1720768296_61589_a575f3a3b6f7763de66d30b8c32e3e67

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Forschungsartikel Chemie
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Zitierweise: Angew. Chem. Int. Ed. 2023, 62, e202304852

Electrocatalysis Hot Paper doi.org/10.1002/anie.202304852
Rechargeable Biomass Battery for Electricity Storage/generation and

Concurrent Valuable Chemicals Production
Jing Li, Kaiyue Ji, Boyang Li, Ming Xu, Ye Wang, Hua Zhou, Qiujin Shi, and
Haohong Duan*
due to their intermittence and uneven distribution. This

Abstract: The development of a rechargeable battery prompts the development of advanced battery technologies,
that can produce valuable chemicals in both electricity such as Li/Na ion,[1] Li metal,[2] Zn MnO2,[3] Zn-air,[4] Li S,[5]
storage and generation processes holds great promise and redox flow batteries.[6] However, the economic viability
for increasing the electron economy and economic of these batteries remains challenging due to the high capex
value. However, this battery has yet to be explored. from materials, device investments, operation and main-
Herein, we report a biomass flow battery that generates tenance costs, etc. Typically, the electricity charging/dis-
electricity while producing furoic acid, and store elec- charging processes over these batteries are coupled with
tricity while yielding furfuryl alcohol. The battery is electrochemical redox reactions with mediocre product
composed of a rhodium-copper (Rh1Cu) single-atom value. For instance, in a typical Zn-air battery, oxygen
alloy as anode, a cobalt-doped nickel hydroxide evolution reaction (OER) and oxygen reduction reaction
(Co0.2Ni0.8(OH)2) as cathode, and furfural-containing (ORR) take place when electricity is charged and dis-
anolyte. In a full battery evaluation, this battery displays charged, respectively, with outcome O2 and H2O as the
an open circuit voltage (OCV) of 1.29 V and a peak products with low value (Figure S1a). It would be attractive
power density up to 107 mW cm 2, surpassing most to couple the electricity storage/generation processes with
catalysis-battery hybrid systems. As a proof-of-concept, electrochemical reactions that produce valuable chemicals
we demonstrate that this battery produces 1 kg furoic or fuels, which would potentially reduce the cost and
acid with 0.78 kWh electricity output, and yields 0.62 kg increase the electron economy and economic value of the
furfuryl alcohol when 1 kWh electricity is stored. This battery system.
work may shed light on the design of rechargeable Recently, hybrid systems by coupling Zn anode with
batteries with value-added functionality such as chem- active cathodes at which value-added reactions are taking
icals production. place have been reported, such as Zn H2O,[7] Zn C2H2,[8]
Zn NO3 ,[9] and Zn NO2 [10] batteries (Scheme 1a and Fig-
ure S1b). These systems generate electricity and simulta-
neously deliver valuable chemicals or fuels at cathodes (H2,
Introduction C2H4, NH3, etc.). However, Zn is a sacrificial anode in these
batteries, the so-called galvanic batteries, which are hardly
Energy storage is essential to harness the increasing capacity rechargeable because of the sluggish kinetics of OER at the
of renewable energy sources (from surplus solar and wind) cathode thus decreasing energy efficiency during electricity
storage process.[11] Another hybrid system is called direct
[*] Dr. J. Li, K. Ji, Y. Wang, Q. Shi, Prof. H. Duan
alcohol fuel cell (DAFC) (Scheme 1b and Figure S1c), which
Department of Chemistry, Tsinghua University generates electricity and carbon-based chemicals simulta-
Beijing 100084 (China) neously by coupling ORR and alcohol (methanol, ethanol,
E-mail: hhduan@mail.tsinghua.edu.cn glycerol, etc.) oxidation processes; nevertheless, this battery
K. Ji, Prof. H. Duan is also non-rechargeable.[12] The non-rechargeability of the
Haihe Laboratory of Sustainable Chemical Transformations above two representative batteries is because of the non-
Tianjin 300192 (China) redox feature of the substrates for electrochemical reactions.
B. Li Recently, rechargeable Li CO2 and Zn CO2 batteries were
Zhili College, Tsinghua University reported (Scheme 1c and Figure S1d), using the redox
Beijing 100084 (China) cycling between CO2 and its reductive derivatives (C, CO,
Prof. M. Xu, Prof. H. Zhou or HCOOH), but the re-oxidized product CO2 shows low
State Key Laboratory of Chemical Resource Engineering College of value.[13] As a result, a rechargeable battery that can
Chemistry, Beijing University of Chemical Technology
generate valuable products in both electricity storage and
Beijing 100029 (China)
generation processes holds great promise, but yet to be
Prof. H. Duan
explored.
Engineering Research Center of Advanced Rare Earth Materials,
(Ministry of Education), Department of Chemistry, Tsinghua In principle, a molecule with redox ability towards
University oxidative and reductive products shows potential as the
Beijing 100084 (China) reactant for the conceived rechargeable battery. Furfural is
Angew. Chem. 2023, 135, e202304852 (1 of 10) © 2023 Wiley-VCH GmbH

