Validation of Electrode Materials and Cell Chemistries...3.6V~4.3V1 3.6V~4.3V2 3.6V~4.3V3 2.6V~4.6V3 Li/HE5050 cell 2 3 4 5-2 0 2 4 dQ/dV, mAh/V Voltage, V 4.2V~4.6V1 4.2V~4.6V2 4.2V~4.6V3

Vehicle Technologies Program

Validation of Electrode Materials and Cell Chemistries

Wenquan Lu (PI)

Q. Wu, J. Kubal, S. Trask, B. Polzin, J. W. Seo, S. B. Ha, J. Prakash, D. Dees, and A. Jansen

Electrochemical Energy Storage

Chemical Sciences and Engineering Division Argonne National Laboratory

This presentation does not contain any proprietary, confidential, or otherwise restricted information

Vehicle Technologies Annual Merit Review and Peer Evaluation

Washington, D.C. May 13th – 17th , 2013

Project ID: ES028

Vehicle Technologies Program Vehicle Technologies Program 2

Overview

Start – Oct. 2012 Finish – Oct. 2014 Percent complete: 25%

An overwhelming number of materials are being marketed by vendors for Lithium-ion batteries.

No commercially available high energy material to meet the 40 mile PHEV application established by the Freedom CAR and Fuels Partnership.

Timeline

Budget

Barriers

Total project funding in FY2013: $550K (as part of CFF effort)

100% DOE

Partners and Collaborators Cell Fabrication Facility (Andrew Jansen, ANL) Materials Engineering Research Facility (Gregory

Krumdick, ANL) Post Test Facility (Ira Bloom, ANL) Prof. Prakash’s group (IIT) Industries, Research institutes, and Universities

Vehicle Technologies Program Vehicle Technologies Program

Objectives

3

To identify and evaluate low-cost cell chemistries that can simultaneously meet the life, performance, abuse tolerance, and cost goals for Plug-in HEV application.

To aid the material scale up under Material engineer and research facility (MERF) and electrode library development under cell fabrication facility (CFF), respectively.

Material Requirements for PHEV40

150 160 170 180 190 200 210 220 230300

350

400

450

500BOL 40 mile PHEV

130kg

Assumption:Fix material density (Gen2)

Norminal Voltage, V 3.6ASI, ohm-cm2 50Range(CD:70%), mile 40Battery power, kW 50.0Capacity at C/3, Ah 60.0Number of modules 7Cells per module 12Cells per battery 84

Cathode Capacity, mAh/g

Anod

e C

apac

ity, m

Ah/g

95.00

100.0

105.0

110.0

115.0

120.0

125.0

130.0

135.0Tota

l Bat

tery

Wei

ght,

kg

120kg

100kg

Calculated using ANL’sBattery Design ModelCalculated using ANL’sBattery Design Model

To enhance the understanding of advanced cell components on the electrochemical performance and safety of lithium-ion batteries.


Approach: Test Protocol

Material Identification

Material Characterization

(XRD, SEM, BET, Particle size, etc.)

Electrochemical Evaluation

1. Formation: Energy density ICL

DSC: Thermal

Investigation

3. Rate Capability

4. Cycling: Capacity Retention

Report Material provider, Battery fabrication,

Testing and post analysis

2. HPPC: ASI

Electrode and Cell fabrication

Electrochemical evaluation of electrode couple will be the focus of this project.

In order to conduct the electrochemical characterization of the battery chemistries for advanced battery research (ABR) program, C rate and pulse current was calculated for coin cells according to PHEV 40 requirements.

Characteristics at EOL (End of Life)

High Power/Energy Ratio

High Energy/Power Ratio

Reference Equivalent Electric Range miles 10 40Peak Pulse Discharge Power (10 sec) kW 45 38Peak Regen Pulse Power (10 sec) kW 30 25Available Energy for CD (Charge Depleting) Mode, 10 kW Rate kWh 3.4 11.6Available Energy for CS (Charge Sustaining) Mode kWh 0.5 0.3Maximum System Weight kg 60 120Maximum System Volume Liter 40 80

USABC Requirements of Energy Storage Systems for PHEV


Technical Accomplishments

Several high energy cathode materials, composite cathode and high voltage spinel, have been identified and studied.

