Acta Phys. -Chim. Sin. ›› 2024, Vol. 40 ›› Issue (6): 2307017.doi: 10.3866/PKU.WHXB202307017
• REVIEW • Previous Articles
Meng-Yin Wang1,2, Ruo-Bei Huang2,3, Jian-Feng Xiong1,2, Jing-Hua Tian1,2,*(
), Jian-Feng Li1,2,*(
), Zhong-Qun Tian1,2
Received:2023-07-11
Revised:2023-08-18
Accepted:2023-08-22
Published:2023-11-29
Contact:
Email: jhtian@xmu.edu.cn (Jing-Hua Tian)Li@xmu.edu.cn (Jian-Feng Li)
Supported by:Meng-Yin Wang, Ruo-Bei Huang, Jian-Feng Xiong, Jing-Hua Tian, Jian-Feng Li, Zhong-Qun Tian. Critical Role and Recent Development of Separator in Zinc-Air Batteries[J]. Acta Phys. -Chim. Sin. 2024, 40(6), 2307017. doi: 10.3866/PKU.WHXB202307017
Table 1
Important parameters for separator materials in modern batteries 60."
| Parameter | Description, target value | Property |
| Thickness | Separator thickness < 25 μm | Mechanical |
| Tensile strength | ≈ 95 MPa | |
| Puncture strength | > 300 g/25.4 μm | |
| Gurley | Air permeability ≈ 25 s·mL−1 | Electrochemical |
| MacMullin number | Resistance ratio, ≤ 11 | |
| Wettability | Fast and complete wetting in electrolytes | |
| Chemical stability | Long term stability in batteries, ≈ 10 years | |
| Pore size | Small pores that direct electrode contact is avoided, < 1 μm | |
| Porosity | Volumetric separator ratio with and without pores, ≈ 40% | |
| Dimensional stability | Shrinkage at 200 ℃, < 5% | Thermal |
| Shut down temperature | 130 ℃ |
Table 2
Properties of separator and its performance in zinc-air batteries."
| Separator | Diffusion coefficient of [Zn(OH)4]2− (cm2·min−1) | σ(OH−) (S·cm−1) | Stability | Mechanical property | Performance | Ref. |
| PPO–TMA | 1.13 × 10−8 | 1.737 × 10−2 | chemical: soaked in KOH, 7 mol·L−1 solution for 150 h at 30 ℃ thermal: ~180–250 ℃ electrochemical: stability window was measured to be 4 V | – | 803 mAh·gZn−1 932 mWh·gZn−1 (15 mA·cm−2 at 0.9 V cut-off voltage) | |
| PBE(Nafion-PVA/PAA) | 4.1 × 10−7 | 6.6 × 10−3 | Good electrochemical stability | tensile modulus 973.1 MPa | ~41.6 h (20 mA·cm−2, 10 min each cycle) | |
| PVA/PAA | – | 0.301 | Stable in Al|PVA/PAA|Al cell with cyclic sweeping range from −1.5 to +1.5 V | – | 50 mW·cm−2 | |
| RDC/N-PAA/KOH | – | 0.430 | −0.8 – +0.8 V | tensile strength 381.43 kPa | round-trip efficiency (69.36%) and longer cycle times (11 h). 40.25 mW∙cm−2 and 731.5 mAh∙g−1 (2 mA∙cm−2) | |
| PAM-based AGEs | – | 0.2156 | – | repeatable mechanical bending and pounding | 105 mW∙cm−2 140 cycles (~23.3 h) (5 mA∙cm−2, 10 min each cycle) | |
| CCNF-PDIL SSEs | – | 0.2865 | – | maximum stress of 105 MPa by virtue of the reinforced concrete architecture | 720 cycles (240 h) (2 mA·cm−2, 10 min each cycle) 135 mW∙cm−2 (current density of 220 mA·cm−2) | |
| BC/PVA | – | 8.08 × 10−2 | high thermal/chemical stability | tensile strength 0.951 MPa | 650 cycles (> 440 h) (0.5 mA·cm−2, 40 min per cycle) | |
| TEAOH-PVA | – | 3.0 × 10−2 | better thermal stability than the KOH-PVA electrolyte | good mechanical flexibility | 74.1 mW∙cm−2 Over 30 h (20 min, 5 mA⋅cm−3) Shelf Life: 15 days | |
| Celgard®3501 (reference) | 2.324 × 10−5 | 1.28 × 10−2 | Non stable in −0.9 – 0.9 V (vs. Pt/Pt2+) | Tensile Modulus 751.4 MPa | 15 h (20 mA·cm−2, each cycle 10 min) |
Fig 3
