real world graphene: industrial applications for the 21st

www.morganadvancedmaterials.com

Richard Clark

Real World Graphene: Industrial Applications for the 21st Century

Graphite Supply Chain 2017

Contents

• Overview of Morgan Advanced Materials

• Graphene – production, challenges and market size

• Applications and state of development

• Summary and conclusions

2Graphite Supply Chain 2017

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Morgan Advanced Materials

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Founded in 1856 by the Morgan brothers to manufacture the

world’s best (clay-graphite) crucibles

Public Limited Company since 1890

London Stock Exchange since 1946

Approximately 9,000 employeesManufacturing in over 30 countriesSelling into more than 100 countries2016 revenue GBP989.2 million

2017: Leaders in Advanced Materials


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Morgan – University of Manchester partnership

Morgan has been an industrial sponsor of the graphene work at Manchester since 2008 • Exploring new horizons in materials science• Understanding the ultimate properties in carbon science• In 2015 signed a joint development agreement with Manchester

• Focus on scaling up a patented process• Morgan embedded 2 R+D engineers to work at the National Graphene Institute

Morgan brings• Processing and manufacturing expertise• Raw material knowledge and selection• Scale-up experience and market access

Manchester brings• IP and experience in graphene exfoliation• An internationally renowned research base• Understanding of graphene IP landscape

Morgan-University of Manchester lab in NGI


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Contents






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Graphene…top down versus bottom up

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Examples of top down processes

Micromechanical cleavage

Anodic bonding

Laser ablation/ Photoexfoliation

Electrochemical exfoliation

Liquid phase exfoliation of graphite

Liquid phase exfoliation of GO

Examples of bottom up processesCVD / PECVD

Chemical conversion of CO2

Metal-carbon solution / precipitation

Chemical synthesis

Unzipping CNT

Epitaxial growth on SiC

Solvo-Thermal methods

Molecular Beam Epitaxy

Cost versus quality versus

scalability versus application

Graphic provided by Professor I. Kinloch, University of Manchester

Top down Bottom up

Electrochemical exfoliation is (relatively) low cost and produces high quality FLG, is industrially scalable and has applicability in numerous bulk applications


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Mechanical exfoliation

FORMAT MAJOR RAW MATERIAL

CVD(Chemical

VaporDeposition)

GO(GrapheneOxide) or

GO derived

GNP(Graphene Nano

Platelets)

KEY PROPERTIES

CH4

Graphite

Graphite

High electron mobility

VersatilityFunctionalization

Low cost

MAIN APPLICATIONS

OptoelectronicsSensors/Biosensors

MembranesFlexible TCO

Advanced PolymersComposites

CoatingsBatteries

SupercapacitorsCompounds

Additives

Bottom up

Top down

Production methods – tied to applications…

Adapted from images provided by and used with permission of Graphenea

…currently 90% of graphene manufacturing is top down (defining graphene as <10 layers)

SEM of GO


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Why the destination makes it worth the journey

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Adapted from slide provided by Professor I. Kinloch, U. Manchester

MatricesRubber is easiest, then thermoplastics, then thermosetsSome work on ceramicsVery little on carbon


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• Morphological• Thinnest imaginable material – one atom• Highest surface area – 2630 m2/g

• Transparent to light (97.7 %)

• Mechanical• Stiffness = 1 TPa• Strength = 130 GPa

• Electrical and thermal• Record thermal conductivity (6000 W/m/K)• Highest current density at room temp (million times of that in copper)• Highest intrinsic mobility (100 times more than Si)• Lightest charge carrier (Dirac fermions)• Longest mean free path at room temp (microns)

• Chemical• Relatively easily functionalised• Processable

• Barrier• Impervious even to He but potentially controlled porosity.

Adapted from slides provided by Professor I. Kinloch, U. Manchester

Graphene properties and one major challenge

The fall-off in properties once graphene is incorporated into composites is dramatic

Property Unit Pristine Composite

Young's Modulus GPA 1000 ~10

Electrical conductivity S/m 108 10

Thermal conductivity W/m/K 6000 <10

References: a) F. He et al. Adv. Mat. 21 (6), 710-715 (2009);b) P. Y. Huang et al, Nature 469, 389-392 (2011);c) A. Bagri et al., Nano Lett., 11 (9), 3917–3921 (2011)


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State of the Union

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Since 2004, graphene research has heavily focused upon

• Production methods (scalability, reproducibility, product quality)

