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 Chapter 4

C/Li2MnSiO4 Nanocomposite
Cathode Material for Li-Ion Batteries

Marcin Molenda, Micha witosawski and Roman Dziembaj

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/48319

1. Introduction
Technological development of portable devices, e.g, mobile phones, laptops, etc., as well as
progress in electrical vehicles (EV) and hybrid electrical vehicles (HEV) technologies require
batteries efficient in volumetric and gravimetric energy storage, exhibiting large number of
charge/discharge cycles and being cheap and safe for users. Moreover, materials used in
energy storage and conversion systems should be environmentally friendly and recyclable.
Currently, rechargeable lithium-ion batteries (LIBs) are the most popular portable energy
storage system, mostly due to their highest energy density among all others rechargeable
battery technologies, like Ni-Cd or Ni-MH cells which reached the theoretical limit of
performance. Commercially available LIBs are based on layered lithium cobalt oxide
(LiCoO2) or related systems, which are expensive and toxic. These materials are unstable in
an overcharged state, thus the battery safety is affected, especially in high power (20-100
kWh) applications for EV, HEV and renewable energy systems. The bigger battery capacity
results in more energy accumulated, thus operational safety is a key issue. On the other
hand, lifetime and capacity retention of LIBs in changeable operation conditions (from -30C
to +60C, average lifetime 2-4 years) are a challenges to develop new materials and cell
assembly technologies.

2. Li-ion battery technology

First rechargeable lithium cells taking advantages of intercalation process were developed in
year 1972 [1]. The cells Li/Li+/LixTiS2 revealed 2V potential and relatively low gravimetric
capacity. Applications of metallic lithium as anode material resulted in common cell
breakdown due to formation of dendritic structures on anode during cell cycling. The
problems forced research and development of new intercalation materials for lithium
batteries. In the eighties a new conception of lithium cell was proposed (so called Li-ion

2012 Molenda, licensee InTech. This is an open access chapter distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
62 Composites and Their Properties

batteries or rocking-chair batteries), which consisted of application of two different

lithium intercalation compounds as anode and cathode materials [2-4]. As anode material a
graphite intercalated with lithium was used while cathode materials were based on layered
3d transition metal oxides.

2.1. Layered LiCoO2 oxide and related systems

The first LixC6/Li+/Li1-xCoO2 Li-ion battery system was commercialized in 1993 by Sony Co.
In Fig. 1 a working mechanism during discharge cycle of Li-ion cell is presented.

Figure 1. Working mechanism of Li-ion batteries (discharge cycle).

The electrochemical reaction at the graphite anode side can be written as (1):

C6 + xLi+ + xe- LixC6 (1)

and suitably at LiCoO2 cathode side (2):

LiCoO2 Li1-xCoO2 + xLi+ + xe- (2)

Commercially available LIBs based on layered lithium cobalt oxide (LiCoO2) or related
systems (LiNiyCo1-yO2, LiMnyCo1-yO2, LiMn1/3Ni1/3Co1/3O2) reveal reversible capacity 130-150
mAh/g and working potential 3.6-3.7 V. The oxide materials are expensive and toxic due to
cobalt content and are unstable in an overcharged state, thus the safety is strongly affected.
This is related to strong oxidizing behavior of the charged layered oxide cathode in contact
with organic electrolyte what may lead to combustion or even explosion [4, 5].
Unfortunately, this effect may be also increased by application of nanosized materials with
high surface area.
 C/Li2MnSiO4 Nanocomposite Cathode Material for Li-Ion Batteries 63

2.2. Spinel LiMn2O4 and related systems

An alternative material for cathode based on layered oxides LiMyCo1-yO2 (M=Ni, Mn, Fe) is
LiMn2O4 spinel. LiMn2O4 reveals a little lower reversible capacity 120 mAh/g at working
potential 4 V, but the material is distinctly cheaper and nontoxic. However, application of
spinel as cathode material in commercial Li-ion batteries is retarded by phase transition
observed near room temperature, i.e. battery operation temperature, and related to Jahn-
Teller distortion of Mn3+ ions, what resulted in capacity fading. Stabilization of cubic spinel
structure is possible by controlled formation of cationic defects [6], by lithium [7] or 3d
metal substitution [8] into spinel lattice as well as by isoelectronic sulfur substitution [9, 10].
Instability of high oxidation state of transition metal in spinel structure observed in charged
state of cathode leads to oxygen evolution, similarly to the layered oxide cathodes, and
reaction with electrolyte. Application of spinel based materials is limited to cheap battery
packs for EV [11].

