REVIEW

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Metal-Redox Bicatalysis Batteries for Energy Storage and

Chemical Production
Shichen Yan, Yangyang Feng, Jing Lin, and Yaobing Wang*

The state-of-art lithium-ion battery (LIBs)

New types of electrochemical energy conversion and storage devices based with Li-ion insertion between graphite an-
on redox electrocatalytic reactions possess great potential in renewable ode and oxides cathode achieves great
energy to maximize energy utilization and balance environmental issues. The improvements in commercial electronic.[3]
typical device is the metal-redox bicatalysis battery, where the cathode is However, it falls short of energy goal of
350 Wh kg−1 , the essential requirements for
redox bifunctional catalyst (named as redox bicatalyst) with gas, solid, liquid
the electric vehicles. Therefore, it undoubt-
as active reactants while anode is metal, driven by cathodic redox edly goes beyond intercalation into conver-
electrocatalytic reactions during charge/discharge processes, which promotes sion storage mechanism where redox reac-
the energy storage and chemical production. In this system, the metal anode, tions are coupled with phase transforma-
redox-bicatalyst cathode, electrolytes, and the redox electrochemical reactions tions during discharge/charge process.[4]
With this perspective, Li–S battery
can be modified and adjusted to achieve the optimal energy conversion and
has been pursued with the S8 and Li2 S
utilization. Therefore, the deep understanding of the electrochemical system conversion.[5] Sulfur, the abundant ele-
is conducive to designing new devices to meet the demand among various ments in earth, owns numerous valuable
applications, including energy storage and conversion. In this review, the properties, including inexpensive, light
authors clarify the fundamentals and design principles of the weight and nonpoisonous features. Over
rechargeable/reversible metal-redox bicatalysis batteries and how each part the past several decades, the Li–S battery
was constructed by lithium anode, sulfur
affects the devices in energy conversion and chemical production. The
composite cathode and organic electrolyte.
authors summarize the electrocatalytic reduction/oxidation reactions, the During the discharge process, Li is oxidized
reported systems relied on redox reactions, and the corresponding redox and provides Li+ and electrons, while sul-
bicatalysts. Finally, a perspective of the key challenges and the possible new fur is reduced into lithium sulfide through
types of metal-redox bicatalysis batteries for efficient energy utilization and three stage conversion by coupling Li+ and
electrons from Li anode. The Li–S battery
chemical production are given.
exhibits considerably higher specific energy
up to 2500 Wh kg−1 comparing with LIBs.
However, its development encounters chal-
lenges as the formed soluble polysulfides
1. Introduction lead to internal shuttles between cathode and anode.[6] With
the development of high-energy-density storage system, non-
Currently, fossil fuels supply more than 80% of energy demand
aqueous metal–gas battery is proposed, where the cathode re-
and contribute to massive release of greenhouse gases, caus-
duces the gas reactant. In 1996, the first rechargeable Li–O2 bat-
ing thorny environmental problems. It is no doubt that devel-
tery was proposed by Abraham et al., which consists of Li an-
oping renewable and sustainable energy will improve the en-
ode, Co(phthalocyanine) based catalyst and polymer electrolyte.[7]
ergy security and balance the global CO2 .[1] Owing to the in-
With the overall reaction of 2Li + O2 → Li2 O2 (2.96 V vs. Li/Li+ ),
termittent renewable energy, the electrochemical energy storage
the Li–O2 battery has extraordinary theoretical energy density
system is pretty vital for large-scale use of renewable energy.[2]
of 3457 Wh kg−1 , which opens the way to explore and inves-
tigate the new types of batteries.[8] In the next few decades,
S. Yan, Y. Feng, J. Lin, Y. Wang a series of metal-gas batteries have been exploited to obtain
CAS Key Laboratory of Design and Assembly of Functional higher-energy-density storage, such as metal–air battery and
Nanostructures and Fujian Provincial Key Laboratory of Nanomaterials metal–CO2 battery, which greatly enriches the energy storage
State Key Laboratory of Structural Chemistry system.
Fujian Institute of Research on the Structure of Matter
Chinese Academy of Sciences These metal-redox bicatalysis batteries are originally aimed at
YangQiao West Road 155#, Fuzhou, Fujian 350002, P. R. China high energy density. Since our group proposed aqueous Zn–CO2
E-mail: wangyb@fjirsm.ac.cn battery system to generate value-added carbon-based products,
the metal-redox bicatalysis battery is also employed for chemi-
The ORCID identification number(s) for the author(s) of this article cal products.[9] Different from the alkali metal–CO2 battery, the
can be found under https://doi.org/10.1002/adma.202212078
aqueous Zn–CO2 battery offers proton-coupled electron transfer
DOI: 10.1002/adma.202212078

