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Energiledarkonferensen: Så räddar tekniken oss till 2030 !Solna, 12 november 2009
Så bra kommer våra batterier att vara 2030!
Josh ThomasThe Ångström Advanced Battery Centre, Department of Materials Chemistry,
Uppsala University, Box 538, SE-751 21 Uppsala, Sweden.&
LiFeSiZE ABBlomgatan 4E, SE-752 31 Uppsala, Sweden.
Energiledarkonferensen: Så räddar tekniken oss till 2030 !Solna, 12 november 2009
Så mycket större/kraftfullare/billigare/säkrare/”grönare”
kommer våra batterier att vara 2030!
Josh ThomasThe Ångström Advanced Battery Centre, Department of Materials Chemistry,
Uppsala University, Box 538, SE-751 21 Uppsala, Sweden.&
LiFeSiZE ABBlomgatan 4E, SE-752 31 Uppsala, Sweden.
What’s wrong in our World today ?
Energyresourcesavailable
Currentutilization
sunwind, wave...
etc.
coal, oil, gas, wood
the cleanones !
!!!
And how can we put it right ?
Energyresourcesavailable
Desiredutilization
sunwind, wave...
etc.
coal, oil, gas, wood
the cleanones !
Sci.&
Techn.
Re: ” Så räddar tekniken oss till 2030 ! ”
Energiformer
i världen
idag
21%
24%
36%
4%
7%
6% 1% 0.5%
De vanligaste
är
de smutsigaste
!
21%
24%
36%
4%
7%
6% 1% 0.5%
How can batteries help ?
Clearly –
we must invest in RENEWABLES !
BUT ... the
wind
doesn’t blow every day, nor does the sun
shine on demand –
or at night !
1% 0.5%6%4% 1% 0.5%6%4%
An indisputable future scenario:Renewable E-sources
+ efficient E-conversion+
E-storage
+ fuel-cells
+ batteries
renewable E-sources
1. EV/HEV:s
2. Quality grid-power(the “smart grid”)
3. “Uninterruptible Power Supply”
(UPS) systems
From renewable E-sources
Transport
Grid
power
Today’s (Li-ion) battery
research
focusses
on:
-
cheaper, larger, safer, greener(Li-ion) batteries with
higher
energy-
and
power-densities
Wind Sun Wave
Bilen = miljöboven !!!!
C O 2emission
Exhaust emission
Global-scale
Energysupply & demand
Storstadsskalan Globalskalan
Världens 10 smutsigastestäder ( 7 i Kina )
1. Taipei2. Milano ! !3. Beijing4. Urumchi5. Mexico6. Lanzhou7. Chongqing8. Jinan9. Shijiazhuang10. Teheran
12000
10000
8000
6000
4000
2000
14000
2000 2005 2010 2015 2020 2025 20300
CarsBuses Trucks
Projektion
0
1.200
1.000
800
600
400
200
1.400CO2
emissioner(milj
ton)
2006 : >300 milj bilar i Europa
Luftföroreningar i världens städer
En tillfällig lösning ...... men en vändpunkt !
*
Fun to Drive
Fuel Economy
Current HEVst.ex. PRIUS
ＩＣＥ Vehicles
“Plug-in” (H)EV’s
Better (H)EVs to come !
På längre sikt ?
ca. 2030 !?
* *
Remote(off-grid)
+-+-+- +-+-+-+-+-+- +-+-+-
LT box
Powergen. HT
HTA (20000V)BT(230V)
LT50 –150 KVA
LT
+-+- +-
+-+- +-
+-+-+- +-+-+-+-+-+- +-+-+-
Solar
panels
(Centralised)
HT
Centralbattery
storage
Grid-coupledsolar
panelssystem
A sustainable E-system:Centralised
och
decentralised
power supplies
Individualbattery
storage
On a broader scale: “sustainable electrical power supplies”
1
2 3
4
(Decentralised)
. . . through ”better batteries”
An el-tank in the basement !
So we need ”better” batteries !
I what way will they be better?
A clay jar containing an iron rod surrounded by a copper cylinder; when filled with vinegar + an electrolytic solution, the “battery” produced 1.1 volts DC.
Present day Iraq: 250 BC to 640 AD
The first battery ?
Where
are we
today
–
after
two
centuries ?
Alessandro Volta, 1799
1839 Fuel cell1859 Pb-battery1899 Ni-Cd
(Swedish)
1973 Li-metal1975 Ni-MH1979 Li-polymer
Li-ion: Sony 1990
(Cu/Zn)
Li-ion-polymer: 2000
Very slow development- definitely NOT Moore’s law !
«Research in the field of batteries moves at glacier pace »N.Y.Times: 2001
80% of electronics market today
Li-jonbatteriet
ger oss bästa möjlighet till uppskalning !(det tar >20 år att ta fram ett helt nytt batterikoncept)
Olika
batterimaterial . . .
