REVIEWS

Organic batteries for a greener

rechargeable world
Jihyeon Kim1,6, Youngsu Kim1,6, Jaekyun Yoo1,6, Giyun Kwon1, Youngmin Ko1,2,5
and Kisuk Kang   1,2,3,4 ✉
The emergence of electric mobility has placed high demands on lithium-ion batteries, inevitably
requiring a substantial consumption of transition-metal resources. The use of this resource raises
concerns about the limited supply of transition metals along with the associated environmental
footprint. Organic rechargeable batteries, which are transition-metal-free, eco-friendly and
cost-effective, are promising alternatives to current lithium-ion batteries that could alleviate
these mounting concerns. In this Review, we present an overview of the efforts to implement
transition-metal-free organic materials as the redox-active component in diverse types of
organic rechargeable batteries. In addition, we critically evaluate the current status of organic
rechargeable batteries from a practical viewpoint and assess the feasibility of their use in various
energy-storage applications with respect to environmental and economic aspects. We believe
this Review provides a timely evaluation of organic rechargeable batteries from a real-world
perspective, and we hope it will spur more intensive efforts towards a greener energy future.

1
Department of Materials
Science and Engineering,
Research Institute of
Advanced Materials (RIAM),
Seoul National University,
Seoul, Republic of Korea.
2
Institute of Engineering
Research, College of
Engineering, Seoul National
University, Seoul, Republic
of Korea.
3
Center for Nanoparticle
Research, Institute of Basic
Science, Seoul National
University, Seoul, Republic
of Korea.
4
School of Chemical and
Bioengineering, College of
Engineering, Seoul National
University, Seoul, Republic
of Korea.
5
Present address: Lawrence
Berkeley National Laboratory,
Berkeley, CA, USA.
6
These authors contributed
equally: Jihyeon Kim,
Youngsu Kim, Jaekyun Yoo.
✉e-mail: matlgen1@snu.ac.kr
https://doi.org/10.1038/
s41578-022-00478-1
Global efforts to lessen our carbon footprint have
prompted a transition to renewable energy and the
increased adoption of electric mobility. Because recharge-
able batteries are a key enabler in these endeavours, a
substantial rise in battery production is foreseeable in
the coming years. Conventional lithium-ion batteries
rely on transition-metal-oxide-based materials — such
as cobalt and nickel oxides — for their positive elec-
trodes, as they offer high energy density and long cycle
life. As the demands for lithium-ion batteries are pro-
jected to soar, these transition metals are likely to see
heavy consumption, which presents a potential supply
problem. The availability of transition-metal resources
is limited, resulting in high production costs, and their
large-scale use is neither sustainable nor environmen-
tally benign. Moreover, transition-metal-based materi-
als are currently responsible for nearly 30–50% of the
global warming impact from battery-manufacturing
processes1,2. Various alternative approaches have thus
been suggested to enable us to break away from con-
ventional transition-metal-based active materials and
proceed towards sustainable battery chemistry3–5.
Organic rechargeable batteries have emerged as a
promising alternative for sustainable energy storage
as they exploit transition-metal-free active materials,
namely redox-active organic materials mostly com-
prising earth-abundant carbon, oxygen, hydrogen
and nitrogen6–9. Fundamental research into the redox
activity in organic compounds has led to the discovery
of several important groups of materials that exhibit
electrochemical performances on par with those of con-
ventional transition-metal-based materials. Given these
potential merits, remarkable efforts have been made over
the past few decades to introduce these redox-active
organic materials as the key electrode component6–11.
More recently, extensive investigations have aimed to
implement these redox-active organic electrodes in
practical battery systems and obtain performance lev-
els comparable to those of transition-metal-containing
commercial batteries. Moreover, some general disadvan-
tages of organic materials, such as their low electronic
conductivity and high dissolution properties, can be
effectively mitigated through advanced electrode design
or converted into technical merits by revising the battery
configuration.
In this Review, we highlight the recent progress in
organic rechargeable battery technologies, focusing
mainly on practical aspects. In addition to providing a
comparative assessment of the individual redox-active
materials 6,9, we propose a more pragmatic evalua-
tion considering the entire electrode composition as
a component for organic batteries. We then discuss
alternative platforms for redox-active materials in
post-lithium-ion-battery systems, covering the inclusion
of Earth-abundant metal ions and the development of
aqueous organic batteries and organic redox-flow batter-
ies. This Review aims to offer a comprehensive and prac-
tical assessment of the current challenges and solutions,
thus aiding in the further development of sustainable
and affordable organic rechargeable batteries.

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Assessment of redox-active organics
Although the use of transition-metal-free active mate-
rials is attractive from a sustainability point of view,
the precise assessment of redox-active organic materi-
als is challenging compared with that of commercially
mass-produced transition-metal-based electrode mate-
rials, especially in terms of practical cost per perfor-
mance and environmental merits. These issues stem
from lack of mass production and related economies
of scale. Nonetheless, rough estimations are possible,
using some relevant indexes such as the current market
price of typical active materials and the global warm-
ing potential (GWP). The GWP is an index referring to
the amount of carbon dioxide (CO2), or gas equivalent
to CO2, generated per the production of one kilogram
of a specific product over a given time12,13. Figure 1a
compares the GWP100 values (GWP over 100 years)
of representative cathode materials — here LiCoO2
(LCO) and LiNi0.6Co0.2Mn0.2O2 (NCM622)1,14 — with
that of several mass-produced organic compounds —
methanol (CH3OH), olefins (ethylene (C2H4), propylene
(C3H6)) and common aromatic compounds (benzene,
toluene and mixed xylenes)15. The commercialized
transition-metal-containing cathode materials clearly
have a substantial effect on greenhouse gas emissions,
generating nearly 20 kg of CO2 for every kilogram of cath-
ode production. Although the GWP100 values for pro-
spective redox-active organic materials are not known,
they can be estimated from the GWP100 values for
common precursors and the corresponding increase in
a b
20
GWP100 (kg CO2-eq kg–1)
15
Price (US$ kg–1)
10
5
0 0
LCO NCM622 Methanol Olefins Common Redox-active
aromatic materials
compounds (estimated)
Fig. 1 | Comparative analysis of environmental and economic merits of
redox-active organic materials. a | Comparison of the global warming
potential (GWP) between common transition-metal-based active materials
(blue bars) and organic materials (green bars). GWP100 denotes the relevant
global warming impact of the specific product compared with the impact
of CO2 gas emissions over 100 years. The GWP100a method from the IPCC
2007 (ref. 236) report is used for LiCoO2 (LCO), whereas the GWP100a
method from the IPCC 2013 (ref.237) report is used for NCM622 and organic
materials. We note that the life cycle assessment for the calculation of
GWP100 excludes the end-of-life stage. The GWP of redox-active organic
materials (orange bar) is an estimated value with the assumption that
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GWP100 for each additional process. Even though com-
plex industrial organic chemicals generally require two
to four steps of additional chemical processes from the
precursors16,17, currently mass-produced simple organic
compounds generate less than one-fifth of the GWP100
of transition-metal-containing cathode materials1,14,15.
This value suggests that the estimated GWP100 of most
redox-active organic materials still remains substantially
lower than that of transition-metal-based materials, as
depicted in Fig. 1a. Moreover, this projection is conserv-
ative, meaning that some redox-active organic materials
requiring simpler synthetic conditions would have a far
lower GWP100 value.
Figure 1b illustrates the changes in prices of repre-
sentative commercial cathode materials over the past
3 years. The costs clearly fluctuate even over a short
period, varying more than two times in price during
this period, which closely correlates with the raw-metal
costs such as that of cobalt (blue line in Fig. 1b). The
transition-metal-based cathode materials usually make
up 40% of the total cell cost, and so their fluctuating
price poses an unpredictable risk factor in the mass
production of lithium-ion batteries18. More importantly,
the long-term supply of the major transition metals
remains vulnerable and may not be able to cope with
the rapid growth of the market. According to recent
reports19, the lithium-ion battery market is expected to
reach a capacity of 3 TWh by 2030, which is approxi-
mately 20 times greater than the current capacity (about
140 GWh in 2020). The 3-TWh capacity of lithium-ion
80
Cobalt metal
LCO
70 NCM622
NCM523
60 Price of conventional electrode materials
50
40
30
20
10 Estimated price of redox-active organic materials
July 2018 July 2019 July 2020 July 2021
Date
redox-active organic materials are synthesized in two to four steps from
simple organic precursors and that little additional energy is needed during
the synthesis process. The error bar denotes the range of estimated GWP
values in accordance with expected two to four synthesis steps. b | Daily
price of cobalt metal (blue), LCO (green), NCM622 (yellow) and NCM523
(red) over a recent 3-year period. Data sources: Shanghai metal market,
2021 (for LCO, NCM622 and NCM523); London metal exchange, 2021
(for cobalt metal). The olefins are ethylene (C2H4) and propylene (C3H6); the
common aromatic compounds are benzene, toluene and mixed xylene.
NCM523 and NCM622 refer to LiNi0.5Co0.2Mn0.3O2 and LiNi0.6Mn0.2Co0.2O2,
respectively.
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 Reviews

