Self-assembled polyelectrolytes with ion-sieving accelerating channels for highly stable Zn-ion batteries

Self-assembled polyelectrolytes with ion-sieving accelerating channels for highly stable Zn-ion batteries | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Self-assembled polyelectrolytes with ion-sieving accelerating channels for highly stable Zn-ion batteries Guanjie He, Xueying Hu, Haobo Dong, Tianlei Wang, Hongzhen He, and 6 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4496958/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 08 Mar, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract Aqueous zinc-ion batteries (AZIBs) are increasingly recognized as a sustainable alternative to lithium-ion batteries (LIBs) due to their abundance, safety, and lower environmental impact. However, the hydrogen evolution reaction (HER) and uncontrolled diffusion of Zn 2+ and SO 4 2- ions lead to the dendrite formation and side reactions, which hinder their practical application by forming a non-conductive layer on the Zn anode. This layer impedes the ion transport and electron flow, reducing the Coulombic efficiency (CE) for the Zn nucleation. Here, to simultaneously regulate the diffusion of H + , Zn 2+ , and SO 4 2- in the electrolyte, an ion-sieving accelerating channel was constructed to unify the Zn deposition by introducing an eco-friendly layer-by-layer self-assembly of a flocculant poly(allylamine hydrochloride) (PAH) and its tautomer poly(acrylic acid) (PAA). The dual-ion channels, created by strong electrostatic interactions between carboxylate anions (COO⁻) and ammonia cations (NH₃⁺), promote the uniform Zn deposition along the (002) plane, exhibiting a CE of 99.8% after 1600 cycles in the Zn||Cu asymmetric cell. With the facile fabrication of the layer-by-layer self-assembled Zn anode, an Ah-level pouch cell (17.36 Ah) with a high mass loading (> 8 mg cm⁻²) demonstrated exceptional performance, retaining a capacity of 93.6% for at least 250 cycles at 1.7 C. This research offers a universal strategy for optimizing electrode mechanisms and advancing the manufacturing process of eco-friendly, high-performance aqueous batteries. Physical sciences/Energy science and technology/Energy storage/Batteries Physical sciences/Chemistry/Energy Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction Aqueous zinc-ion batteries (AZIBs) are regarded as one of the most promising alternatives to lithium-ion batteries for the grid-scale electrochemical energy storage (EES) systems due to their high volumetric capacity (5855 mAh cm − 3 ), low redox potential (-0.762 V vs standard hydrogen electrode (SHE)), and high safety. 1,2 However, the hydrogen evolution reaction (HER) leads to a rapid rise in the local concentration of OH − at the anode/electrolyte interface, which would further react with SO 4 2− in the electrolyte to form the by-product (Zn 4 SO 4 (OH) 6 ⋅xH 2 O, ZHS). 3 Moreover, the generation of the inert by-product would reduce the active sites for Zn deposition, increase the nucleation barrier, and cause uncontrollable dendrite growth on the Zn anode. This results in the shortened cycle life and has hindered the commercial application of ZIBs. 4 Surface modification using inorganic and organic coatings could effectively inhibit the dendrite growth and side reactions at the Zn anode. 5 Inorganic coatings including carbon-based materials, eutectic alloys, and metallic compounds (e.g., carbon dots (CDs), 6 Zn-Cu, 7 Zn-Sn, 8 CaCO 3 , 9 ZnF 2 10 ) could be used as physical barriers to protect the Zn anode from corrosion and regulate Zn 2+ diffusion to achieve uniform Zn deposition. However, the non-uniform physical barriers lead to a low Zn 2+ conductivity and a significant volume change during plating/stripping, ultimately causing the cracking and peeling. In contrast, the flexible organic polyelectrolyte coatings such as polyamide, 11 polyacrylamides, 12 and poly(2-vinylpyridine) 13 with 3D cross-linked polymer channels can provide active sites to facilitate Zn 2+ transference and reduce the interface resistance. 14 But the mono polyelectrolyte interface could not satisfactorily control the ion diffusion and offer a sufficient mechanical strength. For instance, although anionic polyelectrolytes could effectively regulate Zn 2+ flux to homogenous deposition, it has a limited repelling effect on SO 4 2− in the electrolyte, which would cause the by-products formation to a certain extent. 15,16 Owing to the repulsion between anionic polyelectrolytes and the negative charged Zn anode, the adhesivity of the coatings is also not satisfactory. Based on this, the layer-by-layer (LbL) self-assembly of polyelectrolytes with the controllable composition and tunable properties, which allows sequential deposition of versatile polycations and polyanions on a charged substrate, is an attractive approach to enhance the overall performance of Zn anodes 17–19 . The strong electrostatic interactions between polycations and polyanions could provide oppositely charged dual-ion channels to suppress the corrosion and passivation on the Zn anode, while also enhancing the mechanical strength (e.g., toughness, adhesion, self-healing). 20–22 In addition, as summarized in Scheme 1a , the LbL self-assembly technique has outstanding advantages compared with other conventional surface modification techniques in the commercialization of AZIBs. The resource of polycations and polyanions with the characteristics of non-toxic, biocompatible, and biodegradable for the LbL self-assembled SEI layer are extremely abundant, which is not only conductive to the preparation of novel multifunctional SEI layers through the modification of polyelectrolytes, but also can promote the development of eco-friendly Zn-ion batteries. The LbL method also allows precise control of the thickness and composition of coatings, making it a sustainable method that is far superior to other surface modification techniques. 23,24 Moreover, the LbL self-assembly technique is more cost-effective for the practical application due to its simple manufacturing process and low demand on equipment. 25 However, to date, there have been limited studies on the use of LbL self-assembly technique for the interface engineering of Zn anodes. Identifying efficient and appropriate polyelectrolyte combinations for the LbL self-assembled layers remains a challenge, as is demonstrating their effectiveness in protecting Zn anodes and enhancing their applications. To overcome above mentioned challenges, we selected poly(allylamine hydrochloride) (PAH) and its tautomer poly(acrylic acid) (PAA) to prepare the LbL self-assembled PAH/PAA multilayers. Due to the tautomerization, the photon exchange would occur between the carboxylic acid group (-COOH) of PAA and the amine group (-RNH 2 ) of PAH, leading to the negatively charged carboxylate (-COO − ) and the positively charged ammonium (-RNH 3 + ) with the strong electrostatic interactions. 26 Based on this, the PAH/PAA multilayers could be seen as the dual-ion channels for SO 4 2− and Zn 2+ in the electrolyte, like an ionic sieve, the dual-ion channels sieve SO 4 2− at the first shell and attract Zn 2+ , which would regulate the mobility and dispersion of Zn 2+ and suppress the side reactions, thereby improving the electrochemical performance of the Zn anode. Moreover, the strong electrostatic interactions between PAH and PAA could effectively improve the mechanical strength without affecting the ionic conductivity of the coating, and also simplify the preparation process. 19,27 As illustrated in Scheme 1b , the preparation sequence of multilayers is to first coat the PAH layer and then the PAA layer (Anode − − PAH + − PAA − ), followed by a rinsing process after each coating to remove the weakly associated bound chains. Designing in the sequence: Anode − − PAH + − PAA − would enable a high adhesion to the negatively charged Zn anode and increase the zincophilicity of multilayers. PAA layer as the outer layer could first accelerate the desolvation process and regulate the diffusion of Zn 2+ . Meanwhile, PAH layer would capture SO 4 2− due to the low binding energy, resulting in the formation of ion-sieving accelerating channels to inhibit the HER and by-products. Remarkably, the LbL self-assembled PAH/PAA multilayers are favorable for the preferential nucleation and growth of Zn 2+ along Zn(002) surface to form a smooth and dense deposition layer and suppress the dendrite formation (Scheme 1c ). Correspondingly, the PAH/PAA multilayers enable an excellent Coulombic efficiency of up to 99.8% after 1,600 cycles at 0.5 mA cm − 2 and 0.25 mAh cm − 2 for the Zn||Cu asymmetric cell. The Zn||MnO 2 battery with the PAH/PAA coating layers displays an outstanding specific capacity of about 137 mAh g − 1 over 1,000 cycles with 91.3% capacity retention at 2 A g − 1 . Even in a Zn||VO 2 pouch cell with a high loading mass, it exhibits an excellent discharge capacity of 17.36 Ah over 250 cycles at 1.7 C. This work provides a new insight for the surface modification of Zn anodes, the design of the LbL self-assembly of polyelectrolytes could not only effectively enhance the electrochemical performances and mechanical strengths of Zn anode, but also could be applied to other metal anode protection. Results and discussion The LbL self-assembled PAH/PAA multilayers were prepared by the doctor-blading method. 