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GENERAL CAPACITOR

HIGH PERFORMANCE LI-ION CAPACITORS

2017 | GENERAL CAPACITOR LLC

BEN CAO AND JIN YAN

A presentation at 2017 International Battery Seminar, March 23, 2017

FLORIDA STATE UNIVERSITYJIM P. ZHENG

3/23/2017


OUTLINE

• Limitation of electric double-layer capacitors (supercapacitors)

• Introduction of Li-ion capacitors (LICs)

• Comparison of various LIC pre-lithiation methods

• Comparison of various LIC negative electrodes

• GC high performance LIC laminate cells

• Special R&D projects and LIC applications

• Acknowledgement


ENERGY STORAGE DEVICES AND THEIR CHARACTERISTICS

Energy Battery CapacitorCapacity (Wh/kg) Large Small

Time-scales (kW/kg) Slow Very Fast

No. of cycles (Cycles) Thousand Hundred Thousand

10 hr 1 hr 6 min

36 sec

3.6 sec

0.36 sec

36 ms

LIC

Supercapacitors

Batteries


THE ENERGY DENSITY OF EC CAPACITORS IS LIMITED BY AVAIABLE ION IN ELECTROLYTE

• Electrolyte is an active material in EC capacitors• Ion concentration

• 1 M Et4NBF4 in AN or 1 M LiPF6 in PC:EC;DEC : 6x1020 ion/cm3

“Capacity”=22.3 mAh/g or 26.8 mAh/cm3

• LiC6: 1.84x1022 Li/cm3, 372 mAh/g• LiCoO2: 3x1022 Li/cm3, 140 mAh/g• 120 F/g, 3 V activate carbon, ~100 mAh/g

• Conventional Supercapacitors• Electrolyte depletion-low

energy density• Low voltage• 6-7 Wh/kg


THE ENERGY OF EC CAPACITORS IS LIMITED BY SALT CONCENTRATION IN ELECTROLYTE

Electrolyte limitElectrodelimit

lE

MpE

M

mm

Vcm

M

CVE

+==

222

121 22

Specific Energy:Fc

VcVcE

o

iMpMp

αρ

+=

41

181 2

• cp=100F/g, specific capacitance• VM: 2.5V• co: 1M/L, ion concentration• ρi=1.2g/cm3, electrolyte mass

density• F=69,484F/V, Faraday constant

J.P. Zheng, J. Huang, and T.R. Jow, “The Limitation of Energy Density for Electrochemical Capacitors”, J. Electrochem. Soc., 144, 2026 (1997).J.P. Zheng and T.R. Jow, “The Effect of Salt Concentration in Electrolytes on The Maximum Energy Storage For Double Layer Capacitors”, J. Electrochem. Soc., 144, 2417 (1997). (Experimental approval)


STRUCTURE OF LI-ION CAPACITORS (LICS)

Cu Foil Al Foil

Activated Carbon (Cathode)

Hard Carbon (Anode)

SLMP Separator Li Metal Reference

Electrode


OPERATIONAL PRINCIPLES OF DIFFERENT SYSTEMS

• Conventional Supercapacitors• Ion source: salt in electrolyte• Low voltage• 6-7 Wh/kg

• Li-ion Batteries• Ion source: lithiated cathode• Energy density：100-150 Wh/kg• Power density：<0.5 kW/kg• Cycle life：1000-4000

• Li-ion Capacitors• Ion source: lithiated anode• Energy density: 15-30 Wh/kg• Power density: >5 kW/kg• Cycle life: >100,000


TWO DIFFERENT LI-ION CAPACITOR STRUCTURES

• Two-electrode Li-ion capacitors– Load lithium sources on the

surface of anode: SLMP or thin Li foils

– Use ordinary metal foil as current collectors

• Three-electrode Li-ion capacitors– Use sacrificial Li metal foil electrode– Use expanded metal current

collectors or metal foil with holes– Pre-discharge process is needed

GC Technology

Suberu/Fuji Technology


COMPARISON OF VARIOUS LIC PRE-LITHIATION METHODS: SLMP

Gassing After Formation Advantages：

Accurately control the Li loading weight No damage to the electrodes Suitable to mass production

Disadvantages： High Li reaction speed Gassing after formation Safety issues Low Li purity & utilization


COMPARISON OF VARIOUS LIC PRE-LITHIATION METHODS: LI PIECES

Li Pieces Damaged Electrode

Advantages： Accurately control the Li loading weight Less gassing after formation

Disadvantages： Damages to electrodes Not suitable to mass production


COMPARISON OF VARIOUS LIC PRE-LITHIATION METHODS: LI STRIPS

Advantages： Accurately control Li loading weight Less gassing after formation Suitable to mass production

Disadvantages： Less damages to electrodes than Li pieces


LI STRIPS BASED LIC PRE-LITHIATION METHOD

After 18 hours’ soaking, all Li strips on the surface of NE have disappeared and NE has been pre-lithiated. GC Patented Technology

W.J. Cao, J.F. Luo, J. Yan, X.J. Chen, W. Brandt, M. Warfield, D. Lewis, S.R. Yturriaga, D.G. Moye and J.P. Zheng, “High performance Li-Ion capacitor laminate cells based on hard carbon/lithium stripes negative electrodes”, J. Electrochem. Soc., 164 (2), A93 (2017).W.J. Cao and H. Chen, “HIGH PERFORMANCE LI-ION CAPACITOR LAMINATE CELLS”, US Pat. Pub. No. US 2016/0126023 A1.


