K. Amine (PI)

Z. Chen, H. Wu, Y. Li, Z. Chen, J. Lu, and R. Xu,

Argonne National LaboratoryDOE merit review

June 6th ~10th , 2016

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

New High-Energy Electrochemical Couple for Automotive Applications

Project ID: ES208

Overview

Start - October 1st, 2013. Finish - September 30, 2015. 100% Completed

Barriers addressed– High energy (>200wh/kg)– Long calendar and cycle life– Abuse tolerance

• Total project funding– DOE share: 2500K

• Funding received in FY13: 1250K• Funding for FY14: $1250K

Timeline

Budget

Barriers

• Project lead: Khalil Amine• Interactions/ collaborations:- X. Q. Yang (BNL) diagnostic of FCG cathode and SEI

of Si-Sn composite anode - G. Liu (LBNL) development and optimization of

conductive binder for Si-Sn composite anode - ECPRO: provide baseline cathode material- Utah University: provide facility to scale up the

baseline Si-Sn composite anode for baseline cell- Andy Jansen & Polzin, Bryant (ANL) fabrication of

baseline cell- Paul Nelson (ANL) design of cell using BatPac

Partners

Relevance and project Objectives Objective: develop very high energy redox couple (250wh/kg)

based on high capacity full gradient concentration cathode (FCG) (230mAh/g) and Si-Sn composite anode (900mAh/g) with long cycle life and excellent abuse tolerance to enable 40 miles PHEV and EVs

This technology, If successful, will have a significant impact on: – Reducing battery cost and expending vehicle electrification– Reduce greenhouse gases– Reduce our reliance on foreign oil

Milestones• March 2015:

– Improve efficiency of SiO-SnCoC anode to over 80% (completed)

• August 2015:– Finalize the Optimization of the processing of SiO-SnCoC-MAG to

get uniform electrodes and demonstrate up to 100 cycles of SiO-SnCoC-MAG using new LiPAA binder (completed)

• September 2015: – Optimize and scale up of Improve further FCG cathode with

210mA/g at 4.5V (completed).– Provide FCG cathode (1Kg) to CAM facility for cell design and build

( completed)– Supply 14 cells to INL for testing and validation (completed)

4

CenterNi - Rich Composition

: high capacity

Full Gradient CompositionFrom Ni-Rich Composition, To Mn – Rich Composition

SurfaceMn – Rich

Composition: high thermal

stability

0 200 400 600 800 1000 1200 1400 16000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

Vol

rage

Vs.

Li/L

i+

b 1st D 1st C 3rd D 3rd C 100th D 100th C

Specific capacity (mA h g-1)

Approach

0 50 100 150 2002.5

3.0

3.5

4.0

4.5

Core F.G

2.7-4.3V, 0.2 C, R.T

Volta

ge /

VDischarge capacity / mAhg-1

ANODESSiO-SnyCo1-xFexCz composite

coupled with conductive binder

ELECTROLYTESHigh voltage electrolytes with additives to stabilize interface of cathode and

anode

CATHODESFull Gradient concentration

(FCG) LiNixMnyCozO2 with high concentration of Mn at

the surface of the particle

Fluorine based electrolyte with additives:

Floating test at different voltages of LiNi0.5Mn1.5O4/Li4Ti5O12

Cell using fluorinated electrolyteInitial charge & discharge of FCG

cathodeConductive binder

Initial charge & discharge of SiO-SnCoC anode FCG cathode

Technical accomplishments

Optimized the process of making FCG cathode and demonstrate capacity as high as 210mAh/g with 2.7 tap density

Characterized the FCG material using soft and hard X-ray in collaboration with BNL

Scaled up FCG cathode to 1Kg level for electrode making using CAMP facility at Argonne

Build cells based on FCG cathode and graphite anode and demonstrate good cyclability at high voltage

Developed a new prelithiation process to eliminate the large initial irreversible loss of SiO-SnCoC anode

FCG Cathode development approach

1. Design of full concentration gradient

cathode material

2. Preparation of full concentration

gradient (FCG) precursor via CSTR Co-

precipitation with optimized

condition

3. Calcination of FCG cathode with

optimized condition

4. Physical characterization

5. Electrochemical evaluation

FCG material design

CFF for pouch cell evaluation

Electrochemicalevaluation (coin cell)

Optimize the precursor

Optimize the calcination

Characterization(XRD, SEM, TEM)

Reactor Setup

Characteristics of FCG gradient precursor & final active material made from hydroxide process after optimization

High tap density: 2.7 g/ccparticle distribution: D50=11.64 um

The average composition: ~LiNi0.6Co0.2Mn0.2O2Outer: ~LiNi0.46Co0.23Mn0.41O2Inner: ~LiNi0.8Co0.1Mn0.1O2

FCG (6:2:2) : LiNi0.6Co0.2Mn0.2O2

Ni0.6Co0.2Mn0.2(OH)2

0

10

20

30

40

50

60

70

80

00.