Grafit
LiNi0.8
Co0.2
O2
(Kisel)
Nanorör
(VOx)
LiFePO4
NiSi
LiMn2
O4
Cu6
Sn5
(Li2
FeSiO4
)
Cu2
Sb
V6
O13
InSb
*
MnSb
*
Mn2
Sb
SnSb
Sn-glaser
- +
Li+
PF6-
BF4-
CF3
SO2 -
N(SO2
CF3
)2 -
EC
DEC
DMC
etc.organisk
lösningsmedel
electrolyt
Möjliga vägar fram ?
1. Bättre bulk-material (e.g., LiFeSiZE AB !)
2. Nanomaterial
3. Mikro-arkitekturer
1. Bättre bulk-material ?
”Bättrebatteri”
Bättrematerial
Säkrareanod
Stabilareelektrolyt
Katoden måste bli bättre . . .
• Högre kapacitet (”prestanda”)• Högre effekt (”prestanda”)• Högre säkerhet (”prestanda”)• Längre livstid (”prestanda”)..............................................................• Lägre pris (”marknad”)• Lägre toxicitet (”miljö”)
Men vi klarar uppskalningenmed vad vi har redan idag
KATODENfördröjer
uppskalningen av teknologin
Ett
bättre
batteri
= en bättre
KATOD
Betterbatteries
Bettermaterials
Saferanodes
More stable electrolytes
• Higher capacity (”performance”) cathodes• Higher power (”performance”) • Safer (”performance”) • Longer lifetime (”performance”) ................................................................• Lower cost (”market”) • More abundant materials
(”market”/ ”environment”)• Non-toxic (”environment”)
We can scale up with what we already have at lower voltages, but:
* Cu/graphitesustainability !!!
* LiPF6 !!!!
The CATHODE is hindering the
scaling up of the technology!
. . . esp. for EV scale-up
Ett nytt HEV/P-HEV/EV katodmaterial ? . . . från Uppsala
•
Dagens mobiltelefon/laptop material- LiCoO2
, Li(Co,Ni)O2
, LiNi1-y-z
Coy
Alz
O2
• Större
batterier kräver
billigare
katodmaterial
⇒ ⇒ ⇒
Fe-baserad material
• LiFePO4 (A123, etc. idag)
• Li2
FeSiO4 (litiumjärnsilikat)
( Fe-
och Si-oxider >10% av jordskorpan
!)
De gamla grekernas grundelement: ”Earth-Air-Fire-Water”
!
. . . an Uppsala University spin-off Company
Goal: We develop Fe-based cathodes for Li-ion batteries for large-scaleapplications (transport and sustainable energy storage)
. . . an inestimably large - but tough - market !
- develop a CHEAP green synthesis method for Li2 FeSiO4 (”LFS”)- produce/sell Li-ion battery cathodes based on LFS
• Poor electronic conductivity !
• Solutions:
- doping - nano-coating- nano-sizing
a) Layered: LiCoO2 -> Li0.5 CoO2 : ~3.9V, ~140 mAh/g
b) Spinels:LiMn2 O4 -> Mn2 O4 : ~3V or ~4.0V, 148 mAh/g
c) Olivines:LiFePO4 -> FePO4 , ~3.6V, ~170 mAh/g
d) OrthosilicatesLi2 FeSiO4 -> LiFeSiO4 , ~2.85V, ~ 170 mAh/g
• Instability ?• Solution:doping
Common Li-ion battery cathode materials
Extract >1 Li to give higher capacity at higher voltage . . .. . . the ”Holy Grail” of the Li-ion battery?
e.g., for x = 0.5
Li+2(Fe2+1-xMn2+
x)SiO4 ⇒
Li+1-x(Fe3+1-xMn4+
x)SiO4 + (1+x)Li+ + (1+x)e-
” a 1.5-electron reaction”
(transport?)
Solid-state synthesis:
Ball-milling
700
350
Tem
pera
ture
°C
time
e.g., FeC2
O4.2H2
O + Li2
SiO3 + C-precursor
700ºC in a CO/CO2
gas flow (20 h)
Heat treatment
Li2
FeSiO4 synthesis
BUT:Solgel, wet chemical and hydrothermal process routes also result in ”useable” active materials
SEM picture of Li2 FeSiO4 after ball-milling for 12h: 85 mAh/g
200nm
SEM picture of Li2 FeSiO4 after2 months mixing/grinding: 125 mAh/g
A cheap, fast microwave-assisted process ?
Mixture of reagents:LiAc, Fe(Ac)2, TEOS,Solvent: TEG
300oC, 15 minCEM Focused MicrowaveTM
synthesis system
Drying150oC, 4 h(vacuum)Quartz vessel
Ball-milling, 2h
Ball-milling, 2hw/ acetonew/ 20 wt% sucrose
w/ acetone
acetone evap.
acetone evap.
Post heat-treatment
600oC, 30 min (10oC/min)N2 flow (100 ml/min)
Li2 FeSiO4 ?
