Fabrication of Three-Dimensional Copper@Graphene Phase Change Composite with High Structural Stability and Low Leakage Rate

• 李晓明 ^{1, †,} ,
• 高逸丹 ^{1, †,} ,
• 孔庆强 ^1, ,
• 谢莉婧 ^1, ,
• 刘卓 ^1, ,
• 郭晓倩 ^1, ,
• 刘燕珍 ^1, ,
• 卫贤贤 ^3, ,
• 杨晓 ^1, ,
• 张兴华 ^1, ,
• 陈成猛 ^{1, 2, ,}

• 1.

  中国科学院山西煤炭化学研究所，中国科学院炭材料重点实验室，太原 030001

• 2.

  中国科学院大学材料科学与光电技术学院，北京 100049

• 3.

  太原科技大学环境与安全学院，太原 030024

通讯作者: 陈成猛, ccm@sxicc.ac.cn


• 基金项目:

  国家自然科学基金 21922815

  国家自然科学基金 51802325

  山西省自然科学基金 201901D211585

  山西省科技攻关专项 20191102003

  山西省专利推广实施资助专项 20200716

  山西省重点研发项目 201903D121007

摘要: Owing to the continuous increase in energy consumption and the growing depletion of traditional fossil fuels, the development of renewable energy is becoming increasingly urgent. Renewable energy has come to the fore, represented by geothermal energy and solar energy. However, the application of these energy sources is highly susceptible to weather, season, location, and time. Thus, these alternative energies are unstable, random, fluctuating, intermittent, and inefficient. The development of energy storage technologies can efficiently solve these problems, storing and releasing energy when needed. Among the key materials used in various energy-storage technologies, phase-change materials (PCMs) are strong candidates for smart thermal energy management and portable thermal energy sectors. As most innate PCMs face issues of low thermal conductivity, environmental pollution, and leakage over their melting point, encapsulating PCMs into supporting materials is necessary. However, these supporting materials face significant challenges in their application. First, skeleton materials should be resistant to the PCM volume changes during melting and solidification processes to achieve suitable structural stability. Second, skeleton materials should also have high thermal conductivity and a low leakage rate. Graphene aerogel (GA) has proven to be an effective supporting skeleton to improve the shape-stability of PCMs; however, the leakage caused by the phase transition and the brittleness of the network structure is a primary problem restricting its application. Skeleton materials play a crucial role in the performance of PCMs. Herein, we propose a double-pulse plating reinforcement strategy for fabricating copper@graphene aerogel (Cu@GA) as a skeleton material for phase change energy. In this design, individual nanosheets of the GA were uniformly covered and interlinked by copper particles. The Cu@GA interlinked networks ensure suitable thermal conductivity and a robust framework, beneficial for phase change heat transfer and leak-suppression performance. In addition, we prepared a PCM composite with high structural stability and low leakage rate by encapsulating octadecylamine (ODA) in Cu@GA through vacuum impregnation to ensure homogeneous ODA dispersion in the Cu@GA porous structure. The influence of different skeletons on the PCM composite leakage rate was investigated by comparing the weight change of the PCM composite. Benefiting from these structural features, the optimized composite phase change material (CPCM) Cu@GA/ODA showed a reduced leakage rate of 19.82% (w, mass fraction) compared to 80.31% (w) of GA/ODA and 72.99% (w) of GOA/ODA after 20 heat storage and release cycles. The cycled skeleton morphology was investigated using scanning electron microscopy to determine the origin of this influence. The skeleton integrity of Cu@GA/ODA was well maintained, while the three-dimensional network structures of GOA/ODA and GA/ODA showed shrinkage or collapse. Thus, the copper coating increased the skeleton's microstructural stability, conducive to high structural stability and reducing the leakage rate of the PCM composite. This study paves the way for the construction of ideal metal-coating GA composites with an excellent comprehensive performance for future phase change energy storage, porous microwave absorption, and energy storage applications.

关键词:
• 电镀
•  /  铜/石墨烯气凝胶
•  /  三维石墨烯骨架
•  /  相变材料
•  /  脆性

English

Fabrication of Three-Dimensional Copper@Graphene Phase Change Composite with High Structural Stability and Low Leakage Rate

• Xiaoming Li ^{1, †,} ,
• Yidan Gao ^{1, †,} ,
• Qingqiang Kong ^1, ,
• Lijing Xie ^1, ,
• Zhuo liu ^1, ,
• Xiaoqian Guo ^1, ,
• Yanzhen Liu ^1, ,
• Xianxian Wei ^3, ,
• Xiao Yang ^1, ,
• Xinghua Zhang ^1, ,
• Chengmeng Chen ^{1, 2, ,}

• 1.

  Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

• 2.

  College of Materials Sciences and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China

• 3.

  College of Environment and Safety, Taiyuan University of Science and Technology, Taiyuan 030024, China

• ^† These authors contributed equally to this work.

Corresponding author: Chengmeng Chen, ccm@sxicc.ac.cn

• Received Date: 31 December 2020
  Accepted Date: 18 February 2021
  Revised Date: 15 February 2021
  Available Online: 15 January 2022
• Fund Project:

Abstract: Owing to the continuous increase in energy consumption and the growing depletion of traditional fossil fuels, the development of renewable energy is becoming increasingly urgent. Renewable energy has come to the fore, represented by geothermal energy and solar energy. However, the application of these energy sources is highly susceptible to weather, season, location, and time. Thus, these alternative energies are unstable, random, fluctuating, intermittent, and inefficient. The development of energy storage technologies can efficiently solve these problems, storing and releasing energy when needed. Among the key materials used in various energy-storage technologies, phase-change materials (PCMs) are strong candidates for smart thermal energy management and portable thermal energy sectors. As most innate PCMs face issues of low thermal conductivity, environmental pollution, and leakage over their melting point, encapsulating PCMs into supporting materials is necessary. However, these supporting materials face significant challenges in their application. First, skeleton materials should be resistant to the PCM volume changes during melting and solidification processes to achieve suitable structural stability. Second, skeleton materials should also have high thermal conductivity and a low leakage rate. Graphene aerogel (GA) has proven to be an effective supporting skeleton to improve the shape-stability of PCMs; however, the leakage caused by the phase transition and the brittleness of the network structure is a primary problem restricting its application. Skeleton materials play a crucial role in the performance of PCMs. Herein, we propose a double-pulse plating reinforcement strategy for fabricating copper@graphene aerogel (Cu@GA) as a skeleton material for phase change energy. In this design, individual nanosheets of the GA were uniformly covered and interlinked by copper particles. The Cu@GA interlinked networks ensure suitable thermal conductivity and a robust framework, beneficial for phase change heat transfer and leak-suppression performance. In addition, we prepared a PCM composite with high structural stability and low leakage rate by encapsulating octadecylamine (ODA) in Cu@GA through vacuum impregnation to ensure homogeneous ODA dispersion in the Cu@GA porous structure. The influence of different skeletons on the PCM composite leakage rate was investigated by comparing the weight change of the PCM composite. Benefiting from these structural features, the optimized composite phase change material (CPCM) Cu@GA/ODA showed a reduced leakage rate of 19.82% (w, mass fraction) compared to 80.31% (w) of GA/ODA and 72.99% (w) of GOA/ODA after 20 heat storage and release cycles. The cycled skeleton morphology was investigated using scanning electron microscopy to determine the origin of this influence. The skeleton integrity of Cu@GA/ODA was well maintained, while the three-dimensional network structures of GOA/ODA and GA/ODA showed shrinkage or collapse. Thus, the copper coating increased the skeleton's microstructural stability, conducive to high structural stability and reducing the leakage rate of the PCM composite. This study paves the way for the construction of ideal metal-coating GA composites with an excellent comprehensive performance for future phase change energy storage, porous microwave absorption, and energy storage applications.

Key words:
• Electroplating
•  /  Copper@graphene aerogel
•  /  3D graphene skeleton
•  /  Phase change material
•  /  Friability

• 1. [1]

     Li, M.; Mu, B. Y. Appl. Energy 2019, 242, 695. doi: 10.1016/j.apenergy.2019.03.085

  2. [2]

     Gao, H. Y.; Wang, J. J.; Chen, X.; Wang, G.; Huang, X. B.; Li, A.; Dong, W. J. Nano Energy 2018, 53, 769. doi: 10.1016/j.nanoen.2018.09.007

  3. [3]

     Chen, X.; Tang, Z. D.; Gao, H. Y.; Chen, S. Y.; Wang, G. iScience 2020, 23 (6), 101208. doi: 10.1016/j.isci.2020.101208

  4. [4]

