Energy & Environmental Science
·
2024
·Vol. 17
·期 13
·4794-4802
·
IF 32.4
Zhengqiang Hu,Fengling Zhang,Feng Wu,Huirong Wang,Anbin Zhou,Yi Chen,Tianyang Xue,Renjie Chen,Li Li
In electrochemical devices, the electric double layer (EDL) theory posits that the potential difference of the Helmholtz layer significantly influences the activation energy and reaction rate of the electrochemical reaction, which determines the uniformity of metal ion deposition. In this work, we compare the differential capacitance of metal cationic sulfate, along with factors such as cost as well as safety, and Ce(SO4)2 is selected to adjust the EDL at the Zn anode/electrolyte interface. Molecular dynamics simulations show the formation of a more compressed diffuse layer with the help of Ce4+, resulting in a decreased potential difference of the Helmholtz layer, an improved Zn2+ deposition overpotential and a reduced Zn electrode corrosion rate. In situ XRD and Raman spectroscopy reveal that Zn2+ deposition is favored along the (002) crystal plane, and hydrogen evolution is hindered. The Ce4+ modified electrolyte enables a Zn anode with high coulombic efficiency (99.6%) over 600 cycles at 10 mA cm−2. The compressed EDL extends the lifespan of the Zn–Zn cell to 2500 hours at 5 mA cm−2 and stable cycling for 300 cycles at 20 mA cm−2 and 10 mA h cm−2. Assembling Zn full cells with high-loading cathodes shows enhanced long-term cycling performance. Our findings reveal the potential of using high-valence metal cations like Ce4+ to regulate the EDL and uniform Zn2+ deposition in ZIBs, which suggests a promising direction for developing electrolytes for practical ZIBs.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Wenyan Chen,Zhibo Xie,Haichao Chen,Xianfen Wang
Aqueous zinc ion batteries (AZIBs) are attracting increasing research interest due to their intrinsic safety, low cost, and scalability. However, the issues including hydrogen evolution, interface corrosion, and zinc dendrites at anodes have seriously limited the development of aqueous zinc ion batteries. Here, N,N-methylenebis(acrylamide) (MBA) additives with −CONH- groups are introduced to form hydrogen bonds with water and suppress H2O activity, inhibiting the occurrence of hydrogen evolution and corrosion reactions at the interface. In situ optical microscopy demonstrates that the MBA additive promotes the uniform deposition of Zn2+ and then suppresses the dendrite growth on the zinc anode. Therefore, Zn//Ti asymmetric batteries demonstrate a high plating/stripping efficiency of 99.5%, while Zn//Zn symmetric batteries display an excellent cycle stability for more than 1000 h. The Zn//MnO2 full cells exhibit remarkable cycling stability for 700 cycles in aqueous electrolytes with MBA additives. The additive engineering via MBA achieved the dendrite-free Zn anodes and stable full batteries, which is favorable for advanced AZIBs in practical applications.
研究领域:
电化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Nano
·
2021
·
IF 15.881
Xinliang Li,Mian Li,Kan Luo,Yue Hou,Pei Li,Qi Yang,Zhaodong Huang,Guojin Liang,Ze Chen,Shiyu Du,Qing Huang,Chunyi Zhi
Dendrite growth and low Coulombic efficiency caused by uneven diffusion and electrodeposition of Zn2+ ions have emerged as a barrier to exploit the Zn metal anode. In this work, we demonstrate the stoichiometric halogenated MXenes (Ti3C2Cl2, Ti3C2Br2, and Ti3C2I2) as an artificial layer that can induce the uniform Zn deposition. The efficient redistribution effect results from the coherent heterogeneous interface reconstruction and regulated ion tiling by halogen surficial termination. The synergetic effects of high lattice matching (90%) between the adopted MXenes and Zn, as well as the positive halogen regulation, Zn2+ ions are guided to nucleate uniformly on the most extensive (000l) crystal plane of the MXene matrix and grow in a planar manner. In terms of Zn ion regulation, Cl termination is found to be more effective than O/F, Br, and I due to its moderate adsorption and diffusion coefficiency for Zn2+ ions. The Ti3C2Cl2–Zn anode achieves a life extension of over 12 times (840 h at 2 mA cm–2//1 mAh cm–2) over that of the bare Zn anode and serves more than 9000 cycles in a battery with a Ti3C2I2 cathode at a high rate of 3 A g–1. Given the abundance of lattice parameters and terminations of MXene materials, the developed strategy is expected to be extended to other metal anode systems.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Small
