Advanced Materials - 2023 - Yan - Metal Redox Bicatalysis Batteries For Energy Storage and Chemical Production

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: [email protected] 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
Adv. Mater. 2023, 35, 2212078 2212078 (1 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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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
Figure 1. The common electrocatalytic oxidation and reduction reactions
can be achieved. For example, oxygen reduction combined with
and the corresponding metal-redox bicatalysis batteries reported in the
previous literatures (HER: hydrogen evolution reaction; ORR: oxygen re- oxygen evolution can construct metal–O2 battery, while carbon
duction reaction; CO2 RR: carbon dioxide reduction reaction; NRR: nitro- dioxide reduction paired with oxygen evolution can form metal–
gen species reduction reaction; HOR: hydrogen oxidation reduction; OER: CO2 battery. Therefore, it is necessary to summarize the reported
oxygen evolution reaction; MOR: molecule oxidation reaction; NOR: nitro- reduction and oxidation reactions, and the corresponding reac-
gen species oxidation reaction). tion conditions in order to be able to design new types of devices
on demand.
process to reduce CO2 into value-added carbon and hydrocarbon-

based products, including CO, CH4 , CH3 OH, HCOOH, C2 H4 , 2.1. The Reaction Mechanism in Metal-Redox Bicatalysis Battery
C2 H5 OH, and C3 + products, which is highly determined by
the redox-bicatalyst cathode.[10] The discharge voltage varies as 2.1.1. Electrocatalytic Reduction Reactions
the CO2 conversion product and the electrolyte change, leading
to variable theoretical energy densities and operating models, Hydrogen evolution reaction (HER): Hydrogen is recognized as
such as reversible and rechargeable batteries. For example, when an ideal energy carrier because of the high energy density and
paired Zn anode with 3D Pd nanosheet cathode, the Zn–CO2 bat- eco-friendliness. Accordingly, the study aims to investigate HER
tery achieves reversible reaction between CO2 and HCOOH with which serve as the cathodic reaction in water splitting among
high energy efficiency of 81.2%. Additionally, the most common various energy conversation and storage systems. During HER
model is the rechargeable Zn–CO2 battery, where the charge pro- process, hydrogen ions firstly adsorb on the surface of electrode,
cess is not the reversible reaction of discharge process. In our re- followed by Volmer reaction and Heyrovsky (electrochemical) or
cently work, the Ir@Au catalyst is applied as cathode to reduce Tafel (chemical) reactions to release H2 . HER can be carried out
CO2 to CO with 90% Faradaic efficiency during discharge pro- in acidic, alkaline and sometimes intermediate pH solutions. The
cess, meanwhile, oxygen evolution reaction (OER) occurs during reaction is described in Equation (1) and the equilibrium poten-
charging process, offering efficient rechargeable Zn–CO2 battery. tial is based on the concentration of H+ (Equation (2)).[11] The po-
Thus, the design principles of metal-redox bicatalysis batteries tentials in this review are calibrated with respect to the reversible
have strong influence on the mechanisms, operating models and hydrogen electrode (RHE)
applications.
This review will analyze the fundamentals of the design and 2H+ + 2e− → H2 (acid) (1)
construction of metal-redox bicatalysis battery rather than com-
prehensively review the advances in metal-redox bicatalysis bat- 2H2 O + 2e− → H2 + 2OH− (neutral or alkaline) (2)
teries. The main focus will be the design principles of the metal-
redox bicatalysis batteries from redox-bicatalyst cathode, metal Oxygen reduction reaction (ORR): ORR is the fundamental in
anode, aqueous/nonaqueous electrolytes, the charge/discharge various fuel devices and occupies a vital position in the fields of
voltage, and the effect of each part on the energy storage and catalysis. And it is common knowledge that oxygen can undergo a
conversion. To better design and understand the systems to meet two-electron reduction to H2 O2 involving only OOH* reaction in-
the demand among various applications, we summarize the re- termediate (Equations (3) and (4)), or direct four-electron reduc-
ported electrocatalytic reduction and oxidation reactions, and the tion to H2 O according to four steps (Equations (3)–(6)), which is
corresponding redox bicatalysts. Readers can design a new type mainly determined by whether oxygen dissociates before reduc-
of metal-redox bicatalysis battery by using various oxidation re- tion. In nonaqueous electrolyte, O2 can be reduced into O2− 2
or
actions coupled with reduction reaction under the specific elec- O2− (Equations (7) and (8))[12]
trolyte as long as the discharge/charge voltages are matched
(Figure 1). Finally, several perspectives of the key challenges and O2 + 2H+ + 2e− → H2 O2 , E 0 = 0.7 V (3)
the possible new types of metal-redox bicatalysis batteries are
given. O2 + 2H+ + 2e− → ∗ OOH + H+ + e− → H2 O2 (4)
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)
4NH3 + 2NO + 2NO2 → 4N2 + 6H2 O (29) Electrochemical water oxidation to produce H2 O2 provides an
ecofriendly on-site production. The accepted route to synthesize
4NH3 + 3NO2 → 3.5N2 + 6H2 O (30) H2 O2 is via two-electron water oxidation (Equation (35))[18]
Other reduction reaction (S, Se, SO2 , SF6 , NF3 ): Electrocat- 2H2 O → H2 O2 + 2H+ + 2e− , E 0 = 1.76 V (35)
alytic chalcogen reduction reaction (CRR), widely reported and
occurred in alkaline metal-chalcogen battery, contains a complex The two-electron oxidation may compete with the one-electron
16-electron process from S8 /Se8 ring molecules to a series of and four-electron water oxidation to generate hydroxyl and oxy-
soluble polysulfides/polyselenides (PSs). As for metal-S battery gen (Equations (36) and (37)), respectively, where the intermedi-
system, during discharging, the ring of S8 opens and reduces to ates of two-, one-, and four-electron oxidation are separative O*,
high-order MPSs of M2 Sx (6 < x < 8) and then the lower-order OH*, and OOH*. Therefore, the selective 2e− water oxidation
LiPSs of Li2 Sx (2 < x < 6) at the discharge plateaus of 2.3 and 2.1 V, is relied on the proper interaction between O intermediates and
respectively. With regard to metal-Se battery, Se8 ring molecules catalytic surface because the strong binding could induce further
reduce to polyselenides M2 Sex (x > 4) and finally to Li2 Se. How- oxidation of OH to *OH to *O and *OOH, and weak binding
