Bibliographic Information

Bibliographic information:
Title: Recast Nafion/Graphene oxide composite membrane for advanced Vanadium Redox flow
batteries.
Author: Lihong Yu, Feng Lin, Ling Xu
Year of Publication: 2016
Source: RSC Adv., 2016, 6, 3756
1. Introduction
The paper titled “Recast Nafion/Graphene oxide composite membrane for advanced Vanadium Redox
flow batteries” is a research article proposed by Lihong Yu and his colleagues. This research was
supported by the National Natural Science Fund of China and was published in the Royal Society of
Chemistry (RSC) Advances in 2015. The construction of a composite membrane made of Graphene
oxide and Nafion is the primary focus of this study. This experimental study proposes lowering the
permeability of Vanadium ions across the membrane.
2. Summary of the article

2.1 Background Information
According to the statistical data from various scientific publications, it is reported that membrane
effectiveness may account for 30 – 50 % of VRFB system cost [1]. Conventionally used Nafion
membranes are known to have good stability in acidic medium but tend to have higher vanadium
crossover. In contrast, using different membranes, such as porous structured nanofiltration membranes
and non-fluorinated anion exchange membranes, also has some significant drawbacks. When used over
a longer period in an acidic media, these membranes exhibit poor chemical and mechanical stability
[2], [3].
Although commonly used Nafion membranes have higher vanadium crossover, they are recognised to
have strong stability in acidic media. In consideration of their exceptional stability, our author wants to
investigate Nafion membranes. He attempted to change the Nafion membrane through surface
modification [4] and enhanced ion selectivity [5] based on previously published research studies. He
argues that the GO components' unique structure [6] and oxygen functional groups could form an
excellent matrix with Nafion, enhancing the membrane characteristics [7] of the VRFB system.
Throughout the article, comparative studies of recast Nafion, graphene nanoplate-coated Nafion, and
graphene oxide-coated Nafion membranes were performed.
2.2 Research Methodology
The membranes for characterization were prepared in the traditional hydrothermal method [8]. The
writer addressed all the instruments utilised for characterisation. The mechanical property and
morphology of the prepared membranes have also been mentioned. Permeability tests, as well as ion
exchange tests for conductivity and selectivity, are used to examine the fabricated sample membranes.
To support his argument, the author performed electrochemical Impedance spectroscopy on the
fabricated membranes, which confirmed the modified membrane's superior protonic conductivity over
the recast membrane. Further investigation had been done by using the membrane in VRFB single-
flow cell on a laboratory scale. Where these membranes are sandwiched between two electrodes and
have been tested over 200 cycles to determine the membrane's stability and cell efficiency.
2.3 Interpretation
The data of each result have been interpreted in a well-organised manner. The data obtained for
conductivity, selectivity and permeability were interpreted into the graphical plot-bar graphs which
clearly show the better performance GO coated membranes over the recast Nafion membrane. In
addition to this, the Coulombic efficiency, energy efficiency and discharge capacity were determined
by plotting the data obtained from the single-cell test. These data also support the author’s claim that
GO contents reduce the Vanadium permeability and thereby increase the efficiency of the cell.
3. Critique
The article is written in a straightforward, concise, and clear manner. The membrane preparation
procedure was thoroughly demonstrated. All the data collected during the testing of the membrane's
mechanical and physicochemical qualities have been well organised in a table which reduces
complexity and is comprehensible to readers. These analyses have been done extremely well to
evaluate the membrane's qualities. The post-analysis test was also performed to provide extra adequate
evidence for the membrane's stability. There have been no holes/cracks have been detected after the
200 cycles.
The author compared his work to that of another researcher Lee et al., [9] in the field of flow batteries
in terms of membrane alteration and found better results. To back up his arguments, he discovered a
new insight that the incorporated graphene particles potentially operate as a barrier to vanadium ions
