A Sustainable Redox Flow Battery with Alizarin-based Aqueous

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A Sustainable Redox Flow Battery with Alizarin-based Aqueous Organic Electrolyte Yiyang Liu, Shanfu Lu, Sian Chen, Haining Wang, Jin Zhang, and Yan Xiang ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.8b01512 • Publication Date (Web): 05 Feb 2019 Downloaded from http://pubs.acs.org on February 5, 2019

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is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

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ACS Applied Energy Materials

A Sustainable Redox Flow Battery with Alizarinbased Aqueous Organic Electrolyte Yiyang Liu, [a] Shanfu Lu* ,[a] Sian Chen, [a,b] Haining Wang, [a] Jin Zhang[a] and Yan Xiang*[a]

[a]Beijing

Key Laboratory of Bio-inspired Energy Materials and Devices, School of Space

and Environment, Beihang University, Beijing 100191, P. R. China.

[b]Shenyuan

E-mail:

Honors College, Beihang University, Beijing 100191, P. R. China.

[email protected]* [email protected]

ABSTRACT

To achieve sustainable development, biomass materials are alternative options for mitigating the problems associated with energy and the environment. Recently, soluble

ACS Paragon Plus Environment

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anthraquinones in aqueous redox flow batteries have attracted extensive attention. Inspired by a natural anthraquinone dye named alizarin, here report an affordable, sustainable, and efficient redox flow battery electrolyte using a derivative of alizarin, namely, alizarin-3-methyliminodiacetic acid, which has been easily synthesized from alizarin on an industrial scale. The battery exhibit open-circuit voltage of 1.38 V and the maximum power density exceed 0.49 W·cm−2. Also, the battery have an stable cycling performance of 350 cycles with a high coulombic efficiency of 99.6%, energy efficiency of 84.2%, and capacity retention of 99.98% per cycle, 99.97% per hour and 99.19% per day at 0.1 A·cm−2. Moreover, the battery system is environmentally friendly and provides novel ideas for biomass-derived green energy-storage systems.

Keywords: Redox flow battery, Aqueous organic electrolyte, Anthraquinone, Derivative of alizarin, Natural dye

TOC GRAPHICS


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Redox flow batteries (RFBs) are considered to be the most promising large-scale devices for energy storage and conversion because of their flexible and scalable energy capacity that benefit from uncoupled power and energy devices. The unique architecture enables RFBs to solve the mismatch between the intermittent supply of renewable resources and their variable demand.1, 2 Electrolytes are the central materials in RFBs and have a primary effect on battery performance. Generally, RFB electrolytes are based on polyvalent metal elements, such as Fe, Cr, Zn, Ce and V.3 Most of these present challenges in terms of serious ion permeation and sluggish kinetics4, and these challenges lead to low energy efficiency and poor power density for the battery. Furthermore, the low elemental abundance and the potential risk of heavy metal pollution severely inhibit the large-scale application of such RFBs5, 6


3


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Recently, scientists have been attempting to use new organic electroactive systems to address these issues. Such systems have included water-soluble derivatives of viologen7-12, flavin13,

14,

phenazine15 and anthraquinone16-19. Most of these organic

electroactive materials highlight the rapid reaction kinetics and low ion permeation through proton exchange membranes (e.g., Nafion). The feasibility of aqueous organic electrolyte has been proven, which opens new prospects for RFBs (Table 1). However, each different aqueous organic electrolyte has its own advantages and drawbacks, and these must be balanced with practical requirements. Specifically, viologen electrolyte is usually affordable but the energy efficiency and power density of RFBs using viologen electrolyte are relatively lower than other organic RFBs systems. Flavin and phenazine electrolyte are fascinating because they are nontoxic and have high yield14, 15 while the phenazine electrolyte highlighted its high reversible capacity that exceeds 90% of its theoretical value. However, the power density of these RFBs are still not optimal. In contrast, anthraquinone electrolyte achieves a remarkable power density of 1 W·cm-2.20 However, anthraquinone undergoes apparent degradation at acidic or alkaline conditions21 and the high cost of 2,6-dihydroxyanthraquinone restrict large-scale


4

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commercial applications that use these substances. These organic electrolytes provide much more flexible choices for electroactive materials of RFBs.16 Scientists have also conducted calculations14,

16

to investigate theoretically feasible structures of the RFB

electrolytes, but many of these compounds may be difficult to synthesize and may not be economic. In summary, for the large-scale application of RFBs, there are trade-offs among high performance, low cost, and easy scale production, and it is difficult to assess these considerations comprehensively. Moreover, among organic electroactive electrolytes, derivatives of anthraquinone exhibit the best output power density. Thus, an affordable, sustainable biomass derivative of anthraquinone may be an alternative option for the large-scale application of RFBs.

