The disodium salt of 2,5-dihydroxy-1,4-benzoquinone as anode material for rechargeable sodium ion batteries

Article abstract of DOI:10.1039/c4cc08220f

The disodium salt of 2,5-dihydroxy-1,4-benzoquinone has been prepared and proposed as anode material for rechargeable sodium ion batteries for the first time, showing an average operation voltage of ～1.2 V, a reversible capacity of ～265 mA h g^-1

Full text of DOI:10.1039/c4cc08220f

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The disodium salt of 2,5-dihydroxy-1,4-
benzoquinone as anode material for rechargeable
Cite this:DOI: 10.1039/c4cc08220f
sodium ion batteries†
Received 17th October 2014,
Accepted 1st December 2014
Zhiqiang Zhu, Hao Li, Jing Liang, Zhanliang Tao and Jun Chen*
DOI: 10.1039/c4cc08220f
www.rsc.org/chemcomm
The disodium salt of 2,5-dihydroxy-1,4-benzoquinone has been sodiation–desodiation behaviour of a graphene oxide wrapped
prepared and proposed as anode material for rechargeable sodium croconic acid disodium salt has also been tested.32 It rendered
ion batteries for the first time, showing an average operation voltage an initial capacity of B290 mA h gÀ1 with B45% capacity retention
of B1.2 V, a reversible capacity of B265 mA h gÀ1, a long cycle life after 100 cycles at a current density of 20 mA gÀ1. Therefore,
(300 cycles), and high rate capability.
exploiting new carbonyl compound anode material is still needed.
In 2008, a dilithiated 2,5-dihydroxy-1,4-benzoquinone (Li2DBQ)
Lithium ion batteries (LIBs) indeed represent the state-of-the-art based coordination polymer was reported as cathode material for
battery systems,1,2 but developing sodium ion batteries (SIBs) have LIBs with an average potential of B1.65 V (vs. Li+/Li).33 As the
recently captured much research interest because of the natural redox potential of Na/Na+ (À2.71 V vs. SHE) is higher than that of
abundance and the low cost of sodium.3–5 So far, the investigation Li analogues (À3.04 V vs. SHE), the sodium derivative Na2DBQ
of electrode materials for SIBs is mainly focused on transition- should possess lower operation potential (vs. Na/Na+), which
metal inorganic compounds6–8 or alloy-based materials,9–11 which might make it a suitable anode for SIBs. Moreover, it could also
are synthesized from limited resources and thus give rise to the offer good stability due to its highly ionic nature.13 Herein, we
problem of cost and availability concerns. In contrast, organic firstly reported the application of Na2DBQ as an electrode for
materials without expensive elements are potential low cost and SIBs. The as-prepared Na2DBQ exhibits high reversible capacity
sustainable electrodes.12–16 In this regard, various electrochemical (265 mA h gÀ1) with an average storage voltage of B1.2 V (vs.
dopable polymers have been studied for SIBs and gained recent Na+/Na). Furthermore, Na2DBQ also demonstrates high cyclability
achievements.17,18 The energy density of these materials is limited up to 300 cycles and high rate capability up to 5 C, rendering it a
by doping levels as well as the anion–cation doping–de-doping promising anode for SIBs.
mechanism which requires a large excess of electrolytes.19 Mean-
Na2DBQ was synthesized through a simple one-pot reaction
while, organic carbonyl compounds are also attractive electrodes of H2DBQ with sodium methylate in dimethyl sulfoxide (DMSO)
because of their processability, redox stability, structural diversity, solution (left part of Scheme 1, see details in the ESI†). The raw
and high theoretical capacities.20–23 Like in LIBs, most organic material of H2DBQ is commercial available. The products were
carbonyl compounds are designed for cathode application, such as characterized by NMR (Fig. S1, ESI†), FTIR (Fig. S2, ESI†), and
Na2C6O6,24 indigo carmine,25 3,4,9,10-perylene-tetracarboxylicacid- elemental analysis, all confirming the successful synthesis of
dianhydride (PTCDA),26 and a series of dianhydride-based poly- the target Na2DBQ.
imides.27 In comparison, only a few organic carbonyl compounds
The resulting Na2DBQ is in the form of dull red powder and
are suitable candidates for anode materials.28 For example, sodium exhibits irregular morphology with an average size in the sub-
terephthalate and its derivatives have been proposed as anodes micron range as observed in the scanning electron microscope
for SIBs,29–31 showing cycle life up to 100 cycles with reversible (SEM) image (Fig. 1a). The BET specific surface area of Na2DBQ
capacity in the range of 170–300 mA h gÀ1. More recently, the
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education),
Collaborative Innovation Center of Chemical Science and Engineering,
Nankai University, Tianjin, 300071, People’s Republic of China.
E-mail: chenabc@nankai.edu.cn; Fax: +86-22-23509571; Tel: +86-22-23506808
† Electronic supplementary information (ESI) available: The synthetic procedure
of Na2DBQ, 1H NMR spectrum, FTIR spectrum, and elemental analysis of
Scheme 1 The synthetic route (left part) and the proposed electrochemical
redox mechanism (right part) of Na2DBQ.
prepared Na2DBQ. See DOI: 10.1039/c4cc08220f
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Fig. 1 (a) SEM image (b) and the TG curve of prepared Na2DBQ.
was 27.2 m2 gÀ1 (Fig. S3, ESI†), which is favorable for the