ever, after the initial cycle, the chain-like Se8 can be formed in- leads to slow kinetics
stead of circle-like Se8 . The electrocatalytic SRR is presented in
Equation (31)[15]
2H2 O → O2 + 4H+ + 4e− , E 0 = 1.23 V (36)
8
S8 + 2e− → S2− (S:S, Se; x is from 1 to 8) (31) H2 O → OH∗ + H+ + e− , E 0 = 2.38 V (37)
n n
The electrolytes in CRR consists of organic solvents as CRR Oxygen evolution reaction (OER): OER has a pivotal role in hy-
is investigated in alkaline metal-chalcogen battery, in which drogen generation for electrochemical water splitting. The gen-
dimethoxyethane (DME) and 1,3-dioxolane (DOL) are generally eral mechanism for OER is the oxidation reaction of OH− in
applied as the corresponding solvents. the alkaline electrolyte (Equation (38)) or H2 O from acid solu-
In addition to CRR, sulfur dioxide reduction and conversion tion (Equation (36)), including adsorption and desorption of O*,
are significant to alleviate the hazards to environment. Com- OH*, and OOH*. First, OH− is adsorbed at the active sites and
pared with flue gas desulphurization, catalytic reduction could oxidized to OH* by coupling an electron. Then, OH* transfers
be a more simple and flexible technology. SO2 reduction often into O* by proton and electron, and finally forms O2 by combin-
combines with reducing substances, such as H2 , CO, H2 S, CH4 , ing two O*. Besides, the O* can also convert into OOH* and then
to transfer into solid sulfur.[16] The electrocatalytic sulfur dioxide change to O2 by coupling OH−
reduction is commonly found in Li–SO2 battery, which is demon-
strated as the high energy density, long-life and lightweight 4OH− → O2 + 2H2 O + 4e− , E 0 = 1.23 V (38)
battery.[17] The sulfur dioxide reduction is induced during the dis-
charging process (Equation (32))
Small molecule oxidation reaction: With the increasing demand
for energy, efficient utilization of sustainable energy is highly
SO2 + 2e− → S2 O2−
4
(32)
desirable, especially fuel cells to convert chemical into electrical
SF6 and NF3 are powerful greenhouse gases, which require con- energy. For proton-exchange-membrane fuel cell, the methanol,
version and utilization. Compared with the typical decomposed ethanol, and formic acid are oxidized to produce electron and
procedures with high energy consumption, the electroreduction carbon dioxide in the anode. The small molecule oxidation re-
by Li–SF6 and Li–NF3 systems provides a safe, efficient and mild actions, relied highly on their intermediates, are sluggish, which
strategy. Li–SF6 battery, a primary battery, owns high theoretical requires efficient catalysts to facilitate their kinetics and restrain
voltage up to 3.69 V with energy density of 3922 Wh kg−1 . And Li– the intermediates poisoning. The oxidation reactions of formic
NF3 exhibits high energy density up to 5072 Wh kg−1 in spite of acid (FAOR), methanol (MOR) and ethanol (EOR) are demon-
its irreversibility which is similar to Li–SF6 battery. The cathodic strated in Equations (39)–(41)
discharge reactions are provided in Equations (33) and (34)
HCOOH → CO2 + 2H+ + 2e− (39)
SF6 + 8e → S
− 2−
+ 6F −
(33)
CH3 OH + H2 O → CO2 + 6H+ + 6e− (40)
2NF3 + 6e → N2 + 6F
− −
(34)
CH3 CH2 OH + 3H2 O → 2CO2 + 12H+ + 12e− (41)
2.1.2. Electrocatalytic Oxidation Reactions Apart from formic acid, ethanol and methanol, urea and hy-
drazine are also viewed as the ideal alternatives for fuel cells.
Water oxidation reaction (WOR): Hydrogen peroxide (H2 O2 ), a Besides, the urea, hydrazine and ammonia are hydrogen stor-
vital chemical, has wide applications in industries and color age chemicals and the alternatives for water splitting to pro-
removal and detoxification of water. Furthermore, H2 O2 is duce hydrogen as the low theoretical voltage than water splitting.
a promising fuel cell due to its high theoretical voltage of The urea (UOR), hydrazine (HzOR) and ammonia (AOR) oxida-
1.09 V, comparable to methanol (1.09 V) and H2 /O2 (1.23 V). tion reactions contain multielectron/proton transfer. The relative
reactions are presented in Equations (42)–(44) with the electrolyte During the recharging process, reverse reactions normally oc-
of alkaline solutions[19] cur and the species produced in the charging process accept elec-
( ) trons and they are decomposed simultaneously. Moreover, some
CO NH2 2 + 6OH− → CO2 + N2 + 5H2 O + 6e− (42) functional materials involved in the electrolytes are introduced to
decrease the side reactions. For instance, the redox mediators in
N2 H4 + 4OH− → N2 + H2 O + 4e− (43) the electrolyte can promote the electron transfer to catalyze the
charging reactions. Remarkably, the redox-bicatalyst cathode af-
2NH3 + 6OH− → N2 + 6H2 O + 6e− (44) fects the performance of batteries and the preparation of the effi-
cient and stable catalysts remains a great challenge. The progress
Hydrogen oxidation reaction (HOR): In the hydrogen energy will be demonstrated in the following sections.
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- 3. Structures of Rechargeable/Reversible
kaline solution is much slower than that in acid. There are three Metal-Redox Bicatalysis Battery
steps for HOR in alkaline, including Tafel, Heyrovsky and Volmer
As shown in Figure 3a, metal-redox bicatalysis battery systems
steps. Tafel step refers to the adsorption/desorption of hydrogen
are composed of metal anode, redox-bicatalyst cathode and con-
on catalytic surface, while Heyrovsky step indicates the dissocia-
ductive electrolyte. During the discharging process, oxidization
tion of hydrogen with electron transfer to H2 O and Volmer step
reactions occur in the metal anode and reactant on the cathode
is known as the reaction of adsorbed H with OH− and electron
obtains electrons, as a result, the generation of current and con-
to form H2 O. The corresponding reactions are presented (Equa-
version between chemical energy and electric energy are com-
tions (45) and (46))
pleted. Most of electrolytes for metal-redox bicatalysis batteries,
which are conducive to enhancing the mass transport and reac-
H2 → 2H+ + 2e− (acid) (45)
tion kinetics, include alkaline solutions (NaOH/KOH), neutral
solutions (NaCl) and organic electrolytes. Their unique struc-
H2 + 2OH− → 2H2 O + 2e− (alkaline) (46)
tures endow metal-redox bicatalysis battery with different func-
tions of energy storage and chemical production. We will com-
Generally, the HOR activity widely accepted is associated by
ment on the compositions of batteries in this section.
hydroxide binding energy and hydrogen binding energy, which
is highly depended on the electrocatalysts.