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Scheme 1. Electrocatalysis-battery hybrid systems. Previous works: a) Zn-based galvanic batteries. b) direct alcohol fuel cell (DAFC). c) rechargeable
Zn/Li CO2 batteries. This work: d) working principle of rechargeable biomass battery.
a renewable chemical feedstock that can be produced from furfuryl alcohol is close to hydrogen redox (E0 = 0.83 VSHE)
corncobs and woods, and is listed as one of the “Top 10” at pH 14 (Figure 1a, Table S1, S2), making it conceptually
biomass-platform molecules by the United States Depart- possible, if an efficient catalyst is used, to couple with
ment of Energy (DOE) in 2010.[14] Its oxidative derivative, furfural-to-furoic acid at similar potential region. Therefore,
furoic acid, is an important feedstock in medicines, fragran- the redox feature of furfural inspires us to design a
ces, and plastics industries (Figure S2). Electrooxidation of rechargeable biomass battery for electricity storage/gener-
furfural to furoic acids has stimulated great interest due to ation and furfural reduction/oxidation at the same time. The
the benign reaction condition and ideally it can be driven by challenge lies in the design of a high-performance electro-
renewable energy.[15] This transformation can be achieved catalyst with bifunctionality to achieve both furfural reduc-
over transition metal-based electrocatalysts with high far- tion/oxidation in high efficiency, in terms of activity,
adaic efficiency (FE), but a relatively high voltage selectivity, and FE. In addition, an optimal battery electrode
(> 1 VRHE) is required to reach high current density,[16] is also required to meet the critical metric of a practical full
making it previously infeasible to couple with ORR for battery including capacity, power density, and energy
electricity generation in a battery. Recently, Wang and co- density.
workers achieved this battery by lowering the potential of Herein, we report a rechargeable biomass battery
furfural-to-furoic acid at near 0 VRHE (or 0.83 VSHE at (schematically depicted in Scheme 1d) that stores electricity
pH 14) over copper (Cu) catalysts.[17] Nonetheless, this while producing furfuryl alcohol from furfural (marked in
battery is unable to store electricity while producing orange), and generates electricity while producing furoic
reductive chemicals, analogous to the aforementioned acid from furfural (marked in blue). The anode catalyst was
DAFCs hybrid system. prepared by doping rhodium in copper framework, with the
In fact, furfural shows redox ability owing to the formation of rhodium-copper (Rh1Cu) single-atom alloy,
existence of aldehyde group, and its reduction product, delivering higher FE towards furfuryl alcohol compared
namely furfuryl alcohol, can find broad use in manufacturing with Cu (73 % vs. 22 %) at 0.2 VRHE in furfural reduction,
furan resins, preservatives, lubricants, and fuels. The calcu- yielding furoic acid production in high efficiency in furfural
lated standard equilibrium potential (E0) of furfural-to- oxidation. A cobalt-doped nickel hydroxide (Co0.2Ni0.8-

