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BACK TO THE FUTURE: PLASTICS
FROM PLANTS AND CARS THAT
RUN ON ELECTRICITY
Thomas D. Gregory
Borealis Technology Solutions LLC
Midland, Michigan
tdgregory@sbcglobal.net
TDG/9-16 Borealis Technology Solutions LLC 1
The Polymer Industry Didn’t Start with
Hydrocarbons
TDG/9-16 Borealis Technology Solutions LLC 2
Nitrocellulose from
cellulose and nitric acid
considered to be first
man-made plastic (1862)
Celluloid (nitrocellulose
plasticized with
camphor) introduced in
1868
Cellulose acetate from
cellulose and acetic
anhydride first synthesized
in 1865, commercially
introduced in 1904
Polystyrene first
synthesized in 1839 from
resin derived from the
Turkish Sweetgum tree
Duroplast (thermosetting resin made
from phenol obtained from the East
German dye industry reinforced with
waste cotton or wool fibers) used in
body parts for the Trabant starting in
mid-1950s
Distant Past 1800 1900 2000
First commercial synthetic polymer was
thermosetting phenol formaldehyde
(Bakelite; 1907); formaldehyde obtained
from oxidation of methanol produced via
destructive distillation of wood
Mankind has used
cellulose (poly-D-
glucose) for millennia
Electric Vehicles Were Common in the Early
20th Century
TDG/9-16 Borealis Technology Solutions LLC 3
http://blackdiamondnow.typepad.com/.a/6a00e5513924e688330147e21ae817970b-pi http://electricandhybridcars.com/images/uploaded/Fritchle-victoria-phaeton-Ad.jpg
Are we headed back there?
And if so, how do we get there?
TDG/9-16 Borealis Technology Solutions LLC 4
Part I: Assessing the feasibility of making plastics
(and chemicals) from plants: Techhnoeconomic
analysis of renewable feedstock-based processes
The use of economic parameters to guide successful R&D
TDG/9-16 Borealis Technology Solutions LLC 5
Hydrocarbons Opened Up New Avenues in the
20th Century
TDG/9-16 Borealis Technology Solutions LLC 6
1900
2000
Synthetic polystyrene first
commercial production in
1931 (I.G. Farben)
Polyethylene produced
in 1939 (ICI)
PET introduced in
1951 (DuPont)
Polypropylene produced in 1957
(Montecatini)
But Hydrocarbon Price Swings are Notorious
Source: http://www.lankerpack.com/correlation-analysis-of-polyethylene-and-its-upstream/price-comparision-of-el-and-pe//
And sustainability of a petroleum-based economy has come into question
TDG/9-16 Borealis Technology Solutions LLC 7
This Has Fueled a Renaissance of Interest in Plant-
Based Raw Materials
• Fermentation of carbohydrates to form alcohol and carboxylic acid
monomers
• Corn → Lactic Acid → Polylactic acid (NatureWorks)
• Chemical processing of biomass to form hydrocarbons
• Biomass → H2 + CO → Alkanes → Alkenes → Polyalkenes
(Gasification/Fischer-Tropsch/Dehydrogenation/Polymerization)
• Biomass → Intermediates → Aromatics → p-Xylene → Terephthalic Acid
→ PET (Virent’s Aqueous Phase Reforming technology)
TDG/9-16 Borealis Technology Solutions LLC 8
But Will it Play in Peoria?
• Lots of political support for carbohydrate-based products in the Corn Belt
• But experience tells us that few customers will usually pay more for “green
products”
So can we make plant-based chemical products at cost-
parity with hydrocarbon-based products? And if so, how?
Technoeconomic analysis is a useful tool to answer this
question
TDG/9-16 Borealis Technology Solutions LLC 9
What is Technoeconomic Analysis?
Blending of technical and economic evaluation to determine how a
product can be made, what the most economically attractive route is
to make it, and if this activity provides a competitive advantage.
It all starts with an opportunity
• Does the opportunity have commercial merit?
• Is the opportunity technically feasible?
• Does the opportunity have the potential to provide an acceptable economic
return?
• What is the optimum path forward?
TDG/9-16 Borealis Technology Solutions LLC 10
Elements of Technoeconomic Analysis
• Evaluation of market opportunity
• Is there an existing market for the product or is downstream innovation needed?
• Evaluation of competitive environment
• What are the commercial and financial barriers to market entry?
• Evaluation of sustainability
• Is the proposed product and/or process route viable long-term?
• Evaluation of cost of manufacture
• Capital costs to build a production plant
• Raw material costs
• Conversion costs
• Evaluation of profitability
• NPV, DCF, etc.
TDG/9-16 Borealis Technology Solutions LLC 11
Critical Cost Factors for Chemical Products
Capital cost of production plant
• What is the capacity of the proposed plant?
• How many process steps are in the proposed process?
• How many reaction steps?
• What is the total throughput of the plant vs. the net production?
• Does the process involve extreme temperatures, pressures, or corrosive environments?
• Alternatively, what will it cost us to have a contract manufacturer make the product?
Raw material cost
• What is the unit ratio of primary feedstock, other reactants, and solvents to product?
• Carbon efficiency of synthetic route
• Conversion & yield
• Downstream recovery & purification losses
• For organic products, what is the net price of carbon obtained from the primary
feedstock?
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Production Scale is a Critical Issue
TDG/9-16 Borealis Technology Solutions LLC 13
For Organic Products, Cost of Carbon is Critical
Material Price Wt% Carbon Contained Carbon Price,
$/KgMarket
Price
$/Kg
Crude Oil $50/bbl 0.37 84 (avg.) 0.44
Methane (as NG) $3/MSCF 0.15 74.8 0.20
Ethane $200/MT 0.20 79.9 0.25
Ethylene (USGC) $500/MT 0.50 85.6 0.58
Starch $0.15/lb 0.33 44.4 0.74
#11 Sugar (world) $0.15/lb 0.33 42.1 0.78
#16 Sugar (U.S.) $0.30/lb 0.66 42.1 1.57
TDG/9-16 Borealis Technology Solutions LLC 14
Equivalent Carbon Prices
TDG/9-16 Borealis Technology Solutions LLC 15
Location, Location, Location
Source: http://sugarreform.org/wp-content/uploads/2011/07/Wholesale-refined-sugar-prices-US-vs-world-1-10-13.png=3y
TDG/9-16 Borealis Technology Solutions LLC 16
Are Bio-Based Routes to Polymers Economically Viable?
Example: Polyethylene from sugar
• Dow/Crystalsev JV in Brazil
Fermentation: C6H12O6 → 2 C2H5OH + 2 CO2
Dehydration: C2H5OH → C2H4 + H20
Polymerization: n C2H4 → (C2H4)n
Thermodynamics for monomer production are favorable:
Glucose → Ethanol → Ethylene ΔGo = -99.6 kJ/mole
TDG/9-16 Borealis Technology Solutions LLC 17
Carbon Yield Isn’t Always a Pretty Picture, However
Process Route Typical Carbon Yield, % Equivalent Carbon Cost, $/Kg
Ethane → Ethylene 84 0.30
Glucose → Ethanol → Ethylene 47 1.70
• Byproducts of ethane dehydrogenation include valuable H2 & hydrocarbons
• Byproducts of fermentation route include wastewater and CO2
Biomass-based processes typically lose a significant amount of carbon as CO2
Carbon efficiency of bio-based feedstocks is typically better for manufacture of
oxygenated products than hydrocarbons
TDG/9-16 Borealis Technology Solutions LLC 18
Are There Better Opportunities for Bio-Based Products?
• Example: Avantium’s process to make polyethylene furanoate (PET
replacement)
Source: https://www.avantium.com/yxy/yxy-technology/
Subject of Avantium/BASF joint venture
(https://www.basf.com/en/company/news-and-media/news-releases/2016/03/p-16-153.html)
TDG/9-16 Borealis Technology Solutions LLC 19
What are the Relative Costs of PEF and PET?
• Need to know:
• What is the target production rate?
• What would a commercial process look like?
• What raw materials and how much of them are needed?
