3D Cold‐Trap Environment Printing for Long‐Cycle Aqueous Zn‐Ion Batteries

Abstract

excellent rate performance, and fast reaction kinetics. [1][2][3][4] However, the inadequate cycling performance of Zn metal anode (mainly including Zn foil) originates from the growth of Zn dendrites and other side reactions have impeded its further development and extensive commercialization. [5] To date, many efforts have been devoted to regulate the surface structure and characteristics of Zn foil to induce Zn nucleation and growth on the surface of Zn foil via various strategies such as surface coating of Zn foil and modification of electrolyte, [6][7][8] which have greatly enhanced the electrochemical performances of Zn foil. The inherent defects of planar Zn foil are always affecting its practical application, and there are three major factors involved: i) the 2D plane structure of Zn foil can cause spontaneous dendrite formation along the vertical direction on the surface of the Zn foil, which can easily penetrate the separator and cause short circuit of battery; ii) severe pulverization of Zn foil can occur during the charge/ discharge cycles at high current density, resulting in electric contact failure; and iii) the redundant thickness of Zn foil results in its poor utilization in application. [9,10] Compared with Zn foil, Zn powder (Zn-P) is a valuable substitute for Zn foil owing to its low cost and easily available. More importantly, the content of Zn-P can be accurately controlled, Zn powder (Zn-P)-based anodes are always regarded as ideal anode candidates for zinc ion batteries owing to their low cost and ease of processing. However, the intrinsic negative properties of Zn-P-based anodes such as easy corrosion and uncontrolled dendrite growth have limited their further applications. Herein, a novel 3D cold-trap environment printing (3DCEP) technology is proposed to achieve the MXene and Zn-P (3DCEP-MXene/Zn-P) anode with highly ordered arrangement. Benefitting from the unique inhibition mechanism of high lattice matching and physical confinement effects within the 3DCEP-MXene/Zn-P anode, it can effectively homogenize the Zn 2+ flux and alleviate the Zn deposition rate of the 3DCEP-MXene/Zn-P anode during Zn plating-stripping. Consequently, the 3DCEP-MXene/Zn-P anode exhibits a superior cycling lifespan of 1400 h with high coulombic efficiency of ≈9.2% in symmetric batteries. More encouragingly, paired with MXene and Co doped MnHCF cathode via 3D cold-trap environment printing (3 DCEP-MXene/Co-MnHCF), the 3DCEP-MXene/Zn-P//3DCEP-MXene/Co-MnHCF full battery delivers high cyclic durability with the capacity retention of 95.7% after 1600 cycles. This study brings an inspired universal pathway to rapidly fabricate a reversible Zn anode with highly ordered arrangement in a cold environment for micro-zinc storage systems.

Modulating Zinc Metal Reversibility by Confined Antifluctuator Film for Durable and Dendrite‐Free Zinc Ion Batteries

“…Most importantly, the Zn symmetric cells using ZCYSM@Zn film as anode antifluctuator achieve an ultrahigh CPC of 2.25 and 4 Ah cm −2 at the current density of 1 and 10 mA cm −2 , respectively, which has far exceeded the previously reported CPC value of Zn-based powder electrodes. [5,11,12,[14][15][16][17]30,32,33] To further study the mechanism of dendrite suppression by ZCYSM@Zn antifluctuator, the distribution of Zn 2+ concentration field, current density, and electric field in ZCYSM@Zn film are simulated by FEA. The electric field and the distribution of current density on the surface of the Zn-P film is notably inhomogeneous due to the low conductivity and large volume distort the current density and electric field direction of the surface protuberance sites, as presented in Figure 4a-c.…”

“…Lithium-ion batteries (LIBs) have attracted great attention in the market of portable electronic products and electric nucleation, and disjointed electronic transition. [12] Thus, uneven deposition is more likely to occur on the top region of Zn-P, and then the dendrites will accumulate continuously during Zn plating/stripping and eventually penetrate into the separator, causing internal short circuit and the generation of "dead zinc." [13] Besides, the volume shrinkage induced by Zn dissolution during the discharging stage depletes the electrical contact between powders.…”

Research progress on modified Zn substrates in stabilizing zinc anodes

“…Lu et al proposed a novel 3D cold trap environment printing technique to achieve a highly ordered arrangement of MXene and zinc powder (3DCEP-MXene/Zn-P) anodes. 125 The 3DCEP-MXene/Zn-P anode exploits the unique suppression mechanism of high lattice matching and the physical confinement effect to homogenize the Zn 2+ flux and reduce the rate of Zn deposition during the galvanization/dezincification process. Accordingly, the 3DCEP-MXene/Zn-P anode delivers a good cycling stability of 1400 h with a high CE of approximately 99.2% in the symmetric cell.…”

Printable Energy Storage: Stay or Go?

“…In contrast, the introduction of in situ curing technique is important for DIW and IJP to retain the printed structure. One innovative approach is the use of a 3D cold trap, as demonstrated by Lu et al 56 By conducting the entire printing process in a lowtemperature environment, the ink underwent instantaneous freezing, resulting in the elimination of ink flow and the preservation of the original structure. The induction of ice crystal formation further enhanced the directional alignment stability of materials such as MXene nanosheets during the freezing process.…”