The document discusses three projects being conducted by the National Institute of Fundamental Studies in Sri Lanka: 1) Developing advanced materials for rechargeable batteries including transition metal oxides and methods for battery material synthesis. 2) Developing Sri Lankan minerals like vein graphite for batteries by upgrading and modifying the graphite. 3) Investigating devising rechargeable batteries in Sri Lanka using locally developed materials.

1. Development of advanced materials
and Sri Lankan minerals
for rechargeable batteries
NATIONAL INSTITUTE OF
FUNDAMENTAL STUDIES (NIFS)
Nanotechnology/Physics of Materials Project

2. Project Description
Project (A): Development of advanced materials for rechargeable batteries
Study of effect of dopents in advanced transition metal oxide semiconductors
Development of low-cost and nano technological methods for battery material synthesis
Project (B): Development of Sri Lankan minerals for rechargeable batteries
Development of Sri Lankan vein graphite for the direct use in rechargeable Li-ion batteries
Structural modification / Conversion into nano materials of Sri Lankan graphite for future Na-ion,
Mg-ion and hybrid batteries
Project (C): Investigations on devising rechargeable batteries in Sri Lanka
Using locally developed materials

3. Our strategy :
Development of low-cost and performance enhanced transition metal oxide electrode
materials, with cheaper additives and using novel but low-cost nano-material synthesis
techniques
Li(Ni1/3)Mn1/3Co(1/3-xMx)O2, [M = Al, Fe, Mg, Ba, Na, Cu, Zn ..] for Li-ion battery cathodes
NaNi0.4Mn0.4Co0.2MxOδ [M = Li, Mg, Ba, Ag, Al, Cu, Fe, Ti ..] for Na-ion battery cathodes
Mg1-xMxO2, [M = Mn, Co ..] for Mg-ion battery cathodes
MTiO3 [M = Mg, Na ..] for Na and Mg ion battery anodes
Considering the cost and efficiency,
semi-conducting oxides such as transition metal oxides, are the
best practical electrode materials for rechargeable batteries
Project (A): Development of advanced materials for rechargeable batteries
- transition metal oxides
Compounds containing multivalent ions have the potential for
electronic conductivity;
Due to intrinsic non-stoichiometry OR through doping

4. Developement of Glycine Nitrate Combustion (GNC) technique
as a low-cost nano-material synthesis process
G:N = 1.5
G:N = 0.2
G:N = 0.5
G:N = 0.3
G:N = 0.6
G:N = 0.8
G:N = 0.4
G:N = 1.0
Optimization of Glycine:Nitrate (G:N) ratio in GNC process
G:N = 1.2
Li(Ni1/3Mn1/3Co1/3)O2
Successful synthesis of the solid solution phase of the required R3m layered
structure of Li(Ni1/3Mn1/3Co1/3)O2 electrode materials used in Li-ion batteries
A low-cost wet-chemical method
Self sustaining rapid process with
high yield
Can produce homogeneous fine
(nano size) particles with dual particle
morphology appropriate for LIB
G:N Ratio 0.2 0.4 0.6 0.8 1.0
Particle Size (nm) 78 68 64 62 58

5. Performance of the developed Li(Ni1/3Co1/3Mn1/3)O2 based
cathodes in Li-ion rechargeable cells
Very high discharge capacity of 180 mAhg-1 at
room temperature, considerably higher than
that reported for LiCoO2 (128 mAhg-1)
-20 0 20 40 60 80 100 120 140 160 180 200 220
2.5
3.0
3.5
4.0
4.5
PotentialVsLi/Li
+
Capacity mAhg
-1
C rate = C/5 , Cycle Between 2.4 – 4.6 V
In CR2032 coin cells using lithium metal
foil as the counter and reference
electrodes with 1M LiPF6 electrolyte.
M x
1st cycle
charge
capacity
mAhg-1
1st cycle
discharge
Capacity
mAhg-1
1st cycle
irreversible
capacity
mAhg-1
333 0 212 180 42
Mg 0.08
205 143 62
Na 0.04 248 175 73
LiCoO2 147 128 12

6. Project (B): Development of Sri Lankan minerals for rechargeable batteries
- natural vein graphite
STEP I: UPGRADING GRAPHITE
- Development of low-cost but efficient purification techniques
- Surface modification of purified graphite
STEP II: BATTEY GRADE GRAPHITE
Development of upgraded graphite for rechargeable batteries
- Direct use in Li-ion batteries
- Through interlayer expansion / Conversion to nano materials
DEVELOPMENT OF SRI LANKAN NATURAL VEIN GRAPHITE
Sri Lanka is the only commercial producer of vein graphite,
which is the rarest and most valuable form of graphite.
Limitations: Impurities and inferior surface structure
Shiny-slippery-fibrous
Coarse flakes of radial
Needle-platy
Coarse striated-flaky
Many specialized markets such as rechargeable batteries command premium prices
for natural graphite but require upgrading through purification and further modification

