J. Mater. Sci. Technol. ›› 2021, Vol. 69: 212-227.DOI: 10.1016/j.jmst.2020.08.032
• Invited Review • Previous Articles Next Articles
Lei Liua,1, Chao Wanga,*(
),1, Zhenfeng Heb, Rajib Dase,f, Binbin Dongd,*(), Xiaofeng Xiec,*(), Zhanhu Guoe,*()
Received:2020-06-07
Revised:2020-06-29
Accepted:2020-07-14
Published:2021-04-10
Online:2021-05-15
Contact:
Chao Wang,Binbin Dong,Xiaofeng Xie,Zhanhu Guo
About author:zguo10@utk.edu (Z. Guo).1The authors contributed equally to this work.
Lei Liu, Chao Wang, Zhenfeng He, Rajib Das, Binbin Dong, Xiaofeng Xie, Zhanhu Guo. An overview of amphoteric ion exchange membranes for vanadium redox flow batteries[J]. J. Mater. Sci. Technol., 2021, 69: 212-227.
Fig. 1. Schematic diagram of the VRB system.
Fig. 2. The relationship between polymer structure, membrane property and VRB performance.
| Membranes | Ion exchange capacity (mmol g-1) | Ion conductivity (mS cm-1)/Area resistance (Ω cm2) | Vanadium permeability (cm2 min-1) | CE (%) | VE (%) | EE (%) | Current density (mA cm-2) | Synthesis approaches |
|---|---|---|---|---|---|---|---|---|
| PVDF-g-PMAOEDMAC-co-PSSA [ | 1.2 | 54/- | 0.69 × 10-7 | - | - | - | - | Radiation-induced grafting method |
| PE-Pore-filled membrane [ | 0.66 | -/0.51 | 0.83 × 10-9 | 98 | 90.8 | 89 | 50 | Co-polymerization method |
| Nafion-g-PDMAEMA [ | - | 3.1/- | 2.95 × 10-7 | - | - | - | - | Blending method |
| SPEEK-PBI [ | - | 0.44 | - | 98.5 | 91.2 | 89.8 | 80 | Blending method |
| Nafion-g-PSSA [ | 0.80 | 63.8 | 13.6 × 10-7 | 96.2 | 94.0 | 89.6 | 40 | Blending method |
| mSPAEK-6F-co-10 %BI [ | 1.56 | -/11.94 | 2.24 × 10-11 | 99.0 | 90.7 | 89.8 | 30 | Blending method |
| S/GO-NH2-2 [ | 2.07 | -/0.154 | 2.04 × 10-7 | 97.2 | 92.1 | 89.5 | 50 | Blending method |
| ImPSf/SPEEK-17 % [ | 2.04 | -/0.48 | 1.5 × 10-8 | 97.5 | 79.3 | 77.3 | 200 | Blending method |
| PSf-MI-PS 190 % [ | 2.02 | 109/- | 7.9 × 10-9 | 98.9 | 78.3 | 77.4 | 200 | Blending method |
| S/Q-15 [ | 1.553 | 47.37/0.158 | 1.5 × 10-7 | 96.1 | 92.04 | 88.45 | 50 | Blending method |
| AMPBPip-70 [ | 4.19 | -/0.22 | 1.31 × 10-8 | 98.2 | 81.6 | 80.1 | 200 | Co-polymerization method |
Table 1 Performance comparison of various AIEMs.
