Development status and future prospects of flexible metal-air batteries

doi:10.19799/j.cnki.2095-4239.2021.0580

Abstract

Abstract:

A flexible metal-air battery is paid lots of attention because of flexible deformation and energy storage. At present, flexible metal-air batteries are still beset by a host of problems, including battery flexibility, low conductivity and flexibility in air electrodes, and low ionic conductivity and poor mechanical properties in solid gel electrolytes. This review summarizes the structural classification of the main types of flexible metal-air batteries: one-dimensional cable-type, two-dimensional planar-type, and three-dimensional sandwich-structure type. Next, the paper examines the preparation and characteristics of non-free-standing and free-standing air electrodes. Non-free-standing electrodes are prepared using a binder to coat the catalyst onto a conductive substrate (e.g., carbon paper or cloth). Binder additives have disadvantages: they increase the inactive material content, block the pore structure, reduce electrical conductivity, and allow the catalyst to flake off. In contrast, free-standing electrodes use hydrothermal vapor-phase atomic layer deposition to grow catalysts in situ on conductive substrates. This avoids the problems noted above for non-free-standing electrodes. This review goes on to summarize related research into improving electrolyte performance and ionic conductivity (by adding different polymers, reducing polymer crystallinity, and through temperature changes). Finally, the outlook for future development of metal-air batteries is explored. Preparation of free-standing electrodes and investigation of new gel electrolyte materials are expected to become research hotspots. If the interface between air electrode and gel electrolyte can be brought into closer contact, leading to integration, the battery could be started directly by dripping electrolyte and adding metal foil. This would greatly simplify assembly and extend the potential applications of flexible metal-air batteries.

Key words: flexible metal-air batteries, cathode, free-standing, gel electrolyte

CLC Number:

TQ 152

Zhicheng CHEN, Zongxu LI, Ling CAI, Yisi LIU. Development status and future prospects of flexible metal-air batteries[J]. Energy Storage Science and Technology, 2022, 11(5): 1401-1410.

