Mechanochemical synthesis and

investigation of nanomaterials for lithium-ion

batteries

N.V. Kosova
Institute of Solid State Chemistry and Mechanochemistry SB RAS,
Novosibirsk, Russia

MolE 2012
Dubna, August 27-30
 Outline

• Intercalation electrode materials for lithium-ion batteries.

Challenge for nanosized materials
• Mechanical activation as a promising method to prepare
nanomaterials. Synthetic reactions
• Investigation of as prepared materials. Some examples
• Composite cathode materials

2
 Structural types of cathode materials
Spinel (3D) Layered (2D) Frame-work (1D)

LiО2

СоО2

LiО2

c CoО2

LiО2

CoО2

Fe Li P
LiО2

3
 Comparison of cathode materials

Compound/ Electric Structural, Complexity of

property conductivity chemical and synthesis
thermal stability

LiCoO2

decreases

increases
increases
LiMn2O4

LiFePO4

4
 Materials prepared via mechanochemical route
Layered
Layered Spinel
Spinel Frame -work
Frame-work
structured
structured structured
structured structured
structured
• LiCoO2 • LiMn2O4 • LiFePO4
• LiCo1-xMxO2 • LiMn2-xMxO4 • LiFe1-xMnxPO4
• LiCoO2-Li2MnO3 • LiMn1.5Ni0.5O4 • LiMnPO4
• LiNiO2 (5V) • LiCoPO4
• LiNi1-xCoxO2 • Li4Ti5O12 (anode) • LiNiPO4
• LiNi1-x-yCoxMnyO2 • Li2CoPO4F
• LiV3O8 • Li2NiPO4F
• LiVPO4F
• Li2FeP2O7
• LiTi2(PO4)3
(electrolyte) 5
 Pros and cons of nanosized electrode materials
The particle size (and its distribution), morphology and density of the particles
play a fundamental role on electrochemical performance of electrode materials

Shorter Li+ diffusion paths; Smaller dimensional changes

increased electrode/ Better utilization upon cycling; better adaptability
electrolyte surface contact; of nanoparticle volume of nanoparticles to volume
accelerated ionic transport changes under cycling

Enhanced high-rate Increased practical Improved structural

capability capacity stability

 Intensification of undesirable  Inferior packing of

electrode/electrolyte reactions due to  Potentially more
particles (low volumetric complex synthesis
high surface area (self-discharge, poor
energy densities)
cycling and calendar life)
6
Mechanical activation method
Synthetic reactions

7
 Nanomaterials via mechanical activation

MA
Т, С

Two-step process:
1 step (MA) – grinding and plastic deformation of solids 
mixing of components at molecular level (deformation mixing);
2 step (T) – short-time thermal treatment  formation of product
from molecular precursor supersaturated by defects

Laboratory planetary mill

☺ Decrease in a number of intermediate stages
Industrial activator CEM-7
AGO-2 ☺ Acceleration and simplification of the synthetic process
☺ Increase in homogeneity of the final product
☺ Formation of nano-sized / nano-structured material
8
 Synthetic reactions

• Soft mechanochemical synthesis (SMS)

• Mechanochemically assisted carbothermal
reduction of d-metal compounds (CTR)
• Mechanochemically assisted interaction of covalent
compounds with ionic salts

Motivation - to realize fast propagating synthesis in order to

reduce contamination and energy consumption and to prepare
nanosized products.

9
1. Soft mechanochemical synthesis (SMS)
SMS is generally based on the acid-base properties of the reagents.
MA T
А(ОН)х + В(ОН)y → AB(OH)mnH2O → ABOz

1. Acceleration of initial interaction due to

participation of OH groups in the processes
of proton and electron transfer.
2. Formation of chemically active X-ray
amorphous precursor.
3. Formation of final product by heating the
precursor at moderate temperatures.
4. Significant reduction of contamination due
to lower hardness of initial reagents.
5. Preparation of nanosized, pure and
homogeneous final product as a result.

10
 SMS: LiMn2O4
LiOH + MnOx  LiMn2O4
MnO  Mn2O3  MnO2 acidity increases

111
 - MnO
(a) 
 - Mn2O3
(b)

 - Li-Mn spinel


311
MnO

400
 

440
511
222

331
o
800 C
Mn2O 3  


   
    o

600 C
o
 450 C
MnO 2 

  
MA

10 20 30 40 50 60 70 80 20 30 40 50 60 70
2, degree 2, degree

X-Ray patterns of (a) mechanically activated mixtures of LiOH with different

Mn oxides and (b) the products of MA and annealing at different temperatures.

