From energy generation to protection from harm - evolving fiber materials and their applications inside and outside lithium ion batteries

1. www.morganadvancedmaterials.com
From energy generation to protection from harm -
evolving fiber materials and their applications
inside and outside lithium ion batteries
The Battery Show Conference 2017
Richard Clark - Senior Technical Specialist
richard.clark@morganplc.com

2. Contents
• Overview of Morgan Advanced Materials
• Carbon fiber as active anode and conductivity enhancer
• Ceramic oxide fiber for safety outside the cell
• Textile fiber separators replacing polymer
• Textile fiber-based current collectors
• Nanofibers for solid-state lithium-ion batteries
• Conclusions
2The Battery Show Conference 2017
9/12/2017

3. Morgan Advanced Materials
Founded in England in 1856
Ticker on LSE: MGAM
2016 revenue: £989.2 million
6 Global Business Units
3
Global Business Units
Thermal Ceramics 
Molten Metal Systems
Electrical Carbon 
Seals and Bearings
Technical Ceramics
Composites and Defence Systems 
Making or utilizing fiber materials 
9/12/2017
The Battery Show Conference 2017

4. Contents
• Overview of Morgan Advanced Materials
• Carbon fiber as active anode and conductivity enhancer
• Ceramic oxide fiber for safety outside the cell
• Textile fiber separators replacing polymer
• Textile fiber-based current collectors
• Nanofibers for solid-state lithium-ion batteries
• Conclusions
4
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The Battery Show Conference 2017

5. Early use of carbon fiber as an LIB anode material
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Length <1 mm, preferred aspect ratio 1 to 10,
typical diameter d50 15 to 20 microns,
reproducible diameter variation
Carbon fiber was studied extensively as a possible LIB
anode material in the early 1990’s. Mesophase pitch was
considered the most promising precursor (for example, J.
Electrochem. Soc. 140 (2) 315-320 (1993))
Y. Nishimura of Petoka, Ltd. developed a mesophase pitch-
based carbon fiber with a novel structure and texture,
together with a method of manufacturing (EP0742295,
US5,951,959, others) which led to its commercialization
Figures 1 and 4 from US5,951,959
Shell 2 to 5%
of diameter
Conventional fiber:
graphite layers are radial
and core and outer shell
orientation is similar
Nishimura invention:
graphite layers are
circumferential
The Battery Show Conference 2017

6. Carbon fibers as anodes and as conductive additives
• By the early 2000’s, two types of fiber were used within
the Li-ion cell:
• Active anode materials
• Milled mesophase pitch-based carbon fibers (MPCF)
• High energy density
• High charge / discharge capacity and efficiency
• Improved output current performance
• Better than graphite for charging / discharging at high current density
• Can be doped e.g. with boron
• Market leader in tonnage in CY2000 – but by CY2005 essentially zero
• Conductive additives in anode and cathode
• Vapor grown carbon fibers (VGCF)
• CVD process - fixed-catalyst (batch) or floating-catalyst (continuous)
• Ultimately application favored conductive carbon black
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M. Endo et al., “Recent development of carbon materials for Li ion batteries” Carbon 38 (2000) 183 –197
R. Clark, “Technology Trend in the Improved Performance of Anode Materials”, KEBC 2012
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7. Changes in active anode material sales (tons)
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NG Core growth
based on lower price
• CY00 total tonnage 3,500
• CY16 total tonnage 103,500
Data from C. Pillot, avicenne ENERGY; IIT; Morgan Advanced Materials internal analysis
Some work was done to extend the use of graphitized carbon fiber (example dimensions: length 32 µm, diameter 8 µm) in a mixture (60 to 80
wt.%) with spherical natural graphite to obtain high electrode density and conductivity (such as US7,144,659, granted December 5, 2006)
Recent AG growth
related to xEV
Recent re-emergence of fiber – “submicron-scale and lower-micron graphitic fibrils as an active anode material for a lithium ion battery”
(US8,501,348, granted August 6, 2013): fibrils of diameters 100 nm to 1 µm or 1 µm to 6 µm split and separated from carbon or graphite fibers
The Battery Show Conference 2017

8. Contents
• Overview of Morgan Advanced Materials
• Carbon fiber as active anode and conductivity enhancer
• Ceramic oxide fiber for safety outside the cell
• Textile fiber separators replacing polymer
• Textile fiber-based current collectors
• Nanofibers for solid-state lithium-ion batteries
• Conclusions
8
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The Battery Show Conference 2017