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Figure 1. Electrode and electrochemical reactions screening. a) The reaction axis of Zn stripping/plating, furfural redox, and Ni(OH)2/NiOOH
redox. b) CV curves of Ni(OH)2 cathode and Cu anode (with and without furfural) in 1 M KOH anolyte at a scan rate of 2 mV s 1. c) OCVs recorded
by electrochemical workstation.
(OH)2) was fabricated as the cathode for high capacity and ure S4). The potential gap between oxidation and reduction
increased OCV. In a full battery evaluation, the battery potential (ΔE, ΔE = Eoxidation Ereduction) at a current density of
displays high discharge capacity (19.6 mAh cm 2, corre- 10 mA cm 2 was only 0.17 V (Figure S5), which is lower than
sponding to � 150 mAh g 1), coulombic efficiency (95 % at that (ΔE is usually in the range of 0.6–0.8 V) of OER/ORR
20 mA cm 2), energy density (19.8 mWh cm 2) and energy couple in Zn-air battery,[18] making furfural redox a promis-
efficiency (62 %), comparable with mainstream batteries. ing redox selection at one electrode in a rechargeable
More importantly, the integrated battery produces 1 kg battery.
furoic acid while 0.78 kWh electricity is generated, and It should be noted that in a conventional rechargeable
yields 0.62 kg furfuryl alcohol while 1 kWh electricity is battery, reactions at both electrodes are composed of
stored, showing increased economic value to the electricity reversible couples to store and release charges, as shown by
storage/generation processes. Zn/Zn(OH)2 and OER/ORR couples in Zn-air battery.
Since furfural and its reduced (furfuryl alcohol) or oxidized
products (furoic acid) are not reversible couples, this
Results and Discussion requires the reaction at counter electrode to be reversible to
make the battery rechargeable.[19] The counter electrode is
Rechargeable biomass battery design and electrode redox ideally low-cost and a buffer reservoir that is able to rapidly
screening accept and release charges with high battery capacity (Q). It
should also offer a large potential difference (ΔU) without
For the rechargeable battery design based on furfural redox, HER or OER occurring when coupled with furfural redox,
the electrocatalyst at one electrode should be catalytically thus endowing the battery with high energy density (E =
bifunctional for both furfural-to-furoic acid and furfural-to- QΔU) and power density (P = iΔU) (Figure 1a). Therefore,
furfuryl alcohol conversions. Metallic Cu was initially the OCV of a battery is a prerequisite for large ΔU.
employed in this work owing to its catalytic activities both in Considering the high theoretical capacity (Q = 820 mAh g 1),
furfural oxidation and reduction (Figure 1b). Cu was a Zn/Zn2 + redox pair was firstly evaluated. We constructed
prepared by annealing commercial Cu foam to give Cu a Zn( )/Cu(+) battery with furfural in 1 M KOH catholyte,
oxide, followed by an electroreduction process (Figure S3). namely Zn-furfural battery. However, OCV of the Zn-
By OCV measurements, the potential of furfural redox over furfural battery was measured to be merely 0.42 V (Fig-
Cu was further determined at 0.83 VSHE in pH 14 (Fig- ure S4), which is owing to the small potential difference