28–30 By optimizing the preparation process, three double PAH/PAA layers (Zn@PAH/PAA) with a thickness of ~ 280 nm could offer the most stable electrochemical performances (Figure S1 and Figure S3). The composition of Zn@PAH/PAA was successfully confirmed by Fourier Transform Infrared (FTIR) spectroscopy, as shown in Figure S2. The bands at 1710 cm − 1 and 1247 cm − 1 are related to the C = O and C-O stretching vibration of carboxylic acid from the characterization bands of PAA, respectively. 31,32 The bending of amine and amide group from the characterization bands of PAH are about 1633 cm − 1 and 1532 cm − 1 . 32,33 Compared with the bands of pure Zn@PAA and Zn@PAH, the significant band shifts for Zn@PAH/PAA are observed, which are due to the electrostatic interactions between polyelectrolytes during the LbL self-assembly process. To investigate the effect of the LbL self-assembled PAH/PAA multilayers on the behavior of Zn 2+ plating/stripping, the thermostability and Zn 2+ transport kinetics of Zn anodes after coating were compared. The linear polarization curves indicate that the PAH/PAA multilayers could enhance the corrosion resistance of Zn anodes (Fig. 1 a). The corrosion potential of Zn@PAH/PAA is increased from − 0.1 V to -0.984 V, and the corrosion current is reduced to 1.109 mA, which is lower than that of the Bare Zn (2.99 mA). The higher corrosion potential and lower current mean more effective inhibition on the HER and by-products on Zn anodes. 34 To further verify the corrosion resistance of Zn@PAH/PAA, the HER on both Bare Zn and Zn@PAH/PAA electrodes within the initial 20 min at 30 mA cm − 2 was observed, which is shown in Figure S4. After 10 min, small bubbles generate and trend to accumulate on the Bare Zn electrodes. In contrast, no obvious bubbling appears on the Zn@PAH/PAA electrode. Moreover, the XRD pattern of Bare Zn after 50 cycles exhibits the strong diffraction peaks of the by-product (Zn 4 SO 4 (OH) 6 ⋅4H 2 O, ZHS), which was not detected on the cycled Zn@PAH/PAA electrode (Fig. 1 b). The results from SEM-EDS mapping in Figure S5 also show that there is large amount of ZHS on the Bare Zn electrode after 50 cycles, compared with the Zn@PAH/PAA electrode. These results indicate that the PAH/PAA multilayers could significantly suppress the HER and side reactions to enhance the thermostability of Zn anodes. In addition, ion-sieving accelerating channels could modulate interfacial kinetics of Zn 2+ diffusion and deposition. As shown in Figure S6, the PAH/PAA multilayers offer an excellent hydrophilicity, of which the contact angle (58.6°) is smaller than that of Bare Zn (99.9°). The hydrophilicity of Zn@PAH/PAA could enable a lower interfacial energy barrier to regulate the diffusion of Zn 2+ , which is demonstrated in the analysis of activation energy. 35 Based on the EIS plots at different temperatures (Figure S7), the interfacial activation energy ( E a ) was evaluated through the Arrhenius equation (Fig. 1 c). The hydrophilic PAH/PAA multilayers could reduce E a from 17.34 kJ mol − 1 to 6.85 kJ mol − 1 , indicating that the PAH/PAA layers with a high zincophilicity could effectively regulate the Zn 2+ solvation structure and accelerate the transference. The Zn transference numbers of Zn@PAH/PAA and Bare Zn were calculated and shown in Fig. 1 d and Figure S8, where the high ionic conductivity of PAH/PAA multilayers could increase the Zn transference number from 0.284 to 0.481. To investigate the nucleation and growth behaviors of Zn 2+ , the nucleation overpotential (η) on the Zn||Ti cell was evaluated (Fig. 1 e). According to previous research, 11,36 the critical nucleation radius (γ crit ) and nucleation rate (ω) could be described as below: $${\gamma }_{crit}=h\sigma A/2\rho F\eta$$ 1 $$\omega \propto \text{e}\text{x}\text{p}\left(\frac{-\pi LhA{\sigma }^{2}}{2\rho F\eta }\right)$$ 2 Where h is the height of Zn atom, \(\sigma\) is the interface tension, A is the Zn atom mass, \(\rho\) is the nucleus density, F is Faraday’s constant, and L is Avogadro constant. As illustrated in Fig. 1 e, η is increased by 12.1 mV with the PAH/PAA multilayers, and the ratio of γ crit for Zn@PAH/PAA and Bare Zn is 0.47, which is attributed to an increased nucleation rate. Hence, a high nucleation overpotential could be attributed to a uniform and dense Zn deposition. Moreover, the chronoamperometry (CA) test reflects that Zn 2+ exhibits a 2D diffusion behavior on Zn@PAH/PAA, compared with a 3D diffusion on the Bare Zn (Fig. 1 f). The current change with time indicates the increase of effective Zn nucleation sites in chronoamperograms. The current for Zn@PAH/PAA remains stable after 140 s, whereas due to the aggregation of Zn 2+ , the current for the Bare Zn continues to decrease within 400 s. Combined with the result of η, the PAH/PAA multilayers could regulate the Zn nucleation sites and make a uniform deposition to efficiently inhibit dendrite growth. Since PAH/PAA multilayers could enable the 2D diffusion and plating of Zn 2+ , the texture evolution and morphology of Zn anodes during cycling were further studied. XRD patterns of Zn@PAH/PAA under different cycles in Fig. 2 a and table S1 reveal that the (002) peak increases significantly after cycling. The intensity ratio I (002) /I (101) becomes stronger, which is from 0.0611 (pristine Zn) to 0.1995 (15 cycles), 0.2298 (30 cycles), and 0.2973 (50 cycles). Density functional theory (DFT) calculations were carried out to analyze the adsorption energy of Zn 2+ and PAH + /PAA − on Zn(002). PAH + /PAA − exhibits a stronger adsorption energy (-0.760 eV) than Zn 2+ (-0.145 eV) on Zn(002), which is shown in Fig. 2 b. Besides, the diffusion energy barrier of Zn 2+ with the PAH/PAA multilayers coated on Zn(002) increases from 0.014 eV to 0.269 eV, suggesting that Zn@PAH/PAA could inhibit the aggregation of Zn 2+ and lead to a 2D diffusion and parallel plating. 37 These above results indicate that the PAH/PAA multilayers could induce the preferential nucleation and growth of Zn 2+ along Zn(002). SEM images show that with the increase of cycles, more and more (002) textures are observed on the Zn@PAH/PAA electrode (Fig. 2 d). There are many horizontal (002) textures stacked together on the Zn@PAH/PAA after 50 cycles, where the thickness of the deposition layer is about 8 µm (Figure S9). In sharp contrast, the morphology of Bare Zn after 50 cycles is extremely uneven with significant dendrite growth corresponding to a deposition layer of around 11 µm (Figure S10). In-situ optical images and 3D depth profiles also verify that the PAH/PAA layers could guide a smooth and dense plating (Figure S11 and Figure S12). The aggregation and uneven nucleation of Zn 2+ on the Bare Zn electrode result in the dendrite formation and significantly roughens the surface after 5 min, while the surface of the Zn@PAH/PAA electrode remains smooth and homogenous for 20 min. A solid electrolyte interphase (SEI) layer with a thickness of about 19 nm for the 50 cycled Zn@PAH/PAA electrode was observed through TEM images, shown in Fig. 2 e. Further zooming in the SEI layer, the (002) textures are the main plating orientation in SEI layer, of which the area is significantly larger than that of the (100) textures. Therefore, it could be known that the ion-sieving accelerating channels formed by the LbL self-assembled PAH/PAA layers could induce the Zn nucleation and deposition along the (002) lattice plane to form a smooth and dense Zn flake layer. As the PAH/PAA multilayers could effectively enhance the thermostability and Zn 2+ transport kinetics to make the uniform Zn(002) deposition, the stability of Zn@PAH/PAA was discussed in relation to the symmetric Zn cell. The Zn@PAH/PAA electrode exhibits an excellent stability around 1200 h at 1 mA cm − 2 and 1 mAh cm − 2 , whereas the Bare Zn electrode suffers short circuit around 76 h (Fig. 3 a). With increasing the current and capacity densities to 5 mA cm − 2 and 5 mAh cm − 2 , the Zn@PAH/PAA electrode (340 h) still shows a longer cycling performance than the Bare Zn electrode (160 h), illustrated in Fig. 3 b. Furthermore, the Zn@PAH/PAA electrode presents a high depth of discharge (DOD): 53.4% within around 170 h cycling at 8 mA cm − 2 and 4 mAh cm − 2 (Fig. 3 c). As shown in Figure S13, the voltage profile for the Zn@PAH/PAA electrode at different current density and capacity exhibits a larger potential difference than that of the Bare Zn, which is due to the lower nucleation radius and higher nucleation rate of Zn@PAH/PAA as mentioned in Fig. 1 e. In addition, a large voltage difference of the Zn@PAH/PAA electrode may also be caused by the PAH/PAA layers inducing the orientational plating of Zn 2+ along Zn(002). Compared with the Bare Zn electrode, the rate performance of the Zn@PAH/PAA exhibits an outstanding Zn 2+ plating/stripping stability at various current densities from 1 mA cm − 2 to 10 mA cm − 2 at 1 mAh cm − 2 (Figure S14). These GCD tests indicate that the PAH/PAA multilayers enable an excellent stability and reversibility for the Zn anode. The Coulombic efficiency (CE) was analysed by the asymmetric Zn||Cu cell. As shown in Fig. 3 d and Fig. 3 e, the initial CE of Cu@PAH/PAA (92.3%) is higher than that of bare Cu (86.7%), and the Cu@PAH/PAA electrode offers an outstanding CE around 99.8% after 1,600 h, while the bare Cu electrode suffers a rapid decline on CE after about 70 cycles. The CE performance indicates that the PAH/PAA multilayers could efficiently inhibit the side reactions and passivation of Zn anodes. Hence, the initial nucleation overpotential of Cu@PAH/PAA increases from 0.0746 V to 0.0961 V, which once again approves that PAH/PAA layers could enable a lower nucleation radius and a higher nucleation rate, thereby inducing the deposition of the homogenous and dense Zn(002) layer. The cumulative plated capacity (CPC) of the Cu@PAH/PAA electrode is 396 mAh cm − 2 , which is more competitive than most of recent research on the surface modification of Zn anodes (Fig. 3 f and Table S2). To investigate the mechanism of Zn 2+ plating/stripping behaviours on Zn@PAH/PAA, in-situ Raman spectra were recorded during each cycle. As shown in Figure S15, the band assigned to the -CH 2 stretching vibration is at 2928 cm − 1 for Zn@PAH/PAA, while it is at about 2930 cm − 1 for Zn@PAH. 38 This difference is due to the electrostatic interactions between PAH and PAA polyelectrolytes as confirmed by FTIR. After immersing Zn@PAH/PAA to 2 M ZnSO 4 for 15 min, the -CH 2 stretching vibration band moves to 2931 cm − 1 , indicating the ionic interaction between -CH 2 -NH 3 + and SO 4 2− . Moreover, the band shape between 1400 cm − 1 and 1450 cm − 1 is related to the -RNH 3 + deformation and -CH 2 bending, by which the shape change further confirms the interaction between -CH 2 -NH 3 + and SO 4 2− . 