具有高导电性的PVDF/MWCNTs-AgNWs@MXene双层三维网络的电磁屏蔽复合薄膜

施鸥玲; 谭妍妍; 武晓; 龙雪彬; 秦舒浩

doi:10.13801/j.cnki.fhclxb.20231205.004

具有高导电性的PVDF/MWCNTs-AgNWs@MXene双层三维网络的电磁屏蔽复合薄膜

doi: 10.13801/j.cnki.fhclxb.20231205.004

施鸥玲¹,
谭妍妍²,
武晓^{1, 2},
龙雪彬^{1, 2},
秦舒浩^{1, 2, ,}

1.
国家复合改性聚合物材料工程技术研究中心，贵阳 550014
2.
贵州民族大学　化学工程学院，贵阳 550025

基金项目: 黔科合服企〔2023〕001；黔科合中引地〔2023〕035；观科合同〔2022〕02

详细信息

通讯作者:
秦舒浩，博士，研究员，研究方向为聚合物材料的共混改性、聚合物材料的聚集态结构与性能　E-mail：qinshuhao@126.com

中图分类号: TB332
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出版历程
- 收稿日期: 2023-11-02
- 修回日期: 2023-11-20
- 录用日期: 2023-11-23
- 网络出版日期: 2023-12-06
- 刊出日期: 2024-08-15

PVDF/MWCNTs-AgNWs@MXene bilayer 3D networks electromagnetic shielding composite films with highly conductive

SHI Ouling¹,
TAN Yanyan²,
WU Xiao^{1, 2},
LONG Xuebin^{1, 2},
QIN Shuhao^{1, 2
, ,}

1.
National Engineering Research Center for Compounding and Modification of Polymer Materials, Guiyang 550014, China
2.
College of Chemical Engineering, Guizhou Minzu University, Guiyang 550025, China

Funds: Qiankehe Service Enterprises [2023] 001; Qiankehe Zhongyindi[2023]035; Guanke Contract [2022] 02

摘要

摘要: 随着通信网络、无线设备及航空航天的快速发展，电磁波危害日益加剧，因而亟需电磁屏蔽性能更优异的复合材料。本文采用MXene (Ti₃C₂T_x)、银纳米线(AgNWs)和多壁碳纳米管(MWCNTs)构建了双层的高导电三维(导电率最高为1.4×10⁴ S·m⁻¹)网络电磁屏蔽复合薄膜(Ti₃C₂T_x MXene基功能复合薄膜)。特别是采取真空辅助抽滤法(VAF)将10 mL AgNWs及15 mL Ti₃C₂T_x MXene的水溶液吸附于聚偏氟乙烯(PVDF)/MWCNTs复合薄膜之上，制备出的Ti₃C₂T_x MXene基功能复合薄膜的总电磁干扰屏蔽效能(EMI SE_T)高达69.0 dB，比商用标准(20 dB)高出245%，其中吸收损耗效能(SE_A)占比85.1%。说明Ti₃C₂T_x MXene基功能复合薄膜主要的电磁损耗机制为吸收损耗，比电磁屏蔽效能(SSE/t)最高可达2719.8 dB/(cm⁻²·g)。这项工作为新型MXene材料在电磁屏蔽复合材料中的应用提供了结构设计和研究思路。
- Ti₃C₂T_x MXene /
- AgNWs /
- 复合薄膜 /
- 电磁屏蔽 /
- 吸收损耗
Abstract: With the development of communication networks, wireless devices and aerospace industries. Electromagnetic wave hazards become prevalent. Therefore, it is essential to develop composites with better electromagnetic shielding properties. In this paper, highly conductive three-dimensional (conductivity up to 1.4×10⁴ S·m⁻¹) networked electromagnetic shielding composite films (Ti₃C₂T_x MXene-based functional composite films) were constructed using MXene (Ti₃C₂T_x), silver nanowires (AgNWs) and multi-walled carbon nanotubes (MWCNTs) in a bilayer. In particular, the aqueous solutions of 10 mL AgNWs and 15 mL Ti₃C₂T_x MXene were adsorbed on top of poly(vinylidene fluoride) (PVDF)/MWCNTs composite films by vacuum-assisted filtration (VAF), and the total electromagnetic interference shielding effectiveness (EMI SE_T) of the Ti₃C₂T_x MXene-based functional composite film was as high as 69.0 dB, which was 245% higher than that of the commercial standard (20 dB), of which the absorption loss effectiveness (SE_A) accounted for 85.1%. It is shown that the main electromagnetic loss mechanism of Ti₃C₂T_x MXene-based functional composite films is absorption loss, with a specific electromagnetic shielding effectiveness (SSE/t) of up to 2719.8 dB/(cm⁻²·g). This work provides structural design and research ideas for the application of novel MXene materials in electromagnetic shielding composites.
- Ti₃C₂T_x MXene /
- AgNWs /
- composite films /
- electromagnetic shielding /
- absorption loss

