Simulation of Micro/Nanopowder Mixing Characteristics for Dry Spray Additive Manufacturing of Li-Ion Battery Electrodes

[+] Author and Article Information
Brandon Ludwig

Mechanical and Aerospace Engineering,
Missouri University of Science and Technology,
400 West 13th Street,
Rolla, MO 65409

Jin Liu, Yangtao Liu, Zhangfeng Zheng, Yan Wang

Mechanical Engineering,
Worchester Polytechnic Institute,
100 Institute Road,
Worchester, MA 01609

Heng Pan

Mechanical and Aerospace Engineering,
Missouri University of Science and Technology,
400 West 13th Street,
Rolla, MO 65409
e-mail: hp5c7@mst.edu

1Corresponding author.

Contributed by the Manufacturing Engineering Division of ASME for publication in the JOURNAL OF MICRO- AND NANO-MANUFACTURING. Manuscript received June 15, 2017; final manuscript received August 21, 2017; published online September 27, 2017. Assoc. Editor: Yayue Pan.

J. Micro Nano-Manuf 5(4), 040902 (Sep 27, 2017) (8 pages) Paper No: JMNM-17-1033; doi: 10.1115/1.4037769 History: Received June 15, 2017; Revised August 21, 2017

A new dry spraying additive manufacturing method for Li-ion batteries has been developed to replace the conventional slurry-casting technique for manufacturing Li-ion battery electrodes. A dry spray manufacturing process can allow for the elimination of the time- and energy-intensive slurry drying process needed due to the use solvents to make the electrodes. Previous studies into the new manufacturing method have shown successful fabrication of electrodes which have strong electrochemical and mechanical performance. Li-ion battery electrodes typically consist of three basic materials: active material (AM), binder particle additives (BPA), and conductive particle additives (CPA). In this paper, a discrete element method (DEM) simulation was developed and used to study the mixing characteristics of dry electrode powder materials. Due to the size of the particles being in the submicron to micron size range, the mixing characteristics are heavily dependent on van der Waals adhesive forces between the particles. Therefore, the effect the Li-ion battery electrode material surface energy has on the mixing characteristics was studied. Contour plots based on the DEM simulation results where the surface energy components of selected material types are changed were used to predict the mixing characteristics of different particle systems. For the cases studied, it is found that experimental mixing results are representative of the results of the DEM simulations.

Copyright © 2017 by ASME
Your Session has timed out. Please sign back in to continue.


