Materials Chemistry and Physics 113 (2009) 309313

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Carbon anode material formed from template molecules occluded in a

magnesium-substituted aluminophosphate
Yu Zhang, Feng Zhang, Guo-Dong Li, Jin Yang, Jie-Sheng Chen
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A new doped carbon material has been prepared from a magnesium-substituted aluminophosphate with
Received 9 January 2007 occluded organic molecules. The carbon material is mainly composed of microcrystalline graphite and
Received in revised form 26 June 2008 amorphous carbon, and a certain amount of H, N and Al also exist in the material. This carbon material is
Accepted 18 July 2008
useful as anode material for lithium secondary batteries. After 15 cycling tests, the carbon material retains
a reinsertion capacity of 384 mAh g1 at a current density of 10 mA g1 . Even at a high current density of
Keywords:
100 mA g1 , the reversible capacity of the carbon material is 185 mAh g1 after 20 cycling tests.
Carbon material
2008 Elsevier B.V. All rights reserved.
Doped
Zeolite
Anode material

1. Introduction treatment, the graphitization degree of non-graphitized carbon

The fast growth in portable electric devices such as laptop com-
puters, mobile phones and cameras has led to search for new
batteries, which possess a compact light weight, a high energy den-
sity and a high power capacity. Among the conventional batteries
(for example, lead-acid, nickel-metal hydride, nickel- cadmium and
lithium ones), lithium secondary batteries are capable of meeting
these demands [13].
At present, highly graphitized carbon materials are usually used
as the anode material for lithium secondary batteries [4]. These
materials possess some advantages such as acceptable capacity
and very at potential as low as Li metal. However, the prepa-
ration of conventional graphitized carbon materials needs high
temperature treatment and the theoretical capacity of the mate-
rials is limited to 372 mAh g1 , which is much lower than that of Li
metal (3860 mAh g1 ). Accordingly, researchers have been trying
to develop new anode materials that exhibit higher capacities. In
recent years, a variety of species such as non-graphitized carbon
materials, metal alloys, nitrides and metal oxides have been tested
as anode materials for lithium secondary batteries [57]. Among
these materials, non-graphitized carbon materials have attracted
particular attention due to abundance of raw materials, lower
costs and higher capacities. Furthermore, the treatment tempera-
tures for non-graphitized carbon materials are lower (5001200 C)
than those for graphitized carbons. As a result of low temperature
Corresponding author. Fax: +86 431 85168624.
E-mail address: chemcj@jlu.edu.cn (J.-S. Chen).
materials is not high and these materials are mostly composed
of microcrystalline graphite and amorphous carbon. Although
higher capacities have been observed for the previously reported
non-graphitized carbon anode materials, the reversibility of high-
capacity charge/discharge for these materials is usually poor, and
larger cycling numbers are required to achieve the reversible capac-
ities [8].
Usually, non-graphitized carbon materials are prepared via
pyrolysis of small organic molecules with the assistance of cat-
alysts such as Fe, Co and Ni, direct pyrolysis of polymers and
carbonization of other precursors rich in carbon at relatively
low temperatures [9,10]. Recently, in order to improve the per-
formance of the non-graphitized carbons, doped carbons with
heteroatoms such as N, Si and S have been synthesized [11,12].
The conventional approach to synthesis of doped carbon materials
involves co-deposition by chemical vapor deposition (CVD) of car-
bons and heteroatoms, pyrolysis of organic molecules containing
heteroatoms, and chemical treatment of the carbon materi-
als.
In this paper we report an alternative route for the preparation
of doped non-graphitized carbon, which is very useful as an anode
material for lithium secondary batteries. In our experiment, we
used microporous crystalline magnesium aluminophosphate con-
taining template organic molecules as a precursor, and the carbon
material was formed through pyrolysis of the template molecules
and separated by dissolving the inorganic frameworks in HCl solu-
tion. No additional carbon and heteroatom source and transition
metals as catalysts were involved in the preparation process of the
carbon material.

