Metal-free and metal porphyrins: A highly efficient catalysts to Li/SOCl 2 battery

Article abstract of DOI:10.1142/S1088424615500856

Two metal-free porphyrins H2Pp (a, b) and four metalloporphyrins CuPp (a, b) and ZnPp (a, b) have been applied to lithium/thionyl chloride (Li/SOCl2) battery as the high efficient catalysts for the first time. Notably, the battery discharge time in blank

Full text of DOI:10.1142/S1088424615500856

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2015; 19: 1–6
DOI: 10.1142/S1088424615500856
Published at http://www.worldscinet.com/jpp/
Metal-free and metal porphyrins: A highly efficient catalysts
to Li/SOCl2 battery
Na Lia, Chong Dangb, Wanjun Sun*a, Jinning Danga, Xinsheng Lua and Jun Li*c
a Department of Chemistry and Life Science, Basic Chemistry Experimental Demonstration Center,
Gansu Normal University for Nationalities, Hezuo 747000, P.R. China
b School of Information Science and Technology, Northwest University, Xi’an, Shaanxi 710069, P.R. China
c Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education,
College of Chemistry & Materials Science, Northwest University, Xi’an 710069, P.R. China
Received 31 May 2015
Accepted 15 July 2015
ABSTRACT: Two metal-free porphyrins H2Pp(a, b) and four metalloporphyrins CuPp(a, b) and
ZnPp(a, b) have been applied to lithium/thionyl chloride (Li/SOCl2) battery as the high efficient catalysts
for the first time. Notably, the battery discharge time in blank is only 1080 s while that of Li/SOCl2
battery after adding porphyrin/metalloporphyrins is 1980 s for H2Pp(a), 2160 s for H2Pp(b), 1560 s for
CuPp(a), 1320 s for CuPp(b), 1620 s for ZnPp(a), and 1680 s for ZnPp(b), respectively. Furthermore,
the energy of the battery whose electrolyte contains the H2Pp(a, b), CuPp(a, b) and ZnPp(a, b) increases
by approximately 11.88–77.14% than that of the battery without them. And the metal-free porphyrins
H2Pp(a) or H2Pp(b) exhibit higher catalytic activities than that of metalloporphyrins CuPp(a, b) and
ZnPp(a, b). In addition, the possible reasons to explain the excellent results were also analyzed.
KEYWORDS: porphyrin, Li/SOCl2 battery, catalytic activity, discharge properties.
cathode [8]. In order to overcome these problems,
INTRODUCTION
extensive works have recently been done to improve the
There is currently a strong demand for developing
practical application of Li/SOCl2 battery [9–12]. Among
high-performance primary batteries to meet the ever-
these works, one promising method to obviously improve
increasing energy demands and pressing environmental
the performance of the battery is adding macromolecular
concerns [1–5]. As we all known, Li/SOCl2 battery, as a
compounds, especially porphyrin compounds, to the
high energy density among the realized chemical power
electrolyte[13–16]. Furthermore, porphyrins, bynatureof
sources, high working voltage, long shelf-life and wide
their electronic and redox properties, are highly versatile
range operational temperature, has been extensively
functional molecules in catalysis, light harvesting, and
used as an emergency power in commercial, medical,
molecular sensing and so on [17–20]. In this regard,
industrial, and military applications [6, 7]. Here, the
Li et al. reported that some metalloporphyrins (M =
Li/SOCl2 battery system employs a Li anode, a porous
Fe2+, Co2+ and Ni2+) were beneficial to thionyl chloride
carbon cathode, and a LiAlCl4/SOCl2 electrolyte
reduction [21]. At our knowledge, although a few works
solution. However, the Li/SOCl2 batteries suffer from
have reported the catalytic activity of porphyrins to Li/
two obvious problems in practical application, voltage
SOCl2 battery [22–26], the use of porphyrins applied
delay and safety problem, which significantly prohibit
to Li/SOCl2 battery has not been significantly exploited
the wide application of Li/SOCl2 battery. This is mainly
yet. In the present paper, six different ring-modified
because deposition of LiCl clogged the porous carbon
metal-free porphyrins H2Pp(a, b) and metalloporphyrins
CuPp(a, b) and ZnPp(a, b) (Fig. 1) were designed,
synthesized and characterized. The catalytic activity of
the porphyrins to Li/SOCl2 battery was measured. To
the best of our knowledge, the catalytic activity of the
*Correspondence to: Wanjun Sun, email: wanjuns@sina.cn,
tel/fax: +86 941-825-2906; Jun Li, email: junli@nwu.edu.cn,
tel: +86 298-830-2604, fax: +86 298-830-3798
Copyright © 2015 World Scientific Publishing Company

