Insights into the hydronium-ion storage of alloxazine in mild electrolyte

Article abstract of DOI:10.1039/d0ta09316e

Here, it is shown for the first time that alloxazine (ALO) can reversibly store hydronium ions in 1 M Mg(NO3)2 electrolyte. Comprehensive analyses confirm that Mg2+ ions, which possess catalytic properties, can promote hydronium-ion transfer by forming a

Full text of DOI:10.1039/d0ta09316e

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Zhenhai Wen et al.
An electrochemically neutralized energy-assisted low-cost
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DOI: 10.1039/D0TA09316E
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Insights on the Hydronium-ions Storage of Alloxazine in mild
electrolyte
a
a
a
a
a
a
a
Tianjiang Sun, Chang Liu, XiuFang Xu, Qingshun Nian, Shibing Zheng, Xuesen Hou, Jing Liang,
Received 00th January 20xx,
Accepted 00th January 20xx
a
Zhanliang Tao*
DOI: 10.1039/x0xx00000x
Here, it is shown for the first time that the alloxazine (ALO) can more serious than neutral electrolyte, which caused fairly low
reversibly store hydronium ions in 1 M Mg(NO
Comprehensive analysis confirms that the Mg ions, with catalysis electrolyte will affect the redox potential of anode (Table S1). It will
effect, can promote the hydronium-ions transfer by forming a cause the full cells show an unsatisfactory operate voltage, which
3
)
2
electrolyte. coulombic efficiency. Another crucial issue is that the pH value of
2
+
20
stable complex with reducing ALO.
hinder its practical application. Compared with strong acidic
electrolyte, the mild electrolyte will be an ideal candidate due to the
merits of low cost, intrinsic safety, and environmentally friendliness.
Nevertheless, there are lots of metal ions and few hydrogen ions in
the mild electrolyte, the redox reaction mechanism of electrode
materials (inorganic and organic materials) is usually referred to as
metal-ions de-/intercalation or uptake/removal, which is controlled
by both thermodynamics and kinetics. Therefore, finding a suitable
material that can reversibility store hydronium ions in matching mild
electrolyte has become an urgent problem.
Rechargeable batteries have gained great attention in the energy
storage system own to the low cost, flexible operationality and
1
, 2
sustainability. To date, the charge carrier of rechargeable batteries
+
+
+
2+
2+
2+
mainly focus on metal ions, includes Li , Na , K , Zn , Mg , Ca and
3
+
3-10
Al ions.
Among them, lithium ion batteries (LIBs) have been
commercialized due to the low weight and high energy density of Li
metal, but the limited natural resource and increasing price of Li
metal hinder its further development.
other metal ion batteries to surpass LIBs in a short time own to the
larger ionic radius, high mass, and/or strong electrostatic interaction.
Besides metal ion carrier, proton (H ), with smaller radius and lower
1
1-13
Moreover, it is difficult for
2+
The reported literatures suggest that the Mg ion can promote
21, 22
the proton transfer in Flavin molecule in aqueous solution.
+
2+
Meanwhile, the Mg ion, as potential ligand, has ability to stabilize
weight, can also be used as potential charge carrier in rechargeable
23, 24
the Flavin molecule by forming coordination compound.
by this, we develop hydronium-ion battery based on alloxazine (ALO)
anode in mild electrolyte including 1 M Mg(NO . Benefit from the
Inspired
1
4, 15
+
batteries.
3
It is worth noting that the hydronium ion (H O ), rather
+
than naked H ion, is used as charge carrier in aqueous electrolyte
3 2
)
1
6, 17
because of its high dehydration energy (11.66 eV).
Recently, the energy-storage systems based H
achieved in few organic and inorganic materials. For example, Ji
reported hydronium-ion battery with perylenetetracarboxylic
dianhydride (PTCDA) as anode, which exhibits a specific capacity of
same characteristic groups as Flavin, the ALO achieves hydronium-
ions uptake/removal by coordination/incoordination reaction due to
+
3
O ion have been
2+
the Mg -ions catalysis (Figure 1a). Furthermore, the formation of
2+
complex between the charged ALO and Mg ions during charging
process will stabilize its structure, so that the ALO electrode can
obtain excellent electrochemical performance. The as-obtained ALO
-
1 17
8
5 mAh g . Yan investigated redox reaction of MoO
hydronium-ion storage. The MoO shows an excellent rate
performance with a specific capacity of 88 mAh g at an ultrahigh
3
for
-1
3
electrode exhibits a high discharge capacity of 233.6 mAh g at 1 C
-1
-1
(
2 4
250 mA g ). Moreover, the constructed ALO//MgMn O (MMO)
1
8
rate of 100 C. The reported hydronium-ion battery is based on
SO electrolyte with different concentration, but the strong
battery achieves an impressive rate performance with discharge
H
2
4
-1
capacity of 72 mAh g at 100 C and long cycling stability with 80 %
corrosive character of this is inconsistent with the current
development concept of green energy.19 Additionally, for this
system, the hydrogen evolution reaction (HER) in acidic electrolyte is
capacity retention after 30000 cycles.
