Download - Foster Rush Electronics, Nano Technology and Clean Tech CARTS 2013 Novel Ceramic and Metal Materials for Energy Storage and Clean Tech Brian Foster & Dr.

Foster RushElectronics, Nano Technology and Clean Tech

CARTS 2013

Novel Ceramic and Metal Materials for Energy Storage

and Clean Tech

Brian Foster & Dr. Gordon Dayton

Foster RushLeading Edge Materials Technology Consulting

Outline

• Introduction• Fuel Cell Materials• Lithium Ion Battery Materials• Solar Cells• Conclusions


Introduction

• Passive component value chain trends:- Passive component price erosion continues to outpace

unit growth by 5-10%/year Component miniaturization Migration of manufacturing to low cost geographic regions Aggressive competition for high value component market space

- Increasing raw material costs Consolidation in the electronic materials supply chain Supply/demand imbalance Competition among end use applications

- Macro-economic pressures Continuation of European economic malaise Reduced growth expectations for US Moderation of growth rate in China


Introduction

• Search for Adjacent Market Spaces- New and Trending

- Not commoditized

- Value-added materials

- Leverage existing technology platforms and manufacturing competencies to maximize return on investment

- Benefit from development incentives

• Candidate Markets:- Clean Technology (SOFC, Solar Cells)

- Energy Storage (Li Batteries)


Heated Solid Oxide Fuel Cells

• 1930’s development• Early versions difficult to commercialize• Clean technology trends are driving new

development

• Byproducts: H2O, O2-depleted Air, electricity

• Potential for small, highly efficient source of clean energy


Heated SOFC

• Fuel: hydrocarbon gas (i.e., methane)

• Air (Oxygen source)• Electrolyte: ZrO2-based

(YSZ, ScSZ, GDC)• Anode: Ni-ZrO2 Cermet

• Cathode: (La,Sr)MnO3

• Temperature: 500-1000C

• Cathode is bulk material


Hydrothermal Zirconia Process

• High purity raw materials• Co-doping possible• Low-temperature

precipitation• Synthesis at ~400C• PSD can be tailored by

process conditions• Potential for low-

agglomeration

CA 102447125A


Hydrothermal ZrO2 Properties

Sinocera GC-ZO-3Y Hydrothermal YSZ

Parameter Units Value Method

Mean Particle nm ~50 SEM

Surface Area m2/g 18.6 BET

PSD-90 m 0.11 LS 230

PSD-50 m 0.15 LS 230

PSD-10 m 0.24 LS 230

Moisture Wt % 0.69 105 oC, 2-hr

Ignition Loss Wt % 1.17 1100 oC, 1-hr

Crystal Phase Symmetry Cubic X-ray Diffraction

ZrO2+HfO2+Y2O3 Purity % 99.9 Spectroscopy


Sinocera Hydrothermal YSZ

• High surface area• Fine particle size• Highly dispersed• Easily handled• Easily processed


Sinocera YSZ Ceramic

• Uniform microstructure• High density• Fine grain size• Low firing temperature

- Forming: 100 Mpa

- Tsinter: 1360 oC

- Density: 6.03 g/cc


Lithium Ion Battery Technology

• Applications:- Consumer Electronics – established/expanding

- Military/Aerospace – growing

- Electronic Vehicle – development (huge potential)

• Advantages- High energy density

- No memory effect

- Low static drain


Lithium Ion Battery (LIB)

• Cathodes: - Li,Co-Oxide*

- Li,Fe-Phosphate

- Li,Mn-Oxide,

- Li,Mn,Ni,Co-Oxide

• Anode: Graphite• Separator: permeable

membrane**• Electrolytes: Li-salts*LCO cathode is preferred for energy density,

but has safety issues, especially if damaged

**Separator must be permeable to liquidelectrolytes to facilitate charge/discharge


LIB Separator Technology

• Porous polymer Membrane- Typically Polyethylene or Polyproplyene

- Porosity > 40%

- Not developed solely for LIB applications

- Prone to development of Li-dendrites


LIB Separator Failure Mode

• Separator Matrix:- Polyethylene- Polypropylene- Other: PVDF, etc.