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Figure 1. The common electrocatalytic oxidation and reduction reactions
and the corresponding metal-redox bicatalysis batteries reported in the
previous literatures (HER: hydrogen evolution reaction; ORR: oxygen re-
duction reaction; CO2 RR: carbon dioxide reduction reaction; NRR: nitro-
gen species reduction reaction; HOR: hydrogen oxidation reduction; OER:
oxygen evolution reaction; MOR: molecule oxidation reaction; NOR: nitro-
gen species oxidation reaction).
process to reduce CO2 into value-added carbon and hydrocarbon-
based products, including CO, CH4 , CH3 OH, HCOOH, C2 H4 ,
C2 H5 OH, and C3 + products, which is highly determined by
the redox-bicatalyst cathode.[10] The discharge voltage varies as
the CO2 conversion product and the electrolyte change, leading
to variable theoretical energy densities and operating models,
such as reversible and rechargeable batteries. For example, when
paired Zn anode with 3D Pd nanosheet cathode, the Zn–CO2 bat-
tery achieves reversible reaction between CO2 and HCOOH with
high energy efficiency of 81.2%. Additionally, the most common
model is the rechargeable Zn–CO2 battery, where the charge pro-
cess is not the reversible reaction of discharge process. In our re-
cently work, the Ir@Au catalyst is applied as cathode to reduce
CO2 to CO with 90% Faradaic efficiency during discharge pro-
cess, meanwhile, oxygen evolution reaction (OER) occurs during
charging process, offering efficient rechargeable Zn–CO2 battery.
Thus, the design principles of metal-redox bicatalysis batteries
have strong influence on the mechanisms, operating models and
applications.
This review will analyze the fundamentals of the design and
construction of metal-redox bicatalysis battery rather than com-
prehensively review the advances in metal-redox bicatalysis bat-
teries. The main focus will be the design principles of the metal-
redox bicatalysis batteries from redox-bicatalyst cathode, metal
anode, aqueous/nonaqueous electrolytes, the charge/discharge
voltage, and the effect of each part on the energy storage and
conversion. To better design and understand the systems to meet
the demand among various applications, we summarize the re-
ported electrocatalytic reduction and oxidation reactions, and the
corresponding redox bicatalysts. Readers can design a new type
of metal-redox bicatalysis battery by using various oxidation re-
actions coupled with reduction reaction under the specific elec-
trolyte as long as the discharge/charge voltages are matched
(Figure 1). Finally, several perspectives of the key challenges and
the possible new types of metal-redox bicatalysis batteries are
given.
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2. The Fundamentals of Rechargeable/Reversible
Metal-Redox Bicatalysis Battery
Electrochemical reactions are the fundamentals for batteries. Dif-
ferent from the typical batteries, the new types of batteries based
on redox electrochemical reactions are driven by redox bicata-
lysts. The cathode of these batteries are redox bicatalysts instead
of redox-active materials, where the active materials generally ex-
ist in the system, including gas, electrolyte and solid materials on
the catalysts. During the discharging process, the catalysts reduce
the active species at cathode, while oxidation reaction proceeds
during the charging process. To operate these batteries, the re-
dox electrochemical reactions as well as the corresponding redox
bicatalysts are the prerequisites. On the basis of various reduction
and oxidation reactions, diverse metal-redox bicatalysis battery
can be achieved. For example, oxygen reduction combined with
oxygen evolution can construct metal–O2 battery, while carbon
dioxide reduction paired with oxygen evolution can form metal–
CO2 battery. Therefore, it is necessary to summarize the reported
reduction and oxidation reactions, and the corresponding reac-
tion conditions in order to be able to design new types of devices
on demand.
2.1. The Reaction Mechanism in Metal-Redox Bicatalysis Battery
2.1.1. Electrocatalytic Reduction Reactions
Hydrogen evolution reaction (HER): Hydrogen is recognized as
an ideal energy carrier because of the high energy density and
eco-friendliness. Accordingly, the study aims to investigate HER
which serve as the cathodic reaction in water splitting among
various energy conversation and storage systems. During HER
process, hydrogen ions firstly adsorb on the surface of electrode,
followed by Volmer reaction and Heyrovsky (electrochemical) or
Tafel (chemical) reactions to release H2 . HER can be carried out
in acidic, alkaline and sometimes intermediate pH solutions. The
reaction is described in Equation (1) and the equilibrium poten-
tial is based on the concentration of H+ (Equation (2)).[11] The po-
tentials in this review are calibrated with respect to the reversible
hydrogen electrode (RHE)
2H+ + 2e− → H2 (acid) (1)
2H2 O + 2e− → H2 + 2OH− (neutral or alkaline) (2)
Oxygen reduction reaction (ORR): ORR is the fundamental in
various fuel devices and occupies a vital position in the fields of
catalysis. And it is common knowledge that oxygen can undergo a
two-electron reduction to H2 O2 involving only OOH* reaction in-
termediate (Equations (3) and (4)), or direct four-electron reduc-
tion to H2 O according to four steps (Equations (3)–(6)), which is
mainly determined by whether oxygen dissociates before reduc-
tion. In nonaqueous electrolyte, O2 can be reduced into O2− 2
or
O2− (Equations (7) and (8))[12]
O2 + 2H+ + 2e− → H2 O2 , E 0 = 0.7 V (3)
O2 + 2H+ + 2e− → ∗ OOH + H+ + e− → H2 O2 (4)
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O2 + 4H+ + 4e− → H2 O, E 0 = 1.23 V (5) Presented in the equations, the initial CO2 RR needs far more
negative potential of −1.9 V. Consequently, the large overpoten-
tial is required to drive the CO2 RR. Generally, the CO2 RR in-
O2 + 4H+ + 4e− → ∗ OOH + 3H+ + 3e− cludes protonation and hydration reaction processes based on
the electrolytes and catalysts, where the pH, cations and anions
→ ∗ O + 2H+ + 2e− →∗ OH + H+ + e− → H2 O (6)
of electrolytes and the active sites of catalysts can impact on the
stabilization and interaction of intermediates. The much lower
O2 + 2e− → O2−
2
(7)
potentials toward protonation processes suggest that the proton
coupled electron transfer process is favorable for CO2 RR, further
O2 + 2e− → O2− , often in non-aqueous electrolyte (8)
indicating that small overpotential in aqueous electrolyte, espe-
cially acid solution.
From the equations, oxygen is initially adsorbed on the elec-
Nitrogen species reduction reaction (NRR): Nitrogen owns a wide
trocatalyst based on the moderate binding energy. The strong
valence range varying −3 to +5, thus involving complex and vari-
binding can anchor O2 and impede removal of the intermedi-
ous reduction and oxidation reactions. As for the reduction reac-
ates, while the weak binder can reduce the activation of oxygen
tion, electrochemical reductions from N2 and NO3 − to NH3 are
reduction, influenced by the catalytic sites and ambient condi-
pretty vital as NH3 plays vital roles in industries and energy. Un-
tions. ORR can be carried out under various electrolytes, includ-
like CO2 RR reactions, N2 reduction reaction (NRR) covers mul-
ing aqueous acidic, alkaline and neutral solutions and organic
tistep N2 protonation with multielectron transfer. Different from
electrolytes.
the carbon–carbon triple bond, the first protonation of N2 is rel-
Carbon dioxide reduction reaction (CO2 RR): As is well known,
ative difficult and requires high energy (∆H0 = +37.6 kJ mol−1 )
the combustion of fossil fuels will inevitably give rise to exces-
due to the strong triple bond of N2 . The subsequent protonation
sive CO2 emissions. In consideration of the low utilization of in-
to NH3 with the negative Gibbs free energy is much easier (Equa-
termittent energy, CO2 conversion into high-valued-added prod-
tions (21)–(25))[14]
ucts is an appealing solution. There are several approaches to
convert CO2 including thermochemical, photochemical, electro-
N2 + H+ + e− → N2 H, E 0 = −3.2 V (21)
chemical and biochemical ways, among which electrochemical
CO2 RR is desirable from both research and industry due to is ef-
N2 + 2H+ + 2e− → N2 H2 , E 0 = −1.1 V (22)
ficiency, simplicity, controlled selectivity. To our knowledge, the
multielectron–proton transfer process toward CO2 RR always give
N2 + 4H+ + 4e− → N2 H4 , E 0 = −0.36 V (23)
rise to multireduction products (Equations (9)–(20))[13]
N2 + 6H+ + 6e− → NH3 , E 0 = +0.55 V (24)
CO2 + e− → CO−2 , often in non-aqueous electrolyte (9)
N2 + 6e− → 2N3− , often in non-aqueous electrolyte (25)
CO2 + 2H+ + 2e− → CO + H2 O, E = −0.52 V (10)
The rate-limiting steps are the initial one-electron reduction
CO2 + H2 O + 2e− → CO + 2OH− , E = −1.347 V (11) and the four-electron protonation to N2 H4 and the hydrogen evo-
lution are the competing reaction.
CO2 + 2H+ + 2e− → HCOOH, E = −0.61 V (12) In addition to N2 reduction reaction to NH3 , nitrate reduc-
tion reaction (NO3 − RR) is an alternative method to produce
CO2 + 4H+ + 4e− → HCHO + H2 O, E = −0.51 V (13) NH3 because of the low Faraday efficiency and difficulty in break-
ing nitrogen-nitrogen triple bond. Owing to the wide valence
CO2 + 2H2 O + 4e− → HCHO + 4OH− , E = −0.48 V (14) state between NO3 − and NH3 , NO3 − RR can generate numerous
complex products. The NO3 − RR involves an eight-electron trans-
CO2 + 6H+ + 6e− → CH3 OH + H2 O, E = −0.38 V (15) fer from NO3 − → *NO3 → *NO2 → *NO →*NOH → *NHOH
→ *NH → *NH2 → *NH3 → NH3 (g), and the five-electron pro-
CO2 + 5H2 O + 6e− → CH3 OH + 6OH− , E = −1.225 V (16) cess to produce N2 is the competitive reaction (Equations (26) and
(27))
CO2 + 8H+ + 8e− → CH4 + 2H2 O, E = −0.24 V (17)
NO−3 + 12H+ + 10e− → N2 + H2 O, E 0 = 1.17 V (26)
CO2 + 6H2 O + 8e− → CH4 + 8OH− , E = −1.225 V (18)
NO−3 + 9H+ + 8e− → NH3 + 3H2 O, E 0 = −0.12 V (27)
CO2 + 12H + 12e → C2 H4 + 4H2 O,
+ −
E = −0.34 V (19)
Nitrogen oxides (NOx ), in vehicle exhaust and flue gas, are
CO2 + 8H2 O + 12e− → C2 H4 + 12OH− , E = −1.177 V (20) the major air pollutants for environmental problems. One of the
strategies to minimize NOx emission is catalytic technology, us-
E is obtained at the pH = 7, 25 °C, 1 atm in the 1 m aqueous so- ing reducing agent of NH3 to change the NOx into N2 (Equa-
lution. E is calculated based on the standard Gibbs free energies tions (28)–(30))
of reactants and oxidation/reduction products with the consider-
ation of the concentration of H+ and OH− . 4NH3 + 4NO + O2 → 4N2 + 6H2 O (28)

