High safety Lithium ion battery for

EV application

2010 Taipei Forum on Large Format Lithium Batteries

2017/08/09

Dr. Jing-Pin Pan

ITRI/MCL

ITRI organization

MCL-N Division Organization

Power Industries Promotion •Taiwan Battery Association - http://www.taiwanbattery.org.tw

•Promotion of Electrical Vehicle Industries - http://evs.org.tw

•Power Device(Module) Testing and Verification Platform

N600- Dept. of High Power Energy Storage Materials and Devices

N700- Dept. of Batteries Industry Promotion

N000- Energy Storage Materials & Technology Division

N100- Dept. of Nano structure Energy Materials

N500- Dept. of Advanced Thin Battery

N200- Dept. of Lithium Battery Reliability Design

N300- Dept. of Battery System and Application

Battery Technology Development in ITRI

High safety Lithium ion battery for EV application

U.S. considers expanding a laptop ban as lithium battery fires increase

As the U.S. government considers expanding a ban on laptop computers and other electronic

devices from the cabins of commercial flights, federal data show that storing such devices in

the cargo area of a plane could increase the risk of fires.

In 2014, the FAA reported that such batteries were responsible for nine fires, extreme heat or

smoke on cargo and passenger planes. That number grew to 16 in 2015; 31 in 2016 and 17

in the first five months of 2017.

Homeland Security Secretary John Kelly told a House of Representatives panel Wednesday

that he is considering expanding the electronic-device ban to 71 additional international

airports.

This frame grab from video, provided by the Federal Aviation Administration, shows a test at the FAA's technical

center in Atlantic City, N.J., in April 2014, where a cargo container was packed with 5,000 rechargeable lithium-ion

batteries. (Associated Press) http://www.latimes.com/business/la-fi-travel-briefcase-laptop-ban-20170608-story.html

2017/06/08

EV NEED MORE ENERGY = MORE DANGER

10 cells 200-5000 cells 1 cell

Safety is Most Important 9

A Major Challenge-Accident Free

Tesla Model S Tesla Model X

2016/11/04 Indiana, USA 2017/04/25 Guangzhou , China 2017/06/11 Shandong , China

Tesla Model X Tesla Model X

13th International Meeting on Lithium Batteries, at Biarritz, France, June 18-23, 2006.

Strategies to Overcome the Challenge

Safety mechanism of lithium ion battery

(included module & pack)

Overheat

Gas leakage

Fire

Explosion

Internal Short

External Short

Over Charge

Over Discharge

Separator

melt-down

~130℃

PTC

Protected circuit

(PACK)

Protected circuit

(PACK)

Pre-Charge

(PACK)

Abuse condition

Damage 1St : Electronic Design

2nd:Mechanic Design

3rd:Material Design

CID

Protected

circuit(I、V、T

abnormal)

thermal

runaway

STOBA • Solving safety issues of high energy

density battery caused from internal short

circuit.

• Widely application, reducing danger

factors, upgrading lithium ion battery

industries.

2009

Strategies to Overcome the Challenge

What’s STOBA?

A new kind of hyper branched polymers

(IP protected by ITRI)

• Regular molecular shape

Polydispersity Idex(PDI, Mw/Mn)≦1.2;

• Like sphere, Size ～5nm

• A lot of functional groups that can be re-

reacted by thermal energy

2009

13

Copyright 2017 ITRI 工業技術研究院 14

Superiorities of STOBA applied in LIBs Excellent cycle stability @ RT and HT

by reducing metal ion deposition

The cost of batteries can be reduced

by long cycle life and facile process

STOBA

Increase Capacity

Reduce Cost

Enhance Safety

Extend Cyclelife

Enable high loading weight electrode by

improving its flexibility

< with ChemSEI-Linker >< Blank>

(b)(a)

Fail , crack Pass , no crack

(a) Blank (b) with new STOBA

High weight loading electrode (20 28mg/cm2)

Prevent thermal runaway

when batteries suffer from damage

Ion+ & e- transfering path in electrode

Active material

Current collector

STOBA layer

Mechanism of safety STOBA film coating on cathode

Reference paper : RSC Adv., 2014, 4, 56147

What is the function of

STOBA while danger

occurs?

LNCM

Electrode resistance (Ω) Resistance increased rate

0% (wo STOBA)

RT 0.815 1

150℃ 3.49525 4

180℃ 126.785 156

2% (With STOBA)

RT 0.997 1

150℃ 60.7025 61

180℃ 2708.4 2717

20 40 60 80 100 120 140 160 180 200

0

300

600

900

1200

1500

1800

2100

2400

2700

3000

R

esis

tan

ce

in

cre

ase

d r

ate

(times

)

Aging Temperature(0C)

