs,the pre-existing passivating layer can function effectively in isolating the anode from the solvated Li+,thus suppressing the formation of bulky SEI and the destructive intercalation of solvated Li+.The relevant half-cell(graphite as anode)exhibits a high ICE of 92.1%;the relevant pouch cell with thus passivated CNT film as current collectors for both electrodes(LiCoO_(2)as cathode,graphite as anode)displays a high energy density of 255 Wh kg^(-1),spelling an increase of 50%compared with that using the conventional metal current collectors.

Performance evaluation of the incorporation of different wire meshes in between perforated current collectors and membrane electrode assembly on the Passive Direct methanol fuel cell

Passive Direct methanol fuel cells(DMFC)are more suitable for charging small capacity electronic devices.In passive DMFC,the fuel and oxidant are supplied by diffusion and natural convection process on the anode and cathode sides respectively.Current collectors(CC)play a vital importance in fuel cell performance.This paper presents the combined impact of perforated and wire mesh current collectors(WMCC)on passive DMFC performance.Three types of open ratios of perforated current collectors(PCC),such as 45.40%,55.40%and 63.40%and two types of wire mesh current collectors with open ratios of 38.70%and 45.40%were chosen for the experimental work.A combination of TaguchiL9 rule is considered.A combination of three PCC and two WMCC on both anode and cathode was used.Methanol concentration was varied from 1 mol·L^(-1)-5 mol·L^(-1)for nine combinations of PCC and WMCC.From the experimental results,it is noticed that the combination of PCC and WMCC with an open ratio of 55.40%and 38.70%incorporated passive DMFC produced peak power density at 5 mol·L^(-1)of methanol concentration.The passive DMFC performance was evaluated in terms of maximum power density and maximum current density.The combined current collectors of PCC and WMCC open ratios of 55.40%+38.70%have more stable voltage than single PCC of open ratio 63.40%at 4 mol·L^(-1)of methanol concentration.

Electrolyte and current collector designs for stable lithium metal anodes

With the increasing demand for high energy-density batteries for portable electronics and large-scale energy storage systems,the lithium metal anode(LMA)has received tremendous attention because of its high theoretical capacity and low redox potential.However,the commercial application of LMAs is impeded by the uncontrolled growth of lithium dendrites.Such dendrite growth may result in internal short circuits,detrimental side reactions,and the formation of dead lithium.Therefore,the growth of lithium metal must be controlled.This article summarizes our recent efforts in inhibiting such dendrite growth,decreasing the detrimental side reactions,and elongating the LMA lifespan by optimizing the electrolyte structure and by designing appropriate current collectors.After identifying that the unstable solid electrolyte inter-face(SEI)film is responsible for the potential dropping in carbonate electrolytes,we developed LiPF_(6)-LiNO_(3) dual-salt electrolyte and lithium bis(fluorosulfonyl)imide(LiFSI)-carbonate electrolyte to stabilize the SEI film of LMAs.In addition,we achieved controlled lithium depos-ition by designing the structure and material of the current collectors,including selective lithium deposition in porous current collectors,lithio-philic metal guided lithium deposition,and iron carbide induced underpotential lithium deposition in nano-cavities.The limitations of the cur-rent strategies and prospects for future research are also presented.

Understanding the Li diffusion mechanism and positive effect of current collector volume expansion in anode free batteries

In anode free batteries(AFBs), the current collector acts as anode simultaneously and has large volume expansion which is generally considered as a negative effect decreasing the structural stability of a battery. Moreover, despite many studies on the fast lithium diffusion in the current collector materials of AFB such as copper and aluminum, the involved Li diffusion mechanism in these materials remains poorly understood. Through first-principles calculation and stress-assisted diffusion equations, here we study the Li diffusion mechanism in several current collectors and related alloys and clarify the effect of volume expansion on Li diffusion respectively. It is suggested that due to the lower Li migration barriers in aluminum and tin, they should be more suitable to be used as AFB anodes, compared to copper, silver, and lead. The Li diffusion facilitation in copper with a certain number of vacancies is proposed to explain why the use of copper with a thickness≤100 nm as the protective coating on the anode improves the lifetime of the batteries. We show that the volume expansion has a positive effect on Li diffusion via mechanical–electrochemical coupling. Namely, the volume expansion caused by Li diffusion will further induce stress which in turn affects the diffusion. These findings not only provide in-depth insight into the operating principle of AFBs, but also open a new route toward design of improved anode through utilizing the positive effect of mechanical–electrochemical coupling.

