• •
曹磊(
), 许自晓, 徐晨轩, 邵卓, 季石宇()
收稿日期:2025-08-28
修回日期:2025-11-09
出版日期:2025-11-10
通讯作者:
季石宇
作者简介:曹磊（1987—），男，硕士，高级工程师，cao_l2@hdec.com
Lei CAO(), Zixiao XU, Chenxuan XU, Zhuo SHAO, Shiyu JI()
Received:2025-08-28
Revised:2025-11-09
Online:2025-11-10
Contact:
Shiyu JI
摘要：
水系Zn/MnO₂电池凭借高理论容量、高安全性和低成本等优势，已成为最具潜力的水系锌离子电池体系之一。尽管其阴极储能机制复杂，但H+/Zn2+界面传输行为已被证实对容量与循环稳定性具有关键影响。本文系统综述了Zn2+脱嵌、可逆质子反应、H+/Zn2+共嵌入及Mn4+/Mn2+两电子反应等多种反应机制，并总结了晶体结构调控、碳复合、表面修饰和缺陷工程等策略在优化H+/Zn2+传输动力学、提升反应可逆性与电池性能方面的研究进展。最后，对该体系正极材料的未来发展前景进行了展望，以期推动其实际应用。
中图分类号:
曹磊, 许自晓, 徐晨轩, 邵卓, 季石宇. 水系Zn/MnO2体系中H+/Zn2+界面传输调控及反应机理研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.20250959.
Lei CAO, Zixiao XU, Chenxuan XU, Zhuo SHAO, Shiyu JI. Research progress on the H+/Zn2+ interfacial transport regulation and reaction mechanisms in aqueous Zn/MnO2 system[J]. CIESC Journal, DOI: 10.11949/0438-1157.20250959.
| 机理类型 | 典型电压平台 | 优势 | 挑战/局限性 |
|---|---|---|---|
| Zn2+脱嵌 | 1.3~1.4 V | 结构相对明确 | Zn2+扩散动力学慢，结构坍塌 |
| H+转化沉积 | 1.3~1.4 V & 1.2~1.3 V | 容量较高 | Mn溶解，副产物积累 |
| H+/Zn2+共嵌入 | 双平台（H+：较高； Zn2+：较低） | 容量高， 机理互补 | 两种离子相互作用复杂 |
Mn4+/Mn2+两电子 反应 | ~1.95 V（高电压） | 超高容量， 高电压 | 需酸性环境，Mn溶解严重 |
表1 水系Zn/MnO2电池主要储能机理对比
Table 1 Comparison of the main energy storage mechanisms of aqueous Zn/MnO2 batteries
| 机理类型 | 典型电压平台 | 优势 | 挑战/局限性 |
|---|---|---|---|
| Zn2+脱嵌 | 1.3~1.4 V | 结构相对明确 | Zn2+扩散动力学慢，结构坍塌 |
| H+转化沉积 | 1.3~1.4 V & 1.2~1.3 V | 容量较高 | Mn溶解，副产物积累 |
| H+/Zn2+共嵌入 | 双平台（H+：较高； Zn2+：较低） | 容量高， 机理互补 | 两种离子相互作用复杂 |
Mn4+/Mn2+两电子 反应 | ~1.95 V（高电压） | 超高容量， 高电压 | 需酸性环境，Mn溶解严重 |
图1 (a) Zn2+嵌入α-MnO2的机理示意图[27]；(b) δ-MnO2晶格结构的HR-TEM图；(c) Zn/δ-MnO2电池的CV曲线；(d) Zn/δ-MnO2电池第1和第5次放电循环后正极的XRD谱图[31]
Fig.1 (a) Schematic of the mechanism of Zn2+ intercalation into α-MnO2[27]; (b) HR (High resolution)-TEM image of the lattice structure of δ-MnO2; (c) CV curves of Zn/δ-MnO2 batteries; (d) Ex-situ XRD patterns of the cathodes recovered from the Zn/δ-MnO2 cells after 1st and 5th discharge cycles[31]
图2 (a) MGS在不同阶段的非原位XRD图谱；(b) MGS在不同阶段从5°到20°的SAXD
Fig.2 (a) Ex situ XRD patterns of MGS at different stages; (b) SAXD patterns of MGS from 5° to 20° at various stages
图3 (a) N-CNSs和N-CNSs@MnO2电极在0.1 mV·s-1扫描速率下的CV曲线；(b) N-CNSs@MnO2电极在初始、嵌入、脱出状态下的Zn 2p3/2能级光谱；N-CNSs@MnO2阴极(c)嵌入和(d)脱出状态的HR-TEM图像。红色箭头表示δ-MnO2的层状结构。蓝色箭头表示N-CNSs@MnO2中的纳米孔[37]