• From this information, we need to estimate:
• Capital cost to build the production facility
• Cost of raw materials
• Cost to operate the facility, including labor, utilities, waste disposal, maintenance,
overhead, taxes, and insurance
• Sources of process information
• Avantium web site
• Avantium patents & published patent applications
• Publications on FDCA & PEF synthesis
TDG/9-16 Borealis Technology Solutions LLC 20
Analysis Strategy
• Polymerization costs likely similar to PET process
• Key comparison is cost of manufacture of FDCA vs. terephthalic acid
• Utilize available information to estimate FDCA cost of manufacture
• Basis for Analysis:
• 350 kta FDCA + esters capacity
• Fructose is the primary feedstock
• 70% molar yield of MMF/HMF from fructose assumed
• 85% molar yield of FDCA + esters from MMF/HMF assumed (60% overall yield
from fructose)
• 95% recycle of solvents and catalysts assumed
• Methyl levulinate & furfural byproducts credited at $1.00/Kg each
TDG/9-16 Borealis Technology Solutions LLC 21
Avantium FDCA Process Block Flow Diagram
HMF/MMF Synthesis, Reference US 2013/0324708 A1
TDG/9-16 Borealis Technology Solutions LLC 22
Avantium FDCA Process Block Flow Diagram
FDCA from MMF/HMF, Reference US 8,865,921 B2 & related
TDG/9-16 Borealis Technology Solutions LLC 23
MMF/HMF
HOAc
Water
Batch Reactor Air
NaBr
Co(OAc)2
Mn(OAc)2
Catalyst Prep
Separation
Separation
Separation
MeOH
Aq. HOAc/catalyst
FDCA/esters
Purification
Air/CO2
How do we Estimate the Capital Cost of a Conceptual Plant?
• Complexity factor (step counting) methods
• Correlation between number of “major operating steps”, plant
capacity, and operating conditions and capital cost
• Factored cost estimates
• Specify major equipment (type, size, material of construction) and
multiply cost by factors representing installation, construction,
engineering, etc.
• Capital cost is typically ~6X purchased cost of major equipment
• Process simulation-based capital cost estimates
• Example: Aspen process simulation and cost estimation software
TDG/9-16 Borealis Technology Solutions LLC 24
FDCA Process Capital Cost Estimation
What do you do when you have little information to go on?
• Example methodology: Complexity factor cost estimation method of
Bridgewater as modified by G.J. Petley
• G. J. Petley, A method for Estimating the Capital Cost of Chemical Process Plants – Fuzzy Matching, Ph.D. thesis,
Loughborough University, U.K., 1997.
ISBL Capital Cost (2016 $US) = 5010 * N * (Q/s)0.586
Where N = number of major process steps
Q = production capacity, MTA
s = wt. ratio of reactor product:total feed
• Factors used:
• Number of major process steps: 5 for MMF/HMF synthesis, 6 for MMF/HMF conversion to
FDCA/esters
• Production rate, throughput & yields as per analysis bases
• Results:
• Total ISBL capital = $305MM ($0.87/Kg FDCA+esters/yr)
• Total fixed capital = $460MM
TDG/9-16 Borealis Technology Solutions LLC 25
Raw Material Costs
• Raw material requirements are estimated based on Avantium patent literature
Component Moles/mole
Fructose feed
Kg/Kg
FDCA+esters
Price, $/Kg Total Cost, $/Kg
FDCA+esters
Fructose 1.0 1.92 1.00 1.92
Methanol 1.4 0.6 0.38 0.23
H2SO4 Neg. 0
Furfural 0.03 0.03 1.00 (0.03)
Methyl levulinate 0.1 0.15 1.00 (0.15)
HOAc 0.3 0.2 0.55 0.11
Catalyst 0.0051 $11.39/mole 0.034
Total Raw Material Cost 2.11
TDG/9-16 Borealis Technology Solutions LLC 26
Operating Costs
• Labor
• 4 operators/shift + 2 for MMF/HMF @ $75,000 each
• 6 operators/shift + 3 for FDCA/esters @ $75,000 each
• 4 salary total for both operations @ $120,000 each
• Net yearly cost = $3.9MM = $0.01/Kg FDCA+esters
• Utilities & waste treatment
• Estimated as 4% of unit direct fixed capital (ISBL capital)
• $0.035/Kg FDCA+esters
• Total operating costs = $0.045/Kg
TDG/9-16 Borealis Technology Solutions LLC 27
Other Fixed Costs
• Typically estimated as percentages of direct fixed capital for early
stage cost estimates:
Cost Element % Unit direct fixed
capital
$/Kg FDCA+esters
Overhead 4 0.035
Maintenance 6 0.052
Taxes & insurance 2 0.017
Depreciation 10% ISBL + 5% OSBL 0.109
Total fixed costs 0.21
TDG/9-16 Borealis Technology Solutions LLC 28
FDCA Cost of Manufacture Summary
• Note that these numbers have wide error bars
Cost Item $/Kg FDCA+esters
Raw materials 2.11
Operating costs 0.05
Fixed costs 0.21
Total cost of manufacture 2.37
TDG/9-16 Borealis Technology Solutions LLC 29
Compare to long-term price of purified terephthalic acid of <$1/Kg
Dealing with Uncertainty
• Early-stage cost estimates typically involve lots of assumptions
• Experience tells us that final plant construction costs can easily be 2X
early stage estimates
• Lab results do not necessarily mirror plant results
• Sensitivity analysis is used to assess the impact of different variables
on cost
• Simple: percent changes in specific variables
• More complex: Monte Carlo methods (probability function instead of %
changes)
TDG/9-16 Borealis Technology Solutions LLC 30
Sensitivity Analysis of FDCA Cost Estimate
Case Est. FDCA Cost of
Manufacture, $/Kg
% Change from
Base Case
Base 2.37 0
Capital cost +50% 2.47 +4
Capital cost +100% 2.58 +9
Raw materials cost -25% 1.84 -22
Raw materials cost -50% 1.32 -44
This sends a clear message: R&D needs to concentrate
on identification of a cheaper feedstock
TDG/9-16 Borealis Technology Solutions LLC 31
Alternative Carbohydrates
Carbohydrate Source Price, $/Kg
Fructose 1.00
HFCS-42 0.91
Glucose syrup 0.85
Sucrose (world price) 0.33
Starch 0.33
Best case: sucrose as carbohydrate source (10% yield reduction, however)
• Unit capital increases to $0.97/Kg FDCA + esters
• Raw material cost decreases to $1.41/Kg FDCA + esters
• Estimated cost of manufacture decreases to $1.70/Kg FDCA + esters
TDG/9-16 Borealis Technology Solutions LLC 32
Is Biomass a Cheaper Source of Carbohydrates?
• Green wood chips @ $40/ton
• 40% moisture – need to dry
• 30% cellulose – convertible to 6-carbon sugars
• 12 % hemicellulose – convertible to 5-carbon sugars
• 18% lignin – hard to utilize
• Need to convert cellulosic components to useful compounds
• Enzyme hydrolysis – expensive enzymes
• Chemical hydrolysis – cheap acid (H2SO4) but expensive equipment
• Ammonia Fiber Expansion, Steam explosion – high operating expenses
• Cost of sugars from biomass appears to be comparable to cane sugar (Lux
Research, 2013)
• Feedstock cost is a major factor
• Must factor in capital investment for biomass processing
TDG/9-16 Borealis Technology Solutions LLC 33
So Where Do We Stand?
• The two cases examined here (bio-PE & PEF) don’t appear to be cost
competitive with conventional PE & PET
• Customers rarely pay a substantial premium for “green” products
• Successful commercialization of renewable feedstock-based processes
will require careful selection of products and raw materials
• Limit number of process steps and reactor dilution to limit plant capital cost
• Similar C:O ratios in product and feedstock can help limit carbon loss as CO2
• Early-stage technoeconomic analysis is a powerful tool in new process
development
• Limits resources spent on opportunities with low probability of success
• Guides R&D and resource allocation to focus on most important cost variables
TDG/9-16 Borealis Technology Solutions LLC 34
Successful Use of Biomass Feedstock Requires
a Confluence of Positive Factors
TDG/9-16 Borealis Technology Solutions LLC 35
Acceptable
Feedstock Cost
Feedstock Processability
into Viable Products
Product Demand
Part II: Development of advanced battery
technology to enable future societal paradigms
Vehicle electrification and grid-scale electrical energy storage
TDG/9-16 Borealis Technology Solutions LLC 36
Energy Storage & Transportation Was a
Cumbersome Task for Many Years
TDG/9-16 Borealis Technology Solutions LLC 37
Animals & steam engines were the main methods of converting a fuel to useful work
Electricity is an efficient, clean energy source
but transportation has also been difficult . . .