SMS - fast propagating mechanochemical reaction (realized at the stage of MA)

N.V. Kosova et al., Solid State Ionics 135 (2000) 107-114. 11
N.V. Kosova et al., J. Power Sources 97-98 (2001) 406-411.
 SMS: LiV3O8
2LiOH + 3V2O5  2LiV3O8 + H2O
(a) 
as(V-O) (V=O) (b)
 
  

s(V-O)

545
  6

595

950
740

995


 
 

595

    

545


745
5
6

995
Absorbance
  

920
  
     
4
 

   
   
3 5
 4

600
490
 
 
  3 V2O5

955


810
   

1020
2

920


2
 


 


   
1
1
5 10 15 20 25 200 400 600 800 1000
, degree Wavenumber, cm
-1

X-ray patterns (a) and FTIR spectra (b) of the LiOH+V2O5 mixtures activated for
(1) 30 sec, (2) 1 min, (3) 5 min, (4) 10 min, (5) 10 min followed by annealing at
400C, (6) 5 min followed by aging for 6 months.
● V2O5; ♦ LiV3O8; ▼ Li-V bronzes
12
N.V. Kosova et al., J. Solid State Chem. 160 (2001) 444-449.
 2. Carbothermal reduction
Carbothermal reduction method is relied on
The potential low-cost the use of carbon both as a selective reducing
advantage of LiFePO4 is and covering agent (J. Barker, 2003) :
not realized if expensive
1) Fe3+ compounds are cheaper than Fe2+ salts;
Fe2+ precursors are used
as reagents. 2) less hazardous gases are formed during firing;
3) more easy to scale-up.

Cryst. С

LiFePO4
LiFePO4
Amorph. C

13
 Mechanochemically assisted CTR of Fe2O3
Li2CO3 + Fe2O3 + C + 2(NH4)2HPO4  2LiFePO4 + 3H2O + 4NH3 + CO2 + CO
 - LiFePO4 [19-721]
 - Fe2O3 [33-664]
 - Fe3O4 [19-629] ?
 - (NH4 )2HPO4 [29-111] monocl.
 - (NH4 )2HPO4 [20-84] orhtorh.
Velocity, mm/s
 - LiFeP2O7 [80-1371]
 - Li3Fe2(PO4)3 [47-107] -10 -5 0 5 10

111, 201

311
211, 020
 - NH4FeP2O7 {21-26]
 - Li3PO4 [25-1030]
Fe2O3 experiment

102, 221, 401

101

fit
Fe2O3
301

121
200

210

410

112
o

321
700 C
011

212
   
MA experiment
 
 o mixture fit
      550 C Fe2O3
    
   

  

 o
 

 450 C
 
  
      MA mixture experiment
o fit
 
o
+ 320 C Fe2O3
   

300 C Fe
3+
     
       
 

 MA MA mixture experiment
o fit


   



 
 + 700 C 2+
Fe (LiFePO4)


      
   

10 15 20 25 30 35 40 45 50
2, degree

X-Ray patterns and Mössbauer spectra of the activated and annealed mixtures with Fe2O3.
14
N.V. Kosova et al., J. Electrochem. Soc. 157 (2010) A1247-A1252.
Carbothermal reduction: LiMPO4 (M=Mn, Fe, Co)
Li2CO3 + 2MnO2 + 2C + 2(NH4)2HPO4  2LiMnPO4 + 3H2O + 4NH3 + CO2 + 2CO

Li2CO3 + Fe2O3 + C + 2(NH4)2HPO4  2LiFePO4 + 3H2O + 4NH3 + CO2 + CO

3Li2CO3 + 2Co3O4 + C + 6(NH4)2HPO4  6LiCoPO4 + 12H2O + 12NH3 + 3CO2 + CO

Li2CO3 + 2NiO + 2(NH4)2HPO4  2LiNiPO4 + 3H2O + 4NH3 + CO2

LiNiPO4

LiCoPO4

LiFePO4

LiMnPO4

20 30 40 50 60
15
2, degree
 3. Covalent + ionic salts
This approach, called “dimensional reduction”, was first outlined by Long
et al. It involves a deconstruction of the bonding within a covalent metal –
anion framework by reaction with an ionic reagent, to provide a less tightly
connected framework that retains the metal coordination geometry and
polyhedron connectivity of the parent structure (Li2CoPO4F and Li2NiPO4F).
On the other hand, the formation of LiVPO4F by incorporating of LiF into the
framework of VPO4 (S.g. Cmcm) represents a decrease in crystal symmetry,
but here, a three-dimentional framework is maintained.