Kraytsberg, A. , and Ein-Eli, Y. , 2016, “ Conveying Advanced Li-Ion Battery Materials Into Practice The Impact of Electrode Slurry Preparation Skills,” Adv. Energy Mat., 6(21), pp. 1–23. [CrossRef]
Lee, G.-W. , Ryu, J.-H. , Han, W. , Ahn, K. H. , and Oh, S. M. , 2010, “ Effect of Slurry Preparation Process on Electrochemical Performances of LiCoO2,” J. Power Sources, 195(18), pp. 6049–6054. [CrossRef]
Liu, D. , Chen, L.-C. , Liu, T.-J. , Fan, T. , Tsou, E.-Y. , and Tiu, C. , 2014, “ An Effective Mixing for Lithium Ion Battery Slurries,” Adv. Chem. Eng. Sci., 4(04), pp. 515–528. [CrossRef]
Cetinkaya, T. , Akbulut, A. , Guler, M. O. , and Akbulut, H. , 2014, “ A Different Method for Producing a Flexible LiMn2O4/MWCNT,” J. Appl. Electrochem., 44(2), pp. 209–214. [CrossRef]
Wei, Z. , Xue, L. , Nie, F. , Sheng, J. , Shi, Q. , and Zhao, X. , 2014, “ Study of Sulfonated Polyether Ether Ketone With Pendant Lithiated Fluorinated Groups as Ion Conductive Binder in Lithium-Ion Batteries,” J. Power Sources, 256, pp. 28–31. [CrossRef]
Guerfi, A. , Kaneko, M. , Petitclerc, M. , Mori, M. , and Zaghib, K. , 2007, “ LiFePO4 Water-Soluble Binder Electrode for Li-Ion Batteries,” J. Power Sources, 163(2), pp. 1047–1052. [CrossRef]
Spreafico, M. A. , Cojocaru, P. , Magagnin, L. , Triulzi, F. , and Apostolo, M. , 2014, “ PVDF Latex as a Binder for Positive Electrodes in Lithium-Ion Batteries,” Ind. Eng. Chem. Res., 53(22), pp. 9094–9100. [CrossRef]
Daniel, C. , 2008, “ Materials and Processing for Lithium-Ion Batteries,” JOM, 60(9), pp. 43–48. [CrossRef]
Doberdo, I. , Loffler, N. , Laszczynski, N. , Cericola, D. , Penazzi, N. , Bodoardo, S. , Kim, G.-T. , and Passerini, S. , 2014, “ Enabling Aqueous Binders for Lithium Battery Cathodes—Carbon Coating of Aluminum Current Collector,” J. Power Sources, 248, pp. 1000–1006. [CrossRef]
Li, J. , Armstrong, B. L. , Kiggans, J. , Daniel, C. , and Wood, D. L. , 2012, “ Optimization of LiFePO4 Nanoparticle Suspensions With Polyethyleneimine for Aqueous Processing,” Langmuir, 28(8), pp. 3783–3790. [CrossRef] [PubMed]
Bitsch, B. , Dittmann, J. , Schmitt, M. , Scharfer, P. , Schabel, W. , and Willenbacher, N. , 2014, “ A Novel Slurry Concept for the Fabrication of Lithium-Ion Battery Electrodes With Beneficial Properties,” J. Power Sources, 265, pp. 81–90. [CrossRef]
Li, J. , Rulison, C. , Kiggans, J. , Daniel, C. , and Wood, D. L. , 2012, “ Superior Performance of LiFePO4 Aqueous Dispersions Via Corona Treatment and Surface Energy Optimization,” J. Electrochem. Soc., 159(8), pp. A1152–A1157. [CrossRef]
Li, C.-C. , and Wang, Y.-W. , 2013, “ Importance of Binder Composition to the Dispersion and Electrochemical Properties of Water-Based LiCoO2 Cathodes,” J. Power Sources, 227, pp. 204–210. [CrossRef]
Du, Z. , Rollag, K. M. , Li, J. , An, S. J. , Wood, M. , Sheng, Y. , Mukherjee, P. P. , Daniel, C. , and Wood, D. L. , 2017, “ Enabling Aqueous Processing for Crack-Free Thick Electrodes,” J. Power Sources, 354, pp. 200–206. [CrossRef]
Loeffler, N. , von Zamory, J. , Laszczynski, N. , Doberdo, I. , Kim, G.-T. , and Passerini, S. , 2014, “ Performance of LiNi1/3Mn1/3Co1/3O2/Graphite Batteries Based on Aqueous Binder,” J. Power Sources, 248, pp. 915–922. [CrossRef]
Koike, S. , and Tatsumi, K. , 2007, “ Preparation and Performances of Highly Porous Layered LiCoO2 Films for Lithium Batteries,” J. Power Sources, 174(2), pp. 976–980. [CrossRef]
Kuwata, N. , Kawamura, J. , Toribami, K. , Hattori, T. , and Sata, N. , 2004, “ Thin-Film Lithium-Ion Battery With Amorphous Solid Electrolyte Fabricated by Pulsed Laser Deposition,” Electrochem. Commun., 6(4), pp. 417–421. [CrossRef]