Table 1. Parameters of the recently reported aqueous organic negative active materials and performance of the corresponding RFBs Active redox species

N

N

N

N

N

N

D

[cm2·s-1]

K0 EE No. of [cm·s-1] @0.1 Acm-2 cycles [%]

Capacity retention per cycle [%]

Capacity Max power retention per density hour [%] [Wcm-2]

Ref.

98.9/99.98d) 0.08/0.05

7, 9

2.57×10-5 2.8×10-4

45

100/700

99.89/99.9 9

3.3×10-6 2.2×10-2

45

500

99.9989

99.9986

0.12

8


5


3.3×10–6

63c)

1000

99.9997g)

99,9993g)

0.07

12

1.3×10-6 5.3×10-3

55a)

100

99.99

99.987

0.08

13

No Data No Data

82

500

99.98

99.97

0.14

15

3.81×10-6 7.25×10-3

≈76b)

750

99.2

99.92

0.6~1d)

16, 20

84

100

99.9 e)

99.6 e)

0.4

17

84

350

99.96

99.19

0.49

This work.

f)

0.28f)

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O N

N

N

N

HO

O O

HO

O OH

P O O

N

OH

N

OH

O HO

S O

HO

O

O

O

OH

S

S

O

O

O O O

O

4×10-6

7×10-3

O

6.68×10-6 8.37×10-3

a) measured at 0.08 Acm-2. b) measured at 0.2 Acm-2. c) measured at 0.04 Acm-2. d) measured at 40C. e) estimated value. f) referenced from ref. 10. g) the anolyte and catholyte were mixed. Alizarin (1,2-dihydroxyanthraquinone) and its derivatives are natural analogues of anthraquinone and are a class of biodegradable, nontoxic, and renewable natural dyes which are principally used to dye textile fabrics. It has been produced artificially via synthetic methods on an industrial scale.22 Alizarin and its derivatives are also used as pigments, staining agents, and indicators. Though some previous works have introduced the likelihood of using alizarin or its derivative as RFB electrolyte19,

23, 24,

their


6

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application in RFBs has not been systematically studied. We expect that this class of organic molecules are viable low-cost negative electrode materials for RFBs.

Figure 1. Molecular formulas and performances of three alizarin compounds. (a) Molecular formulas. (b) Cyclic voltammograms of 5 mM AL, ARS, and AMA scanned at 50 mVs-1 in 1 M KOH on a glassy carbon electrode. (c) LSV of 5 mM AMA in 1 M KOH


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solution on a glassy carbon working electrode at different rotation rates. (d) Koutecky´– Levich plots derived from the LSV curve. (e) Solubility of K-AMA in aqueous solution with different KOH concentration. (f) Permeability of AMA

and AL through N211

membrane in KOH solution. Here, we report an affordable, sustainable, and efficient aqueous RFB negative electrolyte using a derivative of alizarin, specifically, alizarin-3-methyliminodiacetic acid (AMA). AMA can be synthesized from alizarin via a simple Mannich condensation reaction25. The physical and chemistry properties of AMA were investigated. By pairing AMA with ferri/ferrocyanide as the positive electrolyte, we built a high-performance RFB which stands out from the recently reported new types of aqueous organic RFBs (Table 1). In particular, the use of the AMA electrolyte is conducive to reducing the environmental impact and provides novel ideas for biomass-derived green energystorage systems.

We initially targeted three commercially available alizarin compounds: alizarin (AL), alizarin red S (ARS), and alizarin-3-methyliminodiacetic acid (AMA). The molecular formulas of these three compounds are shown in Figure 1(a). Cyclic voltammetry (CV)


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of AMA, ARS, and AL in 1 M KOH was performed to investigate the electrochemical performance of these three compounds. The CV results for each of these compounds yielded one pair of redox reaction peaks. Of the three anthraquinonoid compounds, AMA exhibited the highest redox peak current, which indicated that AMA had the best electrochemical activity. Also, the values of the potential for the AMA, ARS, and AL redox pairs in 1 M KOH were calculated from the average of the anodic and cathodic peak potentials and were, respectively, -0.67, -0.70, and -0.67 V vs. the Standard Hydrogen Electrode (SHE); each of these values was an appropriate potential for aqueous alkali RFBs. The different redox potential of ARS might be caused by -SO3- in alkaline solution, which could increase the electron density of the aromatic ring due to the inductive effect. Thus, ARS should show lower redox potential than AL and AMA. Furthermore, linear sweep voltammetry (LSV) of AMA, ARS, and AL at various rotation rates was performed (Figure 1 (c) and Figure S5). Figure 1(d) shows plot of the square root of the rotation rate (1/2) versus the limiting current, which has good consistency (R2=0.999), this indicates that the redox reaction of AMA was reversible. Thus, the diffusion coefficient of AMA (D= 6.68×10-6 cm2·s-1) was calculated using the Koutecky´–


