The Architectural Diversity of Metal Oxide Nanostructures ... 2012...The Architectural Diversity of...
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The Architectural Diversity of Metal Oxide Nanostructures: An Opportunity for the Rational Optimization of Group II Cation Based Batteries. Esther S. Takeuchi, Kenneth J. Takeuchi, Amy C. Marschilok [email protected], [email protected], [email protected] Utilize earth abundant, low cost elements with minimal environmental impact as battery materials. Exploit magnesium due to air stability and ~1,000X higher natural abundance than lithium and ~5,000X higher abundance than lead. Cathode materials feature Mn, Fe or V metal centers. Strategy Results Results This project targets some of the unique needs of large scale power storage: 1) reduced cost 2) low environmental impact 3) scalability 4) reversibility 5) capacity retention Results Acknowledgment The authors gratefully acknowledge the support of the Department of Energy/Office of Electricity’s Energy Storage Program. Sandia National Laboratories Results Synthesis and Characterization of Mg x MnO y Electrochemical Testing of Mg x MnO y ICP-OES was used to quantify the elemental composition of > 40 samples. Mg/Mn =0.23 ± 0.07. Precipitation Ion-Exchange Synthesis Mg x MnO y was prepared by a two-step scalable process where the first step was a precipitation reaction followed by ion-exchange. Scanning Electron Microscopy (SEM) Mg x MnOy exhibits a platelet morphology. Mg x MnO y showed electrochemical reversible behavior between 2.8 V and 3.8 V. Li + electrolyte Voltage (V) vs. Li/Li + Discharge capacity (mAh/g) Discharge of Mg x MnO y results in a sloping profile, with ~160 mAh/g delivered above 2 V. Cyclic voltammetry of three-electrode cell Discharge curve Li + electrolyte Discharge capacity (mAh/g) Cycle no. Cycle life of cells at C/20 The material showed initial capacity of 160 mAh/g with good capacity retention at 120 mAh/g Synthesis and Characterization of Mg x V 2 O y Structure Mg x MnO y has a layered structure of edge sharing MnO 6 octahedra, where Mg 2+ cations are found between the layers. Electrochemical Testing of Mg x V 2 O y Student Participants Graduate David Bock PhD - Chemistry Chia-Ying Lee PhD - Chem. Eng. (graduated Aug 2012) Shu Han Lee PhD - Chem. Eng. Chris Milleville PhD - Chemistry Corey Schaffer MS - Chem. Eng. (graduated Dec 2011) Shali Yau PhD - Chemistry (graduated Dec 2011) Undergraduate Jeffery Marvin - Chemistry Sheree Chen – Chemistry Two-Step Synthesis Mg MnO 6 Cyclic voltammetry of three-electrode cell Cyclic voltammetry in Mg 2+ electrolyte Mg 2+ electrolyte Current Voltage (V) vs. Ag/Ag + Electrochemical reversibility in Mg 2+ based electrolyte was observed. Li + electrolyte Current Voltage (V) vs. Li/Li + Discharge of Mg x V 2 O y results in a sloping profile, with 205 mAh/g Discharge curve ICP-OES was used to quantify the elemental composition of > 12 samples. Mg/V =0.12 ± 0.01. Scanning Electron Microscopy (SEM) Mg x V 2 O y exhibits a fibrous morphology. The material showed initial capacity of 205 mAh/g with good capacity retention. Cycle life of cells at C/12 Discharge capacity (mAh/g) Cycle no. Li + electrolyte Successful scalable aqueous based syntheses of pure Mg x VO y and pure Mg x MnO y . Observed electrochemical reversibility in lithium electrolytes. Delivered capacities > 200 mAh/g (Mg x VO y ) and > 150 mAh/g (Mg x MnO y ). High capacity retention observed in lithium electrochemical cells. Observed electrochemical reversibility in magnesium electrolytes. Summary Voltage (V) vs. Li/Li + Li + electrolyte Current (A) Cyclic voltammetry in Mg 2+ electrolyte Electrochemical reversibility in Mg 2+ based electrolyte was observed. Mg 2+ electrolyte Current Voltage (V) vs. Ag/Ag + Sol-Gel Reaction Ion-Exchange Synthesis Mg x V 2 O y was prepared by a two-step scalable process where the first step was a sol-gel reaction followed by ion-exchange. Two-Step Synthesis Voltage (V) vs. Li/Li + Discharge capacity (mAh/g) Li + electrolyte Mg x V 2 O y showed electrochemical reversible behavior between 2.0 and 4.0V Li + electrolyte Impact on DOE OE Energy Storage Mission
Transcript of The Architectural Diversity of Metal Oxide Nanostructures ... 2012...The Architectural Diversity of...