0254-0584/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.07.085
310 Y. Zhang et al. / Materials Chemistry and Physics 113 (2009) 309313

2. Experimental

2.1. Preparation of microporous crystalline magnesium-substituted

aluminophosphate MAPO-11

The synthetic process of the microporous crystalline compound MAPO-11 (AEL)

with occluded template molecules was described previously [13]. Typically, Alu-
minum hydroxide hydrate (Al2 O3 57 wt.%, 17.9 mmol) and MgSO4 7H2 O (1.6 mmol)
were dispersed in 10 mL deionized water. To the mixture were added phosphoric
acid (85 wt.%, 20.3 mmol) and di-n-propylamine (11.7 mmol) under continuous stir-
ring. The gel then was transferred into a 30 mL PTFE-lined autoclave and heated at
180 C for 34 days. White MAPO-11 crystals were obtained from the reaction sys-
tem after ltration and washing with deionized water, and the product was dried at
100 C.

2.2. Preparation of doped non-graphitized carbon materials

The MAPO-11 crystals were carbonized at an elevated temperature (700 C or

800 C) for 8 h under a N2 gas (99.999%) ow (ow rate 100 mL min1 ). To dissolve
the MAPO-11 framework components (Mg, Al, P, etc.), the black carbonized product
thus obtained was reuxed in a HCl solution for 24 h, washed with deionized water Fig. 1. XPS spectrum of the C800 carbon material.
until pH 7, and dried at 100 C. The carbon material obtained through dissolving the
MAPO-11 crystals treated at 800 C is denoted as C800.

Fig. 2 shows the powder X-ray diffraction patterns of the as-

2.3. Electrode preparation and capacitance measurements
The carbon electrodes were prepared by mixing 90 wt.% carbon material, 5 wt.%
PVDF (polyvinylidene uoride) and 5 wt.% acetylene black with NMP (1-methyl-
2-pyrrolidone) to form the slurry, which was spread onto a copper foil and dried
at 100 C for 24 h in a vacuum oven. The diameter of the electrodes was 15 mm.
The batteries were assembled in an argon-lled gloved-box and the electrolyte was
1 M LiPF6 in a mixture of EC (ethylene carbonate), DMC (dimethyl carbonate) and
EMC (ethyl methyl carbonate) (1:1:1 by weight). The batteries were charged and dis-
charged at 10 mA g1 and 100 mA g1 , respectively, over the voltage range 0.022.0 V
versus Li/Li+ .
2.4. Characterization of the non-graphitized carbon materials
Elemental analyses were conducted on a Perkin-Elmer Optima 3300DV induc-
tively coupled plasma (ICP) spectrometer (for Mg, Al) and a Perkin-Elmer 2400LS
II elemental analyzer (for C, H and N). X-ray photoelectron spectroscopy was per-
formed on a Thermo Electron Corporation ESCALAB 250 XPS spectrometer. The XRD
patterns were recorded on a Siemens D5005 diffractometer with Cu K radiation
( = 1.5418 ), whereas the Raman spectroscopy was performed on a Renishaw 1000
model confocal microscopic Raman spectrometer with an excitation wavelength of
514.5 nm. The infrared spectra were recorded on a Bruker IFS 66 V s1 FTIR spec-
trometer using KBr pellets. The transmission electron microscopic (TEM) images
were taken on a JEOL JEM 3010 electron microscope operated at 300 kV, whereas
the electron spin resonance (ESR) spectrum was recorded on a JES-FA200 ESR spec-
trometer. The charge/discharge tests were carried out on a LAND CT2001A cell test
apparatus.
3. Results and discussion
synthesized MAPO-11, the MAPO-11 samples treated at various
temperatures and the C800 carbon material. It is seen that the
framework structure of MAPO-11 remains until at least 700 C
under the protection of owing nitrogen gas because the charac-
teristic reection peaks for the AEL compound exist for the sample
treated at 700 C or below. At 800 C, dense phases of AlPO4 start to
form as indicated by the reection peaks in the 2025 2 region.
Obviously, a treatment temperature of 800 C leads to the collapse
of the MAPO-11 framework, and the carbon material formed in the
compound may not be conned in the channels of the AEL frame-
work. In other words, the particle size of the carbon formed may
well exceed the size of the AEL channels (about 0.5 nm). There is a
broad XRD peak located at 26.0 for C800, indicating that the car-
bon material after HCl dissolution to remove the AEL framework
components is composed of amorphous carbon [10]. It is believed
that the organic template molecules are carbonized in the zeolite
at lower temperatures, while some heteroatoms (Al in this case)
are doped into the nal product via interaction with the carbon
species when the framework structure is disintegrated at high tem-
peratures (800 C in this case). There are two bands in the Raman
spectrum of the nal carbon material C800 (Fig. 3). The band located
at 1595 cm1 is attributed to the vibration of carbon atoms with
sp2 hybridization in graphene sheet structure of the carbon mate-
rial. The peak at 1350 cm1 is related with the presence of carbon