·
2022
·Vol. 18
·期 26
·2202214
·
IF 15.153
Yanmei Li,Yingyu Wang,Yuan Xu,Wenhuai Tian,Jiawei Wang,Liwei Cheng,Honglei Yue,Runa Ji,Qiaonan Zhu,Hao Yuan,Hua Wang
Zn anode is confronted with serious Zn dendrite growth and water-induced parasitic reactions, which severely hinders the rapid development and practical application of aqueous zinc metal batteries (AZMBs). Herein, inspired by sodium hyaluronate (SH) biomolecules in living organisms featured with the functions of water retention, ion-transport regulation, and film-formation, the SH working as a dynamic and self-adaptive “mask” is proposed to stabilize Zn anode. Benefiting from the abundant functional groups with high hydrophilicity and zincophilicity, SH molecule can constrain active water molecules on the Zn-electrolyte interface and participate in Zn 2+ solvation structure to suppress parasitic reactions. Furthermore, the dynamical adsorption of SH with high-density negative charge on the Zn surface could serve as Zn 2+ reservoirs to guide uniform Zn deposition. Consequently, stable Zn plating and an ultrahigh cumulative plating capacity (CPC) of 4.8 Ah cm -2 are achieved even at 20 mA cm -2 (20 mAh cm -2 ) in a Zn||Zn symmetric battery, reaching a record level in AZMBs. In addition, the Zn||β-MnO 2 full battery exhibits a substantially improved cycle stability. This work presents a route to realize a highly reversible and stable Zn metal anode by learning from nature.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yuanwei Chu,Tingting Luo,Jingcheng Li,Hong Zhang,Wenjing Dai,Yingning Zhou,Yijin Zhang,Yaweixue Deng,Bo Zou,Junchen Chen,Yun Huang,Mingshan Wang,Yang Gao,Xing Li
Despite the widely acknowledged and remarkable advantages of aqueous zinc-ion batteries (ZIBs), issues such as uncontrollable dendrite growth and hydrogen evolution reaction, which severely affect their rechargeable stability and cycle life. To address these issues, a dynamic Zn 2+ ions rectification interfacial layer (DRIL) was constructed via in-situ spin coating and crosslinking of hydrophilic borax-modified hydroxypropyl guar gum on the Zn anode (BHPG@Zn). During the process of in-situ crosslinking, BHPG formed a carded molecular chain structure through synergistic crosslinking with borax, which re-regulated the uniform distribution of Zn 2+ ion fluxes at the interface. Leveraging the abundant oxygen-containing functional groups on BHPG, the inherent strong hydrogen-bonding network environment formed by water molecules is disrupted through strong coupling with Zn 2+ ions, thus promoting the transportation and desolvation of Zn 2+ ions. Furthermore, the stronger binding energy and affinity between BHPG and zinc induce the formation of a (002) plane-oriented Zn deposition layer. Based on the DRIL modification, the BHPG@Zn displays stable cycling for over 7100 h at 2 mA cm −2 with coulombic efficiency of 99.3 %, while the AC@Ti||BHPG@Zn zinc-ion capacitor retains a capacity of 65 mAh g −1 after 10,000 cycles at 2 A g −1 .
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Rui-han Li,Bin-bin Sui,Peng-fei Wang,Zhe Gong,Yu-han Wu,Yu-hang Zhang,Li-na Zhao,Jun-jie Tang,Fa-nian Shi
Aqueous zinc ion batteries (AZIBs) are well-suited for current energy storage technologies due to their high safety and low cost. However, battery failures resulting from dendrites and side reactions restrict their widespread application. Here, we designed a polyacrylonitrile (PAN)-zinc trifluoromethanesulfonate (ZnTFSI) nanofibre synergistic glass fibre (PZ-GF) to modulate the interfacial deposition kinetics. The effective coordination of numerous CN functional groups within PZ, in conjunction with Zn 2+ , results in the homogeneous dispersion of the electric field across the electrode, which promotes the uniform deposition of Zn 2+ on the zinc anode and thus significantly inhibits the rapid growth of zinc dendrites. ZnTFSI is hydrophilic and has strong hydrogen bonding interactions with the H 2 O molecule so that the separator can be used as a molecular sieve to regulate the flux of H 2 O, promote the desolvation of hydrated zinc ions , and inhibit side reactions.Tests of the initial nucleation overpotential of the symmetric battery and calculation of the activation energy reflect that PZ-GF has a smaller nucleation energy barrier and enhanced kinetic effect. And the zinc symmetric battery with PZ-GF film shows an ultra-long cycle stability of 1200 cycles with a capacity retention of 75 % even at 0.5 A g −1 for the Zn//VO 2 full cells.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Energy Storage Materials
