P08L-4194 NASA Aerospace Battery Workshop 2008

Safety Design Features of GS Yuasas Large Lithium-ion Cell

Takefumi Inoue and Hiroaki Yoshida

GS Yuasa Technology Ltd.

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Contents
Information about GYT large lithium-ion cells for space applications Published information about 18650 incidents Structure and safety design features of GYT large cell Difference between commercial 18650 cell and GYT large cell Other safety test data on GYT large cell

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Introduction
GYT has developed 50, 100 and 175Ah cells. We fixed their chemical design at 1999 and did not change.

Satellite type Dimensions Capacity H 263mm W 165mm T 50mm Nominal 186Ah (Rated 175Ah) (Long cycle life type) Mass Specific energy*

4.65kg

146 Wh/kg

H 208mm W 130mm T 50mm

Nominal 110Ah (Rated 100Ah)

2.79kg

146 Wh/kg

H 123mm W 130mm T 50mm

Nominal 55Ah (Rated 50Ah)

1.50kg

136 Wh/kg

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Experience in programs
Launched
SERVIS (Japanese experimental LEO satellite): Installed and launched in 2003 THAICOM4 (Very large commercial GEO satellite): Installed and launched in 2005 INSAT4 (ISRO Communication GEO satellite): Installed and launched in 2007 And three other satellites

Near future launch

Other contracts have been made on 16 GEOs, 3 LEO programs(>50 satellites), and other space vehicle programs.

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Published Information
1. Published information on SONY 18650 cell in 2006 1-1. The cell and battery type
Cell: SONY 18650 type cell (G7, 2400mAh) Shape - Cylindrical Diameter - 18mm Length - 65mm Cell case Steel, Negative terminal potential Battery: 4 series or 3 series and 2 parallel string pack

1-2. Production number for whole consumer market

22 Billion cells/ 10 years(1995-2005) All brand included

1-3. Accidents reported from SONY

6 fire accidents SONY published that probability of fire accident is 1 / 3,500,000.

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Published Information
2. Published information on SONY cell in Oct. 2008
Editors Notes: Outline of the Voluntary Recalls by PC Manufacturers and Incidents 1) Affected battery cell type: 2.15Ah cells 2) Number of battery packs to be recalled by PC manufacturers: About 100,000 packs worldwide 3) Reported overheating incidents: 40 overheating incidents 4) Cumulative global shipment quantity of 2.15Ah cells since 2002: About 260 million cells 5) Cumulative incident rate: 0.000016%
Ref. http://www.sony.co.jp/SonyInfo/News/Press/200810/08-140E/index.html

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Published Information (continued)

2. Assembling processes and the major reason of metal contamination published by SONY in Nikkei Electronics, Nov. 6, 2006.
Winding

Case Electrolyte Welding of Insert to indention filling case safety vent

Insertion of parts

Sealing

Metal particles can enter the triangle zone at the electrolyte filling process

Tool

The cell case which has element inside is clamped by a tool from upper side and rotated. Then it is pressed by the process disk tool to make an indentation on the cell case to fix the inside element. At this process, metal particle can be generated by friction between the upper tool and the cell case. Fig 1 Assembling process of cylindrical shape Li-ion cell The process which allows contamination of metal particle is case indention process. The Nickel plating on inside of the cell case peal off and drop into the case when the process that makes an indention on the side top portion.

Metal particle

Tool

Case

Element

Case

Element

Process disk

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Published Information (continued)

3. The mechanism of the fire accident on the DELL PC / SONY Lithium Ion battery published by SONY in Nikkei Electronics, Nov. 6, 2006.
If a internal short occur because of contamination of metal particle such an Ni in this region, the cell quietly lose the function due to separator shut down.

But if a nickel particle enters the triangle zone (the edge of the positive electrode outer end) . Positive electrode Metal particle If a nickel particle particle enters the triangle zone, it fairly infrequently dissolves and deposits on negative side. And then, lithium metal starts deposition on the nickel on negative electrode. Finally the deposited lithium metal go through the separator and create short circuit between negative and positive.

Separator Negative electrode Enlarged illustration of the triangle zone

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Summarized Mechanism
4. The detail mechanism of the fire accident
Separator Spiral wound element
positive/separator/ negative

Triangle zone
at the edge of positive electrode of outer end

Metal particle (go to the edge of

the positive electrode of outer end)

Positive electrode Negative electrode Copper foil ( Negative substrate) Aluminum foil ( Positive substrate) Metal case (Steel with Ni plating) 1) Metal particle can enter the cell inside and fairly infrequently locates the triangle zone after electrolyte filling process

Indention tool

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Summarized Mechanism (continued)

Deposited nickel on negative electrode

2) After electrolyte filling and charge/discharge operation, the particle dissolve and deposit on negative electrode.

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Summarized Mechanism (continued)

3) Lithium metal dendrite grows on the deposited nickel on negative electrode. It go through the separator and reach to the positive electrode. Finally, a short circuit path created between the negative and the positive electrode and cause fire. The fire occurrence can be assisted by existence of thermally active metal lithium and low short circuit resistance because of direct short to aluminum foil which is positive substrate
Notes: Lithium metal dendrite can be created by only high voltage charging, very high rate charging such as more than 2C, or high rate charging under very low temperature. If the short circuit path created on coated positive active material, it result in just consume capacity because of high short circuit resistance.

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Structure of GYT Large Li-ion Cell for Satellite Application

Insulation boards Shut down separators Insulation sheets Laser welding sealing process (No indention process)

Electrically floating case (Aluminum alloy) Internal fuse function at positive current collector

Flat wound element

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Difference Between Commercial 18650 Cell and GYT Large Cell

Commercial 18650 Case material Steel with Ni plate (or Stainless Steel)
It can generate Ni particle that can dissolve on positive electrode potential and can cause the problem.

