Aqueous zinc-based batteries (ZIBs) are considered promising energy storage solutions, particularly targeting low-cost applications needed for levelling electricity production from renewable energy sources. However, numerous challenges need to be overcome to bring the technology to the market, chiefly including cathode dissolution, dendrite formation, hydrogen evolution reaction, and zinc corrosion. The optimisation of the electrolyte, particularly the use of gel-polymer electrolytes (GPEs), is demonstrated as a viable approach to solve or mitigate such issues. In this respect, a comparative study of two GPEs based on biopolymers, agarose and sodium alginate, is presented here. Despite the fast and facile preparation procedure, the GPEs demonstrate to be strongly effective in suppressing dendrite and byproduct formation on zinc metal anodes, due to the abundant ─OH groups along the chains in polymeric matrices. The electrochemical behaviour of GPEs is evaluated in terms of galvanostatic cycling in laboratory-scale zinc metal cells with a CaV6O16·3H2O cathode at low and high active material loadings of 2.5 and 5 mg cm−2, respectively. Resulting cycling performances in terms of specific capacity and rate capability are comparable (low loading electrodes) and even outperform (high loading electrodes) those obtained with a standard liquid electrolyte (2M ZnSO4) laboratory-scale cell, thus accounting for the promising prospects of the bio-polymer GPEs as an alternative green, sustainable electrolyte for next-generation Zn-based batteries.
| [1] |
M. Li, J. Lu, Z. Chen, and K. Amine, “30 Years of Lithium-Ion Batteries,” Advanced Materials30, no. 33 (2018): 1800561.
|
| [2] |
B. E. Lebrouhi, S. Baghi, B. Lamrani, E. Schall, and T. Kousksou, “Critical Materials for Electrical Energy Storage: Li-Ion Batteries,” Journal of Energy Storage55 (2022): 105471.
|
| [3] |
S. Dühnen, J. Betz, M. Kolek, R. Schmuch, M. Winter, and T. Placke, “Toward Green Battery Cells: Perspective on Materials and Technologies,” Small Methods4, no. 7 (2020): 2000039.
|
| [4] |
C. Delmas, “Sodium and Sodium-Ion Batteries: 50 Years of Research,” Advanced Energy Materials8, no. 17 (2018): 1703137.
|
| [5] |
H. Wang, A. Zhou, Z. Hu, et al., “Toward Simultaneous Dense Zinc Deposition and Broken Side-Reaction Loops in the Zn//V2O5 System,” Angewandte Chemie136, no. 11 (2024): e202318928.
|
| [6] |
D. Wang, H. Li, Z. Liu, et al., “A Nanofibrillated Cellulose/Polyacrylamide Electrolyte-Based Flexible and Sewable High-Performance Zn–MnO2 Battery With Superior Shear Resistance,” Small14, no. 51 (2018): 1803978.
|
| [7] |
W. Manalastas, , S. Kumar, V. Verma, L. Zhang, D. Yuan, and M. Srinivasan, “Water in Rechargeable Multivalent-Ion Batteries: An Electrochemical Pandora's Box,” Chemsuschem12, no. 2 (2019): 379-396.
|
| [8] |
M. Liu, P. Wang, W. Zhang, et al., “Strategies for pH Regulation in Aqueous Zinc Ion Batteries,” Energy Storage Materials67 (2024): 103248.
|
| [9] |
D. Frattini, E. G. Gaitán, A. B. Murguialday, M. Armand, and N. Ortiz-Vitoriano, “Essential Data for Industrially Relevant Development of Bifunctional Cathodes and Biopolymer Electrolytes in Solid-State Zinc–Air Secondary Batteries,” Energy & Environmental Science15, no. 12 (2022): 5039-5058.
|
| [10] |
E. García-Gaitán, M. C. Morant-Miñana, D. Frattini, et al., “Agarose-Based Gel Electrolytes for Sustainable Primary and Secondary Zinc-Air Batteries,” Chemical Engineering Journal472 (2023): 144870.
|
| [11] |
J. Zhu, Z. Tie, S. Bi, and Z. Niu, “Towards More Sustainable Aqueous Zinc-Ion Batteries,” Angewandte Chemie136, no. 22 (2024): e202403712.