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Levich equation and the kinetic reduction rate constant (k0) was calculated to be 8.37×10-3 cm·s-1. (Figure S6) The two parameters are greater than those for most other negative active materials used in the recently reported organic aqueous RFBs (Table 1). This implies the high energy efficiency, and high power density of the RFBs using AMA electrolyte.

Besides the energy efficiency and power density, energy density and long-time capacity stability are also the important parameters for RFBs. Solubility is the most directly parameter that determines the energy density. The solubility of the potassium salt of these three compounds (written as K2AL, K3ARS and K4AMA ) were also examined in 1 M KOH solution at 25°C. The order of the solubility of these compounds is: K4AMA (0.40 M) > K2AL (0.19 M) > K3ARS (0.10 M). It is rational to conclude that the two extra carboxylic groups and one imine group on AMA provide high solubility in alkaline solution. The concentration of KOH can also influence the solubility of K4AMA. As shown in Figure 1 (e), with the increasing KOH concentration, the solubility of K4AMA first increase and then decrease. High concentration of OH- is beneficial for the


10

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ionization of AMA which may increase the solubility in aqueous solution. However, high concentration of K+ can also precipitate K4AMA as common-ion effect. The cooperation of these two aspects gives the highest K4AMA solubility of 0.46 M in 0.2 M KOH solution. Coordinating with the two-electron redox reaction of AMA, the theoretical capacity of the corresponding half-cell achieves 24.6 Ah·L-1, which is an acceptable level for an organic aqueous RFB.

Long-time capacity stability can be subdivided into cycling stability and chemical stability. The cycling stability can be diminished by side-reactions and permeation through the membrane. As AMA undergoes a reversible redox reaction with appropriate potential, which means slightly side-reactions during the redox process, the permeation of AMA should be a major factor of the cycling stability. The permeation test of AMA and AL through N211 membrane was performed in Figure 1 (f). The permeability of AMA is calculated as 1.2610-8 cm2∙min-1, which is only 1/5 of that of AL. The low permeability is attributed to the chemical functional groups of AMA, the phenol hydroxyl and carboxylic groups are deprotonated in alkaline solution, which increases the negative


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charges of AMA, and this reduces the ion permeability in PEMs (e.g., Nafion) because of the Gibbs–Donnan effect. Furthermore, to investigate the chemistry stability of AMA, a degradation test was performed in 0.2 M KOH solution at 25°C in Figure S8 (a), the results showed the concentrate of AMA decreased 6.7 % during 246 h. Besides, H1 NMR of AMA and its degradation products were performed in Figure S8 (b), No significant new peaks appeared in the degradation products of AMA.

To further evaluate the efficacy of the AMA electrolyte, an RFB was assembled with 8 ml 0.4 M AMA electrolytes and 16 ml 0.4 M K4[Fe(CN)6] electrolytes, 0.2 M KOH were add in both electrolytes as supporting electrolyte. A pre-treated nafion 211 membrane was used to separate these solutions. Working principle and Performance of the RFB were given in Figure 2. The RFB had a battery voltage of 1.11 V. The OCV of the RFB was 1.38 V at 100 % of SOC, its dependence on SOC was shown in Figure 2(d). The charge/discharge voltage curves of the RFB at various current densities were shown in Figure 2(b). The specific capacity at 0.1 Acm−2 was 6.1 Ah∙L-1, which was 86 % of the theoretical value. With an increase in the current density, the capacity efficiency (CE)


12

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approached 100% (Figure 2(c)), and this confirmed that there were negligible side reactions and a low permeation rate through the membrane. The energy efficiency (EE) of the RFB exceeded 84.9 % at 0.1 Acm−2, which was the highest EE of the recently reported aqueous organic-based RFBs in Table 1. Also, the RFB had fascinating performance at high rates; specifically, the EE remained 50%, and the specific capacity retained 51% (4.0 Ah∙L-1) of the theoretical value at a high current density of 0.5 Acm−2. The polarization curves (Figure 2(e)) showed no sign of redox kinetic limitations and the maximum power density was as high as 0.49 W·cm−2, which was comparable to that of the reported anthraquinone-based aqueous RFBs.