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between Zn/Zn2 + redox ( 1.25 VSHE) and furfural redox efforts to catalyst optimizations for both furfural reduction
( 0.83 VSHE). Thus, the energy and power density of the and oxidation processes. An H-cell reactor was initially used
battery would be very limited without practical significance. to simplify the study.
To increase OCV, an anode with redox potential more For furfural reduction over Cu, the linear sweep
negative than that of Zn/Zn2 + redox pair would be voltammetry (LSV) curves show that current density is
conceptually possible. However, hydrogen evolution reac- notably enhanced before the onset potential (ca.
tion (HER) is kinetically more favorable than the anode 0.15 VRHE) of HER (Figure S6), suggesting furfural elec-
plating process in an aqueous electrolyte, which would result troreduction is more preferential than HER and can occur
in server irreversibility for this battery (Figure 1a). To without utilizing adsorbed hydrogen species (H*). However,
address this issue, we conceive nickel hydroxide/nickel by analyzing high-performance liquid chromatography
oxyhydroxide pair (Ni(OH)2/NiOOH) might be a suitable (HPLC) results, the selectivity toward furfuryl alcohol is
redox to couple with furfural redox in the rechargeable lower than 20 % at 0.2 VRHE owing to the formation of
battery, due to its higher theoretical redox potential dimer (1,2-di(furan-2-yl)ethane-1,2-diol) as byproduct via
(0.49 VSHE).[20] In the Ni(OH)2/NiOOH redox, Ni(OH)2 is furfural dimerization, and also furoic acid via Cannizzaro
oxidized to NiOOH in the charging process, while the reaction (Figure S7). The actual FE of furfuryl alcohol
reverse transformation (namely, NiOOH is reduced to (deduction of the contribution by Cannizzaro reaction of
Ni(OH)2) takes place in the discharging process. Based on furfural) is merely 22 % at 0.2 VRHE (Figure S8). Recent
this concept, we constructed a Cu( )//Ni(OH)2(+) battery studies showed that integrating certain metal into Cu
(Figure 1b), which delivers an OCV of 0.82 V in the absence increased FE of furfuryl alcohol in electroreduction of
of furfural, and more importantly, gives an OCV of 1.31 V furfural,[21] by promoting water dissociation that facilitates
when furfural is added to the anolyte (Figure 1c and the generation of adsorbed H* species for furfural hydro-
Figure S4), indicating its great potential as a high-perform- genation. Therefore, we doped Cu with different metals
ance biomass battery. Noteworthy, the counter electrode is (Ag, Au, Pt, Pd, Ru, Rh) that potentially show activity in
not limited to Ni(OH)2/NiOOH couple in this work. Other water dissociation by a galvanic replacement method (Fig-
redox couples (such as V2 + /V3 +, Fe2 + /Fe3 +, Cr2 + /Cr3 +, etc.) ure S9). Among the samples, Rh-doped Cu (thus, Rh1Cu)
in a general redox flow battery, may also be applicable. gives the highest FE of furfuryl alcohol and the lowest FE of
dimer (Figure S10). In the potential range ( 0.15–
0.35 VRHE), Rh1Cu (Figure 2a) exhibits a similar current
Anode catalyst optimization for furfural conversions density to Cu (Figure S6), but significantly higher FE of
furfuryl alcohol (73 %) compared with that of Cu (22 %) at
Considering that the catalytic performance for furfural 0.2 VRHE (Figure 2b and Figure S11). Time-dependent
redox is a decisive factor to determine the economic value furfural electroreduction study further shows that the
of the conceived biomass battery, we then devoted our
Figure 2. Electrochemical evaluation and characterizations of Rh1Cu anode. Furfural reduction: a) LSV curves (without iR correction) in 1 M KOH
with or without 30 mM furfural. b) Faradaic efficiency of furfuryl alcohol, hydrofuroin dimer, and H2 under the potential from 0.15 to 0.35 VRHE.
Furfural oxidation: c) LSV curves (without iR correction) of Rh1Cu in 1 M KOH with and without 30 mM furfural. d) Faradaic efficiency of furoic acid
under the potential from 0.1 to 0.5 VRHE. e) HAADF-STEM images of Rh1Cu. f)–h) STEM-mapping of Rh1Cu. i) XANES spectra and j) Fourier-
transformed EXAFS spectra of Rh K-edge of Rh foil, Rh2O3, and Rh1Cu, respectively. Scale bars: 2 nm (e); 50 nm (f)–(h).

