Sustainable Nanostructured Materials for Energy Storage M t i l f - - PowerPoint PPT Presentation
Sustainable Nanostructured Materials for Energy Storage M t i l f E St Jaephil Cho I t Interdisciplinary School of Green Energy and di i li S h l f G E d Converging Research Center for Innovative Battery Technologies UNIST Issues
I t di i li S h l f G E d
Interdisciplinary School of Green Energy and Converging Research Center for Innovative Battery Technologies UNIST
400
350 400
/kg)
Future Present
300 250
sity (Wh/
ht Weight
200
rgy dens
Ligh
100 150
ight ener
Li Rechargeable Battery
50
Wei
Small size Li Rechargeable Battery Ni-MH Ni-Cd Pb
100 200 300 400 500 600 700 800 900 1000
Volume energy density (Wh/l)
Pb
♣High Capacity
♣ High Safety ♣ Wide temperature range Car ♣ g p y －Global Communication System － 3G/4G ♣Good cycle life ♣ Wide temperature range ♣ High Power ♣ Low Cost Small y －Cellular Phone －Notebook ♣High Safety
♣ High Power Sepc. Large ♣Low Cost ♣ Fast Charging/Discharging ♣ Low Cost Military Large
5.Energy Storage
♣ Maintenance Free ( ll t l lif ) (excellent cycle life) ♣ Excellent charge/discharge efficiency ♣ Low Cost
♣ High Power ♣ Maintenance Free ♣ Low Cost
etc etc
C ll h C ll h
Note pc Note pc 38% 38% etc etc 12% 12%
Mobile flexible market Mobile flexible market Flexible phone flexible display Flexible phone flexible display
2008 ) 2008 )
Cell phone Cell phone 50% 50% Flexible phone, flexible display, Flexible phone, flexible display, E-
paper, wearable PC, etc
Note Note-
pc 23% 23%
(2008 yr)
2008 yr) Market size: 8 billion
Cell phone Cell phone 30% 30%
Mobile display Mobile display 23% 23%
23% 23%
Market size: 20 billion
Flexible phone (Kyocera) Flexible phone (Kyocera)
Converging BT BT+NT NT+IT IT+ET ET
Shape/ Shape/ Design Flexibility Design Flexibility
Flexible OLED (LG Display)
Flexible & Wireless Wireless-
Charging
Thin Thin-
film type
S f t / L l lif S f t / L l lif
Flexible OLED (LG Display)
Safety / Long cycle life Safety / Long cycle life Wireless/ Fast charging Wireless/ Fast charging
The Morph Concept phone (Nokia)* E-paper FLEPia (Fujitsu)
Solid Type Solid Type *http://www.youtube.com/watch?v=IX-gTobCJHs
*Angew Chem. Int. Ed. 49, 2146, 2010
stability)
Cui et al. Nano Lett. 8, 3948 (2008)
g g p y
Nanoclustered Morphology
18, 2257 (2008)
Birnnesite (KxMnO2) Spinel Nanowire L d N F O Nanoplate Layered α-NaFeO2
Nano Lett. 8, 957(2008)
As-prepared Ni0.3Mn0.7O2
pH = 10, 5hrs
(a) (c)
200oC Layered 150oC
pH = 7, 2hrs
Spinel Layered R-3m
Li[Li Li[Li0.15
0.15Ni
Ni0.25
0.25Mn
Mn0.4
0.4]O
]O2
pH = 10, 2hrs
150oC
(b)
Spinel
pH = 2, 1.5hrs pH = 10, 5hrs pH = 2, 5hrs
3 5 4.0 4.5 5.0 10th cycle 30th cycle 50th cycle
al (V) (vs.Li)
(a)
1000 2000
80th 2nd 1st
mAh/gv)
50 100 150 200 250 300 350 400 2.0 2.5 3.0 3.5 50th cycle 80th cycle
Cell potentia
0.3C rate (120mA/g)
2 0 2 5 3 0 3 5 4 0 4 5
dQ/dV(m
