Co
Lifecycle Analysis for Lithium-Ion Battery Production and Recycling Metal Kokkola November 17, 2010 Linda Gaines Center for Transportation Research Argonne National Laboratory
Outline of Presentation WHO AM I? WHY WAS THIS WORK DONE? WHAT DID WE STUDY? – Material Demand and Supply – Battery Lifecycle Analysis – Battery Recycling Processes
I am a Systems Analyst at the Argonne Center for Transportation Research Education: Ph.D. (Physics, Columbia), B.A. (Chemistry and Physics, Harvard)
Main responsibility: Studying ways to reduce petroleum use and emissions from transportation Some Topics I’ve Studied: Plug-In Hybrid Vehicles Idling of Trucks, Busses, Trains, and Cars Hydrogen and Biofuels Lightweight Vehicles Recycling of Tires, Cars, Batteries, Packaging Energy and Material Flows in the Copper Industry, Petroleum Refining, Plastics Future Treaties Coal vs. Nuclear Power
What does a systems analyst do? Define a problem Identify important factors Choose decision criteria – – – –
Cost Energy use Reducing oil imports Environmental impacts
Gather and interpret facts Report results in scientific way – Be convincing – Make idiot-proof – May be politically incorrect 4
Argonne’s Transportation Technology R&D Center
5
Argonne’s vision is to lead the world in providing scientific and engineering solutions to the grand challenges of our time: plentiful and safe energy, a healthy environment, economic competitiveness and a secure nation.
6
Our work is funded by the Office of Vehicle Technologies
The US Department of Energy's goals are designed to deliver results along five strategic themes Energy Security – Promoting energy security through reliable, clean, and affordable energy
Nuclear Security – Ensuring nuclear security
Scientific Discovery and Innovation – Strengthening U.S. scientific discovery, economic competitiveness, and improving quality of life through innovations in science and technology
Environmental Responsibility – Protecting the environment by providing a responsible resolution to the environmental legacy of nuclear weapons production
Management Excellence – Enabling the mission through sound management
DOE laboratories like Argonne do much of the work.
WHY WAS THIS WORK DONE?
We don’t want to trade one crisis for another! Insure against material shortages Check for unforeseen environmental impacts
10
MATERIAL DEMAND AND SUPPLY
11
We answer these questions to address material supply issues How many electric-drive vehicles will be sold in the US and world-wide?
What kind of batteries might they use? – How much lithium would each battery use?
How much lithium would be needed each year? – How much difference can recycling make?
How does the demand compare to the available resources? Are there possible constraints on other key material supplies? – Will there be enough cobalt? Nickel? Manganese?
12
We chose an optimistic market penetration scenario 35
Electric Vehicle Market Shares
30
HEV PHEV20
25 % of sales
PHEV40
20
EV
15 10 5 0 2000
2010
2020
2030
2040
2050
Source: Multipath Study Phase 1, Maximum Electric Scenario, http://www1.eere.energy.gov/ba/pba/pdfs/multipath_ppt.pdf 13
Then we looked at battery composition System
NCA Graphite
LFP (phosphate) Graphite
MS (spinel) Graphite
MS TiO
LiNi0.8Co0.15Al0.05O2 LiFePO4
LiMn2O4
LiMn2O4
Graphite
Graphite
Li4Ti5O12
Electrodes Positive (cathode)
Negative (anode)
Graphite
We considered four battery chemistries All contain lithium in cathode One uses lithium in anode as well
Electrolyte contains lithium salt (LiPF6) in solution 14
We calculated lithium required per battery pack
Total is sum of Li from cathode, electrolyte, and anode (for titanate)
Battery Type Vehicle range (mi) at 300 Wh/mile Li in cathode (kg)
NCA-G
4
LFP-G
20
40
100
4
20
40
0.34 1.4
2.8
6.9 0.20 0.80 1.6
LMO-G
100
4
20
40
LMO-TiO
100
4
20
40
100
4.0 0.15 0.59 1.18 3.0 0.29 1.2
2.3
5.8
Li in electrolyte (kg) 0.04 0.10 0.20 0.55 0.045 0.14 0.26 0.66 0.03 0.09 0.17 0.43 0.05 0.17 0.34 0.85 Li in anode (kg) 0 0 Total Li in battery pack (kg) 0.37 1.5
0
3.0
0
0
0
0
7.4 0.24 0.93 1.9
0
0
0
0
4.7 0.17 0.67 1.4
0
0.30 1.21 2.4
3.4 0.64 2.5
6.1
5.1 12.7
15
Recycling can drastically reduce virgin lithium demand 60000 Tonnes contained lithium
Effect of recycling
50000