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selectivity of furfuryl alcohol increases up to 60 % over appropriate bi-functional catalyst among the metal-doped
Rh1Cu at 0.2 VRHE (Figure S7 and Figure S12). Cu catalysts for further studies, because it gives lower
To understand the pivotal role of Rh for enhanced dimers production during electroreduction of furfural-to-
furfuryl alcohol production, we conducted more electro- furfuryl alcohol.
chemical studies. As indicated by the LSV curves (Fig- The physicochemical properties of Rh1Cu catalyst were
ure S13a), Rh1Cu gives a much lower overpotential than Cu then investigated. Rh1Cu catalyst shows the same diffraction
in HER (in the absence of furfural), suggesting Rh1Cu’s peaks as Cu catalyst in X-ray diffraction (XRD) pattern
higher activity for water dissociation. In the absence of which is assigned to metallic Cu (JCPDS 04-0836) after
furfural, the CV curves of Rh1Cu from 0.1 to 0.2 VRHE electroreduction (Figure S22). The absence of Rh diffraction
(Figure S13b) reveal an obvious desorption peak that can be signals is probably due to either the extremely low Rh
assigned to active H* species, while no such peak was loading (0.13 wt %, determined by inductively coupled
observed over Cu. The promoted water dissociation to plasma mass spectrometry (ICP-MS) or the atomic disper-
produce H* species over Rh1Cu in the absence of furfural sion of Rh. The dispersion state of Rh was verified by high-
was then verified by its smaller Tafel slope (113 mV dec 1 angle annular dark-field scanning transmission electron
for Rh1Cu and 122 mV dec 1 for Cu) (Figure S14), which microscopy (HAADF-STEM). The microscopy images show
suggests a faster rate-determine step (RDS), namely the that Rh atoms are isolated in the lattice structure of Cu
Volmer step in water dissociation for H* species production. nano-skeleton without observation of Rh clusters or nano-
According to Chadderdon’s and our previous mechanistic particles (Figure 2e and Figure S23), indicative of Rh1Cu in
studies,[21a, 22] the H*-deficient electrochemical surface of Cu a single-atom alloy form. The energy-dispersive spectro-
may favor the direct C C coupling of ketyl radical scopy (EDS) mapping analysis also indicates the uniform
intermediates to form dimerization products via proton- distribution of Rh species (Figure 2f–h). To obtain the
coupled-electron-transfer (PCET) mechanism; while the H*- chemical state and coordination environment information of
rich electrochemical surface of Rh1Cu may favor the electro- the Rh species, X-ray absorption spectroscopy (XAS) was
chemical hydrogenation (ECH) route for enhanced furfural carried out. The X-ray absorption near-edge spectroscopy
reduction (Figure S15). Noteworthy, in the presence of (XANES) at the Rh K edge reveals that the valence of Rh
furfural, Cu exhibits a significantly lower Tafel slope species is close to that in Rh2O3 as indicated by the location
(76 mV dec 1) than that of Rh1Cu (112 mV dec 1), which of absorption edge and the white line peak (Figure 2i),
might be due to the faster kinetics of PCET than ECH which is in line with the result from the X-ray photoelectron
process (detailed discussion is shown in Figure S14 and spectroscopy (XPS) (Figure S24). According to the extended
Figure S15). X-ray absorption fine structure spectroscopy (EXAFS)
The Cu and Rh1Cu catalysts were further employed for results, the dominated Rh O scattering was obtained at ca.
furfural oxidation (Figure 2c, d and Figure S16–S21). Re- 1.5 Å, implying the inevitable oxidation of Rh in open air as
cently it was reported that aldehydes oxidation over Cu- reported previously.[21b] The peak assigned to Rh Rh bond
based catalysts follows a single-electron transfer process at ca. 2.5 Å in Rh foil is not detected in Rh1Cu while the
(R CHO + OH !R COOH + 0.5 H2 + e ) in which H* is peak located at ca. 2.0 Å is likely attributed to Rh Cu
generated by aldehyde’s C H bond cleavage with following scattering.[21a,b] The HAADF-STEM and XAS results collab-
recombination (Tafel step) to release H2.[17a, 23] The LSV oratively infer that Rh is atomically doped into the Cu nano-
curves show that low-potential electrooxidation of furfural is skeleton. Giving the low loading of Rh (0.13 wt %) and its
achieved from 0 to 0.5 VRHE (Figure 2c and Figure S16). The full utilization by atomic dispersion, these features may
peak current declines from approximately 0.5 VRHE due to alleviate the high cost of Rh in the catalyst to some extent,
the oxidation of active Cu to Cu2O (Figure S17), in agree- although more cost-effective catalysts should be developed
ment with previous literature.[17] As shown by HPLC results in future work.
(Figure S18 and Figure S19), the main liquid product in
furfural oxidation is furoic acid with selectivity > 80 % and
carbon balance > 95 % over both Cu and Rh1Cu catalysts at Cathode optimization for promoted battery performance
0.2 VRHE. Meanwhile, furfuryl alcohol was observed in the
products (Figure S18–S21) due to the non-Faradaic reaction, Besides the catalyst optimization for promoted furfural
namely, Cannizzaro disproportionation (2 R CHO + H2O! redox at anode, the performance of battery electrode is also
R COOH + R CH2OH) in a strong base.[17b,c] Considering essential to the battery. According to the law of conserva-
the contribution of Cannizzaro disproportionation to the tion, the maximum charges passing through the furfural
formation of furoic acid, it is not unreasonable to see the redox reactions on the anode (Qa) are equal to the cathode
apparent FE of furoic acid exceed 100 % (Figure S20 and capacity (Qc), and anodic current (ia) is equal to cathodic
Figure S21). By deducting Cannizzaro contribution, the current (ic). This requires the cathode to store/release
actual FE was ca. 100 % in the potential range of 0–0.5 VRHE enough charges at the same current rate as the redox
over Cu (Figure 2d and Figure S20). When Rh was doped reactions occurring on anode (Supporting Information
into Cu, FE of furoic acid over Rh1Cu decreased to some Note 1). Although Ni(OH)2 as the cathode exhibits high
extent (Figure 2d and Figure S21), probably because Rh OCV (0.49 VSHE) when coupled with Cu anode (Figure 1a),
species catalyze the oxidation of active H* species to the redox between Ni(OH)2 and NiOOH suffers from the
H2O.[17a, 23b] In spite of this, we consider Rh1Cu is still a more low reversibility and OER in charging process (0.4 VSHE),

