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1

Supplementary Information

Universal quinone electrodes for long cycle life aqueous

rechargeable batteries

Yanliang Liang,1 Yan Jing,1 Saman Gheytani,1 Kuan-Yi Lee,1 Ping Liu,2 Antonio Facchetti,3*

Yan Yao1,4*

Correspondence to: [email protected] or [email protected]

Table of contents:

Synthesis of quinones 2

Tables (S1 and S2) 5

Figures (Figs. S1 to S34) 7

Additional references 41

http://dx.doi.org/10.1038/nmat4919




2

Materials and equipment. N,N-Dimethylformamide (DMF) was anhydrous grade and dried

over molecular sieves prior to use. MeOH was dried by distillation from Mg chips. All other

chemicals were reagent grade and used as received. Syntheses were carried out in air unless

otherwise specified. Nuclear magnetic resonance (NMR) spectra were recorded on a JEOL ECX-

400P spectrometer at 400 MHz (1H) and 100 MHz (13C). Chemical shifts are referenced to

residual protons or carbons in deuterated solvents. Infrared (IR) spectra were recorded for neat

samples on a Thermo Scientific Nicolet iS5 spectrometer using attenuated total reflectance

(ATR) technique. High resolution mass spectroscopy (HRMS) was performed on a Micromass

Autospec Ultima spectrometer in negative ion mode. Elemental analysis was done by Midwest

Micro Lab. Matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass

spectroscopy was recorded on a Bruker Autoflex II spectrometer. PPTO was measured in

negative ion mode using -cyano-4-hydroxycinnamic acid as the matrix. PAQS was measured in

positive ion mode using dithranol as the matrix. X-ray diffraction (XRD) spectroscopy was

carried out at beamline 11-ID-C of the Advanced Photon Source, Argonne National Laboratory.

The wavelength and energy of the X-ray are 0.117418 Å and 105.1 keV, respectively. Scanning

electron microscopy (SEM) was performed on a Gemini LEO 1525 microscope.





3

Synthesis of quinones

Pyrene-4,5,9,10-tetraone (PTO, 1). This is a slightly adapted procedure from a reported

method1. To a solution of pyrene (5 g, 25.4 mmol) in CH2Cl2 (100 mL) and acetonitrile (100 mL)

was added NaIO4 (44.5 g, 207.9 mmol), H2O (125 mL), and RuCl3xH2O (0.64 g, 3.1 mmol). The

dark brown suspension was heated at 3040 °C overnight. The organic solvents of the reaction

mixture were removed under reduced pressure. A dark green cake was obtained by filtrating the

residue and rinsing with 500 mL of H2O, dried in air at 70 °C, and subjected to column

chromatography (CH2Cl2) to afford 1 as golden needles. Yield: 21%; 1H NMR (400 MHz,

DMSO-d6) δ 8.33 (d, J = 8 Hz, 4H), 7.74 (t, J = 8 Hz, 2H) ppm; IR (neat, ATR) 1704, 1690,

1683, 1673, 1560, 1451, 1422, 1337, 1282, 1273, 1175, 1104, 1055, 1002, 961, 909, 807, 710,

643, 547 cm−1.

2,7-Dinitropyrene-4,5,9,10-tetraone (2). A mixture of fuming nitric acid (1.3 mL) and

9598% sulfuric acid (1.3 mL) was added dropwise to 1 (524 mg, 2.0 mmol), and the resulted

orange solution was heated at 85 C. The same amount of the mixed acid was added to the flask

for two more times at a 1-hour interval. After additional reaction for 1 h, the suspension was

poured into 25 mL of H2O, rinsed with another 100 mL of H2O, and dried in vacuum to afford 2





4

as a bright yellow powder which was used without further purification. Yield: 83%; 1H NMR

(400 MHz, DMSO-d6) δ 8.89 (s, 4H) ppm; 13C NMR (100 MHz, DMSO-d6) δ 174.28, 148.76,

135.92, 134.17, 126.02 ppm; IR (neat, ATR) max 3089, 1720, 1693, 1687, 1651, 1588, 1529,

1519, 1421, 1342, 1282, 1242, 1092, 1013, 986, 949, 932, 746, 712, 583 cm−1; HRMS calcd for

C16H4N2O8 [M]: 351.9968, found 351.9974.

