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Lithium-ion battery for hybrid vehicles EH5

High Power and Long Life Lithium-ion Battery

EH5 for HEVs

Takaaki IguchiÿSeijiro OchiaiÿTaku Kozonoÿ

Kazuji Nittaÿÿ Yasuyuki Abeÿÿ Kenji Konoÿ

Takaaki Iguchi Seijiro Ochiai Suguru Kozono

Kazushi Nitta Yasuyuki Abe Kenji Kohno

Abstract

Li-ion batteries as powertrains for electrified vehicles including HEVs have been strongly expected to be upgraded in those performance in terms of

larger output power and longer lifetime with smaller size and lighter weight. Blue Energy has developed a new-model lithium-ion cell “EH5” which

provides excellent durability over 35,000 cycles in wide range of oprating temperature between -40 to 65 ÿ. Furthermore, EH5 is capable of 60% and

30% larger output power at -10 ÿ and at 25 ÿ, respectively, than those of EH4 which was launched onto the market in 2011 as the former model of

EH5. Both the high durability and the high output performance have been achieved by adopting amorphous carbon as negative active material and

lithium nickel-cobalt-manganese composite oxide as positive active material with new technology in electrode design. EH5 achieved to meet every

requirement for HEV powertrain in a good balance such as electrical performance, durability, reliability, safety and controlability. With those distinctive

features, EH5 is expected to contribute for reduction of CO2 emission with improvement of fuel ef-ficiency of vehicles.

Key words : Lithium-ion battery ; Hybrid electric vehicles (HEVs); High power

[Link] of all The market for Hybrid Electric Vehicles is rapidly expanding.

be. Further expansion of the HEV market will require the development of its main driving force.

Due to global environmental and energy issues, CO2 emissions from automobiles are increasing. The evolution of batteries as energy is essential, and small

There are demands for volume reduction and fuel efficiency improvement, and demand is increasing in various categories. Lithium ion enables smaller size, lighter weight, and higher output

Electrification of automobiles is progressing. Among them, the most practical There are high expectations for batteries (LIB: Lithium-ion batteries).
Hybrid vehicles (HEV: Since its inception, Blue Energy has fulfilled many quality requirements.

With a design concept that can be easily realized, HEV

1-4
* Blue Energy Co., Ltd. Technology Development Department and Since the development and market launch of the ,year 2011

Research and Development Center Fifth Development Department EH4 lithium-ion battery for

**Blue Energy Co., Ltd. Technology Development Department are piling up.

© 2014 GS Yuasa International Ltd., All rights reserved.

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GS Yuasa Technical Report December 2014 Volume 11 Issue 2

At the same time, HEV systems are being developed to improve fuel efficiency and driving quality. However, it allows up to 200 A or more. The exterior is square

Evolution is progressing. Blue Energy responds to this The aluminum (Al) case is lightweight and compact.

Therefore, while significantly improving output performance, durability and reliability are also improved. It contributes to increased cooling efficiency and cooling efficiency while also providing high reliability.

Other qualities such as reliability, safety performance and ease of control are also included. ing.

We have newly developed the EH5, which is well-balanced. This paper 2.2 Features

Next, we will explain the specifications, performance, and features of EH5. The internal structure of EH5 is shown in Fig. 2. Power generation elements and structure

The features of the elements are explained below.

2 Specifications and features 2.2.1 Power generation elements

Low-crystalline carbon is used as the negative electrode active material, and low-crystalline carbon is used as the positive electrode active material.

5
2.1 Specifications uses highly heat-resistant polyolefin for Li(Ni, Co, Mn)O2, ÿSeparator

The specifications of the EH5 are shown in Table 1, and the external appearance is shown in Fig. 1. which has a unique composition.

The rated capacity of EH5 is 5.0 Ah, and the charging/discharging range is -30 to Ta. Each material has key features and characteristics described below.

Can be used in a wide temperature range of 55 °C, and -40 to 65 °C when left unused. EH5 is mainly responsible for b-2 and c-1 settings .

can be tolerated. The current that can be passed is limited by temperature and time. The output performance has been significantly improved through improvements to the meter. but

However, in that it achieved many required qualities in a well-balanced manner,

The design concept has not changed since EH4.

