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Article
Direct Imprinting of Scalable, High-Performance Woodpile
Electrodes for Three-Dimensional Lithium-Ion Nanobatteries
Wenhao Li, Yiliang Zhou, Irene R. Howell, Yue Gai, Aditi R.
Naik, Shengkai Li, Kenneth R. Carter, and James J. Watkins
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b14649 • Publication Date (Web): 25 Jan 2018
Downloaded from http://pubs.acs.org on January 26, 2018
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Page 1 of 22 ACS Applied Materials & Interfaces
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Direct Imprinting of Scalable, High-Performance
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Woodpile Electrodes for Three-Dimensional
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Lithium-Ion Nanobatteries
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17 Wenhao Li, Yiliang Zhou, Irene R. Howell, Yue Gai, Aditi R. Naik, Shengkai Li, Kenneth R.
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19 Carter, James J. Watkins
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Department of Polymer Science and Engineering, University of Massachusetts Amherst,
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24 Amherst, Massachusetts 01003, USA.
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27 W. Li and Y. Zhou contributed equally to this work.
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KEYWORDS: nanoimprint lithography, direct patterning, 3D structures, nanomaterials, lithium-
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33 ion batteries
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38 ABSTRACT: The trend of device downscaling drives a corresponding need for power
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40 source miniaturization. Though numerous microfabrication methods lead to successful
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creation of submillimeter-scale electrodes, scalable approaches that provide cost-effective
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43 nanoscale resolution for energy storage devices such as on-chip batteries remain elusive.
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45 Here, we report nanoimprint lithography (NIL) as a direct patterning technique to
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47 fabricate high-performance TiO2 nanoelectrode arrays for lithium-ion batteries (LIBs)
48 over relatively large areas. The critical electrode dimension is below 200 nm, which enables
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50 the structure to possess favorable rate capability even under discharging current densities
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52 as high as 5000 mAg-1. In addition, by sequential imprinting, electrodes with three-
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dimensional (3D) woodpile architecture were readily made in a “stack-up” manner. The
55 height of architecture can be easily controlled by the number of stacked layers while
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ACS Applied Materials & Interfaces Page 2 of 22
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3 maintaining nearly constant surface-to-volume ratios. The result is a proportional increase
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5 of areal capacity with the number of layers. The structure-processing combination leads to
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7 efficient use of the material and the resultant specific capacity (250.9 mAhg-1) is amongst
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the highest reported. This work provides a simple yet effective strategy to fabricate
10 nanobatteries and can be potentially extended to other electroactive materials.
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16 1. Introduction
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The advent of small devices, from microelectromechanical systems (MEMSs)1 to more recently,
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21 nanoelectromechanical systems (NEMSs),2 requires power sources with commensurate
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23 dimensions. The use of on-chip batteries, e.g. micro- and even nanobatteries, effectively avoids
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interconnection problems and unnecessary signal noise encountered by devices that are
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28 externally powered.3 The downscaling of battery size will significantly enhance the overall
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30 portability and drive MEMS/NEMS toward fully autonomous devices.
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33 A primary challenge for constructing small batteries is to fine-tune the electrode 3D architectures
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35 in order to enable both high capacity and high power using a limited footprint area.4 To date,
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38 several techniques have been applied to create such electrodes including colloidal templating,5-7
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40 vapor deposition on 3D substrates8-11 and direct ink writing.12,13 Though these methods result in
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42 delicate electrode fabrication, some key issues remain to be solved. First, the dimensions of most
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of the reported electrodes are on the order of tens of microns. Further downscaling to sub-
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47 micrometer scale will enhance the reaction-diffusion kinetics however, the cost of fabrication
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49 using traditional subtractive clean room processing techniques soars as dimensions are driven to
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the smaller dimensions. Moreover, from a commercial point of view, any chosen fabrication
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54 technique needs to be facile, scalable and cost-effective. Current methods either require multi-
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3 step processing, extensive post-treatments or are restricted to relatively low throughput
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6 manufacturing as limited by the deposition chamber size or the writing speed.