3.1. Cathode
2.2. The Nature of the Batteries In the metal-redox bicatalysis batteries, the cathode is gener-
ally composed of porous materials which are beneficial to im-
The metal-redox bicatalysis battery consists of redox-catalyst cath- mobilizing or transporting the active reactants. And the ac-
ode, metal anode, aqueous/nonaqueous electrolyte, with the gas, tive species in the cathode are reduced in which the redox-
liquid and solid at cathode serving as the active species. Among bicatalyst cathode plays an important role. The redox-bicatalyst
booming metal-redox bicatalysis battery technologies, there are cathode which has drawn much enthusiasm is needed to pro-
two types of battery systems: aqueous and nonaqueous batter- mote the electrochemical reactions in the metal-redox bicataly-
ies. As is shown in Figure 2, the alkali metals are generally oper- sis batteries. Until now, various redox-bicatalyst cathodes have
ated in the nonaqueous electrolytes and the overall reactions in been designed and prepared in accordance with the following
the batteries are reversible. Nevertheless, for the aqueous elec- principles for metal bicatalysis batteries: i) fast reaction kinet-
trolyte systems, the anode reactions are reversible. Generally, ics; ii) chemical stability in various electrolytes; iii) low-cost cat-
the batteries are rechargeable in which the cathode reactions alysts; iv) promising binding force between the catalysts and
are irreversible. Based on the type of reactants, the metal-redox substrate; v) suppressed side reactions between electrolytes and
bicatalysis battery can be divided into four categories, includ- catalysts.
ing O species (Figure 2a,b), C species (Figure 2c,d), N species For nonaqueous metal batteries, the redox-bicatalyst cathode
(Figure 2e,f), and others (Figure 2g,h). The reactants include promotes the electrochemical reaction and decreases the overpo-
solid, liquid and gas, among which gas is the common reac- tential. The products will combine with the metal ions which are
tant in most cases. The reactive gas flows from the external gas generated in the anode reactions during the discharging process,
tanks into the electrochemical device with the flow controller, leading to the formation of the overall reaction products stick-
while the produced gas passes through the gas outlet into the ing to the cathode surface. During the charging process, the bat-
collector. tery product which is formed in the discharging process will de-
In these battery systems, the metals lose electrons and are compose. As a result, the reversible overall process is achieved
gradually oxidized during the discharging process. Meanwhile, (Figure 2a,c,e,g) and the batteries can be used for energy stor-
the active reactants which diffuse into the battery can accept elec- age. For aqueous metal batteries, the cathode half-reaction sep-
trons. As a result, the charging/discharging processes are fin- arate from the anode half-reaction, where the active species are
ished. During this process, the electrical energy can be gener- also catalyzed by redox-bicatalyst cathode and meanwhile some
ated with some value-added chemicals being produced for certain chemical products can be obtained in some aqueous metal bat-
types of metal-redox bicatalysis batteries. teries (Figure 2b,d,f,h).
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- reaction.[21] In other types of batteries, such as sulfur-based sys-
ode active species. The catalytic activities of metal-redox bicatal- tems, the catalysts also play a vital role in the batteries which will
ysis batteries can be enhanced by rationally designing the re- be presented in Section 4.
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 3.2. Anode
preparation of the redox-bicatalyst cathode. For instance, Guo
et al. prepared Ir nanosheet-doped CNFs which can efficiently The metal-redox bicatalysis batteries are considered as
decrease the charge overpotential and lower the charge voltage ecofriendly energy storage systems that can ascribe to the
below 3.8 V at 100 mA g−1 .[20] When the cut-off capacity was 1000 metal-based anode materials. The anodes applied in metal-redox
mAh g−1 , the corresponding Li–CO2 battery showed a long recy- bicatalysis batteries can be classified as nonaqueous alkaline
cling life of 400 cycles. Li et al. reported a CO2 electrocatalyst with metals [lithium (Li), sodium (Na), potassium (K)] and aqueous
oxygen vacancies and N dopants. The Vo-rich N-SnO2 nanosheet metals [zinc (Zn), aluminum (Al), magnesium (Mg), and iron
catalyzed the transformation of CO2 to HCOOH with a Faradaic (Fe)]. During the discharging process, metal anodes are grad-
efficiency of 83% at −0.9 V and inhibited the hydrogen evolution ually oxidized resulting in the formation of metal ions, and
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 with proper species as the electrolyte, the value-added chemi-
anodes could provide high specific capacities and wide voltage cals can be obtained in the aqueous metal-redox bicatalysis bat-
windows, there are anode passivation and corrosion which tery reactions. For example, in the aqueous electrolytes, metal–
reduce the coulomb efficiency. For example, during the charging CO2 battery systems can consume CO2 along with the generation
and discharging processes in the Li-based battery, the unwanted of carbonaceous product, such as carbon monoxide, methane,
Li dendrites will make the battery system to suffer serious side methanol and others. Additionally, NH3 can serve as a valuable
effects. Therefore, new strategy should be developed to handle product in the metal–N2 batteries. Therefore, the aqueous bat-
these issues, including developing new electrolyte. teries not only store energy but also provide chemicals, showing
bifunctional characters.
For example, current development of electrolytes in Zn–air
3.3. Electrolyte
batteries mainly include both liquid electrolytes and solid elec-
trolytes. The liquid electrolytes often suffer from leakage, there-
Electrolyte has crucial influence on the electrochemical perfor-
fore, nonliquid electrolytes which serve as transport medium
mance of the battery, including operating voltage, temperature,
have attracted more attention recently.[22] Some polymer-based
cyclic stability and rate performance. Owing to that alkali met-
electrolytes, such as solid polymer, gel polymer and composite
als are susceptible to water and oxygen, the electrolytes in al-
polymer, are among the most developed electrolytes. Gel poly-
kali metal systems require oxygen-free and water-free conditions,
mer matrix was often mixed with liquid plasticizer and/or ion-
commonly organic electrolytes. And the properties of electrolytes
conductive electrolyte solutions for further applications in the
have an important impact on the diffusion of reaction species and
batteries.[23] For example, the mechanical strength of gel elec-
products.