120.

240.

360.

48 0.6

0.72

0.84

0.96

1.08

1.21

1.33

1.45

1.57

1.69

1.81

1.93

2.05

2.17

2.29

2.41

2.53

2.65

2.77

2.89

3.01

3.13

3.25

3.38 3.

53.

623.

743.

863.

98 4.1

4.22

Mn K

Co K

Ni KRela

tive

inte

nsity

Distance (µm)center edge

Ni

Mn

Co

• 2.7 – 4.3 V (192 mAh/g)• 2.7 – 4.4 V (198 mAh/g)• 2.7 – 4.5 V (210 mAh/g)

Electrochemical performance of FCG cathode at different cut-off voltages

2\B&++&%.''B/B+4%#'C.)-4+4./').'HH$J'

!"A)M''J0,I)UNMNMK''

Electrochemical performance of FCG cathode at 55oC

JX[WVOX[K' JX[WVOX[K'

TR-XRD/MS of FCG (6:2:2) and NMC (6:2:2) baseline

A! @:)"G'1?'#)C'"&+&)C&'O).'40"'<H='$JS'K8"4%#'G:)C&'.")%C4*$%'T"$3'+)/&"&K'.$'K4C$"K&"&K'CG4%&+'G:)C&'

LiNi0.6Mn0.2Co0.2O4 (Baseline NMC 622) LiNi0.6Mn0.2Co0.2O4 (FCG-6:2:2))

AJ$%B&%.")*$%'#")K4&%.'OFJ]S'C)3G+&' C:$6C'38B:'-&l&"'.:&"3)+'C.)-4+4./' .:)%'-)C&+4%&'(hJ'9??''W'<C.'G:)C&'.")%C4*$%'$BB8""&K').'B)E'<^=' mJ'

845 850 855 860 865 870 875 880

Nor

mal

ized

inte

nsity

(arb

.uni

t)

Energy (eV)845 850 855 860 865 870 875 880

Nor

mal

ized

inte

nsity

(arb

.uni

t)

Energy (eV)

Ni L-edge soft XAS for baseline NMC622 (left ) and FCG-622 (right) Using Fluorescence detection (FY, bulk probing)

25 oC

150 oC

200 oC

250 oC

300 oC

350 oC

400 oC

450 oC

500 oC

25 oC

150 oC

200 oC

250 oC

300 oC

350 oC

400 oC

450 oC

500 oC

Ni reduction reflected as the lower energy peak occurred quickly at low temperature (~150 oC) in baseline NMC622. In contrast, FCG-622 is more stable and Ni is stable up to 250 oC and gradually reduced, and completed at 350 oC

Baseline-NMC622FCG-622

845 850 855 860 865 870 875 880

Nor

mal

ized

inte

nsity

(arb

.uni

t)

Energy (eV)845 850 855 860 865 870 875 880

Nor

mal

ized

inte

nsity

(arb

.uni

t)

Energy (eV)

25 oC

150 oC

200 oC

250 oC

300 oC

350 oC

400 oC

450 oC

500 oC

25 oC

150 oC

200 oC

250 oC

300 oC

350 oC

400 oC

450 oC

500 oC

- The structural change at near surface also shows same trend with bulk structure.- Ni reduction temperature is well coincident with the temperature of the phase

transition and O2 release in TR-XRD/MS data

Ni L-edge soft XAS for Baseline NMC622 (left ) and FCG (right)Using partial electron yield detection (PEY, Surface probing)

Baseline NMC622FCG NMC622

0 10 200

100

200

Cap

acity

Cycle number

Disch,mAh/g Ch,mAh/g

(a)

YC722PFM60% SiO-SnCoC+30%PFM +10%SP+C6H5Cl

Low efficiency: 65%~70%.

Optimization of SiO-SnCoC composite anode

0 300 600 900 1200 15000

1

2

3(b)

Vol

tage

(V)

Capacity (mAh/g)

1 cycle 2 cycle 3 cycle

Half cell SiO-SnCoC : 90/5%Timecal/5%PI

Electrode loading: 2.5mg/cm2

1st cycle reversibility between 70 to 72%.