Several silicon and its composite materials has been identified. The material validation work of silicon and its composite is incorporated with binder investigations.

Other cell components, such as electrolyte and additives, conductive additive, binders, etc., have also been investigated.

Composite LMR-NMC

High voltage spinel

Synthetic graphite

SBR/CMC

Redox shuttle

Additive

Siloxane

Electrode library: LiCoO2, LiFePO4, LiMn2O4, NMC523, etc

Nanofiber, ceramic coating

Electrode library: Li4Ti5O12

Silicon composites


Electrochemistry of Lithium Manganese Rich Metal Oxide (LMR-NMC)

6

After formation, the electrode in half cell was cycled between three voltage windows:

– Low: 2.0V ~ 3.66V – Mid: 3.6V ~ 4.3V – High: 4.2V ~ 4.6V

The voltage profiles during 3rd cycle is plotted as function of specific capacity.

Less hysteresis and reversible capacity at mid and high voltage windows.

Several LMR-NMC materials have been investigated under material validation. In addition to their performance, in depth understanding of LMR-NMC was also attempted electrochemically to aid the material development.

0 50 100 150 200 250

2.0

2.5

3.0

3.5

4.0

4.5

47

2.6V~3.66V 3.6V~4.3V 4.2V~4.6V 2.5V~4.6V

Vol

tage

, V

Capacity, mAh/g

63 85 17 20

127(+)/105(-)

3 66 113 198 215 235


Voltage Window Effect on Capacity Contribution

Discharge capacity in low voltage window partially comes from the activation during mid and high voltage window.

7

2 3 4 5

-2

0

2

4

dQ/d

V, m

Ah/

V

Voltage, V

2V~3.66V1 2V~3.66V2 2.6V~4.6V3

Li/HE5050 cell

2 3 4 5

-2

0

2

4

dQ/d

V, m

Ah/

V

Voltage, V

3.6V~4.3V1 3.6V~4.3V2 3.6V~4.3V3 2.6V~4.6V3

Li/HE5050 cell

2 3 4 5

-2

0

2

4

dQ/d

V, m

Ah/

V

Voltage, V

4.2V~4.6V1 4.2V~4.6V2 4.2V~4.6V3 2.6V~4.6V3

Li/HE5050 cell

2 3 4 5

-2

0

2

4

dQ/d

V, m

Ah/

V

Voltage, V

2.6V~4.6V3 2V~3.66V2 3.6V~4.3V3 4.2V~4.6V3

Li/HE5050 cell

Low: 2.0V ~ 3.66V Mid: 3.6V ~ 4.3V High: 4.2V ~ 4.6V


Single Component Effect

According to the single component study, the blend of Li2MnO3 and LiMO2 showed similar electrochemical performance as LMR-NMC. It is rational to speculate that the voltage fade and voltage hysteresis is caused by Li2MnO3 component.

8

Li/NMC111 cell

Li/Li2MnO3 cell

Li/active (Li2MnO3, NMC, blend) cell

2 3 4 5-3

-2

-1

0

1

2

3

dQ/(d

V*Q

), 1/

V

Voltage, V

blend Li2MnO3 333

2nd cycleC/20C/30C/10

Li/active cell


Aqueous Binders for Lithium Ion Battery

9

Styrene-Butadiene Rubber (SBR) Fluorine acrylic latex (FA)

Technically as electrode: high adhesion as battery: high capacity Cost Shorting drying Cheap material No recycling Environmentally Organic solvent free

Anode Graphite (A12, Phillips66 ) SBR (TRD2001, JSR) CMC (MAC350HC, Nippon Paper) Carbon black (C45, Timcal)

Cathode LMR-NMC (HE5050, Toda) FA (TRD202A, JSR) CMC (MAC350HC, Nippon Paper) Carbon black (C45, Timcal)

Merits of aqueous binder

Electrode Chemistries

Polymer binder core Functional group


1 2 3 4 5 6 7 8 90369

12151821242730

Res

idua

ls o

n su

bstra

te (%

)

Percent of SBR in electrodes(%)

Effect of SBR on Graphite

10

tape electrode 4%

6% 8%

2%

0 50 100 150 2000

-10

-20

-30

-40

-50

Z''

Z'

2% SBR 6% SBR 8% SBR

• Better adhesion and lower impedance were observed for the graphite electrode with lower SBR content, suggesting higher energy density of the cell.