trolytes can be improved by mixing them with crosslinkers,
and corresponding solid polymer electrolytes can be obtained.[24]
3.3.1. Electrolyte of Aqueous Metal-Redox Bicatalysis Batteries for As an example, Chen et al. prepared a crosslinked nanocellu-
Chemical Production lose/graphene oxide as electrolyte and they investigated its ap-
plication in a rechargeable Zn–air battery.[25] In 1990s, the solid
At present, highly conductive electrolytes are still urgently needed polymer with better mechanical strength was applied in Zn–air
to improve the batteries’ performance. As is shown in Figure 3c, battery.[26] Although the solvents’ evaporation and battery leakage
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)
Overall reaction rechargeability and electrochemical performance for accessible

chemical products and high-specific-energy storage. To address
ZnO + HCOOH + H2 O → Zn + CO2 + 2H+ + 2OH− (58) the issues mentioned above, the rational design and synthesis of
redox bicatalysts seem to be a potential and effective strategy. In
In addition, OER take place when charge with high charge cur- this section, the catalysts that have been investigated for various
rent. metal-redox bicatalysis batteries will be reviewed.
Cathode
H2 O → 1∕2O2 + 2H+ + 2e− (59) 4.1. Metal O2 Batteries

Overall reaction
It remains a worthwhile objective to obtain higher energy densi-
ties in metal battery systems. The appearance of metal–O2 bat-
ZnO + H2 O → Zn + 1∕2O2 + 2H + 2OH + −
(60)
teries opened up a new research field. According to the metal an-
Only when charge voltage is over 2.135 V, OER may take place odes, the metal–O2 batteries can be classified as Li–O2 , Zn–O2 ,
in the aqueous reversible Zn–CO2 battery. 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,
3.5. Functions the redox-bicatalyst cathode which can catalyze OER and ORR re-
actions has important effects on the battery performance. Until
Based on the structure of metal-redox bicatalysis battery men- now, there has been a good deal of catalysts that have been re-
tioned above, two functions of energy storage and chemical pro- ported, such as noble metals and non-noble metal-based materi-
duction can be achieved. Generally, a much higher voltage is re- als. Chemists also take research on the nonmetallic species (e.g.,
quired for electrochemical reactions in organic electrolyte. There- carbonaceous materials) in the field of metal–air batteries. Gener-
fore, the metal-redox bicatalysis battery with organic electrolyte ally, fast reaction kinetics, chemical stability and perfect binding
often delivers higher energy density, desirable for energy stor- force between the catalysts and air electrodes are required for the
age (Figure 3b). For example, the alkali metal–CO2 batteries with redox-bicatalyst cathode. Herein, noble-metals, non-noble metals
Li/Na as anode and organic electrolyte, propose high theoretical and metal-free materials will be discussed in detail.
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- 4.1.1. Alkali Metal–O2 Batteries
ples of metal-redox bicatalysis battery, the operating efficiency,
reliability, and reversibility of alkali metal-redox bicatalysis bat- Among the advanced metal batteries, a lot of researches about
tery are mostly determined by the activity and stability of redox- Li/Na–O2 batteries have been reported for energy storage on ac-
bicatalyst cathode, where the operation efficiency is defined as count of their high specific energies. Alkali metal anode and oxy-
the specific value of reduction and oxidation voltages. The effi- gen cathode constitute their electrodes. In recent years, much
cient redox-bicatalyst can facilitate the redox reactions, reduce the progress of Li/Na–O2 batteries has been achieved, ranging from
overpotential and further enhance the operating efficiency, while materials to model devices. However, it is difficult to avoid the
the stable redox-bicatalyst can be beneficial for the reliability, and side reactions which will cause the battery’s destruction. Ad-
reversibility. ditionally, the organic electrolyte and carbon cathode are easy
Separately, aqueous metal-redox bicatalysis battery often ex- to be attacked by the oxygen species, resulting in various side
hibits much lower theoretical energy density of less than reactions.[34]
1000 Wh kg−1 . Notably, the various discharging products can be In terms of Li–O2 battery systems, the charging product Li2 O2
achieved in aqueous systems. As observed in low energy den- often leads to the decomposition of carbon materials when the
sity region of Figure 3b, the metal-redox bicatalysis batteries can charge voltage exceeds 3.5 V. Additionally, when charge voltage
produce chemical productions, such as value-added carbon and is above 4 V, most electrolytes are not stable enough to decom-
hydrocarbon-based chemicals in Zn–CO2 battery, hydrogen in pose. Hence, it is necessary to tackle this problem by reducing
Zn–H2 O and Zn–N2 H4 batteries (Figure 3c). It is concluded that the charge potential. Developing novel OER catalysts is benefi-
the aqueous metal-redox bicatalysis batteries generally own dual cial to achieve this aim. And the categories of OER catalysts in-
functions of energy storage and chemical production. 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-
4. Redox Bicatalysts brid material was used as the catalyst by Nazar et al..[35] They
found that Co3 O4 could reduce LixO2 species’ binding energy and
Toward to the various types of reported metal-redox bicatalysis promote their surface transport, leading to a lowered charge po-
batteries, huge challenges still exist for practical application, such tential below 3.8 V. Wen et al. systematically studied the factor
as sluggish conversion dynamics, high energy decomposition of catalyst activity by comparing various OER catalysts in the Li–
barrier, structural decomposition and complex reaction steps, O2 battery.[36] The surface acidity of catalysts is found as a crucial
which can result in low efficiency, poor rate performance and role to change the desorption energies of Li+ and O2 . They fur-
stability. Therefore, it is urgent to enhance the reaction kinetics, ther corroborated their observation by DFT calculations. On the
basis of the theoretical calculations, the OER activity of the pre- the Fe–N–C catalyst by Wang et al. This catalyst endowed the bat-
pared the CoO catalyst was comparable to that of Co3 O4 (similar tery with a power density of 235 mW cm−2 which could light a
charge potential at 3.5 and 4.05 V at 0.1 mA cm−2 and 1000 mAh LED screen.[50]
g−1 ). On the basis of this research, the principle about how to reg- Compared with Zn–O2 batteries, the investigations of Mg–O2
ulate the catalysts’ activity will be applied in more studies. Com- batteries are still limited. Although Mg–O2 batteries have a the-
pared with Li metal, Na has similar nature. Consequently, most oretical open-circuit voltage value of 2.95 V, the power output
catalysts for Li–O2 battery can efficiently promote the reactions of of most Mg–O2 batteries is below 100 mA cm−2 . This can as-
Na–O2 battery. For example, the Ru-based materials were proved cribe to the Mg corrosion. During the charging recharging pro-
to be efficient for catalyzing Na2 O2 oxidation.[37] cess, O2 is reduced to OH− while Mg is oxidized into Mg2+ .
