From Lithium Raw Materials to New Enabling Technologies: FMC s Play in Li-ion Battery Industry and Progress Report on Stabilized Lithium Metal Powder (SLMP ) Marina Yakovleva Technical Program Manager FMC Lithium BATTERIES 2010, 12 th EDITION September 29 th October 1 st, 2010
FMC Lithium Summary Lithium Division Producing lithium chemicals since 1942 Producing globally: 5 production sites 600 employees 200 different products to 1,200 Customers Headquartered in Charlotte, NC
FMC Lithium Energy Market Offering Grades of : Li Carbonate Industrial Grade Technical Grade Micronized Technical Grade Battery Grade Micronized Battery Grade Li Hydroxide Technical Grade Purified Battery Quality Grade Li metal Stabilized Lithium Metal Powder (SLMP )
FMC s Commitment to Li-ion Battery R&D Lithium carbonate and hydroxide basic precursors for Li-ion battery cathode 1 st carbonate supplier since the inception of Li-ion battery by SONY in Japan in 1993 Leading supplier of hydroxide to battery market Launch of a range of micronized carbonate grades in 2010 Cathode IP and know-how Developed own cathode technology and participated directly in market from 1995-2004 In 2004, began cathode technology out-licensing Remain deeply engaged with the cathode market SLMP (stabilized lithium metal powder) a potential game changer SLMP is an energy enhancer to break limits on current Li-ion batteries Numerous patents filed Active market development effort CLEAR (Center of Lithium Energy Advanced Research) Capability built in 2008 to construct laminated Li-ion cells Enables direct lithium application development to accelerate commercialization
FMC Cathode Technologies FMC has developed a significant cathode IP estate over the years, especially in the area of layered lithium metal oxides with dopants. The patented compositions allow not only high rate capability (high power) at the beginning, but also the maintenance of the high rate/power capability after long cycles by suppressing the impedance build-up on the cathode surface important and unique in the industry. Can be applied to the whole family of the layered lithium metal oxides LiMO 2 (where M= one or combination of Co, Ni and Mn). Relevant issued US patents: 6,277,521; 6,582,852; 6,794,085; 6,361,756 6,589,499; 6,620,400; 7,074,382; 6,878,490 And their corresponding filings in other countries.
Li-ion battery will not work without Li, but Li is not the cost driver. Li is only a small part of the battery cost. Large format battery (i.e. automotive): Cells (150 Cells) $7,395 Mechanical parts, packaging, labor $4,005 Margin $3,600 Total Packed Cost (25 kwh) $15,000 *Assuming NCM cathode Cell Cost Components (%) Lithium is ~1.5% of cell cost Less than 1% of final battery cost Production Cost 35% Ancillaries 22% Cathode Active 23% Separator 8% Anode Active 6% Electrolyte 6% Margin 17% Cathode Break-down (%) Process 43% Li 7% Ni 6% Mn 2% Co 25% Source: Deutsche Bank
Out of Box Thinking needed for Lower Cost, Higher Energy, and Better Safety New electrode materials are required to increase energy density of Li-ion batteries Li-ion technology has expanded into large format batteries Automotive use demands lower cost and improved safety Need more choices for active and inactive materials! Need to break the current limitation that all lithium has to come from the cathode of the Li-ion cell.
Progress Update on Stabilized Lithium Metal Powder (SLMP ), an enabling material for more Li-ion battery design choices for higher energy, better safety and lower cost Core SLMP Technical Team: Brian Fitch, Yangxing Li, Marina Yakovleva, Scott Petit, Terry Arnold, and Chris Woltermann
Lectro Max 100 Series, Stabilized Lithium Metal Powder Normal lithium powder Can only be handled in an argon filled glove box Not commercially available as powder SEM Image of SLMP Optical Microscope Image of SLMP sprayed on the electrode Stabilized Lithium Metal Powder (SLMP ) Safe to handle in a dry room Can be transported by air or sea Metallic Li content is at least 98% FMC has been producing lithium powder for its own use at the level of hundreds of tons/year for over 30 years
Li, % SLMP Capacity, % Dry Room Stability SLMP-derived thin foil 120 100 120 100 SLMP coated onto Cu foil and pressed at 12,000 lbs per 1.2 cm 2 resulting in thin lithium foils Electrodes exposed to a Dry Room environment with Dew Point of ~ -50 o C for predetermined time period 80 60 40 80 60 40 Active Li was measured by the specific capacity from those electrodes using half cells. The cells were charged at 0.1mA to 3.0 V. The average loading per cell was about 1mg. 20 0 20 0 0 100 200 300 400 Hours of Exposure SLMP-powder SLMP-derived thin foil SLMP Powder Dew Point -30 o C or better Material spread in thin layer in Petri dishes Material is not disturbed during exposure Material is thoroughly mixed prior to analytical analyses Ultra thin Li foils generated with SLMP stability same as foils, and electrochemical activity same as foils