Yan, B. , Liu, J. , Song, B. , Xiao, P. , and Lu, L. , 2013, “ Li-Rich Thin Film Cathode Prepared by Pulsed Laser Deposition,” Sci. Rep., 3, pp. 1–5.
Baggetto, L. , Unocic, R. R. , Dudney, N. J. , and Veith, G. M. , 2012, “ Fabrication and Characterization of Li-Mn-Ni-O Sputtered Thin Film High Voltage Cathodes for Li-Ion Batteries,” J. Power Sources, 211, pp. 108–118. [CrossRef]
Chiu, K.-F. , 2007, “ Lithium Cobalt Oxide Thin Films Deposited at Low Temperature by Ionized Magnetron Sputtering,” Thin Solid Films, 515(11), pp. 4614–4618. [CrossRef]
Ludwig, B. , Zheng, Z. , Shou, W. , Wang, Y. , and Pan, H. , 2016, “ Solvent-Free Manufacturing of Electrodes for Lithium-Ion Batteries,” Sci. Rep., 6, pp. 1–10. [CrossRef] [PubMed]
Ludwig, B. , Liu, J. , Chen, I.-M. , Liu, Y. , Shou, W. , Wang, Y. , and Pan, H. , 2017, “ Understanding Interfacial-Energy-Driven Dry Powder Mixing for Solvent-Free Additive Manufacturing of Li-Ion Battery Electrodes,” Adv. Mater. Interfaces, epub.
Li., S. , Marshall, J. S. , Liu, G. , and Yao, Q. , 2011, “ Adhesive Particulate Flow: The Discrete-Element Method and Its Application in Energy and Environmental Engineering,” Prog. Energy Combust. Sci., 37(6), pp. 633–668. [CrossRef]
Deng, X. , Scicolone, J. V. , and Dave, R. N. , 2013, “ Discrete Element Method Simulation of Cohesive Particles Mixing Under Magnetically Assisted Impaction,” Powder Technol., 243, pp. 96–109. [CrossRef]
Chokshi, A. , Tielens, A. G. G. M. , and Hollenbach, D. , 1993, “ Dust Coagulation,” Astrophys. J., 407(2), pp. 806–819. [CrossRef]
Johnson, K. L. , Kendall, K. , and Roberts, A. D. , 1971, “ Surface Energy and the Contact of Elastic Solids,” Proc. R. Soc. London A, 324(1558), pp. 301–313. [CrossRef]
Fowkes, F. M. , 1968, “ Calculation of Work of Adhesion by Pair Potential Summation,” J. Colloid Interface Sci., 28(3–4), pp. 493–505. [CrossRef]
Tsuji, Y. , Tanaka, T. , and Ishida, T. , 1992, “ Lagrangian Numerical Simulation of Plug Flow of Cohesionless Particles in a Horizontal Pipe,” Powder Technol., 71(3), pp. 239–250. [CrossRef]
Wu, S. , 1971, “ Calculation of Interfacial Tension in Polymer Systems,” J. Polym. Sci. C, 34(1), pp. 19–30. [CrossRef]
Morra, M. , Occhiello, E. , Marola, R. , Garbassi, F. , Humphrey, P. , and Johnson, D. , 1990, “ On the Aging of Oxygen Plasma-Treated Polydimethylsiloxane Surfaces,” J. Colloid Interface Sci., 137(1), pp. 11–24. [CrossRef]
Lee, J. , and Lee, B. , 2017, “ A Simple Method to Determine the Surface Energy of Graphite,” Carbon Lett., 21(1), pp. 107–110. [CrossRef]
Mezgebe, M. , Shen, Q. , Zhang, J.-Y. , and Zhao, Y.-W. , 2012, “ Liquid Adsorption Behavior and Surface Properties of Carbon Black,” Colloids Surf. A, 403, pp. 25–28. [CrossRef]
Wang, H. F. , Troxler, T. , Yeh, A. G. , and Dai, H. L. , 2007, “ Adsorption at a Carbon Black Microparticle Surface in Aqueous Colloids Probed by Optical Second-Harmonic Generation,” J. Phys. Chem. C, 111(25), pp. 8708–8715. [CrossRef]
Siebold, A. , Walliser, A. , Nardin, M. , Oppliger, M. , and Schultz, J. , 1997, “ Capillary Rise for Thermodynamic Characterization of Solid Particle Surface,” J. Colloid Interface Sci., 186(1), pp. 60–70. [CrossRef] [PubMed]
Park, S.-J. , Seo, M.-K. , and Nah, C. , 2005, “ Influence of Surface Characteristics of Carbon Blacks on Cure and Mechanical Behaviors of Rubber Matrix Compoundings,” J. Colloid Interface Sci., 291(1), pp. 229–235. [CrossRef] [PubMed]
Arico, A. S. , Antonucci, V. , Minutoly, M. , and Giordano, N. , 1989, “ The Influence of Functional Groups on the Surface Acid-Base Characteristics of Carbon Blacks,” Carbon, 27(3), pp. 337–347. [CrossRef]