Oxygen-containing motif Nitrogen-containing motif

–e,+A
– – – e–, + A– + e–, + M+
O O + A– N N + A– N C N C + M+
+ e–, – A– + e–, – A– – e–, – M+

Ether motif Tertiary amine motif Imine motif

O O
+ e–, + M+ + 2e–, + 2M+ + e–, + M+
C C
+ M+ N N N N + 2M+ C C N C C N + M+
– e–, – M+ – 2e–, – 2M+ – e–, – M+

Carbonyl motif Azo motif Nitrile motif

Sulfur-containing motif
S S
– e–, + A– + e–, + M+ + 2e–, + 2M+
S S C C
+ A – + M+ S S 2 S + 2M+
+ e–, – A– – e–, – M+ – 2e–, + 2M+

Thioether motif Thiocarbonyl motif Disulfide motif

Other types of redox motifs

+ e–, + M+ x + xe–, – xA– + ye–, + yM+ y

+ e–, – A–
N O + A– N O N O + M+ + xA– + yM+
n
– e–, + A– – e–, – M+ n – xe–, + xA– n – ye–, – yM+

Nitroxide radical motif Motifs in conducting polymer

M+ = Li+, Na+, K+, other cations

A– = ClO4–, PF6–, TFSI–, other anions

Fig. 2 | redox motifs in representative redox-active organic electrodes. Representative redox motifs that are
commonly observed in redox-active organic materials in the literature. The blue and red colours indicate p-type and
n-type motifs, respectively. During p-type and n-type redox reactions, charge compensation by anions and cations,
respectively, in the electrolyte is generally required.

batteries would require approximately 2.2 million tons
of transition metal (either cobalt or nickel) based on the
current cathode chemistry. Considering that the annual
production of cobalt is at present 0.14 million tons and
that of nickel is 2.5 million tons, the demand for transi-
tion metals to achieve this 3-TWh capacity cannot eas-
ily be met. According to the United States Geological
Survey (USGS), this demand will be a serious issue in
the near future because competition with other indus-
tries is to be expected. In particular, major demands for
nickel from the competing stainless-steel manufactur-
ing industry could substantially raise the price of nickel
during battery-market growth. Unlike these projections
on transition-metal availability and associated costs
(Fig. 1b), previous studies unequivocally suggest that the
cost of redox-active organic materials would be less than
US$15 per kilogram when mass-produced through con-
ventional organic synthetic routes9,20. We note that this
price was estimated in 2017. This analysis implies that
redox-active organic materials have a greater economic
potential than do cobalt-based (London metal exchange,
2021) and other transition-metal-based materials
(Shanghai metal market, 2021), for TWh-level battery
mass production.
Redox-active organic materials
Redox-active organic materials are usually classified as
n-type, p-type or bipolar-type according to their capabil-
ities to release electrons (oxidation) or receive electrons
(reduction) in their neutral state during the electro-
chemical reaction. n-type redox-active organic materials
typically undergo reduction from their neutral state,
forming negatively charged molecular states that can be
reversed during oxidation. Conversely, the electrochem-
ical reaction of p-type organic materials involves oxida-
tion from their neutral state, forming positively charged
molecular states reversibly. Some organic compounds
are known to undergo a bipolar-type reaction, exploiting
redox moieties capable of both n-type and p-type behavi­
ours. The basic redox nature of redox-active organic
materials depends on the redox motif, a functional
group in the molecule, which confers redox activity.
In the following, we briefly introduce the major redox
motifs constituting representative redox-active organic
materials, as depicted in Fig. 2.
Oxygen-containing motifs
The most common redox motifs found in redox-active
organic materials are oxygen-containing units, which
include two major types of functional groups: car-
bonyl and ether groups. Since the first report on
carbonyl-based organic materials as an active material
in 1969 (ref.21), various carbonyl redox-active organic
materials have been investigated, including quinone
derivatives22–26, carboxylate salts27,28, imides29,30 and
anhydrides31. The carbonyl motif (C=O) in these mate-
rials enables an n-type redox reaction, accompanied by
the reversible formation of a radical monoanion (C–O−)
through the enolization reaction. Quinone derivatives
such as vitamin K, ubiquinone and plastoquinone have
been the most widely studied among carbonyls because
they are abundantly found in nature and play a key part