• LiCoPO4 + LiF  Li2CoPO4F

• LiNiPO4 + LiF  Li2NiPO4F
• VPO4 + LiF  LiVPO4F

LiCoPO4 Li2CoPO4F
(corner-shared CO6) (edge-shared CoO4F2)

J.R. Long, L.S. McCarty, R.H. Holm, J. Am. Chem. Soc. 118 (1996) 4603.
16
 Covalent + ionic salts
LiCoPO4 + LiF  Li2CoPO4F  Li2CoPO4F [Khasanova et al., 2011]
 LiCoPO4
 Li3PO4
 
 
 CoO ?
    Co ? 
 


    
 
     

28C_He

300C
400C
D8 Advance 500C
Bruker 600C
diffractometer,  650C
HTK 1200N  
  700C
temperature-   

controlled X- 
  

   
   650C
 
ray chamber. 600C
500C
400C
     300C
        
  
29C_He

15 20 25 30 35 40 45
2, degree
Phase transformation under heating and cooling of the activated mixture.

Fast propagating mechanochemical reaction (realized at the stage of MA)

17
N.V. Kosova et al., Solid State Ionics doi:10.1016/j.ssi.2011.11.007
Investigation of as prepared materials

18
 Investigation methods
Particle size and Crystal and local Electronic Electrochemical
morphology structure structure properties

• X-ray powder diffraction (XRD)

• Thermal analysis (DTA and TG)
• Infrared spectroscopy (FTIR)
• Raman spectroscopy (RS)
• Mössbauer spectroscopy
• Nuclear magnetic resonance spectroscopy (NMR)
• Electron paramagnetic resonance spectroscopy (EPR)
• X-ray photoelectron spectroscopy (XPS)
• Scanning electron microscopy (SEM)
• Transmission electron microscopy (TEM)
• Galvanostatic cycling
• Impedance spectroscopy
• In situ synchrotron diffraction
19
 Li - Mn spinels
MnO

Mn3O4
C – cubic LiMn3O4
T – tetragonal -Mn2O3

LiMn2O4 Li1-Mn2O4-4/3
LiMn2O4-
4V -MnO2
3V
LiMnO2 C
Т Li2Mn4O9 Li
C Li44Mn
Mn55OO1212–– Mn
Mn33OO44
Li1.05Mn1.95O4 stoichiometric
stoichiometricspinels
Li4Mn5O12 spinels

Li2MnO3
Li Mn55OO1212––-MnO
Li44Mn -MnO22
Li6.5Mn5O12 defect
defectspinels
spinels
Li1+Mn2-O4
LiMn
LiMn22OO44––Li
Li22Mn
Mn44OO99
oxygen
oxygennon-stoichiometric
non-stoichiometricspinels
spinels
20
M. Thackerey et al., 1992
 Cycling of micronsized LiMn3+Mn4+O4

Jan-Teller
5 Fd-3m Fd-3m I41/amd distortion
λ-MnO2 LiMn2O4 Li2Mn2O4 eg
4
Single-phase reaction t2g
U, Volts

Two-phase reaction
Mn3+ (d4)
3
+e +e
Mn4+ -e [Mn4+ ,Mn3+ ] -e Mn3+

2
0 1 2
x in LixMn2O4
V/V = 10 - 16%

21
 Cycling of nanosized LiMn2O4
x Li
0.0 0.5 1.0 1.5 2.0 1500
4.5 450C
600C
450C 800C
1000
4.0 600C
Voltage, V

800C
3.5 500

3.0

dQ/dE
0
2.5
-500
2.0
0 50 100 150 200 250 300
Specific capacity, mAh/g -1000

-1500
Charge-discharge curves of LiMn2O4-MA, annealed at different 2.5 3.0 3.5 4.0
temperatures, and differential capacity plots. Voltage, V

Nano-spinel cannot accommodate domain boundaries between Li-rich and Li-poor phases due to
interface energy, and therefore lithiation proceeds via solid solutions without domain boundaries,
enabling fast Li-ion insertion. 22
N.V. Kosova, E.T. Devyatkina, Russ. J. of Electrochem. 48 (2012) 320-329.
 LiNi0.5Mn1.5O4: structure and properties