World Production
US Battery Demand
40000
US Consumption Available for recycle
30000
Net virgin material needed
20000 10000 0 1990
2010
2030
2050
A word about battery reuse Reuse takes battery directly back to lower-performance use Nissan will reuse batteries to store energy from PV panels or to store back-up power Reuse delays return of material for recycling and increases peak demand for virgin material – Assumes virgin material would not be used for backup batteries
World demand is highly uncertain Lithium demand per vehicle depends on battery size – What size car? Or is it a bicycle? – What range? Is extra range built in? – EV or PHEV? – Incentives can favor models with lowest impacts Need for new supplies can be substantially reduced by recycling – Rapid early demand growth implies rapid early recovered material echo – Recovered material often ignored in alarmist presentations
18
Recycling with smaller batteries reduces world demand in 2050 from 20X current demand to 4X 500
Metric tons (1000s)
450
World lithium demand
400
Smaller (3X) batteries
350
Big batteries
300
Smaller batteries recycled
250 200 150 100
50 0 2010
2020
2030
2040
2050
IEA assumed 12-18 kWh batteries
19
Batteries make up 25% of lithium use, growing fastest % of 2007 Li Consumption
other 22%
batteries 25%
chemical processing 3% continuous casting 3% ceramics and glass 18%
primary aluminum production 4% air conditioning 6% pharmaceuticals and polymers 7%
lubricating greases 12%
Source: SQM, cited in 2007 USGS Minerals Yearbook
20
Electric vehicle batteries are projected to dominate long-term lithium demand 80 70 60 50
Primary
% 40
Secondary EV
30 20 10 0 2000
2005
2010
2015
2020
Lithium Usage by Battery Type
Source: E.R. Anderson, TRU Group
21
Known Li reserves could meet world demand to 2050 Cumulative demand to 2050 (Contained lithium, 1000 Metric tons)
Large batteries, no recycling
6,474
Smaller batteries, no recycling Smaller batteries, recycling
2,791 1,981 Reserve Estimates
USGS Reserves*
9,900
USGS World Resource*
25,500
Other Reserve Estimates
30,000+
*Revised January 2010 http://minerals.usgs.gov/minerals/pubs/commodity/lithium/mcs-2010-lithi.pdf
Could we be trading one cartel for another?
23
U.S. cobalt use could make dent in reserve base by 2050 Material
Availability (million tons)
Cumulative demand
Percent demanded
Basis
Co
13
1.1
9
World reserve base
Ni
150
6
4
World reserve base
Al
42.7
0.2
0.5
US capacity
Iron/steel
1320
4
0.3
P
50,000
2.3
~0
US production US phosphate rock production
Mn
5200
6.1
0.12
World reserve base
Ti
5000
7.4
0.15
World reserve base
24
Lithium-ion batteries can provide a bridge to the future Lithium demand can be met, even with rapid growth of EVs – Scenarios extended to 2050 – Better batteries, additional exploration could extend supply – New technologies are likely in the next 40 years
Co supply and price will reduce importance of NCA-G chemistry Recycling must be an important element of material supply – Economics – Regulations
Material recovered must be maximized
1 GB chip, 20 years ago and now 25
Warnings of disaster are often premature 1885: The US Geological Survey announces there is "little or no chance" of oil being discovered in California, and a few years later they say the same about Kansas and Texas. 1939: The US Department of the Interior says American oil supplies will last only another 13 years. 1949: The Secretary of the Interior says the end of US oil supplies is in sight. 1974: Having learned nothing from its earlier erroneous claims, the US Geological Survey advises that the US has only a 10-year supply of natural gas. 1969: Environmentalist Nigel Calder warns, "The threat of a new ice age must now stand alongside nuclear war as a likely source of wholesale death and misery for mankind". CC Wallen of the World Meteorological Organization says, "The cooling since 1940 has been large enough and consistent enough that it will not soon be reversed". 1970: Senator Gaylord Nelson warns that by 1995 "somewhere between 75 and 85% of all the species of living animals will be extinct". 1972: A report for the Club of Rome warns the world will run out of gold by 1981, mercury and silver by 1985, tin by 1987 and petroleum, copper, lead and natural gas by 1992.
