Hybrid Electrolytes for PHEV Applications
Surya Moganty (PI), Luigi Abbate, Kevin BrownVivian Zhu , John Sinicropi
Rochester, NY
DOE Technical Merit ReviewJune 6-10, 2016
Project ID: ES290
This presentation does not contain any proprietary, confidential, or otherwise restricted information1
Overview
• Start date: 08/15/2015• End date: 02/14/2017• Percent complete: 44%
• Electrolyte High voltage stability: stable at 4.5 to 5V
• Electrolyte Cost : <$10/kg• Electrolyte Safety: Non-
flammable and safe• Wide temperature performance
of electrolyte: @ -30oC to 60oC
• Total project funding: $1,639,044– DOE share: $819,522– NOHMs: $819,522
• FY 2015: $278,481• FY 2016: $1,269,215 (Est)
Timeline
Budget
Barriers
• A123 - Cell Build and Testing• CoorsTek – Ionic liquid
Synthesis and Cost Analysis
Collaborators
2
Relevance and Project Objectives• Significant barriers to commercialization of new battery
technology include:– Use of high voltage electrodes with stable high voltage electrolytes– Demonstrate low-cost manufacturability of the electrolyte at large
volumes.• NOHMs Objective is to develop functional ionic liquid based
electrolytes that exhibit high conductivity, excellent electrodestability and wide temperature operations for applications in 5VLi-ion batteries– Functional ionic liquid design and synthesis– “5.0 V” Electrolyte formulation and optimization– Prototype cell assembly and testing (2Ah) (NMO, NMC532)– Design and cost study of electrolyte production– Building 10Ah pouch cells for USABC final deliverables (NMO,
NMC532)
3
Milestones
4
Approach/Strategy
Functional ionic liquid design/synthesis
Electrolyte formulation design
Transport & Electrochemical
property measurements
Coin & Small pouch cell testing
Pouch cell testing(2Ah and 10 Ah pouch
cells)
Electrolyte cost estimation and manufacturing
Statistical tools: DOE Literature NOHMs technical
knowledge
Viscosity, conductivity Floating current studies >5V Graphite SEI formation Low ICL
Half cells, full cells EIS studies FTIR, SEM, XPS studies
5
Technical Accomplishment:NOHMs Novel Ionic liquids
Hetro-cyclic Cation family containing a functional group
TFSI Anion
Decomposition Temp >300 oC
Elemental analysis (C, H, N) confirmed 99.99% purity with 0% halide concentration (ICP)
6
Technical Accomplishment:NOHMs Novel Ionic liquids
Differential scanning calorimetry traces indicate larger ring size results in liquid salts with no distinctive phase transitions.
Scan rate= 2 oC/min
7
n&
Fb& F'b&
N
n
FGn
.(*2>&H2]"2R&
B(75H&T"*>Q(*%H&)#("?A&+(&H(95#&.(*2>&H2]"2R&72A>(A2+$&BEV'A&FH5>+#(H$+5&T(#U"H%Q(*&A<(9&A2U2H%#&>(*R">Q72Q5A&>(U?%#5R&+(&4%A5&H2*5&5H5>+#(H$+5&
=#,8+%,*)'6,,/>7)%48>#+1?'E)#,1$/)<1#'1$*+47/$1'7$/7#$3#4'
89
1
2
3
4
56789
10
2
Con
duct
ivity
(mS
/cm
)
50403020100-10-20-30
Temperature (oC)
EC:EMC 3:7 1MLiPF6 NOHMs HVE36 NOHMs HVE133 NOHMs HVE137 NOHMs HVE138
High pressure and high temperature reactorwith controlled heating system is developed tocollect the vapor pressure vs temp data
Collected experimental data matches with theAntonie equation
Technical Accomplishment:Vapor pressure measurements
9
Propylene carbonate and Ionic liquid exhibited excellent thermal stability- Significantly less vapor pressure up to 300 oC
Electrolytes with PC and ionic liquid would provide considerably less volatile systems
Technical Accomplishment:Vapor pressure of mixtures
10
!
"
#!
#"
$!
$"
%!
%"
&!
&"
"!