Figures/Tables 7

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References 45

1	曹宁, 孟佳欣, 臧晓蓓. 碳基柔性正极制备的综合性实验研究[J]. 实验室研究与探索, 2021, 40(2): 38-42, 53.
	CAO N, MENG J X, ZANG X B. Comprehensive experimental study on the preparation of carbon-based flexible cathode[J]. Research and Exploration in Laboratory, 2021, 40(2): 38-42, 53.
2	孟锦涛, 周良毅, 钟芸, 等. 柔性钠离子电池研究进展[J]. 材料导报, 2020, 34(1): 1169-1176.
	MENG J T, ZHOU L Y, ZHONG Y, et al. Research progress on flexible sodium-ion batteries[J]. Materials Reports, 2020, 34(1): 1169-1176.
3	马超. 柔性可充锌—空电池锌电极的电化学制备及电池性能[D]. 天津: 天津大学, 2018.
	MA C. Electrochemical preparation and cell performance of zinc electrodes for flexible rechargeable zinc-air batteries[D]. Tianjin: Tianjin University, 2018.
4	刘志成, 彭道刚, 赵慧荣, 等. 双碳目标下储能参与电力系统辅助服务发展前景[J]. 储能科学与技术, 2022, 11(2): 704-716.
	LIU Z C, PENG D G, ZHAO H R, et al. Development prospects of energy storage participating in auxiliary services of power systems under the targets of the dual-carbon goal[J]. Energy Storage Science and Technology, 2022, 11(2): 704-716.
5	LI Y B, FU J, ZHONG C, et al. Recent advances in flexible zinc-based rechargeable batteries[J]. Advanced Energy Materials, 2019, 9(1): doi:10.1002/aenm.201802605.
6	YU H H, LIU D P, FENG X L, et al. Mini review: Recent advances on flexible rechargeable Li-air batteries[J]. Energy & Fuels, 2021, 35(6): 4751-4761.
7	LIU Y S, SUN Q, LI W Z, et al. A comprehensive review on recent progress in aluminum-air batteries[J]. Green Energy & Environment, 2017, 2(3): 246-277.
8	李蕊. 基于材料、集流体与电池结构设计的柔性/可拉伸电池的研究[D]. 北京: 北京科技大学, 2021.
	LI R. The study of materials, current collector and cell structure design for flexible/stretchable batteries[D]. Beijing: University of Science and Technology Beijing, 2021.
9	CAO Z Q, HU H B, WU M Z, et al. Planar all-solid-state rechargeable Zn-air batteries for compact wearable energy storage[J]. Journal of Materials Chemistry A, 2019, 7(29): 17581-17593.
10	ZHANG Y G, DENG Y P, WANG J Y, et al. Recent progress on flexible Zn-air batteries[J]. Energy Storage Materials, 2021, 35: 538-549.
11	SONG Z S, DING J, LIU B, et al. A rechargeable Zn-air battery with high energy efficiency and long life enabled by a highly water-retentive gel electrolyte with reaction modifier[J]. Advanced Materials, 2020, 32(22): doi:10.1002/adma.201908127.
12	ZUO X X, CHANG K, ZHAO J, et al. Bubble-template-assisted synthesis of hollow fullerene-like MoS₂ nanocages as a lithium ion battery anode material[J]. Journal of Materials Chemistry A, 2016, 4(1): 51-58.
13	PARK J, PARK M, NAM G, et al. All-solid-state cable-type flexible zinc-air battery[J]. Advanced Materials, 2015, 27(8): 1396-1401.
14	SHEN Y T, LIANG L J, ZHANG S Q, et al. Organelle-targeting surface-enhanced Raman scattering (SERS) nanosensors for subcellular pH sensing[J]. Nanoscale, 2018, 10(4): 1622-1630.
15	TANG C, WANG B, WANG H F, et al. Defect engineering toward atomic Co-Nx-C in hierarchical graphene for rechargeable flexible solid Zn-air batteries[J]. Advanced Materials, 2017, 29(37): doi:10.1002/adma.201703185.
16	TAN Y Y, ZHANG Z Y, LEI Z, et al. Thiourea-Zeolitic imidazolate Framework-67 assembly derived Co-CoO nanoparticles encapsulated in N, S Codoped open carbon shell as bifunctional oxygen electrocatalyst for rechargeable flexible solid Zn-Air batteries[J]. Journal of Power Sources, 2020, 473: doi:10.1016/j.‍jpowsour.2020.228570.
17	WANG W, TANG M H, ZHENG Z Y, et al. Alkaline polymer membrane-based ultrathin, flexible, and high-performance solid-state Zn-air battery[J]. Advanced Energy Materials, 2019, 9(14): doi:10.1002/aenm.201803628.
18	陈祥, 雷凯翔, 孙洪明, 等. 尖晶石型氧化物催化剂与金属-空气电池[J]. 储能科学与技术, 2017, 6(5): 904-923.
	CHEN X, LEI K X, SUN H M, et al. Spinel-type transition metal oxide electrocatalysts for metal-air batteries[J]. Energy Storage Science and Technology, 2017, 6(5): 904-923.
19	BIDAULT F, BRETT D J L, MIDDLETON P H, et al. Review of gas diffusion cathodes for alkaline fuel cells[J]. Journal of Power Sources, 2009, 187(1): 39-48.
20	LIN C, SHINDE S S, WANG Y, et al. Flexible and rechargeable Zn-air batteries based on green feedstocks with 75% round-trip efficiency[J]. Sustainable Energy & Fuels, 2017, 1(9): 1909-1914.
21	XU N N, CAI Y X, PENG L W, et al. Superior stability of a bifunctional oxygen electrode for primary, rechargeable and flexible Zn-air batteries[J]. Nanoscale, 2018, 10(28): 13626-13637.
22	WANG Z F, RUAN Z H, LIU Z X, et al. A flexible rechargeable zinc-ion wire-shaped battery with shape memory function[J]. Journal of Materials Chemistry A, 2018, 6(18): 8549-8557.