The cycling stability is an important aspect for designing bat- When the battery system is operated in an alkaline electrolyte,
teries, and surface coating of electrode materials was found to the Mg anode will be coated with Mg(OH)2 which can hinder
be an efficient method. Zhou et al. introduced a CNT@RuO2 the continuous discharge of the battery. Owing to that Mg is
material with core–shell structure as redox bicatalyst for ORR not stable in acidic electrolytes, neutral electrolyte is selected as
and OER.[38] The Li–O2 battery had a decreased voltage gap from an ideal choice to avoid the metals’ corrosion. For example, Li
1.16 to 0.3 V and exhibited enhanced cyclic stability for 100 cy- et al. utilized a hybrid catalyst (mullite SmMn2 O5 , fluorite CeO2
cles. In addition to the inorganic catalysts which can reduce and spinel Mn3 O4 )[51] to improve the ORR catalytic activity that
the side reactions, conductive polymers can also play the sim- was comparable to Pt/C catalysts. As a result, the Mg–O2 batter-
ilar role, such as poly(3,4-ethylene dioxythiophene) (PEDOT), ies exhibited an OCV of 1.65 V although the OCV dropped to
polyimide (PI) and polyaniline (PANI). Lee et al. synthesized 1.22 V later. When applying 1.0 mA cm−2 , it could keep stable for
a PI-wrapped carbon nanotube (CNT) to improve the stability 290 min.
of Li–O2 battery (Figure 4f).[39] When the electrolyte was 1 m In aqueous Al–O2 battery systems, Ag/metal oxide compos-
LiTFSI/TEGDME, its cycling stability was found to be twice ites, metal oxide/carbon composites and perovskite-type oxides
improved at 1500 mAh g−1 . They found that the byproducts constitute the types of active ORR catalysts. For example, Liu et al.
such as CH3 CO2 Li and HCO2 Li were suppressed which was synthesized a series of perovskite-based ORR catalysts in the Al–
observed from SEM and FTIR spectra. Subsequently, PEDOT: O2 batteries,[52] and the composite materials (Ce0.75 Zr0.25 O2 and
polystyrene sulfonate (PSS)-coated graphene electrode was de- La0.7 Sr0.3 MnO3 ) could efficiently promote the ORR process for
veloped. The side reactions were decreased between Li2 O2 and Al–O2 battery with a high-power-density of 233.4 mW cm−2 .[53]
carbon electrode.[40] Nevertheless, the stability between polymer In conclusion, chemists have paid most attention on noble metal-
and Li2 O2 is uncertain. Amanchukwu et al. demonstrated that the redox bicatalyst materials for non-lithium metal–air battery. It is
thiophene ring in PEDOT was affected by oxygen species to form a target to explore other cost-effective catalysts and rational de-
sulfone, which weakened the electronic conduction in Li–O2 sign of electrocatalysts is urgently needed, particularly for Al–O2
battery.[41] and Mg–O2 batteries.
Moreover, metal-free electrocatalysts further enrich the types
of ORR catalysts. Heteroatom-doped carbon materials have been
4.1.2. Non-Li Metal–O2 Batteries explored for catalyzing ORR process because of their stable ORR
activity.[54] Liang et al. designed a Zn–O2 battery with a specific
Many studies have been executed for ORR catalysts in the aque- capacity of 615 mAh g−1 and an energy density of 760 Wh kg−1 .
ous metal–O2 battery. Among various ORR catalyst, platinum In this battery, N-doped carbon nanofibers catalyst was used for
(Pt) based materials have been proved to be excellent catalysts.[42] catalyzing the ORR (Figure 4c).[55] Besides, for Al–O2 batteries,
Other non-Pt or less-Pt catalysts have been developed for metal– constructing N-doped graphene was workable. It showed a capac-
O2 batteries due to the high cost of platinum.[43] For instance, ity of 619 mAh g−1 , and the corresponding high energy density
Ag/carbon composites, which were prepared by loading vari- (817 Wh kg−1 ) can be achieved, which was higher than that of
ous Ag nanostructures onto different carbon substrates, served pristine graphene.[56]
as ORR catalysts for metal–O2 batteries, including Zn–O2 ,[44] Another type of fascinating catalyst is conductive polymer. For
Mg–O2 [45] and Al–O2 batteries.[46] Notably, when utilized Ag instance, silk fibroin-polypyrrole was synthesized and applied for
NPs/carbon fiber paper as catalyst, a capacity of 2917 mAh g−1 oxygen catalytic electrode in Mg–O2 batteries.[57] Consequently,
and high-power-density of 108.1 mW cm−2 were achieved. Its en- the battery voltage maintained 1.79–1.72 V and it displayed a
ergy density (4346 Wh kg−1 ) was also higher than other metal–air high-energy-density of 4.70 mWh cm−2 . Besides, it was endowed
battery with commercial Ag powders as catalyst.[47] with a power density of 64.6 μW cm−2 . In brief, metal-free cata-
It is well known that non-noble metal catalysts have many ad- lysts have presented favorable activities toward ORR and nitrogen
vantages, such as comparable activities and low-cost. As reported, atoms are most reported for doping carbon hosts. However, the
Fe/N codoped carbon catalysts have been considered as the po- doping states of heteroatoms are incredibly challenging to con-
tential candidates for primary Zn–O2 [48] and Al–O2 batteries.[49] trol.
Xu et al. prepared a Fe–N–C catalyst via pyrolyzing iron com- Although metal–air batteries have high power densities and
plex precursors and it showed a high ORR activity and excellent capacities, its development remains a great challenge caused by
stability.[48a] And the corresponding Zn–O2 battery showed a high the moisture and CO2 . It has attracted much attention to develop
capacity (727 mAh g−1 ) with the high energy density (965 Wh new type of metal-redox bicatalysis batteries with excellent perfor-
kg−1 ). Afterward, the Fe/N/C framework and bimetallic zeolitic mance. We will elaborate other redox-bicatalysis batteries here-
imidazolate framework were used as the precursors to generate inafter.
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.