COMPARISON OF VARIOUS LIC NEGATIVE ELECTRODES

W.J. Cao, J.S. Zheng, D. Adams, T. Doung and J.P. Zheng, “Comparative study of the power and cycling performance for advanced lithium-ion capacitors with various carbon anodes”, J. Electrochem. Soc., 161 (14), A2087 (2014).

Hard Carbon Soft Carbon Graphite Carbon




0 20 40 60 80 100 120 140 1600.0

0.5

1.0

1.5

2.0

2.5

0.4 mA/cm2 0.8 mA/cm2

1.6 mA/cm2

3.2 mA/cm2

4.8 mA/cm2

6.4 mA/cm2

8 mA/cm2

Pote

ntia

l vs.

Li/L

i+ (V)

Specific Capacity (mAh/g)

Hard Carbon

0 50 100 150 200 2500.0

0.5

1.0

1.5

2.0

2.5 0.4 mA/cm2 0.8 mA/cm2

1.6 mA/cm2

3.2 mA/cm2

4.8 mA/cm2

6.4 mA/cm2

8 mA/cm2

Pote

ntia

l vs.

Li/L

i+ (V)


Soft Carbon

0 50 100 150 200 250 300 3500.0

0.5

1.0

1.5

2.0

2.5 0.4 mA/cm2 0.8 mA/cm2

1.6 mA/cm2

3.2 mA/cm2

4.8 mA/cm2

6.4 mA/cm2

8 mA/cm2

Pote

ntia

l vs.

Li/L

i+ (V)


Graphite

0 50 100 150 200 250 300 350 4000.0

0.5

1.0

1.5

2.0

2.5

3.0

HC 1st Li intercalation SC 1st Li intercalation Graphite 1st Li intercalation

Pote

ntia

l vs.

Li/L

i+ (V)

Discharge Capacity (mAh/g)

Current Density of 0.4 mA/cm2


GC HIGH PERFORMANCE LIC LAMINATE CELLS

GC Part Number GCLIC200F GCLIC3000F

Operating Temperature (oC) -40 to 65 -40 to 65

Rated Voltage (V) 2.2 to 3.8 2.2 to 3.8

Capacitance (F) 200 3000

ESRDC (mΩ) 30 2

Specific Energy (Wh/kg) 14 17

Energy Density (Wh/L) 28 33

Max. Specific Power (kW/kg) 6 7

Max. Power Density (kW/L) 12 13

Self Discharge (3 Months) <5% <5%

Dimension (L×W×T) (cm) 5×5×0.5 23.7×12.6×0.45

Weight (g) 20 250


CYCLE LIFE AND DC LIFE

Cycle life greater than100,000 cycles under60C rate charge-discharge

Passed 2000+ hours3.8 V at 65 °C DC lifetesting


TEMPERATURE DEPENDENCE

0

20

40

60

80

100

120

-40 -20 0 20 40 60 80

Cap

acita

nce,

%

Temperature (°C)

Value at 30 °C is set at 100%

2.2

2.4

2.6

2.8

3

3.2

3.4

3.6

3.8

0 20 40 60 80 100 120

Cel

l Vol

tage

(V)

Discharge Capacity, %

-40°C-30°C-20°C-10°C0°C30°C50°C60°C70°C


SPECIAL R&D PROJECTS

• UEC Electronics 2015 Develop 180 F spec series for use in radio power adapter for infantry communications

• Space Florida 2015 Increase energy density and temperature range for microsatellites

• Army Research Lab 2015 GC partnership with Florida St. University for fundamental research

• Army CERDEC 2015 Develop an LIC module to replace 6T battery for Army tanks and vehicles

• Army CERDEC 2017 Li-ion battery-ultracap hybrid energy storage trailer for tactical micro grids

• Space Florida 2017 Continued research relating to energy density and cycle life for microsatellites


LIC APPLICATIONS

ELECTRONICS TRANSPORTATION Utilities Battery-capacitor hybrid ESS

enable stability & longer lifetime

Well-suited for back-up and uninterruptible power systems

Provide peak power for UAVs and AGVs

Powering electric/hybrid vehicle start-stop idling systems

Regenerative braking systems and auxiliary power during acceleration

Engine-starting in extreme temperatures

Lead-acid battery replacement

Voltage compensation and transient power smoothing for electrical grids

Back-up systems for power generators

Power source for blades on wind turbines

Improve energy collection for solar


ACKNOWLEDGEMENTSFinancial Support:

• Army: ARL&CERDEC

• Space Florida

• Florida State University GAP Program

• UEC Electronics

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