     Aftab, W.; Mahmood, A.; Guo, W. H.; Yousaf, M.; Tabassum, H.; Huang, X. Y.; Liang, Z. B.; Cao, A. Y.; Zou, R. Q. Energy Storage Mater. 2019, 20, 401. doi: 10.1016/j.ensm.2018.10.014

  5. [5]

     Liao, H. H.; Chen, W. H.; Liu, Y.; Wang, Q. Compos. Sci. Technol. 2020, 189, 108010. doi: 10.1016/j.compscitech.2020.108010

  6. [6]

     Sheng, N.; Zhu, R. J.; Nomura, T.; Rao, Z. H.; Zhu, C. Y.; Aoki, Y.; Habazaki, H.; Akiyama, T. Sol. Energy Mater. Sol. Cells 2020, 206, 110280. doi: 10.1016/j.solmat.2019.110280

  7. [7]

     冯英杰, 王进平, 刘丽丽, 王习东. 物理化学学报, 2019, 35 (6), 644. doi: 10.3866/pku.Whxb201805068Feng, Y. J.; Wang, J. P.; Liu, L. L.; Wang, X. D. Acta Phys. -Chim. Sin. 2019, 35 (6), 644. doi: 10.3866/pku.Whxb201805068

  8. [8]

     南光花, 王建平, 王艳, 王赫, 李伟, 张兴祥. 物理化学学报, 2014, 30 (2), 338. doi: 10.3866/pku.Whxb201312231Nan, G. H.; Wang J. P.; Wang Y.; Wang H.; Li W.; Zhang X. X. . Acta Phys. -Chim. Sin. 2014, 30 (2), 338. doi: 10.3866/pku.Whxb201312231

  9. [9]

     Cheng, G.; Wang, X. Z.; He, Y. R. Appl. Therm. Eng. 2020, 178, 115560. doi: 10.1016/j.applthermaleng.2020.115560

  10. [10]

      Cao, Y. F.; Fan, D. L.; Lin, S. H.; Mu, L. Y.; Ng, F. T. T.; Pan, Q. M. Chem. Eng. J. 2020, 389, 124318. doi: 10.1016/j.cej.2020.124318

  11. [11]

      Qi, G. Q.; Yang, J.; Bao, R. Y.; Xia, D. Y.; Cao, M.; Yang, W.; Yang, M. B.; Wei, D. C. Nano Res. 2017, 10 (3), 802. doi: 10.1007/s12274-016-1333-1

  12. [12]

      Khadiran, T.; Hussein, M. Z.; Zainal, Z.; Rusli, R. Energy 2015, 82, 468. doi: 10.1016/j.energy.2015.01.057

  13. [13]

      Sobolciak, P.; Mrlík, M.; AlMaadeed, M. A.; Krupa, I. Thermochim. Acta 2015, 617, 111. doi: 10.1016/j.tca.2015.08.026

  14. [14]

      Xiao, X.; Zhang, P.; Li, M. Appl. Energy 2013, 112, 1357. doi: 10.1016/j.apenergy.2013.04.050

  15. [15]

      Zhang, P.; Meng, Z. N.; Zhu, H.; Wang, Y. L.; Peng, S. P. Appl. Energy 2017, 185, 1971. doi: 10.1016/j.apenergy.2015.10.075

  16. [16]

      Karthik, M.; Faik, A.; D'Aguanno, B. Sol. Energy Mater. Sol. Cells 2017, 172, 324. doi: 10.1016/j.solmat.2017.08.004

  17. [17]

      Li, G. Y.; Hong, G.; Dong, D. P.; Song, W. H.; Zhang, X. T. Adv. Mater. 2018, 30 (30), 1801754. doi: 10.1002/adma.201801754

  18. [18]

      高增强, 王聪勇, 李俊俊, 朱亚廷, 张志成, 胡文平. 物理化学学报, 2021, 37 (7), 2010025. doi: 10.3866/PKU.WHXB202010025Gao, Z. Q.; Wang, C. Y.; Li, J. J.; Zhu, Y. T.; Zhang, Z. C.; Hu, W. P. Acta Phys. -Chim. Sin. 2021, 37 (7), 2010025. doi: 10.3866/PKU.WHXB202010025

  19. [19]

      Xue, F.; Lu, Y.; Qi, X. D.; Yang, J. H.; Wang, Y. Chem. Eng. J. 2019, 365, 20. doi: 10.1016/j.cej.2019.02.023

  20. [20]

