天然粘土矿物材料在质子交换膜中的应用进展

王贝; 凌志伟; 周依琳; 付旭东; 张荣; 胡圣飞; 李骁; 刘清亭

doi:10.13801/j.cnki.fhclxb.20231031.003

天然粘土矿物材料在质子交换膜中的应用进展

doi: 10.13801/j.cnki.fhclxb.20231031.003

王贝^{1, 2},
凌志伟^{1, 2},
周依琳^{1, 2},
付旭东^{1, 2},
张荣^{1, 2},
胡圣飞^{1, 2},
李骁^{1, 3},
刘清亭^{1, 2, ,}

1.
湖北工业大学　绿色轻工材料湖北省重点实验室，武汉 430068
2.
湖北工业大学　材料与化学工程学院，武汉 430068
3.
武汉众宇动力系统科技有限公司，武汉 430079

基金项目: 绿色轻工材料湖北省重点实验室项目(202307B04)

详细信息

通讯作者:
刘清亭，博士，副教授，硕士生导师，研究方向为高分子材料成型加工、质子交换膜燃料电池　E-mail: liuqt@hbut.edu.cn

中图分类号: TM911.4；TB332
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- 文章访问数: 204
- HTML全文浏览量: 172
- PDF下载量: 15
- 被引次数: 0
出版历程
- 收稿日期: 2023-07-18
- 修回日期: 2023-09-28
- 录用日期: 2023-10-19
- 网络出版日期: 2023-10-31
- 刊出日期: 2024-03-01

Application progress of natural clays in proton exchange membrane

WANG Bei^{1, 2},
LING Zhiwei^{1, 2},
ZHOU Yilin^{1, 2},
FU Xudong^{1, 2},
ZHANG Rong^{1, 2},
HU Shengfei^{1, 2},
LI Xiao^{1, 3},
LIU Qingting^{1, 2
, ,}

1.
Hubei Provincial Key Laboratory of Green Materials for Light Industry, Hubei University of Technology, Wuhan 430068, China
2.
School of Materials and Chemical Engineering, Hubei University of Technology, Wuhan 430068,China
3.
Wuhan Troowin Power System Technology CO., LTD., Wuhan 430079, China

Funds: Hubei Provincial Key Laboratory of Green Materials for Light Industry (202307B04)

摘要

摘要: 质子交换膜(PEM)作为聚合物电解质燃料电池关键部件直接影响着电池性能，拓宽其运行温度和湿度范围有利于简化燃料电池水、热管理设计，从而促进电池小型化和降低成本。近些年来，开发天然粘土/聚合物复合膜已成为提升传统PEM性能和拓宽其应用温、湿度范围的重要途径之一。天然粘土矿物多为含水层状硅酸盐化合物，特殊的孔、层结构和纳米尺度赋予其较大的比表面积和表面效应，其表面和层间富含的羟基在提高复合膜机械强度的同时固定了传质介质，从而在复合膜中构建新的质子传导通道用以提高膜的性能。从纳米微观多个维度综述了不同类别粘土矿物的结构与性能，以及其在质子交换膜中的研究进展，对天然粘土矿物复合质子交换膜的研究进行了总结与展望。
- 天然粘土矿物 /
- 质子交换膜 /
- 复合膜 /
- 纳米尺度 /
- 燃料电池
Abstract: As a key component of polymer electrolyte fuel cells, the proton exchange membrane (PEM) directly impacts cell performance. Expanding its operational temperature and humidity range is advantageous for simplifying fuel cell water and thermal management designs, thereby promoting miniaturization and cost reduction. In recent years, the development of polymer composite membranes based on natural clay has emerged as a crucial avenue for enhancing traditional PEM performance and broadening its applicability across varying environmental conditions. Natural clay minerals predominantly consist of hydrated layered silicate compounds, characterized by unique pore and layer structures at the nanoscale, endowing them with substantial specific surface area and surface effects. The abundance of hydroxyl groups on their surfaces and interlayers not only enhances the mechanical strength of composite membranes but also immobilizes mass transport media. Consequently, these materials facili-tate the creation of novel proton-conductive pathways within the composite membrane, thereby elevating membrane performance. We comprehensively review, from a nanoscale perspective, various categories of clay minerals, elucidating their structural and performance attributes. Furthermore, we provide a comprehensive summary and future prospects of research advancements in natural clay mineral-composite proton exchange membranes.
- natural clays /
- proton exchange membrane /
- composite membrane /
- nanoscale /
- fuel cells