23	LU Q, ZOU X H, LIAO K M, et al. Direct growth of ordered N-doped carbon nanotube arrays on carbon fiber cloth as a free-standing and binder-free air electrode for flexible quasi-solid-state rechargeable Zn-Air batteries[J]. Carbon Energy, 2020, 2(3): 461-471.
24	ZHU C Y, MA Y Y, ZANG W J, et al. Conformal dispersed cobalt nanoparticles in hollow carbon nanotube arrays for flexible Zn-air and Al-air batteries[J]. Chemical Engineering Journal, 2019, 369: 988-995.
25	JIN Q Y, REN B W, CUI H, et al. Nitrogen and cobalt co-doped carbon nanotube films as binder-free trifunctional electrode for flexible zinc-air battery and self-powered overall water splitting[J]. Applied Catalysis B: Environmental, 2021, 283: doi:10.1016/j.apcatb.2020.119643.
26	ZHAO X T, ABBAS S C, HUANG Y Y, et al. Robust and highly active FeNi@NCNT nanowire arrays as integrated air electrode for flexible solid-state rechargeable Zn-air batteries[J]. Advanced Materials Interfaces, 2018, 5(9): doi:10.1002/admi.201701448.
27	WU Y G, RAN F. Vanadium nitride quantum dot/nitrogen-doped microporous carbon nanofibers electrode for high-performance supercapacitors[J]. Journal of Power Sources, 2017, 344: 1-10.
28	WANG X D, ZHANG Y F, ZHANG X J, et al. A highly stretchable transparent self-powered triboelectric tactile sensor with metallized nanofibers for wearable electronics[J]. Advanced Materials, 2018, 30(12): doi:10.1002/adma.201706738.
29	WANG P C, WAN L, LIN Y Q, et al. Construction of mass-transfer channel in air electrode with bifunctional catalyst for rechargeable zinc-air battery[J]. Electrochimica Acta, 2019, 320: doi:10.1016/j.electacta.2019.134564.
30	ZHANG L, HUANG Q A, YAN W, et al. Design and fabrication of non-noble metal catalyst-based air-cathodes for metal-air battery[J]. The Canadian Journal of Chemical Engineering, 2019, 97(12): 2984-2993.
31	WANG Y M, SONG S F, XU C H, et al. Development of solid-state electrolytes for sodium-ion battery-A short review[J]. Nano Materials Science, 2019, 1(2): 91-100.
32	WANG Y F, PAN W D, LEONG K W, et al. Solid-state Al-air battery with an ethanol gel electrolyte[J]. Green Energy & Environment, 2021: doi:10.1016/j.gee.2021.05.011.
33	ZAHID A R M, MASRI M N, HUSSIN M H, et al. The preliminary study on cassava (Manihot Esculenta) as gel polymer electrolyte for zinc-air battery[J]. AIP Conference Proceedings, 2018, 2030(1): doi:10.1063/1.5066919.
34	ZHANG Z, ZUO C C, LIU Z H, et al. All-solid-state Al-air batteries with polymer alkaline gel electrolyte[J]. Journal of Power Sources, 2014, 251: 470-475.
35	MIAO H, CHEN B, LI S H, et al. All-solid-state flexible zinc-air battery with polyacrylamide alkaline gel electrolyte[J]. Journal of Power Sources, 2020, 450: doi: 10.1016/j.jpowsour.2019.227653.
36	DEGHIEDY N M, EL-SAYED S M. Evaluation of the structural and optical characters of PVA/PVP blended films[J]. Optical Materials, 2020, 100: doi:10.1016/j.optmat.2020.109667.
37	MANO V, RIBEIRO E SILVA M E S, BARBANI N, et al. Binary blends based on poly(N-isopropylacrylamide): Miscibility studies with PVA, PVP, and PAA[J]. Journal of Applied Polymer Science, 2004, 92(2): 743-748.
38	MIGLIARDINI F, PALMA T M, GAELE M F, et al. Solid and acid electrolytes for Al-air batteries based on xanthan-HCl hydrogels[J]. Journal of Solid State Electrochemistry, 2018, 22(9): 2901-2916.
39	DI PALMA T M, MIGLIARDINI F, GAELE M F, et al. Aluminum-air batteries with solid hydrogel electrolytes: Effect of pH upon cell performance[J]. Analytical Letters, 2021, 54(1/2): 28-39.
40	HATTA F F, YAHYA M Z A, ALI A M M, et al. Electrical conductivity studies on PVA/PVP-KOH alkaline solid polymer blend electrolyte[J]. Ionics, 2005, 11(5/6): 418-422.
41	陆霞, 吴仁香, 朱云峰, 等. PVA-PAA-KOH碱性聚合物电解质膜的制备及其性能[J]. 功能材料, 2013, 44(4): 590-594.
	LU X, WU R X, ZHU Y F, et al. Preparation and properties of PVA-PAA-KOH alkaline polymer electrolyte membrane[J]. Journal of Functional Materials, 2013, 44(4): 590-594.
42	YANG C C, LIN S J. Alkaline composite PEO-PVA-glass-fibre-mat polymer electrolyte for Zn-air battery[J]. Journal of Power Sources, 2002, 112(2): 497-503.
43	WU G M, LIN S J, YANG C C. Alkaline Zn-air and Al-air cells based on novel solid PVA/PAA polymer electrolyte membranes[J]. Journal of Membrane Science, 2006, 280(1/2): 802-808.
44	WANG M X, FAN L D, QIN G, et al. Flexible and low temperature resistant semi-IPN network gel polymer electrolyte membrane and its application in supercapacitor[J]. Journal of Membrane Science, 2020, 597: doi:10.1016/j.memsci.2019.117740.
45	LIAO Y H, RAO M M, LI W S, et al. Fumed silica-doped poly(butyl methacrylate-styrene)-based gel polymer electrolyte for lithium ion battery[J]. Journal of Membrane Science, 2010, 352(1/2): 95-99.