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resulting in capacity decay, especially under large-current and (5) fast charging-discharging rate ( � 80 % capacity
operation conditions.[20b] We alleviate this problem by retention from 1 to 10 A g 1, Figure S27).
doping Co into Ni(OH)2 via an electrodeposition method.
To sift a cathode with high capacity and reversibility,
Co1 xNix(OH)2 with different Co/Ni molar ratios were Full battery assembly and performance investigation
prepared by the same electrodeposition method (Table S3),
showing similar Co/Ni molar in the precursor solution and in Based on the independent study of electrodes in H-cell, we
the final cathode materials determined by ICP-MS measure- then devote our efforts to assembling a flow battery to verify
ments. The subscript numbers in the sample names denote the feasibility of co-production of furfural redox chemicals
the Co/Ni molar ratio in the precursor solution. while electricity is stored or released in one system. As
The increased Co content induces morphology trans- shown in Figure 4a, we assembled a flow battery,
formation (Figure S25), from monolithic bulk (Ni(OH)2) to Rh1Cu( )//Co0.2Ni0.8(OH)2(+), by using the as-prepared
micro-flower clusters (Co0.2Ni0.8(OH)2, Figure 3a) and finally Rh1Cu as the anode, Co0.2Ni0.8(OH)2 as the cathode, and
to nanosheet arrays (Co0.5Ni0.5(OH)2). All the samples Nafion 117 (183 μm) as the cation exchange membrane
exhibit α-type hydroxide structure (Figure S26). We then (CEM). The solution resistance in the flow battery is largely
characterized Co and Ni dispersions in the Co0.2Ni0.8(OH)2 reduced (Rs = 0.7 Ω) compared with that in a two-electrode
for its optimal performance (as discussed later). The STEM- H-type battery (Rs = 15 Ω) (Figure S28). Note that the
mapping result shows that Co and Ni species are highly separation of catholyte and anolyte by a non-permeable film
dispersed (Figure 3b–d). The Co additive shifts the is important because the cathode in charged status (which is
Ni(OH)2/NiOOH redox potential negatively, avoiding com- Co0.2Ni0.8OOH) shows the capacity to catalyze furfural
petition with OER when Co1 xNix(OH)2 is charged (Fig- oxidation[24] and should be avoided. Due to the thick,
ure 3e). However, excessive amount of Co lowers OCV and durable, and recyclable features, Nafion 117 film was used
ΔU, in line with the reduced voltage plateau as shown in the as the film in the two-electrode H-type battery.
discharging curves (Figure 3f). As a result, Co0.2Ni0.8(OH)2 Prior to the test, OCVs of the battery were recorded.
with a Co/Ni mole ratio of 1/4 was selected as the optimal The OCV of Rh1Cu( )//Co0.2Ni0.8(OH)2(+) battery main-
battery electrode based on the following considerations: tained at 0.78 V in the absence of furfural and quickly
(1) relatively high redox potential, (2) no competition with climbed to 1.29 V after furfural was introduced (Figure 4b
OER in charging process, (3) relatively low dosage of Co and Figure S29), as analyzed by the OCVs shifting in the CV
considering its scarcity, (4) higher capacity of 216 mAh g 1 curves (Figure 1b). Due to the high reversibility of furfural
than its counterparts (203 mAh g 1 for Ni(OH)2, redox, the I–V curves of both charging (electricity storage)
205 mAh g 1 for Co0.1Ni0.9(OH)2, 189 mAh g 1 for Co0.4Ni0.6- and discharging (electricity generation) processes initiate at
(OH)2, and 181 mAh g 1 for Co0.5Ni0.5(OH)2 (Figure 3f, g), ca. 1.3 V with a small voltage difference when the current
increases. The battery exhibits a peak power density of
Figure 3. Cathode characterizations and optimizations. a) SEM image and b)–d) STEM-mapping images of Co0.2Ni0.8(OH)2. e) CV curves of
Co1 xNix(OH)2 with different Co/Ni ratios. f) Charging (dashed line)-discharging (solid line) curves of Co1 xNix(OH)2 at a current density of 1 A g 1.
g) The discharge capacity of Co1 xNix(OH)2. Scale bars: 1 μm (a); 100 nm (b)–(d).

