2024 |
|
 | Katz, Michelle E. R.; Cobb, Corie L. High-Viscosity Phase Inversion Separators for Freestanding and Direct-on-Electrode Manufacturing in Lithium-Ion Batteries Journal Article In: ACS Applied Materials & Interfaces, vol. 16, no. 34, pp. 44863–44878, 2024, ISSN: 1944-8244, (Publisher: American Chemical Society). Abstract | Links | Tags: additive manufacturing, batteries, printed batteries @article{katz_high-viscosity_2024,Separators play a critical role in lithium-ion batteries (LIBs) by facilitating lithium-ion (Li-ion) transport while enabling safe battery operation. However, commercial separators made from polypropylene (PP) or polyethylene (PE) impose a discrete processing step in current LIB manufacturing as they cannot be manufactured with the same slot-die coating process used to fabricate the electrodes. Moreover, commercial separators cannot accommodate newer manufacturing processes used to produce leading-edge microbatteries and flexible batteries with customized form factors. As a path toward rethinking LIB fabrication, we have developed a high-viscosity polymer composite separator slurry that enables the fabrication of both freestanding and direct-on-electrode films. A streamlined phase inversion process is used to impart porosity in cast separator films upon drying. To understand the impacts of material composition and rheology on phase inversion processing and separator performance, we investigated four different separator formulations. We used either diethylene glycol (DEG) or triethyl phosphate (TEP) as a nonsolvent, and either silica (SiO2) or alumina (Al2O3) as an inorganic additive in a polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) matrix. Through a down-selection process, we developed a TEP-SiO2 separator formulation that matched or outperformed a commercial Celgard 2325 (PP/PE/PP) separator and a Beyond Battery ceramic-coated PE (CC/PE/CC) separator under rate and cycle life tests in LiFePO4textbarLi4Ti5O12 (LFPtextbarLTO) and LiNi0.5Mn0.3Co0.2O2textbargraphite (NMC-532textbargraphite) coin cells at C/10–1C rates. Our TEP-SiO2 slurry had a viscosity of 298 Pa s at a 1 s–1 shear rate and shear-thinning behavior. When deposited directly onto an LTO anode and cycled against an LFP cathode, the direct-on-electrode TEP-SiO2 separator increased the specific capacity by 58% and 304% at 2C rates relative to the PP/PE/PP and CC/PE/CC separators, respectively. Additionally, the freestanding TEP-SiO2 separator maintained dimensional stability when heated to 200 °C for 1 h and demonstrated a higher elastic modulus and hardness than the PP/PE/PP and CC/PE/CC separators when measured with nanoindentation. |
2018 |
|
 | Cobb, Corie Lynn Structures for interdigitated finger co-extrusion Patent US9899669B2, 2018. Abstract | Links | Tags: additive manufacturing, Co-extrusion, printed batteries @patent{cobb_structures_2018,An electrode structure has an interdigitated layer of at least a first material and a second material, the second material having either higher or similar electrical conductivity of the first material and being more ionically conductivity than the first material, a cross-section of the two materials being non-rectangular. |
 | Cobb, Corie Lynn Co-extrusion print head with edge bead reduction Patent US9855578B2, 2018. Abstract | Links | Tags: additive manufacturing, Co-extrusion, printed batteries @patent{cobb_co-extrusion_2018,A co-extrusion print head has at least one channel, and a set of orifices fluidically connected to the channel, wherein the set of orifices has at least one orifice at each edge of the set has a smaller vertical extent than the other orifices. |
2017 |
|
 | Cobb, Corie Lynn Co-extruded conformal battery separator and electrode Patent US9755221B2, 2017. Abstract | Links | Tags: additive manufacturing, Co-extrusion, printed batteries @patent{cobb_co-extruded_2017,A co-extrusion print head has at least one separator inlet port, at least a first, second and third series of channels arranged to receive a separator material from the separator inlet port, at least one electrode inlet port, a fourth series of channels arranged to receive an electrode material from the electrode inlet port, a first merge portion connected to the first, second, third and fourth series of channels, the merge portion positioned to receive and merge the separator material into a separator flow and the electrode material into an electrode flow, a second merge portion connected to the first merge portion, the second merge portion positioned to receive and merge the separator flows and the electrode flows, and an outlet port connected to the second merge portion, the outlet port arranged to deposit the separator and electrode materials from the merge portion as a stack on a substrate. |