HTML全文

图 1 PVDF/MWCNTs-3wt%-AgNWs@MXene-X (M3-Ag@MX-X)双层复合薄膜的制备流程图

Figure 1. Flow chart for the preparation of PVDF/MWCNTs-3wt%-AgNWs@MXene-X (M3-Ag@MX-X) bilayer composite films

PVDF—Poly(vinylidene fluoride); MWCNTs—Multi-walled carbon nanotubes; AgNWs—Silver nanowires; PVP K30—Polyvinylpyrrolidone

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图 2 Ti₃C₂T_x MXene的SEM图像 (a)和EDS (b)及Ti₃AlC₂ (刻蚀前)和Ti₃C₂T_xMXene (刻蚀后)的XRD图谱(c)；AgNWs的SEM图像(d)和XRD图谱(e)及Ti₃C₂T_x MXene、AgNWs和AgNWs@MXene的FTIR图谱(f)

Figure 2. SEM image (a) and EDS mapping (b) of Ti₃C₂T_x MXene and XRD pattern of Ti₃AlC₂ (before etching) and Ti₃C₂T_x MXene (after etching) (c); SEM image (d) and XRD pattern (e) of AgNWs and FTIR spectra of Ti₃C₂T_x MXene, AgNWs and AgNWs@MXene (f)

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图 3 PVDF/MWCNTs-3wt%-MXene-X双层复合薄膜的SEM图像(a、b、c分别代表M3-MX-0、M3-MX-10、M3-MX-20；1：表观形貌；2：底层局部放大形貌；3：断面形貌；4：抽滤层局部放大形貌)

Figure 3. SEM images of PVDF/MWCNTs-3wt%-MXene-X bilayer composite films (a, b, c represent M3-MX-0, M3-MX-10, M3-MX-20, respectively; 1: Apparent appearance; 2: Local enlargement of the bottom layer; 3: Cross-section appearance; 4: Local enlargement of the extraction layer)

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图 4 PVDF/MWCNTs-3wt%-AgNWs@MXene-X双层复合薄膜的SEM图像(A、B、C分别代表M3-Ag@MX-0、M3-Ag@MX-10、M3-Ag@MX-20；1：表观形貌；2：底层局部放大形貌；3：断面形貌；4：抽滤层局部放大形貌)

Figure 4. SEM images of PVDF/MWCNTs-3wt%-AgNWs@MXene-X bilayer composite films (A, B, C represent M3-Ag@MX-0, M3-Ag@MX-10, M3-Ag@MX-20, respectively; 1: Apparent appearance; 2: Local enlargement of the bottom layer; 3: Cross-section appearance; 4: Local enlargement of the extraction layer)

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图 5 (a) PVDF/MWCNTs-3wt%-MXene-X双层复合薄膜导电率曲线；(b) PVDF/MWCNTs-3wt%-AgNWs@MXene-X双层复合薄膜的导电率曲线

Figure 5. Electrical conductivity curves: (a) PVDF/MWCNTs-3wt%-MXene-X bilayer composite films; (b) PVDF/MWCNTs-3wt%-AgNWs@MXene-X bilayer composite films

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图 6 PVDF/MWCNTs-3wt%-MXene-X双层复合薄膜((a), (b), (e), (f))和PVDF/MWCNTs-3wt%-AgNWs@MXene-X ((c), (d), (g), (h))双层复合薄膜的电磁屏蔽性能

EMI—Electromagnetic interference; SE_T, SE_A, SE_R—Total electromagnetic shielding efficiency, electromagnetic absorption efficiency, electromagnetic reflection efficiency; SSE_t—The ratio of total electromagnetic shielding efficiency

Figure 6. Electromagnetic shielding properties of PVDF/MWCNTs-3wt%-MXene-X bilayer composite film ((a), (b), (e), (f)) and PVDF/MWCNTs-3wt%-AgNWs@MXene-X ((c), (d), (g), (h)) bilayer composite film

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图 7 PVDF/MWCNTs-AgNWs@MXene双层复合薄膜的电磁屏蔽机制分析图