5 V cathode material:
700C Ni2+ two-electron reaction
5.0
P4332 Mn4+ electrochemically non-reactive
4.5
Voltage, V

4.0

3.5
0 50 100 150
-1
Specific capacity, mA*h*g

800C
5,0

4,5
Voltage, V

4,0

3,5

0 50 100
-1
150 Fd3m
Specific capacity, mA*h*g

23
N.V. Kosova et al., 16 IMLB, Jeju, Korea, June 17-22, 2012.
 Synthesis of layered LiNi0.8Co0.2O2

From double hydroxides From anhydrous oxides

1 m 1 m

LiOH + (Ni0.8Co0.2)(OH)2 LiOH + NiO + Co3O4

N.V. Kosova et al., Chemistry for Sustainable Development 17 (2009) 141-149.

24
LiNi1-yCoyO2: local structure and electrochemistry
4,25

4,00

3,75
1 charge

Voltage, V
3,50
C/20 1 discharge
3,25
C/10
3,00

2,75

6 0 20 40 60 80 100 120 140 160 180

Specific capacity, mAh/g
5
4

250
3

Specific capacity, mAhg-1

C/10
2 200 C/5
C/2
1 C
150

30 20 10 0 -10 -20 -30 -40 м.д.

100

7LiMAS NMR spectra of LiNi1-yCoyO2: 50

y = 1 (1); y = 0.8 (2); y = 0.6 (3); y = 0

0.4 (4); y = 0.2 (5); y = 0 (6). 5 10 15
Cycle number
20 25

▲ y = 0,2; ▼ 0,4; ● 0,6; ■ 0,8 25

 LiFePO4: effect of nano-sizing and surface disordering
Prepared from FeC2O4

450C 700C

200 nm

200 nm 200 nm

0 0
450 C 700 C
4,0 4,0

Voltage, V
Voltage, V

3,5 3,5

3,0 3,0

2,5 2,5

100 150 200 50 100 150 200

Specific capacity, mAh/g Specific capacity, mAh/g

Increased ranges of solid solution formation, decreased miscibility gap

26
N.V. Kosova et al., J. Electrochem. Soc. 157 (2010) A1247-A1252.
Mechanism of Li deintercalation in nano-sized LiFePO4
Micro-particles

Nano-particles

Full capacity at Capacity is

high rates partially lost

Two-phase mechanism limits phase boundary movement because of low mutual

solubility and slow migration of charge carriers.
Solid solutions ranges σ and 1-β increase with reduction of particle size.
27
A. Yamada et al., 2001
LiFePO4: effect of nano-sizing and surface disordering
XRD Mössbauer spectroscopy
Velocity, mm/s
700C -10 -5 0 5 10 15
111,201

211,020

311
200 nm
101

222,402,231
450C experiment

102,221,401

040,113,620
a=10.323 fit
b=6.006
301

2+
121
200

412,610
Fe (octa) - 74%
210

c=4.693

312,212

331
410

112
3+
Fe (octa) - 26%

131
022

430
V=290.95
011

600C
a=10.320
b=6.005
c=4.695 600C experiment
fit
V=290.94 2+
Fe (octa) - 86%
3+
Fe (octa) - 14%
450C a=10.315
b=6.002
c=4.696
V=290.74
700C experiment
fit
2+
Fe (octa) - 92%
20 30 40 50 60 70 3+
Fe (octa) - 8%
2, degree

28
N.V. Kosova et al., 16 IMLB, Jeju, Korea, June 17-22, 2012.
 LiFe1-yMnyPO4 solid solutions
1.050 a, Å 0.480
b, Å 7
1.045
c, Å
Li NMR
1.040 PDF
Cell parameters/nm

y = 1.0
1.035 0.475
y = 0.75
1.030
y = 0.5
0.610 0.470 y = 0.25
0.605
y = 0,1
0.600
0.465
y=0
0.595
0.0 0.2 0.4 0.6 0.8 1.0 3000 2000 1000 0 -1000 -2000 -3000 ppm
y in LiFe1-yMnyPO4