EIS spectra Peel test


Fluorine Acrylic Latex Binder for Cathode

The HE5050 electrode with FA binder delivers

– high specific capacity 244 mAh/g, – low Ohmic resistance <50 Ω•cm2, – excellent rate capability (> 178

mAh/g at 2C), and – outstanding capacity retention

(>87% after 50 cycles).

11

HE5050


Total Aqueous Binder Lithium Ion Battery

Lithium ion battery with all aqueous binders for both anode and cathode were demonstrated.

For graphite/LMR-NMC system, no obvious negative effect on electrochemical performance was observed.

12

Formation HPPC


Silicon Electrode and Binder Silicon composite has a better chance to meet the energy requirements for

PHEV40 due to its adjustable high capacity. In addition to material development, the success of silicon electrode for LIB needs

collective efforts, including additive, binder, test protocol, electrode engineering. We has reported the additive effect last year and binder effect and electrode

optimization will be the current focus.

13

Material development Particle size; morphology; composite

Electrode optimization Binder; formulation

Interfacial modification Additive; surface modification

Test condition Cut-off voltages

Volume expansion Mechanical integrity

Solid electrolyte interface Side reaction

Phase transition Structure stability

Collective efforts


Silicon Electrode and Binder

14 14

Binders tested: – Poly(vinylidenefluoride) (PVDF) – Polyacrylic Acid (PAA) – Na-Alginate – Poly Amine Imide (PAI) – carboxymethyl cellulose (CMC) – Styrene-Butadiene Rubber (SBR)

Li/Si-C cell 1.2M LiPF6 in EC/EMC with 3 wt% FEC 5mV to 2V

General Electrode composition – 10% C-45 – 30% Silicon – 45% A12 Graphite – 15% Binder

Better cycle performances of silicon electrode were obtained when PAA and alginic acid binders were used as binder.


Test Condition Effect on Silicon Electrode

Various cut off voltages was applied to the silicon electrode. – Lower cut-off voltage, more deliverable capacity and faster capacity fading. – Higher cut-off voltage, less deliverable capacity and lower capacity fading. – Coulombic efficiency increases with cycling. – Better coulombic efficiency was observed with higher cut-off voltage.

15

Li/Si cell (Electrode provided by Dr. Liu, LBNL) 1.2M LiPF6 EC/EMC with 10% FEC

0 10 20 30 40 500.0

0.2

0.4

0.6

0.8

1.0

10mV 40mV 200mV

Cap

acity

, mA

h

Cycle

formation10mV~1V

cycling

rate: C/10

0 10 20 30 40 500.6

0.7

0.8

0.9

1.0

10mV 40mV 200mV

Effi

cien

cy, Q

/Q0

Cycle

formation10mV~1V

cycling


Impact of Electrolyte on Silicon Electrode

The cycle life of silicon electrode increased 4 times by using 3% FEC as additive when 1000mAh/g specific capacity of silicon electrode was utilized.

The better cycle life can be attributed the better SEI film formed by FEC.

16

Li/Si cell Si/Alginic acid/Carbon = 76%/14%/10% Citric acid buffer Limited capacity to various levels Rate: C/3 Charge/Discharge Electrolyte: 1.2M LiPF6 EC/EMC 1.2M LiPF6 EC/EMC + 3% FEC


Thermal Property of Silicon Electrode

Up to 250oC, lithiated SiOx showed similar heat flow during temperature scan with postponed on-set temperature.