7. STEP I: Upgrading of Sri Lankan vein graphite
Purification
Acid
Leaching
with
5 vol.% HCl
at 60 0C
Roasting
with
5 wt.%
NaOH
Acid
treatment
with
5 vol.%
H2SO4
Alkali
Roasting
Acid
Digestion
HF
digestion
With a
mixture of
HF, HNO3
and H2SO4
Vacuum
drying
Surface modification
Mild
Oxidation
Thermal
Oxidation
At 550 0C
Chemical
Oxidation
01) with
HNO3
02) with
H2O2,
03) With
(NH4)2S2O8
Chemical
decomposition
Mixing with
AgNO3 in
water/ethanol
Adding
formaldehyde
and
depositing
ultrafine Ag
particles on
graphite
surface
Alkali
Coating
Mixing with
0.5%
Li2CO3)aq
Drying
at 100 0C
Simultaneous
purification &
modification

8. Upgraded Sri Lankan vein graphite
Purifying by acid leaching Purifying by alkali roasting
Low cost and easy process with low energy consuming
All these techniques use low concentrations of mineral acids/alkali at low temperatures
More environmental friendly than other purification techniques
Our recent
study with HF
acid digestion
resulted over
99.9 % purity &
modified
surface in all
four structural
varieties
Raw Graphite Purified Graphite Modified Graphite

9. STEP II: Developed Sri Lankan graphite for the anode of Li-ion batteries
LIB anode requires a porous carbon and graphite is the optimum suitor
Graphite is the second largest component by weight in LIB
High cost of synthetic graphite has increased the use of natural graphite
Raw Sri Lankan natural graphite
Electrode from developed graphite
Developed battery grade graphite
Discharge capacity
Theoretically
expected value:
375 mAhg-1
Raw vein graphite :
286 mAhg-1
Our developed
local vein graphite:
378 mAhg-1
SUMMARY: Discharge Capacity & Cycle Performance of graphite anodes
250
300
350
400
450
0 5 10 15 20 25 30 35 40 45 50 55
CC_Discharge(mAhg-1)
Number of Cycles
Charge - discharge rate = 0.2C

10. Project (C): Investigations on Devising rechargeable batteries in Sri Lanka
Performance of a full Li-ion rechargeable battery
with both anode and cathode materials
developed at NIFS
Method:- CCCV (3 -4.2 V),
Charge Discharge 0.2 C rate 3-4.2 V vs Li/Li+
Anode: Developed Sri Lankan Graphite
Cathode: Developed Li(Ni1/3Co1/3Mn1/3)O2
0 2 4 6 8 10
0
50
100
150
0 2 4 6 8 10
0
20
40
60
80
100
ColumbicEfficiency%
Capacity(mAhg
-1
)
Cycle Number
Charge
Discharge
Irreversibl
1st cycle discharge capacity:
98.7 mAhg-1

11. Structural modification / Conversion of Sri Lankan graphite into nano materials
for future Na-ion, Mg-ion and hybrid batteries
- through converting to extended graphite
(by improved Hummers’s method)
ν C=O stretching :- 1720-1680 cm-1,
ν O-H stretching :- 1360 - 1400 cm-1 and
ν C-O stretching :- 1260-1000 cm-1
ν c=c stretching :- 1637 cm-1
Aliphatic C-H :- doublet at 2921 and 2850 cm-
1
The main peak in graphite at 26.7
degrees corresponds to an interlayer
spacing of ~ 0.3 nm.
The newly formed broad peak at 9.6
degrees (corresponding to an
interlayer spacing of ~ 0.9 nm)
indicate formation of EG.
This results in an interlayer
expansion and indicate the
possibility of intercalating bigger
ions such as Na, Mg … ???
5.00 15.00 25.00 35.00 45.00 55.00 65.00 75.00 85.00
Intensity/a.u
2 theta/degrees
SSF vein graphite
5.00 15.00 25.00 35.00 45.00 55.00 65.00 75.00 85.00
Intensity/a.u
2 theta/degrees
Expanded graphite by
SSF
(002)
EG
(004)
a
b
Our recent studies
showed a very
strong dependence
of the expansion of
interlayer spacing
on the vein
graphite variety
and the oxidant
used
Investigations on
ion intercalation to
EG is currently
going on

12. Thank you