|
| [12] |
G. Nazir, A. Rehman, J.-H. Lee, et al., “A Review of Rechargeable Zinc–Air Batteries: Recent Progress and Future Perspectives,” Nano-Micro Letters16, no. 1 (2024): 138.
|
| [13] |
C. Li, X. Xie, S. Liang, and J. Zhou, “Issues and Future Perspective on Zinc Metal Anode for Rechargeable Aqueous Zinc-Ion Batteries,” Energy & Environmental Materials3, no. 2 (2020): 146-159.
|
| [14] |
F. Wan and Z. Niu, “Design Strategies for Vanadium-Based Aqueous Zinc-Ion Batteries,” Angewandte Chemie International Edition58, no. 46 (2019): 16358-16367.
|
| [15] |
G. Li, L. Sun, S. Zhang, et al., “Developing Cathode Materials for Aqueous Zinc Ion Batteries: Challenges and Practical Prospects,” Advanced Functional Materials34, no. 5 (2024): 2301291.
|
| [16] |
Q. Wen, H. Fu, R. Cui, et al., “Recent Advances in Interfacial Modification of Zinc Anode for Aqueous Rechargeable Zinc Ion Batteries,” Journal of Energy Chemistry83 (2023): 287-303.
|
| [17] |
A. Kim, Y. Park, J. Choi, S.-H. Yu, and K. W. Nam, “A Comprehensive Review of Cathode Materials for Advanced Aqueous Zinc-Ion Batteries,” ACS Applied Energy Materials8 (2025): 6806-6828.
|
| [18] |
J. Wei, P. Zhang, J. Sun, et al., “Advanced Electrolytes for High-Performance Aqueous Zinc-Ion Batteries,” Chemical Society Reviews53 (2024): 10335-10369.
|
| [19] |
Y. Wang, Z. Wang, F. Yang, et al., “Electrolyte Engineering Enables High Performance Zinc-Ion Batteries,” Small18, no. 43 (2022): 2107033.
|
| [20] |
S. Guo, L. Qin, T. Zhang, et al., “Fundamentals and Perspectives of Electrolyte Additives for Aqueous Zinc-Ion Batteries,” Energy Storage Materials34 (2021): 545-562.
|
| [21] |
D. Chao, W. Zhou, C. Ye, et al., “An Electrolytic Zn–MnO2 Battery for High-Voltage and Scalable Energy Storage,” Angewandte Chemie131, no. 23 (2019): 7905-7910.
|
| [22] |
T. M. C. Faro, G. P. Thim, and M. S. Skaf, “A Lennard-Jones Plus Coulomb Potential for Al3+ Ions in Aqueous Solutions,” Journal of Chemical Physics132, no. 11 (2010): 114509.
|
| [23] |
R. K. Ghavami and Z. Rafiei, “Performance Improvements of Alkaline Batteries by Studying the Effects of Different Kinds of Surfactant and Different Derivatives of Benzene on the Electrochemical Properties of Electrolytic Zinc,” Journal of Power Sources162, no. 2 (2006): 893-899.
|
| [24] |
H.-I. Kim and H.-C. Shin, “SnO Additive for Dendritic Growth Suppression of Electrolytic Zinc,” Journal of Alloys and Compounds645 (2015): 7-10.
|
| [25] |
C. W. Lee, K. Sathiyanarayanan, S. W. Eom, H. S. Kim, and M. S. Yun, “Novel Electrochemical Behavior of Zinc Anodes in Zinc/Air Batteries in the Presence of Additives,” Journal of Power Sources159, no. 2 (2006): 1474-1477.
|
| [26] |
M. Li, Z. Li, X. Wang, et al., “Comprehensive Understanding of the Roles of Water Molecules in Aqueous Zn-Ion Batteries: From Electrolytes to Electrode Materials,” Energy & Environmental Science14, no. 7 (2021): 3796-3839.
|
| [27] |
K. Wu, J. Huang, J. Yi, et al., “Recent Advances in Polymer Electrolytes for Zinc Ion Batteries: Mechanisms, Properties, and Perspectives,” Advanced Energy Materials10, no. 12 (2020): 1903977.