Sir John Houghton (Scientific Assessment for IPCC, Chairman and Co-Chairman 1988-2002.) said, "Unless we announce disasters no one will listen." Source: Dr Phillip Bratby, Testimony to the UK Parliament. http://snipurl.com/6xytl.
26
BATTERY LIFECYCLE ANALYSIS
Lifecycle analysis compares all process impacts LCA addresses the potential environmental impacts throughout a product's life cycle from raw material acquisition through production, use, end-of-life treatment, recycling, and final disposal if any.
28
METROPOLIS City Limits
Population 23,443 Elevation 1357’
TOTAL
24,800
There is no correct way to aggregate impacts into a single “score.”
30
The bulk of battery materials are well characterized; we are now examining the others Material
Mass (kg)
Mass %
7.7
18.5
Positive active material (LiNi0.8Co0.15Al0.05O2) Lithium* Nickel Cobalt Aluminum Oxygen Graphite and carbon Binder Electrolyte solvent Copper parts Aluminum parts Aluminum casing Plastics Thermal insulation Electronic parts Total battery mass * includes lithium salts used in electrolyte
0.6 3.8 0.7 0.11 2.6 5.9 1.2 4.1 8.8 6.0 4.1 3.3 0.2 0.3 41.7
1.5 9.0 1.7 0.3 6.2 14.1 2.8 9.9 21.0 14.4 9.9 8.0 0.5 0.7 100
We get lithium carbonate from brine or minerals Extraction from brine is slow, not energy-intensive – Use of NaOH or Na2CO3 can contaminate the product
Recovery from minerals includes calcination – More energy intensive, uses fossil fuel
32
Production of electrode materials uses fossil fuels •Cathode LiCoO2 produced from Li2CO3 and Co3O4
•Co3O4 comes from driving SO2 off the sulfate, or as byproduct of electroplating •Water needed for waste treatment, washing, filtration •Sulfuric acid is generated
•Reaction requires 800-850˚C for 6 hours •LiFePO4 is made from Li2CO3 and FePO4 • LiMn2O4 is made from Li2CO3 and MnO2 • Li (NixCoyMnz)O2 or spinel is from Li2CO3 and (NixCoyMnz)CO3 •Ammonia and sulfates must be separated from waste
•LiOH can also be used, but is harder to handle •Anode carbon from pitch requires 2700˚C for full graphitization
34
Although vehicle cycle is a fraction of total energy and CO2 impact, and the battery a fraction of that, battery materials responsible for 20% lifecycle SOx 4,000
120
Lithium
Vehicle Cycle of Battery
Rest of Battery
3,500 100
2,500
Pump-toWheels
2,000
Plastics Nickel
80
Copper
Graphite/Carbon
60 Aluminum
Well-to-Pump Battery Assembly and Testing
1,500 40
1,000 20
500
0
PHEV - Li-Ion Battery
0
PHEV 20 CD Mode US Average Grid
Btu/mile
3,000
Btu/mile
Vehicle Cycle of Car minus Battery
BATTERY RECYCLING PROCESSES
36
Recycling can recover materials at different production stages It is difficult to recover all materials One possible goal is to recover battery-grade materials – More energy saved if more steps avoided
The other extreme recovers basic building blocks There are pros and cons of different approaches LCA identifies “greenest” processes – May not be most economical
37
Recycling reduces lifecycle burdens
38
Smelting processes are operating now These can take just about any input, high volume High-temperature required – Organics are burned for process energy
Valuable metals (Co and Ni) recovered and sent to refining – Suitable for any use
Volatiles burned at high-T Li, Al go to slag – Could be recovered
3
Mining and smelting energy for cobalt is saved
Virgin cobalt Recycled cobalt
70% of cobalt production energy saved; sulfur emissions avoided Impacts from lithium, graphite, separator, electrolyte not changed Credit is taken for combustion of organics and oxidation of Al
Toxco Ohio plant will used improved process to recover lithium
4
Future recycling could reuse materials in batteries Requires as uniform feed as possible Components are separated – Ideal is to retain valuable material structure
All active materials and metals can be recovered – Purify/reactivate components if necessary – Ideal is to use product in new automotive batteries (will be largest market) – Separator is unlikely to be usable, as form cannot be retained