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Figure 4. Full battery performance of Rh1Cu( )//Co0.2Ni0.8(OH)2(+). a) Photograph of the flow battery and the corresponding sectional view.
b) OCVs of the flow battery before and after furfural is injected into the 1 M KOH anolyte. c) I–V curves and the power density. d) OCVs and power
densities in literature and this work. e) Charging-discharging curves at 20 and 50 mA cm 2. f) Demonstration of the rechargeability of the biomass
battery. Four batteries were connected in series and charged by photovoltaic cell, and then it provided stable power supply for external loads
including timer, LED lights and cell phone.
107 mW cm 2 (Figure 4c), which is much higher compared to anode was oxidized after long-term reaction (Figure S34).
Rh1Cu( )//Co0.2Ni0.8(OH)2(+) without furfural Through periodically feeding pure electrolyte to reduce
(17 mW cm 2, Figure S30) and Zn( )//furfural(+) Rh1Cu, the anode activity can be partially regenerated
(3.2 mW cm 2, Figure S31), outperforming all the hybrid (Figure S33b). Further enhancement of anode stability is
systems including Zn NO3 ,[9] Zn NO2 ,[10] Zn NO,[25] necessary, and protecting Cu by other metals, such as the
Zn H2O,[7] Zn CO2,[13a] Zn C2H2,[8] and DAFC batteries[12b,c] formation of Ag layer over Cu, might be a promising
(Figure 4d and Table S4). strategy.[17b, 23a] Noteworthy, the battery performance of the
In addition, the battery shows high capacity and energy obtained rechargeable biomass battery was obtained based
density. Specifically, the discharge capacity of the battery is on preliminary studies, and further improvement (such as
up to 19.6 mAh cm 2 (corresponding to � 150 mAh g 1), and energy-power density, energy efficiency, etc.) can be
the coulombic efficiency is 95 % at 20 mA cm 2 (Figure 4e). envisaged by fabrication of high-capacity and high-redox
The energy density is 19.8 mWh cm 2 and the energy potential cathodes (such as MnO2 and Ce3 + /Ce4 + pair), and
efficiency is 62 % at 20 mA cm 2 (Figure S32), both compa- by membrane optimization to decrease the iR drop.
rable to the well-developed Zn-air battery. The cycling
stability of the battery was also investigated, showing that
the charging voltage remains stable while the discharging
voltage gradually decays (Figure S33a), which can be
explained by the stable Co0.2Ni0.8(OH)2 cathode but Rh1Cu