2,7-Diaminopyrene-4,5,9,10-tetraone (3). Acetic acid (2.0 mL) and concentrated

hydrochloric acid (2.0 mL) were added to 2 (200 mg, 0.57 mmol) to form a yellow suspension,

to which SnCl22H2O (1.02 g, 4.5 mmol) was slowly added and the mixture was heated at 50 °C

for 15 min. Gray solids were obtained by filtration and dried under vacuum. The gray solid (190

mg) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 283 mg, 1.3 mmol) were then

suspended in dry methanol (4.2 mL) under Ar and stirred at 35 °C for 15 h. The reaction mixture

was diluted with ethylacetate (EtOAc, 25 mL), and the dark purple precipitate was filtered,

washed with another 100 mL of EtOAc, and dried under vacuum and used without further

purification. Yield: 64%; 1H NMR (400 MHz, DMSO-d6) δ 7.32 (s, 4H), 5.93 (s, 4H); 13C NMR

(100 MHz, DMSO-d6) δ 178.34, 148.42, 130.79, 124.40, 118.91 ppm; IR (neat, ATR) 3469,

3437, 3343, 3211, 3078, 1663, 1614, 1590, 1447, 1339, 1270, 1074, 1032, 896, 828, 709 cm−1;

HRMS calcd for C16H8N2O4 [M]: 292.0484, found 292.0477.

Polymerized PTO (PPTO, 4). To the dark purple mixture of 3 (40.0 mg, 0.12 mmol), 4-

dimethylaminopyridine (6 mg, 0.06 mmol), and 2.8 mL of anhydrous DMF was added succinyl

chloride (18 L, 0.16 mmol). The mixture was stirred under Ar at 100 C for 24 h. Dry methanol

(10 L) was then added, and the mixture was stirred at 60 C for an additional 1 h. The reaction

mixture was cooled down to room temperature and poured into methanol (100 mL). The

suspension was filtered, washed by methanol till filtrate became colorless, and the cake was





5

dried under vacuum at 70 C to afford 4 as a light brown powder. Yield: 86%; IR (neat, ATR)

3303, 3084, 2931, 1677, 1576, 1513, 1438, 1335, 1254, 169, 1147, 1099, 903, 843, 713 cm−1;

Anal. Calcd for HO(C20H10N2O6)3H0.65DMF: C, 60.26; H, 3.09; N, 7.78. Found: C, 60.14; H,

2.98; N, 8.23. MALDI-TOF spectrum shows oligomers with up to 5 repeating units (Fig. S11).

Poly(anthraquinonyl sulfide) (PAQS). This is a slightly adapted procedure from a reported

method2. To the mixture of 1,5-dichloroanthraquinone (2.77 g, 10 mmol) and sodium sulfide

nonahydrate (2.4 g, 10 mmol) was added methylpyrrolidone (25 mL). The suspension was stirred

under Ar at 200 C overnight. After cooling down, the mixture was filtered and washed with hot

water and acetone till the filtrate became colorless. The cake was dried in vacuum at 120 C for

16 h to yield the product as a reddish-brown powder (2.0 g, 86%). IR (neat, ATR) 1675, 1651,

1569, 1305, 1262, 1206, 1130, 976, 809, 753, 705 cm−1; Anal. Calcd for Cl(C14H6O2S)5Cl: C,

68.35; H, 2.46; S, 10.43. Found: C, 68.21; H, 2.89; S, 10.73. MALDI-TOF spectrum shows

oligomers with up to 20 repeating units (Fig. S12).





6

Table S1. Weight fraction of individual components for the indicated battery technologies. Battery

configuration

Cathode

(g Wh1)

Anode

(g Wh1)

Electrolyte

(g Wh1)

Cathode

(wt.%)

Anode

(wt.%)

Electrolyte

(wt.%)

