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Natural Gas for Synthesis of the Separator and Organic Solvents

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Natural Gas for Synthesis of the Separator and Organic Solvents Electronic Supplementary Material (ESI) for Energy & Environmental Science. This journal is © The Royal Society of Chemistry 2020 Supporting Information Towards More Environmentally and Socially Responsible Batteries Shyam S. Sharma and Arumugam Manthiram* Texas Materials Institute, The University of Texas at Austin, 204 E Dean Keaton Street, Austin, TX, 78712, United States *Corresponding E-mail: [email protected] 1 Table of Contents Battery Cell Modeling 3-6 Heat Capacity and Heat Transfer Calculations 7-14 Raw Material Extraction Energy Calculations 14-15 Transportation Energy Calculations 16-17 Translating Energy to Emissions with GREET® 16-17 Toxicity Scoring 17-19 Habitat Destruction Quantification 20 Social Impact Assessment 20 NMC811-Graphite Manufacturing Process 21-24 LFP-Graphite Manufacturing Process 24-25 Aqueous Na-ion Manufacturing Process 25-27 References 28-31 2 Battery Cell Modeling Generally speaking, the components of a battery include: a cathode, anode, electrolyte, separator, conductive additives, binder, current collectors, and cell casing. In addition, solvents (typically NMP or water) are used to prepare electrode slurries. For this article, a pouch cell form factor with a double-sided cathode, two single-sided anodes, and four layers of separator was assumed. Since the majority of component masses can be determined relative to the amount of cathode material present in the cell, the cathode mass was calculated first using an assumed, practical areal capacity of 2 mAh cm-2.87 Step-by-step example calculations are shown below for a NMC811-Graphite pouch cell. These steps can be adapted to any battery chemistry that contains the components previously listed. Pouch Cell Dimensions Table S1. Areas of Pouch Cell Components88 Pouch Cell Component Area (cm2) Cathode 14.1 Anode 14.9 Separatora 14.9 Cell Casing 28.8 a: separator assumed to have the same area as the anode Step 1. List the Components Positive Electrode o NMC811 o Carbon Black o PVDF Binder o Al foil current collector o NMP solvent Negative Electrode o Graphite o Carbon Black o CMC Binder o Cu foil current collector o Water solvent 3 Separator o Polyethylene Electrolyte o Ethylene carbonate (EC) o Dimethyl carbonate (DMC) o LiPF6 salt Cell Casing o Aluminum Step 2. Calculate Cathode Mass Cathode Area: 14.1 cm2 NMC811 Gravimetric Capacity89: 180 mAh g-1 NMC811 Areal Capacity87: 2 mAh cm-2 2 푚퐴ℎ 푔 푁푀퐶811 푀푎푠푠 표푓 푁푀퐶811 = 14.1 푐푚2 ∗ ∗ ∗ 2 푠푖푑푒푠 = 0.313 푔 푁푀퐶811 푐푚2 180 푚퐴ℎ Step 3. Calculate Remaining Positive Electrode Component Masses Assumed Electrode Weight Distribution: 90% NMC811, 5% PVDF, 5% Carbon Black Assumed NMP: PVDF mass ratio of 40.67 (gives a solids content of 45 wt.