Fig.3 (a) CV curves of N-CNSs and N-CNSs@MnO2 electrodes at a scan rate of 0.1 mV·s-1; (b) Zn 2p3/2 spectra of N-CNSs@MnO2 electrode in initial, intercalated and de-intercalated states; HR-TEM images of N-CNSs@MnO2 cathode at (c) insertion and (d) extraction states. The red and blue arrows represent the layer structure of δ-MnO2 and nanopores in N-CNSs@MnO2[37], respectively.
图4 MnO2电极在第一个循环过程中放电至1.0 V (a) 和充电到1.8 V (b) 的TEM/HR-TEM图像；(c) α-MnO2电极在第一次放电至1.0 V时的XRD图谱；(d) α-MnO2电极在第一个循环过程中放电到1.0 V，然后再充电到1.8 V的XRD图谱[29]
Fig.4 TEM/HR-TEM images of MnO2 electrode discharged to 1 V (a) and charged to 1.8 V (b) during the first cycle; (c) XRD pattern of α-MnO2 electrode discharged to 1 V in the first cycle; (d) XRD patterns collected from α-MnO2 electrodes discharged to 1 V and charged back to 1.8 V in the 1st[29]
图5 (a) PFM电极的GCD曲线；(b) PFM电极在不同放电、充电状态下的非原位XRD图谱；(c) PFM电极的GITT曲线和扩散系数；(d) Zn/PEM电池中H+嵌入存储机制示意图[38]
Fig.5 (a) GCD curves of PFM electrode; (b) Ex situ XRD patterns of PFM electrode at different discharge–charge states; (c) GITT curves and the corresponding diffusion coefficients of PFM electrode; (d) Schematic of the proposed H+ ion insertion energy storage mechanism for the cell with the PEM electrode[38]
图6 (a) Zn/MnO2@CFP电池在2 M ZnSO4 + 0.2 M MnSO4电解液中的循环性能及其在6.5 C和1.3 C速率下相应的库伦效率；(b) Zn/MnO2@CFP电池在不同倍率下第一个循环的充放电曲线；(c) MnO2@CFP正极的GITT曲线；(d) 不同放电深度下的EIS；(e) MnO2@CFP正极在添加或不添加ZnSO4的0.2 M MnSO4电解液中的放电曲线；(f) MnO2@CFP正极在1.3 V和1.0 V放电深度时的非原位XRD图[30]
Fig.6 (a) Cycling performance of Zn/MnO2@CFP cells in 2 M ZnSO4+0.2 M MnSO4 electrolyte and corresponding coulombic efficiencies at 6.5 C and 1.3 C rates; (b) First cycle charge-discharge curves of Zn/MnO2@CFP batteries at different rates; (c) GITT curves of MnO2@CFP cathode; (d) Corresponding EIS at different depth of discharge as indexed by arrows in panel C; (e) Discharge curves of MnO2@CFP cathode in 0.2 M MnSO4 solution with or without ZnSO4 as electrolytes; (f) Ex situ XRD patterns of the MnO2@CFP cathode at depth of discharge at 1.3 and 1.0 V[30]
图7 (a) 在C/3的电流密度下，初始沉积、部分和完全放电MnO2正极的XRD图；(b) 在3C的电流密度下，初始沉积、部分和完全放电MnO2正极的XRD图；(c) Zn/MnO2电池氧化还原反应和晶体结构示意图[41]；(d) MON正极在0.1 C电流下在不同电解液中的放电曲线；(e) 根据ICP结果定量Zn2+和H+对容量的贡献；(f) 第一次和第二次放电平台的DFT计算中Zn/MON电池的电压[42]