Significant effect of electron transfer between current collector and active material on high rate performance of Li_4Ti_5O_(12)

The rate and cycling performances of the electrode materials are affected by many factors in a practical complicated electrode process. Learning about the limiting step in a practical electrochemical reaction is very important to effectively improve the electrochemical performances of the electrode materials. Li4Ti5O12, as a zero-strain material, has been considered as a promising anode material for long life Li-ion batteries. In this study, our results show that the Li4Ti5O12 pasted on Cu or graphite felt current collector exhibits unexpectedly higher rate performance than on A1 current collector. For Li4Ti5O12, the electron transfer between current collector and active material is the critical factor that affects its rate and cycling performances.

Surface-roughened current collectors for anode-free all-solid-state batteries

Anode-free all-solid-state batteries(AFASSBs), composed of a fully lithiated cathode and a bare current collector(CC) that eliminates excess lithium, can maximize the energy density(because of a compact cell configuration) and improve the safety of solid-state systems. Although significant progress has been made by modifying CCs in liquid-based anode-free batteries, the role of CCs and the mechanism of Li formation on CCs in AFASSBs are still unexplored. Here, we systematically investigate the effect of the surface roughness of the CCs on the Li plating/stripping behavior in AFASSBs. The results show that the moderately roughened CC substantially improves the Coulombic efficiency and cycle stability of AFASSBs owing to the increased contact points between the solid electrolyte and the roughened CC. In contrast, the excessively roughened CC deteriorates the performance owing to the contact loss.Moreover, an ex situ interface analysis reveals that the roughened surface of the CC could suppress the interfacial degradation during the Li ion extraction from a sulfide solid electrolyte to a CC. This provides an indication to the origin that hinders the electrochemical performance of AFASSBs. These findings show the potential for the application of surface-engineered CCs in AFASSBs and provide guidelines for designing advanced CCs.

Contribution to the understanding of the performance differences between commercial current collectors in Li–S batteries

Lithium–sulfur batteries have been recognised as highly promising next-generation batteries, due to their low cost and high theoretical energy density. Despite numerous advances in this technology over the last decade, its commercialisation is still a challenge that has not yet been achieved. Many efforts have been made to improve the problems that these batteries present, mainly by investigating different cathode manufacturing strategies, testing novel Li anodes, new additives in the electrolytes, and modified separators or interlayers. However, the characteristics of the current collectors used in the preparation of the electrodes have been rarely addressed. Three commercial collectors are commonly used in basic research on Li–S batteries: Al foil, carbon coated Al foil (Al-C), and carbon paper (gas diffusion layer, GDL). In this work, a detailed study of the electrochemical response of these commercial collectors has been carried out. The tests were carried out on two S composites formed by carbons of a different natures, commercial carbon black and synthetic N-doped graphene. In addition, the S impregnation method was different, using either melt diffusion at 155 ℃ or ethylenediamine as S solvent, respectively. In both systems, the results were similar – the electrodes supported on GDL delivered higher specific capacities than those supported on Al and Al-C, with minimal differences between the two. Of the different collector properties examined to explain this behaviour, namely Al corrosion, electrical conductivities, surface-level composition, and surface texture, only the latter had a significant effect in the performance of GDL-based electrodes. SEM images revealed a rough and cracked surface formed by the agglomerated carbon particles that give rise to a complex pore system, predominantly consisting of macropores. All of these features are beneficial for a better anchoring of the active material on the collector surface, in addition to enhancing the wettability of the electrolyte and favouring reaction kinetics. In contrast, the Al-based collector possesses a very smooth and non-porous surface, detrimental to both the active material-substrate interface and the active material impregnation by the electrolyte.

PREPARATION OF LEAD-ACID BATTERY USING ELECTROPLATED RETICULATED SiC AS THE POSITIVE CURRENT COLLECTOR

The possibility of using Pb-electroplated reticulated SiC as the positive current collector for lead-acid batteries was investigated. Reticulated SiC with two aperture sizes (3 and 2mm) were tested as the substrate of positive electrode. It was found that the reticulated SiC has an excellent corrosion resistance in H2SO4 solution, and the Pb layer electroplated on reticulated SiC showed analogous electrochemical behavior to metal Pb. Preliminary test of the battery performance indicated that the utilization efficiency of the positive active mass of new designed batteries are improved compared with the conventional batteries. The improvement could be ascribed to the high specific surface area of the reticulated structured positive current collector, which was further supported by the even better performance of the battery made from a smaller aperture size (2mm) reticulated SiC as the substrate of the positive electrode.