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Figure 2. (a) The working principle of the RFB Cyclic voltammogram of 5 mM AMA and ferrocyanide scanned at 50 mV∙s-1 on a glassy carbon electrode. The dotted line represents the CV of 1 M KOH background. (b) Open current voltage versus state of charge. (c) Representative galvanostatic charge and discharge curves at various current densities. (d) Cell voltage and power density versus current density at 10, 50, and 100% SOC. (e) CE, VE, and EE at different current densities.


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Figure 3. The stability of AMA during battery operation. (a) CE, EE, charge capacity and discharge capacities in 350 cycles with 100% SOC. (b) 1H NMR of AMA and its degradation products after 350 cycles. Signal peaks are assigned and labelled according to the numbered positions in the drawing of AMA provided as the inset. (600 MHz, DMSO-D6, 25 °C, TMS).

To investigate the stability of AMA during battery operation, an RFB was assembled with 8 ml 0.4 M AMA electrolytes and 24 ml 0.4 M K4[Fe(CN)6] electrolytes, 0.2 M KOH


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were add in both electrolytes as supporting electrolyte. As [Fe(CN)6]3-/[Fe(CN)6]4- redox couple was unstable at strong alkalis condition (Figure S9)26 and showed quite large permeability through N211 membrane (Figure S7)12, Excess amount of K4[Fe(CN)6] was used to exclude the effect of

degradation and permeation of [Fe(CN)6]3- and

[Fe(CN)6]4-. The RFB was cycled at 0.1 A·cm-2 with a potential cut off of 1.6 V during charging and 0.7 V during discharging; this used approximately 100 % SOC. As shown in Figure 3 (a), during a 350 cycles test in 240 h, the CE and EE averaged 99.6% and 84.2%, respectively, and the capacity decayed by 8.1 %. The capacity retention was average 99.98% per cycle, 99.97% per hour and 99.19% per day. To further elucidate the chemical transformation of AMA during the cycling process, 1H NMR post-analysis was conducted on the AMA electrolyte after 350 cycles. As shown in Figure 3 (b), fresh AMA showed nine signal peaks, which are labelled according to the numbered positions in the drawing of AMA provided as the inset. Peak a and b corresponded to the hydrogen on the iminodiacetic acid group and the ratio of the peak intensity was 2:1. Peak c, d and e corresponded to the hydrogen on the aromatic ring and the ratio of the peak intensity was 1:2:2. Peak f and g corresponded to the hydrogen on the phenol


16

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hydroxyl and carboxylic groups. The 1H NMR of AMA after 350 charge and discharge cycles showed similar Peak c, d and e corresponded to the hydrogen on the aromatic ring while Peak a and Peak g were significantly weaker. This phenomenon revealed that the degradation of AMA during the redox cycling process was primarily caused by the shedding of carboxylic groups, which reduced the solubility of the active material and resulted in battery capacity fading.

In summary, the current work presents an affordable, sustainable, and efficient aqueous

RFB

electrolyte

using

a

derivative

of

anthraquinone:

alizarin-3-

methyliminodiacetic acid. Compared to the other anthraquinone electrolytes, AMA have relatively larger diffusion coefficient (D) of 6.68×10-6 cm2·s-1 and kinetic rate constant (k0) of 8.37×10-3 cm·s-1. Moreover, the AMA electrolyte has low cost and is easy to synthetize, which is good for industrial application prospects. Furthermore, we built a high-performance RFB that had an open-circuit voltage of 1.38 V. Excellent EE of 84.9% was achieved at a current density of 0.1 Acm−2, and the maximum power density was as high as 0.49 Wcm−2.Additionally, the RFB had an acceptable cycling


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performance for 350 cycles with a capacity retention of 99.98% per cycle, 99.97% per hour and 99.19% per day at current density of 0.1 Acm−2. The investigation of AMA electrolyte will accelerate the development of sustainable RFBs and will provide novel ideas for biomass-derived green energy-storage systems.

Supporting Information ASSOCIATED CONTENT Supporting Information Available: **[ Measurements of UV-Vis spectrophotometry, atomic absorption spectrometry, electrochemical tests, ion permeability and NMR. Preparation of the electrolyte and pre-treatment of membrane and electrode. The scheme and test condition of the RFB.]** Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT

Shanfu Lu received funding from the National Natural Science Foundation of China (No. 21722601) and Yan Xiang received funding from the National Natural Science Foundation of China (No. 51673006, No. 51761145047).


