Preparation and temperature-sensitive response behavior of graphene-carbon nanotubes-polylactic acid/polyethylene glycol phase change energy storage composites
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摘要: 本文通过溶液-熔融共混法制备了石墨烯-碳纳米管-聚乳酸/聚乙二醇(Gr-CNT-PLA/PEG)相变储能复合材料，详细探究了导电粒子和PEG对PLA相变储能复合材料结晶性能、导电性能和温敏响应行为的影响。在溶液-熔融共混过程中，二维结构的石墨烯和一维结构的碳纳米管在热力学和动力学因素的作用下可以物理复配为三维结构的Gr-CNT杂化粒子，改善导电粒子在复合材料内部的分散性，使复合材料具有较低的导电逾渗域值，约为0.51wt%。此外，在PEG相变储能材料和导电粒子的作用下，进一步改善了Gr-CNT-PLA/PEG复合材料的导电性能和结晶性能，结晶温度从100℃(PLA)提高到了约130℃((Gr-CNT50)0.6-PLA/PEG10)。在恒温温度-电阻测试中发现Gr-CNT-PLA/PEG复合材料的电导率随等温热处理温度的提高表现出先降低后升高的现象；在循环变温温度-电阻测试中，Gr-CNT-PLA复合材料在37℃到140℃的循环温度区间内表现出了低温正温度系数(PTC)和高温负温度系数(NTC)效应；而通过相变储能材料PEG和循环温度值的协同调控，Gr-CNT-PLA/PEG复合材料在降温过程中表现出良好的相转变储能平台，成功地实现了复合材料单调的PTC效应和高温度灵敏度，灵敏度(ΔR/R0)可达3000%；且随着PEG质量含量的提高可以有效地实现复合材料的储能平台越宽，可达16.28 min，为高灵敏度温度传感器的制备奠定了基础。Abstract: In this study, a graphene-carbon nanotube-poly(lactic acid)/polyethylene glycol (Gr-CNT-PLA/PEG) phase change energy storage composite material was prepared using a solution-melt blending method. The effects of conductive particles and PEG on the crystallization behavior, electrical conductivity, and temperature-sensitive response of the PLA phase change energy storage composite material were investigated in detail. During the solution-melt blending process, the two-dimensional graphene and one-dimensional carbon nanotubes can physically hybridize into three-dimensional Gr-CNT hybrid particles under the influence of thermodynamic and kinetic factors, improving the dispersion of conductive particles in the composite material and reducing the percolation threshold to about 0.51wt%. Furthermore, the electrical conductivity and crystallization behavior of the Gr-CNT-PLA/PEG composite material are further improved by the interaction between PEG phase change energy storage material and conductive particles, and the crystallization temperature is increased from 100℃ (PLA) to about 130℃ ((Gr-CNT50)0.6-PLA/PEG10). In the constant temperature-resistance test, the conductivity of the Gr-CNT-PLA/PEG composite material decreases and then increases with the increase of isothermal heat treatment temperature. In the cyclic temperature-resistance test, the Gr-CNT-PLA composite material exhibites low-temperature PTC and high-temperature NTC effects in the cyclic temperature range of 37℃ to 140℃. Through the synergistic regulation of phase change energy storage material PEG and cyclic temperature value, the Gr-CNT-PLA/PEG composite material exhibites a good phase transition energy storage platform during cooling, successfully achieving a monotonic PTC effect and high-temperature sensitivity, with a sensitivity (ΔR/R0) up to 3000%. Moreover, with the increase of PEG mass content, the energy storage platform of the composite material can be effectively widened, up to 16.28 min, providing a basis for the preparation of high-sensitivity temperature sensors.