39,40 The band from 1750 cm − 1 to 1600 cm − 1 for Zn@PAH/PAA corresponds to the vibration of symmetric C-H of PAH and C = O in carboxylate groups of PAA, while it splits into two bands after immersing with ZnSO 4 , owing to the ionic interaction between -COO − and Zn 2+ that enhances the intensity of C = O band. 41,42 The periodic band changes could be observed in each plating/stripping cycle, as illustrated in Fig. 4 a and Table S3. The ionic interaction between SO 4 2− and -CH 2 -NH 3 + would make the band of -CH 2 - vibration shift to a lower wavenumber during Zn 2+ plating and to a higher wavenumber during Zn 2+ stripping. Correspondingly, the relative band intensity of -CH 2 bending and NH 3 + deformation between 1400 cm − 1 and 1450 cm − 1 would change. Moreover, the coordination of Zn 2+ and -COO − would make the band of C = O vibration move to a lower wavenumber during plating, while the band would move to a higher wavenumber due to the escape of Zn 2+ during stripping. These regular and reversible band changes indicate the formation of dual-ion channels between PAH and PAA polyelectrolytes. The binding energy was calculated to further discuss the interfacial mechanism. As shown in Fig. 4 b, the binding energy of [PAA − − Zn(H 2 O) 4 ] + decreases from − 12.913 eV to -15.700 eV, combined with the activation energy calculation (Fig. 1 c), which indicates that PAA − would coordinate with Zn 2+ to form the solvation structure of [PAA − − Zn(H 2 O) 4 ] + , thereby regulating the Zn 2+ diffusion. The interaction of SO 4 2− and Zn@PAH/PAA was also investigated. The binding energy of [Zn(SO 4 ) 2 ] 2− is much larger than that of ZnSO 4 (-10.068 eV and − 3.785 eV, respectively), suggesting that Zn 2+ is likely to bind with two SO 4 2− to form [Zn(SO 4 ) 2 ] 2− (Figure S16). In addition, compared with [(PAH + ) 3 SO 4 ] + and [(PAA − ) 1 SO 4 ] 3− , [(PAH + ) 3 Zn(SO 4 ) 2 ] + exhibits the lowest binding energy (-26.33 eV), indicating that SO 4 2− would bind with PAH + to form the stable [(PAH + ) 3 Zn(SO 4 ) 2 ] + coordination structure (Fig. 4 c). Based on the above results, the interfacial mechanism during Zn 2+ plating/stripping on the Zn@PAH/PAA electrode is illustrated in Fig. 4 d. The ion-sieving accelerating channels in the structure of PAH + − SO 4 2− − Zn(H 2 O) 4 2+ − PAA − is constructed by the LbL self-assembled PAH/PAA multilayers, where PAA − would regulate the Zn 2+ solvation shell and accurate Zn 2+ transport at the inner Helmholtz plane, and PAH + would bind with SO 4 2− to inhibit the formation of ZHS. Indeed, the PAH/PAA multilayers would also induce the Zn nucleation and deposition along (002) texture to form the uniform and dense Zn flake layer, thereby suppressing dendrite formation. A Zn||commercial MnO 2 battery was assembled to investigate the effect of the PAH/PAA multilayers on the electrochemical performance of the full cell. The CV curves at a scan rate of 0.1 mV s − 1 are shown in Figure S17, where two redox peaks are related to the intercalation and de-intercalation of Zn 2+ and H + , respectively. 43 Because of the large nucleation overpotential and high nucleation rate of Zn@PAH/PAA mentioned earlier, the polarization for the Zn@PAH/PAA battery is larger than that of the Bare Zn battery. The rate performance for both electrodes from 0.1 A g − 1 to 5 A g − 1 is illustrated in Fig. 5 a and Figure S18. Due to the improved interfacial kinetics and thermostability of Zn anodes, the Zn@PAH/PAA battery exhibits a higher specific capacity and reversibility than the Bare Zn battery at each current density (262 mAh g − 1 at 0.1 A g − 1 and 101 mAh g − 1 at 5 A g − 1 ). Furthermore, the Zn@PAH/PAA battery displays an outstanding specific capacity of ~ 137 mAh g − 1 over 1,000 cycles with 91.3% capacity retention at 2 A g − 1 , whereas the Bare Zn battery suffers a rapid capacity decline of 73 mAh g − 1 after 620 cycles (Fig. 5 b). These results indicate that the LbL self-assembled PAH/PAA multilayers could significantly inhibit the side reactions and enhance the CE value, thereby improving the overall performance of the batteries. We also further investigate the LbL self-assembly technique in promoting the practical application of AZIBs. As shown in Fig. 5 c, the Zn@PAH/PAA-commercial VO 2 pouch cell with the high mass loading (> 8 mg cm − 2 ) was assembled, which exhibits an excellent Ah-level residual discharge capacity of 17.36 Ah after 250 cycles at 1.7 C, with a capacity retention of 96.3%. The capacity and C-rate achieved in this work are much higher than most previous work on Zn metal anodes, indicating the remarkable effect and huge potential of the LbL self-assembly technique to improve the anode stability in the practical application of Zn-ion batteries (Fig. 5 d and Table S4). 44–48 Conclusion In summary, the LbL self-assembled PAH/PAA multilayers with high mechanical strength and ionic conductivity could effectively enhance the reversibility and stability of the Zn anode. The ion-sieving accelerating channels constructed by the multilayers not only enable a high zincophilicity to regulate Zn 2+ desolvation process, but also could capture SO 4 2− to suppress the formation of by-products. Moreover, the PAH/PAA layers could induce Zn deposition along the (002) crystal plane to form a uniform and dense layer, inhibiting dendrite formation. Since the PAH/PAA multilayers remarkably enhance the interfacial Zn 2+ transport kinetics and thermostability, the Zn||Zn symmetric cell achieves an ultra-long stability over 1200 h at 1 mA cm − 2 and 1 mAh cm − 2 , and the Zn||Cu asymmetric cell exhibits an outstanding Coulombic efficiency of 99.8% and a high CPC of 396 mAh cm − 2 after 1600 cycles at 0.5 mA cm − 2 and 0.25 mAh cm − 2 . Moreover, the PAA/PAH multilayers enable the Zn-MnO 2 full cell an excellent capacity retention (91.3%) after 1,000 cycles at 2 A g − 1 , and the Zn@PAH/PAA-VO 2 pouch cell retains a high discharge capacity of 17.36 Ah after 250 cycles at 1.7 C with a high mass loading. We anticipate that this work inspires a new strategy about the construction of ion-sieving accelerating channels through the LbL self-assembly of polyelectrolytes to protect the metal anode, promoting practical applications of aqueous rechargeable batteries. Declarations Acknowledgement The authors would like to thank the Engineering and Physical Sciences Research Council (EPSRC, EP/V027433/3), UK Research and Innovation (UKRI) under the UK government‘s Horizon Europe funding (101077226; EP/ Y008707/1). Especially thanks to Science and Technology Facilities Council Early Research Award for financial support (ST/R006873/1) and the support from South China University of Technology. Thanks the support for Vastech battery company for pouch cell fabrication. References Dong, H. et al. Bio‐Inspired Polyanionic Electrolytes for Highly Stable Zinc‐Ion Batteries. Angewandte Chemie 135 , e202311268 (2023). Shen, Z. et al. 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Supplementary Files Scheme1.docx Supportinginformation.docx Cite Share Download PDF Status: Published Journal Publication published 08 Mar, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4496958","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":320296264,"identity":"b7f917c9-6a7b-41b1-8cc6-c334a4201035","order_by":0,"name":"Guanjie He","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAArUlEQVRIiWNgGAWjYFACHgaGDwwMMhDOASK1MM4AayRFCzMPSVrkHXgPPrZts+NhYD/8gJnnDBFaDA/wJRvntiXzMPCkGTDz3CBGSwOPmXRu2wGgw3KALvxAnBbz35YgLfxviNQiz8BjxswI0iIBsoUYhwHdbyzZcy6Zh03imcHBOcR4X769x/DDjzI7OX7+5IcP3hwjxpbDUAYbA7ERKd9AlLJRMApGwSgY0QAA/CYrO0KkoMgAAAAASUVORK5CYII=","orcid":"https://orcid.org/0000-0002-7365-9645","institution":"University College London","correspondingAuthor":true,"prefix":"","firstName":"Guanjie","middleName":"","lastName":"He","suffix":""},{"id":320296265,"identity":"88047aad-87e9-41cb-8b2a-2c46b6b6c63a","order_by":1,"name":"Xueying Hu","email":"","orcid":"","institution":"UCL","correspondingAuthor":false,"prefix":"","firstName":"Xueying","middleName":"","lastName":"Hu","suffix":""},{"id":320296266,"identity":"9c59f32b-d1ba-4b64-a2a7-35ffc9e4db9e","order_by":2,"name":"Haobo Dong","email":"","orcid":"","institution":"South China University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Haobo","middleName":"","lastName":"Dong","suffix":""},{"id":320296267,"identity":"1b039512-6d8a-42bd-8eb6-cf5ceca183f2","order_by":3,"name":"Tianlei