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in biochemical electron transfer23,32,33. Organic materi-
als with carbonyl motifs generally supply a discharge
potential of approximately 2.5 V (versus Li+/Li), which
is relatively low for cathodes and too high for anode
applications. However, the carboxylate compounds,
which have analogous C=O bonds in their molecular
structures, can deliver a low potential (approximately 1 V
versus Li+/Li)27, comparable to that of commercialized
anode materials such as Li4Ti5O12.
The ether motif (C–O–C) promotes a high-potential
p-type redox reaction, upon which a radical cation is
reversibly formed. Organic electrodes with ether motifs
often provide the highest redox potential (over 4 V ver-
sus Li+/Li)34 because of their strong electronegativity.
Nonetheless, the exploitation of ether-based materials,
such as phenoxazine derivatives, as high potential elec-
trodes is usually hindered by the limited electrochemical
window of conventional electrolytes and the complica-
tions involved with anion incorporation during p-type
redox reactions35,36.
Nitrogen-containing motifs
Nitrogen-containing redox motifs include the tertiary
amine-, azo-, imine-, and nitrile-redox centres (Fig. 2).
The ability of nitrogen atoms to form three covalent
bonds allows for much more diverse redox moieties
than in their oxygen-containing counterparts. Among
these, the tertiary amine motif permits p-type reactions
similar to the ether motif, thus allowing a high redox
potential over 3 V (versus Li+/Li) in electrode materi-
als based on dihydrophenazine37–40, triphenylamine41,42,
phenothiazine 35,36 and phenoxazine 36,43 derivatives.
In particular, dihydrophenazine-based electrodes are
capable of undergoing a two-electron redox reaction
per molecule, offering a high specific capacity and thus
a specific energy comparable to that of commercial
LiFePO4 (LFP) cathodes37.
The redox motifs of azo compounds (N=N)44–46,
imines (C=N)38,47–51, nitriles (C≡N)34,52–54 and sulfo-
namides (C–N(SO2)–)55 are based on double or triple
bonds between nitrogen and carbon and typically display
n-type activity through the change in the bond order
upon redox reaction. Given their relatively simple struc-
ture and ability to reversibly react with two alkali ions,
the family of azo compounds features a high capacity44.
Imine compounds are often found in biological
charge-transfer systems such as in pteridine and pyrid-
inium derivatives. They generally consist of a hetero­
aromatic ring, with nitrogen atoms on the conjugated
structure, allowing effective simplification or modifica-
tion of the molecular structure through various means,
including by cutting out the conjugated moiety and
keeping only the nitrogen-containing conjugated ring50.
For the nitrile redox motif, 7,7,8,8-tetracyanoquinod-
imethane and its derivatives are the most studied because
they possess the highest redox potential among the
n-type redox-active organic materials (2.4–3.2 V versus
Li+/Li)34,52–54. The high redox potential of nitrile compounds
is attributable to the strong electron-accepting character-
istics originating from the four electron-withdrawing
nitrile groups. The sulfonamide motif — the newest of
this group to be discovered — displays an even higher
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redox potential than the nitrile groups because of elec-
tron delocalization on the sulfonyl group attached next
to the nitrogen centre55. Redox-active organic materi-
als with the sulfonamide motif are usually synthesized
in a reduced form with a negative charge in its pris-
tine state (that is, bound with a counter-cation such
as Li+ or Na+); thus, the initial electrochemical process
involves the extraction of the counter-cations to allow
an n-type reaction.
Sulfur-containing motifs
Sulfur-containing redox motifs have similar redox
characteristics to oxygen-containing redox units, pos-
sibly because sulfur and oxygen are in the same group
in the periodic table. The representative thioether motif
(C–S–C), which consists of two single bonds between
sulfur and carbon atoms, typically triggers a p-type reac-
tion with a redox mechanism similar to that of the ether
motif 56–58. The thiocarbonyl motif (C=S) is comparable
to the carbonyl motif. However, since sulfur is less elec-
tronegative than oxygen, it induces an increased redox
potential and enhanced electronic conductivity 59,60.
The disulfide motif (C–S–S–C), which contains a
single bond between two sulfur atoms, has a distinc-
tive n-type redox mechanism; the S–S bond is broken
after accepting two electrons, and each R–S− anion is
stabilized by a counter-cation at a relatively low redox
potential (approximately 2.2 V versus Li+/Li). Because
of the multi-electron redox per motif, these compounds
can display high specific capacities and have thus been
intensively studied61–63. However, the intrinsically slug-
gish kinetics originating from S–S bond breakage or
formation during reduction and oxidation, respectively,
lead to a high overpotential64. The solubility of the small
molecules generated by the bond-breakage reaction also
leads to premature capacity decay caused by the loss of
active materials65.
Other types of redox motifs
Other types of redox motifs appear in a radical form
or in conducting polymers. One of the most repre-
sentative examples in this class is the 2,2,6,6-tetra
methylpiperidin-1-yl)oxyl (TEMPO)-based compound
containing a nitroxide radical motif (N–O·). They
are intrinsically bipolar in nature but are more often
employed as cathode materials selectively utilizing
p-type reactions to exploit associated high redox poten-
tials (approximately 3.6 V versus Li+/Li). TEMPO-based
compounds are usually reported in the form of polymers
owing to their highly soluble nature66–69 and can exhibit
a high rate capability resulting from their self-exchange
reaction, which is a fast intermolecular electron trans-
fer process69. However, the large redox-inactive parts
in the polymer typically yield a low specific capacity.
Similarly, conducting polymers based on polyacetylene70,
polythiophene71 or polyaniline72 have been studied as
redox-active materials. Doping these polymer elec-
trodes with counter-ions should enable redox reac-
tions, leading to theoretically high capacities. However,
to achieve these predicted capacities, high doping
levels are necessary, which limit the cycle stability because
of the occurrence of side reactions with the dopants61.
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Applications in rechargeable batteries
To date, 56 redox-active organic materials have been
reported to possess the aforementioned redox motifs
(Fig.  3) . Here, we refer to them as organics 1 to 56 .
When incorporated in organic electrodes, these mate-
rials deliver the most remarkable electrochemical per-
formances of the redox-active organics. Regarding the
suitability of these candidates for practical electrodes,
which consist of not only active material but several
other components, it should be noted that their per-
formance in the literature has been evaluated mostly in
the framework of conventional transition-metal-based
battery assessment. Moreover, comparative evaluations
are not straightforward given the different electrode
fabrication procedures employed for each reported
material. These issues imply that the intrinsic capabil-
ities of redox-active organic materials might not have
been properly appraised. The following section dis-
cusses the distinctive characteristics of organic materi-
als (organics 1 to 45 in Fig. 3) with respect to the major
battery performance metrics — specific energy, specific
power and cycle stability — comprehensively considering
their practical applicability. Approaches that exploit the
unique characteristics of organic electrodes that could
aid them to surpass conventional lithium-ion battery
electrochemical performances are also introduced.
Comparative analysis of specific energy
The specific energy is determined by the numerical
product of the specific capacity and the redox potential
of the active material. The specific capacity and the volt-
age (versus Li+/Li) of state-of-the-art organic electrode
materials as well as conventional transition-metal-based
electrode materials are compared in Fig.  4a (and in
Supplementary Fig. 1a, where references for each mate-
rial are noted). The presented values of the specific
capacities and voltages are practical values obtained
from the discharge curves in the literature. We note
that the specific capacities in Figs.  4 and 5 are esti-
mated on the basis of the weight of each material in the
ready-to-charge state (that is, the discharged state) for
fair comparison with those of transition-metal-based
inorganic materials. Since the accompanying anions
are not taken into account in the specific capacities of
the presented p-type materials, the deliverable capacity
may vary depending on the electrolyte systems in some
cases, such as in dual-ion systems. Because of their light
constituent elements and multi-electron transfer capa-
bilities, some organic electrode materials are capable
of delivering specific capacities that are two to three
times greater than those of transition-metal-based elec-
trode materials such as LCO73,74, NCM75,76 and LFP77.
Electrodes based on rhodizonate (organic 1)28,30,78 or
cyclohexanehexone (organic 2)79 derivatives allow four
or six electron transfers per molecule, respectively,
resulting in capacities of approximately 503 mAh g−1
or 723 mAh g−1 and energy densities of 1,117 Wh kg−1 or
1,229 Wh kg−1. This is a clear benefit of organic electrode
materials over conventional layered transition-metal
oxide cathodes, which are rapidly reaching their the-
oretical limit of 270 mAh g −1 owing to their heavy
transition-metal-element content32,80,81.
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Strategies to increase the specific energy of redox-active
organic materials. As shown in Fig. 4, the high spe-
cific capacities of organic electrodes generally come at
the cost of a low redox potential; thus, the increase in the
specific energy is not substantial in most cases. Specific
capacities over 300 mAh g−1 are routinely obtainable for
some organic electrodes; however, their redox poten-
tial mostly lies substantially below 3 V (versus Li+/Li).
Accordingly, extensive efforts have been placed in iden-
tifying high-redox-potential organic electrodes55,59,60,82–86.
For example, a few p-type organic materials exhibit a
high redox potential over 3.5 V (versus Li +/Li) 9,61,
as indicated by the triangular data points in Fig. 4a.
Moreover, chemical modifications of n-type materi-
als were performed to enhance the redox potentials to
values comparable to those of transition-metal-based
materials61. For organic 732,87, the redox potential of
lithium (2,5-dilithium-oxy)-terephthalate could be ele-
vated by as much as 800 mV by including spectator ions
with higher ionic potential than lithium, such as Ca2+,
Ba2+ and Mg2+. A comprehensive overview of the volt-
age engineering of organic electrode materials has been
provided in other review papers6,9,61,88,89.
Electrode-level specific energy assessment of organic
redox-active materials. Since the discovery of organic
redox-active materials with enhanced energy density, their
use in practical battery systems has been arduous. When it
comes to practical energy density, the weight and volume
of the redox-inactive components must also be consid-
ered. These components, such as the conducting agent
and binder, are needed for electrode fabrication to secure
mechanical stability and electrical conductivity. Because
of the insulating nature of organic materials, organic
electrodes usually require high conducting agent and
binder contents. According to our literature survey, most
organic electrodes reported thus far contain 30–70 wt%
of conducting agent to make up for the low electronic
conductivity so that organic electrodes can achieve a spe-
cific energy comparable to that of transition-metal-based
electrodes. This is in contrast with commercial electrodes
where these additives make up less than 5 wt% of the total
electrode90,91. This issue has become an impediment for
organic electrodes92. Although many previous reviews
have evaluated the specific capacity, redox potential or
specific energy of organic electrodes, a critical evalua-
tion of the electrode-level specific energy, covering all
the electrode components, has rarely been performed.
Therefore, we compare the specific energy of the reported
redox-active organic materials at the electrode and mate-
rial level, highlighting the general deviation between the
two (Fig. 4b and Supplementary Fig. 1b, where references
for each material are noted). The x axis is the specific
energy calculated based on the weight of the redox-active
material, as suggested in the literature, and the y axis
is the specific energy calculated based on the weight
of the entire electrode including the redox-active material,
conducting agent and binder. The dashed line in Fig. 4b
indicates the point at which the material-level specific
energy coincides with the electrode-level specific energy.
The analysis indicates that conventional transition-metal-
based electrodes deviate only slightly from this line.
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O O O 2
N N O O
O O M O O Li S O O Li O
Na S S
N N M2
N N
O
O O M O O O S S S Na
Li O
O O N N S S
3 O 4 5
M = Li, Na, K 2 6 O Li O
1 O O Li N M = Mg, Ca, Ba, Mn
Li O
N O O 7
M O S S S
O S N
N N N O O
O O M S S 12
8 M = Li, Na O Li O O
Li O O
11 13
10
9 O O
O n
O O
O O N N O O
Li O O Li
N N
Li O O Li S
O N O O
O O N N O O
O O
14 15 17 18
16