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REFERENCES (1) Cheng, F. Y.; Liang, J.; Tao, Z. L.; Chen, J., Functional Materials for Rechargeable Batteries. Adv. Mater. 2011, 23, 1695-1715. (2) Dunn, B.; Kamath, H.; Tarascon, J. M., Electrical Energy Storage for the Grid: A Battery of Choices. Science 2011, 334, 928-935. (3) Noack, J.; Roznyatovskaya, N.; Herr, T.; Fischer, P., The Chemistry of Redox-Flow Batteries. Angew. Chem. Int. Ed. 2015, 54, 9776-9809. (4) Weber, A. Z.; Mench, M. M.; Meyers, J. P.; Ross, P. N.; Gostick, J. T.; Liu, Q., Redox flow batteries: a review. J. Appl. Electrochem. 2011, 41, 1137-1164. (5) Gong, K.; Xu, F.; Grunewald, J. B.; Ma, X.; Zhao, Y.; Gu, S.; Yan, Y., All-Soluble All-Iron Aqueous Redox-Flow Battery. ACS Energy Letters 2016, 1, 89-93. (6) Winsberg, J.; Hagemann, T.; Janoschka, T.; Hager, M. D.; Schubert, U. S., RedoxFlow Batteries: From Metals to Organic Redox-Active Materials. Angew. Chem. Int.

Ed. 2017, 56, 686-711. (7) Liu, T. B.; Wei, X. L.; Nie, Z. M.; Sprenkle, V.; Wang, W., A Total Organic Aqueous Redox Flow Battery Employing a Low Cost and Sustainable Methyl Viologen Anolyte and 4-HO-TEMPO Catholyte. Adv. Energy Mater. 2016, 6, 15014491501456.


19


Page 20 of 25

(8) Beh, E. S.; De Porcellinis, D.; Gracia, R. L.; Xia, K. T.; Gordon, R. G.; Aziz, M. J., A Neutral pH Aqueous Organic–Organometallic Redox Flow Battery with Extremely High Capacity Retention. ACS Energy Letters 2017, 2, 639-644. (9) Hu, B.; Debruler, C.; Rhodes, Z.; Liu, T., A Long Cycling Aqueous Organic Redox Flow Battery (AORFB) towards Sustainable and Safe Energy Storage. J. Am.

Chem. Soc. 2016, 139, 1207-1214. (10) DeBruler, C.; Hu, B.; Moss, J.; Luo, J.; Liu, T. L., A Sulfonate-Functionalized Viologen Enabling Neutral Cation Exchange, Aqueous Organic Redox Flow Batteries toward Renewable Energy Storage. ACS Energy Letters 2018, 3, 663-668. (11) Hu, B.; Tang, Y.; Luo, J.; Grove, G.; Guo, Y.; Liu, T., Improved Radical Stability of Viologen Anolyte in Aqueous Organic Redox Flow Battery. Chem. Commun. 2018,

54, 6871-6874. (12) Luo, J.; Hu, B.; Debruler, C.; Bi, Y.; Zhao, Y.; Yuan, B.; Hu, M.; Wu, W.; Liu, T. L., Unprecedented Capacity and Stability of Ammonium Ferrocyanide Catholyte in pH Neutral Aqueous Redox Flow Batteries. Joule 2019, 3, 1-15. (13) Orita, A.; Verde, M. G.; Sakai, M.; Meng, Y. S., A biomimetic redox flow battery based on flavin mononucleotide. Nat. Commun. 2016, 7, 13230-13237. (14) Lin, K.; Gómez-Bombarelli, R.; Beh, E. S.; Tong, L.; Chen, Q.; Valle, A.; AspuruGuzik, A.; Aziz, M. J.; Gordon, R. G., A redox-flow battery with an alloxazine-based organic electrolyte. Nature Energy 2016, 1, 16102-16109.