Main Issues:Conductive binder (PFM) shows poor

performance with Si-SnCoC composite

14

Active material composition optimization:- Mixing appropriate amount of graphite with SiO-SnCoC- Best composition based on graphite mixing optimization is:

(33%SiO-SnCoC +57% MAG graphite)

Binder optimization:

PFM conductive binder from LBNLPVDFPolyimide biner(PI)Polyacrylic acid binder (PAA)PVDF mix with PIPVDF mix with PAALiPAA

Approaches to resolving SiO-SnCoCcomposite anode issues

15

0 20 400

200

400

600

800

1000

Cap

acity

(mA

h/g)

Cycle number

Ch Disch

33% SiO-SnCoC+57%GC+5%LiPAA+5%C-45

1st cycle C.E. 81 %.

00.20.40.60.8

11.21.41.6

0 200 400 600 800

Volta

ge, (

V)

Capacity (mAh/g)

1. The cell shows high 1st C.E. efficiency (81%).2. The cell shows good rate performance.3. The cell shows high capacity (670 mAh/g) and

excellent cycle life so far.

33%SiO-Sn30Co30C40/57%MAG graphite with 5%LiPAA shows the best performance with 81% 1st cycle efficiency

33%SiO-Sn30Co30C40/57%MAG graphite /5%LiPAA/ 5%C-45 formulation was used by CAMP facility to fabricate electrode for cell

build

0

50

100

150

200

250

0 5 10 15 20 25 30

Cap

acit

y, m

Ah

/g

Cycle Number

CYCLE PERFORMANCE

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

0 50 100 150 200 250

Vo

ltag

e, V

Capacity, mAh/g

VOLTAGE PROFILE

Initial performance of Full cell SiO-SnCoC-MAG/FCG cathode

• The first discharge capacity is only 170mAh/g due to large initial irreversible loss of SiO-SnCoC-Mag anode

• Need to incorporate a pre-lithiation to maximize cathode capacity

17

1st C cap (mAh/g) 2181st D Cap (mAh/g) 1891st Cycle Eff (%) 86.5

Coupling FCG with Graphite instead of SiO-SnCoC-MAG shows excellent cycle life

00.5

11.5

22.5

33.5

44.5

0 100 200 300

Volta

ge, (

V)

Capacity (mAh/g) 020406080

100120140160180200

0 10 20 30

Capa

city

, (m

Ah/g

)Cycle Number

Discharge Capacity vs Cycle Life

By replacing SiO-SnCoC-MAG composite with graphite, the cycle life of the full cell with FCG cathode improved significantly,

Based on the result above, we decided to build FCG/MAG full cell while developing a pre-lithiation process to enable Si-SnCoC anode

Electrode Architecture and Cell Assembly based on FCG and MAG Graphite

Pouch cell build is using – Anode (LN3012-178) -> MagE graphite– Cathode (LN3012-179) -> FCG

Average Entire Cell Weight, as delivered: 11.0405 g

Electrode Architecture– Cathode Electrode Dimensions : 31.3 mm W x 45.0 mm T

• Cathode Electrode Area : 14.1 cm2 per side

– Anode Electrode Dimension : 32.4 mm W x 46.0 mm T• Anode Electrode Area : 14.9 cm2 per side

Cell Assembly– Total Number of Layers : 13

• Cathode Layers : 5 Double Side Layers + 2 Single Side Layers (outer 2 electrodes)• Anode Layers : 6 Double Side Layers

– Separator Used : Celgard 2325 - Trilayer PP/PE/PP– Electrolyte Used : 1.2M LiPF6 in EC:EMC (3:7 wt%)– Applied Cell Pressure during testing: ~15 kPa

Vehicle Technologies Program19

Cathode & Anode Formulation

Vehicle Technologies Program20

Cathode Formulation (Dry Composition)– 90 wt% FCG, Khal ABR 2014 (Lot 011915/012015)

– 5 wt% Timcal C-45 Carbon Black– 5 wt% Solvay 5130 PVDF Binder

Cathode Electrode Properties– Aluminum Foil Thickness: 20 microns– TTL DS Electrode Thickness: 159 microns– TTL SS Coating Thickness: 69 microns– Cathode Coating: 17.20 mg/cm² (SS)

(Total Material wt; No Foil)– Capacity: 2.87 to 3.06 mAh/cm²– Target Porosity: 39.5 %– Coating Density: 2.47 g/cm3

n:p Ratio: 1.10 to 1.16

Anode Formulation (Dry Composition)– 91.83 wt% Hitachi MagE– 2 wt% Timcal C-45 Carbon Black– 6 wt.% Kureha 9300 PVDF– 0.17wt.% Oxalic Acid