The Architectural Diversity of Metal Oxide Nanostructures:
An Opportunity for the Rational Optimization of Group II Cation Based Batteries.
Esther S. Takeuchi, Kenneth J. Takeuchi, Amy C. Marschilok
[email protected], [email protected], [email protected]
Utilize earth abundant, low cost elements with minimal environmental impact as battery materials. Exploit magnesium due to air stability and ~1,000X higher natural abundance than lithium and ~5,000X higher abundance than lead. Cathode materials feature Mn, Fe or V metal centers.
Strategy
Results Results
This project targets some of the unique needs of large scale power storage:
1) reduced cost 2) low environmental impact 3) scalability 4) reversibility 5) capacity retention
Results
Acknowledgment
The authors gratefully acknowledge the support of the Department of Energy/Office of Electricity’s Energy Storage Program.
Sandia National Laboratories
Results
Synthesis and Characterization of MgxMnOy
Electrochemical Testing of MgxMnOy
ICP-OES was used to quantify the elemental composition of > 40 samples.
Mg/Mn =0.23 ± 0.07.
Precipitation
Ion-Exchange
Synthesis MgxMnOy was prepared by a two-step scalable process where the first step was a precipitation reaction followed by ion-exchange.
Scanning Electron Microscopy (SEM) MgxMnOy exhibits a platelet morphology.
MgxMnOy showed electrochemical reversible behavior between 2.8 V and 3.8 V.
Li+ electrolyte
Vo
ltag
e (
V)
vs. L
i/Li
+
Discharge capacity (mAh/g)
Discharge of MgxMnOy results in a sloping profile, with ~160 mAh/g delivered above 2 V.
Cyclic voltammetry of three-electrode cell
Discharge curve
Li+ electrolyte
Dis
char
ge c
apac
ity
(mA
h/g
)
Cycle no.
Cycle life of cells at C/20
The material showed initial capacity of 160 mAh/g with good capacity retention at 120 mAh/g
Synthesis and Characterization of MgxV2Oy
Structure MgxMnOy has a layered structure of edge sharing MnO6 octahedra, where Mg2+ cations are found between the layers.
Electrochemical Testing of MgxV2Oy
Student Participants
Graduate
David Bock PhD - Chemistry Chia-Ying Lee PhD - Chem. Eng. (graduated Aug 2012) Shu Han Lee PhD - Chem. Eng. Chris Milleville PhD - Chemistry Corey Schaffer MS - Chem. Eng. (graduated Dec 2011) Shali Yau PhD - Chemistry (graduated Dec 2011) Undergraduate
Jeffery Marvin - Chemistry Sheree Chen – Chemistry
Two-Step Synthesis
Mg
MnO6
Cyclic voltammetry of three-electrode cell
Cyclic voltammetry in Mg2+ electrolyte
Mg2+ electrolyte
Cu
rre
nt
Voltage (V) vs. Ag/Ag+
Electrochemical reversibility in Mg2+ based electrolyte was observed.
Li+ electrolyte
C
urr
en
t
Voltage (V) vs. Li/Li+
Discharge of MgxV2Oy results in a sloping profile, with 205 mAh/g
Discharge curve
ICP-OES was used to quantify the elemental composition of > 12 samples.
Mg/V =0.12 ± 0.01.
Scanning Electron Microscopy (SEM) MgxV2Oy exhibits a fibrous morphology.
The material showed initial capacity of 205 mAh/g with good capacity retention.
Cycle life of cells at C/12
Dis
char
ge c
apac
ity
(mA
h/g
)
Cycle no.
Li+ electrolyte
Successful scalable aqueous based syntheses of pure MgxVOy and pure MgxMnOy.
Observed electrochemical reversibility in lithium electrolytes.
Delivered capacities > 200 mAh/g (MgxVOy) and > 150 mAh/g (MgxMnOy).
High capacity retention observed in lithium electrochemical cells.
Observed electrochemical reversibility in magnesium electrolytes.
Summary
Voltage (V) vs. Li/Li+
Li+ electrolyte
Cu
rre
nt
(A)
Cyclic voltammetry in Mg2+ electrolyte
Electrochemical reversibility in Mg2+ based electrolyte was observed.
Mg2+ electrolyte
Cu
rre
nt
Voltage (V) vs. Ag/Ag+
Sol-Gel Reaction
Ion-Exchange
Synthesis MgxV2Oy was prepared by a two-step scalable process where the first step was a sol-gel reaction followed by ion-exchange.
Two-Step Synthesis
Vo
ltag
e (
V)
vs. L
i/Li
+
Discharge capacity (mAh/g)
Li+ electrolyte
MgxV2Oy showed electrochemical reversible behavior between 2.0 and 4.0V
Li+ electrolyte
Impact on DOE OE Energy Storage Mission