Fig.7 (a) XRD patterns of initially deposited, partially and fully discharged MnO2 cathodes at a current density of C/3; (b) XRD patterns of initially deposited, partially and fully discharged MnO2 cathodes at a current density of 3 C; (c) Schematic diagram of redox reaction and crystal structure of Zn/MnO2 battery[41]; (d) Discharge curves of MON cathode in different electrolytes at a current density of 0.1 C; (e) Quantification of Zn2+ and H+ contributions to capacity based on ICP results; (f) Graphical illustration of the voltage of Zn/MON cells in DFT calculations for the first and second discharge plateaus[42]
图8 (a) CV曲线；(b) 不同循环后的GCD曲线；(c) α-MnO2和Zn电极在完全放电状态下的XRD图谱；(d) 不同循环α-MnO2正极的非原位XRD图谱；(e) GITT曲线和扩散率与充电/放电状态的关系；(f) 20次和60次循环后的Nyquist图[44]
Fig.8 (a) CV curves; (b) GCD curves after different cycles; (c) XRD patterns of α-MnO2 and Zn electrodes in fully discharged state; (d) Ex-situ XRD patterns of α-MnO2 cathodes after different cycles; (e) GITT curve and diffusivity vs charge/discharge state; (f) Nyquist plots after 20 and 60 cycles[44]
图9 (a) PPy覆盖无序MnO2表面的最佳构型；(b) 初始MnO2和MnO2/PPy的Zn2+吸附能；(c) 初始MnO2和MnO2/PPy在不同放电/充电状态下的Zn2+扩散系数[47]；(d) BPA和DPA改性的MnO2电极与原始MnO2电在完全充电和放电状态下的Nyquist图；(e) 0.02 mV∙s-1时的CV曲线；(f) 0.1 C 放电速率下第10次循环的GCD曲线[48]；(g) VMP电极的合成示意图；(h) VMP、VM和MO正极的CV曲线；(I) VMP、VM和MO正极的GCD曲线[50]
Fig.9 (a) Optimal configuration of the disordered MnO2 surface covered by PPy; (b) Zn2+ adsorption energy of bare MnO2 and MnO2/PPy; (c) Zn2+ diffusion coefficients at different discharge/charge state of bare MnO2 and MnO2/PPy [47]; (d) Nyquist plots of BPA and DPA modified MnO2 electrodes vs pristine MnO2 electrodes in fully charged and discharged states; (e) CV curves at 0.02 mV s-1; (f) GCD curves of the 10th cycle at 0.1 C discharge rate[48]; (g) Schematic diagram of the synthesis of VMP electrodes; (h) CV curves of VMP, VM (VG-MnO2) and MO (MnO2@CF) cathodes; (i) GCD curves of VMP, VM and MO cathodes[50]
图10 (a) MOC (CNF@MnO2) 电极合成示意图；(b) 据GITT结果计算出的MOC-5 (the feeding weight ratio of KMnO4/CNF of 5:1) 和MO (δ-MnO2) 电极的离子扩散系数；(c) MOC-5电极在给定循环完全充电状态下的Nyquist图；(d) MO电极在给定循环完全充电状态下的Nyquist图[53]；(e) CV曲线和MO、MOP (MnO2/PEDOT)、CMO (CNT/MnO2) 和CMOP (CNT/MnO2/PEDOT) 电极在0.2 mV·s-1时的相对峰值电流密度（插图）的比较；(f) 4 mA·cm-2时的GCD曲线。插图是在(e)中标记的CMOP电极不同放电状态下相应的线性拟合Z'-ω-1/2曲线[54]
Fig.10 (a) Schematic diagram of the synthetic procedure of MOC; (b) Calculated ion diffusion coefficients of MOC-5 and MO based on the GITT results; (c) Nyquist plots of MOC-5 electrode in fully charged state for a given cycle; (d) Nyquist plots of MO electrode in fully charged state for a given cycle[53]; (e) CV curves and a comparison of the relative peak current densities (inset) of MO, MOP, CMO, and CMOP electrodes at 0.2 mV s-1; (f) GCD curves at 4 mA·cm-2. The inset is the corresponding linear fitting Z′-ω-1/2 curves at different discharged states of CMOP electrode marked in (e)[54]
