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化学进展 2020, Vol. 32 Issue (12): 2022-2033 DOI: 10.7536/PC200415 前一篇   后一篇

• 综述 •

纤维素基介电材料

史利娜1, 胡欣2,*(), 朱宁1,*(), 郭凯1   

  1. 1 南京工业大学生物与制药工程学院 材料化学工程国家重点实验室 南京 211800
    2 南京工业大学材料科学与工程学院 南京 211800
  • 收稿日期:2020-04-14 修回日期:2020-09-14 出版日期:2021-10-15 发布日期:2020-10-15
  • 通讯作者: 胡欣, 朱宁
  • 作者简介:
    * Corresponding author e-mail: (Xin Hu); (Ning Zhu)
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Cellulose-Based Dielectric Composite

Lina Shi1, Xin Hu2,*(), Ning Zhu1,*(), Kai Guo1   

  1. 1 College of Biotechnology and Pharmaceutical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211800, China
    2 College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211800, China
  • Received:2020-04-14 Revised:2020-09-14 Online:2021-10-15 Published:2020-10-15
  • Contact: Xin Hu, Ning Zhu

作为电荷的高效存储设备,介电电容器受到学术界和产业界越来越多的关注,其中介电材料是介电电容器的核心。长久以来,双向拉伸聚丙烯和聚对苯二甲酸乙二醇酯等石油基聚合物作为介电材料广泛应用于商用电容器设备。然而,随着服役环境的变化(如工作温度升高等),聚合物材料的介电常数与充放电效率下降,同时介电损耗与电流漏导增加,导致储能密度大幅降低,亟待开发具有高储能密度的新型可持续聚合物介电材料。纤维素是地球上储量最丰富的天然聚合物,具有可持续、价格低廉、可生物降解等特点,是理想的候选生物基材料。近年来,通过将纤维素纳米纤维、氰乙基纤维素、再生纤维素及醋酸纤维素分别与不同填料进行复合,显著提高了介电常数、击穿场强与充放电效率,获得了一系列具有高储能密度的生物基介电材料。本文总结了上述纤维素基介电材料的研究进展,并对该领域面临的挑战与发展前景进行了探讨与展望。

关键词： 纤维素, 填料, 复合材料, 介电性能

As an electric charge storage device, dielectric capacitor has attracted growing research interest from both academy and industry. The dielectric material is the key component for the capacitor. Fossil based commercial polymers, such as biaxially oriented polypropylene (BOPP) and polyethylene terephthalate (PET), have been widely used as the dielectric materials in the capacitors. However, the change of service condition (e.g. increasing the temperature) will resulted in the low energy storage density of the fossil based polymer dielectric materials because of the reduced dielectric constant and discharge-charge efficiency, and the increased dielectric loss and current leakage. Therefore, novel sustainable polymer dielectric materials with high energy storage density are highly desirable. As the most abundant natural polymer on the earth, cellulose is considered as the candidate for the potential dielectric materials due to the renewable feedstock, low price and biodegradability, etc. Recently, cellulose-based dielectric composites with high energy storage density have been developed, which show improved dielectric constant, breakdown strength and discharge-charge efficiency. This article focuses on the advances in cellulose-based dielectric composites mentioned above. Moreover, the challenges and opportunities are discussed for the further development in the related topics.