A superhigh discharge capacity induced by a synergetic effect between high-surface-area carbons and a carbon paper current collector in a lithium–oxygen battery

This paper invesitages the synergetic effect between high-surface-area carbons, such as Ketjan Black(KB) or Super P(SP) carbon materials, and low-surface-area carbon paper(CP) current collectors and it also examines their influence on the discharge performance of nonaqueous Li–O2cells. Ultra-large specific discharge capacities are found in the KB/CP cathodes, which are much greater than those observed in the individual KB or CP cathodes. Detailed analysis indicates that such unexpectedly large capacities result from the synergetic effect between the two components. During the initial discharges of KB or SP materials, a large number of superoxide radical(O·-2) species in the electrolytes and Li2O2 nuclei at the CP surfaces are formed, which activate the CP current collectors to contribute considerable capacities. These results imply that CP could be a superior material for current collectors in terms of its contribution to the overall discharge capacity.On the other hand, we should be careful to calculate the specific capacities of the oxygen cathodes when using CP as a current collector; i.e., ignoring the contribution from the CP may cause overstated discharge capacities.

Constructing nanoporous Ni foam current collectors for stable lithium metal anodes

Lithium metal,as the most ideal anode material for high energy density batteries,has been researched for several decades.However,the dendrite formation and large volume change during repetitive lithium plating/stripping lead to a serious safety issue and impede the practical application of lithium metal anode.Herein,a nanoporous Ni foam current collector with high surface area and surface flaws is constructed via a facile oxidation-reduction method.The inherent macropore structure of Ni foam can partly accommodate the volume variation during Li plating/stripping.The well-distributed nanopores on the skeleton of Ni foam can effectively reduce the local current density,regulate the uniform lithium nucleation and deposition with homogenous distribution of Li^(+) flux.Moreover,the surface flaws induce the formation of ring Li structures at initial nucleation/deposition processes and concave Li metal spontaneously formed based on the ring Li structures during cycling,which can direct the even Li plating/stripping.Therefore,highly stable Coulombic efficiency is achieved at 1 mA cm^(-2) for 200 cycles.The symmetrical cell,based on the nanoporous Ni foam current collector,presents long lifespans of 1200 and 700 h respectively at different current densities of 0.5 and 1 mA cm^(-2) without short circuit.In addition,the LiFePO4 full cell,with the Li metal anode based on the nanoporous Ni foam current collector,shows excellent cycling performance at 1 C for 300 cycles and rate performance.

Powder metallurgical 3D nickel current collectors with plasma-induced Ni3N nanocoatings enabling long-life and dendrite-free lithium metal anode

Building three-dimensional(3D) current collectors is a promising strategy to surmount the bottlenecks of lithium metal anodes(LMAs), but the regulation methodology of a 3D current collector has seldom been considered comprehensively concerning both skeleton architectures and surface coatings. Herein, a robust porous 3D nickel skeleton(NS) with lithiophilic NiN nanocoatings(NiN@NS) is synthesized via an integrative route of powder metallurgy/plasma-enhanced nitridation technics. The facile powder metallurgical method facilitates the adjustment of NS architectures toward sufficient electrolyte adsorption and even current density distribution, while the followed plasma-enhanced chemical vapor deposition(PECVD) method can induce compact NiN nanocoatings on NS, which reduces the Li nucleation overpotential, accelerates the Li-ion transfer, and facilitates a highly reversible oriented texture of Li deposition morphology owing to the dense and homogenous deposition of Li into the pores. The optimized NiN@NS current collector shows a high averaged Coulombic efficiency(CE) of 98.8% over 350cycles, a prolonged lifespan of 1000 h(at 2 mA cm^(-2)) in symmetrical cells, together with the significant performance in full cells. The ingenious methodology reported in this work can also be broadly applicable for the controllable production of other 3D skeletons with nitride nanocoatings for various applications.