Wang","email":"","orcid":"","institution":"UCL","correspondingAuthor":false,"prefix":"","firstName":"Tianlei","middleName":"","lastName":"Wang","suffix":""},{"id":320296268,"identity":"c0879993-6ab5-4bf4-9c47-2dbb9b322ef8","order_by":4,"name":"Hongzhen He","email":"","orcid":"","institution":"University College London","correspondingAuthor":false,"prefix":"","firstName":"Hongzhen","middleName":"","lastName":"He","suffix":""},{"id":320296269,"identity":"b93cde91-8014-47e2-b139-485ebc041512","order_by":5,"name":"Xuan Gao","email":"","orcid":"","institution":"University College London","correspondingAuthor":false,"prefix":"","firstName":"Xuan","middleName":"","lastName":"Gao","suffix":""},{"id":320296270,"identity":"f46ca8f0-62bf-4cdf-b384-0bcdb3a1a9c8","order_by":6,"name":"Yuhang Dai","email":"","orcid":"https://orcid.org/0000-0001-8445-6758","institution":"UCL","correspondingAuthor":false,"prefix":"","firstName":"Yuhang","middleName":"","lastName":"Dai","suffix":""},{"id":320296271,"identity":"04cba973-3ab1-4cc1-ae50-87e35b73e37b","order_by":7,"name":"Yiyang Liu","email":"","orcid":"","institution":"UCL","correspondingAuthor":false,"prefix":"","firstName":"Yiyang","middleName":"","lastName":"Liu","suffix":""},{"id":320296272,"identity":"42f2cc86-8c5c-43d0-850a-65d37f973bae","order_by":8,"name":"Nan Gao","email":"","orcid":"","institution":"Jilin University","correspondingAuthor":false,"prefix":"","firstName":"Nan","middleName":"","lastName":"Gao","suffix":""},{"id":320296273,"identity":"1bd1d8a1-20b4-4943-8245-579ef9bc6717","order_by":9,"name":"Dan Brett","email":"","orcid":"","institution":"Hanwei Co., Ltd.","correspondingAuthor":false,"prefix":"","firstName":"Dan","middleName":"","lastName":"Brett","suffix":""},{"id":320296274,"identity":"e0b80d15-7514-410e-85cd-e0cb2a5239eb","order_by":10,"name":"Ivan Parkin","email":"","orcid":"https://orcid.org/0000-0002-4072-6610","institution":"University College London","correspondingAuthor":false,"prefix":"","firstName":"Ivan","middleName":"","lastName":"Parkin","suffix":""}],"badges":[],"createdAt":"2024-05-29 12:10:44","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4496958/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4496958/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41467-025-57666-0","type":"published","date":"2025-03-08T05:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":59468703,"identity":"cd7bc4ab-4128-4eaa-aad1-e6063cd0e90a","added_by":"auto","created_at":"2024-07-02 07:10:12","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":471654,"visible":true,"origin":"","legend":"\u003cp\u003eEffects of the PAH/PAA multilayers on the diffusion and plating of Zn\u003csup\u003e2+\u003c/sup\u003e. (a) Linear polarization curves of Zn@PAH/PAA and Bare Zn. (b) XRD patterns of Zn@PAH/PAA and Bare Zn after 50 cycles at 0.5 mA cm\u003csup\u003e-2\u003c/sup\u003e and 0.5 mAh cm\u003csup\u003e-2\u003c/sup\u003e. (c) Calculated activation energies for Zn@PAH/PAA and Bare Zn. (d) Zn transference numbers for Zn@PAH/PAA and Bare Zn. (e) Cycling voltammogram (CV) curves of Ti@PAH/PAA and Bare Ti at 0.5 mV s\u003csup\u003e-1\u003c/sup\u003e. (f) Chronoamperograms (CAs) of Zn@PAH/PAA and Bare Zn at an overpotential of -150 mV.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4496958/v1/aff4fd1c464f05ce0e9297fc.png"},{"id":59469224,"identity":"a61bd6a7-dee0-4479-95a2-d2dfcc947f8d","added_by":"auto","created_at":"2024-07-02 07:18:13","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":974788,"visible":true,"origin":"","legend":"\u003cp\u003eSurface texture characterizations for Zn\u003csup\u003e2+\u003c/sup\u003e plating. (a) XRD patterns of Zn@PAH/PAA under different cycles. (b) Adsorption energies of Zn\u003csup\u003e2+ \u003c/sup\u003eand PAH\u003csup\u003e+\u003c/sup\u003e/PAA\u003csup\u003e- \u003c/sup\u003eon the Zn (002) lattice plane. (c) Diffusion energy barriers of Zn\u003csup\u003e2+\u003c/sup\u003e on Zn (002) crystal plane with/without PAH/PAA multilayers. (d) TEM images of Zn@PAH/PAA after 50 cycles. (e) SEM images under different cycles. (all characterizations cycled at 0.5 mA cm\u003csup\u003e-2\u003c/sup\u003e and 0.5 mAh cm\u003csup\u003e-2\u003c/sup\u003e).\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4496958/v1/e46912c666fa77a0547e230f.png"},{"id":59468708,"identity":"8ba8e092-47b6-4129-806f-83e8441b91ea","added_by":"auto","created_at":"2024-07-02 07:10:12","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":582897,"visible":true,"origin":"","legend":"\u003cp\u003eElectrochemical performances of the symmetric and asymmetric cells with the coating of PAH/PAA multilayers. The galvanostatic cycling performances of Zn symmetric cells at 1 mA cm\u003csup\u003e-2\u003c/sup\u003e and 1 mAh cm\u003csup\u003e-2\u003c/sup\u003e (a), 5 mA cm\u003csup\u003e-2\u003c/sup\u003e and 5 mAh cm\u003csup\u003e-2\u003c/sup\u003e (b), and 8 mA cm\u003csup\u003e-2\u003c/sup\u003e and 4 mAh cm\u003csup\u003e-2\u003c/sup\u003e (c). (d) The CE performance of the Zn||Cu asymmetric cells at 0.5 mA cm\u003csup\u003e-2\u003c/sup\u003e and 0.25 mAh cm\u003csup\u003e-2\u003c/sup\u003e. (e) The corresponding voltage profile at the first cycle. (f) Comparison of recent anode performance regarding CPC, cycle number, and average CE.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4496958/v1/f0b35d537703a0ddc9e9d863.png"},{"id":59468710,"identity":"f49410de-8fae-48d5-b0fd-3e28dda61a47","added_by":"auto","created_at":"2024-07-02 07:10:13","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":857574,"visible":true,"origin":"","legend":"\u003cp\u003eMechanism of the Zn\u003csup\u003e2+\u003c/sup\u003e plating/stripping behaviours on Zn@PAH/PAA. (a) \u003cem\u003eIn-situ\u003c/em\u003e Raman spectra of the Zn@PAH/PAA electrode at 35 mA cm\u003csup\u003e-2 \u003c/sup\u003efor 3,600 s each cycle. Binding energy of different coordination structures of PAA\u003csup\u003e-\u003c/sup\u003e (b) and PAH\u003csup\u003e+\u003c/sup\u003e (c). (d) Schematic diagram of the Zn deposition process on Zn@PAH/PAA.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4496958/v1/0a7d44be9d64cbd2d3cb4374.png"},{"id":59468712,"identity":"7d0ac797-f649-4cce-b6e6-c9d65bf390e5","added_by":"auto","created_at":"2024-07-02 07:10:13","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":704482,"visible":true,"origin":"","legend":"\u003cp\u003eElectrochemical performances of the Zn@PAH/PAA full cell. (a) The rate performance of Zn-MnO\u003csub\u003e2\u003c/sub\u003e coin cell at different current density of 0.1, 0.2, 0.5, 1, 2, 5 A g\u003csup\u003e-1\u003c/sup\u003e. (b) Long-term cycling performance of Zn-MnO\u003csub\u003e2\u003c/sub\u003e coin cell at the current density of 2 A g\u003csup\u003e-1\u003c/sup\u003e. (c) Long-term cycling performance of Zn-VO\u003csub\u003e2\u003c/sub\u003e pouch cell at 1.7 C (Optical image of the Zn||VO\u003csub\u003e2\u003c/sub\u003e pouch cell). (d) Comparison of recent anode performance regarding Zn metal pouch cells on capacity, cycle number, and C-rate.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-4496958/v1/2635e69c92283d788af7a517.png"},{"id":78120559,"identity":"79556d18-a70e-4340-aec2-002281db16ec","added_by":"auto","created_at":"2025-03-10 07:08:04","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4656281,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4496958/v1/c612ee63-52d4-4433-86fd-2032bd3cac65.pdf"},{"id":59468707,"identity":"1b71bd19-e48e-4d14-baa5-fd3f21ca4dd9","added_by":"auto","created_at":"2024-07-02 07:10:12","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":269831,"visible":true,"origin":"","legend":"","description":"","filename":"Scheme1.docx","url":"https://assets-eu.researchsquare.com/files/rs-4496958/v1/ed5fedc8a38467973b6f202a.docx"},{"id":59468709,"identity":"56dea51b-c7f6-40f0-a657-2fbaa73e408a","added_by":"auto","created_at":"2024-07-02 07:10:13","extension":"docx","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":3824040,"visible":true,"origin":"","legend":"","description":"","filename":"Supportinginformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-4496958/v1/b8ad921c0fc8fd2e27eb1b3f.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Self-assembled polyelectrolytes with ion-sieving accelerating channels for highly stable Zn-ion batteries","fulltext":[{"header":"Introduction","content":"\u003cp\u003eAqueous zinc-ion batteries (AZIBs) are regarded as one of the most promising alternatives to lithium-ion batteries for the grid-scale electrochemical energy storage (EES) systems due to their high volumetric capacity (5855 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e), low redox potential (-0.762 V vs standard hydrogen electrode (SHE)), and high safety.\u003csup\u003e1,2\u003c/sup\u003e However, the hydrogen evolution reaction (HER) leads to a rapid rise in the local concentration of OH\u003csup\u003e\u0026minus;\u003c/sup\u003e at the anode/electrolyte interface, which would further react with SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e in the electrolyte to form the by-product (Zn\u003csub\u003e4\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e(OH)\u003csub\u003e6\u003c/sub\u003e\u0026sdot;xH\u003csub\u003e2\u003c/sub\u003eO, ZHS).\u003csup\u003e3\u003c/sup\u003e Moreover, the generation of the inert by-product would reduce the active sites for Zn deposition, increase the nucleation barrier, and cause uncontrollable dendrite growth on the Zn anode. This results in the shortened cycle life and has hindered the commercial application of ZIBs.