图11 (a) PANI插入MnO2纳米片形成夹层膨胀结构的示意图；(b) Zn/PANI-MnO2纽扣电池在0.1 mV·s-1下的CV曲线；(c) 50 mA·g-1下的GCD曲线；(d) H+和Zn2+相继插入MnO2的机理示意图[56]
Fig.11 (a) Schematic of expanded intercalated structure of PANI-intercalated MnO2 nanolayers; (b) CV curves of Zn/PANI -intercalated MnO2 coin-type cell at 0.1 mV·s-1; (c) GCD curves at 50 mA·g-1; (d) Schematic diagram of the sequential insertion of H+ and Zn2+ into MnO2[56]
图12 (a) 0.1 mV·s-1时的CV曲线；(b) KMOd电极在不同充/放电状态下的非原位Mn 2p XPS光谱；(c) Zn2+和H+在KMOd、KMO和α-MnO2中的吸附能[63]；(d) MnO2@N电极的N 1s的XPS光谱；(e) MnO2和MnO2@N电极在0.1 mV·s-1扫描速率下的CV曲线；(f) MnO2和MnO2@N放电状态下离子扩散系数对应的GITT曲线[64]；(g) 参考MnO、Mn3O4、Mn2O3和MnO2，Od-MnO2和C-MnO2的XAS曲线；(h) 初始MnO2和具有氧空位的MnO2的Zn2+嵌入/脱出示意图[65]
Fig.12 (a) CV curves at 0.1 mV·s-1; (b) Ex-situ Mn 2p XPS spectra of the KMOd electrode at different charge/discharge states; (c) Adsorption energies of Zn2+ and H+ in KMOd, KMO, and α-MnO2[63]; (d) XPS spectra of N 1s of MnO2@N electrode; (e) CV curves of MnO2 and MnO2@N electrodes at a scan rate of 0.1 mV·s-1; (f) GITT curves of ion diffusion coefficient during discharge for MnO2 and MnO2@N[64]; (g) XAS curves of Od-MnO2 and C-MnO2 with reference to standard MnO, Mn3O4, Mn2O3, and MnO2; (h) Schematic diagram of Zn2+ intercalation/extraction of initial MnO2 and MnO2 with oxygen vacancies[65]
图13 (a) 新型电解Zn/MnO2电池示意图；(b) 具有暴露的(101)晶面和Mn空位（虚线圆圈）的HAADF-STEM图像和晶体结构[66]；(c) 反应路径的相对能量分布（步骤I~IV）；(d) ABC-H电解质的合成方法；(e) MnO2正极在不同充/放电深度下Mn 2p的XPS图谱；(f) 采用ABC-H电解质的Zn/MnO2电池在0.05 A·g-1下初始五个循环中的放电容量[67]
Fig.13 (a) Schematic of the new electrolytic Zn/MnO2 battery; (b) HAADF-STEM image and crystal structure with exposed (101) facets and Mn vacancies (dotted circles)[66]; (c) Relative energy profiles of the reaction pathway (steps I~IV); (d) Synthesis route of the ABC-H electrolyte (A: a strongly acidic “Acid zone” (A zone), B: a mildly alkaline “Buffer zone” (B zone), C: a neutral “Conservation zone” (C zone), H: hydrogel); (e) XPS spectra of Mn 2p at different charge/discharge depth of MnO2 cathode; (f) Discharge capacity of Zn/MnO2 cell with ABC-H electrolyte in the initial five cycles at 0.05 A·g-1[67]
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