Low-temperature process, low energy requirement Energy and processing to produce battery-grade material from raw materials is saved Costs lower than virgin materials Does not require large volume
42
Direct recycling recovers battery grade materials Low energy process – Off the shelf equipment set – Leaching with recyclable solvents – Separation based upon surface and bulk property differences
Waste streams – Water vapor – Packaging materials/separators – Permitting not a problem as no slag, wastewater, or air emissions
Patent portfolio being expanded
Battery/Cells/Modules
Module Breaking
Separation of Cells from Module Components Slitting of Cells
Leaching
Recovered EC/DEC + LiP F 6
Shred Extracted Cells
Remove Iron – Magnetic Separation
Screen
Physical Separation
Met al Oxides, e.g. Li 1 - x CoO 2
Iron
Separators, Grids
Carbon (Li)
Recovery of battery-grade materials avoids all active material synthesis steps
Energy Use: Extraction 4.4 kWh/kg Heat Treatment 0.4 Wh/kg
Auxiliaries 0.1 kWh/kg Total 5.0 kWh/kg
44
Plastics can be made into C-nanotubes Argonne has developed a process for plastic bags – Vilas Pol is developer – Process could be used for battery plastics
React with cobalt acetate catalyst at 700˚ C, cool 3 hours – Recover catalyst when battery recycled
C-nanotube anodes are produced – Now made from petroleum at ~$100/gram
– Recycling process would be cheaper
Argonne solvent extraction process also could be used to recover battery plastics – Could utilize plastic stream from Toxco/Kinsbursky or Eco-Bat
Several strategies could facilitate recycling Standard configuration enables design of recycling equipment Chemistry standardization reduces need for battery sorting
Cell labeling enables sorting Design for disassembly enables material separation
Stay tuned for more results. Thank you! Co-authors: P. Nelson, J. Sullivan, A. Burnham, and I. Belharouak
Work sponsored by DOE Office of Vehicle Technologies Contact me: [email protected]
47
Outline of Presentation WHO AM I? WHY WAS THIS WORK DONE? WHAT DID WE STUDY? – Material Demand and Supply – Battery Lifecycle Analysis – Battery Recycling Processes
I am a Systems Analyst at the Argonne Center for Transportation Research Education: Ph.D. (Physics, Columbia), B.A. (Chemistry and Physics, Harvard)
Main responsibility: Studying ways to reduce petroleum use and emissions from transportation Some Topics I’ve Studied: Plug-In Hybrid Vehicles Idling of Trucks, Busses, Trains, and Cars Hydrogen and Biofuels Lightweight Vehicles Recycling of Tires, Cars, Batteries, Packaging Energy and Material Flows in the Copper Industry, Petroleum Refining, Plastics Future Treaties Coal vs. Nuclear Power
What does a systems analyst do? Define a problem Identify important factors Choose decision criteria – – – –
Cost Energy use Reducing oil imports Environmental impacts
Gather and interpret facts Report results in scientific way – Be convincing – Make idiot-proof – May be politically incorrect 4
Argonne’s Transportation Technology R&D Center
5
Argonne’s vision is to lead the world in providing scientific and engineering solutions to the grand challenges of our time: plentiful and safe energy, a healthy environment, economic competitiveness and a secure nation.
6
Our work is funded by the Office of Vehicle Technologies
The US Department of Energy's goals are designed to deliver results along five strategic themes Energy Security – Promoting energy security through reliable, clean, and affordable energy
Nuclear Security – Ensuring nuclear security
Scientific Discovery and Innovation – Strengthening U.S. scientific discovery, economic competitiveness, and improving quality of life through innovations in science and technology
Environmental Responsibility – Protecting the environment by providing a responsible resolution to the environmental legacy of nuclear weapons production
Management Excellence – Enabling the mission through sound management
DOE laboratories like Argonne do much of the work.
WHY WAS THIS WORK DONE?