GS Yuasa Large Cell Aluminum Alloy The aluminum alloy does not
dissolve on the positive electrode potential.

Case indention process

Yes.
It can generate Ni particle which can fall on the inserted element.

No.
The aluminum alloy case is welded without indention or any deformation process after the element insertion.

Contamination control Insulation film between case and element Soft short (self discharge) inspection Charging voltage / algorism

Depends on each manufacturer / model

Manufactured in clean room Yes It can protect the element from

metallic particle

No

Unknown Max 4.4V/cell / 3C quick pulse (an existing example)

Yes, with very strict criteria Max 4.2V/cell / constant current (C/2) and constant voltage

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Other Safety Test Data

External short circuit
(Experiment) 100Ah Li-ion cells for satellite use were used for the tests. The cells have one rupture plate on the top and four rupture plates on the sides. Before the safety tests, the cells were charged to 100%SOC. The charge method is shown below. Charge: 20A to 3.98V for 8hours by CC/CV method at room temperature. The cell was clamped with the aluminum boards to simulate the environment in a battery unit. Two kinds of condition in external short circuit tests were selected. One was a complete short circuit with only a resistance by the equipment (0.5mohm) (TEST I) and the other was a short circuit in which a resistance (1.4mohm) was used to control the short circuit current (TEST II).

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Other Safety Test Data (continued)

(Results) Figure 1 shows voltage, current and surface temperature of the cell on the external short circuit test (TEST I). The cell voltage became 0V after 3.6 sec. There was little temperature rise, no generation of vent gas and no explosion of the case. The reason for the voltage becoming 0V is that the electrical collector of positive electrode was melt down by joule heat. Figure 2 shows voltage, current and surface temperature of the cell on the external short circuit test (TEST II). The maximum current of the test was 2200A. The cell surface temperature raised up gradually to 86 degree C. There was electrolyte leakage from rupture plate on the top. There was no generation of vent gas and no explosion of the case.

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Other Safety Test Data (continued)

4.5
Max. current 4300A

45 40 35 30
Voltage Temperature Current

4500 4000

400

4000

4 3.5 3

Cell surface temperature / degree C

4
3500

Voltage Current Temperature

300

3000

3000 2500 2000 1500

Voltage / V

2 1.5 1 0.5 0 -0.5 -20

20 15 10 5 0 -5 120

200

2000

1
1000

100
500 0 -500

1000

-1 -2 0 2 4 6 8 10 12 14

20

40

60

80

100

Time / sec

Time / min

Fig. 1. Changes in voltage, current, and surface temperature of 100Ah Li-ion cell on the external short circuit test with 0.5mohm resistance. (TEST I)
Charge before the external short circuit test: 20A to3.98V for 8hours by CC/CV method at 25

Fig. 2. Changes in voltage, current and surface temperature of a 100Ah Li-ion cell on the external short circuit test with a 1.4 mohm resistance. (TEST II)
Charge before the external short circuit test: 20A to3.98V for 8hours by CC/CV method at 25

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Current(A)

2.5

25

Max. current 2200A

Temperature(deg. C)

Current / A

Voltage / V

Other Safety Test Data (continued)

Over discharge
(Experiment) A 100Ah Li-ion cell for satellite use was used for the over discharge test. The cell has a rupture plate on the cover plate and four rupture plates on the narrow side of the case. At the starting, the cell was fully discharged state. The over discharge test condition is shown as follows. Discharge: 100A for 1 hour (100% over discharge) (Result) Figure 4 shows the voltage and temperature profiles at the over discharge test.. The maximum temperature was 48.5 degrees C after 17 min. There was no electrolyte leakage. No rupture plate operated.

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Other Safety Test Data (continued)

3 140 2 120

Current

Voltage

80

-1

60

-2

Cell surface temperature MAX.48.5

40

-3

20

-4

-5 -20

20

40

60

80

-20 100

Time / min

Fig. 4. Voltage and temperature profiles of the 100Ah Li-ion cell at the over discharge test.
Over discharge condition Constant current at 100A for 1hour

Current / A Temperature / degrees C

100

Voltage / V

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Other Safety Test Data (continued)

Press with load
(Experiment) 100Ah lithium ion cells were pressed by a round plate (r=10mm). The press loads were 2800kg from oil pressure pump. It is approximately 1000 times as the cell weight. When the load reached 2800kg, the cell was immediately released from the load. The each test time was within 5 sec. We performed the tests for 4 cells. Each cell was pressed only at one time. The test condition is shown in Table 1. The illustration of the tests is shown in Fig. 5. During the test, we monitored the cell voltage and the situation. Table 1. Test condition. Direction of the press 10Ah charged state X, Y axes (1 press / 1 cell) 100% SOC X, Y axes (1 press / 1 cell) (Result) For X axis, the electrolyte leakage, the voltage drop and the temperature rise were not observed. The change of the cell shape was a little. For Y axis, the cell shape changed largely. There was the electrolyte leakage from rupture plate of a cell case. But, the voltage drop and the temperature rise were not observed.
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Result of 190Ah cells The representative pictures after the tests are shown For Y axis and Z axis tests, there were electrolyte leakage from rupture plate. In all tests, voltage drop and temperature rise were not observed. It is suggested that internal short circuit

didnt happen at the tests.

X axis

Y axis

Z axis
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Conclusion
1. Fire accidents on commercial small cell related to indention process, cell structure, and operational condition such as charging. 2. GYT large Li-ion cells are designed in view of above points. They have never showed internal short accident through more than 10 years production. (>5000 cells) 3.GYT large Li-ion cells showed good result on external short circuit, over discharge and press with load test.

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