相关问题	原因	影响	解决办法
缓慢的反应速率	氧还原(ORR)与析氧反应(OER)的过电位太高^[18]	能量密度与能量效率受到限制	开发高效稳定的电催化剂
空气电极溢流	电解液渗透进空气电极的孔隙	减少氧气进入	用石蜡处理空气电极;优化气相扩散层(GDL)
碳酸盐沉淀	大气中的CO₂与碱性电解液反应产生碳酸盐沉淀^[19]	降低电解液导电性与空气电极活性	用纯氧代替以减少CO₂浓度
电解液渗漏	开放体系水分蒸发	缩短电池寿命	优化气相扩散层(GDL)
电极结构组成复杂、制备繁琐	黏结剂等添加物会增加非活性物质组分	堵塞孔结构、降低电导率等	简化电极结构，采用自支撑式空气电极

凝胶类型	各种物质比例	离子电导率	引用
PVA+PVP+KOH	PVA∶PVP=8∶2 40% KOH	(1.5±1.1)×10 ^-⁴ S/cm	[40]
PVA+AA+KOH	PVA∶AA=7∶3 6 mol/L KOH	3.5510 ^-² S/cm	[41]
PEO+PVA+glass-fiber-mat	PEO∶PVA=1∶1	0.0475 S/cm	[42]
PVA+PAA+KOH	PVA∶PAA=10∶7.5	0.301 S/cm	[43]
PAM+PVP+H₃PO₄	AM∶PVP=1∶0.16	0.138 S/cm	[44]
P(BMA-St)+PEG	P(BMA-St)∶PEG=1.25 g∶0.67 mL	2.2×10 ^-³ S/cm	[45]

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