50 100 150 200 250 300 350 400 96 100 280 300 320
city(mAh/g) icient (%) Capacity(mAh/g)
(d)
2.0 2.5 3.0 3.5 4.0 4.5 Cell potential(V)
84 88 92 220 240 260 280
scharge capac
(b)
280 320
Nanowire
0.3C 3C 1C
y(mAh/g)
10 20 30 40 50 60 70 80 220
Di Cycle number Co
(b) (e)
160 200 240 3C 5C 7C Nanoplate
harge capacity
(c)
10 20 30 40 50 120
Disc Cycle number
(c)
H He Li Be B C N O F Ne Na Mg Al Si P S Cl Ar Na Mg Al Si P S Cl Ar K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn Fr Ra Ac
Lithium reaction mechanisms 1) Sn, Ge, and Si: M + xLi+ + xe- ↔LixM 2) SnO + 4Li+ + 4e− → Sn + 2Li O (1) 2) SnO2 + 4Li + 4e → Sn + 2Li2O (1) Sn + xLi+ + xe− ↔ LixSn (0 ≤ x ≤ 4.4) (2) 3) MIIO + 2Li+ + 2e− ↔ Li2O +M0 (3d transition metal oxide) 4) MPn ↔ LixMPn (Li-intercalation) (1) MPn ↔ M (LixM) + LixP (metallization or metal alloying) (2)
Rapid capacity fade
2.5 1.5 2.0 2.5
3 2 1
ge(V) 0.0 0.5 1.0 Voltag 20 μm 1 μm 1000 2000 3000 4000 Capacity(mAh/g)
4000
Li Li Si
4000 3000
pacity M)
Li4.4Si
3000
ity
2000
etric Cap h/g-LixM
2000
ic Capaci LixM) Li Li4.1Si Li4.1Ge Li4.1Sn Li4Pb
2000
Gravime (mAh
Li4.1Ge
Li4.1Sn
2000
Volumetr (mAh/cc-
1000
G
LiC6 Li4Pb
1000
V ( LiC6
Charge Discharge
*Adv. Funct. Mater. 19, 1497, 2009, Feature article Energy & Environ. Sci. 2, 181, 2009, Invited review article
2.0 2.5
a)
30 20 10 5 2 1
1 5 2.0 2.5
a)
0.07 V 1.1 V
I
0.5 1.0 1.5
V/V
Sn2P2O7
0.5 1.0 1.5
2.0 2.2 2.4 2.6 2.8 3.0
V/V
2/degree
1.5 2.0 0.0
V/V
1 20 10 5 2 30
b)
3.70 3.75
b)
200 400 600 800 1000 1200 0.0 0.5 1.0
V/V
mesoporous/Sn2P2O7
3.60 3.65
d/nm
200 400 600 800 1000 1200
x/mAhg
400 800 1200 1600 3.55 3.60
x/mAhg
Charge
x/mAhg
Discharge
Hollow 0D Nanoparticle
SiO2:CnHm-Metal gels = 7:3 (wt%)
Δ & etching
assembly SiO2 template
Δ & etching
Porous 3D Nanoparicle assembly SiO2:CnHm-Metal gels = 3:7 (wt%) assembly gels = 3:7 (wt%)
Si precursor
Annealing Annealing Et hi SBA-15 Etching Mesoporous nanowires* A li Annealing Etching Al2O3 membrane template Nanotubes
*Nano Lett. 8, 3688 (2008)
(a) silica template, (b) 0D hollow Ge nanoparticle assembly, (c) 3D porous Ge nanoparticle assembly, (d) is expanded image of (c), (e and f) high resolution TEM i d R t image and Raman spectrum
* Adv. Mater. 22, 415, 2010
2500 5000
V(mAh/gV)
0D Hollow Ge 3D Porous Ge
0.0 0.2 0.4 0.6 0.8 1.0 1.2
dQ/dV Potential(V)
Before etching After etching Before etching After etching
*Angew. Chem. Int. Ed., 47, 10151 (2008) (HOT article)
2.5 3.0
(a)
1.0 1.5 2.0 2.5
0.2 1 2 3
metal)
C rate =
Ex situ TEM
0.0 0.5 3.0 V) (vs. Lithium
(b)
1 0 1.5 2.0 2.5 ll Potential (V
(b)
100,70,30,1 C rate = 0.2
500 1000 1500 2000 2500 3000 3500
Capacity (mAh/g)
0.0 0.5 1.0 Ce
Capacity (mAh/g)
2400 2800
(c)
1C rate (2000 mA/g) 0.2 C rate (400 mA/g)
1200 1600 2000 20 40 60 80 100 Cycle number 1200
After ultrasonic treatment After ultrasonic treatment
*Nano Lett. 9, 3844, 2009 Highlighted in Nature Nanotech., Nature
(c) (a) (c) (d) (b) (d)