Table 1 shows the composition of the doped non-graphitized

carbon material C800 we obtained on the basis of the elemental
analyses. It is seen that a certain amounts of H, N and Al besides C
exist in the material, and the total amount in weight percentage is
less than 100%. No Mg and P were detected for the C800 material,
and therefore, the rest of the species apart from C, Al, N and H in
the carbon material should be oxygen. X-ray photoelectron spec-
troscopy (XPS) conrms (Fig. 1) that oxygen does exist in C800. It
is most likely that the O atoms are bound to the Al atoms to form
oxides but the possibility that C-bound O atoms are also present
cannot be excluded.

Table 1
Chemical compositions of the C800 carbon material

Element Composition (wt.%)

C 81.0
H 3.0
N 4.7
Fig. 2. XRD patterns of (a) MAPO-11, (b) MAPO-11 crystals carbonized at 700 C, (c)
Al 1.5
MAPO-11 crystals carbonized at 800 C and (d) C800 carbon material.
 Y. Zhang et al. / Materials Chemistry and Physics 113 (2009) 309313
Fig. 3. Raman spectrum of C800 carbon material.
atoms with dangling bonds (sp3 -bonded carbon atoms) which are
usually found in disordered or amorphous carbons [14,15]. Gener-
ally, the relative intensity of two bands indicates the graphitization
degree of carbon materials. The presence of the relatively strong
band at 1350 cm1 implies that the carbon material C800 we pre-
pared has a low graphitization degree [16]. It should be noted that
the graphitization degree of the carbon materials increases with
the elevation of carbonization temperatures. However, temperature
elevation would reduce the yield of the carbon matter to a consid-
erable extent. The TEM image of the carbon material is shown in
Fig. 4, which demonstrates that C800 is composed primarily of dis-
ordered carbon domains and ordered domains containing stacked
graphene sheets.
In order to better understand the electronic structure of the car-
bon material, the ESR spectrum of the sample was recorded at room
temperature. Fig. 5 shows the ESR spectrum for C800, and an ESR
signal with a Lorentzian line shape, g = 2.00075 and a line width of
0.4 mT (peak to peak width) is observed. In a way similar to those
for most thermally treated carbon materials, the ESR signal of C800
arises from localized radicals. The production of these localized
radicals can be related with imperfection of carbon structure, for
instance, the carbon atoms with unpaired electrons in the border
of small-size graphene layers [1719].
Fig. 4. TEM image of the C800 carbon material.
311
Fig. 5. Room temperature ESR spectrum of the C800 carbon material.
Fig. 6 shows the charge/discharge behavior of the electrode
comprising the carbon material C800 at a current density of
10 mA g1 . Compared to many polymeric precursor-based car-
bons, the carbon material C800 not only has a larger capacity,
but also possesses a better cycling performance. The material
shows a rst-cycle insertion capacity of 1328 mAh g1 and a dein-
sertion capacity of 571 mAh g1 with a coulombic efciency of
43.0%. The charge/discharge irreversibility is attributed to hydrox-
yls and/or sorbed water on the surface of the carbon material [20].
Although the coulombic efciency of the rst cycle is quite low, it
is improved upon cycling. In the 5th cycle, the insertion capacity
of the material is 436 mAh g1 whereas the deinsertion capacity is
414 mAh g1 , with a coulombic efciency of 95.0% being achieved.
After the 15th charge/discharge cycling test, the material retains
an insertion capacity of 403 mAh g1 and a deinsertion capacity of
384 mAh g1 (coulombic efciency 95.3%). The reversible capacity
of the carbon material is considerably higher than the theoreti-
cal one for graphite. From the XRD pattern, Raman spectrum and
TEM, we know that the graphitization degree of C800 is low and
the graphene sheets are present in both parallel and disordered
arrangements in the material. When C800 is used as the anode
material for lithium secondary battery, the lithium atoms are inter-
calated not only in the interspaces between two parallel graphene
sheets as in graphite but also on the surface and the edges of indi-
vidual graphene sheets. In addition, the element analysis indicates
that besides carbon, there are 3.0 wt.% H and 4.7 wt.% N in the
material, respectively. The existence of H inuences the capacity
of carbon materials through the polarized-charge model [21]. On
the other hand, most of the H atoms are bonded to carbon through
CH bonds, and in the discharging process, a covalent CH can react
with lithium to form a covalent CLi bond and increase the capac-
ity of the carbon material [17]. It is also known that N atoms in
carbon material may exist in graphene layers, forming conjugated
C N bonds [22,23]. The electronegativity of nitrogen is higher than
that of carbon so that the nitrogenous graphene sheet tends to
accommodate Li ions more easily than the normal graphene sheets.
Thirdly, the presence of the ESR signal implies that there are some
localized radicals in the carbon material. It has been reported that
localized radicals in carbon materials play a role of electron accep-
tor towards lithium in the course of insertion [19]. Therefore, the
presence of the localized radicals can increase the insertion capac-
ity of the carbon material as well [17]. All these factors contribute
to the enhancement of the charge/discharge capacity of C800. It
is also worth pointing out that there is a voltage hysteresis in the
charge/discharge curves. This is because that the covalent CLi bond
312 Y. Zhang et al. / Materials Chemistry and Physics 113 (2009) 309313