PbPbO2 4.1 3.7 5.0 32 28 39

ACPbO2 6.8 15.4 4.1 26 59 16

PTOPbO2 6.9 2.0 4.2 53 15 32

LiTi2(PO4)3LiMn2O4 5.0 6.1 - 45 55 -

PolyimideLiMn2O4 6.3 4.9 - 56 44 -

PPTOLiMn2O4 7.0 3.8 - 65 35 -

MmHNi(OH)2 2.9 2.7 - 52 48 -

PAQSNi(OH)2 3.5 4.8 4.4 27 38 35

ZnONi(OH)2 2.2 1.2 - 65 35 -

Quinone anodes constitute a noticeably small weight fraction of a battery thanks to their high specific capacities. Take acid batteries as an example: Pb anode constitutes 28 wt.% (about the same as PbO2 cathode’s 32 wt.%) of a full cell, while PTO merely 15 wt.% (less than a third of PbO2’s 53 wt.%). At such small fraction, the volume of PTO does not have as much an impact on cell volume as the anode normally would for other lower-capacity materials. Low-capacity anodes such AC does not help energy density, as it constitutes a whopping 59 wt.% (more than twice as PbO2’s 26 wt.%) of the battery.





7 T

able S2 | Com

parison of anode materials.

Electrolyte/

Cathode

a A

node m

aterial S

pecific E

nergy (W

h kg1) E

nergy density (W

h L1) C

apacity retention

Availability

Price for anode ($ kg

1)

Price for

batteryb

($ kWh1)

Environm

ental consideratons

Fast charge

Stability

towards

oxygen

Stability

towards

alkalis

Acidic/

PbO

2

PTO

76

161 95%

after 1,500 cycles (1,200 h)

Virtually infinite

46 2225

P

otentially m

inimal

N.A

. P

b 78

171 80%

after 240 cycles (4,500 h

c) 3,d

Moderately

abundant but highly recyclable

23 1517

Toxic but highly

recyclable

AC

38

37 83%

after 3,000 cycles (1,300 h) 4

Virtually infinite

1418 230-290

Energy-intensive

synthesis (4501200 C

)

Neutral/

LiMn

2 O4

PP

TO

92

208 80%


Virtually infinite

1015 90110

Potentially

minim

al

LiTi2 (P

O4 )3

90 243

89% after 1,200

cycles (1,600 h) 5

Phosphorous is

Earth-abundant,

but economically

mineable reserve

could be limited. 6

2225 170190

Energy-intensive

synthesis (700900 C

)

Polyim

ides 89

186 70%

after 50,000 cycles (950 h) 7

Virtually infinite

34 6065

Potentially

minim

al

Alkaline/

Ni(O

H)2

PA

QS

79

138 88%


Virtually infinite

34 4550

Potentially

minim

al

Mm

H

180 597

80% after 1,300

cycles (unknown

time) 8

Rare earth

elements can be of

geopolitical concerns.

1518 6575

Mining process

has high environm

ental im

pact

Zn 290

714 80%

after 300 cycles (800 h) 3

Abundant

23 2025

Manageable

a Electrolytes for acidic, neutral, and alkaline conditions are 4.4 M H

2 SO4 , 2.5 M

Li2 SO4 , and 10 M

KO

H, respectively. b C

ost is calculated based on cathode and anode m

aterials. c The unusually long time for the sm

all cycle number is due to the slow

discharge (C/5) and charge (C

/16) required for sustaining cycle life. d Cells m

arked red indicate factors that alone could deny the suitability of a m

aterial for large-scale energy storage.





8

Figure S1 | 1H NMR (400 MHz, DMSO-d6) of PTO.

OO

OO

1 (PTO)





9

Figure S2 | 1H NMR (400 MHz, DMSO-d6) of 2.

OO

OO

NO2NO2

2





10

Figure S3 | 13C NMR (100 MHz, DMSO-d6) of 2.





11

Figure S4 | 1H NMR (400 MHz, DMSO-d6) of 3.

OO

OO

NH2NH2

3





12

Figure S5 | 13C NMR (100 MHz, DMSO-d6) of 3.





13

Figure S6 | IR spectra of PTO.

4,000 3,500 3,000 2,500 2,000 1,500 1,000 500

Tra

nsm

ittan

ce

Wavelength (cm1)





14

Figure S7 | IR spectra of 2.

4,000 3,500 3,000 2,500 2,000 1,500 1,000 500

Tra

nsm

ittan

ce

Wavelength (cm1)

OO

OO

NO2NO2

2





15

Figure S8 | IR spectra of 3.