2
N. LI ET AL.
COOC2H5
COOH
O
O
N
N
N
N
N
N
N
N
M
M
O
O
M = 2H, H2Pp(a)
Cu, CuPp(a)
Zn, ZnPp(a)
M = 2H, H2Pp(b)
Cu, CuPp(b)
Zn, ZnPp(b)
Fig. 1. The chemical structure of metal-free porphyrins H2Pp(a, b) and metalloporphyrins CuPp(a, b) and ZnPp(a, b)
COOC2H5
O
HO
COOC2H5
NH
N
N
M(OAc)2
CuPp(a)
ZnPp(a)
O
CH2Cl2/C2H5OH
HN
Br
NH
N
N
k2CO3
DMF
H2Pp(a)
O
COOH
HN
O
HO
COOH
NH
N
N
M(OAc)2
CuPp(b)
ZnPp(b)
BrH2Pp
O
CH2Cl2/C2H5OH
HN
H2Pp(b)
Scheme 1. Syntheses of the metal-free porphyrins H2Pp(a, b) and metalloporphyrins CuPp(a, b) and ZnPp(a, b)
designed porphyrins H2Pp(a) and H2Pp(b) to Li/SOCl2
battery exhibit higher catalytic activities than that of
other porphyrins or phthalocyanines in previous works
[27, 28]. Furthermore, the possible reasons to explain the
excellent results were also analyzed.
spectra were recorded by a Shimadzu UV-1800 UV-vis-
NIR spectrophotometer. Mass spectrometry (MS) analysis
were carried out on a matrix assisted laser desorption/
ionization time of flight mass spectrometer (MALDI-TOF
MS, Krato Analytical Company of Shimadzu Biotech,
Manchester, Britain) using a standard procedure involving
1 mL of the sample solution.
EXPERIMENTAL
Synthesis of metal-free porphyrins H2Pp(a, b)
and metalloporphyrins CuPp(a, b) and ZnPp(a, b)
Reagents and materials
TheporphyrinsH2Pp(a,b),CuPp(a,b)andZnPp(a,b)
were successfully achieved according to the method
reported in our previous work [31–33]. The synthetic
routes of porphyrins H2Pp(a, b), CuPp(a, b) and
ZnPp(a, b) are illustrated in Scheme 1.
All chemicals were obtained from commercial
sources and used without further purifications. Elemental
analysis (C, H and N) was performed by Vario EL-III
CHNOS instrument. FT-IR spectra were recorded on a
BEQUZNDX-550 spectrometer (KBr pellets). UV-vis
Copyright © 2015 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2015; 19: 2–6

METAL-FREE AND METAL PORPHYRINS: A HIGHLY EFFICIENT CATALYSTS TO LI/SOCL2 BATTERY
3
Synthesis of metal-free porphyrins H2Pp(a, b). The
Found C, 74.53; H, 4.58; N, 6.32%. UV-vis (CH2Cl2):
l
max, nm 420, 549, 593. FT-IR (KBr): n, cm-1 3417, 2925,
2855, 1638, 1616, 1504, 1459, 1372, 1337, 1284, 1240,
1067, 997, 797. MS(FAB):m/z884.48(calcd.for[M+H]+
885.24).
CuPp(b). Yield 85%, mp 250°C (decomposed).