|
| [28] |
R. Qi, W. Tang, Y. Shi, et al., “Gel Polymer Electrolyte Toward Large-Scale Application of Aqueous Zinc Batteries,” Advanced Functional Materials33, no. 47 (2023): 2306052.
|
| [29] |
S. Huang, F. Wan, S. Bi, J. Zhu, Z. Niu, and J. Chen, “A Self-Healing Integrated All-in-One Zinc-Ion Battery,” Angewandte Chemie International Edition58, no. 13 (2019): 4313-4317.
|
| [30] |
W. Zhou, J. Chen, M. Chen, et al., “An Environmentally Adaptive Quasi-Solid-State Zinc-Ion Battery Based on Magnesium Vanadate Hydrate With Commercial-Level Mass Loading and Anti-Freezing Gel Electrolyte,” Journal of Materials Chemistry A8, no. 17 (2020): 8397-8409.
|
| [31] |
J. Cong, X. Shen, Z. Wen, et al., “Ultra-Stable and Highly Reversible Aqueous Zinc Metal Anodes With High Preferred Orientation Deposition Achieved by a Polyanionic Hydrogel Electrolyte,” Energy Storage Materials35 (2021): 586-594.
|
| [32] |
Z. Shen, Y. Liu, Z. Li, et al., “Highly-Entangled Hydrogel Electrolyte for Fast Charging/Discharging Properties in Aqueous Zinc Ion Batteries,” Advanced Functional Materials35 (2024): 2406620.
|
| [33] |
T.-T. Li, P. Chen, X. Fu, et al., “Enhanced Stability-Based Hydroxymethyl Cellulose/Polyacrylamide Interpenetrating Dual Network Hydrogel Electrolyte for Flexible Yarn Zinc-Ion Batteries,” Journal of the Electrochemical Society171 (2024): 070511.
|
| [34] |
W. Lao-atiman, T. Julaphatachote, P. Boonmongkolras, and S. Kheawhom, “Printed Transparent Thin Film Zn-MnO2 Battery,” Journal of the Electrochemical Society164, no. 4 (2017): A859-A863.
|
| [35] |
F. Wang, J. Zhang, H. Lu, et al., “Production of Gas-Releasing Electrolyte-Replenishing Ah-Scale Zinc Metal Pouch Cells With Aqueous Gel Electrolyte,” Nature Communications14, no. 1 (2023): 4211.
|
| [36] |
C. Fu, Y. Wang, C. Lu, et al., “Modulation of Hydrogel Electrolyte Enabling Stable Zinc Metal Anode,” Energy Storage Materials51 (2022): 588-598.
|
| [37] |
H. Zheng, Y. Huang, L. Zhao, et al., “Eco-Friendly Lignocellulosic Gel Polymer Electrolyte for Aqueous Zinc Energy Storage Devices,” ACS Sustainable Chemistry & Engineering10, no. 38 (2022): 12751-12762.
|
| [38] |
W. Yang, W. Yang, J. Zeng, et al., “Biopolymer-Based Gel Electrolytes for Electrochemical Energy Storage: Advances and Prospects,” Progress in Materials Science144 (2024): 101264.
|
| [39] |
H. Lu, J. Hu, X. Wei, et al., “A Recyclable Biomass Electrolyte Towards Green Zinc-Ion Batteries,” Nature Communications14, no. 1 (2023): 4435.
|
| [40] |
D. Ruiz, V. F. Michel, M. Niederberger, and E. Lizundia, “Chitin Nanofibrils From Fungi for Hierarchical Gel Polymer Electrolytes for Transient Zinc-Ion Batteries With Stable Zn Electrodeposition,” Small19, no. 45 (2023): 2303394.
|
| [41] |
Q. Liu, Z. Yu, Q. Zhuang, J. K. Kim, F. Kang, and B. Zhang, “Anti-Fatigue Hydrogel Electrolyte for All-Flexible Zn-Ion Batteries,” Advanced Materials35, no. 36 (2023): 2300498.
|
| [42] |
N. Almenara, R. Gueret, A. J. Huertas-Alonso, U. T. Veettil, M. H. Sipponen, and E. Lizundia, “Lignin–Chitosan Gel Polymer Electrolytes for Stable Zn Electrodeposition,” ACS Sustainable Chemistry & Engineering11, no. 6 (2023): 2283-2294.
