The University of Texas at Austin John B. Goodenough and Youngsik Kim Texas Materials Institute The University of Texas at Austin Solid Electrolyte Batteries This presentation does not contain any proprietary or confidential information. DOE Vehicle Technologies Annual Merit Review Meeting June 7 - 11, 2010 Project ID: ES060
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The University of Texas at Austin
John B. Goodenough and Youngsik Kim
Texas Materials InstituteThe University of Texas at Austin
Solid Electrolyte Batteries
This presentation does not contain any proprietary or confidential information.
DOE Vehicle Technologies Annual Merit Review Meeting
June 7 - 11, 2010
Project ID: ES060
The University of Texas at Austin
Overview
• Project Start Date – Oct. 2009• Project End Date – Sept. 2010 • Percent Complete – 50 % complete
• Design of the battery cell containing a solid electrolyte
• Search for a solid electrolyte that has a high Li-ion conductivity (σ ≥ 10-3
S/cm) and a wide electrochemical window (0 – 9 V vs. Li+/Li0)
• Funding received in FY09– $ 315 K
• Funding received in FY10– $ 315 K
Timeline
Budget
Barriers
Partners
The University of Texas at Austin
Milestones
Develop and test a suitable test cell (Jan. 10): Complete
Optimize components of the cell (Apr. 10) Complete
Develop a Li/Air cell (July. 10)
Test alternative cathode catalysts (Sept. 10).
Comparison of performance test of cells with that of the best reported Li-Air cell (Oct. 10)
The University of Texas at Austin
0 200 400 600 800 1000 1200 1400 16000
1
2
3
4
5
6
Pote
ntia
l (V)
vs.
Li+ /L
i0
Capacity (mAh/g)
TiS2
LiCoPO4
LixCoO2
LiNi0.5Mn0.5O2
LiFePO4
Li3V2(PO4)3
LixMn2O4
LixNi0.5Mn1.5O4
LiTi2(PO4)3
Li4Ti5O12
Li1+xMn2O4
Graphite
TiS2TiS2
LiCoPO4
LixCoO2
LiNi0.5Mn0.5O2LiNi0.5Mn0.5O2
LiFePO4LiFePO4
Li3V2(PO4)3Li3V2(PO4)3
LixMn2O4
LixNi0.5Mn1.5O4LixNi0.5Mn1.5O4
LiTi2(PO4)3
Li4Ti5O12
Li1+xMn2O4
LiTi2(PO4)3
Li4Ti5O12Li4Ti5O12
Li1+xMn2O4
GraphiteGraphite
Electrochemical window of organic liquid electrolytes
O2S
Fe3+ / Fe2+ in aqueous solutions
Problems with the Present Li-ion Batteries
Insertion compounds have limited capacity
Li / Air batteries are inefficient if used for electrical energy storage
Li / S batteries have too low a voltage and need a new electrolyte and a better cycle life
Liquid cathodes need a solid electrolyte stable against Li and H2O with σ > 10-4 S/cm
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0
1
2
3
4
5
6
Li+ ion Conductivity (mS/cm)
Poten
tial (V
) vs.
Li+ /Li
720.02 1 40.18 0.810.03
Sulfi
de G
lass
es
Org
anic
Liq
uid
Ioni
c Li
quid
Poly
mer
Poly
mer
+ O
rgan
ic L
iqui
d
Ioni
c Li
quid
+ O
rgan
ic L
iqui
d
Organic Liquid
Ionic Liquid
Polymer
Inorganic Solid
Hybrid
Electrolytes
Li-ion Conductivity ( ×10-3 S/cm)
NAS
ICO
N
The University of Texas at Austin
Li OrganicLiquid
InorganicSolid
Air (Primary)
Aqueous (Primary or Secondary)
Li 1M LiPF6in EC/DEC
Li1.3Ti1.7Al0.3(PO4)3 Sea Water
Li3N
The Use of Inorganic Solid Electrolyte for Li Batteries
Li 1M LiPF6in EC/DEC Li7Zr2R3O12 Fe(NO3)3 / Fe(NO3)2
Concept
Present Practice (Visco, PolyPlus Battery Company)
Proposed Practice
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Present Li/Air Batteries
1 inch × 1 inch, 150 μm, OHARA in Japan
Steven J. Visco et. al. PolyPlus Battery Company
NASICON structureLiM2(PO4)3
Time, hrs
Pot
entia
l (V
) vs.