The on-set moves to lower temperature when more lithium is reacted with SiOx. In addition, the total heat generation was greater.

17

0 100 200 300 4002

0

-2

-4

-6

-8

-10

-12

-14

-16

-18

Hea

t flo

w, W

/g

Temperature, oC

MCMB SiOx-1000mAh/g SiOx-1660mAh/g

10oC/min1st lithiation DSC

0 400 800 1200 1600

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

DSC1660mAh/g

DSC1000mAh/g

Vol

tage

, V

Capacity, mAh/g

Graphite SiOx

DSC


Future Plan

We will continue to evaluate the high energy density cathode materials, such as lithium manganese rich transition metal oxide (LMR-NMC), and high energy density anode materials, such as silicon/silicon composite, when they become available. For both high energy electrode materials, we will work closely with national labs and industries.

Various electrode materials and cell chemistries will be evaluated under cell fabrication facility to help to build the electrode library.

Materials scaled-up by Material Engineering and Research Facility (MERF) will be validated.

18


Summary

Lithium manganese rich transition metal oxide (LMR-NMC) was electrochemically charged and discharged in low, mid, and voltage windows. The differential capacity analysis indicates that the Li2MnO3 and LiMO2 preserves its electrochemical features, with little off-set, in the composite. Component derived from Li2MnO3 after activation during 1st cycle could be responsible for the voltage hysteresis.

The graphite/LMR-NMC cell using aqueous binders was fabricated and tested. The electrochemical performance of the cell with aqueous binders were determined to be equivalent to the cells with conventional PVDF binder.


Summary

Silicon and its composite was investigated as anode materials for lithium ion batteries. Binder and additive study is still in progress. The current results suggest that collective efforts, such as binder, additive, test protocol, and electrode engineering, are needed to address the challenges (cycle life and surface SEI formation). – Several silicon sources were identified and the evaluation

process is in progress. – Preliminary DSC result indicated the comparable thermal

stability of SiOx to graphite. Other cell components, such as redox shuttle, binder,

separator, carbon additive have been studied and information was delivered to material supplier and internal facilities.

Under CFF, several electrode library materials were collected and validated. Electrolyte and electrode materials from MERF were also validated.

20


Contributors and Acknowledgments Abouimrane, Ali (ANL) Abraham, Daniel (ANL) Amine, Khalil (ANL) Belharouk, Ilias (ANL) Chen, Zonghai (ANL) Croy, Jason (ANL) Dees, Dennis (ANL) Dietz, Nancy (ANL) Gallagher, Kevin (ANL) Henriksen, Gary (ANL) Johnson, Christopher (ANL) Kubal, Joseph (ANL) Liu, Gao (LBNL) Liu, Bo (ANL) Polzin, Bryant (ANL) Scherson, Daniel (CWRU) Thackeray, Mike (ANL) Trask, Steve (ANL) Vaughey, Jack (ANL) Xu, Kang (ARL) Zhai, Dengyun (ANL) Zhang, John (ANL) Electron Microscopy Center (EMC) Jet Propulsion Lab

Support from David Howell and Peter Faguy of the U.S. Department of Energy’s Office of Vehicle Technologies Program is gratefully acknowledged.

BTR (China) Cabot Phillips66 Daikin Inc. (Japan) Dow Corning Dreamweaver Du Pont Electrochemical Materials Energy2 Hanwha (Korea) JSR Micro(Japan/California) Kureha (Japan) Nanosys NEI corporation Nippon Paper (Japan) Porous Power Tech Silatronix Solrayo Solvay Toda Kogyo

(Japan/Michigan) XG Sciences ZEON (Japan/Kentucky)

Documents

Validation of Electrode Materials and Cell Chemistries...3.6V~4.3V1 3.6V~4.3V2 3.6V~4.3V3 2.6V~4.6V3 Li/HE5050 cell 2 3 4 5-2 0 2 4 dQ/dV, mAh/V Voltage, V 4.2V~4.6V1 4.2V~4.6V2 4.2V~4.6V3