20

Page 21 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(15) Hollas, A.; Wei, X.; Murugesan, V.; Nie, Z.; Li, B.; Reed, D.; Liu, J.; Sprenkle, V.; Wang, W., A biomimetic high-capacity phenazine-based anolyte for aqueous organic redox flow batteries. Nature Energy 2018, 3, 508-514. (16) Huskinson, B.; Marshak, M. P.; Suh, C.; Er, S.; Gerhardt, M. R.; Galvin, C. J.; Chen, X. D.; Aspuru-Guzik, A.; Gordon, R. G.; Aziz, M. J., A metal-free organic-inorganic aqueous flow battery. Nature 2014, 505, 195-198. (17) Lin, K. X.; Chen, Q.; Gerhardt, M. R.; Tong, L. C.; Kim, S. B.; Eisenach, L.; Valle, A. W.; Hardee, D.; Gordon, R. G.; Aziz, M. J.; Marshak, M. P., Alkaline quinone flow battery. Science 2015, 349, 1529-1532. (18) Gerhardt, M. R.; Tong, L.; Gómez‐Bombarelli, R.; Chen, Q.; Marshak, M. P.; Galvin, C. J.; Aspuru‐Guzik, A.; Gordon, R. G.; Aziz, M. J., Anthraquinone Derivatives in Aqueous Flow Batteries. Adv. Energy Mater. 2016, 7, 1601488-1601496. (19) Kwabi, D. G.; Lin, K.; Ji, Y.; Kerr, E. F.; Goulet, M.-A.; De Porcellinis, D.; Tabor, D. P.; Pollack, D. A.; Aspuru-Guzik, A.; Gordon, R. G.; Aziz, M. J., Alkaline Quinone Flow Battery with Long Lifetime at pH 12. Joule 2018, 2, 1894-1906. (20) Chen, Q.; Gerhardt, M. R.; Hartle, L.; Aziz, M. J., A Quinone-Bromide Flow Battery with 1 W/cm2 Power Density. J. Electrochem. Soc. 2016, 163, A5010-A5013. (21) Goulet, M. A.; Aziz, M. J., Flow Battery Molecular Reactant Stability Determined by Symmetric Cell Cycling Methods. J. Electrochem. Soc. 2018, 165, A1466-A1477.


21


Page 22 of 25

(22) Vankar, P. S.; Shanker, R.; Mahanta, D.; Tiwari, S. C., Ecofriendly sonicator dyeing of cotton with Rubia cordifolia Linn. using biomordant. Dyes and Pigments 2008, 76, 207-212. (23) Zhang, S.; Li, X.; Chu, D., An Organic Electroactive Material for Flow Batteries.

Electrochim. Acta 2016, 190, 737-743. (24) Cao, J.; Tao, M.; Chen, H.; Xu, J.; Chen, Z., A highly reversible anthraquinonebased anolyte for alkaline aqueous redox flow batteries. J. Power Sources 2018,

386, 40-46. (25) Al-Ani, K.; Leonard, M. A., An improved synthesis of alizarin fluorine blue. Analyst 1970, 95, 1039-1040. (26) Luo, J.; Sam, A.; Hu, B.; DeBruler, C.; Wei, X.; Wang, W.; Liu, T. L., Unraveling pH dependent cycling stability of ferricyanide/ferrocyanide in redox flow batteries. Nano

Energy 2017, 42, 215-221.


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Figure 1. Molecular formulas and performances of three alizarin compounds. (a) Molecular formulas. (b) Cyclic voltammograms of 5 mM AL, ARS, and AMA scanned at 50 mVs-1 in 1 M KOH on a glassy carbon electrode. (c) LSV of 5 mM AMA in 1 M KOH solution on a glassy carbon working electrode at different rotation rates. (d) Koutecky´–Levich plots derived from the LSV curve. (e) Solubility of K-AMA in aqueous solution with different KOH concentration. (f) Permeability of AMA and AL through N211 membrane in KOH solution. 168x190mm (96 x 96 DPI)



Figure 2. (a) The working principle of the RFB Cyclic voltammogram of 5 mM AMA and ferrocyanide scanned at 50 mV∙s-1 on a glassy carbon electrode. The dotted line represents the CV of 1 M KOH background. (b) Open current voltage versus state of charge. (c) Representative galvanostatic charge and discharge curves at various current densities. (d) Cell voltage and power density versus current density at 10, 50, and 100% SOC. (e) CE, VE, and EE at different current densities. 176x190mm (96 x 96 DPI)


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Figure 3. The stability of AMA during battery operation. (a) CE, EE, charge capacity and discharge capacities in 350 cycles with 100% SOC. (b) 1H NMR of AMA and its degradation products after 350 cycles. Signal peaks are assigned and labelled according to the numbered positions in the drawing of AMA provided as the inset. (600 MHz, DMSO-D6, 25 °C, TMS). 207x178mm (96 x 96 DPI)


A Sustainable Redox Flow Battery with Alizarin-based Aqueous

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