Anal. calcd. for C53H36N4O4Cu: C, 74.31; H, 4.25; N,
6.58%. Found C, 74.33; H, 4.24; N, 6.54%. UV-vis
(CH2Cl2): lmax, nm 418, 542. FT-IR (KBr): n, cm-1 3429,
2923, 2855, 1708, 1602, 1507, 1276, 1236, 1071, 1005,
927, 800. MS (FAB): m/z 857.39 (calcd. for [M + H]+
856.22).
target porphyrins H2Pp(a, b) were synthesized through
three steps. Taking H2Pp(a) as an example. 5-mono-[4-
hydroxyphenyl]-10,15,20-triphenylporphyrinwasprepared
firstly by using Adler–Longo method, then reacted with
1,2-dibromoethane to get 5-mono-[4-(2-bromoethoxy)
phenyl]-10,15,20-triphenylporphyrin BrH2Pp, and finally
H2Pp(a) was obtained by hydroquinone substituting
bromine atom in BrH2Pp. The same method was also used
to obtain H2Pp(b) by using p-hydroxybenzoic acid as the
starting material.
H2Pp(a). Yield 38%, mp 250°C (decomposed). Anal.
calcd. for C55H42N4O4: C, 80.25; H, 5.09; N, 6.83%.
Found C, 80.27; H, 5.14; N, 6.81%. UV-vis (CH2Cl2):
ZnPp(b). Yield 80%, mp 250°C (decomposed). Anal.
calcd. for C53H36N4O4Zn: C, 74.20; H, 4.21; N, 6.528%.
Found C, 74.17; H, 4.23; N, 6.53%. UV-vis (CH2Cl2):
l
max, nm 418, 484, 515, 550, 591. FT-IR (KBr): n, cm-1
3442, 3054, 2926, 2856, 1712, 1606, 1510, 1456, 1236,
1069, 965, 800. 1H NMR (400 MHz; CDCl3; Me4Si): dH,
ppm 8.87–8.84 (8H, m, b position of the pyrrole moiety),
8.21 (8H, d, J = 7.58 Hz, Ar), 7.78–7.74 (11H, m, Ar),
7.29 (2H, d, J = 8.40 Hz, Ar), 7.07 (2H, d, J = 8.76 Hz,
Ar), 4.56 (2H, t, J = 4.86 Hz, –OCH2), 4.52 (2H, t, J =
4.93 Hz, –OCH2), 4.41-4.35 (2H, q, –CH2), 1.43–1.39
(3H, t, –CH3), -2.79 (2H, br s, NH). MS (FAB): m/z
822.53 (calcd. for [M + H]+ 822.95).
l
max, nm 420, 557, 598. FT-IR (KBr): n, cm-1 3416, 2925,
2855, 1689, 1639, 1614, 1491, 1372, 1338, 1275, 1240,
1104, 1067, 997, 798. MS (FAB): m/z 856.20 (calcd. for
[M + H]+ 857.21).
Electrochemistry measurements
The model and structural diagram of Li/SOCl2
battery used is shown in Fig. 2. The cathode material
was obtained by the mixture of acetylene black and
a conductive additive in a certain proportion (92:8
wt%) with diluted polytetrafluoroethylene (PTFE)
emulsion. The mixture was churned into a paste and
repeatedly rolled into an established film by a heated
roller machine. Subsequently, the mixture pastes were
dried at 120 °C for 4 h. These carbon electrodes were
used as cathode with the apparent area of 1 cm2, and
lithium foils were used as the counter electrodes. Then
the Li/SOCl2 battery is assembled in dry room facility,
in which the relative humidity is kept below 3%. 2 mg
of porphyrin catalysts was added into 1 mL 1.47 M
LiAlCl4/SOCl2 solution to evaluate the catalytic activity
of the battery. The discharge tests were evaluated
at a constant resistance 40 Ω, and were stopped
when the voltage continuously discharged to 2 V.
All the experiments were conducted in a glove box
under an argon atmosphere (MBRAUN, MBBL-01). In
the progress, the output voltage (U) of the battery is
measured with time. Numerical analysis method is used
to quantify the energy of the battery.
H2Pp(b). Yield 30%, mp 250°C (decomposed). Anal.
calcd. for C53H38N4O4: C, 80.05; H, 4.89; N, 7.10%.