4,000 3,500 3,000 2,500 2,000 1,500 1,000 500

Tran

smitt

ance

Wavelength (cm1)





16

Figure S9 | IR spectra of PPTO.

4,000 3,500 3,000 2,500 2,000 1,500 1,000 500

Tran

smitt

ance

Wavelength (cm1)





17

Figure S10 | IR spectra of PAQS.

4,000 3,500 3,000 2,500 2,000 1,500 1,000

Tra

nsm

ittan

ce

Wavelength (cm1)





18

Figure S11 | MALDI-TOF mass spectrum for PPTO.

500 1,000 1,500 2,000 2,500

Inte

nsity

Mass/charge

PPTO





19

Figure S12 | MALDI-TOF mass spectra for PAQS. a, Full spectrum. b, Zoomed-in spectrum

for mass/charge = 3,5005,000.

3,500 4,000 4,500 5,000

Inte

nsity

Mass/charge

1,000 2,000 3,000 4,000 5,000

Inte

nsity

Mass/charge

a

b





20

Figure S13 | XRD spectra for PTO, PPTO, and PAQS. Wavelength: 0.117418 Å.

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

Inte

nsity

(a.u

.)

2 (degree)

PAQS

PPTO

PTO





21

Figure S14 | SEM images of as-synthesized PTO (a), PPTO (b), and PAQS (c). Scale bar: 5 m.





22

Figure S15 | Voltage profiles for selected quinones. Galvanostatic chargedischarge voltage

profiles for BQ (500 mA g1), PTO (400 mA g1), and AQ (200 mA g1) were measured in 4.4 M

H2SO4. The reduction potentials of BQ, PTO, and AQ are 0.74, 0.49, and 0.16 V vs SHE,

respectively, indicating the opportunity to widely tune the potential of quinone anode via

molecular structure design. Capacities of the quinones are normalized to ease comparison of the

profile shapes.

0.0 0.2 0.4 0.6 0.8 1.0

-0.4

0.0

0.4

0.8

1.2

Pot

entia

l (V

vs

SH

E)

Normalized capacity (a.u.)

BQ

PTO

AQ





23

Figure S16 | Cycling performance of a PTOPbO2 cell under galvanostatic

chargedischarge. Voltage profiles obtained at 2C for selected cycle numbers.

0 50 100 150 200 250 300 350 4000.0

0.4

0.8

1.2

1.6

2.0

2nd

500th

1,000th

1,500th

Vol

tage

(V

)

Specific capacity (mAh g1)

PTO, 2C





24

Figure S17 | Cycling performance of a PTOPbO2 cell under galvanostatic

chargedischarge. a, Capacity retention when cycled at C/5. b, Voltage profiles obtained at C/5

for selected cycle numbers.

0 50 100 150 2000

100

200

300

400

500

Discharge Charge

Spe

cific

cap

acity

(mA

h g

1 )

Cycle number

70

80

90

100110112

Cou

lom

bic

effic

ienc

y (%

)

0 50 100 150 200 250 300 350 4000.0

0.4

0.8

1.2

1.6

2.0

2nd

10th

50th

100th

200th

Vol

tage

(V)


a bPTO, C/5





25

Figure S18 | Cycling performance of PTOPbO2 cells under galvanostatic

chargedischarge. Comparison of the cycling performance of PTO and DHBQ. DHBQ has a

higher solubility (3.1 103 M in the electrolyte) than that of PTO (4.7 106 M), and shows fast

capacity decay. Data were collected in 4.4 M H2SO4.

0 10 20 30 40 500.0

0.2

0.4

0.6

0.8

1.0

1.2

Nor

mal

ized

cap

acity

(a.u

.)

Cycle number

PTO

DHBQ





26

Figure S19 | Determination of the proton diffusivity in PTO/PTO-Hx. a, GITT profile of a

PTO electrode during charging in 4.4 M H2SO4. b, Ion diffusivity calculated from GITT

measurement as a function of the state-of-charge. The diffusivity of proton in PTO/PTO-Hx

ranges from 3.5 1010 to 4.9 108 cm2 s1 with an average of 2.32 109 cm2 s1.