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4NH3 + 2NO + 2NO2 → 4N2 + 6H2 O (29)
4NH3 + 3NO2 → 3.5N2 + 6H2 O (30)
Other reduction reaction (S, Se, SO2 , SF6 , NF3 ): Electrocat-
alytic chalcogen reduction reaction (CRR), widely reported and
occurred in alkaline metal-chalcogen battery, contains a complex
16-electron process from S8 /Se8 ring molecules to a series of
soluble polysulfides/polyselenides (PSs). As for metal-S battery
system, during discharging, the ring of S8 opens and reduces to
high-order MPSs of M2 Sx (6 < x < 8) and then the lower-order
LiPSs of Li2 Sx (2 < x < 6) at the discharge plateaus of 2.3 and 2.1 V,
respectively. With regard to metal-Se battery, Se8 ring molecules
reduce to polyselenides M2 Sex (x > 4) and finally to Li2 Se. How-
ever, after the initial cycle, the chain-like Se8 can be formed in-
stead of circle-like Se8 . The electrocatalytic SRR is presented in
Equation (31)[15]
8
S8 + 2e− → S2− (S:S, Se; x is from 1 to 8) (31)
n n
The electrolytes in CRR consists of organic solvents as CRR
is investigated in alkaline metal-chalcogen battery, in which
dimethoxyethane (DME) and 1,3-dioxolane (DOL) are generally
applied as the corresponding solvents.
In addition to CRR, sulfur dioxide reduction and conversion
are significant to alleviate the hazards to environment. Com-
pared with flue gas desulphurization, catalytic reduction could
be a more simple and flexible technology. SO2 reduction often
combines with reducing substances, such as H2 , CO, H2 S, CH4 ,
to transfer into solid sulfur.[16] The electrocatalytic sulfur dioxide
reduction is commonly found in Li–SO2 battery, which is demon-
strated as the high energy density, long-life and lightweight
battery.[17] The sulfur dioxide reduction is induced during the dis-
charging process (Equation (32))
SO2 + 2e− → S2 O2−
4
(32)
SF6 and NF3 are powerful greenhouse gases, which require con-
version and utilization. Compared with the typical decomposed
procedures with high energy consumption, the electroreduction
by Li–SF6 and Li–NF3 systems provides a safe, efficient and mild
strategy. Li–SF6 battery, a primary battery, owns high theoretical
voltage up to 3.69 V with energy density of 3922 Wh kg−1 . And Li–
NF3 exhibits high energy density up to 5072 Wh kg−1 in spite of
its irreversibility which is similar to Li–SF6 battery. The cathodic
discharge reactions are provided in Equations (33) and (34)
SF6 + 8e → S
− 2−
+ 6F −
(33)
2NF3 + 6e → N2 + 6F
− −
(34)
2.1.2. Electrocatalytic Oxidation Reactions
Water oxidation reaction (WOR): Hydrogen peroxide (H2 O2 ), a
vital chemical, has wide applications in industries and color
removal and detoxification of water. Furthermore, H2 O2 is
a promising fuel cell due to its high theoretical voltage of
1.09 V, comparable to methanol (1.09 V) and H2 /O2 (1.23 V).
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Electrochemical water oxidation to produce H2 O2 provides an
ecofriendly on-site production. The accepted route to synthesize
H2 O2 is via two-electron water oxidation (Equation (35))[18]
2H2 O → H2 O2 + 2H+ + 2e− , E 0 = 1.76 V (35)
The two-electron oxidation may compete with the one-electron
and four-electron water oxidation to generate hydroxyl and oxy-
gen (Equations (36) and (37)), respectively, where the intermedi-
ates of two-, one-, and four-electron oxidation are separative O*,
OH*, and OOH*. Therefore, the selective 2e− water oxidation
is relied on the proper interaction between O intermediates and
catalytic surface because the strong binding could induce further
oxidation of OH to *OH to *O and *OOH, and weak binding
leads to slow kinetics
2H2 O → O2 + 4H+ + 4e− , E 0 = 1.23 V (36)
H2 O → OH∗ + H+ + e− , E 0 = 2.38 V (37)
Oxygen evolution reaction (OER): OER has a pivotal role in hy-
drogen generation for electrochemical water splitting. The gen-
eral mechanism for OER is the oxidation reaction of OH− in
the alkaline electrolyte (Equation (38)) or H2 O from acid solu-
tion (Equation (36)), including adsorption and desorption of O*,
OH*, and OOH*. First, OH− is adsorbed at the active sites and
oxidized to OH* by coupling an electron. Then, OH* transfers
into O* by proton and electron, and finally forms O2 by combin-
ing two O*. Besides, the O* can also convert into OOH* and then
change to O2 by coupling OH−
4OH− → O2 + 2H2 O + 4e− , E 0 = 1.23 V (38)
Small molecule oxidation reaction: With the increasing demand
for energy, efficient utilization of sustainable energy is highly
desirable, especially fuel cells to convert chemical into electrical
energy. For proton-exchange-membrane fuel cell, the methanol,
ethanol, and formic acid are oxidized to produce electron and
carbon dioxide in the anode. The small molecule oxidation re-
actions, relied highly on their intermediates, are sluggish, which
requires efficient catalysts to facilitate their kinetics and restrain
the intermediates poisoning. The oxidation reactions of formic
acid (FAOR), methanol (MOR) and ethanol (EOR) are demon-
strated in Equations (39)–(41)
HCOOH → CO2 + 2H+ + 2e− (39)
CH3 OH + H2 O → CO2 + 6H+ + 6e− (40)
CH3 CH2 OH + 3H2 O → 2CO2 + 12H+ + 12e− (41)
Apart from formic acid, ethanol and methanol, urea and hy-
drazine are also viewed as the ideal alternatives for fuel cells.
Besides, the urea, hydrazine and ammonia are hydrogen stor-
age chemicals and the alternatives for water splitting to pro-
duce hydrogen as the low theoretical voltage than water splitting.
The urea (UOR), hydrazine (HzOR) and ammonia (AOR) oxida-
tion reactions contain multielectron/proton transfer. The relative
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reactions are presented in Equations (42)–(44) with the electrolyte
of alkaline solutions[19]
( )
CO NH2 2 + 6OH− → CO2 + N2 + 5H2 O + 6e− (42)
N2 H4 + 4OH− → N2 + H2 O + 4e− (43)
2NH3 + 6OH− → N2 + 6H2 O + 6e− (44)
Hydrogen oxidation reaction (HOR): In the hydrogen energy
storage and conversion system, the HER and HOR play vital roles
in electrolyzer and fuel cells. The HOR can be occurred in both
acidic and alkaline solutions, where the hydrogen reactions in al-
kaline solution is much slower than that in acid. There are three
steps for HOR in alkaline, including Tafel, Heyrovsky and Volmer
steps. Tafel step refers to the adsorption/desorption of hydrogen
on catalytic surface, while Heyrovsky step indicates the dissocia-
tion of hydrogen with electron transfer to H2 O and Volmer step
is known as the reaction of adsorbed H with OH− and electron
to form H2 O. The corresponding reactions are presented (Equa-
tions (45) and (46))
H2 → 2H+ + 2e− (acid) (45)
H2 + 2OH− → 2H2 O + 2e− (alkaline) (46)
Generally, the HOR activity widely accepted is associated by
hydroxide binding energy and hydrogen binding energy, which
is highly depended on the electrocatalysts.
2.2. The Nature of the Batteries
The metal-redox bicatalysis battery consists of redox-catalyst cath-
ode, metal anode, aqueous/nonaqueous electrolyte, with the gas,
liquid and solid at cathode serving as the active species. Among
booming metal-redox bicatalysis battery technologies, there are
two types of battery systems: aqueous and nonaqueous batter-
ies. As is shown in Figure 2, the alkali metals are generally oper-
ated in the nonaqueous electrolytes and the overall reactions in
the batteries are reversible. Nevertheless, for the aqueous elec-
trolyte systems, the anode reactions are reversible. Generally,
the batteries are rechargeable in which the cathode reactions
are irreversible. Based on the type of reactants, the metal-redox
bicatalysis battery can be divided into four categories, includ-
ing O species (Figure 2a,b), C species (Figure 2c,d), N species
(Figure 2e,f), and others (Figure 2g,h). The reactants include
solid, liquid and gas, among which gas is the common reac-
tant in most cases. The reactive gas flows from the external gas
tanks into the electrochemical device with the flow controller,
while the produced gas passes through the gas outlet into the
collector.
In these battery systems, the metals lose electrons and are
gradually oxidized during the discharging process. Meanwhile,
the active reactants which diffuse into the battery can accept elec-
trons. As a result, the charging/discharging processes are fin-
ished. During this process, the electrical energy can be gener-
ated with some value-added chemicals being produced for certain
types of metal-redox bicatalysis batteries.
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During the recharging process, reverse reactions normally oc-
cur and the species produced in the charging process accept elec-
trons and they are decomposed simultaneously. Moreover, some
