Electrochemical capacitors operating in an aqueous electrolyte solution have become ever-more popular in recent years, mainly because they are cheap and ecofriendly. Additionally, aqueous electrolytes have a higher ionic conductivity than organic electrolytes and ionic liquids. These materials can exist in the form of a liquid or a solid (hydrogel). The latter form is a very promising alternative to liquid electrolytes because it is solid, which prevents electrolyte leakage. In our work, hydrogel polymer electrolytes (HPEs) were obtained via photopolymerization of a mixture of acrylic oligomer Exothane 108 with methacrylic acid (MAA) in ethanol, which was later replaced by electrolytes (1 M Na2SO4). Through the conducted research, the effects of the monomers ratio and the organic solvent concentration (ethanol) on the mechanical properties (tensile test), electrolyte sorption, and ionic conductivity were examined. Finally, hydrogel polymer electrolytes with high ionic conductivity (σ = 26.5 mS∙cm-1) and sufficient mechanical stability (σmax = 0.25 MPa, εmax = 20%) were tested using an AC/AC electrochemical double layer capacitor (EDLC). The electrochemical properties of the devices were investigated via cyclic voltammetry, galvanostatic charge/discharge, and impedance spectroscopy. The obtained results show the application potential of the obtained HPE in EDLC.

The trend of research towards more sustainable materials is pushing the application of biopolymers in a variety of unexplored fields. In this regard, hydrogels are attracting significant attention as electrolytes for flexible electrochemical devices thanks to their combination of ionic conductivity and mechanical properties. In this context, we present the use of cellulose-based hydrogels as aqueous electrolytes for electrochemical devices. These materials were obtained by crosslinking of hydroxyethyl cellulose (HEC) with divinyl sulfone (DVS) in the presence of carboxymethyl cellulose (CMC), creating a semi-IPN structure. The reaction was confirmed by NMR and FTIR. The small-amplitude oscillatory shear (SAOS) technique revealed that the rheological properties could be conveniently varied by simply changing the gel composition. Additionally, the hydrogels presented high ionic conductivity in the range of mS cm-1. The ease of synthesis and processing of the hydrogels allowed the assembly of an all-in-one electrochromic device (ECD) with high transmittance variation, improved switching time and good color efficiency. On the other hand, the swelling ability of the hydrogels permits the tuning of the electrolyte to improve the performance of a printed Zinc/MnO2 primary battery. The results prove the potential of cellulose-based hydrogels as electrolytes for more sustainable electrochemical devices.

Rechargeable aqueous zinc ion batteries (ZIBs) are considered as one of the most promising systems for large-scale energy storage due to their merits of low cost, environmental friendliness, and high safety. The utilization of aqueous electrolyte also brings about some problems such as low energy density, fast self-discharge, and capacity fading associated with the dissolution of metals in water. To combat the issues, we utilize a freestanding vanadium oxide hydrate/carbon nanotube (V2O5·nH2O/CNT) film as the cathode and probe the performance in aqueous/organic hybrid electrolytes. The corresponding structural and morphological evolution of both V2O5·nH2O/CNT cathode and Zn anode in different electrolytes is explored. The integrity of electrodes and the suppression of zinc dendrites during cycles are largely improved in the hybrid electrolytes. Accordingly, the battery in hybrid electrolyte exhibits high capacities of 549 mAh g-1 at 0.5 A g-1 after 100 cycles and 282 mAh g-1 at 4 A g-1 after 1000 cycles, demonstrating an excellent energy density of 102 Wh kg-1 at a high power of 1500 W kg-1 based on the cathode.