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Proof of concept of the rechargeable biomass battery instance, it can store intermittent renewable electricity (e.g.,
from wind and solar) at daytime and output electricity for
As proof-of-concept applications, four biomass batteries households at night. At the same time, biomass resource-
were connected in series to increase the working voltage and derived furfural is converted to value-added chemicals
charged by a photovoltaic cell (Figure 4f, left). To our (furfuryl alcohol or furoic acid), which are collected and
delight, it can supply stable power for external loads separated for further use.
including a timer (1.3 V), LED lights (3.8 V), and even a cell To evaluate the feasibility of the rechargeable biomass
phone (5 V) (Figure 4f, right). More importantly, the battery at a more practical-relevant condition, furfural with
prominent advantage of Rh1Cu( )//Co0.2Ni0.8(OH)2(+) over industrial-level concentration (1 M) was fed into the battery,
the mainstream rechargeable batteries lies in the synchro- and the electrolyte (containing unreacted furfural, furfural
nous generation of valuable furfural-derived products during alcohol, furoic acid) was circulated. The reverse reactions
both electricity storage and generation processes (Fig- (furoic acid-to-furfuryl alcohol when charging, or furfuryl
ure S35). In electricity input process (Figure 5a, right), we alcohol-to-furoic acid when discharging) did not take place
show that 1 kWh of electricity was stored at a rate of (Figure S36), suggesting the high production efficiency.
20 mA cm 2, while 0.7 kg of furfuryl alcohol was generated. After continuous charging and discharging, furfural was
We also evaluated a faster charging rate (50 mA cm 2), and almost consumed (Figure S37), and the main products are
slightly lower production of furfuryl alcohol (0.62 kg) was furoic acid and furfuryl alcohol as expected. Since the
yielded per kWh of electricity input, indicating relatively electrolyte was circulated in one channel, both furfuryl
stable current efficiency (Table S5). In electricity output alcohol and furoic acid exist in the products, which can be
process (Figure 5a, left), 0.46 kWh of electricity was gener- separated by extraction (to collect furfuryl alcohol) and
ated while 1 kg of furoic acid was produced at discharging acidification (to collect furoic acid) (Figure S38). The above
rate of 20 mA cm 2. Higher electricity output of 0.78 kWh results suggest the potential of this rechargeable biomass
per kg of furoic acid production was reached at a faster battery for chemical production in a practical situation.
discharging rate (50 mA cm 2) (Table S6). Considering that both furfuryl alcohol (ca. $1.5/kg) and
Regarding the applicational scenario, we anticipate that furoic acid ($1–99/kg) show higher prices than furfural (ca.
the rechargeable biomass battery is adapted to distributed $1/kg),[17b, 26] we, at first glance, expect that the conversion of
energy storage and chemical production (Figure 5b). For furfural with electricity generation would be an econom-
Figure 5. Electricity/products generation and economic evaluation of the biomass battery. a) The electricity/products ratio in discharging and
charging processes with different rates. b) The potential application scenario of the biomass battery. c) The preliminary LCOE of biomass battery
compared with other energy storage technologies. d) A comprehensive comparison of the biomass battery in this work with the mainstream
batteries.

Angewandte
ically viable process. To quantitatively assess the economical Conflict of Interest

feasibility, levelized cost of electricity (LCOE) was calcu-
lated because it is an economically essential metric for The authors declare no conflict of interest.
distributed energy storage, and a lower LCOE value than
the market price of electricity would be an attractive
prerequisite for practical application. The LCOE was Data Availability Statement
calculated by normalizing all future costs to the present
price per unit of electricity capacity ($/KWh).[27] The future The data that support the findings of this study are available
costs were estimated by a preliminary techno-economic from the corresponding author upon reasonable request.
analysis (TEA) (Figure S39 and Figure S40).[28] The results
show that 132 $ of net profit accompanied with 265 KWh of Keywords: Biomass Upgrading · Flow Battery · Furfural Redox ·
electricity output can be realized when FE of furfuryl Rechargeable Battery · Single-Atom Alloy
alcohol and furoic acid reaches 50 % and 70 %, respectively,
at 20 mA cm 2. As a result, the extra revenue from chemical
production in the biomass battery leads to LCOE with a
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Zitierweise: Angew. Chem. Int. Ed. 2023, 62, e202304852

Rechargeable Biomass Battery for Electricity Storage/generation and

due to their intermittence and uneven distribution. This

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