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9 Nanoimprint lithography (NIL) is widely considered to be a relatively low-cost, high-resolution
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11 and high-throughput surface patterning technique.14-16 Materials that can be patterned range from
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13 self-assembled monolayers (SAMs),17 polymers and colloidal materials,18,19 to inorganic sol-gel
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materials.20 More recently, a number of reports have explored NIL to directly pattern inorganic
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18 nanoparticles/tubes into various architectures.21-23 For example, well dispersed gold and indium
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20 tin oxide (ITO) nanoparticles can be directly molded into designed patterns via solvent-assisted
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22 NIL.24,25 Nevertheless, due to the low modulus of elastomeric stamps,26 insufficient mass
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25 transfer,27 and the shrinkage upon solvent drying, the aspect ratio of the imprinted structures are
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27 generally small especially for non-polymer imprinting.28,29 This makes NIL more of a 2D
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29 patterning technique and limits its use in 3D electrode fabrication. Recently our group has
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32 designed a general imprinting approach to 3D metal oxide nanostructures, including the
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34 woodpile structure.30 We utilized inks comprised predominantly of crystalline nanoparticles and
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36 sequential imprint-planarization cycles, followed by removal of sacrificial planarization layers
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through heating. This “stack-up” protocol enables the attainment of 3D architectures with high,
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41 and importantly, user-defined aspect ratios.
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44 Here, we presented a rapid and scalable approach for the fabrication of high-performance TiO2
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46 woodpile nanoelectrodes for lithium-ion battery (LIB) using solvent-assisted NIL. The electrodes
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48 demonstrate superior rate capability and exhibited a specific capacity of 250.9 mAhg-1, which is
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51 among the highest reported. As the number of stacked layers increases, the electrode’s areal
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53 capacity exhibits a proportional enhancement, demonstrating great potential as an on-chip power
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55 source. To the best of our knowledge, this is the first report on 3D battery electrode fabricated by
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3 direct NIL of electroactive nanoparticles. The compatibility of NIL with the current
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6 micro/nanofabrication process make it potentially a platform technology toward scaled
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8 production and integration of nanobatteries into MEMS/NEMS.
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11 2. Experimental Section
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14 2.1. Fabrication of PDMS Mold: Patterned PDMS stamps were fabricated by casting the
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16 prepolymer mixture against silicon master molds with a line grating pattern (linewidth ~ 425 nm;
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pitch~ 950 nm; height~ 480 nm). The prepolymer mixture (10:1 weight ratio of Sylgard 184
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21 silicone elastomer base and curing agent) was mixed and degassed in vacuum oven for 20 min at
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23 room temperature. Then the mixture was poured onto the master mold and placed at 70 ℃ for 5 h
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in an oven. After curing, PDMS stamps were obtained via peeling off from master mold.
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28 2.2. Preparation of TiO2 Nanoparticle Ink: To obtain TiO2 nanoparticle ink, a commercial
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31 titanium oxide (anatase, 20 wt%) nanoparticle dispersion in 1, 2 propanediol (US Research
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33 Nanomaterials, Inc.) was mixed with 1, 2 propanediol and methanol in 1:1:5 weight ratio. This
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35 mixture dispersion was further vortex-mixed and sonicated for a few minutes to obtain a stable,
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well-dispersed ink. Particle size and distribution were checked by TEM (JEOL 2000FX) and
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40 Malvern Nano Zetasizer.