Anode Electrode Properties– Copper Foil Thickness: 10 microns– TTL DS Electrode Thickness: 162 microns– TTL SS Coating Thickness: 76 microns– Anode Coating: 11.33 mg/cm² (SS)

(Total Material wt; No Foil)– Capacity: 3.44 to 3.50 mAh/cm²– Target Porosity: 31.2 %– Coating Density: 1.49 g/cm3

0255075100125150175200225

050

100150200250300350400450500

0 100 200 300 Capa

city

, (m

Ah/g

of c

atho

de o

xide

)

Capa

city

, (m

Ah)

Cycle #

Average Discharge Capacity

Average Discharge Capacity (mAh)Average Discharge Capacity (mAh/g)

Initial performance of full cell based FCG (6:2:2) /MAG

0

20

40

60

80

100

120

140

160

0 10 20 30 40 50 60 70 80 90 100

ASI.

(ohm

-cm

2 )

Depth of Discharge (%)

Discharge ASI vs DoD (%)

CFF-B19A-P1

0

20

40

60

80

100

120

140

160

3.33.53.73.94.14.3AS

I. (o

hm-c

m2 )

Voltage, (V)

Discharge ASI vs DoD (%)

CFF-B19A-P1

Color Cycle # RangeRed 20 to 70

Orange 120Yellow 170Green 220 to 270

Discharge ASI vs DOD of full cell based FCG (6:2:2) /MAG

Deliverable Device

Battery Performance (Cell Level)

Usable Specific Energy(Wh/kg)

Energy Usable Density (Wh/l)

Power at SOCmin

(W/kg,10sec)

TechnologyInfo

*Baseline 20Ah Cell40Ah CellBatPac Design

(~199)(~237)

(~453)(~548)

(~1591)(~950)

SiO-SnCoCAnd

NMC (6:2:2)

Energy and power of baseline and FCG cells based on BatPac Design

Gen1 20Ah Cell40Ah CellBatPac Design

(~229)(~280)

(~541)(~659)

(~1837)(~1120)

SiO-SnCoC-MAGAnd

FCG (6:2:2)

* Data provided on baseline last year was higher than the one in the table above as we found a mistake in the Pat Pac model input.

ANL discover a new approach to pre-lithiation by activating Li2O at the cathode side at high voltage

Li2O : Li sources to compensate for lithium consumption in lithium-ion batteries (improve fist cycle irreversibility of silicon and other anodes) (capacity of Li2O ~ 1650 mAh/g)

Li2O could be combined with all cathodes non-containing Li such as: S; MnO2, V2O5, FeF3, SeSx……

Pre-lithiation of SiO-SnCoC to reduce the negative impact of large initial irreversible lose

LIB in the market is anode limitedbattery

- To balance battery with Graphite (CE:90%):1 g of graphite delivers 3.2 mAh and needs 2 (+10%)= 2.2g of cathode material with (160 mAh/g) to have a cell with 3.2 mAh. (0.2 g of the cathode is a dead weight in the battery).

- To balance battery with Graphite/Silicon (CE:80%, capacity 728 mAh/g):

1 g of graphite/silicon delivers 6.4 mAh and needs 4 (+20%)= 4.8g of cathode material with (160 mAh/g) to have a cell with 6.4 mAh. (0.8 g of the cathode is a dead weight in the battery).

0 100 200 300 400 500 6002.0

2.5

3.0

3.5

4.0

4.5

5.0

621

Gen II electrolyte Gen I electrolyte

Pot

entia

l (V

) vs.

Li

Capacity in mAh per gram of HEM

585

Voltage profile versus capacity of HEM-Li2O/Li half-cell with Gen I and Gen II electrolytes (I = 10 mA/g).

HEM: Li1.2Ni0.15Mn0.55Co0.1O2

High charge capacity is obtained when adding 15%Li2O. Two times the charge capacity of the HEM material.

Li2O with HEM electrode

Gen I: LiPF6/EC:EMC (3:7)GenII: LiClO4/EC:EMC (3:7)

0 200 400 600 800 1000

1.5

2.0

2.5

3.0

3.5

LTO "HEM" in Gen I

HEM in Gen I

LTO "HEM-Li2O" in Gen IVo

ltage

(V)

Capacity in mAh per gram of HEM

HEM-Li2O in Gen I

Voltage profile versus charge capacities of HEM/ LTO and HEM-Li2O/LTO full cells (I = 3 mA/g) and recovered LTO/Li half-cell in Gen I electrolyte (I = 8 mA/g).