The most investigated conducting polymer (CP) is polyaniline (PANI)), a promising polymer due to its excellent environmental stability, simplicity of synthesis, and high electrical conductivity [1], [2], [3], [4]. In corrosion protection applications, the PANI film has shown promising potential in protecting active metals such as iron by acting as physical barrier coatings, as a primer layer and as component in a multi-layer coating system [5]. The PANI has an excellent potential to replace the toxic metal, such as chromates, in corrosion protection and is considered a green anti-corrosion candidate [5], [6], [7]. The electrochemical synthesis of PANI coatings on active metals is accomplished by the dissolution of the metal at a potential lower than the monomer oxidation potential [8], [9]. Therefore, electrochemical synthesis of PANI coatings on active metal requires a proper choice of the electrolyte and solvent that should strongly passivate the metal without hindering the electropolymerization process [10], [11]. The data reported here are obtained while the anodic polarization of mild steel (MS) is carried out in succinic acid, sulphanilic acid, sodium orthophosphate, sodium potassium tartrate (Na-K tartrate), and benzoic acid in 3:1 alcohol-water (BAW) solutions [11]. However, the results of electrolytes sodium-potassium tartrate (Na-K tartrate) and benzoic acid in alcohol-water (BAW) are reported for the polymerization of aniline onto MS [11]. The SEM image of MS sample polarized in 0.3 M oxalic acid solution and 0.1 M aniline in 0.3 M oxalic acid is reported as a dataset or a supplementary material of the main manuscript 'The Effect of Electrolytes on the Coating of Polyaniline on Mild Steel by Electrochemical Methods and Its Corrosion Behaviour [11].'

Aqueous rechargeable batteries based on aluminum chemistry have become the focus of immense research interest owing to their earth abundance, low cost, and the higher theoretical volumetric energy density of this element compared to lithium-ion batteries. Efforts to harness this huge potential have been hindered by the narrow potential window of water and by passivating effects of the high-electrical band-gap aluminum oxide film. Herein, we report a high-performing aqueous aluminum-ion battery (AIB), which is constructed using a Zn-supported Al alloy, an aluminum bis(trifluoromethanesulfonyl)imide (Al[TFSI]3) electrolyte, and a MnO2 cathode. The use of Al[TFSI]3 significantly extends the voltage window of the electrolyte and enables the cell to access Al3+/Al electrochemistry, while the use of Zn-Al alloy mitigates the issue of surface passivation. The Zn-Al alloy, which is produced by in situ electrochemical deposition, obtained from Al[TFSI]3 showed excellent long-term reversibility for Al electrochemistry and displays the highest performance in AIB when compared to the response obtained in Al2(SO4)3 or aluminum trifluoromethanesulfonate electrolyte. AIB cells constructed using the Zn-Al|Al[TFSI]3|MnO2 combination achieved a record discharge voltage plateau of 1.75 V and a specific capacity of 450 mAh g-1 without significant capacity fade after 400 cycles. These findings will promote the development of energy-dense aqueous AIBs.

Solid electrolyte is the key component in all-solid-state batteries (ASBs). It is required in electrodes to enhance Li-conductivity and can be directly used as a separator. With its high Li-conductivity and chemical stability towards metallic lithium, lithium-stuffed garnet material Li7La3Zr2O12 (LLZO) is considered one of the most promising solid electrolyte materials for high-energy ceramic ASBs. However, in order to obtain high conductivities, rare-earth elements such as tantalum or niobium are used to stabilize the highly conductive cubic phase. This stabilization can also be obtained via high levels of aluminum, reducing the cost of LLZO but also reducing processability and the Li-conductivity. To find the sweet spot for a potential market introduction of garnet-based solid-state batteries, scalable and industrially usable syntheses of LLZO with high processability and good conductivity are indispensable. In this study, four different synthesis methods (solid-state reaction (SSR), solution-assisted solid-state reaction (SASSR), co-precipitation (CP), and spray-drying (SD)) were used and compared for the synthesis of aluminum-substituted LLZO (Al:LLZO, Li6.4Al0.2La3Zr2O12), focusing on electrochemical performance on the one hand and scalability and environmental footprint on the other hand. The synthesis was successful via all four methods, resulting in a Li-ion conductivity of 2.0-3.3 × 10-4 S/cm. By using wet-chemical synthesis methods, the calcination time could be reduced from two calcination steps for 20 h at 850 °C and 1000 °C to only 1 h at 1000 °C for the spray-drying method. We were able to scale the synthesis up to a kg-scale and show the potential of the different synthesis methods for mass production.