Table 1ÿSpecifi cations of EH5 cell. a. Main features and roles of negative electrode active materials

Cell model EH5 a-1. Small volume change during charging and discharging, excellent charging and discharging

Rated capacity 5.0 Ah

Enables cycle life performance
Nominal voltage
Dimensions 112.2 mm a-2. Has a constant potential gradient and enables highly accurate SOC (State
Length
Width 15.7 mm
of Charge) detection
Height(case) 78.5 mm
a-3. Polar solvents with low freezing points can be used in the electrolyte
Height(tab) 95.0 mm
Mass 0.28 kg Therefore, it can be used at extremely low temperatures.

Operational temperature -30 ÿ - 55 ÿ *

a-4. Diffusion within the solid phase is fast and lithium electrodeposition is difficult to occur.
Reservable temperature -40 ÿ - 65 ÿ
200 A --200 A* This enables excellent regeneration performance.
Operational current
*Collateral condition with temperature and time b. Main features and roles of cathode active materials

b-1. Due to the layered crystal structure of our proprietary composition,

enables superior output performance.

112.2
b-2. Uniquely developed surface protection technology provides excellent output.

Enables both strength performance and durability performance

7.51

b-3. High thermal stability enables excellent safety performance

to make

Negative current collector

Negative terminal

Lid Positive terminal

Positive current collector

Negative electrode
5.87

0.59

Active material : Amorphous carbon

Separator
Material : Micro porous polyolefin

Positive electrode
Active material : LiNi
x Coy Mnz O2

Case
Material : Aluminum

Fig. 1ÿOuter appearance of EH5 cell. Fig. 2ÿInner structure of EH5 cell.

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GS Yuasa Technical Report December 2014 Volume 11 Issue 2

c. Main features and roles of separators 3.2 Output performance

c-1. Excellent output performance achieved by improving the void structure. Figure 5 shows the output performance of the EH5 compared to the

enable conventional EH4. As representative data, the output at 10 seconds is shown

c-2. High withstand voltage enables excellent durability performance. when the maximum allowable current is 200 A and the upper and lower limit

do voltages are 4.3 V and 2.4 V, respectively. In the SOC region where the

c-3. Excellent performance achieved by adding a function to suppress thermal shrinkage. maximum allowable current is not limited and the actual internal resistance

Enabling safety performance difference can be compared, EH5 has improved output performance by

2.2.2 Structural elements approximately 60% at -10°C and approximately 30% at 25°C compared to EH4.

Power generation element with positive electrode, negative electrode and separator wound together There is. In particular, the low-temperature performance, which requires

The winding shaft is inserted parallel to the case opening surface, and the improvement in lithium-ion batteries, has been significantly improved, making it

A current collector is welded to the current collector foils provided at both ends of the current element, and the current collector is possible to improve fuel efficiency and start power in cold regions. In addition,

It has a current-carrying path that connects the body to the terminal. on the lid reducing internal resistance reduces the amount of heat generated during large current or continuous en

The battery has a terminal structure that has both insulation and sealing functions, and a

valve that opens at a predetermined internal pressure to prevent the battery from exploding.

It has been done.

1) Main features and roles of seal design

4.5
In order to ensure sealing and insulation between the Al lid, positive electrode

terminal (Al), and negative electrode terminal (Cu), we adopted a caulking

4.0
structure using a polyphenylene sulfide (PPS) gasket. PPS gaskets generate a

large repulsion force through caulking compression, and the decrease in 3.5

repulsion force due to creep over time is small, achieving excellent seal reliability.
/ egatloV

3.0
2) Main features and roles of mechanical resistance

2.5 Charge
Discharge

To ensure mechanical resistance in the dynamic environment (vibration and 2.0

0 1 234 5 6
shock) in which HEVs are used, the power generation element is welded and
Amount of electricity / Ah
fixed to a high-strength current collector. In addition, as explained in section a-1

of Section 2.2.1, the power generation element uses a negative electrode active Fig. 3ÿCharge and discharge characteristics of EH5 cell.