0 50 100 150 200 250 300 350 400

0.2

0.4

0.6

0.8

1.0


Pot

entia

l (V

vs

SH

E)

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.010-11

10-10

10-9

10-8

10-7

10-6

H+

diffu

sivi

ty (c

m2

s1 )

x in PTO-Hx

a b





27

Figure S20 | Micropolarization of a PTO electrode. The exchange current density is calculated

based upon the slope defined by the two points where current and potential are at their maximum

and minimum in the currentpotential curve.

-1.281 -1.278 -1.275 -1.272 -1.269

-0.03

-0.02

-0.01

0.00

0.01

0.02

0.03

Cur

rent

(m

A)

Potential (V vs PbO2)

PTO





28

Figure S21 | Cycling performance of PPTO and PTO in a neutral electrolyte. PTO loses

80% of initial capacity after one cycle owing to high solubility of the lithiated product PTO-Lix

while PPTO does not suffer from this issue. Measurement was performed in 2.5 M Li2SO4 (pH

7).

0 2 4 6 8 100.0

0.2

0.4

0.6

0.8

1.0

1.2

Nor

mal

ized

cap

acity

(a.u

.)

Cycle number

PPTO

PTO





29

Figure S22 | Cycling performance of a PPTOLiMn2O4 cell. Galvanostatic chargedischarge

profiles at 1C for selected cycle numbers.

0 50 100 150 200 2500.0

0.4

0.8

1.2

1.6

2nd

1,000th

2,000th

3,000th


Vol

tage

(V

)

PPTO, 1C





30

Figure S23 | Rate capability of a PPTOLiMn2O4 cell. a, Capacity versus galvanostatic

charge/discharge rate. b, Voltage profiles at varying charge/discharge rates.

0 50 100 150 200 2500.0

0.4

0.8

1.2

1.6

Vol

tage

(V)


50, 20, 10, 5, 2, 1C, C/2, C/5

0.1 1 10 1000

50

100

150

200

250

Spe

cific

cap

acity

(m

Ah

g1 )

Chargedischarge rate (C)

a b





31

Figure S24 | Oxygen consumption by charged (reduced) quinone electrodes. PTO (a) and

PAQS (b) electrodes were studied in 4.4 M H2SO4 and 10 M KOH, respectively. Electrodes were

first discharged and charged under Ar for one cycle. The electrodes at their fully charged state

were then allowed to rest in the presence of air or oxygen for a specified time (marked with

colored background), during which period the open circuit voltage gradually increased. The

electrodes were then charged again at the same current density used for the previous charge. The

restcharge process was consecutively performed twice. A longer resting time led to higher re-

charge capacity. The voltage profiles before and after the restcharge process are largely

identical except that the first reduction plateau of PTO was not recovered by oxygen oxidation

probably because of its high-lying potential.

15.4 15.8 16.2

-1.0

-0.8

-0.6

-0.4

-0.2

0.0

Pot

entia

l (V

vs

SH

E)

19 21 22.5 22.7 24 26 28 30 32 32.8 33.2 33.6

Time (h)

0.5 0.6 0.70.0

0.2

0.4

0.6

0.8

Pot

entia

l (V

vs

SH

E)

2 4.75 20 40 60 68.8 68.9Time (h)

// // // //

4.3 hin O2

10 hin O2

// // // //

4 hin air

64 hin airPTO

PAQS

a

b





32

Figure S25 | Redox potential and specific capacity of various electrode materials for ALIBs.

Grey dashed lines show the thermodynamic potential for O2 (OER) and H2 (HER) evolution at

pH 7. Black dashed lines indicate state-of-the-art ALIB configurations combining previously

reported cathode and anode materials. The specific energy of LiTi2(PO4)3LiMn2O4 and

polyimideLiMn2O4 are 90 and 89 Wh kg1, respectively. Black dotted lines indicate possible

ALIB configurations with PPTO anode and high-voltage cathodes. Among them, the highest

specific energy of 149 Wh kg1 can be expected for PPTOLi0.5Ni0.5Mn1.5O4, a 65% increase

from LiTi2(PO4)3LiMn2O4.