9. Types of high temperature insulation fibers
9
High
Temperature
Insulation
Amorphous
Alkaline Earth
Silicate
(AES)
Melt-spun
CaO, MgO,
SiO2, ZrO2
Superwool®
Plus,
Superwool HT
Aluminosilicate
(ASW / RCF)
Melt-spun /
blown
Al2O3, SiO2,
(ZrO2)
Kaowool®
Crystalline
Polycrystalline
(PCW)
Sol-gel
Al2O3
Denka®
AES: classification temperature 1300°C
ASW/RCF: c.t. up to 1426°C
PCW: c.t. up to 1600°C
Key advantages of AES over RCF:
• Low bio-persistence
• Low shrinkage up to
classification temperature
• Low thermal conductivityDiameter
3 microns
Diameter
2.5 microns
Diameter
6 microns
Typical non-chopped length 40 mm.
Process
Composition
Example
Type
Dimensions
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The Battery Show Conference 2017

10. Fiber products are widely used in automotive applications
10
Airbag Safety
Papers and microporous
solutions for filtration
Engineered Fibers
Ceramic brake pads
Heat Shields
Exhaust / DPF / SCR
Engine compartment
Turbocharger
Under-body
Emission Control
Fibers used in DPF /
catalytic converter
support mat
Electric Vehicles
Thermal runaway
passive fire protection
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The Battery Show Conference 2017

11. Fiber-based products outside LIB cells / modules / packs
Automotive and
Energy Storage
Occupant &
Equipment Protection
Superwool® Papers
Prevention of
Thermal Runaway
Endothermic
Boards and Paper
Fire Protection
of Battery Packs
Laminated
Superwool Papers
Gasketing and
Electrical Isolation
Superwool Papers
Application Products
Another key market is LIB transportation
Superwool paper
between modules
EST Superwool block
cell enclosure
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11The Battery Show Conference 2017
Image of EST Superwool block cell enclosure used with permission of Cadenza Innovation

12. Contents
• Overview of Morgan Advanced Materials
• Carbon fiber as active anode and conductivity enhancer
• Ceramic oxide fiber for safety outside the cell
• Textile fiber separators replacing polymer
• Textile fiber-based current collectors
• Nanofibers for solid-state lithium-ion batteries
• Conclusions
12
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The Battery Show Conference 2017

13. Fiber-based separators for lithium-ion batteries
13
Market information supplied by and used with permission of Christophe Pillot, Avicenne, “The Rechargeable Battery Market and Main Trends 2015 to 2025”, Lithium Battery International Summit, Shenzhen, China, April 9 to 12, 2016;
Image and information provided by and used with permission of Dr. Brian Morin, CEO, DreamWeaver
• Textile-grade fibers fibrillated into a pulp
• Nanofiber (100 to 200 nm) on microfiber
(~5 microns), both with high aspect ratios
• Nanofibers for barrier
• Microfibers for structure and strength
• Has potential to be thinnest high
temperature separator in the world
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The Battery Show Conference 2017
Polyolefin Polyolefin+
ceramic coating
Cellulose
Non-woven

14. 1st, 2nd and 3rd generation separators
• 1st generation shrink ~ 130°C
• 2nd generation shrink ~175°C
• 3rd generation stable >300°C
• No unstable polymer component
• High temperature materials incorporated in
homogenous composite
• Often stable to 500°C
• Manufacturers of 3rd generation separators
include:
• Dreamweaver
• Electrovaya
• Freudenberg
• Mitsubishi Paper
• Optodot
PP Tri Layer
First Generation
Second Generation
Third Generation
Image and information provided by and used with permission of Dr. Brian Morin, CEO, DreamWeaver
1G 3G
Separators saturated with electrolyte and ignited
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The Battery Show Conference 2017 14

15. Comparison of performance during nail penetration test
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Unlike polyolefin separators, DWI Silver and Gold
maintained their voltage and functionality during the test,
and have lower maximum temperature than polyolefins
The aluminum has oxidized and retreated
from the nail under heat, breaking the circuit
Images and information provided by and used with permission of Dr. Brian Morin, CEO, DreamWeaver
Nail
The Battery Show Conference 2017

16. Contents
• Overview of Morgan Advanced Materials
• Carbon fiber as active anode and conductivity enhancer
• Ceramic oxide fiber for safety outside the cell
• Textile fiber separators replacing polymer
• Textile fiber-based current collectors
• Nanofibers for solid-state lithium-ion batteries
• Conclusions
16
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The Battery Show Conference 2017