      吴文昊, 黄心宇, 姚锐敏, 陈人杰, 李凯, 邹如强. 物理化学学报, 2017, 33 (1), 255. doi: 10.3866/pku.Whxb201610181Wu, W. H.; Huang, X. Y.; Yao, R. M.; Chen, R. J.; Li, K.; Zou, R. Q. Acta Phys. -Chim. Sin. 2017, 33 (1), 255. doi: 10.3866/pku.Whxb201610181

  21. [21]

      Li, B. L.; Guo, J. G.; Xu, Bing; Xu, H. T.; Dong, Z. j.; Li, X. K. New Carbon Mater. 2020, 35 (5), 567. doi: 10.1016/S1872-5805(20)60510-8

  22. [22]

      Liu, X.; Deng, H. L.; Zheng, J. H.; Sun, M.; Cui, H.; Zhang, X. H.; Song, G. S. New Carbon Mater. 2020, 35 (5), 576. doi: 10.1016/S1872-5805(20)60511-X

  23. [23]

      Yang, J.; Tang, L. S.; Bao, R. Y.; Bai, L.; Liu, Z. Y.; Yang, W.; Xie, B. H.; Yang, M. B. J. Mater. Chem. A 2016, 4 (48), 18841. doi: 10.1039/c6ta08454k

  24. [24]

      Huang, J. H.; Zhang, B. N.; He, M.; Huang, X.; Wu, G. J.; Yin, G. Q.; Cui, Y. D. J. Mater. Sci. 2020, 55 (17), 7337. doi: 10.1007/s10853-020-04514-9

  25. [25]

      Yang, G. Q.; Zhao, L. Y.; Shen, C. F.; Mao, Z. P.; Xu, H.; Feng, X. L.; Wang, B. J.; Sui, X. F. Sol. Energy Mater. Sol. Cells 2020, 209, 110441. doi: 10.1016/j.solmat.2020.110441

  26. [26]

      Mu, B. Y.; Li, M. Sol. Energy Mater. Sol. Cells 2019, 191, 466. doi: 10.1016/j.solmat.2018.11.025

  27. [27]

      Jiang, L. L.; Fan, Z. J. Nanoscale 2014, 6 (4), 1922. doi: 10.1039/c3nr04555b

  28. [28]

      Wang, P.; Chong, H. D.; Zhang, J. J.; Lu, H. B. ACS Appl. Mater. Interfaces 2017, 9 (26), 22006. doi: 10.1021/acsami.7b07328

  29. [29]

      Woltornist, S. J.; Varghese, D.; Massucci, D.; Cao, Z.; Dobrynin, A. V.; Adamson, D. H. Adv. Mater. 2017, 1604947. doi: 10.1002/adma.201604947

  30. [30]

      Zhong, Y. J.; Zhou, M.; Huang, F. Q.; Lin, T. Q.; Wan, D. Y. Sol. Energy Mater. Sol. Cells 2013, 113, 195. doi: 10.1016/j.solmat.2013.01.046

  31. [31]

      Yang, J.; Zhang, E. W.; Li, X. F.; Zhang, Y. T.; Qu, J.; Yu, Z. Z. Carbon 2016, 98, 50. doi: 10.1016/j.carbon.2015.10.082

  32. [32]

      Zhou, Y.; Li, C. H.; Wu, H.; Guo, S. Y. Colloids Surf. A 2020, 597, 124780. doi: 10.1016/j.colsurfa.2020.124780

  33. [33]

      Zhu, X. Y.; Yang, C.; Wu, P. W.; Ma, Z. Q.; Shang, Y. Y.; Bai, G. Z.; Liu, X. Y.; Chang, G.; Li, N.; Dai, J. J; et al. Nanoscale 2020, 12 (8), 4882. doi: 10.1039/c9nr07861d

  34. [34]

      Qiu, L.; Liu, J. Z.; Chang, S. L.; Wu, Y. Z.; Li, D. Nat. Commun. 2012, 3, 1241. doi: 10.1038/ncomms2251

  35. [35]

      Kashyap, S.; Kabra, S.; Kandasubramanian, B. J. Mater. Sci. 2020, 55 (10), 4127. doi: 10.1007/s10853-019-04325-7

  36. [36]

      Yan, F.; Liu, L.; Li, M.; Zhang, M. J.; Shang, L.; Xiao, L. H.; Ao, Y. H. Compos. Part A 2019, 125, 105530. doi: 10.1016/j.compositesa.2019.105530

  37. [37]