%) Assumed 10 휇푚 thick Al foil 5 푔 푃푉퐷퐹 푀푎푠푠 표푓 푃푉퐷퐹 = 0.313 푔 푁푀퐶811 ∗ = 0.0174 푔 푃푉퐷퐹 90 푔 푁푀퐶811 5 푔 퐶푎푟푏표푛 퐵푙푎푐푘 푀푎푠푠 표푓 퐶푎푟푏표푛 퐵푙푎푐푘 = 0.313 푔 푁푀퐶811 ∗ = 0.0174 푔 퐶푎푟푏표푛 퐵푙푎푐푘 90 푔 푁푀퐶811 40.67 푔 푁푀푃 푀푎푠푠 표푓 푁푀푃 = 0.0174 푔 푃푉퐷퐹 ∗ = 0.707 푔 푁푀푃 푔 푃푉퐷퐹 10 ‒ 4 푐푚 2.7 푔 퐴푙 푀푎푠푠 표푓 퐴푙 푓표푖푙 = 14.1 푐푚2 ∗ 10 휇푚 ∗ ∗ = 0.0380 푔 퐴푙 휇푚 푐푚3 Step 4. Calculate Anode Mass 4 Assume N/P (negative/positive) ratio of 1.1 Graphite Gravimetric Capacity: 372 mAh g-1 Total Cathode Capacity: 56.34 mAh (calculated above for NMC811) 푔 퐺푟푎푝ℎ푖푡푒 푀푎푠푠 표푓 퐺푟푎푝ℎ푖푡푒 = 56.34 푚퐴ℎ ∗ 1.1 ∗ = 0.167 푔 퐺푟푎푝ℎ푖푡푒 372 푚퐴ℎ Step 5. Calculate Remaining Negative Electrode Component Masses Assumed Electrode Weight Distribution: 94% Graphite, 4% CMC, 2% Carbon Black Assumed Water:CMC mass ratio of 40.67 (solids content of 45 wt.%) Assumed 10 휇푚 thick Cu foil 4 푔 퐶푀퐶 푀푎푠푠 표푓 퐶푀퐶 = 0.167 푔 퐺푟푎푝ℎ푖푡푒 ∗ = 0.00709 푔 퐶푀퐶 94 푔 퐺푟푎푝ℎ푖푡푒 2 푔 퐶푎푟푏표푛 퐵푙푎푐푘 푀푎푠푠 표푓 퐶푎푟푏표푛 퐵푙푎푐푘 = 0.167 푔 퐺푟푎푝ℎ푖푡푒 ∗ = 0.00354 푔 퐶푎푟푏표푛 퐵푙푎푐푘 94 푔 퐺푟푎푝ℎ푖푡푒 40.67 푔 푊푎푡푒푟 푀푎푠푠 표푓 푊푎푡푒푟 = 0.00709 푔 퐶푀퐶 ∗ = 0.288 푔 푊푎푡푒푟 푔 퐶푀퐶 10 ‒ 4 푐푚 8.96 푔 퐶푢 푀푎푠푠 표푓 퐶푢 퐹표푖푙 = 14.9 푐푚2 ∗ 10 휇푚 ∗ ∗ ∗ 2 퐴푛표푑푒푠 = 0.267 푔 퐶푢 휇푚 푐푚3 Step 6. Calculate Separator Mass Assumed 4 total layers of separator in pouch cell wrap (one between each pair of electrodes and one on each end of the electrode stack) Assumed separator has the same area as the anode and 25.4 휇푚 thickness90 10 ‒ 4 푐푚 0.92 푔 푃퐸 푀푎푠푠 표푓 푆푒푝푎푟푎푡표푟 = 14.9 푐푚2 ∗ 25.4 휇푚 ∗ ∗ ∗ 4 푙푎푦푒푟푠 = 0.139 푔 푃퐸 푢푚 푐푚3 Step 7. Calculate Electrolyte Mass 5 Assumed 1 M LiPF6 in 3:7 EC/DMC (wt. ratio) Assumed electrolyte loading of 2.6 mL Ah-1.91 Assumed Electrolyte Density: 1.145 g mL-1 (weighted average of EC and DMC) 퐴ℎ 2.6 푚퐿 1.145 푔 푇표푡푎푙 퐸푙푒푐푡푟표푙푦푡푒 푀푎푠푠 = 56.34 푚퐴ℎ ∗ ∗ ∗ = 0.166 푔 퐸푙푒푐푡푟표푙푦푡푒 1000 푚퐴ℎ 퐴ℎ 푚퐿 푀푎푠푠 표푓 퐸퐶 = 0.166 푔 ∗ 0.3 = 0.0499 푔 퐸퐶 푀푎푠푠 표푓 퐷푀퐶 = 0.166 푔 ∗ 0.7 = 0.117 푔 퐷푀퐶 1 푚퐿 퐿 1 푚표푙 퐿푖푃퐹6 151.905 푔 푀푎푠푠 표푓 퐿푖푃퐹 = 0.166 푔 ∗ ∗ ∗ ∗ = 0.0221 푔 퐿푖푃퐹 6 1.145 푔 1000 푚퐿 퐿 푚표푙 6 Step 8. Calculate Cell Casing Mass Assumed cell casing is pure aluminum and 100 휇푚 thick on each side 10 ‒ 4푐푚 2.7 푔 퐴푙 푀푎푠푠 표푓 퐶푎푠푖푛푔 = 28.8 푐푚2 ∗ 100 휇푚 ∗ ∗ ∗ 2 푠푖푑푒푠 = 1.555 푔 퐴푙 휇푚 푐푚3 Table S2. Battery Component Mass Summary Component Mass (g) NMC811 0.313 Graphite 0.167 PVDF 0.0174 CMC 0.00709 Water 0.288 Carbon 0.0209 NMP 0.707 LiPF6 0.0221 EC 0.0499 DMC 0.117 Polyethylene 0.139 Aluminum 1.593 Copper 0.267 Heat Transfer and Heat Capacity Calculations 6 Energy requirements for each intermediate reaction in the battery manufacturing process were assumed to be the sum of the heat needed to heat the reactants (Qreactants) and the heat needed to maintain the reactor temperature (Qreactor) (Equation S1). 푄 = 푄 + 푄 푡표푡푎푙 푟푒푎푐푡푎푛푡푠 푟푒푎푐푡표푟 (Equation S1)1 Calculating Qreactants Consider the following calcination reaction for the NMC811 cathode: 1 LiOH + Ni0.8Mn0.1Co0.1(OH)2 + 1/4O2 LiNi0.8Mn0.1Co0.1O2 + 3/2H2O Reaction Temperature: 800 ℃1 Qreactants is calculated as follows (O2 gas contribution was assumed to be negligible): 푄 = 푛 퐶 (800 ℃ ‒ 25℃) + 푛 퐶 (800℃ ‒ 25℃) 푟푒푎푐푡푎푛푡푠 퐿푖푂퐻 푝퐿푖푂퐻 푁푀퐶(푂퐻)2 푝,푁푀퐶(푂퐻)2 Heat capacities for many compounds are readily available through the NIST Chemistry Webbook. Link: https://webbook.nist.gov/chemistry/ Wherever available, the temperature dependence of heat capacity was accounted for using the Shomate Equation (coefficients are provided in the NIST Chemistry Webbook) (Equation S2). Overwhelmingly, however, the first coefficient (A) contributes the most to the heat capacity value regardless of temperature, so assuming a constant heat capacity would be a reasonable assumption. 