4.2. Metal–C Species Batteries Transition metal-redox bicatalyst materials were accepted as ideal
substitutes. Recently, Fe atoms dispersed in 3D porous carbon
In recent years, many chemists have made efforts to transform were reported by Hu et al, where the carbon consisted of intercon-
CO2 to value-added chemicals for carbon neutrality and carbon nected S,N codoped graphene sheets.[65] This catalyst showed a
peak. And coupling CO2 transformation with energy storage sys- superior specific capacity of 23 174 mAh g−1 and maintained sta-
tems is a promising way. Recently, metal–CO2 batteries have at- ble for more than 200 cycles. The decomposition of Li2 CO3 uni-
tracted much attention for CO2 capture and transformation. Nev- formly dispersed on the HG sheet was facilitated by the catalyst
ertheless, there are many difficulties to be overcome for metal– during charging. Besides, transition metal oxide and carbides-
CO2 battery systems, including poor reversibility, high overpo- based materials have been also developed for Li–CO2 batteries
tential and low energy efficiency. Thus, catalyst’s activity should and numerous researches have been reported. For instance, Hou
be improved in metal–CO2 batteries. The catalysts for metal–CO2 et al. reported a rechargeable battery with Li anode, CO2 cathode
batteries contain noble metals and transition metals-based mate- and Mo2 C/CNT catalyst which was first used in Li–CO2 battery.
rials. Interestingly, the molybdenum in Mo2 C combined with the oxy-
Li–CO2 battery has a high theoretical energy density of gen atom of CO2 during the discharging, leading to the Li2 C2 O4
1847 Wh kg−1 . However, the active catalysts are still limited, formation.[66] Afterward, the reaction mechanism of Mo2 C in Li–
giving rise to slow reaction kinetics in most metal–CO2 batter- CO2 batteries was further studied through DFT calculations by
ies. Similar to metal–air batteries, noble metals and transition Yang et al.[67] They found that the (001) and (101) surfaces of 𝛽-
metals-based materials are explored for catalyzing the Li–CO2 Mo2 C which had lowest Gibbs free energy could catalyze the de-
battery reactions. Among a variety of noble metals, Ru has been composition of discharge product.
used for catalyzing many reactions (Figure 4d).[58] Chen et al. Additionally, covalent-organic frameworks and metal–organic
reported a redox-bicatalyst cathode consisting of Ru nanoparti- frameworks materials show great potential in the field of Li–
cles which were immobilized on carbon nanotubes for Li–CO2 CO2 battery catalysts. Dong et al. reported a 2D porphyrin-based
batteries.[59] The pore structure of carbon nanotubes promoted MOFs (MTPzP-Mn) as the cathode and the intrinsic double Mn
the diffusion of CO2 and improved the conductivity of Ru. Li2 CO3 active sites were proved to efficiently catalyze the CO2 reduction
was found as the discharge product which was investigated with during discharge and decomposition of Li2 CO3 during charge,
X-Ray diffraction of the ectopic grazing incidence synchrotron. respectively.[68] Jiang et al. prepared an ultrathin MnO2 /DQTP-
Li2 CO3 disappeared and its cubic grains covered the Ru/C dur- COF nanosheet cathode for Li–CO2 battery, which showed excel-
ing the charging process. The result showed that Ru/CNT pro- lent cycling performance and delivered a high discharge capacity
moted the decomposition of Li2 CO3 and maintained better dura- (42 802 mAh g−1 ).[69] The quinone moieties of COF nanosheets
bility than that of CNT. The authors found that the dendrites and and MnO2 synergistically enhanced the CORR/COER kinetics,
passivation materials led to the battery destruction at the operated resulting in a higher current density and longer cycling life.
capacity of 500 mAh g−1 . The reaction mechanism was revealed by DFT calculations and
Additionally, the Ru oxides also exhibit superior catalytic per- quinone group played a crucial role in activating CO2 . And at the
formance for Li–CO2 batteries, which can facilitate the decom- interface of MnO2 and COF nanosheets, the decomposition of
position of Li2 CO3 and decrease the charging voltage. Du et al. discharge product (Li2 CO3 ) occurred.
prepared a novel Li–CO2 battery assemble by RuO2 /SWCNTs Besides Li metal, other metals are also devised for metal–CO2
cathode.[60] The redox-bicatalyst cathode was synthesized by com- batteries, including Na, K, Al, Zn and so on. Earth-abundant and
bining RuO2 nanoparticles with single-walled CNTs. The bat- cost-effective (30 times cheaper than Li) Na has similar electro-
tery’s charging plateau was reduced to 4.2 V and RuO2 /SWCNTs chemically behavior. Kim et al. designed a hybrid Na–CO2 battery,
could stably catalyze the decomposition of Li2 CO3 . Remarkably, where hydrogen and electric energy were simultaneously pro-
84.99% of the charging power was utilized for CO2 generation duced through efficient CO2 conversion.[70] When utilized IrO2
and the other energy was consumed by thermal effects and and Pt/C as catalysts, the battery could be operated over 1000 h
byproducts. Whereas, the improvement of the cycle performance and CO2 was converted to NaHCO3 . The efficiency of CO2 con-
of RuO2 /SWCNTs remains a crucial challenge. version was determined to be 47.7%. Notably, CO2 cannot be re-
Furthermore, Ir and IrO2 can be utilized as redox-bicatalyst generated during the charging process in this Na–CO2 battery
cathode in Li–CO2 batteries due to their high chemical stabil- system. Only hydrogen was observed as the discharge product.
ity and they have been proved to be efficient candidates by Li Furthermore, sodium ions could act as fast ionic charge carriers
et al.[61] and Zhai et al.[62] Besides Ru and Ir based materials, Li– which was beneficial to electrochemical energy storage. Dai et al.