31
12 P NMR
7
60 Li 11 y=1

Chemical shift Px10 /ppm

data of Wilcke
10 y = 0.75
Chemical shift Li/ppm

our data
40
9
y = 0.5
7

20 8
y = 0.25
7
31

0 y = 0.1
6
31
P
3

-20 5 y=0
data of Wilcke
our data 4
-40
3 10000 8000 6000 4000 2000 ppm
0,0 0,2 0,4 0,6 0,8 1,0

y in LiFe1-yMnyPO4
29
N.V. Kosova et al., Electrochim. Acta 59 (2012) 404-411.
 LiFe1-yMnyPO4: electrochemistry
175

-1
Discharge capacity/mAh g
150

125

y=0 y = 0.1 100

4 4 75
theor. (total)
50 exper.
3 3
25
Potential vs. (Li/Li )/V

0.00 0.25 0.50 0.75 1.00

2 2 y in LiFe1-yMnyPO4
+

-1
y = 0.25 y = 0.5 175

Discharge capacity/mAh g
4 4 150
theor. Fe /Fe
3+ 2+

125 exper.
100
3 3 75
50
2 2 25

y = 0.75 y = 1.0 0

4 4 0.00 0.25 0.50 0.75 1.00

y in LiFe1-yMnyPO4
3 3

-1
175

Discharge capacity/mAh g
3+ 2+
150 theor. Mn /Mn
exper.
2 2 125
100
0 50 100 150 0 50 100 150 75
-1
Specific capacity/mAh g 50
25
0

0.00 0.25 0.50

y in LiFe1-yMnyPO4
0.75 1.00
30
In situ synchrotron diffraction study of LiFe0.5Mn0.5PO4

0,143

0,38

charge
0,588

0,884

0,999

4 6 8 10
2degree (

N.V. Kosova et al., Solid State Ionics doi:10.1016/j.ssi.2012.01.003

31
 In situ synchrotron diffraction study of LiFe0.5Mn0.5PO4
Change of the Change of the
(200) reflection Charge-discharge curves (200) reflection
4.5 2+ 3+
x=0.14
x=0.21
Mn  Mn x=0.14
x=0.17
4.0 3+
Fe2+ Fe
x=0.27 x=0.26

Voltage, V
x=0.32 x=0.32

discharge
charge

x=0.37
x=0.38
x=0.44
3.5 x=0.43
x=0.49 x=0.49
x=0.60 3.0 x=0.54
x=0.66 x=0.60
x=0.72 2.5 x=0.66
x=0.77 x=0.71
x=0.83 x=0.77
x=0.88 2.0 x=0.83
x=0.94 x=0.88
0 25 50 75 100 125 150 x=0.93

200
x=1.0
200

3.75 4.00 4.25 4.50

Specific capacity, mAh/g 3.75 4.00 4.25 4.50

2, ( = 0.3685 Å) 2, ( = 0.3685 Å)

Cell parameters upon charge and discharge
charge discharge
10.5 10.5
a a
Cell parameter, Å

Cell parameter, Å
10.0 10.0
- phase 1 - phase 1
- phase 2 - phase 2
9.5 9.5
6.0 b 6.0 b
5.5 5.5
5.0 5.0
4.5
c 4.5
c
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
x in LixFe0.5Mn0.5PO4 x in LixFe0.5Mn0.5PO4

Wide intermediate range of single-phase reaction was revealed. 32

 Li1.3Al0.3Ti1.7(PO4)3 (Nasicon) – solid electrolyte
a c

10 μm 10 μm

Without MA With MA
b d

1 μm 1 μm

MA samples are characterized by:

1) lower particle size and larger particle size distribution;
2) rounded form of particles instead of cubic form for ceramic samples;
3) higher Li surface concentration. 33
N.V. Kosova et al., Ionics 14 (2008) 303-311.
 Ionic conductivity of LTP and LATP
1
0

-1 Eb=0.2 eV 0

-2 -1 Eb=0.27 eV

log (T [SK/cm])

log (T [SK/cm])
experiment:
LTP
-3

-4
experiment:
high-frequency
-2 high-frequency
low-frequency LTP-MA
low-frequency
-3 fit:
-5 fit: bulk
bulk -4
grain boundaries σ = 210-5 Scm-1
-6 grain boundaries
total
total
at room T
-7 -5
1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5
-1 -1
1000/T [K ] 1000/T [K ]

1
1
0 Eb=0.23 eV
0
-1
Eb=0.22 eV
log (T [SK/cm])

log (T [SK/cm])