• Metrology (analytical techniques, nomenclature, standards and specifications)

• Measurements of fundamental properties

• Filing copious amounts of graphene IP

Zhuan Ti reports in an article in China Daily on March 2, 2017: “Graphene patents lay base for industry boom” – Jiangnan Graphene Research Institute in Jiangsu province showed that the number of patent applications in the sector surpassed 50,000 worldwide by September 2016. China contributed nearly half of them, more than any other country.

http://www.chinadaily.com.cn/m/qingdao/2017-03/02/content_28406892.htm


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State of “graphene” patenting (as of October 15, 2017)

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Published patents by jurisdiction

Date is filing date for applications and publication date for granted patents, where the word “graphene” appears in the title, abstract and/or claims

33,756 unique applications (60,967 total), of which 11,996 granted to date - 80% of these originate in

China, S. Korea and U.S.A.

10,000

8,000

6,000

Application

Granted

4,000

2,000

“Science” Nobel prize

2,000

1,000“Science” Nobel prize

Data from 103 countries, derived using patsnap “insights” tool

Graphene patent status

6,000

4,000

5,000

3,000


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Licensing deals more common (as of October 15, 2017)

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Data from 103 countries, derived using patsnap “insights” tool

Number of licensing deals –US and China data only

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6

4

2

The Word Cloud displays the most frequent keywords within the most recent 10,000 INPADOC Families


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Graphene activity of key global companies

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Companies active in graphene as mentioned by a weekly “graphene” Google alert from January 2013 to May 2017. Total number of companies = 191.

Images provided by and used with permission of Mark Rahn, MTI Ventures, a graphene investment, advisory and consulting company

Country of operationMain graphene related activity


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Value chain for graphene

• Typical value chain in an established market: • Nearer to end-user means:

• Greater ability to differentiate• Higher margin

• Temptation to move downstream to increase profitability• Assumes no issues with skill requirements and IP…and money• This continues to be a focus of graphite mining companies

• For graphene, the strongest positions in the value chain will vary based on product / application, but intermediate processors and IP owners seem to be in the best position at this time• Products may require a unique supply chain back to production method or

even raw material• This is a significant shift from a traditional value chain structure


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What were we predicting about markets and market size?

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Consistently projecting c.50% CAGR in 5 year period starting report + 5 years Capacitors, structural materials and displays are in top 4 named report +10 years

Data extracted from BCC research reports AVM075A, AVM075B, AVM075C, AVM075D

2010 projected first major markets for graphene: electronics, solar-cells, displays

(“How a bit of sticky tape and a pencil could save the world”, Mail on Sunday, September 19, 2010, published shortly after the UCLA announcement in “Nature” of 300GHz graphene FET design)


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Current market size for “graphene”

• “Graphene” market currently smaller than (growing) CNT market• IDTechEx estimate is current market at US$37million. Most companies have revenue well below $1

million• Rapid growth is projected – BCC projects US$310 million by 2020; IDTechEx projects >US$300 million

by 2027, although there may be some market definition discrepancies• Future Markets reports there are over 200 companies either producing graphene or developing

applications for graphene• User markets are huge, even allowing for the fact that graphene may be a small percentage addition –

conductive inks and pastes (including 3D printing); polymers and composites; thin film solar; thin, flexible displays; thermal management for electronics; touch screens; lithium ion battery anodes (as active material or conductive additive)…

• Timing for new product adoption even without HSEA issues can be very lengthy:• Automotive typical 7 to 10 years, including LIB • Aerospace typical 10 years or more

• R&D commitment estimated (University of Manchester) at >$2.4 billion

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IDTechEx webinar 4/19 “Graphene and Carbon Nanotubes: Progress Update”; BCC research report AVM075D; Future Markets: “The World Market for Graphene to 2025”, May 2015; “Graphene booms in factories, but lacks a killer app” Nature 522, 268-269, June 2015


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Contents






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Proof of ConceptEarly Semi-

Commercial Prototype Semi-Commercial Trials Early Commercial Sales Full Market Launch Market Penetration Maturity

Thermal

Anti-fouling coatings

Thermal plastics

Barrier

Impermeable plastics

Thin film barrier

Water purification membrane

Water purification porous filter

Mechanical

Fishing rod

Bicycle tire

Tennis racquet

Lubricants

Reinforced bike frames

Vehicle tires

Ski

Helmets / shoes

Frames for eyewear

Application timeline - graphene

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Source: adapted from K. Ghaffarzadeh, IDTechEx webinar April 19, 2017, original used with permission