\u003csup\u003e4\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eSurface modification using inorganic and organic coatings could effectively inhibit the dendrite growth and side reactions at the Zn anode.\u003csup\u003e5\u003c/sup\u003e Inorganic coatings including carbon-based materials, eutectic alloys, and metallic compounds (e.g., carbon dots (CDs),\u003csup\u003e6\u003c/sup\u003e Zn-Cu,\u003csup\u003e7\u003c/sup\u003e Zn-Sn,\u003csup\u003e8\u003c/sup\u003e CaCO\u003csub\u003e3\u003c/sub\u003e,\u003csup\u003e9\u003c/sup\u003e ZnF\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e10\u003c/sup\u003e) could be used as physical barriers to protect the Zn anode from corrosion and regulate Zn\u003csup\u003e2+\u003c/sup\u003e diffusion to achieve uniform Zn deposition. However, the non-uniform physical barriers lead to a low Zn\u003csup\u003e2+\u003c/sup\u003e conductivity and a significant volume change during plating/stripping, ultimately causing the cracking and peeling. In contrast, the flexible organic polyelectrolyte coatings such as polyamide,\u003csup\u003e11\u003c/sup\u003e polyacrylamides,\u003csup\u003e12\u003c/sup\u003e and poly(2-vinylpyridine)\u003csup\u003e13\u003c/sup\u003e with 3D cross-linked polymer channels can provide active sites to facilitate Zn\u003csup\u003e2+\u003c/sup\u003e transference and reduce the interface resistance.\u003csup\u003e14\u003c/sup\u003e But the mono polyelectrolyte interface could not satisfactorily control the ion diffusion and offer a sufficient mechanical strength. For instance, although anionic polyelectrolytes could effectively regulate Zn\u003csup\u003e2+\u003c/sup\u003e flux to homogenous deposition, it has a limited repelling effect on SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e in the electrolyte, which would cause the by-products formation to a certain extent.\u003csup\u003e15,16\u003c/sup\u003e Owing to the repulsion between anionic polyelectrolytes and the negative charged Zn anode, the adhesivity of the coatings is also not satisfactory. Based on this, the layer-by-layer (LbL) self-assembly of polyelectrolytes with the controllable composition and tunable properties, which allows sequential deposition of versatile polycations and polyanions on a charged substrate, is an attractive approach to enhance the overall performance of Zn anodes\u003csup\u003e17\u0026ndash;19\u003c/sup\u003e. The strong electrostatic interactions between polycations and polyanions could provide oppositely charged dual-ion channels to suppress the corrosion and passivation on the Zn anode, while also enhancing the mechanical strength (e.g., toughness, adhesion, self-healing).\u003csup\u003e20\u0026ndash;22\u003c/sup\u003e In addition, as summarized in Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1a\u003c/span\u003e, the LbL self-assembly technique has outstanding advantages compared with other conventional surface modification techniques in the commercialization of AZIBs. The resource of polycations and polyanions with the characteristics of non-toxic, biocompatible, and biodegradable for the LbL self-assembled SEI layer are extremely abundant, which is not only conductive to the preparation of novel multifunctional SEI layers through the modification of polyelectrolytes, but also can promote the development of eco-friendly Zn-ion batteries. The LbL method also allows precise control of the thickness and composition of coatings, making it a sustainable method that is far superior to other surface modification techniques.\u003csup\u003e23,24\u003c/sup\u003e Moreover, the LbL self-assembly technique is more cost-effective for the practical application due to its simple manufacturing process and low demand on equipment.\u003csup\u003e25\u003c/sup\u003e However, to date, there have been limited studies on the use of LbL self-assembly technique for the interface engineering of Zn anodes. Identifying efficient and appropriate polyelectrolyte combinations for the LbL self-assembled layers remains a challenge, as is demonstrating their effectiveness in protecting Zn anodes and enhancing their applications.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo overcome above mentioned challenges, we selected poly(allylamine hydrochloride) (PAH) and its tautomer poly(acrylic acid) (PAA) to prepare the LbL self-assembled PAH/PAA multilayers. Due to the tautomerization, the photon exchange would occur between the carboxylic acid group (-COOH) of PAA and the amine group (-RNH\u003csub\u003e2\u003c/sub\u003e) of PAH, leading to the negatively charged carboxylate (-COO\u003csup\u003e\u0026minus;\u003c/sup\u003e) and the positively charged ammonium (-RNH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e) with the strong electrostatic interactions.\u003csup\u003e26\u003c/sup\u003e Based on this, the PAH/PAA multilayers could be seen as the dual-ion channels for SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e and Zn\u003csup\u003e2+\u003c/sup\u003e in the electrolyte, like an ionic sieve, the dual-ion channels sieve SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e at the first shell and attract Zn\u003csup\u003e2+\u003c/sup\u003e, which would regulate the mobility and dispersion of Zn\u003csup\u003e2+\u003c/sup\u003e and suppress the side reactions, thereby improving the electrochemical performance of the Zn anode. Moreover, the strong electrostatic interactions between PAH and PAA could effectively improve the mechanical strength without affecting the ionic conductivity of the coating, and also simplify the preparation process.\u003csup\u003e19,27\u003c/sup\u003e As illustrated in Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1b\u003c/span\u003e, the preparation sequence of multilayers is to first coat the PAH layer and then the PAA layer (Anode\u003csup\u003e\u0026minus;\u003c/sup\u003e \u0026minus; PAH\u003csup\u003e+\u003c/sup\u003e \u0026minus; PAA\u003csup\u003e\u0026minus;\u003c/sup\u003e), followed by a rinsing process after each coating to remove the weakly associated bound chains. Designing in the sequence: Anode\u003csup\u003e\u0026minus;\u003c/sup\u003e \u0026minus; PAH\u003csup\u003e+\u003c/sup\u003e \u0026minus; PAA\u003csup\u003e\u0026minus;\u003c/sup\u003e would enable a high adhesion to the negatively charged Zn anode and increase the zincophilicity of multilayers. PAA layer as the outer layer could first accelerate the desolvation process and regulate the diffusion of Zn\u003csup\u003e2+\u003c/sup\u003e. Meanwhile, PAH layer would capture SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e due to the low binding energy, resulting in the formation of ion-sieving accelerating channels to inhibit the HER and by-products. Remarkably, the LbL self-assembled PAH/PAA multilayers are favorable for the preferential nucleation and growth of Zn\u003csup\u003e2+\u003c/sup\u003e along Zn(002) surface to form a smooth and dense deposition layer and suppress the dendrite formation (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1c\u003c/span\u003e). Correspondingly, the PAH/PAA multilayers enable an excellent Coulombic efficiency of up to 99.8% after 1,600 cycles at 0.5 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e and 0.25 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e for the Zn||Cu asymmetric cell. The Zn||MnO\u003csub\u003e2\u003c/sub\u003e battery with the PAH/PAA coating layers displays an outstanding specific capacity of about 137 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e over 1,000 cycles with 91.3% capacity retention at 2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Even in a Zn||VO\u003csub\u003e2\u003c/sub\u003e pouch cell with a high loading mass, it exhibits an excellent discharge capacity of 17.36 Ah over 250 cycles at 1.7 C. This work provides a new insight for the surface modification of Zn anodes, the design of the LbL self-assembly of polyelectrolytes could not only effectively enhance the electrochemical performances and mechanical strengths of Zn anode, but also could be applied to other metal anode protection.\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cp\u003eThe LbL self-assembled PAH/PAA multilayers were prepared by the doctor-blading method.\u003csup\u003e28\u0026ndash;30\u003c/sup\u003e By optimizing the preparation process, three double PAH/PAA layers (Zn@PAH/PAA) with a thickness of ~\u0026thinsp;280 nm could offer the most stable electrochemical performances (Figure \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e and Figure S3). The composition of Zn@PAH/PAA was successfully confirmed by Fourier Transform Infrared (FTIR) spectroscopy, as shown in Figure S2. The bands at 1710 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1247 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are related to the C\u0026thinsp;=\u0026thinsp;O and C-O stretching vibration of carboxylic acid from the characterization bands of PAA, respectively.