17. 17
Metallized paper for LIB current collector
• Advantages:
• Significantly lighter than standard foil
• Porous, enabling better charge-discharge
balancing for longer life
• Better electrolyte wetting
• Better electrode material adhesion
• Safety: no sharp edges or burrs
• Safety: thermal management if short
occurs
• Nano-Nouvelle is in scale-up mode,
potentially launching in 2018
Images and information provided by and used with permission of Nano-Nouvelle
9/12/2017
The Battery Show Conference 2017

18. Contents
• Overview of Morgan Advanced Materials
• Carbon fiber as active anode and conductivity enhancer
• Ceramic oxide fiber for safety outside the cell
• Textile fiber separators replacing polymer
• Textile fiber-based current collectors
• Nanofibers for solid-state lithium-ion batteries
• Conclusions
18
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The Battery Show Conference 2017

19. Nanofibers for solid-state conductivity enhancement
• Replacing liquid electrolytes with solid-state electrolytes in LIB has benefits of improved safety
and design flexibility plus facilitating (by suppressing dendritic growth) the use of lithium metal
• Major issues include low ionic conductivity at room temperature (minimum requirement is
~10-3 Scm-1) and high interfacial resistances where in contact with electrodes
19
Wei Liu et al, Nano Lett. 2015, 15, 2740-2745; Wei Liu et at, ACS Nano 2016, 10, 11407-11413; Wei Liu et al. Nature Energy 2, 2017, 17035
Solid state electrolytes
Inorganic materials
(solid ceramics)
Garnet oxides, NaSICON-type
phosphates, perovskite-type
LLTO, Thio-LiSICON LGPS
Expensive / complicated to
process; stability issues (high V
cathodes, Li metal, moisture/O2)
Organic polymers
(SPEs, combinations of
polymers and lithium salts)
Polymer examples are
poly(ethylene oxide) (PEO) and
polyacrylonitrile (PAN)
Low ionic conductivity, poor
long-term stability, including
electrochemical, mechanical
and thermal
Categories Examples Issues
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Organic polymers require addition of ceramic materials to increase ionic conductivity

20. Nanofibers for solid-state conductivity enhancement
• Dispersing ceramic nanoparticles (such as SiO2, TiO2,
Al2O3, ZrO2, Sm2O3,LiAlO2) into the polymer matrix
increases ionic conductivity (caused by reduced
crystallinity of host) and improves electrochemical
stability and mechanical properties
• Conductivity can be improved further by incorporating
random nanowires into the polymer and still further by
aligning the nanowires
• Example (Wei Liu et al, 2017):
• PAN/LiClO4 (2:1) as polymer using DMF solvent
• LLTO particles from sol-gel and nanowires from
electrospinning, incorporated at 3 wt.%
• Ionic conductivities (Scm-1 at 30°C):
• Filler-free polymer electrolyte: 3.62 x 10-7
• + Nanoparticles: 1.02 x 10-6
• + Random nanowires (average 138 nm): 5.40 x 10-6
• + Well-aligned nanowires (average 138 nm): 6.05 x 10-5
• Surface conductivity of nanowires: 1.26 x 10-2 Scm-1!!
20
Wei Liu et al, Nano Lett. 2015, 15, 2740-2745; Wei Liu et at, ACS Nano 2016, 10, 11407-11413; Wei Liu et al. Nature Energy 2, 2017, 17035
Li ion conduction Li ion conduction
Nanoparticles
Random
nanowires
Aligned
nanowires
• Higher percentage incorporation will lead to higher (bulk)
ionic conductivities
• Example (Wei Liu et al, 2015)
• PAN/LiClO4 (2:1) as polymer using DMF solvent
• LLTO nanowires from electrospinning (average
diameter 138 nm), incorporated at 5 to 20 wt.%:
• Maximum conductivity at 15 wt. %: 2.4 x 10-4 Scm-1
• Fast ion transport on the surfaces of ceramic
nanowires enhances conduction
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The Battery Show Conference 2017
Li ion conduction

21. Contents
• Overview of Morgan Advanced Materials
• Carbon fiber as active anode and conductivity enhancer
• Ceramic oxide fiber for safety outside the cell
• Textile fiber separators replacing polymer
• Textile fiber-based current collectors
• Nanofibers for solid-state lithium-ion batteries
• Conclusions
21
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The Battery Show Conference 2017

22. Conclusions
• Fiber materials have been, and continue to be,
key components in and around batteries, from
the early generations of liquid electrolyte
lithium-ion batteries to the current generation of
solid-state alternatives
• The latest thermal management materials,
separators, current collectors and conductive
additives are all based on fiber, offering
performance enhancement as well as significant
safety and, in some cases, cost benefits
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Battery components utilizing fiber
Active anode material 
Conductivity enhancer 
Thermal management material 
Separator 
Current collector 
The Battery Show Conference 2017