functional materials involved in the electrolytes are introduced to
decrease the side reactions. For instance, the redox mediators in
the electrolyte can promote the electron transfer to catalyze the
charging reactions. Remarkably, the redox-bicatalyst cathode af-
fects the performance of batteries and the preparation of the effi-
cient and stable catalysts remains a great challenge. The progress
will be demonstrated in the following sections.
3. Structures of Rechargeable/Reversible
Metal-Redox Bicatalysis Battery
As shown in Figure 3a, metal-redox bicatalysis battery systems
are composed of metal anode, redox-bicatalyst cathode and con-
ductive electrolyte. During the discharging process, oxidization
reactions occur in the metal anode and reactant on the cathode
obtains electrons, as a result, the generation of current and con-
version between chemical energy and electric energy are com-
pleted. Most of electrolytes for metal-redox bicatalysis batteries,
which are conducive to enhancing the mass transport and reac-
tion kinetics, include alkaline solutions (NaOH/KOH), neutral
solutions (NaCl) and organic electrolytes. Their unique struc-
tures endow metal-redox bicatalysis battery with different func-
tions of energy storage and chemical production. We will com-
ment on the compositions of batteries in this section.
3.1. Cathode
In the metal-redox bicatalysis batteries, the cathode is gener-
ally composed of porous materials which are beneficial to im-
mobilizing or transporting the active reactants. And the ac-
tive species in the cathode are reduced in which the redox-
bicatalyst cathode plays an important role. The redox-bicatalyst
cathode which has drawn much enthusiasm is needed to pro-
mote the electrochemical reactions in the metal-redox bicataly-
sis batteries. Until now, various redox-bicatalyst cathodes have
been designed and prepared in accordance with the following
principles for metal bicatalysis batteries: i) fast reaction kinet-
ics; ii) chemical stability in various electrolytes; iii) low-cost cat-
alysts; iv) promising binding force between the catalysts and
substrate; v) suppressed side reactions between electrolytes and
catalysts.
For nonaqueous metal batteries, the redox-bicatalyst cathode
promotes the electrochemical reaction and decreases the overpo-
tential. The products will combine with the metal ions which are
generated in the anode reactions during the discharging process,
leading to the formation of the overall reaction products stick-
ing to the cathode surface. During the charging process, the bat-
tery product which is formed in the discharging process will de-
compose. As a result, the reversible overall process is achieved
(Figure 2a,c,e,g) and the batteries can be used for energy stor-
age. For aqueous metal batteries, the cathode half-reaction sep-
arate from the anode half-reaction, where the active species are
also catalyzed by redox-bicatalyst cathode and meanwhile some
chemical products can be obtained in some aqueous metal bat-
teries (Figure 2b,d,f,h).
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Figure 2. Illustrations of the fundamentals of devices from a,b) metal–O species battery to c,d) metal–C species battery, e,f) metal–N species battery,
and g,h) others.
For example, in the metal–CO2 batteries, CO2 is used as cath-
ode active species. The catalytic activities of metal-redox bicatal-
ysis batteries can be enhanced by rationally designing the re-
dox bicatalyst according to these principles mentioned above,
along with better cycling efficiencies. Up to now, significant de-
velopment has been obtained owing to the innovative design and
preparation of the redox-bicatalyst cathode. For instance, Guo
et al. prepared Ir nanosheet-doped CNFs which can efficiently
decrease the charge overpotential and lower the charge voltage
below 3.8 V at 100 mA g−1 .[20] When the cut-off capacity was 1000
mAh g−1 , the corresponding Li–CO2 battery showed a long recy-
cling life of 400 cycles. Li et al. reported a CO2 electrocatalyst with
oxygen vacancies and N dopants. The Vo-rich N-SnO2 nanosheet
catalyzed the transformation of CO2 to HCOOH with a Faradaic
efficiency of 83% at −0.9 V and inhibited the hydrogen evolution
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reaction.[21] In other types of batteries, such as sulfur-based sys-
tems, the catalysts also play a vital role in the batteries which will
be presented in Section 4.
3.2. Anode
The metal-redox bicatalysis batteries are considered as
ecofriendly energy storage systems that can ascribe to the
metal-based anode materials. The anodes applied in metal-redox
bicatalysis batteries can be classified as nonaqueous alkaline
metals [lithium (Li), sodium (Na), potassium (K)] and aqueous
metals [zinc (Zn), aluminum (Al), magnesium (Mg), and iron
(Fe)]. During the discharging process, metal anodes are grad-
ually oxidized resulting in the formation of metal ions, and
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Figure 3. a) The structures of aqueous and nonaqueous metal-redox bicatalysis batteries. b) Theoretical energy densities and voltages for various
batteries. c) The chemicals produced by different batteries. Part (b) was drawn using data from Refs. [9a,35,37,48,49,60,70,73,76,78,83,90].
the electrons escape from the anodes. Although most metal
anodes could provide high specific capacities and wide voltage
windows, there are anode passivation and corrosion which
reduce the coulomb efficiency. For example, during the charging
and discharging processes in the Li-based battery, the unwanted
Li dendrites will make the battery system to suffer serious side
effects. Therefore, new strategy should be developed to handle
these issues, including developing new electrolyte.
3.3. Electrolyte
Electrolyte has crucial influence on the electrochemical perfor-
mance of the battery, including operating voltage, temperature,
cyclic stability and rate performance. Owing to that alkali met-
als are susceptible to water and oxygen, the electrolytes in al-
kali metal systems require oxygen-free and water-free conditions,
commonly organic electrolytes. And the properties of electrolytes
have an important impact on the diffusion of reaction species and
products.
3.3.1. Electrolyte of Aqueous Metal-Redox Bicatalysis Batteries for
Chemical Production
At present, highly conductive electrolytes are still urgently needed
to improve the batteries’ performance. As is shown in Figure 3c,
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with proper species as the electrolyte, the value-added chemi-
cals can be obtained in the aqueous metal-redox bicatalysis bat-
tery reactions. For example, in the aqueous electrolytes, metal–
CO2 battery systems can consume CO2 along with the generation
of carbonaceous product, such as carbon monoxide, methane,
methanol and others. Additionally, NH3 can serve as a valuable
product in the metal–N2 batteries. Therefore, the aqueous bat-
teries not only store energy but also provide chemicals, showing
bifunctional characters.
For example, current development of electrolytes in Zn–air
batteries mainly include both liquid electrolytes and solid elec-
trolytes. The liquid electrolytes often suffer from leakage, there-
fore, nonliquid electrolytes which serve as transport medium
have attracted more attention recently.[22] Some polymer-based
electrolytes, such as solid polymer, gel polymer and composite
polymer, are among the most developed electrolytes. Gel poly-
mer matrix was often mixed with liquid plasticizer and/or ion-
conductive electrolyte solutions for further applications in the
batteries.[23] For example, the mechanical strength of gel elec-
trolytes can be improved by mixing them with crosslinkers,
and corresponding solid polymer electrolytes can be obtained.[24]
As an example, Chen et al. prepared a crosslinked nanocellu-
lose/graphene oxide as electrolyte and they investigated its ap-
plication in a rechargeable Zn–air battery.[25] In 1990s, the solid
polymer with better mechanical strength was applied in Zn–air
battery.[26] Although the solvents’ evaporation and battery leakage
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can be avoided, its low ion conductivity and poor contact with meanwhile zinc ions accept the electrons.[33] The charge reac-
air cathode need to be addressed in the future.[27] In general, tions are as follows.
composite polymer-based electrolytes can be prepared by mix- Cathode
ing gel polymer electrolyte with other materials. And KOH so-
lutions are often mixed with polymers which include represen- H2 O → 1∕2O2 + 2H+ + 2e− (47)
tative polyethylene oxide (PEO), polyacrylic acid (PAA) and poly
vinyl alcohol (PVA).[28] Anode