HTML全文

图 1 不同粘土矿物的层结构：(a) 1∶1型粘土的晶胞堆积；(b) 2∶1型粘土；(c) 不同晶体结构的各种堆叠排列^[22]

Figure 1. Different layer structures: (a) Stacking of unit cell of 1∶1 type clays; (b) 2∶ 1 type clays; (c) Various stacking arrangements of different crystal structures^[22]

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图 2 已报道的用于燃料电池中的质子交换膜(PEM)的粘土矿物总结^{[26, 29-32]}

Figure 2. Summary of the reported clays-based for proton exchange membrane (PEM) in fuel cells^{[26, 29-32]}

PBI—Polybenzimidazole

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图 3 磺化沸石复合膜的制备流程^[33]

Figure 3. Scheme for fabricating the sulfonated zeolite composite membranes^[33]

SPAES—Sulfonated poly(arylene ether sulfone)

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图 4 (a) 聚乙烯亚胺@海泡石纳米棒(PEI@SNR)纳米颗粒、聚(2, 5-苯并咪唑) (ABPBI)/PEI@SNR膜的制备图；(b) 磷酸(PA)掺杂的ABPBI/PEI@SNR膜的质子传导途径^[25]

Figure 4. (a) Schematic representation of the preparation of polyethyleneimine (PEI)@silicon nanorods (SNR) nanoparticles, poly(2, 5-benzimidazole) (ABPBI)/PEI@SNR membranes; (b) Proton conducting pathways in phosphoric acid (PA)-doped ABPBI/ PEI@SNR membrane^[25]

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图 5 离子液体(IL)@埃洛石(HNTs)和ABPBI/IL@HNTs复合膜的制备过程示意图^[28]

Figure 5. Preparation process schematic of ionic liquid (IL)@halloysite (HNTs) and ABPBI/IL@HNTs composite membrane^[28]

AHNTs—HNTs were subjected to microwave-assisted heating in hydrochloric acid to obtain AHNTs; DABA—3, 4-diaminobenzoic acid; MEA—Membrane electrode assembly

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图 6 氧化石墨烯(GO)@微生物蒙脱土(mMMT)层状结构制备示意图^[34]

Figure 6. Schematic illustration of the preparation of graphene oxide (GO)@microbial montmorillonite (mMMT) lamellae^[34]

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图 7 PA/聚苯并咪唑(PBI)/天然白云母(Mus)复合膜的制备示意图^[31]

Figure 7. Schematic representation of the preparation of PA/PBI/muscovite (Mus) composite membrane^[31]

HT-PEMFC—High–temperature proton exchange membrane fuel cells; DMAc—N, N-dimethylacetamide

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表 1 各类应用于质子交换膜燃料电池(PEMFCs)的天然粘土/聚合物复合膜性能对比

Table 1. Comparison of performance of polymer/natural clay composite membranes applied to proton exchange membrane fuel cells (PEMFCs)