We don’t want to trade one crisis for another! Insure against material shortages Check for unforeseen environmental impacts
10
MATERIAL DEMAND AND SUPPLY
11
We answer these questions to address material supply issues How many electric-drive vehicles will be sold in the US and world-wide?
What kind of batteries might they use? – How much lithium would each battery use?
How much lithium would be needed each year? – How much difference can recycling make?
How does the demand compare to the available resources? Are there possible constraints on other key material supplies? – Will there be enough cobalt? Nickel? Manganese?
12
We chose an optimistic market penetration scenario 35
Electric Vehicle Market Shares
30
HEV PHEV20
25 % of sales
PHEV40
20
EV
15 10 5 0 2000
2010
2020
2030
2040
2050
Source: Multipath Study Phase 1, Maximum Electric Scenario, http://www1.eere.energy.gov/ba/pba/pdfs/multipath_ppt.pdf 13
Then we looked at battery composition System
NCA Graphite
LFP (phosphate) Graphite
MS (spinel) Graphite
MS TiO
LiNi0.8Co0.15Al0.05O2 LiFePO4
LiMn2O4
LiMn2O4
Graphite
Graphite
Li4Ti5O12
Electrodes Positive (cathode)
Negative (anode)
Graphite
We considered four battery chemistries All contain lithium in cathode One uses lithium in anode as well
Electrolyte contains lithium salt (LiPF6) in solution 14
We calculated lithium required per battery pack
Total is sum of Li from cathode, electrolyte, and anode (for titanate)
Battery Type Vehicle range (mi) at 300 Wh/mile Li in cathode (kg)
NCA-G
4
LFP-G
20
40
100
4
20
40
0.34 1.4
2.8
6.9 0.20 0.80 1.6
LMO-G
100
4
20
40
LMO-TiO
100
4
20
40
100
4.0 0.15 0.59 1.18 3.0 0.29 1.2
2.3
5.8
Li in electrolyte (kg) 0.04 0.10 0.20 0.55 0.045 0.14 0.26 0.66 0.03 0.09 0.17 0.43 0.05 0.17 0.34 0.85 Li in anode (kg) 0 0 Total Li in battery pack (kg) 0.37 1.5
0
3.0
0
0
0
0
7.4 0.24 0.93 1.9
0
0
0
0
4.7 0.17 0.67 1.4
0
0.30 1.21 2.4
3.4 0.64 2.5
6.1
5.1 12.7
15
Recycling can drastically reduce virgin lithium demand 60000 Tonnes contained lithium
Effect of recycling
50000
World Production
US Battery Demand
40000
US Consumption Available for recycle
30000
Net virgin material needed
20000 10000 0 1990
2010
2030
2050
A word about battery reuse Reuse takes battery directly back to lower-performance use Nissan will reuse batteries to store energy from PV panels or to store back-up power Reuse delays return of material for recycling and increases peak demand for virgin material – Assumes virgin material would not be used for backup batteries
World demand is highly uncertain Lithium demand per vehicle depends on battery size – What size car? Or is it a bicycle? – What range? Is extra range built in? – EV or PHEV? – Incentives can favor models with lowest impacts Need for new supplies can be substantially reduced by recycling – Rapid early demand growth implies rapid early recovered material echo – Recovered material often ignored in alarmist presentations
18
Recycling with smaller batteries reduces world demand in 2050 from 20X current demand to 4X 500
Metric tons (1000s)
450
World lithium demand
400
Smaller (3X) batteries
350
Big batteries
300
Smaller batteries recycled
250 200 150 100
50 0 2010
2020
2030
2040
2050
IEA assumed 12-18 kWh batteries
19
Batteries make up 25% of lithium use, growing fastest % of 2007 Li Consumption
other 22%
batteries 25%
chemical processing 3% continuous casting 3% ceramics and glass 18%
primary aluminum production 4% air conditioning 6% pharmaceuticals and polymers 7%
lubricating greases 12%
Source: SQM, cited in 2007 USGS Minerals Yearbook
20
Electric vehicle batteries are projected to dominate long-term lithium demand 80 70 60 50
Primary
% 40
Secondary EV
30 20 10 0 2000
2005
2010
2015
2020
Lithium Usage by Battery Type
Source: E.R. Anderson, TRU Group
21
Known Li reserves could meet world demand to 2050 Cumulative demand to 2050 (Contained lithium, 1000 Metric tons)
Large batteries, no recycling
6,474
Smaller batteries, no recycling Smaller batteries, recycling
2,791 1,981 Reserve Estimates
USGS Reserves*
9,900
USGS World Resource*
25,500
Other Reserve Estimates
30,000+
*Revised January 2010 http://minerals.usgs.gov/minerals/pubs/commodity/lithium/mcs-2010-lithi.pdf
Could we be trading one cartel for another?