Flow chart of membrane preparation and schematic diagram of ion selectivity for zinc-air batteries. (A) Schematic diagram of the membrane preparation process 61. (B) (a) Schematic representation depicting the overall manufacturing procedure of the PBE membrane. (b) Conceptual illustration underlying the unique function of the PBE membrane as a selective ion transport channel, wherein anions are allowed to migrate predominantly through the ion-conducting PVA/PAA nanofiber mat due to the existence of the ion-repelling (i.e., Donnan exclusion effect) continuous Nafion phase 47. (C) Schematic representation of stepwise manufacturing procedure and morphological characterization (FE-SEM images) of ERC membrane: (a) electrospun PEI nanomat; (b) impregnation of PEI nanomat with PVA; (c) ERC membrane and conceptual illustration depicting its unique permselective transport behavior, wherein an inset shows morphology of the ERC membrane after the (NMP-assisted) selective removal of PEI nanofibers 62. (D) Schematic illustration underlying the exceptional permselectivity of ERC membrane as an alternative separator membrane for rechargeable Zn-air cells, which lies far beyond those achievable with conventional microporus polyolefin separators 62. (E) (a) Schematic representation of PPO-6CO-Br, PPO-6CH2-Br, and PPO-6CH2-Q Polymer Preparation. (b) Schematic representation of DAPCl Synthesis. (c) Schematic diagram of the AEM fabrication protocol 64."
Fig 4
(A) Schematic illustration of a specially-designed diffusion cell 62. (B) Structural change of separator membranes and air cathodes after the cycle time of 900 min, with a particular focus on deposited ZnO powders 47. (B) (a)–(c) Celgard3501: SEM and EDS images (yellow dots represent Zn elements of ZnO powders) of the (a) Celgard3501 surface facing the air cathode and (b) air cathode surface (an inset is a digital photograph); (c) conceptual illustration of Zn(OH)42− crossover through Celgard3501. (d) SEM and EDS images of the PBE membrane surface facing the air cathode."
Fig 5
Membrane preparation process and structure diagram with high ionic conductivity for Zinc-air batteries. (A) Schematic depiction of the chemical structure of RDC/N-PAA/KOH polyelectrolyte 71. (B) Schematic diagram showing the key structural features of PVA/PEO/KOH membranes without (a) and with LD-MCC (b). LD-MCC entrapped KOH and water through the interactions of hydrogen bonds. In this way, compared to case (a), the incorporation of LD-MCC (case (b)) provided more opportunities for OH− transfer via the surface site hopping along the chains of polyelectrolyte polymers and the chains of water molecules 74. (C) Overall fabrication process of the PGG-GP membrane 75."
Fig 6
Preparation and schematic diagram of high water retention and transparent flexible Zinc-air battery. (A) Synthesis of the TEAOH-PVA electrolyte and the schematic diagram of a flexible ZAB 88. (B) Top: Schematic of the fabrication process for KI-PVAA-GO GPE, highlighting the microstructure of the PVAA-GO polymer network. Bottom: Configuration of sandwich- and cable-type flexible ZABs utilizing PVAA-GO GPE 86. (C) Assembly mechanism of the G-CyBA SN hydrogel and the G-CyBA/PAAm SP-DN hydrogel. Atoms are colored as follows: red – oxygen, blue – nitrogen, gray – carbon, pink – boron, white – hydrogen, and purple – potassium (yellow for hydrogen in the enlarged view for clear visualization) 91. (D) An illustrative schematic of the transparent ZAB and its components. The included optical microscope image shows the battery's configuration as seen from the top of the cathode surface 59."
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