2.3. Olivine LiFePO4 cathode material

An interesting and very promising group of insertion materials are LiMXO4 (M= metal 3d,
X=S, P, As, Mo, W) type compounds [12], with LiFePO4 among them. LiFePO4 lithium iron
phosphate of olivine structure is chemically and thermally stable material with relatively
high gravimetric capacity 170 mAh/g at working potential 3.5 V. The material is cheap,
nontoxic and environmental friendly. Its high chemical stability towards electrolyte, related
to strong P-O bonds, significantly improves safety of LIBs. However, very low electrical
conductivity of LiFePO4 system (10-9 S/cm @RT) requires application of carbon coatings and
composite formation [13, 14].

3. Orthosilicates Li2MSiO4 New high capacity cathode materials

Application of orthosilicates Li2MSiO4 (M=Fe, Mn, Co, Ni) compounds as insertion materials
for LIBs was firstly proposed by Prof. Goodenough [12, 15]. The materials mainly
crystallizes in orthorhombic system of Pmn21 space group in olivine structure [16-18]. The
Li2MSiO4 olivine structure may be described as wavy layers of [SiMO4] on ac axis plane and
connected along b axis by LiO4 tetrahedra [16]. Within the layers every tetrahedron SiO4
shares its corner with four next MO4 tetrahedra. Lithium ions occupy the tetrahedral sites
(LiO4) between two layers and share 3 and 1 oxygen atoms with the layers. In fact, diffusion
of lithium ions in this structure is possible only through the canals formed by LiO4
tetrahedra. Li2MSiO4 silicates reveal a possibility of reversible insertion of two lithium ions
per molecule, so this leads to exchange of two electrons by transition metal. As a results the
silicates reveal very high theoretical gravimetric capacity, up to 330 mA/g. However,
structural limitation due to sharing of LiO4 between two wavy layers, should affect a little
the capacity. Calculations of electrochemical potential of lithium insertion/deinsertion show
a two stage process:

Li2M2+SiO4 LiM3+SiO4 + Li+ (3)

64 Composites and Their Properties

LiM3+SiO4 2M4+SiO4 + Li+ (4)

Depending on transition metal potential of the reaction (3) vary from 3.2 V (for Fe) to 4.1-4.4
V (for Mn, Co, Ni), while the potential of reaction (4) is in range 4.5-5.0 V. Deinsertion of the
second lithium ion requires applying high potential above 4.5 V, and this is a challenge for
electrolyte. Orthosilicates Li2MSiO4 (M=Fe, Mn, Co, Ni) materials reveal very low electrical
conductivity (10-12 - 10-15 S/cm @RT) and carbon coating of the materials is required. On the
other hand, downsizing of material grains should improve electrochemical performance
[18]. Very strong covalent bonding of Si-O results in high chemical stability towards
electrolyte, strongly increasing the safety of LIBs based on silicates. The materials are
nontoxic, environmental friendly and cheap. The properties mentioned above provide a
challenge for developing a composite cathode materials based on Li2MSiO4 orthosilicates.

4. Li2MnSiO4 nanostructured cathode material

Li2MnSiO4 is a member of dilithiumorthosilicates Li2MSiO4 (M = Fe, Mn, Co) family,
thanks to strong covalent Si-O bond, it shows high thermal and chemical stability. High
theoretical capacity 333 mAh/g, low production costs, safety and optimal working
potential make them an attractive cathode material. Very low electrical conductivity
(10-12 - 10-15 S/cm @RT) can be improved by coating with conductive carbon layers (CCL)
and by grains size downsizing [18-20]. The properties of Li2MnSiO4 material comes to a
conclusion that cathode material for LIBs based on this compound should be prepared as
C/Li2MnSiO4 nanocomposite. Thus, the special preparation techniques have to be applied
in terms to obtain nanocrystaline grains of Li2MnSiO4 cathode material coated by
conductive carbon layers (CCL). During last few years several different technics of
Li2MnSiO4 synthesis were proposed. Hydrothermal synthesis [21-24] as well as solid-state
reactions [25-28] can lead to one phase product but the control of the grain size is
significantly limited. Sol-gel method is one of the soft chemistry techniques which can be
used in synthesis of nanosized lithium orthosilicates [29-33]. Sol-gel processes, especially
Pechinis method is a simple technic, characterized by low cost and low temperature of
treatment, resulting in homogenous, high purity materials.