O O
O O O O O
N N H
O N N N N
N N O
O N N
N 20 N N N
O O H
O O N N O n
19 21 22 N 23
O

N
O O HO OH O O O O O
O O S

N N O O
S
NH NH O
O O
27
n 29
28
n O O
24 25 30
O 26 n
O Li O Li O
O O HO n
N S
O O O O
O O S
O N n
N S N
O O
O Li O Li n 34 N HO N
O 31 O 33 36
32 O
O O O
S 35 37
O Li O
N O
S Li S O
I M O O M
N N N
O O N N N
O S Li N
O I M O O M
S N
O 41 O
43
n S Li
39 40 M = Li, Na
38 n O O 42
O
O
O O O Na O3S
O O
O O
H
N N N SO3 Na
O O O S
O
O O
44 O 45 n n 48 O O
46 47

O O
OH OH
M O HO N N OH
N O
S O N
HO N N OH
O O O M
49 n M = Li, Na, K OH OH O O
51
50
O O O O
O O 52
O O 4
S
N N
4Cl
S N N
O O n O O
O O 54 55 56
53

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◀ Fig. 3 | Molecular structures of representative redox-active organic materials.
Representative redox-active organic materials that exhibit high battery performances.
Their redox characteristics are usually determined from their redox motif.
By contrast, most of the organic electrodes display con-
siderably lower electrode-level specific energy than would
be expected from the material level. It is noteworthy that
organic 1 appears to retain a high specific energy at the
electrode level. Nevertheless, this specific energy rapidly
degrades within a few cycles, implying that the content
of the redox-inactive components (conducting agent or
binder) is too low to enable the components to effectively
perform their intended roles24.
Strategies to increase the specific energy of redox-active
organic materials at the electrode level. Unlocking the
potential high specific energy of organic materials at
the electrode level is an imperative step for their prac-
tical applicability. Certain strategies can close the gap
and achieve a high electrode-level specific energy, as
schematically illustrated in Fig. 4c–e. For instance, the
formation of a charge-transfer complex (Fig. 4c), when in
a particular intermolecular arrangement facilitating elec-
tron conduction, may reduce the amount of conducting
agent needed in the electrode owing to the increased elec-
tronic conductivity of the complex. The charge-transfer
complexes consisting of organics 3 and 10 (depicted
as 3•10 in ref.34, Fig. 4b) or organics 3 and 11 (depicted as
3•11 in ref.52, Fig. 4b) exhibit an electronic conductivity
markedly enhanced beyond the intrinsic conductivities
of individual organics 3, 10 or 11. Thus, the electrode
comprising one of these complexes can be fabricated
with more than 90 wt% of active material, enhancing the
electrode-level specific energy. This type of approach, if
further developed, would allow high electronic conduc-
tivity while retaining the intrinsic redox activities from
the two precursor organic materials. Similarly, connect-
ing redox-active organic materials (organic 13) into a
covalent organic framework structure provided a high
conductivity by π–π interactions through the eclipsed
stacking structure of the framework45. Consequently,
even with a small amount of conducting agent (less than
20 wt%), a high specific energy at the electrode level can
be achieved, retaining nearly the same specific energy as
at the material level.
Using a multifunctional redox-active conducting
agent with a high electronic conductivity93,94 (Fig. 4d) also
achieves a high electrode-level specific energy. For exam-
ple, titanium disulfide (TiS2) not only displays a high
electronic conductivity of 74.4 S cm−1 but can addition-
ally contribute to the specific capacity through reversible
intercalation. When the redox-inactive conducting agent
in an electrode fabricated from organic 13 is partially
replaced with TiS2 (ref.94), the resulting hybrid electrode
can achieve a specific energy of 286 Wh per kilogram
of electrode, outperforming the electrode made only
with the conventional conducting agent (167 Wh per
kilogram of electrode).
Considering that the conventional electrode fabrica-
tion process has been optimized for commercial electrode
materials (Fig. 4e), engineering new electrode configura-
tions that take advantage of the distinctive properties of
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organic materials may be another strategy. The distinc-
tive properties of organic materials may offer unexplored
benefits in electrode manufacturing. For instance, some
molecules, such as organic 14, exhibit a strong π–π inter-
action with graphitic carbon owing to their polycyclic
aromatic hydrocarbon-bearing molecular structure.
Molecular interactions with the carbon-based conduct-
ing agent lead to an electrically well connected electrode
structure even with a small amount of carbon additive95.
Moreover, carbon nanotube additives further facilitate
electrical connections between the organic particles
in the electrode because they have higher aspect ratios
than spherical carbon additives95. Through the combi-
nation of the abovementioned approaches, an electrode
with 90 wt% of active materials was fabricated from
the microporous redox-active organic polymer 15 and
single-walled carbon nanotubes, delivering an enhanced
electrode-level specific energy96. Usually, fabricating a
thick electrode using the conventional slurry-casting
method results in cracking and delamination owing
to the mechanical instability of the electrode. However,
the interaction between carbon additives, such as car-
bon nanotubes, and microporous polymer leads to well
connected and high-mass-loading electrodes (Fig. 4e).
Further efforts should optimize organic electrode fabri-
cation processes to bring electrode-level specific energy
on par with material-level specific energy (as represented
by the dashed line in Fig. 4b).
Comparative analysis of specific power
High power capability is needed for batteries to generate a
large amount of energy in a short time and to make the
charge process faster97–99. Although the most intuitive
approach to realize high power is to employ electrode
materials with fast ion- and electron-transfer capabili-
ties, it remains challenging for most organic electrodes
owing to their generally low electronic conductivity.
In Fig. 5a (and in Supplementary Fig. 2a, where refer-
ences for each material are noted), we selected repre-
sentative high-power organic electrodes and plotted the
normal­ized rate capabilities in comparison with those of
conventional inorganic electrodes.
Our analysis indicates that radical polymer electrodes
such as the ones with (2,2,6,6-tetramethylpiperidin-1-yl)
oxyl units (organic 35) exhibit a competitive rate capa-
bility up to nearly 20C, which is comparable to that
of transition-metal-based materials67,100,101. Moreover,
a radical polymer electrode based on organic 16 proved
to have a superior power capability by delivering 46%
of the theoretical capacity within less than 1 min of
charging and discharging (100C)35, as indicated by the
circular data points in Fig. 5a. This power capability is
attribu­table to the high electronic conductivity of the
radical polymers stemming from the electron-hopping
mechanism through electron self-exchange69,102–104.
Strategies to increase the rate capability of redox-active
organic materials. To improve performance, a charge-
transfer complex composed of two redox-active organic
materials, 3 and 25, (3•25 in Fig. 5a) was produced and
operated at 965 mA g−1, showing a remark­able capac-
ity utilization corresponding to 76% retention of the
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capacity delivered at 48 mA g−1 (ref.34). This performance 3•25 charge-transfer complex was increased by more
stems from the enhanced electronic conductivity of the than 10,000 times compared with that of the pristine
charge-transfer complex, where the charge transport constituting materials (3 and 25)34,52.
is facilitated in the rearranged molecular structure34,52, A sulfur-substituted dicarboxylate compound such as
as discussed earlier. The electronic conductivity of the organic 5 can also deliver a respectable specific power

a 34 LCOb n-type redox-active organics

4 LCOa p-type redox-active organics
20 NCMa Transition-metal-based inorganics
16 21 LFP NCMb
23
7 9
3⋅11 3a
3⋅25 24
Voltage (V versus Li+/Li)

3 3⋅10
3b
6 29 33
28 32 30a 31 19a
13a 1c 17 22 1b Energy density (Wh kg–1)
2 15 4 18a
26a 1,500
19b 2
12 1a
14 1,000
8b 5
1 700
8a
500 27
200
0
0 100 200 300 400 500 600 700 800 1,200 1,300
Specific capacity (mAh g–1)
b1,000 c Molecular rearrangement
n-type redox-active organics
p-type redox-active organics 1b Single redox-active Organic
Transition-metal-based inorganics organic electrode complex
Electron donor
Electron acceptor
800 Organic complex
Low intrinsic High intrinsic Conducting agent
NCMa
Specific energy of electrode (Wh kg–1)

electronic electronic
conductivity conductivity
LCOa
d Hybrid electrode
2
27 Conventional Hybrid
600
31 electrode electrode
LCOb
NCMb Redox-active
19a organic materials
3⋅11 3a
24 Conducting agent
22 Conductive inorganic
400 23 32 33 Low density High density cathode materials
LFP Low capacity High capacity
19b
1a 9
13a 5 e New electrode engineering
15 26a Redox-active
3⋅10 21 30a Conventional Buckypaper organic materials
1 3⋅25 slurry-casting approach
14 7 4 c 18a Single-walled
200 17 Low mass High mass carbon nanotube
12 6 20 29 loading loading
28 Reduced graphene
16 8 34 oxide
b
8a 3b
Current
collector Electrically connected network:
0 high capacity, high rate capability
0 200 400 600 800 1,000 1,200 1,400
Specific energy of material (Wh kg–1)