ALO is synthesized by a simple one-step reaction at room
temperature. The as-obtained ALO is confirmed by nuclear magnetic
resonance spectroscopy (NMR) (Figure S1, S2) and Fourier transform
infrared spectroscopy (FTIR) (Figure S3). The scanning electron
microscopy (SEM) and transmission electron microscopy energy-
dispersive X-ray spectroscopy elemental mappings (TEM-EDS)
images of ALO in Figure S4 show homogeneous rod morphology. The
a. Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education),
College of Chemistry, Nankai University, Tianjin 300071, P. R. China. E-mail:
taozhl@nankai.edu.cn
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI:10.1039/x0xx00000x
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To investigated the hydronium-ion uptake/removal performance,
View Article Online
DOI: 10.1039/D0TA09316E
the cyclic voltammogram (CV) of ALO is tested in a three-electrode
system with 1 M Mg(NO
ALO anode exhibits unsymmetrical redox peaks (two oxidation peaks
-0.52 V and -0.16 V vs Ag/AgCl) and a reduction peak (-0.61 V vs
3 2
) electrolyte. As illustrated in Figure 2a, the
(
-
1
Ag/AgCl) at a scan rate of 0.5 mV s ), which are different from the
reported ALO electrode in other systems (CV curves of reported ALO
electrodes are symmetrical).
2
5, 28-30
The galvanostatic charge-
discharge profile of the ALO anode in Figure 2b shows two charge
plateaus (a flat plateau and a sloping plateau) and one discharge
plateau, which are consist with CV measurement. In addition, the
-1
ALO anode achieves a high discharge capacity of 233.6 mAh g at 1
-1
C (250 mA g ), which is close to theoretical specific capacity (250
-1
mAh g ). Meanwhile, the ALO anode displays an excellent rate
-1
performance with a high discharge capacity of 143.6 mAh g even at
-1
2
0 C (5000 mA g ) (Figure 2c). Based on excellent rate performance,
the cycling stability of ALO anode is tested at higher current density.
As shown in Figure 2d, the long-term cycle life of ALO anode over
Figure 1. (a) The schematic for reaction mechanism of ALO
2
000 cycles with 80% capacity retention is obtained, which is better
anode 1 M Mg(NO
b) The in-situ UV-vis spectroscopy of ALO//AC in 1 M Mg(NO
electrolyte (at a current density of 1 C). (c) The in-situ UV-vis
3 2
) electrolyte (Dis.: Discharge; Ch.: Charge).
than recent reports (Table S2).
To fundamentally understand the reasons of remarkable rate
performance of ALO in 1 M Mg(NO ) electrolyte, we investigate the
3 2
reaction kinetics by CV curves with different scan rates (Figure S10a).
The calculated b values of peak 1, peak 2, and peak3 are 0.71, 0.87
and 0.79, respectively, indicating a pseudocapacitive characteristic
(
3 2
)
spectroscopy of ALO//AC in 1 M MgSO
density of 1 C).
4
electrolyte (at a current
termogravimetric analysis (TGA) in Figure S5 shows a good
thermostability of ALO.
(Figure S10b). In addition, the hydronium-ion diffusion coefficient on
Different magnesium-containing salt electrolytes are used to study
the electrochemical performance of ALO because of the unique
the surface of ALO electrode is tested by CV measurement. As shown
in Figure S10c, the diffusion coefficients at Peak 1, Peak 2 and Peak 3
2
+
effect of Mg ion. Unfortunately, the reported ALO material has
dissolution problem both in alkaline aqueous and organic
-
6
2
-1
-6
2
-1
-6
are calculated to be 3.17×10 cm s , 1.42×10 cm s and 1.44×10
2
-1
cm s , suggesting ultrafast hydronium-ion diffusion. This is one of
the reasons for the high rate performance of the ALO electrode.
In-situ pH monitoring technology is carried out to elucidate the
2
5, 26
electrolytes.