4.1. Preparation of nanostructured Li2MnSiO4

Li2MnSiO4 was produced using sol-gel synthesis Pechini type. Starting reagents were:
lithium acetate dihydrate (Aldrich), manganese acetate tetrahydrate (Aldrich),
tetraethoxysilane (TEOS) (98%, Aldrich) as a source of silicon, ethylene glycol (POCh), citric
acid (POCh) and ethanol (POCh). Thanks to chelating metal ions in solution by citric acid
the cations can be mixed at the molecular level and the stoichiometric composition can be
achived. The reactants were mixed in a molar ratio 1:1:18:6:4:16 -
Mn:Si:C2H6O2:C6H8O7:C2H5OH:H2O. Based on previous studies it was affirmed, that using
20% excess of lithium acetate leads to one-phase product. All reagents were dissolved in
glass reactor under constant argon flow (Ar 5.7). As a solvent, only stoichiometric amount of
distilled water was used. Heating water to 35 C assure fast and complete dissolution of
 C/Li2MnSiO4 Nanocomposite Cathode Material for Li-Ion Batteries 65

metal acetates. Prepared mixture was heated to 60 C and few drops of concentrated
hydrochloric acid was added to initiate polymerization of metal citrates using ethylene
glycol and TEOS. Reaction was conducted for 24h in close reactor. Obtained gel was aged
for 3 days at 60 C in close reactor (Ar atmosphere) and for 3 days at 60 C in an air-drier
(Air atmosphere).

Thermogravimetric analysis (TGA) coupled with simultaneous differential thermal analysis

(SDTA) and mass spectrometry evolved gas analysis (MS-EGA) of precursor were
performed in Mettler-Toledo 851e thermo-analyzer using 150 l corundum crucibles under
flow of air/argon (80 ml/min), within temperature range 20800 C with heating rate of 10
C/min. The simultaneous MS-EGA was performed in on-line joined quadruple mass
spectrometer (QMS) (Thermostar-Balzers). The 17, 18 and 44 m/z mass lines, ascribed to OH,
H2O and CO2 species respectively, were collected during the TGA experiments. TGA of the
Li2MnSiO4 precursor are shown in the Fig. 2 and Fig. 3.

Figure 2. Thermal analysis (TGA/DTG/SDTA) conducted under air atmosphere (a) with evolved gas
analysis (EGA-QMS) (b) of Li2MnSiO4 precursor.

Figure 3. Thermal analysis (TGA/DTG/SDTA) of Li2MnSiO4 precursor performed under inert

atmosphere (Ar 5.0).
66 Composites and Their Properties

According to TGA curve (Fig. 2a) a complete decomposition of gel organic matrix occurs
above 500 C. Evolved gas analysis confirmed the disintegration of organic components.
Amount of active material can be estimated at about 12 wt.% of the precursor. Basing on
TGA results calcination conditions were chosen. Li2MnSiO4 precursor was calcined under Ar
flow at 600, 700, 800 and 900 C.

4.2. Properties of nanostructured Li2MnSiO4

X-ray powder diffraction patterns of the samples were collected on BRUKER D2 PHASER
using Cu K radiation = 1.5418 . In Fig. 4 XRD patterns of Li2MnSiO4 obtained at different
temperatures (600, 700, 800 and 900 C) are collected.

Figure 4. XRD patterns of Li2MnSiO4 after calcination at 600 C, 700 C, 800 C and 900 C. Li2MnSiO4
(Pmn21 phase) diffraction lines positions are marked in the top of the figure.