 | Cobb, Corie Lynn; Bae, Chang-Jun Three dimensional co-extruded battery electrodes Patent US9590232B2, 2017. Abstract | Links | Tags: additive manufacturing, Co-extrusion, printed batteries @patent{cobb_three_2017-1,A three dimensional electrode structure having a first layer of interdigitated stripes of material oriented in a first direction, and a second layer of interdigitated stripes of material oriented in a second direction residing on the first layer of interdigitated stripes of material. A method of manufacturing a three dimensional electrode structure includes depositing a first layer of interdigitated stripes of an active material and an intermediate material on a substrate in a first direction, and depositing a second layer of interdigitated stripes of the active material and the intermediate material on the first layer in a second direction orthogonal to the first direction. |
 | Cobb, Corie Lynn; Bae, Chang-Jun Three dimensional co-extruded battery electrodes Patent US9793537B2, 2017. Abstract | Links | Tags: additive manufacturing, Co-extrusion, printed batteries @patent{cobb_three_2017,A three dimensional electrode structure having a first layer of interdigitated stripes of material oriented in a first direction, and a second layer of interdigitated stripes of material oriented in a second direction residing on the first layer of interdigitated stripes of material. A method of manufacturing a three dimensional electrode structure includes depositing a first layer of interdigitated stripes of an active material and an intermediate material on a substrate in a first direction, and depositing a second layer of interdigitated stripes of the active material and the intermediate material on the first layer in a second direction orthogonal to the first direction. |
2016 |
|
 | Cobb, Corie Lynn Co-Extrusion: Advanced Manufacturing for Energy Devices Miscellaneous 2016. Abstract | Links | Tags: additive manufacturing, Co-extrusion, printed batteries @misc{cobb_co-extrusion:_2016,The U.S. Department of Energy's Office of Scientific and Technical Information |
 | Cobb, Corie L; Ho, Christine C Additive Manufacturing: Rethinking Battery Design Journal Article In: The Electrochemical Society Interface, vol. 25, no. 1, pp. 75-78, 2016, ISSN: 1064-8208, 1944-8783. Abstract | Links | Tags: additive manufacturing, printed batteries @article{cobb_additive_2016,This article outlines emerging trends in the use of additive manufacturing techniques for the manufacture of batteries with customized geometries. Following a brief overview of conventional battery manufacturing, we discuss additive manufacturing strategies such as extrusion and dispenser printing, ink-jet printing, and screen printing in the context of battery manufacturing, and highlight the pros and cons of each technique. We provide some examples of 2D and 3D battery structures created by additive manufacturing, and highlight current and future research directions for battery design, manufacturing, and integration for small, portable and wearable electronics. |
 | Cobb, Corie Lynn Co-extrusion print head for multi-layer battery structures Patent US9337471 B2, 2016. Abstract | Links | Tags: additive manufacturing, Co-extrusion, printed batteries @patent{cobb_co-extrusion_2016,A co-extrusion print head capable of extruding at least two layers vertically in a single pass having a first inlet port connected to a first manifold, a first series of channels connected to the first inlet port arranged to receive a first fluid from the first inlet port, a second inlet port connected to one of either a second manifold or the first manifold, a second series of channels connected to the second inlet port arranged to receive a second fluid from the second inlet port, a merge portion of the print head connected to the first and second series of channels, the merge portion arranged to receive the first and second fluids, and an outlet port connected to the merge portion, the outlet port arranged to deposit the first and second fluids from the merge portion as a vertical stack on a substrate. |