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图 1 聚乳酸/聚乙二醇(PLA/PEG)导电复合材料的制备示意图
Figure 1. Schematic diagram of poly(lactic acid)/polyethylene glycol (PLA/PEG) conductive composite
CNT—Carbon nanotube; Gr—Graphene
图 2 (Gr-CNTx)-PLA (a)、(Gr-CNT50)y-PLA (b)和(Gr-CNT50)0.6-PLA/PEGz (c)复合材料的电导率曲线
Figure 2. Conductivity curves of (Gr-CNTx)-PLA (a), (Gr-CNT50)y-PLA (b) and (Gr-CNT50)0.6-PLA/PEGz (c) composites
pc—Percolationthreshold
图 3 (Gr-CNT50)0.6-PLA/PEGz复合材料微观形貌
Figure 3. Microstructure of (Gr-CNT50)0.6-PLA/PEGz composites
图 4 (Gr-CNT50)y-PLA (a) 和(Gr-CNT50)0.6-PLA/PEGz (b) 复合材料的非等温DSC曲线；(Gr-CNT50)y-PLA (c) 和(Gr-CNT50)0.6-PLA/PEGz (d) 复合材料的相对结晶度随时间变化曲线
Figure 4. Non-isothermal DSC curves of (Gr-CNT50)x-PLA (a) and (Gr-CNT50)0.6-PLA/PEGz (b) composites; Relative crystallinity curves of (Gr-CNT50)x-PLA (c) and (Gr-CNT50)0.6-PLA/PEGz (d) composites with time
图 5 (Gr-CNT50)0.6-PLA (a)和(Gr-CNT50)0.6-PLA/PEG10 (b) 复合材料不同热处理温度Tend下电导率随时间变化图
Figure 5. Conductivity varies of (Gr-CNT50)0.6-PLA (a) and (Gr-CNT50)0.6-PLA/PEG10 (b) composites with time under different heat treatment temperatures Tend
图 6 (Gr-CNT50)0.6-PLA (a) 和(Gr-CNT50)0.6-PLA/PEG10 (b) 复合材料在不同温度下热处理后的DSC曲线
Figure 6. DSC curves of (Gr-CNT50)0.6-PLA (a) and (Gr-CNT50)0.6-PLA/PEG10 (b) composites after heat treatment at different temperatures
图 7 (Gr-CNT50)0.6-PLA (a)、(Gr-CNT50)0.6-PLA/PEG5 (b)和(Gr-CNT50)0.6-PLA/PEG10 (c)复合材料的循环变温电阻曲线
Figure 7. Cyclic resistance curves of (Gr-CNT50)0.6-PLA (a), (Gr-CNT50)0.6-PLA/PEG5 (b) and (Gr-CNT50)0.6-PLA/PEG10 (c) composites
图 8 (Gr-CNT50)0.6-PLA/PEGz复合材料在循环温度处理前后的XRD曲线
Figure 8. XRD curves of (Gr-CNT50)0.6-PLA/PEGz composites before and after temperature cycling test
图 9 (Gr-CNT50)0.6-PLA/PEG10复合材料在37~80℃ (a)、37~90℃ (b)、37~100℃ (c)和37~140℃ (d)内的循环变温电阻曲线
Figure 9. Cyclic temperature variable resistance curves of (Gr-CNT50)0.6-PLA/PEG10 composite at 37~80℃ (a), 37~90℃ (b), 37~100℃ (c) and 37~140℃ (d)
表 1 (Gr-CNTx)0.6-PLA/PEGz复合材料配比表
Table 1. Ratio table of (Gr-CNTx)0.6-PLA/PEGz composites
Sample PLA
/wt%CNT
/wt%Gr
/wt%PEG
/wt%(Gr-CNT20)0.6-PLA 99.4 0.12 0.48 0 (Gr-CNT30)0.6-PLA 99.4 0.18 0.42 0 (Gr-CNT50)0.6-PLA 99.4 0.3 0.3 0 (Gr-CNT70)0.6-PLA 99.4 0.4 0.2 0 (Gr-CNT80)0.6-PLA 99.4 0.48 0.12 0 (Gr-CNT50)0.6-PLA/PEG1 98.4 0.3 0.3 1 (Gr-CNT50)0.6-PLA/PEG3 96.4 0.3 0.3 3 (Gr-CNT50)0.6-PLA/PEG5 94.4 0.3 0.3 5 (Gr-CNT50)0.6-PLA/PEG7 92.4 0.3 0.3 7 (Gr-CNT50)0.6-PLA/PEG10 89.4 0.3 0.3 10 (Gr-CNT50)0.6-PLA/PEG20 79.4 0.3 0.3 20 
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表 2 (Gr-CNT50)0.6-PLA/PEGz复合材料相对结晶度Xi变化
Table 2. Change in relative crystallinity Xi of (Gr-CNT50)0.6-PLA/PEGz composites
Samples Tend/℃ ∆Hcc/
(J·g−1)∆Hm/
(J·g−1)$ {X}_{i} $/% (Gr-CNT50)0.6-PLA 25 24.6 39.7 16.2 100 0 40.5 43.3 120 0 46.9 50.2 135 0 49.2 52.6 (Gr-CNT50)0.6-PLA/
PEG1025 8.3 42.9 37.8 100 0 42.8 46.8 120 0 53.9 59.0 135 0 56.0 61.2 Notes: Tend—Isothermal heat treatment temperature; ∆Hcc—Enthalpy of cold crystallization; ∆Hm—Melting enthalpy.
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