To choose a suitable electrolyte with considerable
compatibility, the ionic conductivity and solubility tests of ALO in
different electrolytes are collected. As shown in Figure S6, the 1 M
3 2
hydronium-ion storage mechanism of ALO anode in 1 M Mg(NO )
Mg(NO
3
)
2
shows impressive ionic conductivity in comparison with
SO , 1 M MgCl , and 1 M MgSO ).
electrolyte (Figure S11). As shown in Figure 3a, it can be observed
that the pH value of the electrolyte increasing during discharging,
and gradually decreases during charging. This is due to the reaction
other electrolytes (1 M Mg(CF
3
3
)
2
2
4
Further, the solubility of ALO in different electrolytes is tested by UV-
vis spectroscopy (Figure S7) after standing 24 h (Figure S8). As
displayed in Figure S7, the absorption peak at 264 nm corresponds
2
7, 28
to the signal of ALO.
M Mg(NO and 1 M MgSO
the electrolytes still remain clear (Figure S8), indicating that ALO has
lower solubility in 1 M Mg(NO and 1 M MgSO solutions in a resting
Obviously, the absorption peaks of ALO in 1
)
3 2
4
electrolytes are weaker than others, and
3
)
2
4
state. The solubility of ALO can attribute to the different pH of the
electrolytes (Figure S9).
To select more suitable electrolyte, the in-situ UV-vis spectroscopy
technology is further developed to observe the solubility of ALO
during charging/discharging process in 1 M Mg(NO
electrolytes. As shown in Figure 1b, for the cell (ALO//activated
carbon (AC)) with 1 M Mg(NO solution, only weak absorption
3 2 4
) and 1 M MgSO
3 2
)
peaks are observed, and the peaks hardly strengthen during the
charging/discharging process. While the adsorption peaks have
gradually increased in 1 M MgSO
charging/discharging process. The analysis of UV-vis patterns
indicate the ALO anode is nearly insoluble in 1 M Mg(NO
electrolyte. Thus, benefit by the high ion conductivity and
4
electrolyte (Figure 1c) during
-
1
Figure 2. (a) The CV curve of ALO anode at 0.5 mV s . (b)
The discharge-charge profile of ALO anode at 1 C (250 mA
g ). (c) Rate performance of ALO anode at different current
densities from 2 to 20 C. (d) The cycling performance of ALO
3 2
)
-1
considerable compatibility with the ALO, 1 M Mg(NO
more suitable for this system.
3 2
) electrolyte is
-1
anode at 20 C (5000 mA g ).
2
| J. Name., 2012, 00, 1-3
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of hydronium ions with ALO during charging and discharging
To improve the understanding on the ions storage VmieewcAhrtaicnleisOmnlionef
processes, resulting in a reversible decrease and increase in the ALO, density functional theory (DFT) calculatDioOnI:s1a0r.1e0c3a9r/rDie0dTAo0u9t3.1A6Es
concentration of hydrogen ions in the electrolyte and
corresponding change of pH value. Interestingly, the pH value of 1 M one H and two H ions are negative (-7.145 eV and -14.349 eV),
Zn(NO electrolyte is almost constant during the indicating the efficient utilization of the nitrogen sites. The ALO
a
shown in Figure 3g and Table S4, The energies of ALO bonded with
+
+
3 2
)
charging/discharging process, indicating not hydronium ions but zinc transforms into ALO-2H by one-step reaction during discharging
ions are de-/insert into ALO electrode (Figure S12), which is consist process due to the large energy gaps (∆E = -14.349 eV). During
2
8
with the reported literature. Thus, the successful hydronium-ions charging process, the energy of ALO-Mg (-11.339 eV) is lower than
2
+
uptake/removal in ALO suggests that the Mg ions, with catalytic ALO-H (-7.145 eV), indicating the ALO-2H is more likely become ALO-
st
2+
effect, promote the hydronium-ions transfer.
Mg during the 1 step charging. Then, the ALO-Mg will extract Mg
+
nd
To further understand the reaction mechanism of ALO, ex-situ XPS and residual H ion and revert to ALO during the 2 step charging
and in-situ FTIR were developed. The XPS spectrum of C 1s is used as process.