0 50 100 150 200 250 300

-0.8

-0.4

0.0

0.4

0.8

1.2

1.6

2.0

Pot

entia

l (V

vs

SH

E)


2.4

2.8

3.2

3.6

4.0

4.4

4.8

Pot

entia

l (V

vs

Li/L

i+ )

LiTi2(PO4)3

LiMn2O4

AC

LiCoO2

VOx

Polyimide

“Li-rich”

PPTO

Cur

rent

art

Pro

ject

ed g

oal

OER

HER

LiNi0.5Mn1.5O4





33

Figure S26 | Electrochemical performance of an aqueous lithium-ion battery operating in a

mildly alkaline electrolyte. Galvanostatic chargedischarge profile (a) and cycling performance

(b) of a PPTOLiCoO2 cell measured in 2.5 M Li2SO4 (pH 13) at 1C.

0 100 200 300 400 500 600 7000

50

100

150

200

Spe

cific

cap

acity

(m

Ah

g1 )

Cycle number

a b

0 50 100 150 2000.0

0.3

0.6

0.9

1.2

1.5

Vol

tage

(V)






34

Figure S27 | Electrochemical performance of an aqueous sodium-ion battery. Galvanostatic

chargedischarge profile (a) and cycling performance (b) of a PPTONa3V2(PO4)3 cell measured

in 5 M NaNO3 (pH 7) at 1C.

0 20 40 60 800

50

100

150

200

Spe

cific

cap

acity

(mA

h g

1 )

Cycle number0 50 100 150 200

0.0

0.3

0.6

0.9

1.2

Vol

tage

(V)


a b





35

Figure S28 | Voltage profiles of PPTO electrodes in near-neutral electrolytes. Galvanostatic

chargedischarge profile PPTO electrodes cycled at 1C in 2.5 M Li2SO4 (pH 13), 5 M NaNO3

(pH 7), and 4.5 M Mg(NO3)2 (pH 34). The cutoff potential for reduction in the Mg electrolyte is

200 mV higher than those for Li and Na to avoid hydrogen evolution.

0 50 100 150 200 250-0.8

-0.4

0.0

0.4

0.8

Pot

entia

l (V

vs

SH

E)


Li+Na+Mg2+

200 mV





36

Figure S29 | Electrochemical performance of an aqueous magnesium-ion battery.

Galvanostatic chargedischarge profile (at C/2) (a), cycling performance (at C/2) (b), and rate

capability (at 2CC/2) (c) of a PPTOMgxCuHCF cell measured in 4.5 M Mg(NO3)2 (pH 34).

0 200 400 600 800 10000

30

60

90

120

150

Spe

cific

cap

acity

(mA

h g

1 )

Cycle number

0 20 40 60 800

40

80

120

160

Spe

cific

cap

acity

(mA

h g

1 )

Cycle number

2C 1C C/2

0 40 80 120 1600.0

0.3

0.6

0.9

1.2

Vol

tage

(V

)


a b

c





37

Figure S30 | Cycling performance of a PAQSNi(OH)2 cell. Voltage profiles obtained at 1C

for selected cycle numbers.

0 50 100 150 2000.0

0.4

0.8

1.2

1.6

2nd

500th

1,000th

1,350th

Vol

tage

(V)


PAQS





38

Figure S31 | PAQS electrodes cycled in alternative alkaline electrolytes. Voltage profile (a,

c) and cycling performance (b, d) for galvanostatic chargedischarge at 1C in 4 M LiOH (a, b)

and 8 M NaOH (c, d). PAQS electrodes show high specific capacity and coulombic efficiency in

all alkaline metal hydroxide electrolytes.

0 40 80 120 160 200-1.0

-0.8

-0.6

-0.4

-0.2

0.0

Pot

entia

l (V

vs

SH

E)


0 40 80 120 160 200-1.0

-0.8

-0.6

-0.4

-0.2

0.0

Pot

entia

l (V

vs

SH

E)


0 5 10 15 20

50

100

150

200

250

Charge Discharge

Spe

cific

cap

acity

(mA

h g

1 )

Cou

lom

bic

effic

ienc

y (%

)

Cycle number

80

85

90

95

100

0 5 10 15 200

50

100

150

200

250

300

Charge Discharge

Spe

cific

cap

acity

(mA

h g

1 )

Cou

lom

bic

effic

ienc

y (%

)

Cycle number

80

85

90

95

100

a b

c d





39

Figure S32 | Temperature-dependent electrochemical properties of a PAQS electrode. a,

Nyquist plots obtained from electrochemical impedance spectroscopy measurements. b,

Micropolarization curves measured immediately after impedance measurements.