| Membranes | Ion exchange capacity (mmol g-1) | Ion conductivity (mS cm-1)/Area resistance (Ω cm2) | Vanadium permeability (cm2 min-1) | CE (%) | VE (%) | EE (%) | Current density (mA cm-2) | Synthesis approaches |
|---|---|---|---|---|---|---|---|---|
| PVDF-g-PMAOEDMAC-co-PSSA [ | 1.2 | 54/- | 0.69 × 10-7 | - | - | - | - | Radiation-induced grafting method |
| PE-Pore-filled membrane [ | 0.66 | -/0.51 | 0.83 × 10-9 | 98 | 90.8 | 89 | 50 | Co-polymerization method |
| Nafion-g-PDMAEMA [ | - | 3.1/- | 2.95 × 10-7 | - | - | - | - | Blending method |
| SPEEK-PBI [ | - | 0.44 | - | 98.5 | 91.2 | 89.8 | 80 | Blending method |
| Nafion-g-PSSA [ | 0.80 | 63.8 | 13.6 × 10-7 | 96.2 | 94.0 | 89.6 | 40 | Blending method |
| mSPAEK-6F-co-10 %BI [ | 1.56 | -/11.94 | 2.24 × 10-11 | 99.0 | 90.7 | 89.8 | 30 | Blending method |
| S/GO-NH2-2 [ | 2.07 | -/0.154 | 2.04 × 10-7 | 97.2 | 92.1 | 89.5 | 50 | Blending method |
| ImPSf/SPEEK-17 % [ | 2.04 | -/0.48 | 1.5 × 10-8 | 97.5 | 79.3 | 77.3 | 200 | Blending method |
| PSf-MI-PS 190 % [ | 2.02 | 109/- | 7.9 × 10-9 | 98.9 | 78.3 | 77.4 | 200 | Blending method |
| S/Q-15 [ | 1.553 | 47.37/0.158 | 1.5 × 10-7 | 96.1 | 92.04 | 88.45 | 50 | Blending method |
| AMPBPip-70 [ | 4.19 | -/0.22 | 1.31 × 10-8 | 98.2 | 81.6 | 80.1 | 200 | Co-polymerization method |
Fig. 3. Polymer architecture and representative chemistry schemes of AIEM.
Fig. 4. Amphoteric-side chain functional membranes based various main chains. Modified from Refs. [71,76,29].
Fig. 5. Preparation route of partially fluorinated AIEMs. (a) ETFE/St/DMAEMA membrane. Modified from Ref. [77]. (b) PVDF/St/DMAEMA membrane. Modified from Ref. [78].
Fig. 6. Synthesis of SAM-PEEK (sodium form). Modified from Ref. [79].
Fig. 7. Mobile ions associated with SAM-PEEK in acidic and basic media. eproduced with permission from Ref. [79]. Copyright ? Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2016.
Fig. 8. Chemical structure of polymer structures. (a) mSPAEK-6F-co-x%BI. Modified from ref [80]. (b) 60SPAEK-6F-co-x%BI in salted form. Modified from Ref. [81].
Fig. 9. Synthesis and preparation procedure of different blend membranes based on SPEEK. (a) SPEEK/PEI blend membranes. Modified from Ref. [91]. (b) SPEEK/QAPEI blend membranes. Modified from Ref. [68]. (c) SPEEK/PBI blend membrane. Modified from Ref. [99]. (d) SPEEK/ImPSf membranes. Modified from Ref. [101].
| Characterization of AIEMs | Equation | Note |
|---|---|---|
| Water Uptake | $ \begin{array}{l}\text { Wu }=\frac{W_{\text {vet }}-W_{\mathrm{dx} \gamma}}{W_{\mathrm{drg}}} \times 100 \%\end{array}$ | Wwet and Wdry are membrane’s weight in the wet and dry state, respectively. |
| Swelling Ratio | $ \begin{array}{l}\mathrm{Sr}=\frac{L_{\text {wret }}-L_{\text {dry }}}{L_{\text {dry }}} \times 100 \%\end{array}$ | Lwet and Ldry are membrane’s length in the wet and dry state, respectively. |
| Ion Exchange Capacity (IEC) | $ \begin{array}{l}\text { IEC }=\frac{c_{\mathrm{Na}} \mathrm{OH} V_{\mathrm{Na}} O \mathrm{H}}{W_{\mathrm{dry}}}\end{array}$ | CNaOH and VNaOH are concentration and volume of NaOH aq, respectively. |
| Oxidation Stability | $ Weightloss=\frac{Wbefore-Wafter}{ Wbefore }\times 100 \%$ | Wbefore and Wafter are the weight of dried membranes before and after immersing in Fenton’s reagent, respectively. |
| Ion Conductivity | $σ=\frac{L}{ RS }$ | σ is ion conductivity of membranes, R is the resistances of simples, L and S are thickness and effective area, respectively. |
| VO2+ Permeability | $V\frac{ dc(t)}{ dt } =A\frac{P}{L}[ c_{0}-c(t)] $ | V is the volume of mixed solution in the right reservoir; A and L is the effective area and thickness of membranes separately; P is the vanadium ion permeability; c0 is the VO2+ concentration in the right reservoir; c(t) is the VO2+ concentration in the left reservoir, which is a function of time. |
Table 2 Characterization of AIEMs and testing process.