Studies have shown that some electrolytes, including Na+ and K+, play important roles in embryonic development. However, these studies evaluated these electrolytes by using inhibitors or knockout mice, with no mention on the changes in the intracellular electrolyte concentrations during embryogenesis. In this study, we used the electrolyte indicators CoroNa Green AM and ION Potassium Green-2 AM to directly visualise intracellular concentrations of Na+ and K+, respectively, at each embryonic developmental stage in mouse embryos. We directly observed intracellular electrolyte concentrations at the morula, blastocyst, and hatching stages. Our results revealed dynamic changes in intracellular electrolyte concentrations; we found that the intracellular Na+ concentration decreased, while K+ concentration increased during blastocoel formation. The degree of change in intensity in response to ouabain, an inhibitor of Na+/K+ ATPase, was considered to correspond to the degree of Na+/K+ ATPase activity at each developmental stage. Additionally, after the blastocyst stage, trophectoderm cells in direct contact with the blastocoel showed higher K+ concentrations than in direct contact with inner cell mass, indicating that Na+/K+ ATPase activity differs depending on the location in the trophectoderm. This is the first study to use CoroNa Green AM and ION Potassium Green-2 AM in mouse embryos and visualise electrolytes during embryonic development. The changes in electrolyte concentration observed in this study were consistent with the activity of Na+/K+ ATPase reported previously, and it was possible to image more detailed electrolyte behaviour in embryo cells. This method can be used to improve the understanding of cell physiology and is useful for future embryonic development studies.

Micro-sized silicon anodes can significantly increase the energy density of lithium-ion batteries with low cost. However, the large silicon volume changes during cycling cause cracks for both organic-inorganic interphases and silicon particles. The liquid electrolytes further penetrate the cracked silicon particles and reform the interphases, resulting in huge electrode swelling and quick capacity decay. Here we resolve these challenges by designing a high-voltage electrolyte that forms silicon-phobic interphases with weak bonding to lithium-silicon alloys. The designed electrolyte enables micro-sized silicon anodes (5 µm, 4.1 mAh cm-2) to achieve a Coulombic efficiency of 99.8% and capacity of 2175 mAh g-1 for >250 cycles and enable 100 mAh LiNi0.8Co0.15Al0.05O2 pouch full cells to deliver a high capacity of 172 mAh g-1 for 120 cycles with Coulombic efficiency of >99.9%. The high-voltage electrolytes that are capable of forming silicon-phobic interphases pave new ways for the commercialization of lithium-ion batteries using micro-sized silicon anodes.

Among post-lithium ion battery technologies, rechargeable chemistries with Zn anodes bear notable technological promise owing to their high theoretical energy density, lower manufacturing cost, availability of raw materials and inherent safety. However, Zn anodes, when employed in aqueous electrolytes, suffer from hydrogen evolution, passivation, and shape changes. Alternative electrolytes can help tackle these issues, preserving the green and safe characteristics of aqueous-based ones. Deep eutectic solvents (DESs) are promising green and low-cost non-aqueous solvents for battery electrolytes. Specifically, the cycling of Zn anodes in DESs is expected to be reversible, chiefly owing to their dendrite-suppression capability. Nevertheless, apart from a few studies on Zn plating, insight into the cathodic-anodic electrochemistry of Zn in DESs is still very limited. In view of developing DES-based battery electrolytes, it is crucial to consider that a potential drawback might be their low ionic conductivity. Water molecules can be added to the eutectic mixtures by up to 40% to increase the diffusion coefficient of the electroactive species and lower the electrolyte viscosity without destroying the eutectic nature. In this study, we address the electrochemistry of Zn in two different hydrated DESs (ChU and ChEG with ~30% H2O). Fundamental electrokinetic and electrocrystallization studies based on cyclic voltammetry and chronoamperometry at different cathodic substrates are completed with a galvanostatic cycling test of Zn|Zn symmetric CR2032 coin cells, SEM imaging of electrodes and in situ SERS spectroscopy. This investigation concludes with the proposal of a specific DES/H2O/ZnSO4-based electrolyte that exhibits optimal functional performance, rationalized on the basis of fundamental electrochemical data, morphology evaluation and modeling of the cycling response.

Aqueous dye-sensitized solar cells (DSSCs) have recently emerged as promising systems, which can combine low cost and environmental compatibility with appreciable efficiency, long-term durability and enhanced safety. In the present study, we thoroughly investigate the chemistry behind the iodide/triiodide-based redox mediator, which presents - in a completely aqueous environment - several differences when compared to the behavior observed in the conventionally used organic solvents. The speciation of ions, the effect of the concentration of the redox mediator and the type of counter-ion are characterized from the electrochemical, spectroscopic, photovoltaic and analytical viewpoints. Furthermore, we demonstrate that aqueous DSSCs, often assumed as unstable, hold the potential to assure unparalleled stability after five months of aging without any addition of stabilizers or gelling agents, thus envisaging the construction of eco-friendly photovoltaic devices free of expensive, flammable and toxic solvents.