Proof of activation : amount of Li in the full cell using LTO anode

The amount of lithium inserted in the LTO (from HEM-Li2O) in mAh/g equivalent is 600 mAh/g.

The amount of lithium inserted in the LTO (from HEM) in mAh/g equivalent is only 275 mAh/g.

F4"C.AB/B+&'5$+.)#&'G"$c+&'5&"C8C'B)G)B4./')%K'B/B+4%#'G&"T$"3)%B&'O4%C&.S'$T'N2hM,4?1Q@41A@%J$J')%K'N2hQ@41A@%J$J'T8++'B&++CE''

#!a:&'T8++'B&++'B)G)B4./'6)C'43G"$5&K'T"$3'<e9'3!:Q#'.$'?HY'3!:Q#E'

#!($'&w&B.'$%'.:&'B/B+4%#'$T'T8++'B&++C'$"':)+T'B&++CE'

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?%K''G"$$T'$T'B$%B&G.'64.:'T8++'B&++'@41A@%J$1'3).&"4)+'64.:'+$6'J2';99Ae=I''

Responses to Previous Year Reviewers’ Comments

• Question: reviewer 2 The anode material target of 900 mAh/g, the reviewer said, can be sufficient for the DOE PHEV-40 target. It would be of additional benefit, the reviewer concluded, to investigate the potential of the material to exceed 1,000 mAh/g and thus also to address EV application !

• Answer: the reviewer is absolutely righ. However, the targeted energy density in this project is 200wh/kg and we believe less than 900mAh/g anode capacity can easily meet this target

• Question : reviewer No:4 The key barriers that must be addressed, the reviewer stated, is long calendar and cycle life, but it is not clear how to address this challenge. In particular, the reviewer said, a solution for the instability of the SEI layer and attack by dissolved Mn from the surface of the FCG cathode to the anode side were not clearly discussed or planned. Also, the current anode system shows poor capacity and cycle life, problems the reviewer said could not be solved by addressing only the binder

• Answer: the issue of Mn dissolution and its imp[act on the SEI of the anode was resolved by adding LiBDOF electrolyte additive that resist any attack by Mn dissolution. In the past we have demonstrated 1000 cycle with 91% retention using FCG/MCMB.

• The Si anode we developed can provide very high capacity, however, we blend it with large amount of carbon to get 600mAh/g that we believe can meet the 200wh/kg energy requirement. The cycle life vs lithium is excellent , however, the cycle life in full cell was not satisfactory because of the difficulty of CAM lab to make good electrodes during scale up!

29

Responses to previous year reviewers' comments

• Question: reviewer 1: the Nickel contact on FCG should increase to get high capacity.

• Answer: we totally agree with the reviewer. The development of Ni rich gradient will require more time to optimize the gradient slop. This will be the subject of a different project that we hope will be supported by DOE.

30

Collaborations• X.Q. Yang of BNL

• Diagnostic of FCG and SEI of Si-Sn composite electrodes using soft & hard X-ray.

• G. Liu (LBNL) •Development and optimization of conductive binder for Si-Sn composite anode

•H. Wu (ANL) •Optimize the synthesis of FCG cathode

•A. Abouimrane (ANL) •Development of SiO-SnyCo1-xFexCz anode

•J.Lu & Z. Chen (ANL)•Characterization of cathode, anode and cell during cycling using In-situ techniques

• ECPRO : Baseline cathode material

•University of Utah : Facility to scale up the baseline Si-Sn composite anode for baseline cell

• A. Jansen & B. Polzin (ANL)•Design & fabrication of baseline cell

Summary Relevance

• enable low battery cost by increasing energy density • Low battery cost will lead to mass electrification of vehicle and reduction of both

greenhouse gases and our reliance on foreign oil Approaches

• develop very high energy redox couple (250wh/kg) based on high capacity full gradient concentration cathode (FCG) (210mAh/g) and Si-Sn composite anode (670mAh/g) with long cycle life and excellent abuse tolerance to enable 40 miles PHEV and EVs

Technical Accomplishments• Optimize the process of making FCG cathode and demonstrate capacity as high as

210mAh/g with 2.7 tap density• Scale up FCG cathode to 1Kg level for electrode making using CAMP facility at Argonne• Improve the efficiency of SiO-Sn30 Co30C40 anode to 81% by Developing SiO-Sn30

Co30C40 –MAG graphite composite formulation and scale up the new composite to 1Kg level.

• Develop a novel pre-lithiation process to overcome the first irreversible loss at the Si0SnCoC anode

Proposed Future work• The project ended at the end of September 2015

32