• Wire transmission requires being tethered to a current source
• Batteries freed us from this but early batteries were rather
cumbersome and unreliable
TDG/9-16 Borealis Technology Solutions LLC 38
Plante, 1859: Lead-acid battery
https://upload.wikimedia.org/wikipedia/commons/c/c0/Plante_lead_acid_cell.jpg
Volta, 1799: Silver-zinc “pile”
https://de.wikipedia.org/wiki/Voltasche_S%C3%A4ule#/media/File:Pila_di_Volta_01.jpg
Edison, 1901: Nickel-iron battery
http://ichef.bbci.co.uk/news/304/media/images/61299000/jpg/_61299222_008972010-1.jpg
But just as with synthetic polymers, hydrocarbons
became the preferred fuel for vehicles early in the
20th century . . .
• More energy-dense than batteries
• Gasoline: 46.4 MJ/Kg
• Edison’s Ni-Fe battery: 0.072 MJ/Kg
• Rapid improvement in combustion engines & vehicle technology
around the beginning of the 20th century
• Could transport gasoline by truck or train to remote locations not
served by electricity at the time
TDG/9-16 Borealis Technology Solutions LLC 39
And the few devices requiring batteries
weren’t very demanding. . .
TDG/9-16 Borealis Technology Solutions LLC 40
Flashlights “Portable” Radios
https://en.wikipedia.org/wiki/Radio_receiver#/media/File:Edwin_Armstrong_
wife_and_portable_superhet_radio.jpg
http://www.wordcraft.net/flashlitestemp/09127otbuggcandle.jpg
And cameras were mostly mechanical
https://upload.wikimedia.org/wikipedia/commons/2/26/Hawkeye_brownie.JPG
Advances in the mid-1900’s mostly involved
improved Ni-Cd rechargeable batteries and
miniature primary batteries
TDG/9-16 Borealis Technology Solutions LLC 41
https://pbs.twimg.com/media/CLuXnqQVAAATFzM.jpg
Cordless Drills
http://i.kinja-img.com/gawker-media/image/upload/s--waSC8JJM--
/182he57oi6vrijpg.jpg
Cordless Phones
http://www.relic-watches.com/uploads/watches/10/160490138695-1.jpg
Electric Watches
The first cell phones were extremely bulky and
electric mobility was limited mostly to small
vehicles not much bigger than golf carts
TDG/9-16 Borealis Technology Solutions LLC 42
http://cdn2.knowyourmobile.com/sites/knowyourmobilecom/files/3/11/marty_cooper.jpg
https://s-media-cache-ak0.pinimg.com/236x/96/42/4c/96424cc9550337164b68104aa46cbc1d.jpg
But in the late 20th century everything changed . . .
TDG/9-16 Borealis Technology Solutions LLC 43
http://www.sonyenergy-devices.co.jp/en/keyword/images/img_keyword_01.jpg
1991: First Commercial Li-Ion Battery by Sony
http://cdn.shopify.com/s/files/1/0257/3165/products/dfpz40407_grande.jpeg?v=1454544577
1989: First commercial nickel-metal hydride battery (Ovonic)
This enabled dramatic advances in devices
powered by portable energy sources
TDG/9-16 Borealis Technology Solutions LLC 44
http://www.oldcomputers.net/pics/osborne1.jpg http://images.clipartpanda.com/laptop-computer-images-
laptop-and-netbook-computers-5131.jpg
http://media.graytvinc.com/images/smartphone13.jpg
http://images.businessfinancenews.com/bfn/960-does-tesla-motors-
inc-need-to-worry-from-aston-martin-faraday-future-tie-up.jpg
Li-Ion Batteries Have Taken Over the Global
non-SLI Rechargeable Battery Market
TDG/9-16 Borealis Technology Solutions LLC 45
Source: Avicenne, 2016
What’s so Special About Lithium-Ion Batteries?
TDG/9-16 Borealis Technology Solutions LLC 46
https://static-content.springer.com/image/prt%3A978-1-4419-0851-3%2F2/MediaObjects/978-1-4419-0851-3_2_Part_Fig1-497_HTML.gif
What’s Inside a Lithium-Ion Battery?
TDG/9-16 Borealis Technology Solutions LLC 47
2LiCoO2 + 6C
charge
discharge
2Li0.5CoO2 + LiC6
Kang Xu, Chem. Rev. 2004
Separator
Anode current
collector: Copper,
~12-16 microns thick
Anode: 90-95% active material, 3-5% conductive carbon, 3-5% binder, 25-30%
porous, 25-90 microns thick depending on intended battery characteristics
Separator: Typically microporous
polyolefin, 20-25 microns thick,
40-50% porous
Cathode: up to 95% active
material, remainder
conductive carbon + binder,
25-30% porous, 30-100
microns thick depending on
battery characteristics
Cathode current collector:
Aluminum, ~12-16
microns thick
Li+ Ion Movement During Charge & Discharge
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Li-Ion Batteries Utilize Intercalation Electrochemistry
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Desired Cathode Reactions: LiCo+3O2 ↔ Li0.5Co0.5
+3Co0.5
+4O2 + 0.5 Li+ + 0.5 e-
Desired Anode Reactions: Li+ + e- + C6 ↔ C6
-0.17Li+
(Note: there is some disagreement in the literature whether Li+ completely follows classical intercalation
chemistry as shown or whether some electron transfer to Li+ occurs)
Undesired Anode Reaction: Li+ + e- + C6 ↔ C6 + Li (Li metal deposition on C surface)
Scherson, ECS Interface, 2006
Battery Construction
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Coin or Button Cell
Cylindrical or Wound Cell
Prismatic Cell
Laminate or Pouch Cell
Cathode Materials Determine Cell Characteristics
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• Layered metal oxides
LiCoO2, Li(Ni,Co,Al)O2, Li(Ni,Mn,Co)O2
• Good capacity & rate capability, but tend to be expensive and can react violently
with electrolytes at high temperatures
• Single phase materials (LixMO2) = sloping voltage profiles
• Olivines
LiFePO4, LiMnPO4, LiNiPO4, etc.
• Can have excellent rate capability & low cost, but need C-coating, nano-size, doping
to work well; some have low voltage (thus low energy density)
• 2-phase materials (MPO4/LiMPO4) = flat voltage profiles
• Manganates
LiMn2O4
• Good rate capability & low cost, but stability is an issue and capacity is relatively low
Layered Metal Oxides Are Used in High Specific Energy
Batteries
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Technology Advances & Market Growth Have
Resulted in Dramatic Price Declines
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Source: Avicenne, 2016
So Why Don’t We Have Affordable EVs?