·
2024
·
IF 18.9
Hanning Zhang,Tao Shui,Wei Zhang,ZhengMing Sun
Given the high safety, cost-effectiveness, and volumetric capacity, aqueous zinc-ion batteries (ZIBs) constitute a promising energy system, but the severe side reactions and dendrite growth at the anode/electrolyte interface limited ZIBs from large-scale utilization. Here, we proposed a facile strategy to stabilize the anode/electrolyte interface and enhance the reversibility of the zinc plating/stripping via additive engineering. A trace amount of the diethylene triaminepentaacetic acid (DTPA, 3 mM) was employed as an additive, which spontaneously adsorbed onto the Zn anode, and in-situ formed a complex interlayer. This interlayer effectively shielded the water molecules, leading to a superior anti-corrosion property, facilitating the desolvation and diffusion of Zn 2+ , and inducing the Zn (002) oriented deposition. As a result, outstanding durability was achieved at ultrahigh current density (3000 cycles at 100 mA·cm −2 ) and relatively high depth of discharge (140 h at 5 mA·cm −2 , 85 % DOD) in the Zn||Zn symmetric cell. Superior cyclability was also observed in the coin cell (1000 cycles at 5 A· g −1 ) and pouch cell (500 cycles at 1 A· g −1 ) with an NH 4 V 4 O 10 cathode. Furthermore, the formation of complex molecule clusters was elucidated via in-situ Raman and the “bowl” morphologies are firstly visualized by SEM and AFM. These morphologies enable the rapid trapping of Zn 2+ oriented Zn deposition in the hollow area. We believe this work provides a novel strategy for long-term ZIB designs and offers new insights into the mechanisms for regulating zinc-oriented-deposition behavior at the molecular scale.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Hongcheng He,Wentao Qu,Jichun Lian,Yu Yan,Changmiao Chen,Qiaotian Xiong,Guanhua Zhang,Ming Zhang
Zinc anodes tend to form irregular and non-planar electrodeposits during repeated cycles, leading to the dendrite growth and consequently resulting in internal short circuits of Zn-based batteries and security problems. A progressive deposition is investigated in the present study by introducing oxygen functional groups and macropores into the carbon nanofiber film to regulate the nucleation and growth of Zn. Experimental analyses and theoretical simulation show that zincophilic oxygen functional groups act as preferred deposition sites with ultralow Zn nucleation overpotential to guide the initial nucleation of Zn on the whole surface of carbon nanofibers. The macropores with higher Zn 2+ concentration and current density serve as the preferred paths for the subsequent growth of Zn inside. Deposited Zn will progressively fill the internal void space of the entire carbon nanofiber film. The carbon nanofiber film with the progressive deposition enables dendrite-free Zn plating/stripping. Symmetric cells with OPCNF-Zn electrodes exhibit a long cycle life over 1300 h at 1 mA cm −2 for 1 mA h cm −2 .
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Energy Materials
·
2025
·Vol. 5
·期 3
·N
·
IF 11.2
Yulin Xie,Qingyun Dou,Guosheng Li,Yuecong Chen,Xingbin Yan
Zinc-ion batteries (ZIBs) are being explored as a potential alternative to lithium-ion batteries owing to the growing demand for safer, more sustainable, cost-effective energy storage technologies. In such systems, electrolytes, as one of the key components, have a decisive impact on their electrochemical performance. However, Zn anodes in traditional aqueous electrolytes exhibit drawbacks such as severe hydrogen evolution reactions, Zn corrosion and passivation especially at high temperatures, leading to poor cycling performance of ZIBs. Herein, we designed and evaluated a series of hybrid electrolytes consisting of zinc tetrafluoroborate hydrate [Zn(BF4)2·xH2O] as the solute and various organic solvents [tetraglyme (G4), propylene carbonate, and dimethylformamide] for high-temperature ZIBs. Comparative analysis revealed that G4-based hybrid electrolytes exhibit a unique Zn2+ solvation structure primarily surrounded by organic solvent rather than H2O, which substantially reduces H2O-related side reactions and thus promotes more reversible Zn deposition than propylene carbonate-based and dimethylformamide-based hybrid electrolytes. The superiority of G4-based hybrid electrolyte is further confirmed by long stable cycling life of the corresponding Zn||Zn symmetric cell (> 350 h) and Zn-ion capacitor full cell (over 1,400 cycles with 90.7% capacity retention) at 60 °C.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2024