a reference (Figure 3b). The XPS spectrum of N 1s and O 1s in Figure
c and 3d exhibit reversible transformation in different state, mechanism of ALO (Figure 3h). In the initial state, the chemical shifts
In addition, the ex-situ 1H NMR is used to study the redox
3
suggesting that the group of C=N and C=O are redox-active centers of ALO are 7.78 (m, 1H), 7.93 (d, 2H), 8.17 (d, 1H), 11.75 (s, 1H), 11.94
of ALO. In-situ FTIR analysis shown in Figure 3e further confirmed the (s, 1H). After discharging to -0.55 V, a new peak, corresponding to
-
1
reversible change in the molecular structure. The peaks at 1658 cm
corresponding to the vibrational modes of C=O bond) gradually transform into ALO-2H during discharge, which also coincided with
weaken and enhance during charging/discharging process. While no the discharge capacity. When charged to -0.3 V, the 6’ peak shifts to
two hydrogen ions at 7’ and 8’ in Figure 3g, suggesting that the ALO
(
-1
obvious change about the groups of C=N (at 1581 cm ) appeared, a high field forming 6’’ peak, and the peak at 7’ 8’ weakened into 7’’
which may be caused by the weak signal of vibrational modes of C=N. peak (the area of the 7’’ peak is only half that of the 7’ 8’ peak) and
Moreover, the XPS spectrum of Mg 1s are collected in different state. shifted towards the high field, indicating the ALO-2H lose a
As displayed in Figure 3e, no Mg peak is observed in initial state and hydronium ion during the first charging flat (-0.3 V). The shift and
discharged state to -0.55 V of the ALO electrode. While the Mg peak weaken of peaks are caused by the extraction of hydronium ion and
2
+
appeared when charged to -0.3 V, which implies Mg ions may complex effect of magnesium ion. The analysis about hydrogen
participate in the transformation reaction of ALO anode during numbers and sites is consist well with the molecular structure of
1
charging process.
ALO-Mg in Figure 3g. Continue to charge to 0.1 V, the H NMR
To confirmed the result, the CV curves of ALO anodes in 1 M spectrum of the electrode material is the same as that of the original
NaNO , 1 M Zn(NO , and 1 M HNO electrolytes are collected, electrode material ALO, indicating the reversibility of charge and
respectively. As shown in Figure S13, the ALO anodes show a discharge of the electrode material. Both analysis of ex-situ XPS and
symmetrical redox peaks in 1 M NaNO , 1 M Zn(NO , and 1 M HNO
electrolytes, which are different from the CV curve of ALO in 1 M
3
)
3 2
3
3
3
)
2
3
2
+
3 2
Mg(NO ) electrolyte. The result suggests that Mg ion selection will
alter the electrochemical response of ALO. Moreover, as shown in
Figure S14a and 14b, the ALO displays unsymmetrical redox peaks in
1
4 4
M MgSO electrolyte but symmetrical redox peaks in 1 M ZnSO
electrolyte, implying that the redox reaction of ALO is independent
of the type of anion. The unsymmetrical redox peaks of ALO anode
3 2
in 1 M Mg(NO ) electrolyte can attribute to the redox reaction
2
+
including transformation of Mg ion with ALO, which is different
from reported reaction mechanism about simple metal-ions
+
+
2+ 25, 26, 28
coordination/incoordination reaction (Li , Na , and Zn ).
As the reported literature, ALO molecular structure characterized
by the presence of chelation centres mainly located on the groups of
C=N and C=O, which can form complex compound between ALO and
2
+
22, 31
Mg ion.
Thus, the reaction mechanism of ALO during
charging/discharging process is speculated as below (Figure 1a):
When discharging, ALO obtains two electrons and gets two
hydronium ions to form ALO-2H, which experiences one-step
reaction. Subsequently, ALO-2H first removes a hydronium ion, and
3 2
Figure 3. (a) In-situ pH monitor for 1 M Mg(NO ) electrolyte
during charging/discharging process (Potential (V vs Ag/AgCl);
current density: 1 C). (b~e) Ex-situ XPS spectrum of b) C 1s, c) N
2
+
is rapidly replaced by Mg ion to form ALO-Mg complex during the
charging process from -0.55 V to -0.3 V. The substitution process may
attribute to the physico-chemical properties of the functional groups
and the electron density at the donor atom in ALO molecular, and
1
s, d) O 1s, e) Mg 1s. (f) In-situ FTIR of ALO anode during
charging/discharging process. (g) The energy change of ALO
during discharging/charging process by DFT calculations. (h) Ex-
2
+
2+
strong electroaffinity of Mg ions. Then the Mg ion and hydronium
ion are removed to form ALO with continuously charging to 0.1 V,
which may be affected by the external electric field.
1
situ H NMR patterns of ALO anode at different state (Potential
(V vs Ag/AgCl); current density: 1 C).
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operate at a low temperature (Figure S23). Noted that the
View Article Online
DOI: 10.1039/D0TA09316E
discharge capacity of this battery is higher at 50 and 70 °C, it
-1
-1
reaches 81 mAh g and 91 mAh g , respectively (Figure S22b).