Zn (OH)2−
4
→ Zn2+ + 4OH− (48)
3.3.2. Electrolyte of Nonaqueous Metal-Redox Bicatalysis Batteries
for Energy Storage
Zn2+ → Zn2 − 2e− (49)
Different from aforementioned aqueous metal batteries, alkali
Overall reaction
metal batteries generally have no valuable discharging prod-
ucts. Notably, compared with aqueous metal batteries, they have
Zn (OH)2−
4
+ H2 O → Zn + 1∕2O2 + 2H+
higher theoretical energy densities and discharge voltage (Fig-
ure 3b). Hence they can be used for energy storage. However, + 4OH− , Echarge = 2.041 V (50)
it has been an urgent issue to develop stable electrolytes because
of the harsh oxygen environment. And its stability of withstand- For reversible batteries, the charging voltage is approximately
ing reactive oxygen species is a critical aspect for the recharge- same to the discharging voltage. Xie et al. prepared an aqueous
able alkali metal batteries.[29] As the first-generation electrolytes, Zn–CO2 battery and CO2 was transformed to HCOOH by a bi-
a variety of organic carbonate-based electrolytes have been in- functional Pd cathode.[9a] It should be noted that the conversion
troduced into the batteries. Unfortunately, they were proved to between CO2 and HCOOH is a reversible process. The voltage
be unsuitable to sustain reversible peroxide reactions.[30] The of 1 V was observed in the charging process, which could remain
ether-based electrolytes with excellent stability, such as tetraethy- stable over 100 cycles. The discharging reactions for Zn–CO2 bat-
lene glycol dimethyl ether (TEGDME) and 1,2-dimethoxyethane tery are proposed as follows.
(DME) were further studied.[31] Meanwhile, Xu et al. first stud- Cathode
ied dimethyl sulfoxide as electrolyte which exhibited low viscos-
ity and high conductivity.[23] Additionally, amides, ionic liquids CO2 + 2H+ + 2e− → HCOOH (51)
and acetonitrile are also studied as substitutes for alkali metal–
O2 batteries.[32] However, most electrolytes mentioned above are Anode
not stable enough for practical application, so chemists have
made many efforts to develop more stable electrolytes in recent Zn + 2e− → Zn2+ ; Zn2+ + 4OH− → Zn (OH)2−
4
; Zn (OH)2−
4
years. In contrast to the aqueous electrolyte systems, the main
application is energy storage due to the high energy densities → ZnO + 4OH− − H2 O (52)
(Figure 3b).
In brief, alkaline metal-redox bicatalysis batteries have high Overall reaction
theoretical energy densities in nonaqueous electrolytes (Fig-
ure 3b) and the corresponding devices can be applied in the en- Zn + CO2 + 2H+ + 2OH− → ZnO + HCOOH + H2 O (53)
ergy storage fields. While the theoretical energy densities of most
aqueous metal-redox bicatalysis batteries are lower. It is gratify- HER competed with CO2 -to-HCOOH conversion during bat-
ing that value-added chemicals can be obtained in the aqueous tery discharge
electrolytes.
2H+ + 2e− → H2 (54)

3.4. Voltage Overall reaction of discharge process including HER and Zn

oxidation
The discharge voltage, which is lower or equal to the charge volt-
age, is an important indicator for the battery. For the reversible Zn + 2H+ + 2OH− → ZnO + H2 + H2 O (55)
batteries, the oxidation reactions are inverse to the reduction re-
actions, thus the voltages are same for charging and discharg- When the Zn–CO2 battery charges, the reaction is the reverse
ing. As for the rechargeable batteries, where the reduction and of the discharge reaction, and the following reactions are pro-
oxidation reactions are completely distinct, they require higher posed.
charge voltage than discharge voltage. Generally, in the nonaque- Cathode
ous system with alkali-metal anode, almost all the secondary bat-
teries are reversible. On the contrary, the aqueous systems con- HCOOH → CO2 + 2H+ + 2e− (56)
taining aqueous-metal anode, such as Zn, Al, Mg, Ca, often ex-
hibit rechargeable properties and few are reversible. Anode
For instance, for aqueous rechargeable Zn–CO2 battery, dur-
ing the charging process, H2 O decomposes to release the O2 , Zn + H2 O + 2e− → Zn + 2OH− (57)