      Lu, L.; Shen, Y. F.; Chen, X. H.; Qian, L. H.; Lu, K. Science 2004, 304 (5669), 422. doi: 10.1126/science.1092905

  38. [38]

      Chen, C. M.; Zhang, Q.; Yang, M. G.; Huang, C. H.; Yang, Y. G.; Wang, M. Z. Carbon 2012, 50 (10), 3572. doi: 10.1016/j.carbon.2012.03.029

  39. [39]

      Hu, H.; Zhao, Z. B.; Wan, W. B.; Gogotsi, Y.; Qiu, J. S. Adv. Mater. 2013, 25 (15), 2219. doi: 10.1002/adma.201204530

  40. [40]

      Yang, J.; Qi, G. Q.; Bao, R. Y.; Yi, K. Y.; Li, M. L.; Peng, L.; Cai, Z.; Yang, M. B.; Wei, D. C.; Yang, W. Energy Storage Mater. 2018, 13, 88. doi: 10.1016/j.ensm.2017.12.028

  41. [41]

      Zhao, J. L.; Luo, W. J.; Kim, J. K.; Yang, J. L. ACS Appl. Energy Mater. 2019, 2 (5), 3657. doi: 10.1021/acsaem.9b00374

  42. [42]

      Tian, B. Q.; Yang, W. B.; Luo, L. J.; Wang, J.; Zhang, K.; Fan, J. H.; Wu, J. Y.; Xing, T. Sol. Energy 2016, 127, 48. doi: 10.1016/j.solener.2016.01.011

  43. [43]

      Biener, J.; Stadermann, M.; Suss, M.; Worsley, M. A.; Biener, M. M.; Rose, K. A.; Baumann, T. F. Energy Environ. Sci. 2011, 4 (3), 656. doi: 10.1039/c0ee00627k

  44. [44]

      Xu, Y.; Fleischer, A. S.; Feng, G. Carbon 2017, 114, 334. doi: 10.1016/j.carbon.2016.11.069

  45. [45]

      Padmajan Sasikala, S.; Poulin, P.; Aymonier, C. Adv. Mater. 2016, 28 (14), 2663. doi: 10.1002/adma.201504436

  46. [46]

      Balandin, A. A. Nat. Mater. 2011, 10 (8), 569. doi: 10.1038/nmat3064

  47. [47]

      Zhang, X.; Wan, D. Q.; Peng, K.; Zhang, W. J. Mater. Eng. Perform. 2019, 28 (8), 5165. doi: 10.1007/s11665-019-04212-x

  48. [48]

      Gao, W. W.; Zhao, N. F.; Yao, W. Q.; Xu, Z.; Bai, H.; Gao, C. RSC Adv. 2017, 7 (53), 33600. doi: 10.1039/c7ra05557a

  49. [49]

      Almajali, M.; Lafdi, K.; Prodhomme, P. H.; Ochoa, O. Carbon 2010, 48 (5), 1604. doi: 10.1016/j.carbon.2009.12.060

  50. [50]

      Cao, A. Y.; Dickrell, P. L.; Sawyer, W. G.; Ghasemi-Nejhad, M. N.; Ajayan, P. M. Science 2005, 310 (5752), 1307. doi: 10.1126/science.1118957

  51. [51]

      Zhang, Q. Q.; Lin, D.; Deng, B. W.; Xu, X.; Nian, Q.; Jin, S. Y.; Leedy, K. D.; Li, H.; Cheng, G. J. Adv. Mater. 2017, 29 (28), 69469. doi: 10.1002/adma.201605506

  52. [52]

      Park, J. H.; Lee, J. H.; Soon, A. Phys. Chem. Chem. Phys. 2016, 18 (31), 21893. doi: 10.1039/c6cp03249d

  53. [53]

      He, L. J.; Mo, S. P.; Lin, P. C.; Jia, L.; Chen, Y.; Cheng, Z. D. Appl. Energy 2020, 268. 115020. doi: 10.1016/j.apenergy.2020.115020

  54. [54]

      Liang, K.; Shi, L.; Zhang, J. Y.; Cheng, J.; Wang, X. D. Thermochim. Acta 2018, 664, 1. doi: 10.1016/j.tca.2018.04.002

  55. [55]

      Shen, J.; Zhang, P.; Song, L. X.; Li, J. P.; Ji, B. Q.; Li, J. J.; Chen, L. Compos. Part B 2019, 179, 107545. doi: 10.1016/j.compositesb.2019.107545

•