Found C, 80.08; H, 4.82; N, 7.05%. UV-vis (CH2Cl2):
l
max, nm 418, 516, 551, 590, 646. FT-IR (KBr): n, cm-1
3434, 2925, 2859, 1630, 1508, 1441, 1250, 1098, 861,
1
800, 705. H NMR (400 MHz; CDCl3; Me4Si): dH, ppm
8.87 (9H, d, J = 11.7 Hz), 8.22 (7H, d, J = 6.3 Hz), 7.75
(11H, s, 7.35 (3H, d, J = 8.6 Hz), 6.99 (1H, d, J = 6.7 Hz),
6.85 (1H, d, J = 6.8 Hz), 4.62 (2H, t, J = 4.7 Hz), 4.48
(2H, s), -2.78 (2H, s). MS (FAB): m/z 794.29 (calcd. for
[M + H]+ 795.23).
Synthesis of metalloporphyrins CuPp(a, b) and
ZnPp(a, b). Metalloporphyrins CuPp(a) was synthesized
by the reaction of H2Pp(a) with a little excess of Cu(OAc)2
in mixture of CH2Cl2 and C2H5OH at room temperature.
ThereactionwasmonitoredbyTLCuntilthedisappearance
of the H2Pp(a). The unreacted Cu(OAc)2 was filtered out
and the solvent was removed under vacuum. The crude
product was purified by chromatography on a silica-gel
column with CH2Cl2 as eluant. CuPp(a) and was obtained
in nearly quantitative yield.
The energy of Li/SOCl2 battery is:
The synthetic procedure for CuPp(b) and ZnPp(a, b)
was similar to that for CuPp(a) in almost good
quantitative yield by using Cu(OAc)2 and Zn(OAc)2 as
the starting material, respectively.
U2
U2
Re
1
∑
(1)
C = Pdt =
dt =
∆t =
U2 ∆t
∑
∫
∫
Re
Re
CuPp(a). Yield 92%, mp 250°C (decomposed). Anal.
calcd. for C55H40N4O4Cu: C, 75.31; H, 4.35; N, 6.82%.
Found C, 74.69; H, 4.56; N, 6.33%. UV-vis (CH2Cl2):
where P is the discharge power of the battery, Re is the
constant resistance, U is the voltage discharged in the
test, t stands for the discharged time.
l
max, nm 416, 540. FT-IR (KBr): n, cm-1 3435, 2925,
2856, 1710, 1605 1509, 1240, 1072, 1005, 800. MS
The relative energy of the battery is:
(FAB): m/z 886.75 (calcd. for [M + H]+ 884.25).
C
ZnPp(a). Yield 89%, mp 250°C (decomposed). Anal.
calcd. for C55H40N4O4Zn: C, 74.51; H, 4.58; N, 6.30%.
(2)
X(%) =
×100
C0
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J. Porphyrins Phthalocyanines 2015; 19: 3–6

4
N. LI ET AL.
Fig. 2. The model (a) and structural diagram (b) of Li/SOCl2 battery
where C stands for the energy of the battery in the
presence of porphyrins, C0 stands for the energy of the
battery without them.
During the electrode reaction of the Li/SOCl2 battery,
the electrode reaction of Li/SOCl2 battery is as follows:
Anode: Li → Li+ + e
(3)
Cathode: 2SOCl2 + 4e → S + SO2 + 4Cl-
(4)
RESULTS AND DISCUSSION
In the above reaction, the Li+ ion around the lithium
electrode migrate to the carbon electrode surface and
react with the Cl- anion:
The typical discharge curves of Li/SOCl2 battery
catalyzed by metal-free porphyrins H2Pp(a, b) and
metalloporphyrins CuPp(a, b) and ZnPp(a, b) was
showed in Fig. 3. It can be obviously seen that the
porphyrin show high catalytic activity to Li/SOCl2
battery as well as their open-circuit voltage of Li/SOCl2
battery much more stable. Simultaneously the battery
discharge time above 2 V is 1980 s for H2Pp(a), 2160 s
for H2Pp(b), 1560 s for CuPp(a), 1320 s for CuPp(b),
1620 s for ZnPp(a), and 1680 s for ZnPp(b), respectively,
while that in the absence of porphyrins is only 1080 s. In
particular, the battery’s discharge time is lengthened 545 s
for H2Pp(a) and 193 s for ZnPp(b) above 3 V, which is
absolutely crucial to the Li/SOCl2 battery’s applications.