Benefits of SLMP Opening up choices for active materials Anode choice no longer limited to graphite. Allows the use of new materials with both large reversible and irreversible capacities, such as Si composites and Sn intermetallics. Cathode choice no longer limited to lithium providing materials. Much wider selections of non lithium providing materials offering more possibilities: more overcharge tolerant, lower cost, and larger capacities. Use of SLMP in battery material synthesis Si and Sn Composite anode materials Bottom line: increase in energy density, improvements in safety and calendar life, cost reductions Using Lithium from SLMP will cost less than using Lithium from LiCoO 2 cathode and you can pocket other advantages too
Specific Capacity, (discharge mah/g) A non-lithium providing cathode is now possible e.g., MnO 2 lower cost and safer A Li-ion cell: EMD/Graphite+SLMP 300 200 100 Constant Current 0.1mA, Charge 4.3V, Disharge 1.5V 0 0 5 10 15 20 25 30 Cycle Number
High capacity anode is now possible SLMP value * Data courtesy of Shin Etsu
Cell examples 4.5 4.0 3.5 A Li-ion cell: Graphite+SLMP //LiCoO 2 Voltage (V) 3.0 2.5 2.0 Baseline First Cycle Discharge Graphite/LiCoO 2 Cell First Cycle Discharge SLMP+Graphite/LiCoO 2 Cell Improvement 1.5 1.0 0.0% 20.0% 40.0% 60.0% 80.0% 100.0% Capacity First Cycle Efficiency Improvement in LiCoO 2 /Graphite System Using SLMP (Data courtesy of MaxPower Corporation)
Cell examples A Li-ion cell: (Graphite+SLMP)/ LiMn 2 O 4 4.5 60 4.0 3.5 50 Voltage (V) 3.0 2.5 2.0 1.5 1.0 0.5 Baseline First Cycle Discharge Graphite/LiMn 2 O 4 Cell Improvement First Cycle Discharge SLMP+Graphite/LiMn 2 O 4 Cell Capacity (mah) 40 30 20 10 Baseline cell: charge Baseline cell: discharge SLMP incorporated: charge SLMP incorporated: discharge 0.0 0 20 40 60 80 100 Capacity (%) Based on First Charge 0 0 10 20 30 40 50 60 Cycle number (n) First Cycle Efficiency Improvement in LiMn 2 O 4 /Graphite System Using SLMP, and it cycles better too!
Voltage, V Cell examples A Li-ion cell: (Hard Carbon+SLMP)/LiMn 2 O 4 5 4.5 4 3.5 3 2.5 2 Baseline First Cycle Discharge Hard Carbon/ LiMn 2 O 4 Cell Improvement 1.5 1 First Cycle Discharge Hard Carbon+ SLMP/ LiMn 2 O 4 Cell 0.5 0 0 10 20 30 40 50 60 70 80 Capacity, mah First Cycle Efficiency Improvement in LiMn 2 O 4 /Hard Carbon System Using SLMP, more benefits for automotive systems!
SLMP Introduction into the Cell Two general methods to apply SLMP Surface application Coat an SLMP suspension on the surface of pre-fabricated anode sheet no need to change the existing anode fabrication process Slurry application Include SLMP in the slurry mix when the anode sheet is being cast no additional step but the slurry solvent needs to be compatible with lithium.
Industrially Scalable Processes Set-up designed for D-cell production with SLMP TM Technology incorporated under US Army contract W15P7T-06-C- P242. Slurry based Micro Gravure coating method
SLMP can be transferred to electrode surface through a carrier film Solvent free!
Lithium Metal Carrier Film Anode sheet Carrier film coated with SLMP The carrier film before it is applied video next to see how it is applied
Advantage: No solvent involved at cell assembly place. Just attach, press and peel Video clip
SLMP applied on anode surface (spray method) As sprayed After pressing Graphite anode
Anode lithiation with SLMP applied onto the surface Prior to electrolyte addition Right after electrolyte addition, time=0 time=2 min Time =30 min Graphite anode
Lithiation with thin Li foils a very slow process Rolled Li thin foil (<30 micron): macro view Thin Li foil as applied onto the surface of pre-fabricated anode After 7 days of storage at 25 o C After 9 days of storage at 25 o C Graphite anode
Lithiation with thin Li foils a very slow process Rolled Li thin foil (<30 micron): micro view Prior to electrolyte addition after electrolyte addition, time=1hr time=1 day time=7 days
Li/Graphite Voltage curve courtesy of Tao Zheng, PhD Thesis Simon Fraser University 1996 Li 0.25 C 6 Li 0.5 C 6 LiC 6 The Li concentration inside of the graphite electrode near the foil remains high due to slow Li diffusion in graphite it takes a long time for Li concentration to equalize due to the distance Li has to travel. SLMP provides a localized Li distribution much faster to reach equilibrium with SLMP treated electrode compared to foil treated one. Optical observation of Li staging in graphite. The color bands indicate different Li concentration phases, as Li ions move from the foil attached into the graphite electrode Unless you want to wait for days, use SLMP to lithiate your electrode much faster diffusion
Summary FMC Lithium has an extensive play in the lithium-ion battery market, from providing basic lithium raw materials to developing new materials and technologies. Out of box thinking is needed to meet the more challenging requirements of large format batteries. SLMP enables more material choices to meet the increasing demands for more energy, lower cost and better safety for Li-ion batteries by providing an independent source of lithium for Li-ion batteries. SLMP can be introduced into the cell through industrially scalable methods. We welcome the Battery Community to visit CLEAR and apply SLMP onto your current and advanced electrode materials and get trained in safe Lithium handling