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![Page 1: Major Improvement of the TMV for Li/SOCl System - major improvement of... · Tadiran Confidential and Proprietary Major Improvement of the TMV for Li/SOCl2 System H.Yamin ,A. Ulus](https://reader030.fdocuments.in/reader030/viewer/2022013110/5ad543387f8b9a177c8cc0ce/html5/thumbnails/1.jpg)
Tadiran Confidential and Proprietary
Major Improvement
of the TMV
for
Li/SOCl2 System
H.Yamin ,A. Ulus and J. Heller
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Tadiran Confidential and Proprietary
Outline
• Introduction
- TMV & the voltage delay phenomena
- TMV Improvement –historical perspective
• Experimental
- The electrochemical cells
- Test equipment
• Results & Discussion
- Pulse and discharge tests
- EIS & SEM study
Summary & Conclusions
2
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Tadiran Confidential and Proprietary
Introduction
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Tadiran Confidential and Proprietary
TMV & Voltage Delay Phenomena
Volt
age
Time
OCV
TMV
0
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Tadiran Confidential and Proprietary 5
Transition Minimum Voltage (TMV)
• The major drawback of Li/SOCl2 system is the voltage delay phenomenon
• Formation of LiCl film on the Li surface increases cell impedance with storage/operation time
• The ionic conductivity of the LiCl film is relatively low and its thickness is very difficult to be controlled
• Our idea is to coat the Li by a proprietary, unique and stable film
The TMV drawback
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Tadiran Confidential and Proprietary
Improvement of voltage delay- historical perspective
Gabano claims dissolving Li2O or Li2S in electrolyte
Carl Schlaikjer GTE Labs : Li2B10Cl10
Chua & Merz 5% SO2 in electrolyte
A.N. Dey Duracell SO2 caused film to acquire more orderly appearance
J.W. Boyd addition of PVC in electrolyte coat the lithium surface
Fleischer & Thomas Ray O Vac coat the lithium foil by cyanoacrylate
Yamin & Eichinger patented polymer and Acid in solution
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Tadiran Confidential and Proprietary
The Two Layers Model
7
Li
SEI 10-1000Å
Secondary
Layer
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Tadiran Confidential and Proprietary
Experimental
The Electrochemical cell
• Standard size AA/2 , AA ,D
• Surface area : 5 Cm2 , 14 Cm2 ,45 Cm2
• Bobbin type construction
• Electrolyte
- Reference cells LiAlCl4 ,standard electrolyte
- Test cells : standard electrolyte + additive
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Tadiran Confidential and Proprietary
Experimental
• Pulse test – Fast response Arbin data collecting system
• Electrochemical Impedance Spectroscopy - Solartron Sl 1260 impedance analyzer - typical 10mHz to 1MHz
• SEM study
- Specimens were prepared at dry room
- -40ºC due point
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Tadiran Confidential and Proprietary
Voltage Transient after 427 Days
R&D Cell
Reference XOL Cell
D size cells @ 100mA Pulse @ RT
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Tadiran Confidential and Proprietary
Voltage Transient after 180 Days
40mA pulse XOL electrolyte AA size cell
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Tadiran Confidential and Proprietary
Treated Lithium AA size XOL
40mA pulse 154 days old
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Tadiran Confidential and Proprietary
The Role of the new film
The new film separates between lithium and
SOCl2:
It prevents the vigorous reaction of SOCl2 with lithium metal :
- More ordered film is formed
- More dense and more compact SEI
- Less structural defects are formed by the slow reaction
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2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
0 10 20 30 40 50 60 70 80 90 100 110 120 130
V (
@1
ms)
t (Days from connecting the load)
OCV 360kΩ 180kΩ
Voltage after 1 mSec
Pulse test with background currents
20mA pulse for AA/2 Cell
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Tadiran Confidential and Proprietary
Additives decrease capacity variations
TL 7903 AA size XOL electrolyte @ 330 Ω
15% more capacity with the TMV improved cell
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Tadiran Confidential and Proprietary
Additives decrease capacity variations
TL 7903 AA size XOL electrolyte @ 680Ω
15% more capacity with the TMV improved cell
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Tadiran Confidential and Proprietary
Additives to Xtra Version cells
TL 8903 discharged @ 330 ohm Xtra
10 % more capacity than iXtra cell
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Tadiran Confidential and Proprietary
Additives to Xtra version AA cells
TL 8903 discharged @ 680 ohm
15% more capacity than iXtra cell
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Tadiran Confidential and Proprietary
Cell Types in Production
Tadiran Rapid Response Series TRR*
TRR 79XX – TMV improved XOL Type cells
AA size TRR 7903
D size TRR 7930
TRR 89XX – TMV improved Xtra type cells
AA size TRR 8903
D size TRR 8930
* Series Name Creator - Lou Adams
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Tadiran Confidential and Proprietary
Electrochemical Impedance Spectroscopy
Reference cells Test cells
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Tadiran Confidential and Proprietary
SEM Photograph 1M Old Cell
Reference cell
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Tadiran Confidential and Proprietary
SEM Photograph 1M Old Cell
Test Cells
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Tadiran Confidential and Proprietary
SEM Photograph 1 Y old Cell
Reference cell
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Tadiran Confidential and Proprietary
SEM photograph 1 Y old cell
Test Cell
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Tadiran Confidential and Proprietary
Summary & Conclusions
• Lithium anode was coated in situ by lithium ion conducting solid electrolyte interphase.
• The film morphology and cell impedance exhibit a small variation with storage time.
• This leads to a significant improvement of the voltage delay behavior of the Li/SOCl2 cells.
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Tadiran Confidential and Proprietary
Thank You