-0.48 -0.47 -0.46 -0.45 -0.44 -0.43 -0.42

-0.20

-0.15

-0.10

-0.05

0.00

0.05

0.10

0.15

0.20

Cur

rent

(mA

)

Potential (V vs AC)

0 5 10 15 20 25 30

-5

0

5

10

15

20

Z' (

)

Z ()

a

b25 C 35 C

25 C 35 C





40

Figure S33 | Rate capability of a PAQSNi(OH)2 cell. Voltage profiles for galvanostatic

chargedischarge from C/2 to 20C.

0 40 80 120 160 2000.0

0.4

0.8

1.2

1.6


C/2 5C 1C 10C 2C 20C

Vol

tage

(V)

PAQS





41

Figure S34 | Specific energy and power of aqueous rechargeable batteries. a, Ragone plot for

specific energy versus power. Open plots indicate commercial and previously reported battery

configurations, while solid plots are for quinone-based ones. Symbol colors red, green, and blue

indicate batteries with strongly acidic, near neutral, and strongly alkaline electrolytes. b, Voltage

and cell specific capacity of commercial and previously reported batteries, plus batteries with

hypothetically improved cathode and anode materials. Dashed lines denote the voltage and

capacity needed to achieve certain specific energy (100 and 200 Wh kg1). Arrows show how the

specific energy of a cell can be increased with improved electrode materials of the same type.

0 40 80 120 160 2000.0

0.5

1.0

1.5

2.0

2.5

100 Wh kg1

PbO2 (50%) | Pb PbO2 (90%) | Pb PbO2 (50%) | AC PbO2 (50%) | PTO PbO2 (90%) | Quinone† LiMn2O4 | LiTi2(PO4)3

LiMn2O4 | PPTO LiCoO2† | Quinone† Ni(OH)2 | MmH Ni(OH)2 | Zn Ni(OH)2 | PAQS Ni(OH)2 | Quinone†

Vol

tage

(V

)

Cell specific capacity (mAh g1)

200 Wh kg1

10 100 1000 10000

5

20

50

200

10

100

Ni(OH)2 | PAQS

Ni(OH)2 | PAQS (25 C)

Ni(OH)2 | MmH

Ni(OH)2 | MmH (25 C)

Ni(OH)2 | Zn

PbO2 | PTO

PbO2 | Pb PbO2 | AC LiMn2O4 | PPTO LiMn2O4 | LiTi2(PO4)3

LiMn2O4 | polyimide

Spe

cific

ene

rgy

(Wh

kg1

)

Specific power (W kg1)

a

b





42

Additional references

1 Hu, J., Zhang, D. & Harris, F. W. Ruthenium(III) chloride catalyzed oxidation of pyrene and 2,7-disubstitued pyrenes: An efficient, one-step synthesis of pyrene-4,5-diones and pyrene-4,5,9,10-tetraones. J. Org. Chem. 70, 707-708. (2005).

2 Song, Z., Zhan, H. & Zhou, Y. Anthraquinone based polymer as high performance cathode material for rechargeable lithium batteries. Chem. Commun., 448-450. (2009).

3 Reddy, T. B. Linden's handbook of batteries. fourth edn (McGraw-Hill, 2011). 4 Yu, N., Gao, L., Zhao, S. & Wang, Z. Electrodeposited PbO2 thin film as positive

electrode in PbO2/AC hybrid capacitor. Electrochim. Acta 54, 3835-3841. (2009). 5 Sun, D. et al. Long-lived aqueous rechargeable lithium batteries using mesoporous

LiTi2(PO4)3@C anode. Sci. Rep. 5, 17452. (2015). 6 Cordell, D. & White, S. Peak phosphorus: Clarifying the key issues of a vigorous debate

about long-term phosphorus security. Sustainability 3, 2027. (2011). 7 Dong, X. et al. Environmentally-friendly aqueous Li (or Na)-ion battery with fast

electrode kinetics and super-long life. Science Advances 2, e1501038. (2016). 8 Bäuerlein, P., Antonius, C., Löffler, J. & Kümpers, J. Progress in high-power nickel–

metal hydride batteries. J. Power Sources 176, 547-554. (2008).


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