In the sample calcined at 600 C all diffraction lines can be attributed to pure Li2MnSiO4
phase (Pmn21). In other specimens obtained at higher temperatures, MnO and Li2SiO3
impurities starts to appear. Formation of MnO and Li2SiO3 in samples calcined at
temperatures above 700 C can be connected, with Li2MnSiO4 decomposition. Average
crystallites sizes calculated from diffraction lines broadening based on Scherrer equation are
in the range of 17-19 nm depending on calcination temperature of the sample (Tab. 1). The
calcination under carefully selected conditions leads to a transformation of a part of organic
compounds from the gel matrix into thick carbon layer covering the active material. The
temperature programmed oxidation (TPO) performed using TGA equipment confirmed
presence of carbon in samples. Fig. 5b presents exemplary TG/DTG/SDTA curves from TPO
conducted under air flow in temperature range of 20-1000 C. The amounts of carbon in
samples calcined in different temperatures were calculated from TPO measurements and are
collected in Table 1.
 C/Li2MnSiO4 Nanocomposite Cathode Material for Li-Ion Batteries 67

Measurements of the specific surface area of the samples were performed in Micrometrics
ASAP 2010 using BET isotherm method. About 500 mg of each sample was preliminary
degassed at 250300 C for 3 h under pressure 0.260.4 Pa. Then, N2 sorption was performed
at pressure of 8 104 Pa. One of pore size distribution plot with the adsorption-desorption
curves inset is presented in Fig. 5a. Exact values of specific surface area and average pores
diameters are presented in table 1.

Figure 5. Adsorption-desorption isotherm and pore diameter distribution of C/Li2MnSiO4 calcined at

600C, b) TGA/DTG/SDTA curves of C/Li2MnSiO4 calcined at 600 C.

Low temperature N2-adsorption (BET) measurements of C/Li2MnSiO4 composites show that

specific surface area of samples decrease with increasing calcination temperature. Decrease
of specific surface area is connected with graphitization of carbon during calcination at
higher temperatures.

Average
Precursor Specific Crystallite
Carbon pore
Sample name calcination surface size (from
content dimension
temperature area (BET) XRD)
(BJH)
C/Li2MnSiO4@600 600 C 34% 169 m2/g 50 17 nm
C/Li2MnSiO4@700 700 C 32% 152 m2/g 72 18 nm
C/Li2MnSiO4@800 800 C 32% 144 m2/g 73 19 nm
C/Li2MnSiO4@900 900 C 35% 57 m2/g 73 19 nm
Table 1. Morphology parameters of C/Li2MnSiO4 composites calcined at different temperatures.

Electrical conductivity was measured using the AC (33Hz) 4-probe method within
temperature range of -4055 C. The carbon coated composite powders were so elastic that
the standard preparation of pellets was impossible. The fine powder samples were placed
into a glass tube and pressed by a screw-press between parallel gold disc electrodes (=5
mm) till the measured resistance remained constant. The results of electrical conductivity
measurements are gather in Fig. 6. All composites exhibit good electrical conductivity (up to
0,36 S/cm for C/Li2MnSiO4@900) in comparison with Li2MnSiO4 itself ( 10-15 S/cm at room
68 Composites and Their Properties

temperature - RT). It can be observed that temperature dependence of conductivity for

composites calcined at higher temperatures (700, 800 and 900 C) seem unaffected, by
temperature (metallic-like behavior). Conductivity value and its invariability against
temperature indicate that carbon layers consist of graphite-like domains. In case of
C/Li2MnSiO4@600C the carbon layers is more disordered and probably consist of an
activated-like carbon. Those results are consistent with BET measurements in case of
graphitization process occurring at higher temperatures.

Figure 6. Electrical conductivity measurement of C/Li2MnSiO4 (temp. range: -20 to 40C). Dash line
represent room temperature (RT).

Selected samples were investigated using transmission electron microscope (TEM) (Fig. 7
and Fig. 8). Micrographs were collected on TECNAI G2 F20 (200 kV) coupled with an
energy dispersive X-ray spectrometer (EDAX).