Figure 7. Analysis of electromagnetic shielding mechanism of PVDF/MWCNTs-AgNWs@MXene bilayer composite film

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表 1 聚偏氟乙烯/多壁碳纳米管-3wt%-银纳米线@MXene-X (PVDF/MWCNTs-3wt%-AgNWs@MXene-X)各层铸膜液配方

Table 1. Poly(vinylidene fluoride)/multi-walled carbon nanotubes-3wt%-silver nanowires@MXene-X ( PVDF/MWCNTs-3wt%-AgNWs@MXene-X) formulations for each layer of cast film solution

Sample	The bottom layer				The top layer
Sample	PVDF/wt%	MWCNTs/wt%	PVP K30/wt%	DMAC/wt%	RGO@Fe₃O₄/mL	PVP K30/g	AgNWs/mL
M3-MX-0	13	3	0.5	83.5	0	0.5	0
M3-MX-5	13	3	0.5	83.5	5	0.5	0
M3-MX-10	13	3	0.5	83.5	10	0.5	0
M3-MX-15	13	3	0.5	83.5	15	0.5	0
M3-MX-20	13	3	0.5	83.5	20	0.5	0
M3-MX-25	13	3	0.5	83.5	25	0.5	0
M3-Ag@MX-0	13	3	0.5	83.5	10	0.5	0
M3-Ag@MX-5	13	3	0.5	83.5	10	0.5	5
M3-Ag@MX-10	13	3	0.5	83.5	10	0.5	10
M3-Ag@MX-15	13	3	0.5	83.5	10	0.5	15
M3-Ag@MX-20	13	3	0.5	83.5	10	0.5	20
M3-Ag@MX-25	13	3	0.5	83.5	10	0.5	25
Notes: PVP K30—Polyvinyl pyrrolidone; DMAC—Dimethylacetamide; RGO—Reduced graphene oxide.

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表 2 不同Ti₃C₂T_x MXene含量的双层复合薄膜的导电性能数据

Table 2. Conductivities of bilayer composite films with different Ti₃C₂T_x MXene contents

Sample	Thickness/ mm	Electrical conductivity/(S·m⁻¹)	Conductivity growth rate/%
M3-MX-0	0.57	2.5	—
M3-MX-5	0.46	5.9	57.6
M3-MX-10	0.42	7.9	25.3
M3-MX-15	0.39	8.7	9.2
M3-MX-20	0.50	7.5	−16.0
M3-MX-25	0.44	5.5	−36.4
M3-Ag@MX-0	0.51	4.1×10³	99.9
M3-Ag@MX-5	0.46	5.1×10³	19.6
M3-Ag@MX-10	0.60	8.5×10³	40.0
M3-Ag@MX-15	0.47	1.4×10⁴	39.3
M3-Ag@MX-20	0.43	1.3×10⁴	−7.7
M3-Ag@MX-25	0.46	1.2×10⁴	−8.3

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表 3 不同Ti₃C₂T_x MXene含量的双层复合薄膜的电磁屏蔽效能数据

Table 3. Electromagnetic shielding effectiveness data of bilayer composite films with different Ti₃C₂T_x MXene contents

Sample	SE_T/dB	SE_R/dB	SE_A/dB	SE_A/SE_R/%	SSE_t/(dB·(cm⁻²·g)⁻¹)
M3-MX-0	5.0	0.9	4.0	4.3	87.6
M3-MX-5	6.8	1.5	5.3	3.5	147.5
M3-MX-10	7.2	1.7	5.5	3.2	171.0
M3-MX-15	7.0	1.7	5.3	3.0	180.2
M3-MX-20	6.9	1.8	5.0	2.8	137.1
M3-MX-25	6.9	1.6	5.4	3.5	157.7
M3-Ag@MX-0	60.2	9.5	50.8	4.6	2487.7
M3-Ag@MX-5	60.4	10.7	49.5	5.3	2102.2
M3-Ag@MX-10	61.5	9.5	52.0	5.5	2068.3
M3-Ag@MX-15	69.0	10.3	58.7	5.7	2356.6
M3-Ag@MX-20	68.2	10.3	57.8	5.6	2719.8
M3-Ag@MX-25	67.9	10.0	57.9	5.8	2439.4
Notes: The values of SE_T (dB), SE_A (dB), and SE_R (dB) in the table are the average values obtained at 8.2-12.4 GHz; SE_A/SE_R is the ratio of absorption loss SE_A to reflection loss SE_R; SSEt denotes the ratio of EMI SE.

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