material that exhibits small volume changes during charging and discharging,
Charge: 5 A, 4.20 V (CC/CV) for 3 hours at 25 ÿ.
which reduces spatial fluctuations within the case and provides a more stable
Discharge: 5 A to 2.40 V (CC) at 25 ÿ.
repulsion force. This structure ensures mechanical resistance. The cells

themselves have excellent mechanical resistance, increasing the degree of

freedom in battery assembly design. 4.5

4.0
3 Electrical performance

3.5
3.1 Charge and discharge performance
/ egatloV

Figures 3 and 4 show the rated charge/discharge curve and open circuit 3.0
0ÿ
voltage (SOC-OCV) characteristics of EH5, respectively. Because low-crystalline 25 ÿ
2.5 45 ÿ
carbon is used as the negative electrode active material, it has a voltage

gradient over the entire capacity region, and its temperature dependence is
2.0
0 10 20 30 40 50 60 70 80 90 100
small. This voltage gradient makes it possible to improve the accuracy of SOC
SOC / %
detection and use a wider SOC range of energy.

Fig. 4ÿOCV-SOC characteristics of EH5 cell at 0, 25 and 45 ÿ.

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GS Yuasa Technical Report December 2014 Volume 11 Issue 2

Reducing power saving due to cooling frequency and excessive temperature rise At a constant current of 40 A and a maximum allowable temperature of 55 °C,

can also be expected to contribute to improved fuel Continuously cycles from 20 to 80% SOC without pauses.

efficiency. 3.3 Durability and Ta. Capacity and output performance were checked at each predetermined cycle, and

features 3.3.1 Charge/discharge cycle life performance the maintenance rate of each performance over the course of the cycle was shown.

Figure 6 shows the charge/discharge cycle life performance of EH5. After 35,000 cycles, the performance has been maintained at more than

Assuming the average load of HEV as a typical test condition 85% of the initial capacity and 85% of the output.

800 1000
•ÿ Assist ÿÿ
900
700 Regenerative
EH5
800
600
700
EH5
500
600
/W
wsP
oi

/wW
sP
oi
400 500
EH4
400
300

300
200
200
100 •ÿ Assist ÿÿ
EH4 100
Regenerative

0 10 20 30 40 50 60 70 80 90 0 10 20 30 40 50 60 70 80 90

SOC / ÿ SOC / ÿ

(a) -10 ÿ (b) 25 ÿ

Fig. 5ÿAssist and regenerative power characteristics of EH5 and EH4 cells for 10 second operation as a function of SOC at (a)–10 ÿ and (b) 25 ÿ. The allowable limit
current and voltage range are 200 A and 4.3 - 2.4 V, respectively.

110 110

100 100

90 90
/ noritenweot%
ePr

80 80
nyrotaiicthnacepstai%
eDcr

70 70
/g
e

60 60
0 10000 20000 30000 40000 0 10000 20000 30000 40000

Number of cycle / cycle Number of cycle /cycle

(a) Capacity retention (b) Power retention

Fig. 6ÿ(a) Capacity and (b) power retentions of EH5 cell throughout 40 A constant current cycle test between 80% and 20% SOC at 55 ÿ.

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GS Yuasa Technical Report December 2014 Volume 11 Issue 2

35,000 cycles is equivalent to approximately 6,000 hours in terms of time, and if the lifetime Increase in current collection resistance

average speed of the HEV is 25 km/h, it can be considered a test equivalent to 150,000 km. b) Specific deterioration Significant crystal structure on the surface of the positive electrode active material

Therefore, the EH5 has excellent performance over the lifetime of an HEV. Changes (inhibition of lithium transfer)

It is expected that the product will continue to demonstrate its performance. Here, normal deterioration means that the deterioration mechanism does not change during

3.3.2 Calendar life performance use, and the rate of deterioration is determined by the use conditions (temperature, SOC, etc.)