XRD,SEMTGA,
EC test…
Microwave heating
Shorter, cheaper synthesis methods
Grinding
RT, 2 m
onths750
oC, 24 h
Hydrotherm
al150
oC, 14 days
Sol -formation
RT, 12 h
700 oC, 1 h Solvotherm
al120
oC, 20 h
600oC
, 10 h
Microw
ave, 300oC
,15 min
600oC
,30 minSolid state
reactionHydrothermal
synthesis Pechini
synthesis
ProjectST-
process
time
14days
2 months
12 h
45 min
20
120
140
130122
Project-2MW-
process
capacity(mAh/g)
2. Nanomaterial ?
year1970 1980 1990 2000 2010
Ener
gyde
nsity
(Wh/
kg)
100
300
200
NiCdNiMH
Li-ion
Nano-materials
?
Incremental changes:The chances of making significant advances are slim
Nano-materials
!
0 0.5 1x in LixFe2O3
1.5
2
2.5
3
3.5
4
4.5
5
Volta
ge (V
olts
vs.
Li+
/Li)
n-Fe2O3
4 8 12 16 20 24 28 32 36 40Cycle number
0
0.1
0.2
0.3
0.4
0.5
0.6
Cha
rge
Cap
acity
(Li p
er F
e 2O
3)
0
20
40
60
80
100
Capacity (m
Ah/g)
0.51
1.52
2.53
3.54
4.5
Volta
ge (V
olts
vs.
Li+
/Li)
0 0.5 1x in LixFe2O3
M-Fe2O3
4 8 12 16 20Cycle number
0
0.1
0.2
0.3
0.4
0.5
0.6
Cha
rge
Cap
acity
(Li p
er F
e 2O
3)
0
20
40
60
80
100
Capacity
(mA
h/g)
Particle-size: cathode material
bulk-Fe2
O3
vs. nano-Fe2
O3
Larcher et al. J. Electrochem. Soc., 150 (2003) A133-A139.
3. Mikro-arkitekturer?
Today’s rechargeable Li-ion battery
2D !
A basic MB design principle: Perforated substrates with hiA basic MB design principle: Perforated substrates with high gh aspectaspect--ratio give higher electrode surface arearatio give higher electrode surface area--toto--volume ratiovolume ratio
( )2. . 22
d dAG td sπ ⎛ ⎞= − +⎜ ⎟
⎝ ⎠+
d-diameter
s-interhole spacing
t-substrate thickness
The geometric Area Gain (A.G.) per given substrate footprint
Porous alumina as a template for nano-electrodes
Along the poresFrom the side
Johansson, Boman et al.
(Materialkemi/UU)
.... for ”3D-microbatteries”
(3D-MB:s)!!
Al-pillared CC(Edström et al.)
TiO2 ALD-coated onto Al CC pillars(Edström et al.)
Result:
TiO2
AlPillars
0.0
20.0
40.0
60.0
80.0
100.0
120.0
0 10 20 30 40 50
Cycle Number
Nor
mal
ized
Cap
acity
2D
3D
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0 5 10 15 20 25 30 35 40
Cycle Number
Dis
char
ge C
apac
ity (m
Ah)
Complete coverage of the nanostructured CCGood cycling stability
Solkraft källa
e.g., “Smart dust”
-
för
miljöbevakningIntegrerad solcell/3D-MB
mm-kuber !
*
Att sammanfatta . . .
Portable/on-board electrical energy demands will continue to increase over the coming decades:
• Portable communications:- more laptops, PDA’s, cellular phones, video cameras,power tools, and integrated applications like PDA’s witha cellular phone.
• (Hybrid?) electric cars, scooters, bicycles:- motivated by higher gasoline costs and the need for a “greener" environment.
These will all need better batteries of different types . . .
PROBABLE TECHNOLOGICAL TRENDS IN BATTERIES OVER THE NEXT 10-20 YEARS . . .
• More hybrid systems - integrating the advantages of different devices, e.g., battery + supercapacitor, battery + fuel cell, primary + rechargeable cell, etc.
• Li-ion technology will penetrates new applications, esp. with larger Li-ion batteries replacing other technologies.
• No dramatically new “battery chemistries” yet – but new battery engineering will soon emerge.
Sony
Sony
1990 2005
Conversion
cathodes (nano)
20151995
Ener
gy d
ensi
ty
Sony
Organic
cathodes
2020
250 Wh/kg, 800Wh/l
Sustai
nabil
ity !
A123
2007 Future
Li-air
Future
Li-S
Na-ion
chemistry
Future
The development of Li-ion batteries over the next 20-30 years
??????
x 2Still far from Moore’s law !!!
Vi har knappast kommit igång, spec. i den stora-batteri världen . . .
. . . 2030:s batterier kommer säkerligenatt vara bättre
än dagens på
alla sätt !
Tack för mig !
[email protected]@LiFeSiZE.se