Contents

1 Introduction

2 Cellulose nanofiber dielectric composite

2.1 Cellulose nanofiber/conductive filler dielectric composite

2.2 Cellulose nanofiber/ceramic (rare earth ion) dielectric composite

3 Cyanoethyl cellulose dielectric composite

3.1 Cyanoethyl cellulose/ceramic dielectric composite

3.2 Cyanoethyl cellulose/montmorillonite dielectric composite

3.3 Porous cyanoethyl cellulose dielectric composite

4 Regenerated cellulose dielectric composite

4.1 Regenerated cellulose/organic filler dielectric composite

4.2 Regenerated cellulose/ceramic dielectric composite

5 Cellulose acetate dielectric composite

6 Conclusion

Key words: cellulose, filler, composite, dielectric property
()
表 1 纤维素基复合材料的介电性能
Table 1 Dielectric properties of cellulose-based composites
Cellulose-fillers Dielectric constant Dielectric loss E b(MV/m) Ue (J/cm 3) ref
CEC-BTO
CEC-BTO-ATO
CEC-TiO 2
CEC-MMT
CEC-MMT-RGO
Porous-CEC
RC-PPy
RC-BNNS
RC-BTNF
RC
CNF-CNT
CNF-RGO
CNF-Modify-GO
TOCN-BNNS
TOCN-Eu 3+
CNF-TiO 2
CNF-BTO
CA-Al 2O 3 		27.24
147.30
207
42
472
3.27
25
\
18.6
\
3198
164
3044
9.6
9
19.51
188.03
27.57 		0.3023
4.30
<0.3
\
4.1
\
\
\
\
\
\
\
\
0.025
0.021
3.32
1.21
0.64 		\
\
\
\
\
\
\
249
380
500
42.58
\
\
384
208
\
\
\ 		\
\
\
\
\
\
\
2.01
13.14
16.78
0.8±0.1
\
\
3.9
1.5
\
\
\ 		31
32
35
39
43
44
53
56
57
58
66
68
69
70
74
75
76
86
图1 CNF/CNT纸的制备[36]
Fig.1 Preparation of the CNF/CNT papers[36]
图2 不同CNT负载量的CNF/CNT纸的介电常数随频率变化[36]
Fig.2 Frequency dependence of dielectric constant of the CNF/CNT papers with different CNT loadings[36]
图3 RGO/CNF气体干燥(干凝胶)与定向冷冻(冻凝胶)干燥复合材料的制造示意图[38]
Fig.3 RGO/CNF gas drying (xerogel) and directional freezing (cryogel) drying composite material manufacturing schematic[38]
图4 (a)纤维素及其纳米复合材料的介电常数和(b)介电损耗与频率关系[39]
Fig.4 Variation of (a) dielectric constant and (b) dielectric loss of cellulose and its nanocomposites with frequency (at 1.0 V, 25.0% RH and 25.0 ℃)[39]
图5 CLTOCN/BNNS薄膜的制备和结构示意图[40]
Fig.5 Schematic of the preparation and structure of the CLTOCN/BNNS film[40]
图6 不同含量BNNSs的CLTOCN/BNNS薄膜的介电常数与频率关系[40]
Fig.6 Frequency dependence of the dielectric constant for CLTOCN/BNNS films with different loadings of BNNSs[40]
图7 TOCN-Eu 1与TOCN-Na 1薄膜的介电常数(损耗)与频率关系[44]
Fig.7 Frequency dependence of dielectric constant(loss) of TOCN-Na 1 and TOCN-Eu 1 film[44]
图8 TOCN-Eu 1与TOCN-Na 1薄膜的击穿强度和放电能量密度[44]
Fig.8 Breakdown strength and discharged energy density of TOCN-Na 1 and TOCN-Eu 1 film[44]
图9 CNF/TiO 2复合膜的制备流程[45]
Fig.9 The flow diagram illustrates the preparation of CNF/TiO 2 composite film[45]
图10 CNF/BTO纳米复合膜的制备流程[46]
Fig.10 Preparation of CNF/BTO nanocomposite films[46]
图11 纤维素羟基氰基化示意图[47]
Fig.11 Schematic diagram of cellulose hydroxycyanation[47]
图12 CEC/BTO/ATO纳米复合膜制备的示意图[52]
Fig.12 The schematic illustration of the preparation of CEC/BTO/ATO nanocomposite films[52]
图13 (a) CEC/BTO和(b) CEC/BTO/ATO纳米复合薄膜的介电常数与频率关系[51,52]
Fig.13 Dependence of dielectric permittivity of (a) CEC/BTO and (b) CEC/BTO/ATO nanocomposite films on frequency [51,52]
图14 所提出的MMT和CEC分散RGO的机制[63]
Fig.14 Proposed mechanism for the dispersion of RGO with MMT and CEC[63]
图15 (a) CEC/MMT和(b)CEC/RGO/MMT纳米复合薄膜的介电常数与频率的关系[59,63]
Fig.15 Dependence of dielectric permittivity of (a) CEC/MMT and (b)CEC/RGO/MMT nanocomposite films on frequency[59,63]
图16 不同混凝浴中的CEC溶液(14 wt%、16 wt%和20 wt%)介电常数与频率关系[64]
Fig.16 The dielectric constant as a function of frequency of the CEC solutions(14 wt%, 16 wt%, and 20 wt%) by using different coagulating bath[64]
图17 RC/PPy复合膜的制备示意图[73]
Fig.17 Schematic of fabrication RC/PPy composite film[73]
图18 RC和RC/PPy介电常数(损耗)与频率关系[73]
Fig.18 Variation of dielectric constant (loss) of RC and RC/PPy with frequency[73]
图19 RC/BN纳米复合膜实现高击穿强度和热传导的层状结构示意图[76]
Fig.19 Schematic of the layered structure of the RC/BN nanocomposite film to achieve high breakdown strength and thermal conduction[76]
图20 复合材料中纤维素分子(顶部)和BN纳米板(底部)之间相互作用的模型[76]
Fig.20 Model of interaction between cellulose molecules (top) and BN nanoplate (bottom) in the composite[76]
图21 RC/BTNF制备示意图[77]
Fig.21 Schematic of RC/BTNF Preparation[77]
图22 纤维素膜循环示意图[78]
Fig.22 Schematic of the circulation of cellulose films[78]
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摘要

纤维素基介电材料