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Pathways to Higher Energy Density and Lower Cost
• Higher capacity/higher voltage
cathode materials
• “Li-rich” metal oxides – xLiMO2
.(1-
x)Li2MnO3 where M = Ni, Co, Mn
• Lifetime, capacity fade are key
development challenges
• Higher capacity anodes
• Alloy anodes such as Si or Sn
• Li metal
• Degradation, morphological stability
are key development challenges
TDG/9-16 Borealis Technology Solutions LLC 55
“Beyond Li-Ion” Batteries – Li/air & Li/S
TDG/9-16 Borealis Technology Solutions LLC 56
http://www.nature.com/ncomms/journal/v4/n5/images/ncomms2855-f6.jpg
https://upload.wikimedia.org/wikipedia/commons/e/e4/Li-air-charge-discharge.jpg
http://www.frontiersin.org/files/Articles/110133/fenrg-03-00017-HTML/image_m/fenrg-03-00017-g001.jpg
Li/Air & Li/S Batteries
• Very high theoretical specific energy
• Li/air – 3400 Wh/Kg
• Li/S – 2680 Wh/Kg
• But practical volumetric energy density may not exceed that of the
best Li-ion batteries
• Need excess Li to account for coulometric efficiency <100%
• Cathode structures are porous with high carbon content
• Poor voltage efficiency for Li/air
• Air contaminants can impair Li/air performance
• Cycle life has been an issue for both chemistries
• OK for niche applications like UAV, but automotive may be difficult to address
TDG/9-16 Borealis Technology Solutions LLC 57
Multivalent Metal Anodes Have Potential
Advantages Over Li
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Most Multivalent Metal Battery Effort is
Directed at Mg
• Electrolyte chemistry is more complex than Li
• Solutions of simple Mg salts in organic solvents not reversible to Mg
plating/stripping
• Mg does not form an ion-conducting SEI layer
• Limits solvent choices
• Intercalation cathodes identified, but possibilities are far fewer than
with Li
• Many Li intercalation cathodes act as irreversible conversion cathodes with Mg
• High charge density of Mg2+ cation limits ion mobility in solid structures and
often results in ion trapping
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Electrolyte Development has Driven Mg Battery R&D
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Mg Battery Cathode Material Development
• Longest cycle life obtained with MgxMo6S8 Chevrel phase materials
• High ionic mobility
• Low cell voltage (~1.1V) and reversible capacity (~100 mAh/g), however
• MgxV2O5 shows improved performance when water is incorporated
into the electrolyte or into the cathode material during synthesis
• Co-intercalates from electrolyte with Mg2+
• Shields cathode material from high charge density of cation
• Capacity increase from 60 mAh/g to ~160 mAh/g when adding water to Mg
perchlorate/propylene carbonate reported (L. Yu, X. Zhang, J. Colloid
Interfacial Sci., 2004)
• Water interaction with anode appears to cause capacity fade and impedance
growth, however
TDG/9-16 Borealis Technology Solutions LLC 61
Polyanion Cathode Materials Have Shown Promise
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MgFeSiO4
• Reversible capacity >300 mAh/g @
2.4V demonstrated in Mg(TFSI)2-AN
electrolyte
• Capacity, voltage lower in Mg(TFSI)2-
triglyme (<120 mAh/g, <1.5V midpoint)
MgMnSiO4
• Capacity up to ~300 mAh/g @ 1.65V
demonstrated (NuLi et al, Chem.
Commun., 2010) Orikasa, Y. et al. High energy density rechargeable magnesium
battery using earth-abundant and non-toxic elements. Sci. Rep. 4, 5622; DOI:10.1038/
srep05622 (2014).
Can Mg-based batteries compete with Li-ion?
TDG/9-16 Borealis Technology Solutions LLC 63
400 Wh/Kg active material (comparable to graphite/NCA)
700 Wh/Kg active material (comparable to Si/Li-rich)
Active material energy density, 2X theoretical Mg anode capacity
Mg/S
Mg/CuF2
Mg/MnO2
Mg/AgCl
Mg system active material ED estimated @ 2/3 theoretical cathode capacity, discharge voltage 0.75 V below std. potential
Mg/MgMnSiO4
Commercial Developments in Mg Batteries
TDG/9-16 Borealis Technology Solutions LLC 64
• Pellion Technologies
• Prototype cells up to 2 Ah, 1000 Wh/L claimed
• US 9,240,612 (2016) claims cathode material with interlayer spacing at least 4.8Å and
anatase & rutile TiO2, TiS2, FeS2, MoS2, Mo6S8 & combinations
• US 9,172,111 (2015) claims layered crystalline cathode materials with interlayer spacing
modified by insertion of organic compounds to improve Mg2+ transport
• Sony
• Occasional publications & presentations, press reports claim development of Li/S & Mg/S
batteries with 2020 introduction & 1000 Wh/L goals
(http://techon.nikkeibp.co.jp/atclen/news_en/15mk/121800252/)
• Toyota
• Frequent technical publications & presentations; exploring multiple EV power source
technologies
Stationary Energy Storage
Grid stabilization, solar & wind energy storage, load leveling, etc.
• Small capacity – lead-acid, lithium-ion batteries
• Storage of energy from rooftop solar, small wind turbines, or cheap night time grid energy
• Uninterruptable power supplies
• Intermediate capacity – lithium-ion batteries
• Grid stabilization
• Smart micro-grids
• Large capacity – Na-S, redox flow batteries
• Grid-scale energy storage for renewable energy, reserve capacity, etc.
• Critical Factor is life cycle cost
• Initial system cost
• Maintenance
• Round-trip efficiency
• Lifetime
TDG/9-16 Borealis Technology Solutions LLC 65
Redox Flow Batteries for Stationary Energy Storage
TDG/9-16 Borealis Technology Solutions LLC 66
• Flow batteries decouple energy &
power
• Improved mass transfer
• Cost issues
• Cell stack cost is proportional to area
• Increased power density = lower cell stack
cost due to reduced electrode and
membrane area
• Electrolyte cost is dependent on cost of
active materials & system efficiency
• Abundant, low-cost materials preferable
• Flow system cost dependent on size,
materials of construction
• Higher electrolyte concentration = more
compact flow system
• Electrolyte corrosivity influences flow system
cost
+ -
V5+ /V4+
V3+ /V2+
Innovations in Flow Battery Technology
TDG/9-16 Borealis Technology Solutions LLC 67
0
50
100
150
200
250
300
350
400
0 100 200 300 400 500 600 700 800
Est.CellStack+ElectrolyteCost,$/kWh
Power Density, mW/cm2
Conventional VRB
CWRU Fe/Fe
WattJoule VRB
1 MW/4 MWH
Systems
PNNL VRB
Near term
OptimisticPNNL Fe/V
Near term
Optimistic
Novel Approaches to Redox Flow Batteries
TDG/9-16 Borealis Technology Solutions LLC 68
Technology
Goal(s)
Innovation(s) Organization
5-10X increased
power density
• Improved fluid dynamics & components
• VRB @ ~1300 mW/cm2
United Technologies
Research Center
Low cost active
materials &
components
• Quinone redox chemistry
• Rapid electrode kinetics with inexpensive
current collectors
Harvard University
Electrolyte =
active material
• Ionic liquid electrolyte & active material
• Flexible chemistry
Sandia National Lab
Chemical process design principles can yield improvements in flow battery technology
Process intensification – increased power density and electrolyte concentration
Process simplification – reduced capital and operating cost
Where it the Battery Field Heading?
• Li-ion will continue to be the battery technology of choice for
vehicle electrification
• Incremental improvements (higher capacity & voltage cathodes, improved
electrolytes, migration to alloy anodes) will push technology to acceptable
cost & energy density
• Multivalent metal batteries may provide a longer-term pathway to step-
change improvements
• Stationary energy storage markets will be served by a variety of
battery chemistries
• Li-ion seems to have the inside track for high value, low capacity applications
like grid stabilization & distributed wind & solar energy storage
• More flexible redox flow batteries may be used in larger-scale grid storage
applications
• Need to reduce complexity & cost
TDG/9-16 Borealis Technology Solutions LLC 69
A Few Closing Words
“Engineers create the world that never was.”