Fig. 4 | Comparative analysis of specific energy of representative redox-active organic materials. a | Specific capacity,
voltage and corresponding specific energy (dashed line) of representative redox-active organic materials. The specific
capacity and voltage are the values from the discharge process. In particular, the discharge voltage was obtained by dividing
the capacity from the integrated value of the discharge curves. b | Correlation between the specific energy at the material
and electrode level of selected redox-active organic materials. The dashed line indicates the point at which the specific
energy at the material level coincides with that at the electrode level. c–e | Approaches that can lead to high-specific-energy
redox-active organic materials at the electrode level (grey shading in Fig. 4b). The formation of organic complexes, such as
charge-transfer complexes, by molecular rearrangement can enhance the electronic conductivity of organic compounds,
leading to an increase of the active material content (part c). By replacing the conducting agent with inorganic materials
with reversible redox activity as well as high conductivity, both the gravimetric and volumetric energy density of
the electrode can be improved (part d). A novel electrode engineering method exploiting the advantages of organic
materials, combined with the use of carbon nanotubes, allows slurry casting to be bypassed, enabling the fabrication
of a high-mass-loaded electrode with high energy density (part e). LCO, LiCoO2; LFP, LiFePO4.

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a b 300
3⋅25 36
100 LCOa Radical
Charge-transfer complex
NCMb Sulfur-substituted dicarboxylate compound
Capacity retention (%)

80 Morphology tailoring
35b
35a Nanohybrid with carbon
250
Transition-metal-based inorganics
60
LFP
Radical
40 Charge-transfer complex 5

Specific capacity of electrode (mAh g–1)

16
Sulfur-substituted
dicarboxylate compound 200
20 Morphology tailoring
Nanohybrid with carbon 6
LCOb NCMb
Transition-metal-based inorganics
0
0.1 1 10 100 32
C-rate 150
c
100 41 LFP 12
40 37 38a 16
7 18a 16
13a
13b 35b NCMb 24 23
28 14 33 17
31 LFP
Capacity retention (%)

80 LCOb 39 45 NCMa
LCOa 100
43 3 44
37
3⋅10 30b 42 18b 17
20 21 26a 28
6
30a 19a
60
1b 6 22 35a
15
19b 50 3⋅10
36
40 Non-treated organics 16
Polymerization Separator engineering
Nanohybrid with carbon Multiple engineering 35b
Electrolyte engineering Transition-metal-based inorganics
20 0
10 100 1,000 10,000 0.1 1 10 100
Cycle number C-rate

Fig. 5 | Comparative analysis of rate capability and cycle performance. a | Capacity retention of selected redox-active
organic materials, where representative strategies were applied to improve the rate capability with increasing current
rate (blue data points represent redox-active organic materials, red data points represent transition-metal-based
materials). Each curve shows how much capacity was maintained compared with that at the lowest current in each
report. A gentler slope indicates better rate capability, the redox-active organic materials performing just as well as the
transition-metal-based electrodes. b | Reversible capacity of electrodes containing redox-active organic materials as a
function of increasing current rate. c | Capacity retention after the number of charge/discharge cycles reported in each
paper. Multiple engineering signifies redox-active organic materials to which two or more engineering strategies were
applied. All the capacities are the discharge capacities in a Li half-cell. LCO, LiCoO2; LFP, LiFePO4.

of 909 W per kilogram of material with a capacity of in an increase of the contact area with the conducting
176 mAh g−1 at 4.2C. Although this performance is not agent. This enhanced contact area enables efficient
remarkable, it represents a substantial enhancement over uptake of electrons from the conducting agent as well
that of the pristine dicarboxylate motif of 225 W per kilo- as a decrease of the ion-diffusion path, thereby success-
gram of material. It has been speculated that replacing fully enhancing the rate capability105,106, as illustrated by
oxygen with sulfur in the dicarboxylate-based motif could the triangular data points in Fig. 5a. Moreover, hybrid
increase the electronic conductivity to about 10−5 S cm−1 structures employing advanced carbon materials can
because of the higher electron polarizability of sulfur59,60, achieve high power by exploiting the exceptionally high
enhancing power capability by a factor of almost ten. conductivity (higher than 104 S cm−1) of graphene or car-
Although most redox-active organic materials exhibit bon nanotubes107,108. Through the path connected by the
low electronic conductivity (less than 10−10 S cm−1, interaction between the π systems in the organic skel-
Supplementary Table 1) relative to that of transition- eton and the carbon material, the electronic transport
metal-based materials (approximately 10−5 S cm−1), to and from the redox-active organic material can be
structural or chemical modifications can result in tailored, resulting in improved rate capability. Using this
higher power capability. The rate capabilities of com- strategy, various organic electrodes including electrodes
mon redox-active organic materials for which the spe- with organics 17, 28, 32, 35 and 37 could successfully
cific power was enhanced through various engineering deliver a respectable specific energy that is comparable
approaches are displayed in Fig.  5a. Morphological with inorganic electrodes even at a charge/discharge rate
control of organic particles has been demonstrated of 10C or higher48,109–112.
to be effective. For example, the modification of the
morphology to a sheet-type rather than a sphere-type Electrode-level specific power assessment of redox-active
morphology with organic 32 or the reduction of the organic materials. The power capability has been
particle size to the nanoscale with organic 36 results improved substantially using the approaches listed