| Characterization of AIEMs | Equation | Note |
|---|---|---|
| Water Uptake | $ \begin{array}{l}\text { Wu }=\frac{W_{\text {vet }}-W_{\mathrm{dx} \gamma}}{W_{\mathrm{drg}}} \times 100 \%\end{array}$ | Wwet and Wdry are membrane’s weight in the wet and dry state, respectively. |
| Swelling Ratio | $ \begin{array}{l}\mathrm{Sr}=\frac{L_{\text {wret }}-L_{\text {dry }}}{L_{\text {dry }}} \times 100 \%\end{array}$ | Lwet and Ldry are membrane’s length in the wet and dry state, respectively. |
| Ion Exchange Capacity (IEC) | $ \begin{array}{l}\text { IEC }=\frac{c_{\mathrm{Na}} \mathrm{OH} V_{\mathrm{Na}} O \mathrm{H}}{W_{\mathrm{dry}}}\end{array}$ | CNaOH and VNaOH are concentration and volume of NaOH aq, respectively. |
| Oxidation Stability | $ Weightloss=\frac{Wbefore-Wafter}{ Wbefore }\times 100 \%$ | Wbefore and Wafter are the weight of dried membranes before and after immersing in Fenton’s reagent, respectively. |
| Ion Conductivity | $σ=\frac{L}{ RS }$ | σ is ion conductivity of membranes, R is the resistances of simples, L and S are thickness and effective area, respectively. |
| VO2+ Permeability | $V\frac{ dc(t)}{ dt } =A\frac{P}{L}[ c_{0}-c(t)] $ | V is the volume of mixed solution in the right reservoir; A and L is the effective area and thickness of membranes separately; P is the vanadium ion permeability; c0 is the VO2+ concentration in the right reservoir; c(t) is the VO2+ concentration in the left reservoir, which is a function of time. |
Fig. 10. Preparation route of Nafion-g-PDMAEMA and protonated Nafion-g-PDMAEMA. Reproduced with permission from Ref. [120]. Copyright ? Elsevier Ltd. 2013.
Fig. 11. Preparation route of the PVDF film with St and DMAEMA. Modified from Ref. [123].
Fig. 12. Preparation procedure of the PVDF powder with St and DMAEMA. Reproduced with permission from Ref. [124]. Copyright ? Elsevier B. V. 2012.
Fig. 13. Synthesis and preparation procedure of ASIPN membrane. Modified from Ref. [127].
Fig. 14. Schematic depiction of the preparation of organic/inorganic hybrid composite membranes. (a) Nafion/amino-SiO2 hybrid membrane. Reproduced with permission from Ref. [28]. Copyright ? Elsevier B. V. 2015. (b) SPEEK/GO-NH2 membranes. Reproduced with permission from Ref. [141]. Copyright ? Elsevier Ltd. 2017. (c) S/CNT@PDA MMM.
Fig. 15. Schematic diagram of the LbL self-assembly of PDDA/PSS bilayers on SPFEK. Reproduced with permission from Ref. [159]. Copyright ? The Royal Society of Chemistry 2013.
Fig. 16. Preparation and schematic principle of LbL/porous-SPFEK composite membrane. Reproduced with permission from Ref. [150]. Copyright ? Elsevier Ltd. 2014.
Fig. 17. Synthetic route of the AIEM with quarternary ammonium group. Modified from Ref. [151].
Fig. 18. Schematic illustration of the preparation of pore filled membranes. Reproduced with permission from Ref. [59]. Copyright ? The Royal Society of Chemistry 2011.
Fig. 19. Synthesis of AIEMs by different quartenizing agents. Modified from Ref. [158].
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