23
U.S. cobalt use could make dent in reserve base by 2050 Material
Availability (million tons)
Cumulative demand
Percent demanded
Basis
Co
13
1.1
9
World reserve base
Ni
150
6
4
World reserve base
Al
42.7
0.2
0.5
US capacity
Iron/steel
1320
4
0.3
P
50,000
2.3
~0
US production US phosphate rock production
Mn
5200
6.1
0.12
World reserve base
Ti
5000
7.4
0.15
World reserve base
24
Lithium-ion batteries can provide a bridge to the future Lithium demand can be met, even with rapid growth of EVs – Scenarios extended to 2050 – Better batteries, additional exploration could extend supply – New technologies are likely in the next 40 years
Co supply and price will reduce importance of NCA-G chemistry Recycling must be an important element of material supply – Economics – Regulations
Material recovered must be maximized
1 GB chip, 20 years ago and now 25
Warnings of disaster are often premature 1885: The US Geological Survey announces there is "little or no chance" of oil being discovered in California, and a few years later they say the same about Kansas and Texas. 1939: The US Department of the Interior says American oil supplies will last only another 13 years. 1949: The Secretary of the Interior says the end of US oil supplies is in sight. 1974: Having learned nothing from its earlier erroneous claims, the US Geological Survey advises that the US has only a 10-year supply of natural gas. 1969: Environmentalist Nigel Calder warns, "The threat of a new ice age must now stand alongside nuclear war as a likely source of wholesale death and misery for mankind". CC Wallen of the World Meteorological Organization says, "The cooling since 1940 has been large enough and consistent enough that it will not soon be reversed". 1970: Senator Gaylord Nelson warns that by 1995 "somewhere between 75 and 85% of all the species of living animals will be extinct". 1972: A report for the Club of Rome warns the world will run out of gold by 1981, mercury and silver by 1985, tin by 1987 and petroleum, copper, lead and natural gas by 1992.
Sir John Houghton (Scientific Assessment for IPCC, Chairman and Co-Chairman 1988-2002.) said, "Unless we announce disasters no one will listen." Source: Dr Phillip Bratby, Testimony to the UK Parliament. http://snipurl.com/6xytl.
26
BATTERY LIFECYCLE ANALYSIS
Lifecycle analysis compares all process impacts LCA addresses the potential environmental impacts throughout a product's life cycle from raw material acquisition through production, use, end-of-life treatment, recycling, and final disposal if any.
28
METROPOLIS City Limits
Population 23,443 Elevation 1357’
TOTAL
24,800
There is no correct way to aggregate impacts into a single “score.”