Theodore von Kármán, co-founder of NASA Jet Propulsion Lab
• Me-too products & technology won’t achieve this
• Hard to compete with entrenched technology without a significant advantage
• Incremental improvements only accomplish this if the target is already
close
• Virtually all work on Li-ion battery technology since 1991 has been incremental
• Revolutionary advances often come about from seeing the world from a
different perspective
• Looking at what everyone else has looked at and seeing what no one else has seen
TDG/9-16 Borealis Technology Solutions LLC 70
Upcoming Events
• Key Challenges Facing Rechargeable Magnesium Batteries: A Peek
Outside the Box
• Invited presentation, The Electrochemical Society PRiME 2016, Honolulu HI, Oct. 4,
2016
• Technoeconomic Analysis of Battery Material Development and
Production
• Tutorial, 34th International Battery Seminar & Exhibition, Ft. Lauderdale FL, March
20-23, 2017
• Cost Reduction Strategies for Electric Vehicle Battery Packs
• Workshop, Advanced Automotive Batteries 2017, TBD
TDG/9-16 Borealis Technology Solutions LLC 71

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Thomas D. Gregory at the Michigan State University Bioeconomy Insitute, 9-14-16

  • 1. BACK TO THE FUTURE: PLASTICS FROM PLANTS AND CARS THAT RUN ON ELECTRICITY Thomas D. Gregory Borealis Technology Solutions LLC Midland, Michigan tdgregory@sbcglobal.net TDG/9-16 Borealis Technology Solutions LLC 1
  • 2. The Polymer Industry Didn’t Start with Hydrocarbons TDG/9-16 Borealis Technology Solutions LLC 2 Nitrocellulose from cellulose and nitric acid considered to be first man-made plastic (1862) Celluloid (nitrocellulose plasticized with camphor) introduced in 1868 Cellulose acetate from cellulose and acetic anhydride first synthesized in 1865, commercially introduced in 1904 Polystyrene first synthesized in 1839 from resin derived from the Turkish Sweetgum tree Duroplast (thermosetting resin made from phenol obtained from the East German dye industry reinforced with waste cotton or wool fibers) used in body parts for the Trabant starting in mid-1950s Distant Past 1800 1900 2000 First commercial synthetic polymer was thermosetting phenol formaldehyde (Bakelite; 1907); formaldehyde obtained from oxidation of methanol produced via destructive distillation of wood Mankind has used cellulose (poly-D- glucose) for millennia
  • 3. Electric Vehicles Were Common in the Early 20th Century TDG/9-16 Borealis Technology Solutions LLC 3 http://blackdiamondnow.typepad.com/.a/6a00e5513924e688330147e21ae817970b-pi http://electricandhybridcars.com/images/uploaded/Fritchle-victoria-phaeton-Ad.jpg
  • 4. Are we headed back there? And if so, how do we get there? TDG/9-16 Borealis Technology Solutions LLC 4
  • 5. Part I: Assessing the feasibility of making plastics (and chemicals) from plants: Techhnoeconomic analysis of renewable feedstock-based processes The use of economic parameters to guide successful R&D TDG/9-16 Borealis Technology Solutions LLC 5
  • 6. Hydrocarbons Opened Up New Avenues in the 20th Century TDG/9-16 Borealis Technology Solutions LLC 6 1900 2000 Synthetic polystyrene first commercial production in 1931 (I.G. Farben) Polyethylene produced in 1939 (ICI) PET introduced in 1951 (DuPont) Polypropylene produced in 1957 (Montecatini)
  • 7. But Hydrocarbon Price Swings are Notorious Source: http://www.lankerpack.com/correlation-analysis-of-polyethylene-and-its-upstream/price-comparision-of-el-and-pe// And sustainability of a petroleum-based economy has come into question TDG/9-16 Borealis Technology Solutions LLC 7
  • 8. This Has Fueled a Renaissance of Interest in Plant- Based Raw Materials • Fermentation of carbohydrates to form alcohol and carboxylic acid monomers • Corn → Lactic Acid → Polylactic acid (NatureWorks) • Chemical processing of biomass to form hydrocarbons • Biomass → H2 + CO → Alkanes → Alkenes → Polyalkenes (Gasification/Fischer-Tropsch/Dehydrogenation/Polymerization) • Biomass → Intermediates → Aromatics → p-Xylene → Terephthalic Acid → PET (Virent’s Aqueous Phase Reforming technology) TDG/9-16 Borealis Technology Solutions LLC 8
  • 9. But Will it Play in Peoria? • Lots of political support for carbohydrate-based products in the Corn Belt • But experience tells us that few customers will usually pay more for “green products” So can we make plant-based chemical products at cost- parity with hydrocarbon-based products? And if so, how? Technoeconomic analysis is a useful tool to answer this question TDG/9-16 Borealis Technology Solutions LLC 9
  • 10. What is Technoeconomic Analysis? Blending of technical and economic evaluation to determine how a product can be made, what the most economically attractive route is to make it, and if this activity provides a competitive advantage. It all starts with an opportunity • Does the opportunity have commercial merit? • Is the opportunity technically feasible? • Does the opportunity have the potential to provide an acceptable economic return? • What is the optimum path forward? TDG/9-16 Borealis Technology Solutions LLC 10
  • 11. Elements of Technoeconomic Analysis • Evaluation of market opportunity • Is there an existing market for the product or is downstream innovation needed? • Evaluation of competitive environment • What are the commercial and financial barriers to market entry? • Evaluation of sustainability • Is the proposed product and/or process route viable long-term? • Evaluation of cost of manufacture • Capital costs to build a production plant • Raw material costs • Conversion costs • Evaluation of profitability • NPV, DCF, etc. TDG/9-16 Borealis Technology Solutions LLC 11
  • 12. Critical Cost Factors for Chemical Products Capital cost of production plant • What is the capacity of the proposed plant? • How many process steps are in the proposed process? • How many reaction steps? • What is the total throughput of the plant vs. the net production? • Does the process involve extreme temperatures, pressures, or corrosive environments? • Alternatively, what will it cost us to have a contract manufacturer make the product? Raw material cost • What is the unit ratio of primary feedstock, other reactants, and solvents to product? • Carbon efficiency of synthetic route • Conversion & yield • Downstream recovery & purification losses • For organic products, what is the net price of carbon obtained from the primary feedstock? TDG/9-16 Borealis Technology Solutions LLC 12
  • 13. Production Scale is a Critical Issue TDG/9-16 Borealis Technology Solutions LLC 13
  • 14. For Organic Products, Cost of Carbon is Critical Material Price Wt% Carbon Contained Carbon Price, $/KgMarket Price $/Kg Crude Oil $50/bbl 0.37 84 (avg.) 0.44 Methane (as NG) $3/MSCF 0.15 74.8 0.20 Ethane $200/MT 0.20 79.9 0.25 Ethylene (USGC) $500/MT 0.50 85.6 0.58 Starch $0.15/lb 0.33 44.4 0.74 #11 Sugar (world) $0.15/lb 0.33 42.1 0.78 #16 Sugar (U.S.) $0.30/lb 0.66 42.1 1.57 TDG/9-16 Borealis Technology Solutions LLC 14
  • 15. Equivalent Carbon Prices TDG/9-16 Borealis Technology Solutions LLC 15
  • 16. Location, Location, Location Source: http://sugarreform.org/wp-content/uploads/2011/07/Wholesale-refined-sugar-prices-US-vs-world-1-10-13.png=3y TDG/9-16 Borealis Technology Solutions LLC 16
  • 17. Are Bio-Based Routes to Polymers Economically Viable? Example: Polyethylene from sugar • Dow/Crystalsev JV in Brazil Fermentation: C6H12O6 → 2 C2H5OH + 2 CO2 Dehydration: C2H5OH → C2H4 + H20 Polymerization: n C2H4 → (C2H4)n Thermodynamics for monomer production are favorable: Glucose → Ethanol → Ethylene ΔGo = -99.6 kJ/mole TDG/9-16 Borealis Technology Solutions LLC 17
  • 18. Carbon Yield Isn’t Always a Pretty Picture, However Process Route Typical Carbon Yield, % Equivalent Carbon Cost, $/Kg Ethane → Ethylene 84 0.30 Glucose → Ethanol → Ethylene 47 1.70 • Byproducts of ethane dehydrogenation include valuable H2 & hydrocarbons • Byproducts of fermentation route include wastewater and CO2 Biomass-based processes typically lose a significant amount of carbon as CO2 Carbon efficiency of bio-based feedstocks is typically better for manufacture of oxygenated products than hydrocarbons TDG/9-16 Borealis Technology Solutions LLC 18