Flexible hydrogels are attracting significant interest as solid-like electrolytes for energy storage devices, especially for supercapacitors, because of their lightweight and anti-deformation features. Here, we present a comparative study of four ionic conductive hydrogels derived from biopolymers and doped with 0.1 M NaCl. More specifically, such hydrogels are constituted by κ-carrageenan (κC), carboxymethyl cellulose (CMC), poly-γ-glutamic acid (PGGA) or a phenylalanine-containing polyesteramide (PEA). After examining the morphology and the swelling ratio of the four hydrogels, which varies between 483% and 2356%, their electrical and capacitive behaviors were examined using electrochemical impedance spectroscopy. Measurements were conducted on devices where a hydrogel film was sandwiched between two identical poly(3,4-ethylenedioxythiophene) electrodes. The bulk conductivity of the prepared doped hydrogels is 76, 48, 36 and 34 mS/cm for PEA, PGGA, κC and CMC, respectively. Overall, the polyesteramide hydrogel exhibits the most adequate properties (i.e., low electrical resistance and high capacitance) to be used as semi-solid electrolyte for supercapacitors, which has been attributed to its distinctive structure based on the homogeneous and abundant distribution of both micro- and nanopores. Indeed, the morphology of the polyestermide hydrogel reduces the hydrogel resistance, enhances the transport of ions, and results in a better interfacial contact between the electrodes and solid electrolyte. The correlation between the supercapacitor performance and the hydrogel porous morphology is presented as an important design feature for the next generation of light and flexible energy storage devices for wearable electronics.

As essential components of ionic polymer electrolytes (IPEs), ionic liquids (ILs) with high ionic conductivity and wide electrochemical window are promising candidates to enable safe and high-energy-density lithium metal batteries (LMBs). Here, we describe a machine learning workflow embedded with quantum calculation and graph convolutional neural network to discover potential ILs for IPEs. By selecting subsets of the recommended ILs, combining with a rigid-rod polyelectrolyte and a lithium salt, we develop a series of thin (~50 μm) and robust (>200 MPa) IPE membranes. The Li|IPEs|Li cells exhibit ultrahigh critical-current-density (6 mA cm-2) at 80 °C. The Li|IPEs|LiFePO4 (10.3 mg cm-2) cells deliver outstanding capacity retention in 350 cycles (>96% at 0.5C; >80% at 2C), fast charge/discharge capability (146 mAh g-1 at 3C) and excellent efficiency (>99.92%). This performance is rarely reported by other single-layer polymer electrolytes without any flammable organics for LMBs.

Next-generation Li-ion batteries must guarantee improved durability, quality, reliability, and safety to satisfy the stringent technical requirements of crucial sectors such as e-mobility. One breakthrough strategy to overcome the degradation phenomena affecting the battery performance is the development of advanced materials integrating smart functionalities, such as self-healing units. Herein, we propose a gel electrolyte based on a uniform and highly cross-linked network, hosting a high amount of liquid electrolyte, with multiple advantages: (i) autonomous, fast self-healing, and a promising PF5-scavenging role; (ii) solid-like mechanical stability despite the large fraction of entrapped liquid; and (iii) good Li+ transport. It is shown that such a gel electrolyte has very good conductivity (>1.0 mS cm-1 at 40 °C) with low activation energy (0.25 eV) for the ion transport. The transport properties are easily restored in the case of physical damages, thanks to the outstanding capability of the polymer to intrinsically repair severe cracks or fractures. The good elastic modulus of the cross-linked network, combined with the high fraction of anions immobilized within the polymer backbone, guarantees stable Li electrodeposition, disfavoring the formation of mossy dendrites with the Li metal anode. We demonstrate the electrolyte performance in a full-cell configuration with a LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode, obtaining good cycling performance and stability.