Copper-coated Porous Polyimide as Ultralight and Safe Current Collectors for Advanced LIBs

Metallic copper is widely used as current collector(CC) for graphite anode of lithium-ion batteries(LIBs) due to its high electrical conductivity and electrochemical stability. However, the large volume density of commercial copper foil(~8.9 g·cm^(-3)) limits the increase of energy density of battery. Here, copper-coated porous polyimide(Cu@PPI) was prepared by vacuum evaporation as collector for the graphite anode. The sandwich structure connects the copper metal on both sides of the collector with excellent electrical conductivity. Compared to commercial Cu foil, Cu@PPI has lighter mass(≤3.9 mg for disc of 12 mm diameter versus 9.9 mg of ~10 μm Cu foil) and lower volume density(≤3.3 g·cm^(-3)). In addition, the porous structure allows of better adhesion of reactive substances and electrochemical properties than pure Cu foils. It is estimated that the energy density of Cu@PPI should be much higher than that of Cu foil. This strategy should be applicable for other current collectors.

Porous current collector enables carbon superior electrochemical performance for K-ion capacitors

The current collector is an indispensable component in potassium-ion hybrid capacitors,which not only provides mechanical support to load electrode materials,but also collects and outputs the current generated.Herein,we investigate the effect of three different current collectors on the electrochemical properties of potassium ion capacitors using carbon black anode as a demonstration.Because of better adhesion and lower charge transfer resistance,the specific capacity of half-cells assembled using three-dimensional(3D)porous copper foil(PCu)and copper as current collector is better than that of Al foil,which stabilizes at 138.2 and 132.8 mAh·g^(-1)after 100 cycles at 0.05 A·g^(-1).The potassium-ion capacitor assembled using PCu exhibits an excellent energy/power density of 86.1 Wh·kg^(-1)and 4000 W·kg^(-1),respectively.This work will boost the rational design and provide an effective strategy to improve the performance of potassium-ion capacitors.

Present and future of functionalized Cu current collectors for stabilizing lithium metal anodes

Li metal has been recognized as the most promising anode materials for next-generation high-energy-density batteries,however,the inherent issues of dendrite growth and huge volume fluctuations upon Li plating/stripping normally result in fast capacity fading and safety concerns.Functionalized Cu current collectors have so far exhibited significant regulatory effects on stabilizing Li metal anodes(LMAs),and hold a great practical potential owing to their easy fabrication,low-cost and good compatibility with the existing battery technology.In this review,a comprehensive overview of Cu-based current collectors,including planar modified Cu foil,3D architectured Cu foil and nanostructured 3D Cu substrates,for Li metal batteries is provided.Particularly,the design principles and strategies of functionalized Cu current collectors associated with their functionalities in optimizing Li plating/stripping behaviors are discussed.Finally,the critical issues where there is incomplete understanding and the future research directions of Cu current collectors in practical LMAs are also prospected.This review may shed light on the critical understanding of current collector engineering for high-energy-density Li metal batteries.

Current collectors based on multiwalled carbon-nanotubes and fewlayer graphene for enhancing the conversion process in scalable lithium-sulfur battery

We investigated herein the morphological,structural,and electrochemical features of electrodes using a sulfur(S)-super P carbon(SPC)composite(i.e.,S@SPC-73),and including few-layer graphene(FLG),multiwalled carbon nanotubes(MWCNTs),or a mixture of them within the current collector design.Furthermore,we studied the effect of two different electron-conducting agents,that is,SPC and FLG,used in the slurry for the electrode preparation.The supports have high structural crystallinity,while their morphologies are dependent on the type of material used.Cyclic voltammetry(CV)shows a reversible and stable conversion reaction between Li and S with an activation process upon the first cycle leading to the decrease of cell polarization.This activation process is verified by electrochemical impedance spectroscopy(EIS)with a decrease of the resistance after the first CV scan.Furthermore,CV at increasing scan rates indicates a Li+diffusion coefficient(D)ranging between 10^(−9) and 10^(−7) cm^(2)·s^(−1)in the various states of charge of the cell,and the highest D value for the electrodes using FLG as electron-conducting agent.Galvanostatic tests performed at constant current of C/5(1 C=1675 mA·g_(s)^(−1))show high initial specific capacity values,which decrease during the initial cycles due to a partial loss of the active material,and subsequently increase due to the activation process.All the electrodes show a Coulombic efficiency higher than 97%upon the initial cycles,and a retention strongly dependent on the electrode formulation.Therefore,this study suggests a careful control of the electrode in terms of current collector design and slurry composition to achieve good electrode morphology,mechanical stability,and promising electrochemical performance in practical Li-S cells.