|
| [43] |
N. Mittal, A. Ojanguren, D. Kundu, E. Lizundia, and M. Niederberger, “Bottom-up Design of a Green and Transient Zinc-Ion Battery With Ultralong Lifespan,” Small19, no. 7 (2023): 2206249.
|
| [44] |
Y. Meng, L. Zhang, M. Peng, et al., “Developing Thermoregulatory Hydrogel Electrolyte to Overcome Thermal Runaway in Zinc-Ion Batteries,” Advanced Functional Materials32, no. 46 (2022): 2206653.
|
| [45] |
H. Peng, X. Gao, K. Sun, et al., “Physically Cross-Linked Dual-Network Hydrogel Electrolyte With High Self-Healing Behavior and Mechanical Strength for Wide-Temperature Tolerant Flexible Supercapacitor,” Chemical Engineering Journal422 (2021): 130353.
|
| [46] |
J. Yu, H. Lin, J. Peng, et al., “In Situ Construction of Ultra-Stable Zincophilic Sodium Alginate Artificial Interface Layer for Dendrite-Free Anode in Aqueous Zinc-Ion Batteries,” Electrochimica Acta488 (2024): 144191.
|
| [47] |
B. Zhang, L. Qin, Y. Fang, et al., “Tuning Zn2+ Coordination Tunnel by Hierarchical Gel Electrolyte for Dendrite-Free Zinc Anode,” Science Bulletin67, no. 9 (2022): 955-962.
|
| [48] |
A. Fernández-Benito, J. C. Martinez-López, M. Javad Jafari, et al., “Green and Scalable Biopolymer-Based Aqueous Polyelectrolyte Complexes for Zinc-Ion Charge Storage Devices,” ChemElectroChem10, no. 22 (2023): e202300327.
|
| [49] |
H. Dong, J. Li, S. Zhao, et al., “Investigation of a Biomass Hydrogel Electrolyte Naturally Stabilizing Cathodes for Zinc-Ion Batteries,” ACS Applied Materials & Interfaces13, no. 1 (2021): 745-754.
|
| [50] |
M. Chen, J. Chen, W. Zhou, X. Han, Y. Yao, and C. P. Wong, “Realizing an All-Round Hydrogel Electrolyte Toward Environmentally Adaptive Dendrite-Free Aqueous Zn–MnO2 Batteries,” Advanced Materials33, no. 9 (2021): 2007559.
|
| [51] |
Q. Han, X. Chi, S. Zhang, et al., “Durable, Flexible Self-Standing Hydrogel Electrolytes Enabling High-Safety Rechargeable Solid-State Zinc Metal Batteries,” Journal of Materials Chemistry A6, no. 45 (2018): 23046-23054.
|
| [52] |
L. Luo, Y. Liu, Z. Shen, Z. Wen, S. Chen, and G. Hong, “High-Voltage and Stable Manganese Hexacyanoferrate/Zinc Batteries Using Gel Electrolytes,” ACS Applied Materials & Interfaces15, no. 24 (2023): 29032-29041.
|
| [53] |
S. Zhang, N. Yu, S. Zeng, et al., “An Adaptive and Stable Bio-Electrolyte for Rechargeable Zn-Ion Batteries,” Journal of Materials Chemistry A6, no. 26 (2018): 12237-12243.
|
| [54] |
P. Liang, K. Zhu, Y. Rao, et al., “Hydrated Calcium Vanadate Nanoribbons With a Stable Structure and Fast Ion Diffusion as a Cathode for Quasi-Solid-State Zinc-Ion Batteries,” ACS Applied Materials & Interfaces16, no. 19 (2024): 24723-24733.
|
| [55] |
P. Sun, W. Liu, D. Yang, et al., “Stable Zn Anodes Enabled by High-Modulus Agarose Gel Electrolyte With Confined Water Molecule Mobility,” Electrochimica Acta429 (2022): 140985.
|
| [56] |
Y. Tang, C. Liu, H. Zhu, et al., “Ion-Confinement Effect Enabled by Gel Electrolyte for Highly Reversible Dendrite-Free Zinc Metal Anode,” Energy Storage Materials27 (2020): 109-116.