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Overall reaction
ZnO + HCOOH + H2 O → Zn + CO2 + 2H+ + 2OH− (58)
In addition, OER take place when charge with high charge cur-
rent.
Cathode
H2 O → 1∕2O2 + 2H+ + 2e− (59)
Overall reaction
ZnO + H2 O → Zn + 1∕2O2 + 2H + 2OH + −
(60)
Only when charge voltage is over 2.135 V, OER may take place
in the aqueous reversible Zn–CO2 battery.
3.5. Functions
Based on the structure of metal-redox bicatalysis battery men-
tioned above, two functions of energy storage and chemical pro-
duction can be achieved. Generally, a much higher voltage is re-
quired for electrochemical reactions in organic electrolyte. There-
fore, the metal-redox bicatalysis battery with organic electrolyte
often delivers higher energy density, desirable for energy stor-
age (Figure 3b). For example, the alkali metal–CO2 batteries with
Li/Na as anode and organic electrolyte, propose high theoretical
discharge voltage of higher than 2 V, which results in high en-
ergy density of more than 1000 Wh kg−1 , much higher than the
state-of-art lithium-ion battery. According to the design princi-
ples of metal-redox bicatalysis battery, the operating efficiency,
reliability, and reversibility of alkali metal-redox bicatalysis bat-
tery are mostly determined by the activity and stability of redox-
bicatalyst cathode, where the operation efficiency is defined as
the specific value of reduction and oxidation voltages. The effi-
cient redox-bicatalyst can facilitate the redox reactions, reduce the
overpotential and further enhance the operating efficiency, while
the stable redox-bicatalyst can be beneficial for the reliability, and
reversibility.
Separately, aqueous metal-redox bicatalysis battery often ex-
hibits much lower theoretical energy density of less than
1000 Wh kg−1 . Notably, the various discharging products can be
achieved in aqueous systems. As observed in low energy den-
sity region of Figure 3b, the metal-redox bicatalysis batteries can
produce chemical productions, such as value-added carbon and
hydrocarbon-based chemicals in Zn–CO2 battery, hydrogen in
Zn–H2 O and Zn–N2 H4 batteries (Figure 3c). It is concluded that
the aqueous metal-redox bicatalysis batteries generally own dual
functions of energy storage and chemical production.
4. Redox Bicatalysts
Toward to the various types of reported metal-redox bicatalysis
batteries, huge challenges still exist for practical application, such
as sluggish conversion dynamics, high energy decomposition
barrier, structural decomposition and complex reaction steps,
which can result in low efficiency, poor rate performance and
stability. Therefore, it is urgent to enhance the reaction kinetics,
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rechargeability and electrochemical performance for accessible
chemical products and high-specific-energy storage. To address
the issues mentioned above, the rational design and synthesis of
redox bicatalysts seem to be a potential and effective strategy. In
this section, the catalysts that have been investigated for various
metal-redox bicatalysis batteries will be reviewed.
4.1. Metal O2 Batteries
It remains a worthwhile objective to obtain higher energy densi-
ties in metal battery systems. The appearance of metal–O2 bat-
teries opened up a new research field. According to the metal an-
odes, the metal–O2 batteries can be classified as Li–O2 , Zn–O2 ,
Al–O2 batteries and so on. For non-Li metal–air batteries, they
have high energy densities and low production cost, which may
meet the practical requirements. In non-Li metal–O2 batteries,
the redox-bicatalyst cathode which can catalyze OER and ORR re-
actions has important effects on the battery performance. Until
now, there has been a good deal of catalysts that have been re-
ported, such as noble metals and non-noble metal-based materi-
als. Chemists also take research on the nonmetallic species (e.g.,
carbonaceous materials) in the field of metal–air batteries. Gener-
ally, fast reaction kinetics, chemical stability and perfect binding
force between the catalysts and air electrodes are required for the
redox-bicatalyst cathode. Herein, noble-metals, non-noble metals
and metal-free materials will be discussed in detail.
4.1.1. Alkali Metal–O2 Batteries
Among the advanced metal batteries, a lot of researches about
Li/Na–O2 batteries have been reported for energy storage on ac-
count of their high specific energies. Alkali metal anode and oxy-
gen cathode constitute their electrodes. In recent years, much
progress of Li/Na–O2 batteries has been achieved, ranging from
materials to model devices. However, it is difficult to avoid the
side reactions which will cause the battery’s destruction. Ad-
ditionally, the organic electrolyte and carbon cathode are easy
to be attacked by the oxygen species, resulting in various side
reactions.[34]
In terms of Li–O2 battery systems, the charging product Li2 O2
often leads to the decomposition of carbon materials when the
charge voltage exceeds 3.5 V. Additionally, when charge voltage
is above 4 V, most electrolytes are not stable enough to decom-
pose. Hence, it is necessary to tackle this problem by reducing
the charge potential. Developing novel OER catalysts is benefi-
cial to achieve this aim. And the categories of OER catalysts in-
clude metals and their oxides, carbides, nitrides and phosphides.
Herein, we will discuss some representative reports as examples.
In the Li–O2 battery, a Co3 O4 /reduced graphene oxide (rGO) hy-
brid material was used as the catalyst by Nazar et al..[35] They
found that Co3 O4 could reduce LixO2 species’ binding energy and
promote their surface transport, leading to a lowered charge po-
tential below 3.8 V. Wen et al. systematically studied the factor
of catalyst activity by comparing various OER catalysts in the Li–
O2 battery.[36] The surface acidity of catalysts is found as a crucial
role to change the desorption energies of Li+ and O2 . They fur-
ther corroborated their observation by DFT calculations. On the
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basis of the theoretical calculations, the OER activity of the pre-
pared the CoO catalyst was comparable to that of Co3 O4 (similar
charge potential at 3.5 and 4.05 V at 0.1 mA cm−2 and 1000 mAh
g−1 ). On the basis of this research, the principle about how to reg-
ulate the catalysts’ activity will be applied in more studies. Com-
pared with Li metal, Na has similar nature. Consequently, most
catalysts for Li–O2 battery can efficiently promote the reactions of
Na–O2 battery. For example, the Ru-based materials were proved
to be efficient for catalyzing Na2 O2 oxidation.[37]
The cycling stability is an important aspect for designing bat-
teries, and surface coating of electrode materials was found to
be an efficient method. Zhou et al. introduced a CNT@RuO2
material with core–shell structure as redox bicatalyst for ORR
and OER.[38] The Li–O2 battery had a decreased voltage gap from
1.16 to 0.3 V and exhibited enhanced cyclic stability for 100 cy-
cles. In addition to the inorganic catalysts which can reduce
the side reactions, conductive polymers can also play the sim-
ilar role, such as poly(3,4-ethylene dioxythiophene) (PEDOT),
polyimide (PI) and polyaniline (PANI). Lee et al. synthesized
a PI-wrapped carbon nanotube (CNT) to improve the stability
of Li–O2 battery (Figure 4f).[39] When the electrolyte was 1 m
LiTFSI/TEGDME, its cycling stability was found to be twice
improved at 1500 mAh g−1 . They found that the byproducts
such as CH3 CO2 Li and HCO2 Li were suppressed which was
observed from SEM and FTIR spectra. Subsequently, PEDOT:
polystyrene sulfonate (PSS)-coated graphene electrode was de-
veloped. The side reactions were decreased between Li2 O2 and
carbon electrode.[40] Nevertheless, the stability between polymer
and Li2 O2 is uncertain. Amanchukwu et al. demonstrated that the
thiophene ring in PEDOT was affected by oxygen species to form
sulfone, which weakened the electronic conduction in Li–O2
battery.[41]
4.1.2. Non-Li Metal–O2 Batteries
Many studies have been executed for ORR catalysts in the aque-
ous metal–O2 battery. Among various ORR catalyst, platinum
(Pt) based materials have been proved to be excellent catalysts.[42]
Other non-Pt or less-Pt catalysts have been developed for metal–
O2 batteries due to the high cost of platinum.[43] For instance,
Ag/carbon composites, which were prepared by loading vari-
ous Ag nanostructures onto different carbon substrates, served
as ORR catalysts for metal–O2 batteries, including Zn–O2 ,[44]
Mg–O2 [45] and Al–O2 batteries.[46] Notably, when utilized Ag
NPs/carbon fiber paper as catalyst, a capacity of 2917 mAh g−1
and high-power-density of 108.1 mW cm−2 were achieved. Its en-
ergy density (4346 Wh kg−1 ) was also higher than other metal–air
battery with commercial Ag powders as catalyst.[47]
It is well known that non-noble metal catalysts have many ad-
vantages, such as comparable activities and low-cost. As reported,
Fe/N codoped carbon catalysts have been considered as the po-
tential candidates for primary Zn–O2 [48] and Al–O2 batteries.[49]
Xu et al. prepared a Fe–N–C catalyst via pyrolyzing iron com-
plex precursors and it showed a high ORR activity and excellent
stability.[48a] And the corresponding Zn–O2 battery showed a high
capacity (727 mAh g−1 ) with the high energy density (965 Wh
kg−1 ). Afterward, the Fe/N/C framework and bimetallic zeolitic
imidazolate framework were used as the precursors to generate
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the Fe–N–C catalyst by Wang et al. This catalyst endowed the bat-
tery with a power density of 235 mW cm−2 which could light a
LED screen.[50]
Compared with Zn–O2 batteries, the investigations of Mg–O2
batteries are still limited. Although Mg–O2 batteries have a the-
oretical open-circuit voltage value of 2.95 V, the power output
of most Mg–O2 batteries is below 100 mA cm−2 . This can as-
cribe to the Mg corrosion. During the charging recharging pro-
cess, O2 is reduced to OH− while Mg is oxidized into Mg2+ .
When the battery system is operated in an alkaline electrolyte,
the Mg anode will be coated with Mg(OH)2 which can hinder
the continuous discharge of the battery. Owing to that Mg is
not stable in acidic electrolytes, neutral electrolyte is selected as
an ideal choice to avoid the metals’ corrosion. For example, Li
et al. utilized a hybrid catalyst (mullite SmMn2 O5 , fluorite CeO2
and spinel Mn3 O4 )[51] to improve the ORR catalytic activity that
was comparable to Pt/C catalysts. As a result, the Mg–O2 batter-
ies exhibited an OCV of 1.65 V although the OCV dropped to
1.22 V later. When applying 1.0 mA cm−2 , it could keep stable for
290 min.
In aqueous Al–O2 battery systems, Ag/metal oxide compos-
ites, metal oxide/carbon composites and perovskite-type oxides
constitute the types of active ORR catalysts. For example, Liu et al.
synthesized a series of perovskite-based ORR catalysts in the Al–
O2 batteries,[52] and the composite materials (Ce0.75 Zr0.25 O2 and
La0.7 Sr0.3 MnO3 ) could efficiently promote the ORR process for
Al–O2 battery with a high-power-density of 233.4 mW cm−2 .[53]
In conclusion, chemists have paid most attention on noble metal-
redox bicatalyst materials for non-lithium metal–air battery. It is
a target to explore other cost-effective catalysts and rational de-
sign of electrocatalysts is urgently needed, particularly for Al–O2
and Mg–O2 batteries.
Moreover, metal-free electrocatalysts further enrich the types
of ORR catalysts. Heteroatom-doped carbon materials have been
explored for catalyzing ORR process because of their stable ORR
activity.[54] Liang et al. designed a Zn–O2 battery with a specific
capacity of 615 mAh g−1 and an energy density of 760 Wh kg−1 .
In this battery, N-doped carbon nanofibers catalyst was used for
catalyzing the ORR (Figure 4c).[55] Besides, for Al–O2 batteries,
constructing N-doped graphene was workable. It showed a capac-
ity of 619 mAh g−1 , and the corresponding high energy density
(817 Wh kg−1 ) can be achieved, which was higher than that of
pristine graphene.[56]
Another type of fascinating catalyst is conductive polymer. For
instance, silk fibroin-polypyrrole was synthesized and applied for
oxygen catalytic electrode in Mg–O2 batteries.[57] Consequently,
the battery voltage maintained 1.79–1.72 V and it displayed a
high-energy-density of 4.70 mWh cm−2 . Besides, it was endowed
with a power density of 64.6 μW cm−2 . In brief, metal-free cata-
lysts have presented favorable activities toward ORR and nitrogen
atoms are most reported for doping carbon hosts. However, the
doping states of heteroatoms are incredibly challenging to con-
trol.
Although metal–air batteries have high power densities and
capacities, its development remains a great challenge caused by
the moisture and CO2 . It has attracted much attention to develop
new type of metal-redox bicatalysis batteries with excellent perfor-
mance. We will elaborate other redox-bicatalysis batteries here-
inafter.
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Figure 4. a) Design principles of redox bicatalysts. b) Main progress of different types of catalysts for metal-redox bicatalysis batteries. c) N-CNF
aerogels electrocatalysts for Zn–air battery, reproduced with permission.[55] Copyright 2015, Elsevier. d) Ru complex electrocatalysts for Li–CO2 batteries,
reproduced with permission.[58] Copyright 2021, Wiley-VCH. e) Ti4 O7 /S for Li–S battery, reproduced with permission.[81] Copyright 2014, Springer Nature
publications. f) Polyimide-wrapped carbon nanotube for Li–air battery, reproduced with permission.[39] Copyright 2015, The Royal Society of Chemistry.
g) Pt-decorated Ni3 N nanosheet for Li–H2 O battery, reproduced with permission.[89] Copyright 2017, Wiley-VCH.