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R&D materials

Key

GCMCs / Concrete

Graphene latex

Covetics

Opaque black paint

LiS batteries

Si anode LIB

Anti-corrosion coatings

TIM

Durable paints

Multifunctional

TEM support films

DNA sequencing

Corrosion-resistant composites

Solar cells

Optoelectronics

LED Lighting

Electrical / electronic / optical

Conductive 3DP filament

Heater

Biosensors

ECA

Transistors / logic

RFID Tags

EMI shielding plastics

Smart Packaging InterconnectsPSCA

Lead acid batteries

TCF

Glucose test strips

Chemical sensors

Memory

Photosensor

LIB componentsESD filmGraphene cable

Conductive plastics (automotive) Supercapacitors

Textile interconnect / heater

Quantum dots

Colored conductive plastics

Geotextiles

LIB conductive additives

Thin film barrier

Water purification membrane

R&D materials

TEM support films

DNA sequencing

TCF

Glucose test strips

Chemical sensors

Memory

Photosensor

CVD preferred

Vast number of applications at prototype stage –

progression to commercialization is dominated by those

utilizing the mechanical and/or electrical

characteristics of graphene

• RFID’s (11/11) (from Vorbeck)• Tennis racquets (01/13) and skis (12/14) (from Head)• Flexible battery straps (from Vorbeck) (06/14)• Oil drilling fluid (07/14) (from Graphene Nanochem) • High-performance bicycle tire rims (10/14) and tires (09/15) (from Vittoria)• Graphene supercapacitor charger (10/15) (from Zap&Go)• Cycling helmets (12/14) and Cycling shoes (12/14) (from Catlike)• Graphene-enhanced sportswear (01/16) (from Directa Plus and Colmar)• RFID tags (03/16) (from Graphene Security)• Graphene light bulbs (03/16) (from Graphene Lighting)• Filaments for 3D printing (from Directa Plus and Filoalfa) (09/16) and Graphene 3D Lab (10/16))• Fishing rods (10/16) (from Century Fishing)• Motorcycle helmets (11/16) (from Momodesign)• Graphene Oxide sensors (11/16) (from Biolin Scientific/ICN2) • Graphene-based sensors (12/16) (from Nanomedical Diagnostics)• Flexible screen smartphone (12/16) (from Chongqing Moxi)

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Graphene products launched in the market…pre-2017

https://www.graphene-info.com/ and company websites


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https://vorbeck.com/pages/products-rfid

http://www.head.com/us/sports/tennis/technology/graphene-xt/

http://www.head.com/us/sports/ski/technology/graphene/

https://vorbeck.com/pages/zpr_20140512_batterystraps

http://www.graphenenanochem.com/business-segments/advanced-chemicals/oilfield-chemicals

https://www.vittoria.com/news/vittorias-2016-graphene-tire-range/

https://www.vittoria.com/news/vittorias-2016-graphene-tire-range/

https://www.zapgo.com/markets/mobile/

https://www.catlike.es/pl/en/innovation/helmets-technologies/graphene/

http://www.catlike.es/blog/en/zapatillas-ciclismo/

http://directa-plus.com/EventsItem.asp?NewsID=2

http://graphenesecurity.co/

http://graphenelighting.co/

http://www.directa-plus.com/3DPrinting.asp

http://www.graphene3dlab.com/s/technology.asp#materials

http://www.century.uk/

http://www.momodesign.com/en/moto-helmets/

http://icn2.cat/en/news/3910-a-graphene-oxide-sensor-with-icn2-technology-is-commercialised-by-biolin-scientific

https://www.nanomedicaldiagnostics.com/

http://www.techtimes.com/articles/161111/20160526/china-startup-moxi-to-launch-worlds-first-bendable-smartphone-this-year.htm

https://www.graphene-info.com/

• Titanium-graphene watches (01/17) (from Richard Mille/McLaren) (01/17)• In-ear monitor earphones (02/17) (from FiiO Electronics) (02/17)• Eyewear (03/17) (from Luxottica/Ray-Ban)• Engine start supercapacitors (03/17) (from Skeleton Technologies)• LED bulbs with graphene-enhanced filaments (04/17) (from JTX/Graphene Lighting)• Graphene-coated stirrups (08/17) (from Tata Steel)• SSDs with graphene copper foil heat spreaders (10/17) (from Team Group)

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Graphene products launched in the market…2017

• Big users initially:

• (GNP) conductive additives in lithium-ion batteries replacing conductive black and in tires replacing (part of) furnace black

• (CVD) touch panels / screenshttps://www.graphene-info.com/ and company websites


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http://richardmille.com/watch/rm-50-03/

http://www.fiio.net/en/fiio

http://www.luxottica.com/en/luxottica-and-ray-ban-graphene-eyewear-revolution

https://www.skeletontech.com/

http://www.sdjtx.cn/

http://www.business-standard.com/article/companies/tata-steel-eyes-commercialisation-of-advanced-material-graphene-117073100791_1.html

http://www.teamgroupinc.com/en/News/Media/New%20Forces%20Join%20Popular%20Team%20Group%20Gaming%20T-FORCE%20Series%3Cbr%20/%3E%3Cbr%20/%3ETeam%20Group%20Releases%20T-%20FORCE%20CARDEA%20ZERO%20M.2%20PCIe%20SSD%20and%20T-%20FORCE%20FORCE%20SABLE%20Gaming%20Mouse%20Pad

https://www.graphene-info.com/

Context for quantities

Tire market – Carbon Black = 8.4 million tons in 4 billion tires (2014, 1)- 2% replacement would be 168,000 tons

Lithium-ion battery market – anodes (mainly graphite) 88,000 tons, conductive additives (mainly carbon black) 13,600 tons (5% of anode and cathode) (2016, 2)- GnP as conductive additive can be at a lower percentage (~0.5 to 2%), hence allowing incorporation of additional active material as well as providing ancillary benefits

Conductive ink and paste: 1,900 tons (2017,3) - ITO replacement could be a GnP market if resistance could be made low enough (and the product made uniform enough) without high loading affecting light transmission- Transparent Conductive Film market: >60 million square meters (2017, 4)

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1. Grand View Research, “Carbon Black Market Analysis By Application (Tires, High Performance Coatings, Plastics) And Segment Forecasts To 2022”, published April 2016; 2. C. Pillot, Avicenne Energy, “The Rechargeable Battery Market and Main Trends 2016 – 2025” March 20, 2017; 3. IDTechEx “Conductive Ink Markets 2017-2027: Forecasts, Technologies, Players”, published February 2017; 4. Energy Harvesting Journal (hosted by IDTechEx) reporting on March 14, 2017


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Example of a potential large user (1)

• Avanzare: Graphene in resin-based composites• Corrosion-resistant tanks and pipes made using graphene composites

instead of the usual metals for the storage and transport of potentially explosive chemicals

• Due to the electrical conductivity of graphene, one can avoid explosions due to electrostatic charges

• Cheaper, lighter and with very good corrosion resistance• 30% reduction in the cost of the final product


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http://www.avanzare.es/divisions/graphene/

Example of a potential large user (2)

• Imagine Intelligent Materials: graphene-enhanced geotextiles• Initial application in Queensland (Coal Seam Gas leak detection)

• imgne® X3 coating applied to Geofabrics Australasia’s bidim C geotextile• 10,000 m2 installed, enabling detection of holes in a lining system as

small as 0.7 mm. using standard electrical leak location methodologies• Estimated total demand for CSG in Queensland by 2030 is 400 tons of

graphene• One application in one state of one country

• Big picture is supplying material for mines, dams, water storage facilities, tanks and landfills

• Dispersion is critical, purity is not


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http://www.imgne.com/

https://www.geosynthetica.net/graphene-enhanced-geotextiles-coal-seam/

Other important applications for athletes and others


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Stronger hockey sticks (last ~25 times longer)

Bicycle (5.5 kg. instead of usual 6.8 kg.)

Fishing rods (stronger)

Drones(lighter weight)

Frying pans (faster heating and cooling)

All these from one company (Standard Graphene, www.standardgraphene.com)

http://www.standardgraphene.com/

Another important application


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Contents






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Summary and conclusions

• Graphene continues to draw large amounts of investment, despite challenges of scale-up and uncertain IP landscape

• Major apps for volume are currently:(GNP) - conductive additives in lithium-ion batteries replacing conductive black and in tires replacing (part of) furnace black(CVD) - touch panels / screens

• Some significant volumes of material will be needed…question is when

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Images provided by and used with permission of Iñigo Charola,Business Development Director, Graphenea

Graphene Oxide production plant

Class 1000 CVD facilities


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www.morganadvancedmaterials.com

Questions?

real world graphene: industrial applications for the 21st

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