!""#$#"%&'(#)*+%%),-. !"#$%&'$()$*&+!,-&./")#0&1&23405
678697&:8;&29,$<=3&
=#,8+%,*)'6,,/>7)%48>#+1?':1*2%)%1<'*;*%+41'I$*78%1#'*+/-#'
.(*2>&H2]"2RA&%#5&*(+&A+%4H5&%)%2*A+&h#%?<2+5&%*(R5&%+&H(9&7(H+%)5A&
G(&"*R5#A+%*R&+<5&%k5>+&(T&.1&>%Q(*&+$?5&%*R&T"*>Q(*%H&)#("?0&2##575#A24H5&>%?%>2+$&H(AA&(T&12Jh#%?<2+5&<%HT&>5HH&%+&bdKL&#%+5&2A&"A5R&%&A>#55*2*)&U5+<(R(H()$&&
BEV'A&T"*>Q(*%H&2(*2>&H2]"2RA&A<(95R&5^>5HH5*+R">Q(*&A+%42H2+$&%)%2*A+&)#%?<2+5&%*(R5&575*&%+&75#$&<2)<&>(*>5*+#%Q(*A&,KI&j&4$&U%AA&2*&+<5&5H5>+#(H$+5/&&
KK&
100
101
102
103
104
Leak
cur
rent
(µA
/cm
2 )
20151050Time(hr)
Base line HVE136 HVE137 HVE138
WXm:& YXL:&
1
2
3
456
10
2
3
456
100
2
3
456
1000
Leak
cur
rent
(µA
/cm
2 )
151050Time(hr)
Base line HVE136 HVE137 HVE138
WXm:& YXL:&
MY&(b& WY&(b&
=#,8+%,*)'6,,/>7)%48>#+1?':1*2%)%1<'*;*%+41'@5JKLM'
!! BEV'A&?#(?#25+%#$&.1&5H5>+#(H$+5A&A<(95R&75#$&H(9&H5%f&>"##5*+&%)%2*A+&B'bYcM&>%+<(R5&575*&%+&5H57%+5R&+5U?5#%+"#5A&
KM&
4.95V 5.2V 4.95V 5.2V
25 oC 45 oC
NOHMs proprietary IL electrolytes showed very low leak current against NMO cathode even at elevated temperatures
Technical Accomplishment:Stability against NMO
13
KW&
SO
O O
!! 8%A5&H2*5&5H5>+#(H$+5A&FbOF'b&cOm&%*R&FbOF'bO.1&cOIOK&A<(95R&A2U2H%#&>$>H5&>%?%>2+$+5*Q(*&
!! _"#+<5#&%RR2Q(*&(T&2(*2>&H2]"2R&H(95#5R&+<5&>%?%>2+$+5*Q(*&
!! 3RR2Q75&2*&>(*N"*>Q(*&92+<&BEV'A&T"*>Q(*%H&2(*2>&H2]"2R&5^<242+5R&2U?#(75R&?5#T(#U%*>5&
=#,8+%,*)'6,,/>7)%48>#+1?'@5!NI$*78%1#N'J<,)%+;'
WXPY&+(&cXY&:&bdc&@%+5&
=#,8+%,*)'6,,/>7)%48>#+1?'@5JKLMNI$*78%1#N'F/)1*;#'4#+4%3"%1<'
BEV'A&R5A2)*5R&5H5>+#(H$+5A&A<(95R&?#(U2A5&2*&B'bYcMJh#%?<2+5&?("><&>5HHA&%+&Mb&R2A><%#)5&#%+5&&
KY&
Response to Previous Reviewers
• This is a new project and was not reviewed last year
16
J/))*2/$*3/+4'
•! FH5>+#(R5&>(*A+#">Q(*&,B'b&%*R&B'E/&%*R&U%HH&T(#U%+&>5HHA&T(#&?#((T&(T&>(*>5?+&
•! D5H275#&M&3<&%*R&KL3<&?#2AU%Q>&?("><&>5HHA&,B'b&e&B'E/&92+<&BEV'A&5H5>+#(H$+5&
•! -#(R">5&AU%HH&]"%*QQ5A&(T&2(*2>&H2]"2RA&
•! b(A+&3*%H$A2A&(T&<2)<&7(H"U5&5H5>+#(H$+5&?#(R">Q(*&
•! B59&-%#+*5#&G8D&
Km&
Challenges and Barriers
• NMO cathode presents challenges to create high loadingfor 2Ah and 10 Ah cell builds
• Ionic liquid stable against cathode are not stable againstgraphite anode
• Additive that form a stable SEI on graphite react withNMO/NMC532 cathodes at high voltages
• Optimization of additive and functional ionic liquidcombination is important to achieve high voltagestability and full cell operation
18
Proposed Future Work
• 2016 (Q3 & Q4)– Down select to the best electrolyte for NMC and NMO and
make 2Ah pouch cells for USABC delivery.– Based on USABC test results improve on electrolyte
formulation, continue Electrochemical testing and abuse tolerance testing
– ByDec 2016 – produce liter quantities of final electrolyte for NMC and NMO
– 2016 Q4 – Develop cost model for final electrolytes• 2017 Q1
– Build and Deliver sixty 10Ah pouch cells with NOHMs electrolyte (30 NMO; 30 NMC)
19
Summary Slide
• Narrowed down IL based electrolytes from 130 to 10
• Promising performance Results
• Established multiple screening methods to down select electrolyte formulations
Gap Chart
20