  • 19. Are There Better Opportunities for Bio-Based Products? • Example: Avantium’s process to make polyethylene furanoate (PET replacement) Source: https://www.avantium.com/yxy/yxy-technology/ Subject of Avantium/BASF joint venture (https://www.basf.com/en/company/news-and-media/news-releases/2016/03/p-16-153.html) TDG/9-16 Borealis Technology Solutions LLC 19
  • 20. What are the Relative Costs of PEF and PET? • Need to know: • What is the target production rate? • What would a commercial process look like? • What raw materials and how much of them are needed? • From this information, we need to estimate: • Capital cost to build the production facility • Cost of raw materials • Cost to operate the facility, including labor, utilities, waste disposal, maintenance, overhead, taxes, and insurance • Sources of process information • Avantium web site • Avantium patents & published patent applications • Publications on FDCA & PEF synthesis TDG/9-16 Borealis Technology Solutions LLC 20
  • 21. Analysis Strategy • Polymerization costs likely similar to PET process • Key comparison is cost of manufacture of FDCA vs. terephthalic acid • Utilize available information to estimate FDCA cost of manufacture • Basis for Analysis: • 350 kta FDCA + esters capacity • Fructose is the primary feedstock • 70% molar yield of MMF/HMF from fructose assumed • 85% molar yield of FDCA + esters from MMF/HMF assumed (60% overall yield from fructose) • 95% recycle of solvents and catalysts assumed • Methyl levulinate & furfural byproducts credited at $1.00/Kg each TDG/9-16 Borealis Technology Solutions LLC 21
  • 22. Avantium FDCA Process Block Flow Diagram HMF/MMF Synthesis, Reference US 2013/0324708 A1 TDG/9-16 Borealis Technology Solutions LLC 22
  • 23. Avantium FDCA Process Block Flow Diagram FDCA from MMF/HMF, Reference US 8,865,921 B2 & related TDG/9-16 Borealis Technology Solutions LLC 23 MMF/HMF HOAc Water Batch Reactor Air NaBr Co(OAc)2 Mn(OAc)2 Catalyst Prep Separation Separation Separation MeOH Aq. HOAc/catalyst FDCA/esters Purification Air/CO2
  • 24. How do we Estimate the Capital Cost of a Conceptual Plant? • Complexity factor (step counting) methods • Correlation between number of “major operating steps”, plant capacity, and operating conditions and capital cost • Factored cost estimates • Specify major equipment (type, size, material of construction) and multiply cost by factors representing installation, construction, engineering, etc. • Capital cost is typically ~6X purchased cost of major equipment • Process simulation-based capital cost estimates • Example: Aspen process simulation and cost estimation software TDG/9-16 Borealis Technology Solutions LLC 24
  • 25. FDCA Process Capital Cost Estimation What do you do when you have little information to go on? • Example methodology: Complexity factor cost estimation method of Bridgewater as modified by G.J. Petley • G. J. Petley, A method for Estimating the Capital Cost of Chemical Process Plants – Fuzzy Matching, Ph.D. thesis, Loughborough University, U.K., 1997. ISBL Capital Cost (2016 $US) = 5010 * N * (Q/s)0.586 Where N = number of major process steps Q = production capacity, MTA s = wt. ratio of reactor product:total feed • Factors used: • Number of major process steps: 5 for MMF/HMF synthesis, 6 for MMF/HMF conversion to FDCA/esters • Production rate, throughput & yields as per analysis bases • Results: • Total ISBL capital = $305MM ($0.87/Kg FDCA+esters/yr) • Total fixed capital = $460MM TDG/9-16 Borealis Technology Solutions LLC 25
  • 26. Raw Material Costs • Raw material requirements are estimated based on Avantium patent literature Component Moles/mole Fructose feed Kg/Kg FDCA+esters Price, $/Kg Total Cost, $/Kg FDCA+esters Fructose 1.0 1.92 1.00 1.92 Methanol 1.4 0.6 0.38 0.23 H2SO4 Neg. 0 Furfural 0.03 0.03 1.00 (0.03) Methyl levulinate 0.1 0.15 1.00 (0.15) HOAc 0.3 0.2 0.55 0.11 Catalyst 0.0051 $11.39/mole 0.034 Total Raw Material Cost 2.11 TDG/9-16 Borealis Technology Solutions LLC 26
  • 27. Operating Costs • Labor • 4 operators/shift + 2 for MMF/HMF @ $75,000 each • 6 operators/shift + 3 for FDCA/esters @ $75,000 each • 4 salary total for both operations @ $120,000 each • Net yearly cost = $3.9MM = $0.01/Kg FDCA+esters • Utilities & waste treatment • Estimated as 4% of unit direct fixed capital (ISBL capital) • $0.035/Kg FDCA+esters • Total operating costs = $0.045/Kg TDG/9-16 Borealis Technology Solutions LLC 27
  • 28. Other Fixed Costs • Typically estimated as percentages of direct fixed capital for early stage cost estimates: Cost Element % Unit direct fixed capital $/Kg FDCA+esters Overhead 4 0.035 Maintenance 6 0.052 Taxes & insurance 2 0.017 Depreciation 10% ISBL + 5% OSBL 0.109 Total fixed costs 0.21 TDG/9-16 Borealis Technology Solutions LLC 28
  • 29. FDCA Cost of Manufacture Summary • Note that these numbers have wide error bars Cost Item $/Kg FDCA+esters Raw materials 2.11 Operating costs 0.05 Fixed costs 0.21 Total cost of manufacture 2.37 TDG/9-16 Borealis Technology Solutions LLC 29 Compare to long-term price of purified terephthalic acid of <$1/Kg
  • 30. Dealing with Uncertainty • Early-stage cost estimates typically involve lots of assumptions • Experience tells us that final plant construction costs can easily be 2X early stage estimates • Lab results do not necessarily mirror plant results • Sensitivity analysis is used to assess the impact of different variables on cost • Simple: percent changes in specific variables • More complex: Monte Carlo methods (probability function instead of % changes) TDG/9-16 Borealis Technology Solutions LLC 30
  • 31. Sensitivity Analysis of FDCA Cost Estimate Case Est. FDCA Cost of Manufacture, $/Kg % Change from Base Case Base 2.37 0 Capital cost +50% 2.47 +4 Capital cost +100% 2.58 +9 Raw materials cost -25% 1.84 -22 Raw materials cost -50% 1.32 -44 This sends a clear message: R&D needs to concentrate on identification of a cheaper feedstock TDG/9-16 Borealis Technology Solutions LLC 31
  • 32. Alternative Carbohydrates Carbohydrate Source Price, $/Kg Fructose 1.00 HFCS-42 0.91 Glucose syrup 0.85 Sucrose (world price) 0.33 Starch 0.33 Best case: sucrose as carbohydrate source (10% yield reduction, however) • Unit capital increases to $0.97/Kg FDCA + esters • Raw material cost decreases to $1.41/Kg FDCA + esters • Estimated cost of manufacture decreases to $1.70/Kg FDCA + esters TDG/9-16 Borealis Technology Solutions LLC 32
  • 33. Is Biomass a Cheaper Source of Carbohydrates? • Green wood chips @ $40/ton • 40% moisture – need to dry • 30% cellulose – convertible to 6-carbon sugars • 12 % hemicellulose – convertible to 5-carbon sugars • 18% lignin – hard to utilize • Need to convert cellulosic components to useful compounds • Enzyme hydrolysis – expensive enzymes • Chemical hydrolysis – cheap acid (H2SO4) but expensive equipment • Ammonia Fiber Expansion, Steam explosion – high operating expenses • Cost of sugars from biomass appears to be comparable to cane sugar (Lux Research, 2013) • Feedstock cost is a major factor • Must factor in capital investment for biomass processing TDG/9-16 Borealis Technology Solutions LLC 33
  • 34. So Where Do We Stand? • The two cases examined here (bio-PE & PEF) don’t appear to be cost competitive with conventional PE & PET • Customers rarely pay a substantial premium for “green” products • Successful commercialization of renewable feedstock-based processes will require careful selection of products and raw materials • Limit number of process steps and reactor dilution to limit plant capital cost • Similar C:O ratios in product and feedstock can help limit carbon loss as CO2 • Early-stage technoeconomic analysis is a powerful tool in new process development • Limits resources spent on opportunities with low probability of success • Guides R&D and resource allocation to focus on most important cost variables TDG/9-16 Borealis Technology Solutions LLC 34