2014 |
|
 | Cobb, Corie Lynn Co-extrusion print head for multi-layer battery structures Patent US20140186519A1, 2014. Abstract | Links | Tags: additive manufacturing, Co-extrusion, printed batteries @patent{cobb_co-extrusion_2014,A co-extrusion print head capable of extruding at least two layers vertically in a single pass having a first inlet port connected to a first manifold, a first series of channels connected to the first inlet port arranged to receive a first fluid from the first inlet port, a second inlet port connected to one of either a second manifold or the first manifold, a second series of channels connected to the second inlet port arranged to receive a second fluid from the second inlet port, a merge portion of the print head connected to the first and second series of channels, the merge portion arranged to receive the first and second fluids, and an outlet port connected to the merge portion, the outlet port arranged to deposit the first and second fluids from the merge portion as a vertical stack on a substrate. |
 | Cobb, Corie L; Blanco, Mario Modeling mass and density distribution effects on the performance of co-extruded electrodes for high energy density lithium-ion batteries Journal Article In: Journal of Power Sources, vol. 249, pp. 357–366, 2014, ISSN: 0378-7753. Abstract | Links | Tags: battery modeling, Co-extrusion, printed batteries @article{cobb_modeling_2014,Utilizing an existing macro-homogeneous porous electrode model developed by John Newman, this paper aims to explore the potential energy density gains which can be realized in lithium-ion battery electrodes fabricated with co-extrusion printing technology. This paper conducts an analysis on two-dimensional electrode cross-sections and presents the electrochemical performance results, including calculated volumetric energy capacity for a general class of lithium cobalt oxide (LiCoO2) co-extruded cathodes, in the presence of a lithium metal anode, polymer separator and liquid ethylene carbonate, propylene carbonate, and dimethyl carbonate (EC:PC:DMC) electrolyte. The impact of structured electrodes on cell performance is investigated by varying the physical distribution of a fixed amount of cathode mass over a space of dimensions which can be fabricated by co-extrusion. By systematically varying the thickness and aspect ratio of the electrode structures, we present an optimal subset of geometries and design rules for co-extruded geometries. Modeling results demonstrate that ultra-thick LiCoO2 electrodes, on the order of 150–300 μm, can garner a substantial improvement in material utilization and in turn capacity through electrolyte channels and fine width electrode pillars which are 25–100 μm wide. |
 | Bae, Chang-Jun; Shrader, Eric J; Cobb, Corie Lynn Advanced, high power and energy battery electrode manufactured by co-extrusion printing Patent US20140186700A1, 2014. Abstract | Links | Tags: additive manufacturing, Co-extrusion, printed batteries @patent{bae_advanced_2014,A battery has an anode, a separator adjacent the anode, and a cathode adjacent the separator opposite the anode, the cathode comprising interdigitated stripes of materials, one of the materials forming a pore channel. |
2012 |
|
 | Shrader, Eric J; Cobb, Corie L Co-Extrusion Printing for Low Cost and High Performance Energy Devices Proceedings Article In: Nanotechnology 2012: Bio Sensors, Instruments, Medical, Environment and Energy, pp. 537 – 540, NSTI, Santa Clara, CA, 2012, ISBN: 978-1-4665-6276-9. Abstract | Links | Tags: additive manufacturing, Co-extrusion, printed batteries, solar @inproceedings{shrader_co-extrusion_2012,The method of co-extrusion of dissimilar materials has been developed at the PARC, a Xerox Company, to successfully produce high aspect ratio structures for solar cell gridlines. In the solar application, the process is stable and repeatable, and a fully integrated tool has been developed that is now being demonstrated at a customer site. The co-extrusion process is capable of non-contact, direct deposition of features as small as 1 – 10 um with aspect ratios in the range of 1:1 to 30:1. Alternating fluids are co-extruded to form a fine vertically interdigitated lamina structure. The relative thickness, width, and length of the deposited features can be varied by altering the printhead geometry and printing process conditions. |