is strong and it needs a high voltage to dissociate during the charge

process.
We also tested the electrode comprising the C800 carbon mate-
rial at a current density of 100 mA g1 . As shown in Fig. 7, the
insertion capacity of the carbon material varies slightly with cycling
and the deinsertion capacity reaches a nearly steady value after
ve cycles. This means that the electrode in the charge/discharge
test at a high current density needs only several cycles to activate
the carbon material. Another superior feature for C800 is that even
when the electrode is tested for 20 cycles at 100 mA g1 , the inser-
tion capacity of the carbon material is still 185 mAh g1 whereas
the deinsertion capacity reaches 184 mAh g1 , with a coulombic

Fig. 7. Cycling behavior of the C800 carbon material. The charge/discharge was
performed at a current density of 100 mA g1 between 2.0 V and 0.02 V.

efciency of 99.5% being achieved. The element analysis indicates

that there is about 1.5 wt.% Al in the C800 carbon material. The Al
and N atoms in the carbon material may affect the chemical prop-
erties of the material so that the Li ions can move faster in the
material [24,25]. As a result, Li ions may be inserted into the car-
bon species more easily under high current density. Moreover, the
presence of localized radicals also leads to fast insertion of Li ions
into the carbon material [19].

4. Conclusions

A doped carbon material has been prepared from a magnesium-

substituted aluminophosphate containing occluded organic
molecules. XRD, Raman and TEM studies show that the carbon
material is composed mainly of domains of disordered and ordered
graphene sheets. Elemental analysis indicates the existence of
heteroatoms such as H, N and Al in the carbon material. The
novel composition and structure confer high charge/discharge
capacity and good cycling performance upon the carbon material
as anode material of lithium secondary batteries. Although it may
not be practical to use the carbon material C800 commercially,
the behavior of the material helps us gain further insights into
the factors that contribute to the performance improvement
of carbon anode materials. On the other hand, the preparation
strategy of C800 may be exploited to design other more econom-
ical routes for manufacture of high-performance carbon anode
materials.

Acknowledgement

Financial support by the National Natural Science Foundation of

China is gratefully acknowledged.

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