Next Generation Processes for Carbonate Electrolytes for Battery Applications
Dr. Kausik Mukhopadhyay & Dr. Krishnaswamy K. Rangan
Materials Modification, Inc. 2809-K Merrilee Drive, Fairfax. VA 22031
ABSTRACT PERVAPORATION SET UP POWDER XRD: CATALYST SYNTHESIS SAED Dimethyl Carbonate (DMC) is a promising electrolyte BIMETALLIC NANOPARTICLES DMC + CH3OH + H2O mixture solvent for lithium battery applications due to its MMI’s SYNTHETIC ROUTE Zeolite Y (Si:Al = 12:1) inherent safety and robustness. Despite the enormous H3PW12O40. xH2O Nickel and Copper salts promise of its industrial use, this chemical is currently Membrane Cell Ligand Precursors entirely imported from China. The global battery Cu0 on Ni0 Core-Shell market is about US$ 50 billion, of which approximately u.) (a. Intensity Rotor $ 5.5 billion is captured by the rechargeable batteries u.) (a. Intensity CHARACTERIZATION for use in electric vehicles, laptops, consumer Flow Meter HRSEM, HRTEM, BET (Particle Size, Shape) electronics, rechargeable batteries etc. XRD, SAED, EDS, XPS (Characteristics & Cu-Ni CSNP Composition) 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
Indigenous manufacture of DMC will enormously 2 (); Co-K 2 (); Co-K
benefit not only the American lithium battery industry
HRTEM
O O
but also other industrial processes that use DMC as a Tank Feed
2 2 H
methylating agent and fuel additive. HETEROGENEOUS CATALYST Ni-Cu_PTA-Y H
CATALYST MATRIX
PTA-Y Cold Trap Cold Trap
(011) Ni
Existing processes of DMC synthesis either use SiO2, Zeolite, Mesoporous Materials Feed Pump
Cu(111)
Cu(200) Ni (012) Ni toxic materials or require improvements in terms of (010) Ni FUNCTIONALIZATION (a.u.) Intensity Temperature Controlling yield. Use of inexpensive raw materials and benign (a.u.) Intensity System APTS (-NH ), PTA (PW O 3-) 5 Å reaction conditions will enable easy manufacture of 2 12 40 Vacuum Pump DMC within the country and eliminate reliance on Incipient Wetness (Matrix, Salts, H2)
imports. Catalytic conversion of carbon dioxide and 5 nm TETHERING methanol is being increasingly considered for the 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 COMMERCIALIZATION SIGNIFICANCE 2 (); Co-K 2 (); Co-K process, but yields have not been encouraging enough CuNi_NP-NH2, CuNi_NP-PW12O40 Zeolite Y matrix for industrial manufacturing. Industrial processes using World capacity Amount of CO2 as raw material per year fixed CO2 Urea 143 Mton 105 Mton
MMI’s APPROACH POWDER XRD: Cu-Ni Catalyst HRTEM EDS ANALYSIS Salicylic acid 70 kton 25 kton
MMI proposes a three-pronged approach for DMC Methanol 20 Mton 2 Mton
51
60
synthesis from CO and CH OH by developing an
2 3 Cyclic carbonates 80 kton 40 kton
efficient catalyst system and novel pervaporation Poly(propylene carbonate) 70 kton 40 kton membrane. Core-shell bimetallic catalysts on inorganic supports will be used as heterogeneous catalysts in a
high pressure reactor for DMC reaction. Pervaporation Ni(111); 2
Ni (200); Ni(200); 2 FUTURE PLANS 3.8
membranes will be used to separate products and 3.8 Cu enhance the DMC yield (> 15%), thereby making the Cu CATALYSIS AND KINETIC STUDY process economical.
DEVELOP OTHER EFFECTIVE CATALYSTS
INCREASE DMC YIELD 15% DIMETHYL CARBONATE (DMC)
Ni NP Ni DEVELOP NOVEL PERVAPORATION MEMBRANES - WORLD PRODUCTION Cu STUDY COMMERCIALIZATION POTENTIAL 1000 Barrels/ Day (1997)a Co-K Radiation/ JADE 6.1 Catalyst 300,000 – 600,000 Ton/ Year (Future demand) 20 nm Tasks Description Months 1 2 3 4 5 6 7 8 9 1 Materials Procurement USES Synthesis of Supported Methylating and Carbonylating Agent (Biodegradable) 2 Nanocatalysts Green Solvent (Non-VOC; Low toxicity) by US EPA, 2009 Synthesis of Pervaporation Fuel Oxygenate Additive§ DMC CATALYSIS: MMI’s APPROACH 3 Membrane Carbonate Electrolytes (Battery applications) 4 Design of Reactor CH3OH + (OCH3)2CO CO2 + 2CH3OH (OCH3)2CO + H2O INDUSTRIAL/ DIFFERENT ROUTES GAS-LIQUID-SOLID CHARACTERIZATION 5 Study of Catalytic Efficiency 2CH3OH + COCl2 (Phosgene) b STIRRED HIGH PRESSURE REACTOR GC, GC-MS, HPLC (Products) 6 Reporting, Planning for Phase II Propylene Carbonate + CH3OH (Transesterification) BATCH REACTOR c CO + O2 + CH3OH + Catalyst Urea Methanolysis PARAMETERS ESSENTIAL STUDIES Carbon SUMMARY OF TASKS PERFORMED dioxide SELECTIVITY (Goal: 15%) ISSUES Methanol H2O HETEROGENEOUS CATALYSTS (Solid) Chitosan-SiO2 SYNTHESIS OF NANO-CATALYSTS Phosgene’s toxicity Membrane SOLVENT (CH3OH) + REACTANT (CO2) ACTIVITY (Conversion & TOF) Low Yield and Conversion DEVELOPED PERVAPORATION MEMBRANE Solid CONCENTRATION (CH3OH : CO2) YIELD (DMC) Product Separation Catalyst PRESSURE (~ 1.0 – 1.6 MPa) RECYCLABILITY (Catalyst) DESIGNED REACTOR SYSTEM DMC + H2O ACETONE TEMPERATURE (~ 80 – 130C) CONCENTRATION vs. TIME CHARACTERIZATION OF CATALYSTS MMI APPROACH STIRRING FREQUENCY (600 rpm) PROFILE (Reaction Kinetics) CH3OH + (OCH3)2CO + H2O CH3OH + CO2 + Heterogeneous Catalyst + Pervaporation ACKNOWLEDGEMENTS a) Pacheco et al., Energy Fuels, 1997, 11, 2 b) Unnikrishnan et al. I&EC Research, 2012, 51, 6356 Funding: DOE SBIR Phase I Contract # DE-SC0008278 (2012) c) Xu et al., J. Am. Chem. Soc. 2011, 133, 20378