-1
-2

LATP -3
experiment:
high-frequency -2
experiment:
high-frequency LATP-MA
low-frequency low-frequency
-4
-3 fit:
fit:
bulk bulk σ = 610-5 Scm-1
-5 grain boundaries
total -4
grain boundaries
total
at room T
-6
1,5 2,0 2,5 3,0 3,5 4,0 4,5 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0
-1 -1
1000/T [K ] 1000/T [K ]

MA leads to a significant increase (by a factor of a thousand) in grain boundary

34
conductivity of LTP and LATP.
Nano-micro ‘core-shell’ materials

35
 Nano-micro ‘core-shell’ materials
capsulation modification composites
(non-conductive (diffusion into (conductive coating)
coating) the ‘core’)
MOx LiMn2O4 cryst. С

LiCoO2
LiFePO4

LiMeO2 amorph. С

LiCoO2/MOx LiMn2O4/LiMeO2 LiFePO4/C

Suppression of side Suppression of Mn Increased electronic

reactions with electrolyte, dissolution in electrolyte, conductivity
improved stability to acceleration of electron-
overcharge Li-ion transport 36
 Surface modification of LiCoO2 (Al2O3)
MOx
- non-conductive coating
- of small thickness (<50 nm)
- porous (permeable for electron and Li-ion
LiCoO2 transport)
- prevents side reactions with electrolyte
- improves stability to overcharge

10 m 1 m

N. Kosova et al., Solid State Ionics 179 (2008) 1745-1749. 37

Solution and MA surface modification approaches

Sol

10 m 1 m

MA

10 m 1 m
38
Electrochemical performance of LiCoO2/MOx

200

54.7
o
LiCoO2/Al2O3 (80 C)

4.8
6.2
o
LiCoO2/Al2O3 (400 C)
Specific capacity, mAh/g

61.4

47.2
o
LiCoO2/Al2O3 (800 C)

40.2
150

62.1
55.9

32.6
56.1
61.6
100 80 60 40 20 0 -20 -40 -60 -80
ppm

LiCoO2, initial
+ Al2O3 27Al
50 + TiO2
MAS NMR of
+ B2O3 LiCoO2/Al2O3
+ MgO
0
5 10 15 20
Cycle number

Increased discharge capacity due to a higher cut-off voltage

(4.5 V) and improved cyclability

N.V. Kosova et al., J. Power Sources 174 (2007) 959-964. 39

 LiMn2O4/LiMO2 (M: Co, Ni, Ni0.8Co0.2)
LiMn2O4 - conductive coating
- “reactive” coating
- suppresses Mn
dissolution in electrolyte
- accelerates electron/ion
LiMeO2
transport at SEI
200 nm

Initial LiMn2O4

200 nm 200 nm

Solution method MA 40
 LiMn2O4/LiMeO2: cycling

526
520
590

530
Specific discharge capacity, mAh/g

150
0.22 mA
defect spinel
125
0.44 mA
1.1 mA *
100
2.2 mA
* *
4.4 mA 2
75
substituted
50 LiMn2O4 initial
4 spinel
+ LiCoO2
25 + LiNi0.8Co0.2O2

0 3
0 10 20 30 40 50 1
Cycle number
700 600 500 ppm
Improvement of high-rate performance 6Li
MAS NMR of LiMn2O4, surface
modified by LiCoO2: 1 – bare, 2 –
annealed at 400C, 3 – 600C, 4 – 750C.

N.V. Kosova et al., Solid State Ionics 192 (2011) 284-288.

41
 XPS study of LiMn2O4/LiMO2
Core/shell Atomic ratio Atomic ratio
[Co]/[Mn] [Ni]/[Mn]
4+
Mn LiMn2O4/LiCoO2 0.044/0.049* -
LiMn2O4/LiNi0.8Co0.2O2 0.020/0.021* 0.016/0.024*
XPS Mn2p3/2 Intensity [arb. un.]

3+
Mn

* after Ar etching

‘Shell’ practically disappears after heat

treatment of ground samples at 800C due
2
to the interaction with the ‘core’.
In the case of LiNi0.8Co0.2O2 coating, the
surface concentration of Ni is lower than
that of Co, probably due to accelerated
1 diffusion of Ni ions into the bulk.
636 638 640 642 644 646 648 650 The surface concentration of Mn3+
Binding Energy [eV] decreases.