Figure 7 shows the calendar life performance of EH5. Typical test conditions include It is defined that there is a certain dependence on .

leaving the product at 80% SOC and 65°C, checking the capacity and output performance at Figure 8 shows the temperature dependence of the deterioration rate of capacity and output

predetermined intervals, and showing the maintenance rate of each performance over the performance when EH5 was subjected to storage tests at various temperatures. It can be

time the product was left unused. seen that there is a certain relationship between the deterioration rate up to 85°C for capacity

After 400 days, performance has been maintained at over 83% of the initial capacity and performance and 70°C for output performance. Based on the basis that the deterioration

over 85% of the output. EH5 has a certain SOC and temperature dependence in its mechanism remains unchanged and long-term lifespan is guaranteed, we allow the product to

deterioration rate when left unused. If we assume that the lifetime average SOC of the HEV be used unused up to temperatures as high as 65°C.

is 60% and the temperature is 30°C, this test would be accelerated by more than 10 times, In addition, the durability of output performance, which is especially important for HEV applications, is improved.

which would correspond to a period of more than 4,000 days, or more than 10 years.

110
You can get it. EH5 allows storage temperature up to 65ÿ

This makes it possible to ease restrictions on vehicle mounting position and cooling.
100
Therefore, it is expected that the EH5 will continue to demonstrate excellent performance over

the lifetime of the HEV. 3.3.3 Mechanism of

90
performance deterioration This section explains

the mechanism of deterioration in capacity and output performance during EH5 durability
80
/g
e nyrotaiicthnacepstai%
eD
cr

tests. Due to the design features explained in sections a-1 and c-2 of Section 2.2.1, EH5 can

easily express complex deterioration mechanisms, and the classification and main factors of 70

performance deterioration are organized as follows . are doing. 1) Capacity performance a)

Normal deterioration * Increase in coating on the surface of the negative 60

0 100 200 300 400 500
electrode active
Calendar period / day (a)
material (deactivation of lithium) b) Specific deterioration ** Electrodeposition of metallic lithium
Capacity retention
on the negative

electrode (deactivation of lithium)

110

Significant crystal structure on the surface of the positive electrode active material
100
Change (decrease in lithium deintercalation amount)

2) Output performance 90
eo
/ noritenw t%
ePr

a) Normal deterioration Increased film on the surface of negative electrode active material

(inhibition of lithium transfer) 80

Changes in the crystal structure of the surface of the positive electrode active material (reduction)

(inhibition of tium transfer)

70

60
* The deterioration mechanism does not change, and the deterioration rate has a certain
0 100 200 300 400 500
dependence on the load of the usage conditions (temperature, SOC, etc.)
Calendar period / day (b)
There is
Power retention
** The deterioration mechanism changes, and the deterioration rate is independent of the load
Fig. 7ÿ(a) Capacity and (b) power retentions of EH5 cell throughout calendar life test at 80%
of the usage conditions (temperature, SOC, etc.) and exhibits specific behavior.
SOC and at 65 ÿ.

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GS Yuasa Technical Report December 2014 Volume 11 Issue 2

explain about. EH5 incorporates special surface protection technology on the surface A comparison cell with the same specifications as EH5 was subjected to a transmission

of the positive electrode active material in order to suppress specific deterioration in electron microscope (TEM) to analyze the crystal structure of the surface of each

output performance. Fig. 9 shows that except for EH5 and surface protection technology, cathode active material before and after performing the storage test described in Section 3.3.2.

85 ÿ

row
/ tnatsesstna P
e
o
c-rl
iC
/ tnatsesystntaop
a
o
c-rl

35 ÿ
35 ÿ 70 ÿ

2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.4 2.7 2.8 2.9 3.0 3.1 3.2 3.3 3.4

Storage temperature / 1000 T-1 Storage temperature / 1000 T-1

(a) Capacity (b) Power

Fig. 8ÿDependence of rate constants of (a) capacity loss and (b) power loss rate constant on temperature of cal-endar life test range of
35 - 85 ÿ.

Initial After calendar test

EH5 cell

Structure change layer;

Film about 5 nm

Fm-3m
R-3m structure
Structure change layer;
(Hexagonal) R-3m
about 5 nm
-100 incidence

Film
Fm-3m structure
(Cubic)
-101 incidence

Relative cell

Film
Fm-3m structure Fm-3m
(Cubic)
-101 incidence
Structure change layer;
about 30 nm
Film
R-3m structure R-3m
(Hexagonal)
Structure change layer;
-100 incidence
about 5 nm

Fig. 9ÿTEM(Transmission Electron Microscopy) images for surface of positive active particles before and after calendar life test for 300
days under the condition of 80% SOC at 65 ÿ.