electrode–electrolyte contact. Also, the small particle size could
shorten the ion diffusion path and thus help to achieve high
rate performance. In addition, thermogravimetric (TG) analysis
of Na2DBQ demonstrates that no obvious mass loss is observed
up to around 255 1C (Fig. 1b). Thermal stability is acceptable for
practical application concerning the safety issue.34
Na2DBQ contains two carbonyl groups as redox centers and
can afford a high theoretical capacity of 291 mA h gÀ1 through
reversible uptake of two sodium ions per formula unit (right
part of Scheme 1). On the other hand, because of the ionic
nature of Na2DBQ, the dissolution issue of low molecular
organic compounds is expected to be restrained.35 To prove
this concept, the electrochemical performance of Na2DBQ was
evaluated using CR2032 coin-type half cells with sodium foil as
a counter electrode. The working electrodes consist of Na2DBQ
(60 wt%), conductive carbon (30 wt%), and the PVdF binder
(10 wt%). The mass loading of the active material on the
Fig. 2 (a) Initial three voltage profiles and (b) cycling performance of
Na2DBQ in the voltage range of 0.5–2.5 V at a 0.1 C rate.
electrode is about 1.2 mg cmÀ2. The thickness of the electrode 265 mA h gÀ1, which is comparable with previous proposed
is about 20 mm (Fig. S4, ESI†). The electrolyte was 1 M NaClO4 in carbonyl-based anode materials.29–32 Furthermore, the Na2DBQ
a mixture of ethylene carbonate (EC) and dimethyl carbonate electrode can offer satisfactory cycle performance. The capacity
(DMC) (1 : 1 by volume). Glass fiber was used as an electrolyte. remained at 231 mA h gÀ1 after 50 cycles. Thus, the capacity
The cell was cycled in the voltage window of 0.5–2.5 V. The retention reaches 87% from the second cycle to the fiftieth
specific capacity values are calculated on the basis of the mass cycle. The good cycle stability is benefited from the increased
of the active materials.
polarities through salt formation which can effectively suppress
Fig. 2a shows the initial three discharge–charge profiles of dissolution.13 Additionally, the coulombic efficiency quickly
the assembled cell at a 0.1 C rate (1 C = 291 mA h gÀ1). The first increased to 99% after initial few cycles, even though it was
discharge curve exhibits a long plateau at about 1.22 V, giving relatively low at the first cycle. It should be pointed out that a
an initial discharge capacity of 398 mA h gÀ1. However, only very recent work demonstrated that polymerization of an
67% of the capacity is reversible. Meanwhile, the discharge organic salt could completely prevent the active material from
curves changed significantly in the following cycle, showing two dissolving.23 It is believed that this strategy should also be very
plateaus at B1.28 and B1.20 V, respectively. This is indicative of useful for further increasing the cycling stability of Na2DBQ.
an activation process associated with the large volume expansion
The rate performance of Na2DBQ was also investigated.
during the first sodiation. Such a phenomenon shows the results Fig. 3a presents the typical discharge and charge profiles of
of some organic electrodes with large volume changes such as Na2DBQ at various current densities. At a 0.1 C rate, the
croconic acid.32 The two discharge plateaus in the subsequent obtained capacity reaches 265 mA h gÀ1. When the current
cycles should correspond to a two-step 2eÀ reduction reaction of density became 10 times higher (1 C), a specific capacity of
the quinonoid carbonyl groups, accompanied by the insertion of 248 mA h gÀ1 can still be achieved with small polarization.
Na+ into Na2DBQ. Moreover, these two processes are reversible Even at a rate of 5 C, 60% of the capacity delivered at 0.1 C can
in the charge process. Two distinct plateaus located at 1.28 and be realized. The good rate capability should be ascribed
1.59 V can be clearly seen in the charge curves. The shape of the to the large surface area and short ion diffusion length pro-
voltage profiles remained nearly unchanged after the first cycle, vided by the small Na2DBQ particles. Furthermore, organic
demonstrating good redox reversibility. The reversible reaction molecules usually possess less rigid crystal structure com-
is further confirmed by the cyclic voltammetry as shown in pared to inorganic compounds, thus favoring Na+ insertion–
Fig. S5 (ESI†). Note that the capacity of the second cycle reaches deinsertion.30 As a result, Na2DBQ can operate at high current
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This work was supported by the Programs of National 973
(2011CB935900), NSFC (51231003), and MOE (B12015 and
IRT13R30) and Tianjin City (13JCQNJC06400).
Notes and references
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In summary, the disodium salt of 2,5-dihydroxy-1,4-benzo-
quinone was prepared through a simple one-pot solution
method using commercial available raw materials and found
to be suitable as anode material for SIBs for the first time.
Without any modification, Na2DBQ can operate at an average
discharge voltage of B1.2 V with good electrochemical perfor-
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long cycle life (up to 300 cycles at 1 C), and high rate capability
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