30
The bulk of battery materials are well characterized; we are now examining the others Material
Mass (kg)
Mass %
7.7
18.5
Positive active material (LiNi0.8Co0.15Al0.05O2) Lithium* Nickel Cobalt Aluminum Oxygen Graphite and carbon Binder Electrolyte solvent Copper parts Aluminum parts Aluminum casing Plastics Thermal insulation Electronic parts Total battery mass * includes lithium salts used in electrolyte
0.6 3.8 0.7 0.11 2.6 5.9 1.2 4.1 8.8 6.0 4.1 3.3 0.2 0.3 41.7
1.5 9.0 1.7 0.3 6.2 14.1 2.8 9.9 21.0 14.4 9.9 8.0 0.5 0.7 100
We get lithium carbonate from brine or minerals Extraction from brine is slow, not energy-intensive – Use of NaOH or Na2CO3 can contaminate the product
Recovery from minerals includes calcination – More energy intensive, uses fossil fuel
32
Production of electrode materials uses fossil fuels •Cathode LiCoO2 produced from Li2CO3 and Co3O4
•Co3O4 comes from driving SO2 off the sulfate, or as byproduct of electroplating •Water needed for waste treatment, washing, filtration •Sulfuric acid is generated
•Reaction requires 800-850˚C for 6 hours •LiFePO4 is made from Li2CO3 and FePO4 • LiMn2O4 is made from Li2CO3 and MnO2 • Li (NixCoyMnz)O2 or spinel is from Li2CO3 and (NixCoyMnz)CO3 •Ammonia and sulfates must be separated from waste
•LiOH can also be used, but is harder to handle •Anode carbon from pitch requires 2700˚C for full graphitization
34
Although vehicle cycle is a fraction of total energy and CO2 impact, and the battery a fraction of that, battery materials responsible for 20% lifecycle SOx 4,000
120
Lithium
Vehicle Cycle of Battery
Rest of Battery
3,500 100
2,500
Pump-toWheels
2,000
Plastics Nickel
80
Copper
Graphite/Carbon
60 Aluminum
Well-to-Pump Battery Assembly and Testing
1,500 40
1,000 20
500
0
PHEV - Li-Ion Battery
0
PHEV 20 CD Mode US Average Grid
Btu/mile
3,000
Btu/mile
Vehicle Cycle of Car minus Battery
BATTERY RECYCLING PROCESSES
36
Recycling can recover materials at different production stages It is difficult to recover all materials One possible goal is to recover battery-grade materials – More energy saved if more steps avoided
The other extreme recovers basic building blocks There are pros and cons of different approaches LCA identifies “greenest” processes – May not be most economical
37
Recycling reduces lifecycle burdens
38
Smelting processes are operating now These can take just about any input, high volume High-temperature required – Organics are burned for process energy
Valuable metals (Co and Ni) recovered and sent to refining – Suitable for any use
Volatiles burned at high-T Li, Al go to slag – Could be recovered
3
Mining and smelting energy for cobalt is saved
Virgin cobalt Recycled cobalt
70% of cobalt production energy saved; sulfur emissions avoided Impacts from lithium, graphite, separator, electrolyte not changed Credit is taken for combustion of organics and oxidation of Al
Toxco Ohio plant will used improved process to recover lithium
4
Future recycling could reuse materials in batteries Requires as uniform feed as possible Components are separated – Ideal is to retain valuable material structure
All active materials and metals can be recovered – Purify/reactivate components if necessary – Ideal is to use product in new automotive batteries (will be largest market) – Separator is unlikely to be usable, as form cannot be retained
Low-temperature process, low energy requirement Energy and processing to produce battery-grade material from raw materials is saved Costs lower than virgin materials Does not require large volume
42
Direct recycling recovers battery grade materials Low energy process – Off the shelf equipment set – Leaching with recyclable solvents – Separation based upon surface and bulk property differences
Waste streams – Water vapor – Packaging materials/separators – Permitting not a problem as no slag, wastewater, or air emissions
Patent portfolio being expanded
Battery/Cells/Modules
Module Breaking
Separation of Cells from Module Components Slitting of Cells
Leaching
Recovered EC/DEC + LiP F 6
Shred Extracted Cells
Remove Iron – Magnetic Separation
Screen
Physical Separation
Met al Oxides, e.g. Li 1 - x CoO 2
Iron
Separators, Grids
Carbon (Li)
Recovery of battery-grade materials avoids all active material synthesis steps
Energy Use: Extraction 4.4 kWh/kg Heat Treatment 0.4 Wh/kg
Auxiliaries 0.1 kWh/kg Total 5.0 kWh/kg
44
Plastics can be made into C-nanotubes Argonne has developed a process for plastic bags – Vilas Pol is developer – Process could be used for battery plastics
React with cobalt acetate catalyst at 700˚ C, cool 3 hours – Recover catalyst when battery recycled
C-nanotube anodes are produced – Now made from petroleum at ~$100/gram
– Recycling process would be cheaper
Argonne solvent extraction process also could be used to recover battery plastics – Could utilize plastic stream from Toxco/Kinsbursky or Eco-Bat
Several strategies could facilitate recycling Standard configuration enables design of recycling equipment Chemistry standardization reduces need for battery sorting
Cell labeling enables sorting Design for disassembly enables material separation
Stay tuned for more results. Thank you! Co-authors: P. Nelson, J. Sullivan, A. Burnham, and I. Belharouak
Work sponsored by DOE Office of Vehicle Technologies Contact me: [email protected]
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