\u003csup\u003e31,32\u003c/sup\u003e The bending of amine and amide group from the characterization bands of PAH are about 1633 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1532 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003csup\u003e32,33\u003c/sup\u003e Compared with the bands of pure Zn@PAA and Zn@PAH, the significant band shifts for Zn@PAH/PAA are observed, which are due to the electrostatic interactions between polyelectrolytes during the LbL self-assembly process. To investigate the effect of the LbL self-assembled PAH/PAA multilayers on the behavior of Zn\u003csup\u003e2+\u003c/sup\u003e plating/stripping, the thermostability and Zn\u003csup\u003e2+\u003c/sup\u003e transport kinetics of Zn anodes after coating were compared. The linear polarization curves indicate that the PAH/PAA multilayers could enhance the corrosion resistance of Zn anodes (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ea). The corrosion potential of Zn@PAH/PAA is increased from \u0026minus;\u0026thinsp;0.1 V to -0.984 V, and the corrosion current is reduced to 1.109 mA, which is lower than that of the Bare Zn (2.99 mA). The higher corrosion potential and lower current mean more effective inhibition on the HER and by-products on Zn anodes.\u003csup\u003e34\u003c/sup\u003e To further verify the corrosion resistance of Zn@PAH/PAA, the HER on both Bare Zn and Zn@PAH/PAA electrodes within the initial 20 min at 30 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e was observed, which is shown in Figure S4. After 10 min, small bubbles generate and trend to accumulate on the Bare Zn electrodes. In contrast, no obvious bubbling appears on the Zn@PAH/PAA electrode. Moreover, the XRD pattern of Bare Zn after 50 cycles exhibits the strong diffraction peaks of the by-product (Zn\u003csub\u003e4\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e(OH)\u003csub\u003e6\u003c/sub\u003e\u0026sdot;4H\u003csub\u003e2\u003c/sub\u003eO, ZHS), which was not detected on the cycled Zn@PAH/PAA electrode (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003eb). The results from SEM-EDS mapping in Figure S5 also show that there is large amount of ZHS on the Bare Zn electrode after 50 cycles, compared with the Zn@PAH/PAA electrode. These results indicate that the PAH/PAA multilayers could significantly suppress the HER and side reactions to enhance the thermostability of Zn anodes. In addition, ion-sieving accelerating channels could modulate interfacial kinetics of Zn\u003csup\u003e2+\u003c/sup\u003e diffusion and deposition. As shown in Figure S6, the PAH/PAA multilayers offer an excellent hydrophilicity, of which the contact angle (58.6\u0026deg;) is smaller than that of Bare Zn (99.9\u0026deg;). The hydrophilicity of Zn@PAH/PAA could enable a lower interfacial energy barrier to regulate the diffusion of Zn\u003csup\u003e2+\u003c/sup\u003e, which is demonstrated in the analysis of activation energy.\u003csup\u003e35\u003c/sup\u003e Based on the EIS plots at different temperatures (Figure S7), the interfacial activation energy (\u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sub\u003e) was evaluated through the Arrhenius equation (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ec). The hydrophilic PAH/PAA multilayers could reduce \u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sub\u003e from 17.34 kJ mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to 6.85 kJ mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, indicating that the PAH/PAA layers with a high zincophilicity could effectively regulate the Zn\u003csup\u003e2+\u003c/sup\u003e solvation structure and accelerate the transference. The Zn transference numbers of Zn@PAH/PAA and Bare Zn were calculated and shown in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ed and Figure S8, where the high ionic conductivity of PAH/PAA multilayers could increase the Zn transference number from 0.284 to 0.481. To investigate the nucleation and growth behaviors of Zn\u003csup\u003e2+\u003c/sup\u003e, the nucleation overpotential (\u0026eta;) on the Zn||Ti cell was evaluated (Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ee). According to previous research,\u003csup\u003e11,36\u003c/sup\u003e the critical nucleation radius (\u0026gamma;\u003csub\u003ecrit\u003c/sub\u003e) and nucleation rate (\u0026omega;) could be described as below:\u003c/p\u003e\n\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e$${\\gamma }_{crit}=h\\sigma A/2\\rho F\\eta$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e$$\\omega \\propto \\text{e}\\text{x}\\text{p}\\left(\\frac{-\\pi LhA{\\sigma }^{2}}{2\\rho F\\eta }\\right)$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\n\u003c/div\u003e\n\u003cp\u003eWhere h is the height of Zn atom, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\sigma\\)\u003c/span\u003e\u003c/span\u003e is the interface tension, A is the Zn atom mass, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\rho\\)\u003c/span\u003e\u003c/span\u003e is the nucleus density, F is Faraday\u0026rsquo;s constant, and L is Avogadro constant. As illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ee, \u0026eta; is increased by 12.1 mV with the PAH/PAA multilayers, and the ratio of \u0026gamma;\u003csub\u003ecrit\u003c/sub\u003e for Zn@PAH/PAA and Bare Zn is 0.47, which is attributed to an increased nucleation rate. Hence, a high nucleation overpotential could be attributed to a uniform and dense Zn deposition. Moreover, the chronoamperometry (CA) test reflects that Zn\u003csup\u003e2+\u003c/sup\u003e exhibits a 2D diffusion behavior on Zn@PAH/PAA, compared with a 3D diffusion on the Bare Zn (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ef). The current change with time indicates the increase of effective Zn nucleation sites in chronoamperograms. The current for Zn@PAH/PAA remains stable after 140 s, whereas due to the aggregation of Zn\u003csup\u003e2+\u003c/sup\u003e, the current for the Bare Zn continues to decrease within 400 s. Combined with the result of \u0026eta;, the PAH/PAA multilayers could regulate the Zn nucleation sites and make a uniform deposition to efficiently inhibit dendrite growth.\u003c/p\u003e\n\u003cp\u003eSince PAH/PAA multilayers could enable the 2D diffusion and plating of Zn\u003csup\u003e2+\u003c/sup\u003e, the texture evolution and morphology of Zn anodes during cycling were further studied. XRD patterns of Zn@PAH/PAA under different cycles in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea and table \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e reveal that the (002) peak increases significantly after cycling. The intensity ratio I\u003csub\u003e(002)\u003c/sub\u003e/I\u003csub\u003e(101)\u003c/sub\u003e becomes stronger, which is from 0.0611 (pristine Zn) to 0.1995 (15 cycles), 0.2298 (30 cycles), and 0.2973 (50 cycles). Density functional theory (DFT) calculations were carried out to analyze the adsorption energy of Zn\u003csup\u003e2+\u003c/sup\u003e and PAH\u003csup\u003e+\u003c/sup\u003e/PAA\u003csup\u003e\u0026minus;\u003c/sup\u003e on Zn(002). PAH\u003csup\u003e+\u003c/sup\u003e/PAA\u003csup\u003e\u0026minus;\u003c/sup\u003e exhibits a stronger adsorption energy (-0.760 eV) than Zn\u003csup\u003e2+\u003c/sup\u003e (-0.145 eV) on Zn(002), which is shown in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eb. Besides, the diffusion energy barrier of Zn\u003csup\u003e2+\u003c/sup\u003e with the PAH/PAA multilayers coated on Zn(002) increases from 0.014 eV to 0.269 eV, suggesting that Zn@PAH/PAA could inhibit the aggregation of Zn\u003csup\u003e2+\u003c/sup\u003e and lead to a 2D diffusion and parallel plating.\u003csup\u003e37\u003c/sup\u003e These above results indicate that the PAH/PAA multilayers could induce the preferential nucleation and growth of Zn\u003csup\u003e2+\u003c/sup\u003e along Zn(002). SEM images show that with the increase of cycles, more and more (002) textures are observed on the Zn@PAH/PAA electrode (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ed). There are many horizontal (002) textures stacked together on the Zn@PAH/PAA after 50 cycles, where the thickness of the deposition layer is about 8 \u0026micro;m (Figure S9). In sharp contrast, the morphology of Bare Zn after 50 cycles is extremely uneven with significant dendrite growth corresponding to a deposition layer of around 11 \u0026micro;m (Figure S10). \u003cem\u003eIn-situ\u003c/em\u003e optical images and 3D depth profiles also verify that the PAH/PAA layers could guide a smooth and dense plating (Figure S11 and Figure S12). The aggregation and uneven nucleation of Zn\u003csup\u003e2+\u003c/sup\u003e on the Bare Zn electrode result in the dendrite formation and significantly roughens the surface after 5 min, while the surface of the Zn@PAH/PAA electrode remains smooth and homogenous for 20 min. A solid electrolyte interphase (SEI) layer with a thickness of about 19 nm for the 50 cycled Zn@PAH/PAA electrode was observed through TEM images, shown in Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ee. Further zooming in the SEI layer, the (002) textures are the main plating orientation in SEI layer, of which the area is significantly larger than that of the (100) textures. Therefore, it could be known that the ion-sieving accelerating channels formed by the LbL self-assembled PAH/PAA layers could induce the Zn nucleation and deposition along the (002) lattice plane to form a smooth and dense Zn flake layer.