through his investigations. This finding has also aided other researchers in continuing research in the
region, such as altering the orientation of graphene particles or adding additional nanoparticles to the
barrier, which could be an effective approach to increase efficiency [10].
3.1 Strengths
Overall, the author gives a brief overview of the subject and addresses the significance of creating
more durable and effective membranes for Vanadium redox flow batteries.
The study can be replicated for further research because the experimental design is well-structured, and
the technique is clearly stated.
The results demonstrate that the recast Nafion/graphene oxide composite membrane outperforms and is
more stable than traditional Nafion membranes, hence validating the author's hypothesis.
3.2 Weaknesses
The potential difficulties or restrictions of adopting this graphene oxides composite membrane such as
price or production challenges are not well discussed by the authors.
More specifically, the economy of the presented membrane is not clearly stated. It is unknown how the
novel membrane would function in practical application because the study was carried out in a lab
setting.
There is a lack of innovation in membrane characterisation because earlier research investigations used
the same standard methods.
3.3 Suggestions
Rather than just stirring the Nafion membrane over the GO solution, the GO content across the
membrane might have been optimised.
As the planned experimental investigation is intended to improve the properties of the membrane,
studies do not appear to be sufficient. The test procedures used here are simply adapted from earlier
research papers. To help the research in a novel approach, a membrane test might have been performed
while it was functioning, allowing us to gather exact water and vanadium crossover data.
4. Conclusion
Overall, the research shows promise for using a recast Nafion/graphene oxide composite membrane in
vanadium redox flow batteries. Further research, however, is required to properly comprehend the
potential drawbacks and applications of this technology.
References
[1] B. R. Chalamala, T. Soundappan, G. R. Fisher, M. R. Anstey, V. v. Viswanathan, and M. L. Perry,
‘Redox flow batteries: An engineering perspective’, Proceedings of the IEEE, vol. 102, no. 6, pp. 976–
999, 2014, doi: 10.1109/JPROC.2014.2320317.
[2] Z. Yuan, X. Li, J. Hu, W. Xu, J. Cao, and H. Zhang, ‘Degradation mechanism of sulfonated poly(ether
ether ketone) (SPEEK) ion exchange membranes under vanadium flow battery medium’, Physical
Chemistry Chemical Physics, vol. 16, no. 37, pp. 19841–19847, Aug. 2014, doi: 10.1039/c4cp03329a.
[3] D. Chen and M. A. Hickner, ‘V5+ degradation of sulfonated Radel membranes for vanadium redox
flow batteries’, Physical Chemistry Chemical Physics, vol. 15, no. 27, pp. 11299–11305, Jul. 2013,
doi: 10.1039/c3cp52035h.
[4] D. Düerkop, H. Widdecke, C. Schilde, U. Kunz, and A. Schmiemann, ‘Polymer membranes for all-
vanadium redox flow batteries: A review’, Membranes (Basel), vol. 11, no. 3, Mar. 2021, doi:
10.3390/membranes11030214.
[5] Z. Mai, H. Zhang, X. Li, S. Xiao, and H. Zhang, ‘Nafion/polyvinylidene fluoride blend membranes
with improved ion selectivity for vanadium redox flow battery application’, J Power Sources, vol. 196,
no. 13, pp. 5737–5741, Jul. 2011, doi: 10.1016/j.jpowsour.2011.02.048.
[6] D. R. Dreyer, S. Park, C. W. Bielawski, and R. S. Ruoff, ‘The chemistry of graphene oxide’, Chemical
Society Reviews, vol. 39, no. 1. pp. 228–240, Jan. 2010. doi: 10.1039/b917103g.
[7] R. Raccichini, A. Varzi, S. Passerini, and B. Scrosati, ‘The role of graphene for electrochemical energy
storage’, Nat Mater, vol. 14, no. 3, pp. 271–279, 2015, doi: 10.1038/nmat4170.
[8] J. Kim, J. D. Jeon, and S. Y. Kwak, ‘Nafion-based composite membrane with a permselective layered
silicate layer for vanadium redox flow battery’, Electrochem commun, vol. 38, pp. 68–70, 2014, doi:
10.1016/j.elecom.2013.11.002.
[9] K. J. Lee and Y. H. Chu, ‘Preparation of the graphene oxide (GO)/Nafion composite membrane for the
vanadium redox flow battery (VRB) system’, Vacuum, vol. 107, pp. 269–276, 2014, doi:
10.1016/j.vacuum.2014.02.023.
[10] L. Su, D. Zhang, S. Peng, X. Wu, Y. Luo, and G. He, ‘Orientated graphene oxide/Nafion ultra-thin
layer coated composite membranes for vanadium redox flow battery’, Int J Hydrogen Energy, vol. 42,
no. 34, pp. 21806–21816, Aug. 2017, doi: 10.1016/j.ijhydene.2017.07.049.

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