|
| [57] |
X. Liu, H. Zhang, D. Geiger, et al., “Calcium Vanadate Sub-Microfibers as Highly Reversible Host Cathode Material for Aqueous Zinc-Ion Batteries,” Chemical Communications55, no. 16 (2019): 2265-2268.
|
| [58] |
L.-M. Zhang, C.-X. Wu, J.-Y. Huang, X.-H. Peng, P. Chen, and S.-Q. Tang, “Synthesis and Characterization of a Degradable Composite Agarose/HA Hydrogel,” Carbohydrate Polymers88, no. 4 (2012): 1445-1452.
|
| [59] |
Siddaramaiah, T. M. M. Swamy, B. Ramaraj, and J. H. Lee, “Sodium Alginate and Its Blends With Starch: Thermal and Morphological Properties,” Journal of Applied Polymer Science109, no. 6 (2008): 4075-4081.
|
| [60] |
W. Cai, X. Zhang, G. Li, and L. Chen, “Tailoring Codirectional Zn2+ Pathways With Biomaterials for Advanced Hydrogel Electrolytes in High-Performance Zinc Metal Batteries,” Chemical Engineering Journal484 (2024): 149390.
|
| [61] |
L. Xu, T. Meng, X. Zheng, et al., “Nanocellulose-Carboxymethylcellulose Electrolyte for Stable, High-Rate Zinc-Ion Batteries,” Advanced Functional Materials33, no. 27 (2023): 2302098.
|
| [62] |
X. Zhong, P. Tian, C. Chen, X. Meng, H. Mi, and F. Shi, “Preparation and Interface Stability of Alginate-Based Gel Polymer Electrolyte for Rechargeable Aqueous Zinc Ion Batteries,” Journal of Electroanalytical Chemistry927 (2022): 116968.
|
| [63] |
Y. Gong, B. Wang, H. Ren, et al., “Recent Advances in Structural Optimization and Surface Modification on Current Collectors for High-Performance Zinc Anode: Principles, Strategies, and Challenges,” Nano-Micro Letters15, no. 1 (2023): 208.
|
| [64] |
S. Huang, L. Hou, T. Li, Y. Jiao, and P. Wu, “Antifreezing Hydrogel Electrolyte With Ternary Hydrogen Bonding for High-Performance Zinc-Ion Batteries,” Advanced Materials34, no. 14 (2022): 2110140.
|
| [65] |
S. Wu, M. Hua, Y. Alsaid, et al., “Poly (Vinyl Alcohol) Hydrogels With Broad-Range Tunable Mechanical Properties via the Hofmeister Effect,” Advanced Materials33, no. 11 (2021): 2007829.
|
| [66] |
F. Wang, O. Borodin, T. Gao, et al., “Highly Reversible Zinc Metal Anode for Aqueous Batteries,” Nature Materials17, no. 6 (2018): 543-549.
|
| [67] |
Z. Cao, P. Zhuang, X. Zhang, M. Ye, J. Shen, and P. M. Ajayan, “Strategies for Dendrite-Free Anode in Aqueous Rechargeable Zinc Ion Batteries,” Advanced Energy Materials10, no. 30 (2020): 2001599.
|
| [68] |
A. R. Mainar, E. Iruin, L. C. Colmenares, et al., “An Overview of Progress in Electrolytes for Secondary Zinc-Air Batteries and Other Storage Systems Based on Zinc,” Journal of Energy Storage15 (2018): 304-328.
|
| [69] |
M. Chen, J. Chen, W. Zhou, X. Han, Y. Yao, and C. P. Wong, “Realizing an All-Round Hydrogel Electrolyte Toward Environmentally Adaptive Dendrite-Free Aqueous Zn–MnO2 Batteries,” Advanced Materials33, no. 9 (2021): e2007559.
|
| [70] |
F. Wan, L. Zhang, X. Dai, X. Wang, Z. Niu, and J. Chen, “Aqueous Rechargeable Zinc/Sodium Vanadate Batteries With Enhanced Performance From Simultaneous Insertion of Dual Carriers,” Nature Communications9, no. 1 (2018): 1656.
|
| [71] |
J. Ding, Z. Du, L. Gu, et al., “Ultrafast Zn2+ Intercalation and Deintercalation in Vanadium Dioxide,” Advanced Materials30, no. 26 (2018): 1800762.