LNCM

LNCM+2% STOBA

2717 times

Electrode resistance

Analysis of LNCM(424) electrodes With/Wo STOBA @ 100%SOC -thermal process

1000 500 0 -500 -1000

2.4

Li

/ppm

LNCM - 100% SOC

(LNCM + 1%STOBA) - 100% SOC

(LNCM + 2%STOBA) - 100% SOC

(LNCM + 2%STOBA)- 100% SOC for 150oC/30min

(LNCM + 2%STOBA) - 100% SOC for 180oC/30min

**

*

*

*138

Solid-state Li NMR

400 300 200 100 0 -100 -200

2.4

Li

/ppm

LNCM - 100% SOC

(LNCM + 1%STOBA) - 100% SOC

(LNCM + 2%STOBA) - 100% SOC

(LNCM + 2%STOBA)- 100% SOC for 150oC/30min

(LNCM + 2%STOBA) - 100% SOC for 180oC/30min

138

LNCM

b a

LNCM

1. The signal/peak at 138 ppm is the Li ion in the STOBA layer on the LNCM electrode.

2. After the heat treatment, 138ppm peak disappeared gradually.

What is the safety mechanism of STOBA

e-

e-

e-

e-

STOBA can suppress electron and ion conduction while danger occurs

Nail

cathode(LMO)

Separator

Anode

Al foil

Cu foil

LixC6 -> xLi+ + xe- + 6C

Li1-xMO2 + xLi+ + xe- -> LiMO2

Li+

STOBA e- Li+ Li+

Cathode

material

STOBA T

herm

al d

iffus

ion

Th

erm

al d

iffusio

n

w/ STOBA w/ STOBA w/ STOBA w/o STOBA

Melt-down of Separator

Thermal decomposition

in Cathode

Li+ Li+ Li+

Cell with STOBA Cell w/o STOBA

Times Times

Cell

Cell

Mechanism of Nail vs. Short circuit of cell

(with & without STOBA of 5Ah pouch cell)

Separator

Anode

Cu foil

cathode(LMO) Al foil

0 2 4 6 8 10 12 14 16 18 200.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

0

100

200

300

400

500

600

700

800

Te

mp

. (o

C)

Vo

lta

ge

(V

)

Time (sec)

Voltage 5Ah w/o STOBA

5Ah with STOBA

Short point temp. 5Ah w/o STOBA

5Ah with STOBA

STOBA

activated

Nail Φ = 2.5mm

Nail Speed = 10 mm/sec

Nail test of 5Ah pouch cell (with & without STOBA )

21

200Wh/kg NCA Batteries

Electrochemical table of 436070 STOBA-inside cells

Nail test results of 436070 STOBA -inside cells

436070

pouch cell

Ave. 6 cells

0.2C

Dis.Capacity

mAh

0.2C

Dis. Capacity

mAh/g

DCIR, Ω

C-rate

3C vs. 0.2C,

(%)

Blank 2203±62 175±2.9 0.070±0.003 89.9%

new STOBA 2256±13 175±1.0 0.053±0.004 88.5%

Fire, Explosion

Max. Temp.~591oC

NS, NF

Max. Temp.~120oC

STOBA Blank

Temp Voltage Distance Temp Voltage Distance

new STOBA electrode with high flexibility

< with ChemSEI-Linker >< Blank>

(b)(a)

Fail , crack Pass , no crack

Folding test of high weight loading electrode (28mg/cm2) (a) Blank; (b) with new STOBA

[Blank] [new STOBA]

小米(mi) 5000 -3.3Ah Power Bank

Fire + explosion

JS 4.35V 5Ah Power Bank (wo STOBA)

JS 4.35V 5Ah Power Bank (STOBA)

Pass, No fire

http://www.tanker.com.tw/

O.D.=3mm ; speed=20mm/sec ; Fully Nail Penetration

Fire + explosion

STOBA, keeping your power bank safe!

Nail test of 39Ah LNCM VDA-PHEV2 cells ITRI cell vs. Commercial cell

Nail Φ = 5mm

Nail Speed = 30 mm/sec

Voltage

Voltage

Temp.

Temp.

ITRI cell

Commercial cell

24

Application of STOBA cell for products

中華(CMC) EM系列

electric scooter

ITRI-CPEV

Sharp robot

喬信Tanker® Power bank

2016 ASIS (Orlando, US)

Sharp robot

UPS system

• Through hyper branch nano structure, STOBA can

suppress electron and ion conduction while danger

occurs.

• STOBA batteries can have higher capacity, higher

safety, and high cycle life.

• STOBA batteries have already commercialized in Taiwan.

Conclusion

Experimental Design Assemble LNCM/Li pouch

cells (0% & 2% old STOBA)

Disassembly in the golvebox & Take out

the LNCM cathode electrodes

After Formation & 4.3V charged state

Charged LNCM electrodes with electrolyte were

sealed in the high pressure Ti tube and then were

heated to 150 & 180℃(Simulated Tinternal short circuit )

Measured the electron resistance of dry

cathode sheet in the dry room

The heated electrodes were clean and

washed by DMC in the golvebox, and

then dry in Vacuum at RT

The electrodes with electrolyte were

measured the Li7 NMR

the local environments of the Li+ ions and their

interaction and mobility in the STOBA–cathode

interface as functions of temperature and

charge states