\u003c/p\u003e\n\u003cp\u003eAs the PAH/PAA multilayers could effectively enhance the thermostability and Zn\u003csup\u003e2+\u003c/sup\u003e transport kinetics to make the uniform Zn(002) deposition, the stability of Zn@PAH/PAA was discussed in relation to the symmetric Zn cell. The Zn@PAH/PAA electrode exhibits an excellent stability around 1200 h at 1 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e and 1 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, whereas the Bare Zn electrode suffers short circuit around 76 h (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ea). With increasing the current and capacity densities to 5 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e and 5 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, the Zn@PAH/PAA electrode (340 h) still shows a longer cycling performance than the Bare Zn electrode (160 h), illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003eb. Furthermore, the Zn@PAH/PAA electrode presents a high depth of discharge (DOD): 53.4% within around 170 h cycling at 8 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e and 4 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ec). As shown in Figure S13, the voltage profile for the Zn@PAH/PAA electrode at different current density and capacity exhibits a larger potential difference than that of the Bare Zn, which is due to the lower nucleation radius and higher nucleation rate of Zn@PAH/PAA as mentioned in Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ee. In addition, a large voltage difference of the Zn@PAH/PAA electrode may also be caused by the PAH/PAA layers inducing the orientational plating of Zn\u003csup\u003e2+\u003c/sup\u003e along Zn(002). Compared with the Bare Zn electrode, the rate performance of the Zn@PAH/PAA exhibits an outstanding Zn\u003csup\u003e2+\u003c/sup\u003e plating/stripping stability at various current densities from 1 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e to 10 mA cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e at 1 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e (Figure S14). These GCD tests indicate that the PAH/PAA multilayers enable an excellent stability and reversibility for the Zn anode. The Coulombic efficiency (CE) was analysed by the asymmetric Zn||Cu cell. As shown in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ed and Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ee, the initial CE of Cu@PAH/PAA (92.3%) is higher than that of bare Cu (86.7%), and the Cu@PAH/PAA electrode offers an outstanding CE around 99.8% after 1,600 h, while the bare Cu electrode suffers a rapid decline on CE after about 70 cycles. The CE performance indicates that the PAH/PAA multilayers could efficiently inhibit the side reactions and passivation of Zn anodes. Hence, the initial nucleation overpotential of Cu@PAH/PAA increases from 0.0746 V to 0.0961 V, which once again approves that PAH/PAA layers could enable a lower nucleation radius and a higher nucleation rate, thereby inducing the deposition of the homogenous and dense Zn(002) layer. The cumulative plated capacity (CPC) of the Cu@PAH/PAA electrode is 396 mAh cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, which is more competitive than most of recent research on the surface modification of Zn anodes (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003ef and Table S2).\u003c/p\u003e\n\u003cp\u003eTo investigate the mechanism of Zn\u003csup\u003e2+\u003c/sup\u003e plating/stripping behaviours on Zn@PAH/PAA, \u003cem\u003ein-situ\u003c/em\u003e Raman spectra were recorded during each cycle. As shown in Figure S15, the band assigned to the -CH\u003csub\u003e2\u003c/sub\u003e stretching vibration is at 2928 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for Zn@PAH/PAA, while it is at about 2930 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for Zn@PAH.\u003csup\u003e38\u003c/sup\u003e This difference is due to the electrostatic interactions between PAH and PAA polyelectrolytes as confirmed by FTIR. After immersing Zn@PAH/PAA to 2 M ZnSO\u003csub\u003e4\u003c/sub\u003e for 15 min, the -CH\u003csub\u003e2\u003c/sub\u003e stretching vibration band moves to 2931 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, indicating the ionic interaction between -CH\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e and SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e. Moreover, the band shape between 1400 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1450 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is related to the -RNH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e deformation and -CH\u003csub\u003e2\u003c/sub\u003e bending, by which the shape change further confirms the interaction between -CH\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e and SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e.\u003csup\u003e39,40\u003c/sup\u003e The band from 1750 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to 1600 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for Zn@PAH/PAA corresponds to the vibration of symmetric C-H of PAH and C\u0026thinsp;=\u0026thinsp;O in carboxylate groups of PAA, while it splits into two bands after immersing with ZnSO\u003csub\u003e4\u003c/sub\u003e, owing to the ionic interaction between -COO\u003csup\u003e\u0026minus;\u003c/sup\u003e and Zn\u003csup\u003e2+\u003c/sup\u003e that enhances the intensity of C\u0026thinsp;=\u0026thinsp;O band.\u003csup\u003e41,42\u003c/sup\u003e The periodic band changes could be observed in each plating/stripping cycle, as illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ea and Table S3. The ionic interaction between SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e and -CH\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e would make the band of -CH\u003csub\u003e2\u003c/sub\u003e- vibration shift to a lower wavenumber during Zn\u003csup\u003e2+\u003c/sup\u003e plating and to a higher wavenumber during Zn\u003csup\u003e2+\u003c/sup\u003e stripping. Correspondingly, the relative band intensity of -CH\u003csub\u003e2\u003c/sub\u003e bending and NH\u003csub\u003e3\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e deformation between 1400 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1450 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e would change. Moreover, the coordination of Zn\u003csup\u003e2+\u003c/sup\u003e and -COO\u003csup\u003e\u0026minus;\u003c/sup\u003e would make the band of C\u0026thinsp;=\u0026thinsp;O vibration move to a lower wavenumber during plating, while the band would move to a higher wavenumber due to the escape of Zn\u003csup\u003e2+\u003c/sup\u003e during stripping. These regular and reversible band changes indicate the formation of dual-ion channels between PAH and PAA polyelectrolytes. The binding energy was calculated to further discuss the interfacial mechanism. As shown in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003eb, the binding energy of [PAA\u003csup\u003e\u0026minus;\u003c/sup\u003e\u0026minus; Zn(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e decreases from \u0026minus;\u0026thinsp;12.913 eV to -15.700 eV, combined with the activation energy calculation (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ec), which indicates that PAA\u003csup\u003e\u0026minus;\u003c/sup\u003e would coordinate with Zn\u003csup\u003e2+\u003c/sup\u003e to form the solvation structure of [PAA\u003csup\u003e\u0026minus;\u003c/sup\u003e\u0026minus; Zn(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e, thereby regulating the Zn\u003csup\u003e2+\u003c/sup\u003e diffusion. The interaction of SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e and Zn@PAH/PAA was also investigated. The binding energy of [Zn(SO\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e2\u0026minus;\u003c/sup\u003e is much larger than that of ZnSO\u003csub\u003e4\u003c/sub\u003e (-10.068 eV and \u0026minus;\u0026thinsp;3.785 eV, respectively), suggesting that Zn\u003csup\u003e2+\u003c/sup\u003e is likely to bind with two SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e to form [Zn(SO\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e2\u0026minus;\u003c/sup\u003e (Figure S16). In addition, compared with [(PAH\u003csup\u003e+\u003c/sup\u003e)\u003csub\u003e3\u003c/sub\u003e SO\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e and [(PAA\u003csup\u003e\u0026minus;\u003c/sup\u003e)\u003csub\u003e1\u003c/sub\u003e SO\u003csub\u003e4\u003c/sub\u003e]\u003csup\u003e3\u0026minus;\u003c/sup\u003e, [(PAH\u003csup\u003e+\u003c/sup\u003e)\u003csub\u003e3\u003c/sub\u003e Zn(SO\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e exhibits the lowest binding energy (-26.33 eV), indicating that SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e would bind with PAH\u003csup\u003e+\u003c/sup\u003e to form the stable [(PAH\u003csup\u003e+\u003c/sup\u003e)\u003csub\u003e3\u003c/sub\u003e Zn(SO\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e]\u003csup\u003e+\u003c/sup\u003e coordination structure (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ec). Based on the above results, the interfacial mechanism during Zn\u003csup\u003e2+\u003c/sup\u003e plating/stripping on the Zn@PAH/PAA electrode is illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003ed. The ion-sieving accelerating channels in the structure of PAH\u003csup\u003e+\u003c/sup\u003e \u0026minus; SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e \u0026minus; Zn(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2+\u003c/sup\u003e \u0026minus; PAA\u003csup\u003e\u0026minus;\u003c/sup\u003e is constructed by the LbL self-assembled PAH/PAA multilayers, where PAA\u003csup\u003e\u0026minus;\u003c/sup\u003e would regulate the Zn\u003csup\u003e2+\u003c/sup\u003e solvation shell and accurate Zn\u003csup\u003e2+\u003c/sup\u003e transport at the inner Helmholtz plane, and PAH\u003csup\u003e+\u003c/sup\u003e would bind with SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e to inhibit the formation of ZHS. Indeed, the PAH/PAA multilayers would also induce the Zn nucleation and deposition along (002) texture to form the uniform and dense Zn flake layer, thereby suppressing dendrite formation.