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in Fig. 5a; however, organic electrodes still require a large
amount of conducting agent, leading to reduced specific
power and energy at the electrode level. Figure 5b (and
Supplementary Fig. 2b, where references for each mate-
rial are noted) present the rate capability of the afore-
mentioned redox-active organic materials based on
electrode-level capacity. Even though radical polymers
exhibit power capabilities that are competitive with those
of inorganic materials (Fig. 5a), practical rate capabilities,
considering the weight of the entire electrode, are far
from what is delivered at the material level. Fabricating
electrodes with a large amount of advanced carbon mate-
rial may not be an optimal strategy for high-performance
organic rechargeable batteries because of the associated
reduction in the volumetric and gravimetric energy and
the power density. The organic battery field still awaits a
solution that would enable high power density without
sacrificing the energy density, possibly by combining
material- and electrode-level strategies.
Comparative analysis of cycle life
The cycle life of an organic rechargeable battery is
governed mainly by common factors, such as the age-
ing and degradation of the electrolyte and electrodes
because of repetitive electrochemical reactions, which
also contribute to the cycle stability of conventional
lithium-ion batteries113. However, several attributes of
organic materials are particularly critical for the cycle
stability of organic rechargeable batteries, such as
the structural integrity of the organic crystal6. Unlike
transition-metal-based electrode materials, organic
crystals are held together by weak van der Waals forces
between molecules. Accordingly, redox-active organic
materials are often vulnerable to dissolution in the liquid
electrolyte and can fall from the electrode through solva-
tion by the solvent molecules in the electrolyte. The con-
tinuous loss of redox-active organic materials from the
electrode leads to a gradual decrease of capacity upon
cycling, which is a key obstacle limiting their practical
use. Moreover, the organic crystal structure becomes
easily disordered and degraded with repeated guest-ion
insertion and extraction, causing undesirable changes in
the electrochemical activity40,114.
Strategies to increase the cycle life of redox-active
organic materials. Many strategies have addressed these
issues and improved the cycle stability. In Fig. 5c (and in
Supplementary Fig. 2c, where references for each mate-
rial are noted), we compare and summarize the cycle per-
formances of redox-active organic electrodes obtained
through various strategies with respect to the reported
cycle number and the capacity retention rate. One of the
most intuitive examples includes dimer-/trimer- and/or
polymer-based organic species35,38,39,45,110,115–121 (denoted
with pentagonal data points), such as organic 31 (ref.116)
and organic polymer 16 (ref.35), which have displayed
cycle stability as high as 93% after 10,000 cycles35. When
individual redox motifs are anchored to each other by
covalent bonds, the enlarged size of the molecules hin-
ders the solvation process, thus reducing their tendency
to be dissolved. As another example, anthraquinone,
which has high solubility and subsequently suffers from
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poor cycling performance in its molecular form122,
was tailored into a polymer form119,123–127 (organic 38).
Further inclusion of advanced carbon material in the
electrode led to a capacity retention of about 57% after
9,000 cycles (organic 15)128. Although polymerization
improves the cycle life of organic electrodes, there are
clear trade-offs; the polymerization results in poor rate
capability, stemming from the low electronic conductivi-
ties of common polymers, and reduced capacity because
of the addition of redox-inactive backbones61. To address
these trade-offs, a few new polymers are noteworthy. For
instance, a ladder-type polymer (organic 22), synthe-
sized with a configuration minimizing redox-inactive
components, achieves a high capacity along with long
cycle life120. A donor–acceptor polymer (organic 39)
that directly links the electron-donating polymer back-
bones with electron-accepting pendants129 simultane-
ously achieves high cycle stability and rate capability.
The use of advanced carbon materials is another way to
secure cycle stability, as they stably anchor redox-active
organic materials against dissolution through π–π inter-
actions. These approaches were effective for redox-active
compounds including organic 3•10, 14, 15, 17, 28, 35
and 37 (refs.34,48,95,109–111,128).
The dissolution issue of organic electrodes can
also be tackled by engineering the electrolyte proper-
ties. Because the free solvents in the electrolyte trigger
the solvation and dissociation of organic compounds,
attempts to reduce or eliminate free solvents in the elec-
trolyte have been sought after. One way to reduce the
effect of free solvents is to adopt high-concentration
electrolytes 130–132. Because the number of free sol-
vent molecules greatly decreases with the change of
the solvation structure in high-concentration elec-
trolytes, the dissolution of the organic electrodes is
subsequently obstructed. Small redox-active organic
materials such as organics 13, 20 and 40 are able to
retain stable cycling performance without any molec-
ular engineering because of the suppressed dissolution
in the high-concentration electrolyte, as depicted in
refs.36,55,94, Fig. 5c. The use of solvent-free electrolytes,
such as ionic liquids, is also a promising route to sup-
press the dissolution22,133–136. An electrode made from
organic 18 (calix[6]quinone) could exhibit a capacity
retention of 69% after 1,000 cycles with the ionic liquid
N-methyl-N-propylpyrrolidinium bis(trifluorometh-
anesulfonyl)amide134. This performance represents
an important enhancement over the conventional
electrolyte system (ethylene carbonate/dimethyl car-
bonate containing 1 M lithium hexafluorophosphate),
which delivers only 53.7% of the initial capacity after
100 cycles137. Similarly, polymer- or plastic-crystal-type
electrolytes could support the cycle stability of
redox-active compounds such as organics 18, 19, 37
and 41 (refs.109,133,138,139). The low molecular mobility
in these systems could hinder the free movement of
the molecules, suppressing the undesirable dissolu-
tion. Furthermore, the introduction of an inorganic
solid electrolyte, a new electrolyte type investigated for
lithium-ion battery research140,141, is an effective coun-
termeasure, precluding the dissolution of redox-active
organic materials. Though this latter approach remains
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in the early stages of research and has been adopted
only for organics 30, 42 and 43 (refs.142–144), its obvious
merits, particularly the prevention of organic materials
dissolution140,145–147, may open up new opportunities for
organic electrode materials.
Capacity degradation is attributable not only to the
dissolution of the organic electrode itself but also to side
reactions caused by the crossover of the dissolved species
in the electrochemical cell, leading to counter-electrode
passivation or to the shuttle effect, in which dissolved
species move between the anode and the cathode with
repetitive oxidation and reduction148–150. The passing
of the dissolved redox-active organic materials to the
counter-electrode can be inhibited through rational
separator engineering. One simple approach is to coat
an additional layer such as graphene or Nafion on com-
monly used polypropylene or polyethylene separators
to regulate the transport through the separator, because
additional layers allow small lithium ions and electro-
lytes to permeate but usually inhibit the permeation of
organic species. Enhanced cycle stability was achievable
for organic electrodes from organics 3, 13, 26 and 44
by employing a coated separator in comparison with a
bare separator under the same electrode and electro-
lyte conditions97,151–153. The electrode with organic 44
was capable of retaining 76% of the initial capacity after
400 cycles through the employment of a Nafion-coated
separator, whereas the capacity retention was only 64%
after 50 cycles with the bare polypropylene separator152.
A new type of permselective separator has also been
proposed, where novel membrane engineering could
enable the precise control of the pore size, selectively
blocking the redox-active organic molecules while
transporting the ions in the electrolyte 149. In that
regard, a monolithic gel-type membrane with perm­
selective properties was synthesized, taking advantage
of the nanopores of metal–organic framework (MOF)
materials. The pores in MOF materials can be adjusted
to desired sizes and distributions, thus allowing the
customized design of the membrane separator against
target organic molecules. A model organic compound,
quinone derivative organic 45, displayed a remark­
able cycle stability with a retention of about 83% after
2,000 cycles at a current density of 269 mA g −1 by
employing a MOF-gel separator based on zinc and
2-methylimidazole.
Alternative energy storage platforms
The applicability of redox-active organic materials has
usually been examined in lithium-ion-battery configu-
rations. However, despite the extensive efforts described,
the application of redox-active organic materials still
presents unresolved issues, such as the inevitable sol-
ubility into the electrolyte and the low power density,
only improvable by substantially sacrificing the energy
density. Efforts to produce battery platforms beyond
lithium-ion batteries (the so-called post-lithium-ion
batteries) have led to new opportunities for redox-active
organic materials. Because of their diverse physical
and chemical configurations, these organic materials
are more easily applied to these new platforms than
conventional transition-metal-based electrode materials.
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Earth-abundant metal-ion organic rechargeable
batteries
Concerns about the supply of lithium raw materials
have motivated the exploration of battery chemistries
based on Earth-abundant metal ions such as sodium,
potassium, magnesium, calcium and aluminium154–159.
Batteries based on sodium ions and potassium ions have
been studied the most extensively because the operating
mechanism for the monovalent-ion system is expected
to be similar to that of lithium-ion batteries. Moreover,
they share several important electrode material groups
such as AxMO2 (A = Li, K or Na; M = transition metal),
allowing the reversible intercalation of not only lith-
ium ions but also sodium and potassium ions160–164.
Nevertheless, the use of larger ions such as Na+ (1.02 Å)
and K+ (1.38 Å), relative to Li+ (0.76 Å), often involves
a greater alternation of the crystal structure, which
requires a larger volumetric change of the electrode and
more rapid degradation of the intercalation host165–171.
Unlike the rigid structure of conventional inorganic
intercalation hosts, redox-active organic materials offer
a much more flexible framework. Because organic
crystals are generally bound by weak van der Waals
forces, a space can be provided that is large enough to
accommodate various guest ions, compared with rigid
inorganic compounds, rendering redox-active organic
materials less susceptible to the size of charge-carrying
ions6,172. This feature enables the stable insertion of larger
guest-ions such as Na+ and K+ (refs.30,173–184) in various
redox-active organic compounds, as presented in Fig. 6a
(and in Supplementary Fig. 3a, where references for
each material are noted). For example, organic 13 can
reversibly store both Na+ and K+ ions, utilizing the two
carbonyl motifs in the structure181,182,185. Li (ref.186), Na
(ref.181) and K (ref.182) half-cells employing electrodes
with organic 13 can deliver specific capacities of 127, 107
and 105 mAh g−1, respectively, showing that the choice of
metal has an insignificant effect on the specific capacity.
Furthermore, a respectable cycle and power performance
is possible in Na and K cells, where around 94% and 87%
of the initial capacity can be delivered after 200 cycles and
1,000 cycles, respectively, while retaining 81 mAh g−1 at
895 mA g−1 for the Na cell and 70 mAh g−1 at 4,475 mA g−1
for the K cell. These results offer a notable contrast to typ-
ical inorganic hosts, whose intercalation capabilities vary
substantially depending on the guest-ion species61,155.
Similarly, given its azo redox motif, organic 50 can store
two equivalent ions in Li (ref.44), Na (ref.177) and K (ref.184)
half-cells. All half-cells presented decent and compa-
rable capacity retention, indicating that redox-active
organic materials are less susceptible to the type of guest
ion. Moreover, organic 49 delivered a high capacity of
232 mAh g−1, based on the full utilization of all four car-
bonyl motifs, and maintained 97% of the initial capacity
after 10,000 cycles, which is considered an outstanding
stability for sodium-ion battery cathodes180.
Redox-active organic materials can also be suc-
cessfully used in multivalent-ion batteries. Despite the
potential merits of multivalent-ion battery systems187,188,
the lack of a suitable host for multivalent ions has
remained one of the critical impediments. One of the
main issues is the severely sluggish diffusion kinetics
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a 10–3 b 10–3
Sodium-ion batteries Magnesium-ion batteries
Potassium-ion batteries 49a Calcium-ion batteries 53