Grahic Jump Location
Fig. 1

Solvent-free manufacturing process: (a) schematic of dry electrostatic spraying system, (b) representation of poorly mixed Li-ion battery electrode powders with agglomerations of additive particles, and (c) representation of well mixed Li-ion battery electrode powders with uniform distribution of additive particles

Grahic Jump Location
Fig. 2

Contact mechanics of colliding particles: (a) contact interface and radius representation due to the collision of i and j particles and (b) representation of the i − j particle overlap due to collision

Grahic Jump Location
Fig. 3

AM-BPA mixing. DEM simulation snapshots of AM-BPA mixing showing (a) premixing, (b) aggregation, and (c) intermixing. Analytical (d) and DEM (e) contour plots showing similar mixing behavior. (f) Comparison of mixing time found in DEM cases where intermixing and aggregation occurs.

Grahic Jump Location
Fig. 4

AM-CPA mixing. DEM simulation snapshots of AM-CPA mixing showing (a) premixing, (b) intermixing, and (c) aggregation. (d) DEM contour plot showing the number of CPA in contact with the AM surface when the AM polar component is 2 mN m−1. (e) DEM contour plot showing the number of CPA in contact with the AM surface when the AM polar component is 100 mN m−1. (f) CPAs showing increased contact with higher polar surface energy AM as compared to low polar surface energy. (g) Comparison of mixing time found in DEM cases where intermixing and aggregation occurs.

Grahic Jump Location
Fig. 5

BPA-CPA mixing: confirmation of analytical modeling results where a predicted intermixed case is confirmed by a DEM simulation (a) and where a predicted aggregation case is confirmed by another DEM simulation (b)

Grahic Jump Location
Fig. 6

AM-BPA-CPA mixing: (a) DEM simulation showing mixing behavior of all three materials when the AM polar surface energy is 2 mN m−1 and (b) DEM simulation showing the mixing behavior of all three materials when the AM polar surface energy is increased to 100 mN m−1

Grahic Jump Location
Fig. 7

Experimental mixing comparison: (a) SEM micrograph showing PVDF (representing BPA) particles attached to the surface of LCO (representing AM), (b) DEM confirmation of the experimental mixing result of AM-BPA with BPA particles attached to the AM surface, (c) SEM micrograph showing PVDF particles embedded within Super C65 carbon (representing CPA), and (d) DEM confirmation of the experimental mixing result of CPA-BPA with BPA particles embedded within the CPA




Some tools below are only available to our subscribers or users with an online account.

Related Content

Customize your page view by dragging and repositioning the boxes below.

Related Journal Articles
Related eBook Content
Topic Collections

Sorry! You do not have access to this content. For assistance or to subscribe, please contact us:

  • TELEPHONE: 1-800-843-2763 (Toll-free in the USA)
  • EMAIL: asmedigitalcollection@asme.org
Sign In