TEM micrographs reveal well dispersed lithium manganese orthosilicate grains (dark grey
and black dots) in the carbon matrix. Figures 7a; 7c; 7d present C/Li2MnSiO4@600 at different
magnifications. Fig. 7b shows STEM-HAADF (Scanning Transmission Electron Microscopy
High Angular Annular Dark Field) image of the C/Li2MnSiO4@600 composite. Energy
dispersive X-ray spectroscopy (EDS) (Fig. 7b1; 7b2) confirmed presence of lithium
manganese silicate in the spots marked in the micrograph 7b (Cu peaks in all EDS spectra
originate from TEM copper grid). High resolution electron microscopy image (HREM)
shows single grain of Li2MnSiO4 (Fig. 7e). Corresponding to that IFFT (Inverse Fast Furrier
Transform) image (Fig. 7f) clearly shows a crystalline structure of obtained material which
can be identified as Li2MnSiO4. Grains in the composite have sizes in a range of 5-10 nm.
Microstructure of a C/Li2MnSiO4 composite calcined at 700 C is shown in Fig. 8.
C/Li2MnSiO4@700 C composite has a bimodal distribution of a crystallite size. TEM
micrographs show presence of small (5-10 nm) Li2MnSiO4 crystallites, analogues of
C/Li2MnSiO4@600 C and a bigger, well crystallized silicates grains, in a range of 50-150 nm
(Fig. 8a, c, d). Both types of crystallites in the sample have the same composition which is
confirmed by EDS analysis presented in fig. 8b1, b2, b3.
 C/Li2MnSiO4 Nanocomposite Cathode Material for Li-Ion Batteries 69

Figure 7. TEM micrographs of C/Li2MnSiO4@600. Micrographs a), c) and d) present bright field images
of C/Li2MnSiO4@600 composite in different magnification; b) microstructure image observed in STEM-
HAADF with EDS analysis (b1; b2) from marked points; e) high resolution micrograph (HREM) of a
single grain and IFFT image f) from the same region.
70 Composites and Their Properties

Figure 8. TEM micrographs of C/Li2MnSiO4@700. Micrographs a), c) and d) presents bright field images
of C/Li2MnSiO4@700 composite in different magnification; b) microstructure image observed in STEM-
HAADF with EDS analysis (b1; b2; b3) from selected points; d1) high resolution micrograph (HREM) of
region marked in Fig. 8d; d2) IFFT image from square marked in d1).
 C/Li2MnSiO4 Nanocomposite Cathode Material for Li-Ion Batteries 71

STEM-HAADF image (Fig. 8b) from the same region as a bright field Fig. 8a shows points
from where EDS analysis was conducted. All of lithium manganese orthosilicate
crystallites in C/Li2MnSiO4@700 C are well dispersed and fully covered in amorphous
carbon. HREM image in Fig. 8d1 with IFFT in Fig. 8d2 shows crystalline structure of
Li2MnSiO4 grain.

5. C/Li2MnSiO4 composite cathode material

Nevertheless obtained composites show homogeneous distribution of particles in carbon
matrix and exhibit good electrical conductivity they work poorly in a battery cell (see
paragraph 5.2). Thickness of primary carbon coating on active material grains strongly
limits the electrochemical performance of composite.

5.1. CCL/Li2MnSiO4 composite preparation and properties

Preparation of composites with well define morphology of carbon layers and optimal
carbon content was achieved by burning out the primary carbon and recoating
Li2MnSiO4 nanosized grains with conductive carbon layers (CCL/Li2MnSiO4 composites).
Burning out of primary carbon formed in the sample during synthesis process was
carried through calcination of C/Li2MnSiO4@600 and C/Li2MnSiO4@700 under air flow at
300 C for 3 h. CCL/Li2MnSiO4 composites were produced by wet polymer precursor
deposition on active material grains and subsequent controlled pyrolysis [14, 20, 34].
Poly-N-vinylformamide (PNVF) obtained by radical-free polymerization of N-
vinylformamide (Aldrich) with pyromellitic acid (PMA) additive (5-10 wt%) was used as
a carbon polymer precursor [34]. To achieve an impregnation, Li2MnSiO4 grains were
suspended in water polymer solution (8-15 wt%). Finally, samples were dried up in an
air drier at 90 C for 24 h. Prepared samples were pyrolyzed at 600 C for 6 h under inert
atmosphere (Ar).

Burning out primary carbon from the surface of lithium manganese silicate in air
atmosphere leads to partial decomposition of active material. Fig. 9 shows XRD patterns of
C/Li2MnSiO4@600, Li2MnSiO4@600 without carbon and CCL/Li2MnSiO4@600 composite after
coating with CCL from polymer precursor.