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4.2. Metal–C Species Batteries
In recent years, many chemists have made efforts to transform
CO2 to value-added chemicals for carbon neutrality and carbon
peak. And coupling CO2 transformation with energy storage sys-
tems is a promising way. Recently, metal–CO2 batteries have at-
tracted much attention for CO2 capture and transformation. Nev-
ertheless, there are many difficulties to be overcome for metal–
CO2 battery systems, including poor reversibility, high overpo-
tential and low energy efficiency. Thus, catalyst’s activity should
be improved in metal–CO2 batteries. The catalysts for metal–CO2
batteries contain noble metals and transition metals-based mate-
rials.
Li–CO2 battery has a high theoretical energy density of
1847 Wh kg−1 . However, the active catalysts are still limited,
giving rise to slow reaction kinetics in most metal–CO2 batter-
ies. Similar to metal–air batteries, noble metals and transition
metals-based materials are explored for catalyzing the Li–CO2
battery reactions. Among a variety of noble metals, Ru has been
used for catalyzing many reactions (Figure 4d).[58] Chen et al.
reported a redox-bicatalyst cathode consisting of Ru nanoparti-
cles which were immobilized on carbon nanotubes for Li–CO2
batteries.[59] The pore structure of carbon nanotubes promoted
the diffusion of CO2 and improved the conductivity of Ru. Li2 CO3
was found as the discharge product which was investigated with
X-Ray diffraction of the ectopic grazing incidence synchrotron.
Li2 CO3 disappeared and its cubic grains covered the Ru/C dur-
ing the charging process. The result showed that Ru/CNT pro-
moted the decomposition of Li2 CO3 and maintained better dura-
bility than that of CNT. The authors found that the dendrites and
passivation materials led to the battery destruction at the operated
capacity of 500 mAh g−1 .
Additionally, the Ru oxides also exhibit superior catalytic per-
formance for Li–CO2 batteries, which can facilitate the decom-
position of Li2 CO3 and decrease the charging voltage. Du et al.
prepared a novel Li–CO2 battery assemble by RuO2 /SWCNTs
cathode.[60] The redox-bicatalyst cathode was synthesized by com-
bining RuO2 nanoparticles with single-walled CNTs. The bat-
tery’s charging plateau was reduced to 4.2 V and RuO2 /SWCNTs
could stably catalyze the decomposition of Li2 CO3 . Remarkably,
84.99% of the charging power was utilized for CO2 generation
and the other energy was consumed by thermal effects and
byproducts. Whereas, the improvement of the cycle performance
of RuO2 /SWCNTs remains a crucial challenge.
Furthermore, Ir and IrO2 can be utilized as redox-bicatalyst
cathode in Li–CO2 batteries due to their high chemical stabil-
ity and they have been proved to be efficient candidates by Li
et al.[61] and Zhai et al.[62] Besides Ru and Ir based materials, Li–
CO2 batteries are studied with Au and Ag as catalysts. Kong et al.
synthesized Au nanoparticles dotted on CNTs as redox-bicatalyst
cathode, which can cycle 46 times continuously.[63] Zhang et al.
prepared TiO2 nanotube arrays loading with silver nanoparticles
which were taken as active redox-bicatalyst cathode for Li–CO2
batteries.[64] Ag ions promoted the photogenerated carriers’ sep-
aration and transfer on surface of the catalyst. Notably, the plas-
monic interaction and synergistic photoelectric effect accelerated
the oxidation and reduction of CO2 in the batteries.
Although the precious metals have superior performance for
Li–CO2 batteries, their high cost hinders it further applications.
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Transition metal-redox bicatalyst materials were accepted as ideal
substitutes. Recently, Fe atoms dispersed in 3D porous carbon
were reported by Hu et al, where the carbon consisted of intercon-
nected S,N codoped graphene sheets.[65] This catalyst showed a
superior specific capacity of 23 174 mAh g−1 and maintained sta-
ble for more than 200 cycles. The decomposition of Li2 CO3 uni-
formly dispersed on the HG sheet was facilitated by the catalyst
during charging. Besides, transition metal oxide and carbides-
based materials have been also developed for Li–CO2 batteries
and numerous researches have been reported. For instance, Hou
et al. reported a rechargeable battery with Li anode, CO2 cathode
and Mo2 C/CNT catalyst which was first used in Li–CO2 battery.
Interestingly, the molybdenum in Mo2 C combined with the oxy-
gen atom of CO2 during the discharging, leading to the Li2 C2 O4
formation.[66] Afterward, the reaction mechanism of Mo2 C in Li–
CO2 batteries was further studied through DFT calculations by
Yang et al.[67] They found that the (001) and (101) surfaces of 𝛽-
Mo2 C which had lowest Gibbs free energy could catalyze the de-
composition of discharge product.
Additionally, covalent-organic frameworks and metal–organic
frameworks materials show great potential in the field of Li–
CO2 battery catalysts. Dong et al. reported a 2D porphyrin-based
MOFs (MTPzP-Mn) as the cathode and the intrinsic double Mn
active sites were proved to efficiently catalyze the CO2 reduction
during discharge and decomposition of Li2 CO3 during charge,
respectively.[68] Jiang et al. prepared an ultrathin MnO2 /DQTP-
COF nanosheet cathode for Li–CO2 battery, which showed excel-
lent cycling performance and delivered a high discharge capacity
(42 802 mAh g−1 ).[69] The quinone moieties of COF nanosheets
and MnO2 synergistically enhanced the CORR/COER kinetics,
resulting in a higher current density and longer cycling life.
The reaction mechanism was revealed by DFT calculations and
quinone group played a crucial role in activating CO2 . And at the
interface of MnO2 and COF nanosheets, the decomposition of
discharge product (Li2 CO3 ) occurred.
Besides Li metal, other metals are also devised for metal–CO2
batteries, including Na, K, Al, Zn and so on. Earth-abundant and
cost-effective (30 times cheaper than Li) Na has similar electro-
chemically behavior. Kim et al. designed a hybrid Na–CO2 battery,
where hydrogen and electric energy were simultaneously pro-
duced through efficient CO2 conversion.[70] When utilized IrO2
and Pt/C as catalysts, the battery could be operated over 1000 h
and CO2 was converted to NaHCO3 . The efficiency of CO2 con-
version was determined to be 47.7%. Notably, CO2 cannot be re-
generated during the charging process in this Na–CO2 battery
system. Only hydrogen was observed as the discharge product.
Furthermore, sodium ions could act as fast ionic charge carriers
which was beneficial to electrochemical energy storage. Dai et al.
first demonstrated a CO2 battery with K anode and metal-free
carbon-based electrocatalysts which were composed of a hybrid
N-doped carbon nanotube and N-doped rGO 3D network.[71] The
porous architecture of N-CNT was beneficial to the electron/CO2
transport and storage of the discharge product (K2 CO3 ). The as-
sembled K–CO2 battery had a cut-off capacity of 300 mAh g−1
and a cycle life of 250 cycles, respectively. A rechargeable Al–CO2
battery was demonstrated by Ma et al. and they synthesized a Pd-
coated porous gold (NPG@Pd) pieces.[72] In this catalyst, Pd was
taken as the active sites for CO2 reduction and NPG promoted
electronic conductivity. Therefore, CO2 can be cycled in the
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cathode. The battery showed an energy efficiency of 87.7% and
a low charge/discharge voltage gap of 0.091 V, smaller than that
of Li–CO2 , Na–CO2 , and Al–air batteries.
4.3. Metal–N Species Batteries
N2 fixation into valuable chemicals is critical for developing var-
ious fields that sustain human life. Nevertheless, energy con-
sumption is inevitable in traditional Haber–Bosch process which
results in environmental pollution. It has become a critical
challenge to develop ecofriendly technologies. As a promising
platform, metal–N2 battery systems provide a simple and effi-
cient strategy for simultaneous artificial N2 fixation and power
generation. Metal–N2 batteries also possess high energy density,
meanwhile, NH3 which is generated through electrochemical N2
reduction reaction (NRR) is an attractive product. In this pro-
cess, catalysts have a significant effect on electrochemical N2 fix-
ation. Zhang et al. first illustrated a Li–N2 battery with Ru-CC
as the redox-bicatalyst cathode. The potential became more posi-
tive and the current density was larger than those of ZrO2 -CC or
pure CC cathode.[73] Besides, a longer cycle life was achieved for
Li-N2 batteries constructed by Ru-CC and ZrO2 -CC catalysts. In
addition, compared with pure N-doped carbon nanosheets (NC),
ultrasmall Mo2 C particles dispersed on NC were more efficient
N2 electroreduction catalyst. The Li–N2 battery further enriched
the types of energy storage devices. Nevertheless, low Faraday ef-
ficiency, unfavorable reaction kinetics, poor NH3 selectivity and
high overpotential of most of the reported NRR electrocatalyst
will affect their electrochemical performance.[74]
Furthermore, Yang et al. for the first time demonstrated a
lithium–nitrogen dioxide (Li–NO2 ) battery without any catalysts
which was used for the reduction of nitrogen dioxide (NO2 ) at
room temperature.[75] This Li–NO2 battery’s capacity was 884
mAh g−1 and the Faraday efficiency reached 67%. This research
not only increases the types of gas available in rechargeable bat-
teries but also provides a way to recycle NO2 . Owing to the un-
satisfactory efficiency of electrochemical NRR, other metal–N
species batteries are also developed.[76] Nitrate electroreduction
(NORR) into NH3 is explored as a potential alternative for NH3
production.[77] A Pd-doped TiO2 catalyst which was used to pro-
duce NH3 with a yield of 1.12 mg cm−2 h−1 was reported by
Chunyi Zhi et al. And its Faradic efficiency reached 92.1%. They
also proposed a Zn-nitrate cell with a high NH3 FE of 81.3% and
power density of 0.87 mW cm−2 for the first time.[78]
4.4. Metal–Chalcogen Batteries
In recent years, metal–chalcogen batteries have attracted an in-
creasing research attention because of the environmental friend-
liness and high theoretical energy density. Hebert and Ulam gave
a proof-of-concept report using sulfur as the cathode material in
1962. Owing to the considerably higher specific energy of Li–S
batteries (2600 W h kg−1 ) than that of lithium-ion batteries, more
recently, a lot of original researches have been conducted to de-
velop metal–chalcogen batteries with high energy density. How-
ever, there are some issues that impede the high energy density,
such as self-discharge and capacity degradation and high internal
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resistance. The researches testified that introducing conductive
carbons and polymers into sulfur electrodes is accepted as an ef-
fective strategy to enhance their performances. The active sulfur
was loaded in carbon which was first reported by Wang et al and
the rechargeable battery displayed a specific discharge capacity of
440 mAh g−1 .[79] As a result, better cyclability was obtained and
many chemists devoted themselves to developing sulfur-porous
carbon composites. For instance, Ji et al. reported a battery with
the specific capacity of 1320 mAh g−1 which was benefiting from
the sulfur-mesoporous carbon composite.[80] Furthermore, vari-
ous metal-based materials have been applied for catalyzing the
electrochemical reactions, such as metal sulfide, metal oxide,
metal carbide and metal nitride based catalysts. Nazar et al. uti-
lized Ti4 O7 as the catalyst to promote electron transfer and mean-
while the transformation of the polysulfides (Figure 4e).[81] Sub-
sequently, Pt, Ni, etc. metal catalysts were investigated to catalyze
sulfur redox reactions in Li–S batteries.[82]