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GS Yuasa Technical Report December 2014 Volume 11 Issue 2

110 110
• EH5 cell • EH5 cell
ÿ Relative cell ÿ Relative cell
100 100

90 90

%
Pr
te
t%
ePr

eo
eo

/noritenw
/noritenw

80 80

70 70

60 60
0 50 100 150 200 250 300 350 400 0 50 100 150 200 250 300 350 400

Calendar period / day Calendar period / day

(a) Power retention at 25 ÿ (b) Power retention at -10 ÿ

Fig. 10ÿRetention of output power at (a) 25 ÿ and (b) -10 ÿ throughout calendar life test under the condition of 80% SOC at 65 ÿ.

: Transmission Electron Microscopy) image. surface Can be used within a range. At the same time, many of the evolving HEVs

Comparison cells without protection technology were tested after being left unused. It satisfies the required quality in a well-balanced manner and will last a lifetime.

The crystal structure of the active material surface has changed approximately six times compared to the initial state. Continue to contribute to reducing CO2 emissions and improving fuel efficiency of HEVs

However, in EH5, there is almost no change in the crystal structure. We can expect that. Currently, EH5 is installed in HEVs in Japan and overseas.

It turns out that there is no. Significant crystal structure changes in comparative cells The reliability of its performance and quality is being proven.

(mainly change from hexagonal structure to cubic structure) Blue Energy provides valuable information obtained from market performance.

Since the movement of lithium is inhibited, the resistance increases and the In order to meet the ever-evolving demands of HEVs by taking advantage of

This is accompanied by a decrease in output performance. We are steadily continuing product development.

Fig. 10 shows EH5 with the same specifications as EH5 except for surface protection technology.

shows the change in output performance during durability tests of comparative cells. literature
vinegar. For the EH5 and comparison cells, there is a clear difference in output performance at 25°C.

Although there is no significant difference, there is significant deterioration of the comparison cell at -10°C. 1. T. Iguchi, K. Okamoto, J. Kuratomi, Y. Harada, M.

Is recognized. There is a distinctive difference only in output performance at low temperatures. Tsutsumi, K. Kohno, S. Izuchi, and M. Oshitani, Pro-

The reason is that the proportion of the positive electrode active material in the internal resistance of the battery decreases as the temperature decreases. ceedings of the 45th Battery Symposium in Japan ,

This is because the contribution rate of the surface resistance component is high. Also, deterioration p. 520(2004).

The speed is also fast, and a long-term lifespan cannot be guaranteed. 2. T. Iguchi, T. Sasaki, K. Kohno, and M. Oshitani, “De-velopment of Lithium-ion

From these facts, EH5 is the surface of the positive electrode active material. Battery for Hybrid Elec-tric Vehicles (HEVs)”,

Protection technology suppresses specific deterioration while significantly improving output performance. 23rd International Electric

Improvement (reduction in internal resistance) has been achieved. Therefore, EH5 Vehicle Symposium (EVS23) , USA, 12.2-5 (2007).

will last a lifetime, withstanding use in high temperatures and in cold regions. 3. T. Iguchi, J. Nakamura, J. Kuratomi, T. Sasaki, Y. Ha-

It can support improved fuel efficiency and starting power, and has a wide temperature range. council, K. Kohno, Proceedings of the 52nd Battery

We can expect that it will continue to demonstrate excellent performance. Symposium in Japan , p. 304(2011).

4. K. Oguri and N. Maruno, SAE2011 World Congress

4 Summary Exhibition& , USA, Paper Number 2011-01-1372.

5. T. Iguchi, K. Okamoto, J. Kuratomi, K. Ohkawa, K.S.

The EH5 described in this paper has significantly improved output performance compared to the EH4. Kohno, and S. Izuchi, 1(1), GS Yuasa Technical Report ,

wide temperature range based on the degradation mechanism while improving 25(2004).

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