·
IF 5.5
Yunxun Pu,Kailimai Su,Chengshuai Wang,Yan Wang,Bingjun Yang,Guangke Tian,Hongyan Du,Junwei Lang
Zinc-ion batteries, known for safety and efficiency, are a hotspot in electrochemical energy storage field. Nonetheless, the emergence of dendrites on zinc anodes during electrochemical cycles can lead to capacity attenuation and even failure, particularly under low temperatures. In this study, we develop a novel dendrite-free and low-temperature resistant Zn(ClO 4 ) 2 /Li 2 SO 4 /Dimethyl sulfoxide (DMSO) hybrid electrolyte by using DMSO as a hydrogen bond acceptor and solvation regulator. Our research demonstrates that, by reducing the desolvation energy barrier of the Zn 2+ solvation sheath and the nucleation overpotential of Zn deposition, DMSO effectively inhibits zinc dendrites and side reactions. Furthermore, DMSO disrupts hydrogen bonding between water molecules, preventing electrolyte freezing at low temperatures. As a result, at 0.5 mA cm −2 , the Zn||Zn symmetric device using this hybrid electrolyte exhibits consistent operation for over 4000 h even at -25 °C, featuring a minimal deposition/dissolution overpotential of approximately 0.045 mV. Additionally, at -20 °C, the Zn||Zn(ClO 4 ) 2 -Li 2 SO 4 -DMSO||LiFePO 4 battery demonstrates stable cycling for over 600 cycles at 0.6 C (1 C = 170 mA g − 1 ), delivering a capacity of 103 mA h g −1 .
研究领域:
电化学能源存储
·
材料科学
✓ 已验证
DOI
高影响因子
Energy Storage Materials
·
2024
·
IF 18.9
Kuo Wang,Tong Qiu,Lu Lin,Hongtu Zhan,Xiao-Xia Liu,Xiaoqi Sun
Zn anode experiences dendrite issues in aqueous Zn batteries. They result from uneven Zn 2+ flux and Sand behavior depending on the current density. Herein, the amino alcohol of 2,2′,2′′-nitrilotriethanol (NTE) additive with chelation ability is introduced to achieve stable and parallel Zn deposition. NTE preferentially adsorbs on Zn surface, which chelates with Zn 2+ at interface upon geometry transformation. It not only homogenizes Zn 2+ flux to inhibit dendrites at low current densities, but also supply sufficient Zn 2+ to delay Sand behavior at high current densities. Parallel growth of Zn hexagonal plates is realized. Thus, Zn plating/stripping in symmetric cells at 10 mA cm −2 reaches >1600 h cycle life with the addition of 2.5% NTE in the ZnSO 4 electrolyte, corresponding to a high cumulative plated capacity of 8.5 Ah cm −2 . At the conditions of 5 °C or 70% depth of discharge, the lifespans of symmetric cells also extend to 6977 h and 230 h, respectively. In anode free full cells, a Zn 2+ pre-inserted V 6 O 13 ·H 2 O cathode retains 250 mAh g −1 capacity after 300 cycles at 6 A g −1 , superior to 83 mAh g −1 with NTE free electrolyte.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Storage
·
2024
·
IF 8.9
Yikun Zhou,Junhong Ma,Yang Yuan,Chaoyun Ma,Shaorui Jia,Xinbo Zhang,Guirong Zhang,Xuye Zhou
Aqueous zinc-ion batteries (AZIBs) have a great application prospect in large-scale energy storage, but rampant dendrite growth and continuous side reactions cause the deterioration of zinc electrode performance. Herein, a distinctive additive, sodium p-toluene sulfonate (STS) is shown to enable stable and reversible zinc deposition. Both density functional theory (DFT) calculation and experimental observation demonstrate that STS additive not only can modulate solvation structure to reduce the number of active water molecules, but also is preferentially adsorbed on the Zn(101) plane and guide the preferentially growth of the Zn(002) plane. Moreover, the water-poor electric double layer (EDL) formed on the Zn anode and the reduction of pH value of the electrolyte caused by STS have a positive effect on the inhibition of side reactions. Moreover, the formation of hydrophobic layer and the regulation of pH have a positive effect on the inhibition of side reactions. Consequently, the cycle life of corresponding Zn//Zn symmetric battery with STS additive can reach up to 3500 h at 1 mA cm −2 /1 mAh cm −2 , and >900 h at 5 mA cm −2 /5 mAh cm −2 . Moreover, the STS additive endows the Zn//MnO 2 full cell to achieve an excellent capacity retention rate of 78 % over 800 cycles at 1 A g −1 .
研究领域:
电化学
·
能源材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）