  • 35. Successful Use of Biomass Feedstock Requires a Confluence of Positive Factors TDG/9-16 Borealis Technology Solutions LLC 35 Acceptable Feedstock Cost Feedstock Processability into Viable Products Product Demand
  • 36. Part II: Development of advanced battery technology to enable future societal paradigms Vehicle electrification and grid-scale electrical energy storage TDG/9-16 Borealis Technology Solutions LLC 36
  • 37. Energy Storage & Transportation Was a Cumbersome Task for Many Years TDG/9-16 Borealis Technology Solutions LLC 37 Animals & steam engines were the main methods of converting a fuel to useful work
  • 38. Electricity is an efficient, clean energy source but transportation has also been difficult . . . • Wire transmission requires being tethered to a current source • Batteries freed us from this but early batteries were rather cumbersome and unreliable TDG/9-16 Borealis Technology Solutions LLC 38 Plante, 1859: Lead-acid battery https://upload.wikimedia.org/wikipedia/commons/c/c0/Plante_lead_acid_cell.jpg Volta, 1799: Silver-zinc “pile” https://de.wikipedia.org/wiki/Voltasche_S%C3%A4ule#/media/File:Pila_di_Volta_01.jpg Edison, 1901: Nickel-iron battery http://ichef.bbci.co.uk/news/304/media/images/61299000/jpg/_61299222_008972010-1.jpg
  • 39. But just as with synthetic polymers, hydrocarbons became the preferred fuel for vehicles early in the 20th century . . . • More energy-dense than batteries • Gasoline: 46.4 MJ/Kg • Edison’s Ni-Fe battery: 0.072 MJ/Kg • Rapid improvement in combustion engines & vehicle technology around the beginning of the 20th century • Could transport gasoline by truck or train to remote locations not served by electricity at the time TDG/9-16 Borealis Technology Solutions LLC 39
  • 40. And the few devices requiring batteries weren’t very demanding. . . TDG/9-16 Borealis Technology Solutions LLC 40 Flashlights “Portable” Radios https://en.wikipedia.org/wiki/Radio_receiver#/media/File:Edwin_Armstrong_ wife_and_portable_superhet_radio.jpg http://www.wordcraft.net/flashlitestemp/09127otbuggcandle.jpg And cameras were mostly mechanical https://upload.wikimedia.org/wikipedia/commons/2/26/Hawkeye_brownie.JPG
  • 41. Advances in the mid-1900’s mostly involved improved Ni-Cd rechargeable batteries and miniature primary batteries TDG/9-16 Borealis Technology Solutions LLC 41 https://pbs.twimg.com/media/CLuXnqQVAAATFzM.jpg Cordless Drills http://i.kinja-img.com/gawker-media/image/upload/s--waSC8JJM-- /182he57oi6vrijpg.jpg Cordless Phones http://www.relic-watches.com/uploads/watches/10/160490138695-1.jpg Electric Watches
  • 42. The first cell phones were extremely bulky and electric mobility was limited mostly to small vehicles not much bigger than golf carts TDG/9-16 Borealis Technology Solutions LLC 42 http://cdn2.knowyourmobile.com/sites/knowyourmobilecom/files/3/11/marty_cooper.jpg https://s-media-cache-ak0.pinimg.com/236x/96/42/4c/96424cc9550337164b68104aa46cbc1d.jpg
  • 43. But in the late 20th century everything changed . . . TDG/9-16 Borealis Technology Solutions LLC 43 http://www.sonyenergy-devices.co.jp/en/keyword/images/img_keyword_01.jpg 1991: First Commercial Li-Ion Battery by Sony http://cdn.shopify.com/s/files/1/0257/3165/products/dfpz40407_grande.jpeg?v=1454544577 1989: First commercial nickel-metal hydride battery (Ovonic)
  • 44. This enabled dramatic advances in devices powered by portable energy sources TDG/9-16 Borealis Technology Solutions LLC 44 http://www.oldcomputers.net/pics/osborne1.jpg http://images.clipartpanda.com/laptop-computer-images- laptop-and-netbook-computers-5131.jpg http://media.graytvinc.com/images/smartphone13.jpg http://images.businessfinancenews.com/bfn/960-does-tesla-motors- inc-need-to-worry-from-aston-martin-faraday-future-tie-up.jpg
  • 45. Li-Ion Batteries Have Taken Over the Global non-SLI Rechargeable Battery Market TDG/9-16 Borealis Technology Solutions LLC 45 Source: Avicenne, 2016
  • 46. What’s so Special About Lithium-Ion Batteries? TDG/9-16 Borealis Technology Solutions LLC 46 https://static-content.springer.com/image/prt%3A978-1-4419-0851-3%2F2/MediaObjects/978-1-4419-0851-3_2_Part_Fig1-497_HTML.gif
  • 47. What’s Inside a Lithium-Ion Battery? TDG/9-16 Borealis Technology Solutions LLC 47 2LiCoO2 + 6C charge discharge 2Li0.5CoO2 + LiC6 Kang Xu, Chem. Rev. 2004 Separator Anode current collector: Copper, ~12-16 microns thick Anode: 90-95% active material, 3-5% conductive carbon, 3-5% binder, 25-30% porous, 25-90 microns thick depending on intended battery characteristics Separator: Typically microporous polyolefin, 20-25 microns thick, 40-50% porous Cathode: up to 95% active material, remainder conductive carbon + binder, 25-30% porous, 30-100 microns thick depending on battery characteristics Cathode current collector: Aluminum, ~12-16 microns thick
  • 48. Li+ Ion Movement During Charge & Discharge TDG/9-16 Borealis Technology Solutions LLC 48
  • 49. Li-Ion Batteries Utilize Intercalation Electrochemistry TDG/9-16 Borealis Technology Solutions LLC 49 Desired Cathode Reactions: LiCo+3O2 ↔ Li0.5Co0.5 +3Co0.5 +4O2 + 0.5 Li+ + 0.5 e- Desired Anode Reactions: Li+ + e- + C6 ↔ C6 -0.17Li+ (Note: there is some disagreement in the literature whether Li+ completely follows classical intercalation chemistry as shown or whether some electron transfer to Li+ occurs) Undesired Anode Reaction: Li+ + e- + C6 ↔ C6 + Li (Li metal deposition on C surface) Scherson, ECS Interface, 2006
  • 50. Battery Construction TDG/9-16 Borealis Technology Solutions LLC 50 Coin or Button Cell Cylindrical or Wound Cell Prismatic Cell Laminate or Pouch Cell
  • 51. Cathode Materials Determine Cell Characteristics TDG/9-16 Borealis Technology Solutions LLC 51 • Layered metal oxides LiCoO2, Li(Ni,Co,Al)O2, Li(Ni,Mn,Co)O2 • Good capacity & rate capability, but tend to be expensive and can react violently with electrolytes at high temperatures • Single phase materials (LixMO2) = sloping voltage profiles • Olivines LiFePO4, LiMnPO4, LiNiPO4, etc. • Can have excellent rate capability & low cost, but need C-coating, nano-size, doping to work well; some have low voltage (thus low energy density) • 2-phase materials (MPO4/LiMPO4) = flat voltage profiles • Manganates LiMn2O4 • Good rate capability & low cost, but stability is an issue and capacity is relatively low
  • 52. Layered Metal Oxides Are Used in High Specific Energy Batteries TDG/9-16 Borealis Technology Solutions LLC 52
  • 53. Technology Advances & Market Growth Have Resulted in Dramatic Price Declines TDG/9-16 Borealis Technology Solutions LLC 53 Source: Avicenne, 2016
  • 54. So Why Don’t We Have Affordable EVs? TDG/9-16 Borealis Technology Solutions LLC 54
  • 55. Pathways to Higher Energy Density and Lower Cost • Higher capacity/higher voltage cathode materials • “Li-rich” metal oxides – xLiMO2 .(1- x)Li2MnO3 where M = Ni, Co, Mn • Lifetime, capacity fade are key development challenges • Higher capacity anodes • Alloy anodes such as Si or Sn • Li metal • Degradation, morphological stability are key development challenges TDG/9-16 Borealis Technology Solutions LLC 55
  • 56. “Beyond Li-Ion” Batteries – Li/air & Li/S TDG/9-16 Borealis Technology Solutions LLC 56 http://www.nature.com/ncomms/journal/v4/n5/images/ncomms2855-f6.jpg https://upload.wikimedia.org/wikipedia/commons/e/e4/Li-air-charge-discharge.jpg http://www.frontiersin.org/files/Articles/110133/fenrg-03-00017-HTML/image_m/fenrg-03-00017-g001.jpg