Capacity decay rate (% per cycle)

Capacity decay rate (% per cycle)

Aluminium-ion batteries
50a Inorganic 6a 46b
48
10–2 46a 10–2 52 38b
13c 49b 26b
Inorganic 3
47b Inorganic 8
50b
54 30c
Inorganic 5
10–1 13d 51 10–1 13e
1a
Inorganic 2
Inorganic 1
1d Inorganic 6b
Inorganic 4
Inorganic 7
47a
100 100
0 100 200 300 400 0 100 200 300
Initial specific capacity (mAh g–1) Initial specific capacity (mAh g–1)
c 15,000 d Energy density
Nonaqueous
Aqueous 260.4C
Specific power (W kg–1)

50C
10,000 Cost Power
40.7C merit density

5,000

7C
3.4C 1C
1C Cycle life Energy efficiency
0.34C
0
Organic 10 Organic 55 Organic 13 Organic 30 Vanadium Zn-Fe
ORFB 1 ORFB 2

Fig. 6 | Potential of employing redox-active organic materials for post-lithium-ion battery configurations.
a,b | Initial specific capacity and capacity decay rate of some organic materials (blue) and representative inorganic
materials (red) for monovalent-ion batteries (part a) and multivalent-ion batteries (part b). The initial specific capacity
is the reversible specific discharge capacity. We note that the y axis is inversed such that the points at the top-right
side of the plot indicate better performing materials. Inorganic 1, Na0.66Li0.18Mn0.71Ni0.21Co0.08O2; inorganic 2, Na3V(PO4)2;
inorganic 3, Na3MnZr(PO4)3; inorganic 4, K0.45MnO2; inorganic 5, K2Ni2TeO6; inorganic 6, Mo6S8; inorganic 7, Ti2S4;
inorganic 8, Na0.5VPO4.8F0.7. c | Specific power of selected organic batteries with aqueous and nonaqueous electrolyte.
All the specific powers are based on the C-rate and are presented with the highest reported value in each reference.
Organic 10, nonaqueous (ref.208) and aqueous (ref.207); organic 55, nonaqueous (ref.206) and aqueous (ref.205); organic 13,
nonaqueous (ref.182) and aqueous (ref.209); organic 30, nonaqueous (ref.22) and aqueous (ref.210). d | Performance and
cost evaluations for selected inorganic and organic redox-flow batteries222–226. The scores of each evaluation item were
normalized based on the maximum and minimum values of each item. Cost merits were calculated based on the inverse
value of the cost per kilogram of the active material. The cycle life was estimated from the capacity retention of each
system per year. ORFB 1, anolyte (1,8-bis(2-(2-(2-hydroxyethoxy)ethoxy)-ethoxy)anthracene-9,10-dione) and catholyte
(potassium ferrocyanide); ORFB 2, anolyte ((((9,10-dioxo-9,10-dihydroanthracene-2,6-diyl)bis(oxy))bis(propane-3,1-diyl))
bis(phosphonic acid)) and catholyte (potassium ferrocyanide).

typically observed in most intercalation hosts for multi- ion insertions in a magnesium half-cell150. Moreover,
valent ions188–192. As such, only a few inorganic host mate- 82% of the initial capacity is successfully retained even
rials have been reported to date, including Chevrel phases after 200 cycles, which is almost comparable to the
(Mo6S8, Mo6Se8) and vanadium oxides (V2O5, VO2), performance observed in the lithium cell22,150. A multi­
for magnesium- or aluminium-ion batteries6,193. valent aluminium complex ion can be reversibly stored
Although their development remains in its in the triangular macrocycle organic 52, which forms
infancy, several redox-active organic materials have a layered organic crystal structure. The insertion and
been identified as promising cathode materials for extraction of a cationic aluminium complex allows
multivalent-ion batteries, as presented in Fig. 6b (and in a reversible capacity of 75 mAh g–1 along with a cycl­
Supplementary Fig. 3b, where references for each mate- ability of up to 5,000 cycles196. The synthesis of the
rial are noted)150,194–200. Organic 30, containing four tetradiketone macrocycle organic 53 with a reduced
carbonyl redox motifs, can deliver a remarkably high benzene-ring-to-carbonyl-group ratio also leads to
capacity of 266 mAh g−1, which corresponds to two Mg2+ a high-capacity aluminium-ion battery cathode 197.

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Divalent ions (AlCl2+) are preferably stored over their
competing monovalent counterpart (AlCl2+), leading to a
higher specific capacity of 237 mAh g−1. In that regard,
a truly multivalent aluminium-ion battery based on
organic active materials can be realized, unlike previously
reported systems relying on monovalent aluminium
complex ions for the main redox reaction.
Aqueous organic rechargeable batteries
The electrolytes currently employed in lithium-ion
batteries are flammable and toxic 201–203. Aqueous
rechargeable batteries can circumvent these problems
while providing a much higher ionic conductivity
(about 1 S cm−1) than typical organic-based electrolytes
(10−3–10−2 S cm−1)204. Thus, their use may help to com-
pensate for the low kinetic performance of redox-active
organic materials. In this regard, several attempts have
been made to achieve high power capabilities from
organic electrodes in aqueous battery systems, as depicted
in Fig. 6c (and in Supplementary Fig. 3c, where references
for each material are noted)22,182,205–210. For example, when
organic 13 was used in an electrode in a sodium half-cell
with an ethylene carbonate/diethyl carbonate electrolyte,
only 65% of the capacity could be delivered when the
current rate was increased from 0.07C to 7C (ref.181). In
contrast, the same electrode could retain nearly 62.6% of
the capacity when the current rate was increased to the
extremely high value of 260.4 C from 1.6C when employ-
ing a 2 M zinc chloride (ZnCl2) aqueous electrolyte in
a zinc half-cell209. The specific power of 12.7 kW per
kilogram of material of this system was even higher than
that of conventional lithium-ion batteries (around 1 kW
per kilogram of material)9. Moreover, organic 30 with a
2 M zinc sulfate (ZnSO4) aqueous electrolyte exhibited
a specific power of 10.2 kW per kilogram of material at
50C in a zinc half-cell, which far exceeds the specific
power of 0.83 kW per kilogram of material obtained
when the same organic was exploited in a nonaqueous
system composed of 1 M lithium hexafluorophosphate
and ethylene carbonate/diethyl carbonate22,210.
Although aqueous electrolytes can offer extraordinary
power capability for redox-active organic electrodes,
their introduction results in a narrow electro­chemical
window (theoretically 1.23 V for water splitting). The
narrow electrochemical window would lead to not only
a limited deliverable energy density but also to various
side effects such as swelling of the cell by gas genera-
tion during repeated cycles211. The adoption of a highly
concentrated electrolyte, a so-called water-in-salt elec-
trolyte, is one of the strategies that may overcome these
shortcomings130,131,212. In the water-in-salt system, the
electrochemical window is widened because of its unique
solvation structure, which leads to a reduction of the elec-
trochemical activity of water. Concentrated water-in-salt
electrolytes with 30 m potassium bis(fluorosulfonyl)imide
effectively suppress the hydrogen evolution, extend-
ing the electrochemical window to nearly 4 V (ref.213).
Accordingly, organic 13 can function as a stable anode
in aqueous potassium batteries with improved cycling
stability. Moreover, the dissolution of the redox-active
organic material could be substantially suppressed in
water-in-salt electrolytes.
Nature Reviews | Materials
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Reviews
As the field of aqueous organic rechargeable batter-
ies continues to grow, approaches that have been effec-
tive in aqueous inorganic battery applications should
be explored. For example, the confinement of the water
solvent within a polymer network reduces the activity of
water214, and a spatially separated acid–alkaline dual elec-
trolyte expands the electrochemical window of the full
cell by lowering the hydrogen-evolution reaction poten­
tial and elevating the oxygen-evolution reaction potential
based on their pH dependence 215. Applying such
approaches to aqueous organic batteries should help to
overcome concerns about the low energy density.
Organic redox-flow batteries
Redox-flow batteries, which rely on the solution-based
redox chemistry of active materials, have often employed
soluble inorganic redox pairs such as V/V (ref. 216) ,
Zn/Fe (ref.217) or Zn/Br (ref.218). Given the concerns
about their highly volatile price and toxicity, there has
been increasing interest in replacing these redox pairs
with redox-active organic materials. Redox-active
organic materials have advantages over their inor-
ganic counterparts not only because of their potential
cost-effectiveness but also because of their chemical
tunability, which enables target electrochemical perfor-
mances through the modulation of solubility or molec-
ular size. In Fig. 6d, we compare performance and cost
metrics such as energy density, power density, energy
efficiency, cycle life and cost of organic redox-flow bat-
teries in reference to representative inorganic redox-flow
batteries. In the graph, the scores of each evaluation
item were normalized based on the maximum and
minimum values of each item, which were collected
from previous studies on inorganic vanadium-based
and Zn/Fe-based redox-flow batteries and organic
1,8-bis(2-(2-(2-hydroxyethoxy)ethoxy)-ethoxy)
anthracene-9,10-dione/ferrocyanide (ORFB 1)-based
and (((9,10-dioxo-9,10-dihydroanthracene-2,6-diyl)
bis(oxy))bis(propane-3,1-diyl))bis(phosphonic acid)/
ferrocyanide (ORFB 2)-based redox-flow batteries219–223.
It is clear from Fig. 6d that the performance of organic
redox-flow batteries can complement some aspects of
representative inorganic-based redox-flow batteries.
In terms of energy density, tailoring the solubilizing
group has been an effective strategy to increase the solu-
bility of the active material, thus enhancing the volumet-
ric specific capacity of organic redox-flow batteries224,225.
Introducing a non-ionic polyethylene-glycol-based
functional group to anthraquinone produced a
water-miscible 1,8-bis(2-(2-(2-hydroxyethoxy)ethoxy)-
ethoxy)anthracene-9,10-dione, which provided a
volumetric capacity of 80.4 Ah per litre and an energy
density of 25.2 Wh per litre for ORFB 1 (ref.222). The
molecular structure of a representative ferrocyanide
catholyte can be redesigned by symmetry breaking of
their ligands226, where the substitution of hydrophilic
bipyridine ligands for cyanide ligands allows a higher
solubility of 1.09 M in water, compared with 0.62 M for
sodium ferrocyanide. Moreover, the redox potential
for sodium ferrocyanide can be enhanced from 0.26 V
(versus Ag/AgCl) to 0.65 V (versus Ag/AgCl) because of
the weaker interaction of the bipyridine ligand with the
Reviews