In diffraction patterns of Li2MnSiO4@600 it is clearly visible that after burning out primary
carbon layer new phase appears in the sample (LiMn2O4). Proposed carbon coating process
can reverse decomposition of Li2MnSiO4. After coating Li2MnSiO4 (Pmn21) is a dominant
phase in CCL/Li2MnSiO4@600 and all the lines, except for very low intensity line around 19,
can be associated with Li2MnSiO4 phase. CCL preparation procedure influence active
material grain size. Average crystallite size calculated using Scherer equation in
CCL/Li2MnSiO4@600 is ca. 25 nm. TEM analysis confirms increase of crystallites diameters.
Li2MnSiO4 grains observed under TEM are in the range 25-75 nm. TEM micrographs of
CCL/Li2MnSiO4@600 are presented in Fig. 10.
72 Composites and Their Properties

Figure 9. XRD patterns of C/Li2MnSiO4@600, Li2MnSiO4@600 and CCL/Li2MnSiO4@600.

Bright field micrographs (Fig. 10a, c, d) shows crystallites of Li2MnSiO4 covered with
conductive carbon layers (CCL). Formed carbon coatings adhere well to the surface of active
material grains, no voids are visible at the CCL/Li2MnSiO4 interface (Fig. 10e). Silicate grains
are uniformly covered with approximately 4-5 nm thick CCL. EDS analysis once again
confirm presence of lithium manganese silicate in the composite (Fig. 10b, b1). Carbon
content in samples was calculated from TPO measurements and they are displayed in
Table 2.

Precursor calcination
Sample name Carbon content
temperature

CCL/Li2MnSiO4@600_7.5% 600 C 7.5%

CCL/Li2MnSiO4@600_12% 600 C 12%

CCL/Li2MnSiO4@700_5% 700 C 5%

CCL/Li2MnSiO4@700_10% 700 C 10%

Table 2. Carbon content of CCL/Li2MnSiO4 composites.

 C/Li2MnSiO4 Nanocomposite Cathode Material for Li-Ion Batteries 73

Figure 10. TEM micrographs of CCL/Li2MnSiO4@600. Micrographs a), c) and d) presents bright field
images of CCL/Li2MnSiO4@600 composite; b) microstructure image observed in STEM-HAADF with
EDS analysis (b1) from selected point; e) HREM micrograph of carbon coating on the active material
grain surface.
74 Composites and Their Properties

5.2. Electrochemical properties of C/Li2MnSiO4 composite cathode

The charge-discharge cycling studies of Li/Li+/(C/Li2MnSiO4) cells were conducted in a four
electrode configuration using CR2032 assembly between 2.7 and 4.7 V at C/200 rate at room
temperature. LiPF6 solution 1M in EC/DEC (1:1) was used in the cells as an electrolyte. The
galvanostatic measurements were carried out using ATLAS 0961 MBI test system. Charge-
discharge tests were conducted for all CCL composites listed in table 2, composites with
primary carbon (C/Li2MnSiO4@600, C/Li2MnSiO4@700 and C/Li2MnSiO4@800) and standard
composites (Li2MnSiO4@600_CB and Li2MnSiO4@700_CB). Standard composites were
prepared by mixing Li2MnSiO4 powder with commercial carbon additive carbon black
(CB). 15 wt.% of carbon was used. Results collected from charge/discharge tests are
presented in fig. 11-16.

C/Li2MnSiO4@600 sample did not show any reversible capacity (Fig. 11a). Lack of
electrochemical activity of C/Li2MnSiO4@600 is connected with too high carbon loading.
High carbon content (34%) is responsible for limiting of ionic conductivity in the
composite and for surface polarization. Galvanostatic cycling studies of
C/Li2MnSiO4@700 and C/Li2MnSiO4@800 revealed reversible capacity in a range of 30
mAhg-1. Fig. 11b show charge and discharge capacity for 7 cycles of C/Li2MnSiO4@700
composite. After first four cycles reversible capacity stabilizes at about 30 mAhg-1. Very
poor performance of this sample is also connected with high amount of carbon in
prepared composite (32%).
Standard composites obtained by mixing active silicate materials with carbon black (15%)
show extremely low reversible capacity as well (Fig. 12a and 12b). In this case, carbon
additive does not provide sufficient electrical contact between active material grains. Due to
this fact, even under low C/200 rate samples performed very poorly in charge/discharge
tests.