Such result is the highest capacity ever reported for a
Li/SOCl2 battery to our knowledge [27, 28].
Furthermore, the energy of Li/SOCl2 battery is used
to evaluate the electrochemical effects of the battery
catalyzed by these catalysts. It shows that the energy
of Li/SOCl2 battery with H2Pp(a), H2Pp(b), CuPp(a),
CuPp(b), ZnPp(a) and ZnPp(b) is 177.14, 170.75,
125.96, 111.88, 139.19 and 145.33 J, respectively, higher
than that of Li/SOCl2 battery in the absence of porphyrins,
which is only 97.27 J (shown in Fig. 4 and Table 1). It can
be easily seen that H2Pp(a) and H2Pp(b) shows the most
effective improvement to Li/SOCl2 battery. The capacity
of battery with these porphyrins is in range from 10.64
to 16.82 mA.h, higher than that of battery in absence
of porphyrins (8.98 mA.h). Taking all this into account,
the metal-free porphyrins H2Pp(a) and H2Pp(b) exhibit
higher catalytic activities than that of metalloporphyrins
CuPp(a, b) and ZnPp(a, b).
Li+ + Cl- → LiCl
(5)
Why these porphyrins, especially metal-free porphyrins
H2Pp(a, b), show high catalytic activity to Li/SOCl2
battery? The possible reasons for the excellent results
were discussed. On one hand, owing to the low solubility
of LiCl crystallite in SOCl2 electrolyte as the discharge
goes on, the amount of LiCl crystallite deposited on the
carbon cathode is increased. It can affect the electrode
kinetics of the cathode discharge reaction and also causes
a voltage delay owing to its overly passive nature [29, 30].
We supposed that the formation or growth of LiCl film
was restrain effectively, due to the coordination of Li+ to
the metal-free porphyrin H2Pp(a) or H2Pp(b). However,
for the metalloporphyrins CuPp(a, b) or ZnPp(a, b), the
Cl anions may coordinate weakly to the metals from axial
direction, thus the H2Pp(a) and H2Pp(b) exhibit higher
catalytic activity than that of metalloporphyrins CuPp(a, b)
and ZnPp(a, b). On the other hand, it is increase the
reaction rate of SOCl2 reduction due to the coordination
to metalloporphyrins CuPp(a, b) or ZnPp(a, b) in the
electrolyte. We also found that metalloporphyrins exhibit
different catalytic activity to the Li/SOCl2 battery. In
addition, both the porphyrins itself and their peripheral
groups may be the catalytic active sites, the synergic effect
between them achieves the high catalytic activity of the
battery. Under these conditions, the output voltage of the
battery is enhanced and the battery’s discharge time is
obviously lengthened [28].
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J. Porphyrins Phthalocyanines 2015; 19: 4–6

METAL-FREE AND METAL PORPHYRINS: A HIGHLY EFFICIENT CATALYSTS TO LI/SOCL2 BATTERY
5
In the second place, the adduct MPp·SOCl2 accepts the
electrons. S, SO2 and Cl− leave, and thus MPp is returned.
CONCLUSION
In conclusion, six porphyrins H2Pp(a, b), CuPp(a, b)
andZnPp(a, b)weresynthesizedandappliedtoLi/SOCl2
battery firstly. The results show that the discharge time
of Li/SOCl2 battery with porphyrin/metalloporphyrins is
approximately 240–1080 s longer than that of Li/SOCl2
batteryinblank.Furthermore,theenergyofthebattery,the
electrolyte of which contains the H2Pp(a, b), CuPp(a, b)
and ZnPp(a, b) increases by 11.88–77.14% than that of
the battery without them. Furthermore, the metal-free
porphyrins H2Pp(a) and H2Pp(b) exhibit higher catalytic
activities than that of metalloporphyrins CuPp(a, b) and
Fig. 3. The discharge curves of Li/SOCl2 battery
ZnPp(a, b). In addition, the possible reasons to explain
the excellent results were also discussed.
Acknowledgements
The authors acknowledge the research grant provided
by the National Nature Science Foundation of China
(21271148) that resulted in this article. The authors also
acknowledge the kindly assistance from Xi’an Institute
of Electromechanical Information Technology.
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