The reason of higher capacity is that higher temperatures
improve the ions transport and electronic conductivity of the
cathode and anode. In addition, the battery could still maintain
-1
a usable capacity of 49 mAh g after cycling 10000 cycles at 70
C, corresponding to a capacity decay of as low as 0.005% per
°
cycle with excellent coulombic efficiency of nearly 99% (Figure
S22c). In a word, the ALO//MMO battery represents a balanced
and highly competitive capacity retention rate and cycling
performance over a wide temperature range from 0 °C to 70 °C.
In conclude, the ALO material is used as anode in
hydronium-ion battery. The insoluble character of ALO in 1 M
3 2
Mg(NO ) electrolyte is confirmed by ex-/in-situ UV-vis
spectroscopy technology. Post-mortem analyses including in-
situ pH monitor, ex-situ XPS, in-suit FTIR, DFT calculation, along
Figure 4. (a) Discharge-charge profiles of full cell of
ALO//MMO battery at different current densities of 1, 5,
1
with ex-situ H NMR demonstrate the rapid hydronium-ion
1
0, 20, 50, and 100 C (the specific capacity is calculated
2
+
based on the total mass of active materials in both
electrodes). (b) Rate performance of ALO//MMO battery at
different current densities of 1, 5, 10, 20, 50, and 100 C. (c)
The cycling performance and coulombic efficiencies of
uptake/removal in ALO. We also confirm the Mg ions, with
catalytic effect, promote the hydronium-ions transfer in ALO,
2
+
and the Mg ions can form complex with charged ALO to
stabilize its structure. The constructed ALO//MMO battery
achieves an excellent cycling stability with 80 % capacity
retention after 30000 cycles, and remarkable rate performance
-1
ALO//MMO battery at 100 C (25000 mA g ).
1H NMR patterns are in excellent agreement with the speculation.
Benefit by the formation of complex, the ALO electrode shows
-1
with considerable discharge capacity of 72 mAh g at 100 C.
Furthermore, this system is successfully operated at a wide
temperature range from 0 to 70 °C and shows significant
electrochemical performance. The ALO, with unique reaction
excellent cycling stability in 1 M Mg(NO
with in 1 M Zn(NO electrolyte (Figure S15).
To further study the practical application prospect of ALO, the
MgMn (MMO) is used as cathode to construct a full cell. The
3 2
) electrolyte in comparison
3 2
)
3 2
mechanism in 1 M Mg(NO ) electrolyte, shows impressive
electrochemical performance and can be considered as an ideal
anode material for hydronium ion batteries.
2 4
O
corresponding synthesis, characterization and electrochemical study
are displayed in the supporting information (Figure S16-S19). The full
cell, consists of ALO anode, MMO cathode and 1 M Mg(NO
3 2
)
electrolyte, shows excellent electrochemical performance. As shown
Conflicts of interest
“There are no conflicts to declare”.
-1
in Figure 4a, a discharge capacity of 93 mAh g and an energy density
-1
of 80 Wh kg at 1 C are delivered by this system (calculated based on
the total mass of active materials in both electrodes). As shown in
Figure 4b, the battery exhibits excellent rate performance with a
-1
Acknowledgment
This study was supported by the National Key R&D Program of
discharge capacity of 72 mAh g even at the high rate of 100 C, which
is benefit by the pseudocapacitive characteristic and the high ions
diffusion coefficient of ALO anode and MMO cathode. Benefit by the
high rate capacity, The ALO//MMO battery is tested at 100 C. As
displayed in Figure 4c, the battery achieves a long-life cycling stability
with capacity retention of 80% after 30000 cycles, corresponding to
a capacity decay of as low as 0.00067% per cycle. The impressive
cycling stability of this system is benefit from the insoluble character
China
(2016YFB0901500,
2016YFB0202500
and
2
019YFA0705600); the National Natural Science Foundation of
China (51771094, 21835004, 21673243 and 52001170),
Ministry of Education of China (B12015 and IRT13R30), and
Tianjin Natural Science Foundation (No. 18JCZDJC31500).
of ALO and stable structure of MMO in 1M Mg(NO
Figure S20, S21).
Moreover, the ALO//MMO battery is tested in a wide
temperature range from 0 to 70 °C. Electrochemical impedance
spectroscopy (EIS) of ALO// MMO battery in Figure S22a shows
low charge transfer impedance at different temperatures,
suggesting rapid ion diffusion kinetic. Figure S22b shows the
charge-discharge profiles of the ALO//MMO battery at different
temperatures. The system exhibits 67 % capacity retention at 0
3 2
) electrolyte
(
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DOI: 10.1039/D0TA09316E
2
+
The Mg , with catalysis effect, can promote the hydronium ion
3 2
transfer in alloxazine in 1 M Mg(NO ) electrolyte.
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| J. Name., 2012, 00, 1-3
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