Li+ /
Li0
LiLi+
Li+
e- e-
+ 1/2O2 + e- = 1/2Li2O2 E = 2.96 V
A. Debart, A.J. Paterson, J. Bao, P.G. Bruce, Angew. Chem. Int, Ed. 47 (2008) 4521.
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Design of Test Cell
Two design challenges
(1) to find sealing agents stable in both highly reducing and oxidizing environments
(2) to accommodate the electrode volume changes during cycling
-
+
LiSeparatorOrganic Liquid electrolyte
-
+ Current CollectorFe(NO3)3 / Fe(NO3)2
Solid Electrolyte
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Water as Cathode
0 5 10 15 200
1
2
3
4
5
Pote
ntia
l (V)
vs.
Li+ /L
i0
Time (h)
Li+ + H2O + e- LiOH + ½ H2
LiOH – e- + ½ O2 Li+ + ½ H2O
Poor charge efficiency, Poor cycle life
Theoretical Capacity
O2 1675 mAh/g
H2O 1489 mAh/g
0.1 mA
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Li1.3Ti1.7Al0.3(PO4)3
Ti4+
Ti4+
Ti4+
Li+
Li+
Li+
Li+
Li
Problems with NASICON Solid Electrolyte for Water Cathode
E
Li+/Li0
2.5 eV
Ti: 4s0
Ti4+/Ti3+
O2-: 2p6
N (E)
Li1.3 Ti1.7Al0.3(PO4)3
Li+ + H2O + e- LiOH + ½ H22.2 eV
100 200 300 400 500
-100
-200
-300
-400
-500
Z"
Z'
Original After Discharge
3.0 × 10-4 S/cm 1.0 × 10-4 S/cm
H2OTin+
After discharge
1400 1200 1000 800 600 400 200
Original
After discharge
Raman
Inte
nsity
(A.U
.)
Wavenumber (cm-1)
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Problems of NASICON Electrolyte with Cell Designs for Air Cathode
E
Li+/Li0
2.5 eV
Ti: 4s0
Ti4+/Ti3+
O2-: 2p6
N (E)
Li1.3 Ti1.7Al0.3(PO4)3
Pacific Northwest National Laboratory
3.0 eV2Li+ + O2 + e- Li2O2
End of discharge
PolyPlus Battery Company
0.2 mA/cm2
1.0 mA/cm2 0.5 mA/cm2
Solid electrolyte
The current collectors reduceTi4+ to Ti3+
Not rechargeable
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Transition-Metal Redox Couples in Aqueous Solutions
Li+/Li0
Li1.3 Ti1.7Al0.3(PO4)3
EV
EC
2.5 eV
EC
EV
1.0 eV
4.5 eV
1M LiPF6in EC:DEC (1:1)
EC: 3.1 eV
EV: 4.3 eV
H2O
Separator
SEI
Fe(NO3)3 / Fe(NO3)23.8 eV
0 5 10 15 200
1
2
3
4
5
Pote
ntia
l (V)
vs.
Li+ /L
i
Time (h)
Water Redox Couples in Water0.1 mA
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Instability of Solid Electrolytes in Acid Solution
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Future WorkExploration of new solid electrolytes Closed packed O2- framework
a0
Spinel Structure Garnet Structure
A[B2]O4 = B2(AO4) A3B2Si3O12 = A3B2(SiO4)3
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Future Work
R. Murugan, V. Thangadurai, W. Weppner, Angew. Chem. Int. Ed. 46 (2007) 7778
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Summary
A Li / aqueous Fe(NO3)3 / Fe(NO3)2 battery has been shown to be feasible and to offer a capacity in excess of 1000 mAh/g compared to a Li/insertion cathode with a Q/W < 250 mAh/g.
Commercial success of an aqueous cathode depends on development of a robust solid electrolyte with σLi > 10-4 S/cm.
The commercially available inorganic Li+-ion solid electrolyte having σLi≈ 10-4 S/cm is unstable with an acidic aqueous cathode.
The inorganic solid electrolyte Li7Zr2R3O12 having σLi ≈ 10-4 S/cm shows promise.