Figure 11. Cell cycling behavior of: a) C/Li2MnSiO4@600, b) C/Li2MnSiO4@700.

 C/Li2MnSiO4 Nanocomposite Cathode Material for Li-Ion Batteries 75

Figure 12. Cell cycling behavior of standard composites Li2MnSiO4 + carbon black (15% carbon
content)

Figure 13. Cell cycling behavior of CCL/Li2MnSiO4@600 (7.5% carbon content)

76 Composites and Their Properties

Figure 14. Cell cycling behavior of CCL/Li2MnSiO4@600 (12% carbon content)

Figure 15. Cell cycling behavior of CCL/Li2MnSiO4@700 (5% carbon content)

 C/Li2MnSiO4 Nanocomposite Cathode Material for Li-Ion Batteries 77

Figure 16. Cell cycling behavior of CCL/Li2MnSiO4@700 (10% carbon content)

Fig. 13-16 show cycling behavior of CCL composites with different amounts of carbon.
Delithation of CCL composites after initial charging is in the range of 48-68% (charged
CCL/Li2MnSiO4@600_12%C correspond to composition Li1.04MnSiO4 and charged
CCL/Li2MnSiO4@700_10%C correspond to composition Li0.64MnSiO4). The observed
capacity loss in the first cycles is related to SEI formation in CCL. During lithium extraction,
Mn3+ and Mn4+ appear, and at the same time Li2MnSiO4 undergoes decomposition caused by
Jahn-Teller distortion associated with changes in lattice parameters during Mn3+ Mn4+
transition [30]. Despite the fact that crystalline structure collapses, discharge capacity is
around 90-110 mAh/g. CCL composites produced from Li2MnSiO4 calcined at 600 C exhibit
better coulombic efficiency than Li2MnSiO4 calcined at 700 C, the reversible capacity after
10 cycle is close to 100 mAh/g. The results indicate that coulombic efficiency of cathode
material depends on grain size and homogeneity in grain size distribution, while cell
capacity is limited by carbon coating performance.

6. Conclusions
Dilithium manganese orthosilicate a high energy density cathode material was
successfully synthesized by sol-gel Pechini method. Encapsulation of nanosized grains of
Li2MnSiO4 in carbon matrix, resulted from organic precursor, avoided further sintering.
Different crystallite size was obtained, in particular, nanoparticles within range of 5-10 nm.
High chemical stability of this material under a highly reductive environment was observed.
Application of carbon coating improved electrical conductivity of cathode material to the
78 Composites and Their Properties

satisfactory level of ~10-0.5 S/cm. Thickness of carbon coating on active material grains
strongly limits the electrochemical performance of composite. Formation of CCL/Li2MnSiO4
composites significantly improved electrochemical performance of cathode materials,
showing a reversible capacity of 90-110 mAh/g after 10 cycles. Electrochemical tests
indicated that composite preparation should be optimized in terms of carbon content, CCL
performance and homogeneity of a crystallite size. It was found that coulombic efficiency of
cathode material depends on grain size and homogeneity in grain size distribution, while
cell capacity is limited by carbon coating performance.

Author details
Marcin Molenda*, Micha witosawski and Roman Dziembaj
Jagiellonian University, Faculty of Chemistry, Krakow, Poland

Acknowledgement
This work has been financially supported by the Polish National Science Centre under
research grant no. N N209 088638, and by the European Institute of Innovation and
Technology under the KIC InnoEnergy NewMat project. The part of the measurements
was carried out with the equipment purchased thanks to the financial support of the
European Regional Development Fund in the framework of the Polish Innovation
Economy Operational Program (POIG.02.01.00-12-023/08). One of the authors (M..)
acknowledge a financial support from the International PhD-studies programme at the
Faculty of Chemistry Jagiellonian University within the Foundation for Polish Science
MPD. TEM analysis were carried out in Laboratory of Transmission Analytical Electron
Microscopy at the Institute of Metallurgy and Material Science, Polish Academy of
Sciences.

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