CO2 batteries are studied with Au and Ag as catalysts. Kong et al. first demonstrated a CO2 battery with K anode and metal-free
synthesized Au nanoparticles dotted on CNTs as redox-bicatalyst carbon-based electrocatalysts which were composed of a hybrid
cathode, which can cycle 46 times continuously.[63] Zhang et al. N-doped carbon nanotube and N-doped rGO 3D network.[71] The
prepared TiO2 nanotube arrays loading with silver nanoparticles porous architecture of N-CNT was beneficial to the electron/CO2
which were taken as active redox-bicatalyst cathode for Li–CO2 transport and storage of the discharge product (K2 CO3 ). The as-
batteries.[64] Ag ions promoted the photogenerated carriers’ sep- sembled K–CO2 battery had a cut-off capacity of 300 mAh g−1
aration and transfer on surface of the catalyst. Notably, the plas- and a cycle life of 250 cycles, respectively. A rechargeable Al–CO2
monic interaction and synergistic photoelectric effect accelerated battery was demonstrated by Ma et al. and they synthesized a Pd-
the oxidation and reduction of CO2 in the batteries. coated porous gold (NPG@Pd) pieces.[72] In this catalyst, Pd was
Although the precious metals have superior performance for taken as the active sites for CO2 reduction and NPG promoted
Li–CO2 batteries, their high cost hinders it further applications. electronic conductivity. Therefore, CO2 can be cycled in the
cathode. The battery showed an energy efficiency of 87.7% and resistance. The researches testified that introducing conductive
a low charge/discharge voltage gap of 0.091 V, smaller than that carbons and polymers into sulfur electrodes is accepted as an ef-
of Li–CO2 , Na–CO2 , and Al–air batteries. 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
4.3. Metal–N Species Batteries 440 mAh g−1 .[79] As a result, better cyclability was obtained and
many chemists devoted themselves to developing sulfur-porous
N2 fixation into valuable chemicals is critical for developing var- carbon composites. For instance, Ji et al. reported a battery with
ious fields that sustain human life. Nevertheless, energy con- the specific capacity of 1320 mAh g−1 which was benefiting from
sumption is inevitable in traditional Haber–Bosch process which the sulfur-mesoporous carbon composite.[80] Furthermore, vari-
results in environmental pollution. It has become a critical ous metal-based materials have been applied for catalyzing the
challenge to develop ecofriendly technologies. As a promising electrochemical reactions, such as metal sulfide, metal oxide,
platform, metal–N2 battery systems provide a simple and effi- metal carbide and metal nitride based catalysts. Nazar et al. uti-
cient strategy for simultaneous artificial N2 fixation and power lized Ti4 O7 as the catalyst to promote electron transfer and mean-
generation. Metal–N2 batteries also possess high energy density, while the transformation of the polysulfides (Figure 4e).[81] Sub-
meanwhile, NH3 which is generated through electrochemical N2 sequently, Pt, Ni, etc. metal catalysts were investigated to catalyze
reduction reaction (NRR) is an attractive product. In this pro- sulfur redox reactions in Li–S batteries.[82]
cess, catalysts have a significant effect on electrochemical N2 fix- For instance, NiMoO4 dotted on N,S codoped carbon cloth for
ation. Zhang et al. first illustrated a Li–N2 battery with Ru-CC Li–S batteries was reported by Wang’s group.[83] They found that
as the redox-bicatalyst cathode. The potential became more posi- Mo reduced the band gap and improved the electron density near
tive and the current density was larger than those of ZrO2 -CC or the Fermi energy level, as a result, the Li–S battery was endowed
pure CC cathode.[73] Besides, a longer cycle life was achieved for with an excellent cycling stability. Moreover, it is well known that
Li-N2 batteries constructed by Ru-CC and ZrO2 -CC catalysts. In the accumulation of a large amount of Li2 S can reduce the oxi-
addition, compared with pure N-doped carbon nanosheets (NC), dation kinetics during charging owing to the affinity of the active
ultrasmall Mo2 C particles dispersed on NC were more efficient sites of metal catalysts toward to polysulfides. The heterostruc-
N2 electroreduction catalyst. The Li–N2 battery further enriched tures have been found to efficiently promote sulfur reaction ki-
the types of energy storage devices. Nevertheless, low Faraday ef- netics and accelerate charge transfer which is beneficial for the
ficiency, unfavorable reaction kinetics, poor NH3 selectivity and Li–S batteries.[84] Chu et al. reported a highly efficient catalyst
high overpotential of most of the reported NRR electrocatalyst consisting of the CoSe2 /Co3 O4 heterostructures with NC layers
will affect their electrochemical performance.[74] and CNT.[85] In this heterostructure, polysulfides were adsorbed
Furthermore, Yang et al. for the first time demonstrated a at the Co3 O4 interface and catalyzed by CoSe2 . The result showed
lithium–nitrogen dioxide (Li–NO2 ) battery without any catalysts that the shuttle effect was restrained by CoSe2 /Co3 O4 @NC-CNT
which was used for the reduction of nitrogen dioxide (NO2 ) at and the cathode delivered an initial capacity of 1457 mAh g−1 at
room temperature.[75] This Li–NO2 battery’s capacity was 884 0.1 C.
mAh g−1 and the Faraday efficiency reached 67%. This research As one type of lithium batteries, the lithium-sulfur dioxide (Li–
not only increases the types of gas available in rechargeable bat- SO2 ) battery with SO2 as the cathode has many advantages, such
teries but also provides a way to recycle NO2 . Owing to the un- as excellent working life, high cell voltage and wide operating
satisfactory efficiency of electrochemical NRR, other metal–N temperature range and high energy density. Lim et al. used LiI as
species batteries are also developed.[76] Nitrate electroreduction a model catalyst and achieved the first rechargeable Li–SO2 bat-
(NORR) into NH3 is explored as a potential alternative for NH3 tery with a capacity of 5400 mAh g−1 at 3.1 V.[86] The discharge
production.[77] A Pd-doped TiO2 catalyst which was used to pro- product, Li2 S2 O4 , was reversibly formed and decomposed. How-
duce NH3 with a yield of 1.12 mg cm−2 h−1 was reported by ever, the cycling performance is still limited and more efforts
Chunyi Zhi et al. And its Faradic efficiency reached 92.1%. They should be made for suppressing the byproducts to enhance the
also proposed a Zn-nitrate cell with a high NH3 FE of 81.3% and cyclicity.
power density of 0.87 mW cm−2 for the first time.[78]
4.5. Other Metal-Redox Bicatalysis Batteries

4.4. Metal–Chalcogen Batteries
In addition to a wide variety of metal redox bicatalysis batteries
In recent years, metal–chalcogen batteries have attracted an in- mentioned above, there are still many other high-performance
creasing research attention because of the environmental friend- battery systems. The Li–SOCl2 battery was first reported by Ga-
liness and high theoretical energy density. Hebert and Ulam gave bano in 1969. And the catalysts have an important influence
a proof-of-concept report using sulfur as the cathode material in on the discharge capacity and operating voltage. For instance,
1962. Owing to the considerably higher specific energy of Li–S platinum can greatly improve cells’ performances.[87] Moreover,
batteries (2600 W h kg−1 ) than that of lithium-ion batteries, more other pure metals also have a catalytic effect in Li–SOCl2 batter-
recently, a lot of original researches have been conducted to de- ies, including copper, iron, silver and palladium. Copper powders
velop metal–chalcogen batteries with high energy density. How- play a catalytic role on the Li–SOCl2 cells.[88] The transition metal
ever, there are some issues that impede the high energy density, complexes are also employed as catalysts to improve the perfor-
such as self-discharge and capacity degradation and high internal mance of Li–SOCl2 cells and Co and iron phthalocyanines are
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- and almost 100% H2 Faradic efficiency. The entire battery pos-
sity, long working life and good low temperature performance, sessed a power density of 80 mW cm−2 and an energy density of
the voltage delay should be solved for Li–SOCl2 cells. 934 Wh kg−1 . Besides, the catalyst could maintain H2 output for
In contrast, metal–H2 O batteries can simultaneously gener- a long time when tested at 1.16 V under 10 mA cm−2 .