For instance, NiMoO4 dotted on N,S codoped carbon cloth for
Li–S batteries was reported by Wang’s group.[83] They found that
Mo reduced the band gap and improved the electron density near
the Fermi energy level, as a result, the Li–S battery was endowed
with an excellent cycling stability. Moreover, it is well known that
the accumulation of a large amount of Li2 S can reduce the oxi-
dation kinetics during charging owing to the affinity of the active
sites of metal catalysts toward to polysulfides. The heterostruc-
tures have been found to efficiently promote sulfur reaction ki-
netics and accelerate charge transfer which is beneficial for the
Li–S batteries.[84] Chu et al. reported a highly efficient catalyst
consisting of the CoSe2 /Co3 O4 heterostructures with NC layers
and CNT.[85] In this heterostructure, polysulfides were adsorbed
at the Co3 O4 interface and catalyzed by CoSe2 . The result showed
that the shuttle effect was restrained by CoSe2 /Co3 O4 @NC-CNT
and the cathode delivered an initial capacity of 1457 mAh g−1 at
0.1 C.
As one type of lithium batteries, the lithium-sulfur dioxide (Li–
SO2 ) battery with SO2 as the cathode has many advantages, such
as excellent working life, high cell voltage and wide operating
temperature range and high energy density. Lim et al. used LiI as
a model catalyst and achieved the first rechargeable Li–SO2 bat-
tery with a capacity of 5400 mAh g−1 at 3.1 V.[86] The discharge
product, Li2 S2 O4 , was reversibly formed and decomposed. How-
ever, the cycling performance is still limited and more efforts
should be made for suppressing the byproducts to enhance the
cyclicity.
4.5. Other Metal-Redox Bicatalysis Batteries
In addition to a wide variety of metal redox bicatalysis batteries
mentioned above, there are still many other high-performance
battery systems. The Li–SOCl2 battery was first reported by Ga-
bano in 1969. And the catalysts have an important influence
on the discharge capacity and operating voltage. For instance,
platinum can greatly improve cells’ performances.[87] Moreover,
other pure metals also have a catalytic effect in Li–SOCl2 batter-
ies, including copper, iron, silver and palladium. Copper powders
play a catalytic role on the Li–SOCl2 cells.[88] The transition metal
complexes are also employed as catalysts to improve the perfor-
mance of Li–SOCl2 cells and Co and iron phthalocyanines are
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Figure 5. Development and proposed future directions for metal-redox bicatalysis battery. a) Redox bicatalyst. b) Electrolyte. c) Redox reactions.
d) Metal-redox bicatalysis battery.
the most effective alternatives. In spite of its high energy den-
sity, long working life and good low temperature performance,
the voltage delay should be solved for Li–SOCl2 cells.
In contrast, metal–H2 O batteries can simultaneously gener-
ate electrical energy and hydrogen although there are some
critical problems, such as low efficiency of H2 production and
low output of electrical energy. Recently, Wang et al. proposed
a Li–H2 O battery with Pt-decorated Ni3 N nanosheet as redox-
bicatalyst cathode.[89] This integrated cell could sustain hydrogen
production for more than 60 h. Hydrogen can serve as a clean
energy which is produced by water splitting in the battery, and
electricity generate simultaneously. Furthermore, Zn–H2 O bat-
teries are also demonstrated as new type of devices. For instance,
Wen et al. reported an alkaline-acid Zn–H2 O fuel cell, where
the redox-bicatalyst cathode was constructed by Pt nanoparticles
loaded on the carbon nanotubes on carbon cloth and Zn plate
served as the anode.[90] It kept an open circuit voltage of 1.25 V
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and almost 100% H2 Faradic efficiency. The entire battery pos-
sessed a power density of 80 mW cm−2 and an energy density of
934 Wh kg−1 . Besides, the catalyst could maintain H2 output for
a long time when tested at 1.16 V under 10 mA cm−2 .
Owing to the intrinsic architectural advantages of MOFs,
they are also explored as cathodes for Zn–H2 O battery. Hou
et al. prepared Ni-MOF/Ni2 P@EG with nickel-based MOFs
(Ni-MOFs) deposited on exfoliated graphite (EG), followed by
phosphorization.[91] When applied in alkaline Zn–H2 O cell, high
stability and power density (4.1 mW cm−2 ) were obtained. The
electricity generation and hydrogen production were realized
simultaneously in this alkaline Zn–H2 O battery. Subsequently,
they designed a hybrid catalyst which was configured with Mo-
doped WC core and N-doped carbon (Mo-WC@NCS). They
found that Mo doping onto tungsten carbide could tune the d-
band center for hydrogen evolution. The obtained Mo-WC@NCS
hybrid delivered an overpotential of 179 mV at 10 mA cm−2 for
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HER., And the power density of 41.4 mW cm−2 was reached in
alkaline-acid Zn–H2 O cell because the Mo-WC@NCS hybrids
could keep H2 generation for a long-term.[92]
Moreover, Wei et al. proposed a Zn–H2 O2 battery in which car-
bon nanosheet doped with Co/N (Co/N-CNS) was used as a mul-
tifunctional catalyst and hydrogen peroxide provided oxygen for
the battery.[93] The activated carbon and Co/N-CNS-750 exhibited
catalytic rates of 199 and 1164 mL g−1 min−1 for H2 O2 decompo-
sition. Enhanced rate performance from 20 to 120 mA cm−2 was
observed in the Zn–H2 O2 battery. And its discharge performance
at 120 mA cm−2 was 23% which was higher than that of the
Zn–air battery. Benefiting from its excellent performance, a red
LED array can be lightened.
5. Summary and Prospective
In this review, we summarize the design principles of the metal-
redox bicatalysis batteries, including the fundamentals and devel-
opment of redox-bicatalyst cathode, anode and electrolyte. Based
on the high-energy-density and cost-effective advantages, metal-
redox bicatalysis batteries represent one of the potential technolo-
gies for ever-increasing energy requirements. In recent years,
promising progress has been achieved in the field of metal-redox
bicatalysis batteries, while many challenges still remain to be ad-
dressed. In this review, the mechanisms of the batteries and re-
dox bicatalysts have been summarized. On the basis of the design
principles, the corresponding anodes, cathodes, electrolytes and
theoretical energy densities are presented. In particular, the ad-
vancement of a variety of redox bicatalysts is discussed in this
review. For nonaqueous metal-redox bicatalysis batteries, most
components are sensitive to moisture and should be assembled
under inert atmosphere. Generally, nonaqueous batteries pos-
sess higher energy densities than aqueous counterparts. Never-
theless, in aqueous species, such as Zn–CO2 batteries, energy
storage and chemical production can be achieved simultaneously.
However, novel redox bicatalysts need to be developed to decrease
the energy barrier and overcome the sluggish reaction kinetics.
In spite of great progress in this field, there are still consider-
able scientific and technological challenges to restrict the practi-
cal applications. To look for new strategies and opportunities to
develop metal-redox bicatalysis batteries, more academic atten-
tion should be paid on the following possible directions.
1) Design and explore efficient, ecofriendly and cost-effective re-
dox bicatalysts (Figure 5a). Redox bicatalyst can not only drive
the discharge/charge process in the device, but also decrease
reaction overpotential and enhance the energy efficiency as
well as improve the cyclic stability. Notably, to design the re-
dox bicatalysts, the mismatch between the multi-element and
multi-charge transfer rates during redox reactions is the key
point. Therefore, it is desirable to design and fabricate the ma-
terials with coupled redox electrocatalytic sites under atomic
and molecular level.
2) Explore and develop quasi-or solid-state electrolytes with good
chemical stability, high ionic conductivity and fire-resistant
property (Figure 5b). The general liquid electrolyte can in-
evitably lead to some safe issues during cycling, especially for
alkali metal anode. The quasi- or solid-state electrolytes pos-
sess better operability and security. Furthermore, owing to the
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solubility of some chemical products in the liquid electrolyte,
quasi- or solid-state electrolytes seem the feasible solution to
separate and obtain the chemicals.
3) Develop new types of metal-redox bicatalysis battery. Based on
the essentials and fundamental principles of these batteries
(Figure 5c), there are many other types of metal-redox bicatal-
ysis batteries to be explored and investigated. We can design
and fabricate them as needed. For example, Li-N2 /H2 battery
can be designed for efficient electrosynthesis of NH3 , which
is constructed by using Li foil as anode and redox bicatalyst as
cathode. During discharge process, N2 is reduced into Li3 N,
while H2 is oxidized into H+ during charge process. The NH3
is formed by the combination of Li3 N and H+ . The new types
of batteries based on different reactions maybe alternatives of
next generation rechargeable batteries (Figure 5d).
Acknowledgements
S.C.Y. and Y.Y.F. contributed equally to this work. This work was supported
by the National Natural Science Foundation of China (No. 22101149,
22209182, 21872147, 22022110, and 22279141), the Key Research Pro-
gram of Frontier Sciences, CAS (No. ZDBS-LY-SLH028), National key Re-
search & Development Program of China (2021YFA1501501), Fujian Sci-
ence & Technology Innovation Laboratory for Optoelectronic Information
of China (No. 2021ZZ106 and 2021ZR123), the Nature Science Founda-
tion of Fujian Province (2022J05094). Science and Technology Service Net-
work Initiative (KFJ-STS-QYZD-2021-09-003).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
chemical production, design principles, energy storage, reaction mecha-
nism, redox bicatalysis
Received: December 24, 2022
Revised: February 13, 2023
Published online: July 27, 2023
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Shichen Yan is currently an assistant professor at the Fujian Institute of Research on the Structure of
Matter, Chinese Academy of Sciences (P. R. China). He received his Ph.D. degree from Jilin University
in 2019, and later worked as a postdoctoral fellow in the Department of Chemistry, Tsinghua Univer-
sity, China. His research interests include the design and synthesis of photoelectrochemical materials.

Yangyang Feng is an associate professor at the Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Sciences (P. R. China). She received her Ph.D. degree from Chongqing University
in 2017. Her research is focused on the design, preparation and application of electrocatalysts for
energy storage and conversion.

Adv. Mater. 2023, 35, 2212078 2212078 (17 of 18) © 2023 Wiley-VCH GmbH
 15214095, 2023, 40, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202212078 by Shanghai University, Wiley Online Library on [12/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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Jing Lin is an assistant professor at the Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences (P. R. China). He received his Ph.D. degree from Fuzhou University in 2019. His
research interests include the first-principles calculation of photoelectrochemical materials.

Yaobing Wang is a professor at the Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences (P.R. China). He received his Ph.D. degree from the Institute of Chemistry, Chi-
nese Academy of Sciences (P.R. China), in 2008. His research is focused on the design and synthesis of
novel electrocatalysts and their application in energy conversion and storage.

Adv. Mater. 2023, 35, 2212078 2212078 (18 of 18) © 2023 Wiley-VCH GmbH