Fe centre, relative to that of the cyanide ligand with
the Fe centre.
The low cycle life, which is mainly attributable to the
instability of redox-active organic materials at charged
states, is the main bottleneck hindering the practical use
of organic redox-flow batteries. As the molecules in solu-
tion are relatively free to interact with other elements,
various side reactions, such as dimerization or nucleop-
hilic attack from solvent molecules227,228, are likely to be
more facile than for solid-state materials. These unde-
sirable reactions decrease the amount of active materials
and subsequently shorten the lifetime of the redox-flow
batteries. However, these limitations can be poten-
tially overcome. For example, more positively charged
functional groups can inhibit radical dimerization in
the charged state of both a ferrocene derivative and
organic 56 through electrostatic repulsion224. Redesign
of redox-active organic materials also mitigates the cross-
over known to greatly contribute to cycle degradation,
resulting in a marked capacity retention of 99.9943% per
cycle and 99.967% per day. Furthermore, the study of the
degradation mechanism of carboxylated anthraquinone
inspired a molecular redesign of carboxylated anthra­
quinone to phosphonated anthraquinone, restricting
the carboxylate-mediated intramolecular nucleophilic
substitution223. As a result, ORFB 2, with a (((9,10-dioxo-
9,10-dihydroanthracene-2,6-diyl)bis(oxy))bis(propane-
3,1-diyl))bis(phosphonic acid) anolyte and a potassium
ferrocyanide catholyte, demonstrated a remarkably low
capacity decay rate of 0.014% per day. These accom-
plishments suggest that redox-active organic materials
are rapidly approaching the level needed for the practical
application of redox-flow battery systems.
Perspective
Growing concerns about global environmental pol-
lution have triggered the development of sustainable
and eco-friendly battery chemistries. In that regard,
organic rechargeable batteries are considered promising
next-generation systems that could meet the demands
of this age.
Electrode-level performance metrics should be
more carefully assessed for the practical realization of
organic rechargeable battery systems, eventually being
extended to cell-level performance metric evaluation.
That is, the type or amount of electrolyte should also
be considered, in order to attain a high gravimetric or
volumetric energy density for the cells, although such
performance-metric standards have not yet been set94,96.
Moreover, optimization procedures should be performed
with a fundamental understanding of the compatibility
of the organic electrodes with the electrolyte systems,
which has yet to be explored. The type of energy-storage
platform that will most effectively exploit the benefits
of redox-active organic materials should also be taken
into account. For instance, organic rechargeable batter-
ies are generally disadvantageous in terms of volumetric
energy or power density because of their intrinsically
low density229. To establish practically feasible organic
batteries, innovative electrode engineering along with
system design are warranted. An alternative strategy may
be to establish target applications for which environmen-
tal friendliness and cost-effectiveness are crucial, such as
stationary energy storage systems, which usually store a
large amount of intermittent renewable energy, rather
than applications for mobile devices.
Redox-active organic materials are regarded as
eco-friendly materials, as they are generally produced
under mild synthetic conditions with low environ-
mental impact and can even be obtained from natural
products32,33,230,231. Nonetheless, because the produc-
tion and recycling processes of redox-active organic
materials have not been thoroughly examined, it could
be said that the sustainability of redox-active organic
materials is simply conjecture. However, initial steps
towards recycling redox-active organic materials have
been taken to promote recyclability from the decompo-
sition products232. Although this strategy must be further
developed in order to recycle such a battery completely,
the possibility of recycling redox-active organic materials
improves the outlook of organic rechargeable batteries
for next-generation energy storage. Future efforts should
also examine how prospective organic electrode materi-
als can be produced with a minimal environmental foot-
print. Moreover, similar attention should be paid to the
other components that constitute organic rechargeable
batteries, considering that conventionally used battery
components, such as the binder and electrolyte233–235, are
often either not environmentally benign or not based
on sustainable chemistry. The appropriate selection or
tailoring of redox-active organic materials may enable
the replacement of these components with environ-
mentally and economically more viable options. With
continued and concerted efforts to improve the perfor-
mance and sustainability of organic batteries, a greener
rechargeable world is probably not too far off.
Published online xx xx xxxx

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Acknowledgements
This study was supported by the Creative Materials Discovery
Program through the National Research Foundation of Korea
(NRF), funded by the Ministry of Science, ICT and Future
Planning (NRF-2017M3D1A1039553). This work was also
supported by the Center for Nanoparticle Research at
Institute for Basic Science (IBS) (IBS-R006-A2).
Author contributions
J.K. led the process, and prepared the content in the
‘Applications in rechargeable batteries’ section and
the ‘Perspective’ section. Y. Kim prepared the content of the
‘Alternative energy storage platforms’ section. J.Y. prepared
the content of the ‘Introduction’, ‘Assessment of redox-active
organics’ and ‘Redox-active organic materials’ sections. J.K.,
Y. Kim and J.Y. revised and edited the manuscript before pub-
lication. All authors participated in researching data and
substantial discussion about organization of manuscript.
Competing interests
The authors declare no competing interests.
Peer review information
Nature Reviews Materials thanks Stefan Freunberger,
Alexandru Vlad and the other, anonymous, reviewer(s) for
their contribution to the peer review of this work.
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Supplementary information
The online version contains supplementary material available
at https://doi.org/10.1038/s41578-022-00478-1.
Related links
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United states Geological survey (UsGs): https://minerals.
usgs.gov/minerals/pubs/mcs/2020/%20mcs2021.pdf
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