Mn2p3/2 XPS spectra of pristine LiMn2O4 (1)

and LiMn2O4/LiCoO2 (2). 42
Composite (nanodomain) materials

43
Composites xLiMn2O4/(1-x)LiCoO2 (nanodomains)

1 μm 1 μm

LiMn2O4 LiCoO2

1 μm

MA in high-energy planetary mill followed by heat 44

treatment at 200-400C
 Composites xLiMn2O4/(1-x)LiCoO2: cycling

10000

4.15
3.93
LiCoO2 2000
LiMn2O4

4.03
1000
5000
1st cycle

dQ/dU
2nd cycle
0
10th cycle
dQ/dU

4.09
4.19
0
-1000 1st cycle

4.15
4.06
2nd cycle

3.96
10th cycle
-2000
3.90

4.10
-5000
3.0 3.5 4.0 4.5 3.0 3.5 4.0 4.5
Voltage, V Voltage, V

N.V. Kosova et al., Russ. J. of Electrochemistry 45 (2009) 277-285.

45
 Composites xLiMn2O4/(1-x)LiCoO2: cycling

2000 0.5LiMn2O4/0.5LiCoO2

3.94

4.15
4.03
dQ/dU 1000

0
1st cycle
2nd cycle

3.98
-1000

3.88
10th cycle

4.10
3.0 3.5 4.0 4.5
Voltage, V

The redox peaks of LiCoO2 gradually vanished during cycling indicating the occurrence
of chemical interaction.
The composites are characterized by good capacity retention (100 mAh/g).
46
Synthesis of the LiFePO4/Li3V2(PO4)3 composites

Method A: (one-step) mechanochemically assisted combined CTR

synthesis:
Li2CO3 + Fe2O3 + V2O5 + C + (NH4)2HPO4  xLiFePO4 / (1-x)Li3V2(PO4)3

Method B: (two-step) mechanochemically assisted mixing of two individual

components:
xLiFePO4 + (1-x)Li3V2(PO4)3  xLiFePO4 / (1-x)Li3V2(PO4)3

N.V. Kosova et al., 63rd Annual Meetinf of ISE, Prague, August 19-24, 2012.
47
 LiFePO4/Li3V2(PO4)3: cycling
4.5

3.46
4.0
LFP 5000

3.5
0
3.0
2.5 -5000

3.34
4.5 2000
LVP

4.10
3.70
3.62
4.0 1000
3.5
0
3.0
Voltage, V

3.54
-1000

3.63
2.5

4.03
dQ/dE
4.5 6000
-2000

3.48
4.0
0.96LFP / 0.04LVP 4000
2000

4.04 4.10
3.5
0
3.0 -2000
2.5 -4000

3.37
4.5 4000
-6000

4.09
3.48
0.5LFP / 0.5LVP

3.70
3.61
4.0 2000
3.5
0
3.0

3.54
3.63
-2000

4.03
3.35
2.5
-4000
0 50 100 150 2.5 3.0 3.5 4.0 4.5
Specific capacity, mA*h/g Voltage, V

Some distinct plateaus are observed on the charge-discharge curves corresponding to two redox pairs:
Fe3+/Fe2+ (at 3.4 V) and V3+/V4+ (above 3.4 V).
Low degree of polarization in the cycling curves shows that the electron and ion transport is facile.
48
As-prepared nanocomposites show excellent stability on cycling.
 Conclusions

• Mechanical activation using high-energy planetary mills is a

promising solid-state method to prepare nanostructured
electrode materials for Li-ion batteries

• Mechanical activation allows one to synthesize new composite

(‘core-shell’, ‘nano-domain’) materials

• As prepared nanostructured materials differ from bulk

materials by morphology, surface/bulk composition and
electrochemical properties

• In situ synchrotron diffraction studies evidence the differences

in the mechanism of lithium insertion/deinsertion upon cycling
of nanostructured and bulk electrode materials

49
 Acknowledgements

• E.T. Devyatkina - XRD, cycling

• V.V. Kaichev - XPS
• A.T. Titov - SEM
• A.K. Gutakovsky - TEM
• A.B. Slobodyuk - NMR
• A.P. Stepanov, A.L. Buzlukov - NMR relaxation
• D.G. Kellermen - magnetic measurements
• S.A. Petrov - Mössbauer spectroscopy
• A.S. Ulikhin - impedance spectroscopy
• V.V. Ehler, A.V. Markov,
V.K. Makukha - engineering

50
Thank you for your attention!

51