ate electrical energy and hydrogen although there are some Owing to the intrinsic architectural advantages of MOFs,
critical problems, such as low efficiency of H2 production and they are also explored as cathodes for Zn–H2 O battery. Hou
low output of electrical energy. Recently, Wang et al. proposed et al. prepared Ni-MOF/Ni2 P@EG with nickel-based MOFs
a Li–H2 O battery with Pt-decorated Ni3 N nanosheet as redox- (Ni-MOFs) deposited on exfoliated graphite (EG), followed by
bicatalyst cathode.[89] This integrated cell could sustain hydrogen phosphorization.[91] When applied in alkaline Zn–H2 O cell, high
production for more than 60 h. Hydrogen can serve as a clean stability and power density (4.1 mW cm−2 ) were obtained. The
energy which is produced by water splitting in the battery, and electricity generation and hydrogen production were realized
electricity generate simultaneously. Furthermore, Zn–H2 O bat- simultaneously in this alkaline Zn–H2 O battery. Subsequently,
teries are also demonstrated as new type of devices. For instance, they designed a hybrid catalyst which was configured with Mo-
Wen et al. reported an alkaline-acid Zn–H2 O fuel cell, where doped WC core and N-doped carbon (Mo-WC@NCS). They
the redox-bicatalyst cathode was constructed by Pt nanoparticles found that Mo doping onto tungsten carbide could tune the d-
loaded on the carbon nanotubes on carbon cloth and Zn plate band center for hydrogen evolution. The obtained Mo-WC@NCS
served as the anode.[90] It kept an open circuit voltage of 1.25 V hybrid delivered an overpotential of 179 mV at 10 mA cm−2 for
HER., And the power density of 41.4 mW cm−2 was reached in solubility of some chemical products in the liquid electrolyte,
alkaline-acid Zn–H2 O cell because the Mo-WC@NCS hybrids quasi- or solid-state electrolytes seem the feasible solution to
could keep H2 generation for a long-term.[92] separate and obtain the chemicals.
Moreover, Wei et al. proposed a Zn–H2 O2 battery in which car- 3) Develop new types of metal-redox bicatalysis battery. Based on
bon nanosheet doped with Co/N (Co/N-CNS) was used as a mul- the essentials and fundamental principles of these batteries
tifunctional catalyst and hydrogen peroxide provided oxygen for (Figure 5c), there are many other types of metal-redox bicatal-
the battery.[93] The activated carbon and Co/N-CNS-750 exhibited ysis batteries to be explored and investigated. We can design
catalytic rates of 199 and 1164 mL g−1 min−1 for H2 O2 decompo- and fabricate them as needed. For example, Li-N2 /H2 battery
sition. Enhanced rate performance from 20 to 120 mA cm−2 was can be designed for efficient electrosynthesis of NH3 , which
observed in the Zn–H2 O2 battery. And its discharge performance is constructed by using Li foil as anode and redox bicatalyst as
at 120 mA cm−2 was 23% which was higher than that of the cathode. During discharge process, N2 is reduced into Li3 N,
Zn–air battery. Benefiting from its excellent performance, a red while H2 is oxidized into H+ during charge process. The NH3
LED array can be lightened. 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).
5. Summary and Prospective
In this review, we summarize the design principles of the metal-
Acknowledgements
redox bicatalysis batteries, including the fundamentals and devel-
opment of redox-bicatalyst cathode, anode and electrolyte. Based S.C.Y. and Y.Y.F. contributed equally to this work. This work was supported
on the high-energy-density and cost-effective advantages, metal- by the National Natural Science Foundation of China (No. 22101149,
redox bicatalysis batteries represent one of the potential technolo- 22209182, 21872147, 22022110, and 22279141), the Key Research Pro-
gram of Frontier Sciences, CAS (No. ZDBS-LY-SLH028), National key Re-
gies for ever-increasing energy requirements. In recent years, search & Development Program of China (2021YFA1501501), Fujian Sci-
promising progress has been achieved in the field of metal-redox ence & Technology Innovation Laboratory for Optoelectronic Information
bicatalysis batteries, while many challenges still remain to be ad- of China (No. 2021ZZ106 and 2021ZR123), the Nature Science Founda-
dressed. In this review, the mechanisms of the batteries and re- tion of Fujian Province (2022J05094). Science and Technology Service Net-
dox bicatalysts have been summarized. On the basis of the design work Initiative (KFJ-STS-QYZD-2021-09-003).
principles, the corresponding anodes, cathodes, electrolytes and
theoretical energy densities are presented. In particular, the ad-
Conflict of Interest
vancement of a variety of redox bicatalysts is discussed in this
review. For nonaqueous metal-redox bicatalysis batteries, most The authors declare no conflict of interest.
components are sensitive to moisture and should be assembled
under inert atmosphere. Generally, nonaqueous batteries pos-
sess higher energy densities than aqueous counterparts. Never- Keywords
theless, in aqueous species, such as Zn–CO2 batteries, energy chemical production, design principles, energy storage, reaction mecha-
storage and chemical production can be achieved simultaneously. nism, redox bicatalysis
However, novel redox bicatalysts need to be developed to decrease
the energy barrier and overcome the sluggish reaction kinetics. Received: December 24, 2022
In spite of great progress in this field, there are still consider- Revised: February 13, 2023
able scientific and technological challenges to restrict the practi- Published online: July 27, 2023
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.
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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.
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.

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Metal-Redox Bicatalysis Batteries for Energy Storage and

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

2. The Fundamentals of Rechargeable/Reversible

process to reduce CO2 into value-added carbon and hydrocarbon-

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