Composite membrane	Clay	Tensile strength/ MPa	Proton conductivity/ (S·cm⁻¹)	Peak power density/ (W·cm⁻²)	Temperature T/℃	Ref.
Nafion/Zeolite	Zeolite	—	0.129 (80℃)	0.51 (85℃/100%RH)	70-120	[83]
Nafion/HZSM/IL	Zeolite	—	0.2 (80℃/60%RH)	0.6 (80℃)	100	[84]
Aquvion/pHNT-SF	HNT	—	0.28 (90℃/90%RH)	—	—	[60]
Nafion/HNTs-SO₃H	HNT	—	0.073 (80℃/90%RH)	—	—	[85]
MgAl-Sep Nafion	Sep	—	0.132 (100℃/100%RH)	0.55 (80℃/100%RH)	—	[59]
GO@mMMT/Nafion	MMT	19.2	0.0364 (80℃/98%RH)	0.546 (50℃/100%RH)	40-90	[34]
PBI+IL/NaY	Zeolite	—	0.054 (200℃)	0.269 (150℃)	20-200	[50]
ABPBI/IL@HNTs	HNT	149.28	0.045 (180℃/0%RH) 0.071 (90℃/98%RH)	0.38 (160℃/0%RH)	20-180	[28]
ABPBI/S-Sep	Sep	99	0.051 (180℃/0%RH)	0.23 (180℃/0%RH)	40-180	[59]
ABPBI/IL@SNR	Sep	204.24 (undoped)	0.048 (180℃/0%RH)	0.28 (180℃/0%RH)	40-180	[26]
ABPBI/PEI@SNR	Sep	190 (undoped) 54 (PA-doped)	0.04 (180℃/0%RH)	0.27 (180℃/0%RH)	40-180	[25]
ABPBI-MMT/SPVA	MMT	79.39 (undoped) 60.35 (PA-doped)	0.157 (140℃/100%RH)	1.1 (140℃/100%RH)	20-140	[86]
PBI/Mus	Mica	135 (undoped) 7.5 (PA-doped)	0.042 (150℃/0%RH)	0.586 (150℃/0%RH)	140-170	[31]
SP/SZ	Zeolite	18.72	0.03 (120℃/50%RH)	0.791 (80℃/100%RH)	120	[33]
SPEES-SA/SMZ	Zeolite	62	0.124 (80℃)	0.45 (80℃/30%RH)	80	[37]
SPEEK/DHNTs/HPW	HNT	41.3	0.117 (25℃/20%RH)	—	—	[63]
SPEEK/DSNT-A@B	HNT	47.4	0.084 (80℃/100%RH)	—	—	[87]
LDH/Sepiolite/SPEEK	Sep	47.5	0.093 (110℃/100%RH)	—	—	[55]
Notes: Sep—Sepiolite; MMT—Montmorillonite; HZSM—Na-ZSM zeolite in acid form; pHNT-SF—Pretreated-perfluorosulfonated halloysite; HNTs-SO₃H—Sulphonic acid functionalized halloysite; S-Sep—Sulfonated sepiolite; SPVA—Sulfonated polyvinyl alcohol; SP—Sulfonated poly(arylene ether sulfone); SZ—Sulfonated zeolite; SPEES-SA—Sulfanilic acid functionalized poly(1,4-phenylene ether ether sulfone); SMZ—Sulfonic acid functionalized zeolites of Na-mordenite zeolite; SPEEK—Sulfonated poly(ether ether ketone); DHNTs—Polydopamine coated halloysite nanotubes; HPW—Phosphotungstic acid; DSNT-A@B—Acid-base double-shell nanotubes with carboxylate inner shell and an imidazole outer shell; LDH—Layered double hydroxide; RH—Relative humidity.

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表 2 各类应用于直接甲醇燃料电池(DMFCs)的天然粘土/聚合物复合膜性能对比

Table 2. Comparison of performance of polymer/natural clay composite membranes applied to direct methanol fuel cells (DMFCs)

Composite membrane	Clay	Tensile strength/ MPa	Proton conductivity/ (S·cm⁻¹)	Peak power density/ (W·cm⁻²)	Temperature T/℃	Ref.
Nafion/AFB	Zeolite	25	0.088 (room temperature)	5 mol/L MeOH: 0.12 (70℃)	—	[88]
MOR/NF	Zeolite	16.6	0.0501 (30℃)	4 mol/L MeOH: 0.01064 (70℃)	—	[47]
Nafion®/BMMT	MMT	—	0.08 (25℃/95%RH)	—	—	[89]
PBI/m-MMT	MMT	70.4 (undoped) 47.3 (PA-doped)	—	—	—	[90]
SSA-sPEEK-HSO₃-zeolite-13X	Zeolite	11.9	0.12 (70℃)	0.130 (70℃)	25-70	[91]
SMMT/SPEEK	MMT	51.2	0.105 (100℃/100%RH)	1.5 mol/L MeOH: 0.021 (60℃)	—	[92]
Notes: AFB—Acid functionalized zeolite Beta; MOR/NF—Mordenite/Nafion; BMMT—Bio-functionalized montmorillonite; m-MMT—Modified MMT; SSA-sPEEK—Sulfosuccinic acid-sulfonated polyether ether ketone; SMMT—Sulfonated montmorillonite.

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