2 3 1 푆ℎ표푚푎푡푒 퐸푞푢푎푡푖표푛:퐶푝° = 퐴 + 퐵 ∗ 푡 + 퐶 ∗ 푡 + 퐷 ∗ 푡 + 퐸 ∗ 푡2 Where t = temperature (T)/1000 Integrating the Shomate Equation for a reaction occurring at T2 with reactant heating from T1 (assumed to be room temp.) yields: 2 2 3 3 4 4 푄푟푒푎푐푡푎푛푡푠 푡2 ‒ 푡1 푡2 ‒ 푡1 푡2 ‒ 푡1 1 1 = 퐶 ∆푇 = 퐴 ∗ (푇 ‒ 푇 ) + 퐵 ∗ + 퐶 ∗ + 퐷 ∗ + 퐸 ∗ ( ‒ ) 푚표푙 푝 2 1 ( 2 ) ( 3 ) ( 4 ) 푡 푡 1 2 The Shomate Equation coefficients were used for Cp,LiOH and an assumed literature heat 퐶푝,푁푀퐶(푂퐻) capacity for Ni(OH)2 for 2 to determine Qreactants = 0.313 Btu for this reaction. Calculating Qreactor 7 As mentioned in the article, it was assumed that the three possible reactors used in the battery manufacturing process are: (i) fixed bed reactor (gas-state reactions), (ii) batch reactor (liquid- state reactions), and (iii) tube furnace (solid-state reactions). Fixed Bed Reactor In a fixed bed reactor, gas streams are passed into a cylinder that contains a packed catalyst bed. The gas molecules react in the presence of the catalyst to produce a product gas stream. These reactors are primarily used during the battery manufacturing process for production of petrochemicals from natural gas for synthesis of the separator and organic solvents. Fig. S1. Fixed bed reactor. The governing equation for Qreactor of the fixed bed reactor is given below in Equation S2. This equation is an adaptation of Fourier’s Law of Heat Conduction. It operates under the crucial assumption that the energy required to heat the reactor is equivalent to the energy removed from the reactor through conduction throughout the reaction. It was assumed that the reactors had no insulation, so this equation can be thought of as the upper bound energy requirement for a reaction. 푘퐴푡(푇푟푥푛 ‒ 25℃) 푄푟푒푎푐푡표푟,푡표푡푎푙 푟푥푛 = 푥 (Equation S2)1 W k = thermal conductivity ;A = surface area (m2);x = wall thickness (m);t = rxn time (s) (m * K) For simplicity, constant k, A, and x values were assumed. As most gas phase reactions take place at high temperatures, the reactor was assumed to be made of stainless steel (rather than glass). 푊 k = 16.26 푚 ∗ 퐾 (stainless steel thermal conductivity)92 A = 0.628 m2 (for a 20 cm inner diameter, 100 cm long reactor) x = 0.00635 m (0.25” thick; reasonable thickness for a reactor) 8 As fixed bed reactors are continuous reactors (reactants are continuously being sent into the reactor and products are continuously being produced), gas residence time (amount of time spent by a gas molecule in the reactor) is the most important metric for determining reaction energy requirement. Residence times for gas phase reactions involved in battery manufacturing were found in publications and patents.
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