2011 |
|
 | Littau, Karl A; Cobb, Corie L; Spengler, Nils; Solberg, Scott; Weisberg, Michael; Chang, Norinne; Rodkin, Alexandra Developments in MEMS scale printable alkaline and Li-ion technology Proceedings Article In: Micro- and Nanotechnology Sensors, Systems, and Applications III, pp. 80311L, International Society for Optics and Photonics, 2011. Abstract | Links | Tags: additive manufacturing, Co-extrusion, MEMS, printed batteries @inproceedings{littau_developments_2011,Two technologies for MEMS (Microelectromechanical Systems) scale cell formation are discussed. First, the fabrication of planar alkaline cell batteries compatible with MEMS scale power storage applications is shown. Both mm scale and sub-mm scale individual cells and batteries have been constructed. The chosen coplanar electrode geometry allows for easy fabrication of series connected cells enabling higher voltage while simplifying the cell sealing and electrode formation. The Zn/Ag alkaline system is used due to the large operating voltage, inherent charge capacity, long shelf life, and ease of fabrication. Several cells have been constructed using both plated and spun-on silver. The plated cells are shown to be limited in performance due to inadequate surface area and porosity; however, the cells made from spun-on colloidal silver show reasonable charge capacity and power performance with current densities of up to 200 uA/mm$^textrm2$ and charge capacities of up to 18 mA-s/mm$^textrm2$. Second, a new printing method for interdigitated 3-D cells is introduced. A microfluidic printhead capable of dispensing multiple materials at high resolution and aspect ratio is described and used to form fine interdigitated cell features which show >10 times improvement in energy density. Representative structures enabled by this method are modeled, and the energy and power density improvements are reported. |
2024 |
|
| High-Viscosity Phase Inversion Separators for Freestanding and Direct-on-Electrode Manufacturing in Lithium-Ion Batteries Journal Article In: ACS Applied Materials & Interfaces, vol. 16, no. 34, pp. 44863–44878, 2024, ISSN: 1944-8244, (Publisher: American Chemical Society). |
2018 |
|
| Structures for interdigitated finger co-extrusion Patent US9899669B2, 2018. |
| Co-extrusion print head with edge bead reduction Patent US9855578B2, 2018. |
2017 |
|
| Co-extruded conformal battery separator and electrode Patent US9755221B2, 2017. |
| Three dimensional co-extruded battery electrodes Patent US9590232B2, 2017. |
| Three dimensional co-extruded battery electrodes Patent US9793537B2, 2017. |
2016 |
|
| Co-Extrusion: Advanced Manufacturing for Energy Devices Miscellaneous 2016. |
| Additive Manufacturing: Rethinking Battery Design Journal Article In: The Electrochemical Society Interface, vol. 25, no. 1, pp. 75-78, 2016, ISSN: 1064-8208, 1944-8783. |
| Co-extrusion print head for multi-layer battery structures Patent US9337471 B2, 2016. |
2014 |
|
| Co-extrusion print head for multi-layer battery structures Patent US20140186519A1, 2014. |
| Modeling mass and density distribution effects on the performance of co-extruded electrodes for high energy density lithium-ion batteries Journal Article In: Journal of Power Sources, vol. 249, pp. 357–366, 2014, ISSN: 0378-7753. |
| Advanced, high power and energy battery electrode manufactured by co-extrusion printing Patent US20140186700A1, 2014. |
2012 |
|
| Co-Extrusion Printing for Low Cost and High Performance Energy Devices Proceedings Article In: Nanotechnology 2012: Bio Sensors, Instruments, Medical, Environment and Energy, pp. 537 – 540, NSTI, Santa Clara, CA, 2012, ISBN: 978-1-4665-6276-9. |
2011 |
|
| Developments in MEMS scale printable alkaline and Li-ion technology Proceedings Article In: Micro- and Nanotechnology Sensors, Systems, and Applications III, pp. 80311L, International Society for Optics and Photonics, 2011. |