|
| [72] |
F. Wan and Z. Niu, “Design Strategies for Vanadium-Based Aqueous Zinc-Ion Batteries,” Angewandte Chemie131, no. 46 (2019): 16508-16517.
|
| [73] |
V. Soundharrajan, B. Sambandam, S. Kim, et al., “Na2V6O16· 3H2O Barnesite Nanorod: An Open Door to Display a Stable and High Energy for Aqueous Rechargeable Zn-Ion Batteries as Cathodes,” Nano Letters18, no. 4 (2018): 2402-2410.
|
| [74] |
P. He, G. Zhang, X. Liao, et al., “Sodium Ion Stabilized Vanadium Oxide Nanowire Cathode for High-Performance Zinc-Ion Batteries,” Advanced Energy Materials8, no. 10 (2018): 1702463.
|
| [75] |
M. H. Alfaruqi, V. Mathew, J. Song, et al., “Electrochemical Zinc Intercalation in Lithium Vanadium Oxide: A High-Capacity Zinc-Ion Battery Cathode,” Chemistry of Materials29, no. 4 (2017): 1684-1694.
|
| [76] |
B. Sambandam, V. Soundharrajan, S. Kim, et al., “Aqueous Rechargeable Zn-Ion Batteries: An Imperishable and High-Energy Zn2V2O7 Nanowire Cathode Through Intercalation Regulation,” Journal of Materials Chemistry A6, no. 9 (2018): 3850-3856.
|
| [77] |
S. Chen, Y. Zhang, H. Geng, Y. Yang, X. Rui, and C. C. Li, “Zinc Ions Pillared Vanadate Cathodes by Chemical Pre-Intercalation Towards Long Cycling Life and Low-Temperature Zinc Ion Batteries,” Journal of Power Sources441 (2019): 227192.
|
| [78] |
D. Kundu, B. D. Adams, V. Duffort, S. H. Vajargah, and L. F. Nazar, “A High-Capacity and Long-Life Aqueous Rechargeable Zinc Battery Using a Metal Oxide Intercalation Cathode,” Nature Energy1, no. 10 (2016): 16119.
|
| [79] |
Y. Zhang, F. Wan, S. Huang, S. Wang, Z. Niu, and J. Chen, “A Chemically Self-Charging Aqueous Zinc-Ion Battery,” Nature Communications11, no. 1 (2020): 2199.
|
| [80] |
C. Xia, J. Guo, P. Li, X. Zhang, and H. N. Alshareef, “Highly Stable Aqueous Zinc-Ion Storage Using a Layered Calcium Vanadium Oxide Bronze Cathode,” Angewandte Chemie130, no. 15 (2018): 4007-4012.
|
| [81] |
N. Xu, X. Lian, H. Huang, Y. Ma, L. Li, and S. Peng, “CaV6O16·3H2O Nanorods as Cathode for High-Performance Aqueous Zinc-Ion Battery,” Materials Letters287 (2021): 129285.
|
| [82] |
H. Yu, M. Aakyiir, S. Xu, J. D. Whittle, D. Losic, and J. Ma, “Maximized Crystal Water Content and Charge-Shielding Effect in Layered Vanadate Render Superior Aqueous Zinc-Ion Battery,” Materials Today Energy21 (2021): 100757.
|
| [83] |
J. Wang, J. Wang, Y. Jiang, et al., “CaV6O16·2.8 H2O With Ca2+ Pillar and Water Lubrication as a High-Rate and Long-Life Cathode Material for Ca-Ion Batteries,” Advanced Functional Materials32, no. 25 (2022): 2113030.
|
| [84] |
M. Yan, P. He, Y. Chen, et al., “Water-Lubricated Intercalation in V2O5·nH2O for High-Capacity and High-Rate Aqueous Rechargeable Zinc Batteries,” Advanced Materials30, no. 1 (2018): 1703725.
|
| [85] |
L. Suo, D. Oh, Y. Lin, et al., “How Solid-Electrolyte Interphase Forms in Aqueous Electrolytes,” Journal of the American Chemical Society139, no. 51 (2017): 18670-18680.
|
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