\u003c/p\u003e\n\u003cp\u003eA Zn||commercial MnO\u003csub\u003e2\u003c/sub\u003e battery was assembled to investigate the effect of the PAH/PAA multilayers on the electrochemical performance of the full cell. The CV curves at a scan rate of 0.1 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are shown in Figure S17, where two redox peaks are related to the intercalation and de-intercalation of Zn\u003csup\u003e2+\u003c/sup\u003e and H\u003csup\u003e+\u003c/sup\u003e, respectively.\u003csup\u003e43\u003c/sup\u003e Because of the large nucleation overpotential and high nucleation rate of Zn@PAH/PAA mentioned earlier, the polarization for the Zn@PAH/PAA battery is larger than that of the Bare Zn battery. The rate performance for both electrodes from 0.1 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to 5 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ea and Figure S18. Due to the improved interfacial kinetics and thermostability of Zn anodes, the Zn@PAH/PAA battery exhibits a higher specific capacity and reversibility than the Bare Zn battery at each current density (262 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 0.1 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 101 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at 5 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). Furthermore, the Zn@PAH/PAA battery displays an outstanding specific capacity of ~\u0026thinsp;137 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e over 1,000 cycles with 91.3% capacity retention at 2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, whereas the Bare Zn battery suffers a rapid capacity decline of 73 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 620 cycles (Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003eb). These results indicate that the LbL self-assembled PAH/PAA multilayers could significantly inhibit the side reactions and enhance the CE value, thereby improving the overall performance of the batteries. We also further investigate the LbL self-assembly technique in promoting the practical application of AZIBs. As shown in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ec, the Zn@PAH/PAA-commercial VO\u003csub\u003e2\u003c/sub\u003e pouch cell with the high mass loading (\u0026gt;\u0026thinsp;8 mg cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e) was assembled, which exhibits an excellent Ah-level residual discharge capacity of 17.36 Ah after 250 cycles at 1.7 C, with a capacity retention of 96.3%. The capacity and C-rate achieved in this work are much higher than most previous work on Zn metal anodes, indicating the remarkable effect and huge potential of the LbL self-assembly technique to improve the anode stability in the practical application of Zn-ion batteries (Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003ed and Table S4).\u003csup\u003e44\u0026ndash;48\u003c/sup\u003e\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn summary, the LbL self-assembled PAH/PAA multilayers with high mechanical strength and ionic conductivity could effectively enhance the reversibility and stability of the Zn anode. The ion-sieving accelerating channels constructed by the multilayers not only enable a high zincophilicity to regulate Zn\u003csup\u003e2+\u003c/sup\u003e desolvation process, but also could capture SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2−\u003c/sup\u003e to suppress the formation of by-products. Moreover, the PAH/PAA layers could induce Zn deposition along the (002) crystal plane to form a uniform and dense layer, inhibiting dendrite formation. Since the PAH/PAA multilayers remarkably enhance the interfacial Zn\u003csup\u003e2+\u003c/sup\u003e transport kinetics and thermostability, the Zn||Zn symmetric cell achieves an ultra-long stability over 1200 h at 1 mA cm\u003csup\u003e− 2\u003c/sup\u003e and 1 mAh cm\u003csup\u003e− 2\u003c/sup\u003e, and the Zn||Cu asymmetric cell exhibits an outstanding Coulombic efficiency of 99.8% and a high CPC of 396 mAh cm\u003csup\u003e− 2\u003c/sup\u003e after 1600 cycles at 0.5 mA cm\u003csup\u003e− 2\u003c/sup\u003e and 0.25 mAh cm\u003csup\u003e− 2\u003c/sup\u003e. Moreover, the PAA/PAH multilayers enable the Zn-MnO\u003csub\u003e2\u003c/sub\u003e full cell an excellent capacity retention (91.3%) after 1,000 cycles at 2 A g\u003csup\u003e− 1\u003c/sup\u003e, and the Zn@PAH/PAA-VO\u003csub\u003e2\u003c/sub\u003e pouch cell retains a high discharge capacity of 17.36 Ah after 250 cycles at 1.7 C with a high mass loading. We anticipate that this work inspires a new strategy about the construction of ion-sieving accelerating channels through the LbL self-assembly of polyelectrolytes to protect the metal anode, promoting practical applications of aqueous rechargeable batteries.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003eAcknowledgement\u003c/p\u003e\n\u003cp\u003eThe authors would like to thank the Engineering and Physical Sciences Research Council (EPSRC, EP/V027433/3), UK Research and Innovation (UKRI) under the UK government\u0026lsquo;s Horizon Europe funding (101077226; EP/ Y008707/1). Especially thanks to Science and Technology Facilities Council Early Research Award for financial support (ST/R006873/1) and the support from South China University of Technology. Thanks the support for Vastech battery company for pouch cell fabrication. \u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eDong, H.\u003cem\u003e\u0026nbsp;et al.\u003c/em\u003e Bio‐Inspired Polyanionic Electrolytes for Highly Stable Zinc‐Ion Batteries. \u003cem\u003eAngewandte Chemie\u003c/em\u003e \u003cstrong\u003e135\u003c/strong\u003e, e202311268 (2023).\u003c/li\u003e\n \u003cli\u003eShen, Z.\u003cem\u003e\u0026nbsp;et al.\u003c/em\u003e Electrocrystallization regulation enabled stacked hexagonal platelet growth toward highly reversible zinc anodes. \u003cem\u003eAngewandte Chemie\u003c/em\u003e \u003cstrong\u003e135\u003c/strong\u003e, e202218452 (2023).\u003c/li\u003e\n \u003cli\u003eLiang, P.\u003cem\u003e\u0026nbsp;et al.\u003c/em\u003e Highly reversible Zn anode enabled by controllable formation of nucleation sites for Zn‐based batteries. \u003cem\u003eAdvanced Functional Materials\u003c/em\u003e \u003cstrong\u003e30\u003c/strong\u003e, 1908528 (2020).\u003c/li\u003e\n \u003cli\u003eCui, Y.\u003cem\u003e\u0026nbsp;et al.\u003c/em\u003e An interface‐bridged organic\u0026ndash;inorganic layer that suppresses dendrite formation and side reactions for ultra‐long‐life aqueous zinc metal anodes. \u003cem\u003eAngewandte Chemie International Edition\u003c/em\u003e \u003cstrong\u003e59\u003c/strong\u003e, 16594-16601 (2020).\u003c/li\u003e\n \u003cli\u003eLi, T. 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However, the hydrogen evolution reaction (HER) and uncontrolled diffusion of Zn\u003csup\u003e2+\u003c/sup\u003e and SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2-\u003c/sup\u003e ions lead to the dendrite formation and side reactions, which hinder their practical application by forming a non-conductive layer on the Zn anode. This layer impedes the ion transport and electron flow, reducing the Coulombic efficiency (CE) for the Zn nucleation. Here, to simultaneously regulate the diffusion of H\u003csup\u003e+\u003c/sup\u003e, Zn\u003csup\u003e2+\u003c/sup\u003e, and SO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2-\u003c/sup\u003e in the electrolyte, an ion-sieving accelerating channel was constructed to unify the Zn deposition by introducing an eco-friendly layer-by-layer self-assembly of a flocculant poly(allylamine hydrochloride) (PAH) and its tautomer poly(acrylic acid) (PAA). The dual-ion channels, created by strong electrostatic interactions between carboxylate anions (COO⁻) and ammonia cations (NH₃⁺), promote the uniform Zn deposition along the (002) plane, exhibiting a CE of 99.8% after 1600 cycles in the Zn||Cu asymmetric cell. With the facile fabrication of the layer-by-layer self-assembled Zn anode, an Ah-level pouch cell (17.36 Ah) with a high mass loading (\u0026gt; 8 mg cm⁻²) demonstrated exceptional performance, retaining a capacity of 93.6% for at least 250 cycles at 1.7 C. This research offers a universal strategy for optimizing electrode mechanisms and advancing the manufacturing process of eco-friendly, high-performance aqueous batteries.\u003c/p\u003e","manuscriptTitle":"Self-assembled polyelectrolytes with ion-sieving accelerating channels for highly stable Zn-ion batteries","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-07-02 07:10:07","doi":"10.21203/rs.3.rs-4496958/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"8a1659c6-7fef-46a4-9f96-4df78320d9b4","owner":[],"postedDate":"July 2nd, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":33869575,"name":"Physical sciences/Energy science and technology/Energy storage/Batteries"},{"id":33869576,"name":"Physical sciences/Chemistry/Energy"}],"tags":[],"updatedAt":"2025-03-10T07:07:57+00:00","versionOfRecord":{"articleIdentity":"rs-4496958","link":"https://doi.org/10.1038/s41467-025-57666-0","journal":{"identity":"nature-communications","isVorOnly":false,"title":"Nature Communications"},"publishedOn":"2025-03-08 05:00:00","publishedOnDateReadable":"March 8th, 2025"},"versionCreatedAt":"2024-07-02 07:10:07","video":"","vorDoi":"10.1038/s41467-025-57666-0","vorDoiUrl":"https://doi.org/10.1038/s41467-025-57666-0","workflowStages":[]},"version":"v1","identity":"rs-4496958","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4496958","identity":"rs-4496958","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}