• Separator Porosity- > 40%

• Failure mode- Li dendrite growth- Electrical shorting- Overheating- Separator melting / fireLithium metal precipitates in porous membrane and

forms dendrites under EMF - EP1401037, Mar 2010

EP1401037


Lithium Ion Battery Risks


LIB Composite Separators

Entek Exxon Degussa Celgard

Product Teklon Tonen Separion 2325

Thickness 25 m 25 m 25 m 25 m

Layers Single Single Trilayer Trilayer

Materials PE PE Cer-PET-Cer PP-PE-PP

Process Wet extrude Wet extrude Wet-lay mat Dry extrude

Porosity 38% 36% > 40% 41%

Melt Temp 135 oC 135 oC 220 oC 134/166 oC

KEY: PE = Polyethylene, PP = Polypropylene, PET = Polyethylene terpathalate, Cer = Ceramic


LIB Separator Filler Materials

• Limit growth of Li-dendrites• Established options:

- CaCO3, SiO2, Al2O3, TiO2, SiS2, SiPO4

• Development: high K filler enhances electrolyte dissociation- BaTiO3


High Purity BaTiO3 for Fillers

• High purity raw materials• Fine control of reactant

ratio• Low-temperature

reaction• Highly crystalline output

powder

Samsung Oxalate BaTiO3 Process


Samsung Fine Chemical Oxalate BaTiO3 - SBT Powder


Samsung Fine Chemical Oxalate BaTiO3 Properties

Samsung Fine Chemical – SBT Powder

Property SBT Series MethodBa/Ti Ratio 0.999 +/- 0.002 X-ray Fluor.

Impurity (wt %)

SrO < 0.10

ICP

CaO < 0.005

Na2O < 0.005

SiO2< 0.01

Al2O3< 0.005

Fe2O3< 0.005

Moisture (wt %) < 0.30 120 oC, 30-m

Ignition Loss (wt %) < 1.0 1200 oC, 2-hr


Solar Cell Technology

• Established Technology- Trend for clean energy

- Potential for off grid or grid connected applications

- Recent government subsidies drive growth

• Competition in material market for cost and performance - Aluminum backside conductor

- Highly engineered silvers for front conductor


Solar Cell Technology

• Front Conductor- Silver powder ink

• Cell Material- Doped silicon wafer

• Back Conductor- Silver powder ink

- Aluminum powder ink


Silver conductor Technology

• Fine powders for conduction efficiency• Good adhesion to Si-wafer

- “Ohmic” contact critical to efficiency

• Resinate additives improve function- Lower processing temperature

- Increase network development


Daiken Chemical Company Resinate Technology

Metal Product Metal Solvent Application

Pt Pt-R06YL 5% BC Film catalyst

Pd Pd-R06YL 5% BC Film catalyst

Rh Rh-R01YL 5% BCA Additive Catalyst

Ru Ru-R01YL 5% IB Additive Catalyst

Ir Ir-R02YL 5% BA Additive Catalyst

Ni Ni-R02YL 5% BC Additive

KEY: BC = butyl carbonate, BCA = butyl carbonate acetate,IB = isobutanol, BA = butyl acetate


Typical Resinate Performance

• Low temperature sintering• Halogen and sulfur free to

eliminate corrosive decomposition products

• Thin film formation on a nano scale

• Homogeneous mixing at molecular level for conductive paste additive applications


Conclusions

• High price pressure on passive component value chain

• Adjacent markets may offer profitable opportunities• Leveraging existing core competencies combined

with development incentives offers attractive return on investment

• Follow global megatrends• Market examples include:

- Clean Technology: SOFC, Solar Ceramic Fuel Cells alliance with Chaozhou Three Circle Group Murata Ag paste for solar cell (metal wrap through technology)

- Energy Storage: Li Batteries EnerSys and Ioxus joint development agreement