  • 57. Li/Air & Li/S Batteries • Very high theoretical specific energy • Li/air – 3400 Wh/Kg • Li/S – 2680 Wh/Kg • But practical volumetric energy density may not exceed that of the best Li-ion batteries • Need excess Li to account for coulometric efficiency <100% • Cathode structures are porous with high carbon content • Poor voltage efficiency for Li/air • Air contaminants can impair Li/air performance • Cycle life has been an issue for both chemistries • OK for niche applications like UAV, but automotive may be difficult to address TDG/9-16 Borealis Technology Solutions LLC 57
  • 58. Multivalent Metal Anodes Have Potential Advantages Over Li TDG/9-16 Borealis Technology Solutions LLC 58
  • 59. Most Multivalent Metal Battery Effort is Directed at Mg • Electrolyte chemistry is more complex than Li • Solutions of simple Mg salts in organic solvents not reversible to Mg plating/stripping • Mg does not form an ion-conducting SEI layer • Limits solvent choices • Intercalation cathodes identified, but possibilities are far fewer than with Li • Many Li intercalation cathodes act as irreversible conversion cathodes with Mg • High charge density of Mg2+ cation limits ion mobility in solid structures and often results in ion trapping TDG/9-16 Borealis Technology Solutions LLC 59
  • 60. Electrolyte Development has Driven Mg Battery R&D TDG/9-16 Borealis Technology Solutions LLC 60
  • 61. Mg Battery Cathode Material Development • Longest cycle life obtained with MgxMo6S8 Chevrel phase materials • High ionic mobility • Low cell voltage (~1.1V) and reversible capacity (~100 mAh/g), however • MgxV2O5 shows improved performance when water is incorporated into the electrolyte or into the cathode material during synthesis • Co-intercalates from electrolyte with Mg2+ • Shields cathode material from high charge density of cation • Capacity increase from 60 mAh/g to ~160 mAh/g when adding water to Mg perchlorate/propylene carbonate reported (L. Yu, X. Zhang, J. Colloid Interfacial Sci., 2004) • Water interaction with anode appears to cause capacity fade and impedance growth, however TDG/9-16 Borealis Technology Solutions LLC 61
  • 62. Polyanion Cathode Materials Have Shown Promise TDG/9-16 Borealis Technology Solutions LLC 62 MgFeSiO4 • Reversible capacity >300 mAh/g @ 2.4V demonstrated in Mg(TFSI)2-AN electrolyte • Capacity, voltage lower in Mg(TFSI)2- triglyme (<120 mAh/g, <1.5V midpoint) MgMnSiO4 • Capacity up to ~300 mAh/g @ 1.65V demonstrated (NuLi et al, Chem. Commun., 2010) Orikasa, Y. et al. High energy density rechargeable magnesium battery using earth-abundant and non-toxic elements. Sci. Rep. 4, 5622; DOI:10.1038/ srep05622 (2014).
  • 63. Can Mg-based batteries compete with Li-ion? TDG/9-16 Borealis Technology Solutions LLC 63 400 Wh/Kg active material (comparable to graphite/NCA) 700 Wh/Kg active material (comparable to Si/Li-rich) Active material energy density, 2X theoretical Mg anode capacity Mg/S Mg/CuF2 Mg/MnO2 Mg/AgCl Mg system active material ED estimated @ 2/3 theoretical cathode capacity, discharge voltage 0.75 V below std. potential Mg/MgMnSiO4
  • 64. Commercial Developments in Mg Batteries TDG/9-16 Borealis Technology Solutions LLC 64 • Pellion Technologies • Prototype cells up to 2 Ah, 1000 Wh/L claimed • US 9,240,612 (2016) claims cathode material with interlayer spacing at least 4.8Å and anatase & rutile TiO2, TiS2, FeS2, MoS2, Mo6S8 & combinations • US 9,172,111 (2015) claims layered crystalline cathode materials with interlayer spacing modified by insertion of organic compounds to improve Mg2+ transport • Sony • Occasional publications & presentations, press reports claim development of Li/S & Mg/S batteries with 2020 introduction & 1000 Wh/L goals (http://techon.nikkeibp.co.jp/atclen/news_en/15mk/121800252/) • Toyota • Frequent technical publications & presentations; exploring multiple EV power source technologies
  • 65. Stationary Energy Storage Grid stabilization, solar & wind energy storage, load leveling, etc. • Small capacity – lead-acid, lithium-ion batteries • Storage of energy from rooftop solar, small wind turbines, or cheap night time grid energy • Uninterruptable power supplies • Intermediate capacity – lithium-ion batteries • Grid stabilization • Smart micro-grids • Large capacity – Na-S, redox flow batteries • Grid-scale energy storage for renewable energy, reserve capacity, etc. • Critical Factor is life cycle cost • Initial system cost • Maintenance • Round-trip efficiency • Lifetime TDG/9-16 Borealis Technology Solutions LLC 65
  • 66. Redox Flow Batteries for Stationary Energy Storage TDG/9-16 Borealis Technology Solutions LLC 66 • Flow batteries decouple energy & power • Improved mass transfer • Cost issues • Cell stack cost is proportional to area • Increased power density = lower cell stack cost due to reduced electrode and membrane area • Electrolyte cost is dependent on cost of active materials & system efficiency • Abundant, low-cost materials preferable • Flow system cost dependent on size, materials of construction • Higher electrolyte concentration = more compact flow system • Electrolyte corrosivity influences flow system cost + - V5+ /V4+ V3+ /V2+
  • 67. Innovations in Flow Battery Technology TDG/9-16 Borealis Technology Solutions LLC 67 0 50 100 150 200 250 300 350 400 0 100 200 300 400 500 600 700 800 Est.CellStack+ElectrolyteCost,$/kWh Power Density, mW/cm2 Conventional VRB CWRU Fe/Fe WattJoule VRB 1 MW/4 MWH Systems PNNL VRB Near term OptimisticPNNL Fe/V Near term Optimistic
  • 68. Novel Approaches to Redox Flow Batteries TDG/9-16 Borealis Technology Solutions LLC 68 Technology Goal(s) Innovation(s) Organization 5-10X increased power density • Improved fluid dynamics & components • VRB @ ~1300 mW/cm2 United Technologies Research Center Low cost active materials & components • Quinone redox chemistry • Rapid electrode kinetics with inexpensive current collectors Harvard University Electrolyte = active material • Ionic liquid electrolyte & active material • Flexible chemistry Sandia National Lab Chemical process design principles can yield improvements in flow battery technology Process intensification – increased power density and electrolyte concentration Process simplification – reduced capital and operating cost
  • 69. Where it the Battery Field Heading? • Li-ion will continue to be the battery technology of choice for vehicle electrification • Incremental improvements (higher capacity & voltage cathodes, improved electrolytes, migration to alloy anodes) will push technology to acceptable cost & energy density • Multivalent metal batteries may provide a longer-term pathway to step- change improvements • Stationary energy storage markets will be served by a variety of battery chemistries • Li-ion seems to have the inside track for high value, low capacity applications like grid stabilization & distributed wind & solar energy storage • More flexible redox flow batteries may be used in larger-scale grid storage applications • Need to reduce complexity & cost TDG/9-16 Borealis Technology Solutions LLC 69
  • 70. A Few Closing Words “Engineers create the world that never was.” Theodore von Kármán, co-founder of NASA Jet Propulsion Lab • Me-too products & technology won’t achieve this • Hard to compete with entrenched technology without a significant advantage • Incremental improvements only accomplish this if the target is already close • Virtually all work on Li-ion battery technology since 1991 has been incremental • Revolutionary advances often come about from seeing the world from a different perspective • Looking at what everyone else has looked at and seeing what no one else has seen TDG/9-16 Borealis Technology Solutions LLC 70
  • 71. Upcoming Events • Key Challenges Facing Rechargeable Magnesium Batteries: A Peek Outside the Box • Invited presentation, The Electrochemical Society PRiME 2016, Honolulu HI, Oct. 4, 2016 • Technoeconomic Analysis of Battery Material Development and Production • Tutorial, 34th International Battery Seminar & Exhibition, Ft. Lauderdale FL, March 20-23, 2017 • Cost Reduction Strategies for Electric Vehicle Battery Packs • Workshop, Advanced Automotive Batteries 2017, TBD TDG/9-16 Borealis Technology Solutions LLC 71