Efforts to lower the operating temperature of solid oxide fuel cells include producing electrolytes that are sufficiently conductive and stable below 600 °C. Doped ceria is one such electrolyte being considered. During this study, codoped ceria powders (Ce0.8Sm0.2-xMxO2-δ, M = Bi3+, Zn2+ and x = 0, 0.05, 0.1, 0.15, 0.2) were prepared via coprecipitation by the addition of sodium carbonate and annealed at 800 and 1200 °C, respectively. Poor solubility of the codopants in the ceria was observed for samples annealed at 800 °C, resulting in a mixed-phase product including stable phases of the oxides of these codopants. A second-stage partial incorporation of these codopants into the ceria lattice was observed when the annealing temperature was increased to 1200 °C, with both codopants forming cubic-type phases of their respective oxides. Materials were characterized using X-ray diffraction (XRD), Raman spectroscopy, and Fourier transform infrared spectroscopy (FTIR), as well as scanning electron microscopy (SEM) for structural and morphological investigations. The oxide ion conductivity was evaluated using electrochemical impedance spectroscopy between 550 and 750 °C. Fuel cell performance tests of selected samples (annealed at 1200 °C) showed remarkable improvement in peak power densities when the test temperature was increased from 500 to 600 °C (∼720 mW/cm2 for Ce0.8Sm0.15Bi0.05O2-δ and ∼1230 mW/cm2 for Ce0.8Sm0.15Zn0.05O2-δ), indicating possible contribution from the distinct cubic-type oxide phases of the codopants in performance enhancement.

This study is focused on the structural influence of 1,2,4-triazolium ionic liquid (IL), that is, the effect of the length of the substituent and the type of substitution (1-methyl-4-alkyl or 1-alkyl-4-methyl) used in the mixture with propylene carbonate (PC) on the properties of thiol-ene polymer ionogels and on the preparation of an ionogel with satisfactory mechanical and conductive properties. PC allows for higher conductivity but also causes electrolyte leakage from the gel. When using triazolium IL (instead of the imidazolium one), because of the stronger interactions between components of the system, the ionogels do not leak. In this study, 1,4-dialkyl-1,2,4-triazolium ILs were successfully synthesized by the alkylation of 1,2,4-triazole. Subsequently, gel polymer electrolytes were obtained by one-pot thiol-ene photopolymerization reactions of tetrafunctional thiols with different chemical structures: pentaerythritol tetra(3-mercaptopropionate) (PETMP) or pentaerythritol tetra(3-mercaptobutyrate) (PETMB) and trifunctional ene (TATT) in the presence of a mixture of 1,4-dialkyl-1,2,4-triazolium IL with PC. Measurements made by electrochemical impedance spectroscopy showed that all ionogels with TATT+PETMB as a polymer matrix presented smaller relative ionic conductivity compared to ionogels containing TATT+PETMP. The puncture resistance and elongation at puncture, measured by the puncture resistance method, were higher for ionogels with poly(TATT+PETMB) than for those with poly(TATT+PETMP). Moreover, ILs containing a methyl group in position N1 of the 1,2,4-triazole ring presented lower puncture resistance than ionogels with ILs containing a methyl group in position N4, especially for shorter alkyl chains. Additionally, the photo-differential scanning calorimetry method was employed to characterize the course of photopolymerization. The compositions and their constituents were characterized by UV and IR spectroscopy.

Various electrolytes have been reported to enhance the reversibility of Li-metal electrodes. However, for these electrolytes, concurrent and balanced control of Li-metal and positive electrode interfaces is a critical step toward fabrication of high-performance Li-metal batteries. Here, we report the tuning of Li-metal and lithium cobalt oxide (LCO) interfaces with fluoroethylene carbonate (FEC)-containing electrolytes to achieve high cycling stability of Li/LCO batteries. Reversibility of the Li-metal electrode is considerably enhanced for electrolytes with high FEC contents, confirming the positive effect of FEC on the stabilization of the Li-metal electrode. However, for FEC contents of 50 wt % and above, the discharge capacity is significantly reduced because of the formation of a passivation layer on the LCO cathodes. Using balanced tuning of the two interfaces, stable cycling over 350 cycles at 1.5 mA cm-2 is achieved for a Li/LCO cell with the 1 M LiPF6 FEC/DEC = 30/70 electrolyte. The enhanced reversibility of the Li-metal electrode is associated with the formation of LiF and polycarbonate in the FEC-derived solid electrolyte interface (SEI) layer. In addition, electrolytes with high FEC contents lead to lateral Li deposition on the sides of Li deposits and larger dimensions of rodlike Li deposits, suggesting the elastic and ion-conductive nature of the FEC-derived SEI layer.

Aqueous lithium-ion batteries are promising electrochemical energy storage devices owing to their sustainable nature, low cost, high level of safety, and environmental benignity. The recent development of a high-salt-concentration strategy for aqueous electrolytes, which significantly expands their electrochemical potential window, has created attractive opportunities to explore high-performance electrode materials for aqueous lithium-ion batteries. This study evaluates the compatibility of large-capacity oxygen-redox cathodes with hydrate-melt electrolytes. Using conventional oxygen-redox cathode materials (Li2 RuO3 , Li1.2 Ni0.13 Co0.13 Mn0.54 O2 , and Li1.2 Ni0.2 Mn0.6 O2 ), it is determined that avoiding the use of transition metals with high catalytic activity for the oxygen evolution reaction is the key to ensuring the stable progress of the oxygen redox reaction in concentrated aqueous electrolytes.

Pertinent to cryopreservation as well as energy storage and batteries, nonaqueous electrolytes and their mixtures with water were investigated. In particular, specific ion-induced effects on the modulation of a poly(N-isopropylacrylamide) (PNIPAM) brush were investigated in various dimethyl sulfoxide (DMSO)-water solvent mixtures. Spectroscopic ellipsometry and neutron reflectometry were employed to probe changes in brush swelling and structure, respectively. In water-rich solvents (i.e., pure water and 6 mol % DMSO), PNIPAM undergoes a swollen to collapsed thermotransition with increasing temperature, whereby a forward Hofmeister series was noted; K+ and Li+ electrolytes composed of SCN- and I- salted-in (stabilized) PNIPAM chains, and electrolytes of Cl- and Br- salted-out (destabilized) the polymer. The cation was seen to play a lesser role than that of the anion, merely modulating the magnitude of the anion effect. In 70 mol % DMSO, a collapsed to swollen thermotransition was noted for PNIPAM. Here, concentration-dependent specific ion effects were observed; a forward series was observed in 0.2 mol % electrolytes, whereas increasing the electrolyte concentration to 0.9 mol % led to a series reversal. While no thermotransition was observed in pure DMSO, a solvent-induced specific ion series reversal was noted; SCN- destabilized the brush and Cl- stabilized the brush. Both series reversals are attributed to the delicate balance of interactions between the solvent, solute (ion), and substrate (brush). Namely, the stability of the solvent clusters was hypothesized to drive polymer solvation.

In this work, CMC-AFT biopolymer electrolytes system was developed using Carboxymethyl cellulose (CMC) doped with varied amount (10-50 wt.%) of ammonium formate (AFT) in order to study the effect of AFT on the biopolymer-salt system. The chemical structure of the biopolymer was studied using Fourier-Transform infrared (FTIR) and X-ray diffraction (XRD). The interaction between the COO- of CMC and the weakly-bound H+ of NH4+ AFT occurred at 1573 cm-1 as seen in FTIR analysis and the amorphous phase was found to increase with the addition of AFT as seen from XRD pattern. Both FTIR and XRD testing indicates that the AFT had disrupted the CMC crystalline structure. The ionic conductivity of the CMC-AFT biopolymer electrolytes increases and achieved the highest value of 1.47 × 10-4 S·cm-1 with the addition of AFT. The impedance measurement showed that the capacitive and resistive behavior inside the biopolymer diminished when 50 wt.% of AFT was added. Dielectric analysis confirmed the increased number of charge carriers is due to the increase in AFT composition. Further dielectric analysis showed the occurrence of conductivity relaxation peak thus affirmed the charge carriers' ability to travel further to a longer distances when AFT composition increases from 10 to 50 wt.%. The dielectric properties confirmed the non-Debye behavior of the CMC-AFT biopolymer electrolytes.

The life span of lithium batteries as energy storage devices is plagued by irreversible interfacial reactions between reactive anodes and electrolytes. Occurring on polycrystal surface, the reaction process is inevitably affected by the surface microstructure of anodes, of which the understanding is imperative but rarely touched. Here, the effect of grain boundary of lithium metal anodes on the reactions was investigated. The reactions preferentially occur at the grain boundary, resulting in intercrystalline reactions. An aluminum (Al)-based heteroatom-concentrated grain boundary (Al-HCGB), where Al atoms concentrate at grain boundary, was designed to inhibit the intercrystalline reactions. In particular, the scalable preparation of Al-HCGB was demonstrated, with which the cycling performance of a pouch cell (355 Wh kg-1) was significantly improved. This work opens a new avenue to explore the effect of the surface microstructure of anodes on the interfacial reaction process and provides an effective strategy to inhibit reactions between anodes and electrolytes for long-life-span practical lithium batteries.