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43 2.3. Fabrication of Woodpile Structure and the Planar Control Samples: Silicon dioxide
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45 wafer substrates were sonicated in ethanol and acetone for 5 min. Then, these substrates were
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washed with deionized water, and dried under nitrogen gas. A Ti/Au (5 nm/50 nm) bilayer was
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50 deposited on the silicon dioxide wafer with a designed pattern, controlled by a customized
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52 shadow mask. The TiO2 nanoparticle ink was spin-coated onto the silicon dioxide substrate
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54 (3000 rpm, 90 s) in a glove box with a 5 % relative humidity environment. Then, PDMS stamp
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3 was placed on the ink and dried on the hot plate at 55 °C for 5 min. After drying, PDMS stamp
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6 was peeled off and the patterned film was obtained. A UV-crosslinkable thiol-ene acrylate
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8 prepolymer (NOA60, Norland Products Inc.) was used for planarization. After imprinting the
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10 first layer, the patterned structure was first pretreated with UV-ozone for 15 min. Then two
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layers of NOA60 (10 wt% in propylene glycol monomethyl ether acetate) were deposited by
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15 consecutively spin coating at 1000 rpm for 1 min and curing. The imprinting-planarization
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17 process was simply repeated for the desired number of layers. Finally, TiO2 with designed layers
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was calcined at 750 °C for 5 min. Structure dimensions were checked under SEM (Magellan
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22 400). All control samples were fabricated by multi-time spin coating and thermal annealing. The
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24 film was thermally annealed at lower temperature (400 ℃) for 5 min after each spin coating
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26 except for the last time that the sample was calcined at 750 ℃ for 5 min like the woodpiles. Film
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29 thickness and porosity were checked by ellipsometry.
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32 2.4. Electrochemical Tests: All electrochemical measurements were conducted in the half-cell
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34 configuration, assembled in an argon glove box. LiClO4 (1M, in EC/DMC=1/1v) was used as the
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36 liquid electrolyte. A piece of lithium foil served as both the counter and reference electrode.
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39 Charge and discharge profiles of the electrodes were measured by galvanostatic tests (Maccor
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41 4304) under different C-rates, within a voltage window of 1.0-3.0 V. Extended cycling tests were
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43 performed with voltage window of 0.4-3.0 V. Control samples of un-patterned TiO2 films with
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varied thickness were tested under same conditions and used for comparison.
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3. Results and Discussions
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3 The TiO2 ink used in this study was first engineered to provide imprintability. Nanoparticle size,
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6 dispersity, solid concentration, and ink viscosity are among the key factors. Here, the imprint ink
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8 was made from a 20 wt% commercial TiO2 dispersion in 1, 2-propanediol. Transmission electron
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10 microscopy (TEM) shows that the particle size is below 10 nm (Figure 1a). This is comparable
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13 with the dynamic light scattering (DLS) measurement where the number- and volume-averaged
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15 particle sizes are 13.6 and 15.7 nm (Figure 1b). The slight difference results mainly from the
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17 inclusion of solvation effect and ligands in DLS. The ink was then diluted in a 1,2-
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propanediol/methanol mixture solvent to have a 3 wt% solid concentration. The incorporation of
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22 methanol is critical in three ways: 1). Methanol lowers the ink viscosity and improves wettability
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24 to facilitate film formation; 2). The low boiling-point nature (b.p. 64.7 ℃ ) leads to fast
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evaporation during spin coating and quickly concentrates the ink while the high boiling-point
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29 1,2-propanadiol (b.p. 188.2℃) provides reasonable fluidity for molding; 3). The evaporation
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31 induced composition change of ink does not lead to severe particle aggregation as a result of
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good miscibility. As shown in Figure 1c, the ink exhibits very low viscosity of 1.8 mPa ∙ s which
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36 is close to the viscosity of the mixture solvent (1.37 mPa ∙ s at 25 ℃ ). This relatively low
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38 concentration and viscosity is critical to mold filling and residual layer-free imprinting. The ink
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was stable with negligible precipitation observed over several months (zeta potential measured to
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43 be +13.4 mV). In fact, with 5-min sonication, ink stored for extended periods of time can be used
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45 as successfully as fresh ink in the imprinting process. The electron diffraction (ED) pattern of the
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47 TiO2 nanoparticles (Figure 1d) demonstrates a series of distinct diffraction rings, indicative of
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50 the polycrystalline feature and is indexed to anatase phase. The calculated d-spacing of the (101)
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52 planes is 0.36 nm as confirmed by high resolution TEM imaging (Figure 1e).
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25 Figure 1. (a) TEM image of TiO2 nanoparticles showing particle size below 10 nm. (b) DLS
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27 measurement of nanoparticle size in 1,2-propanediol/methanol mixture solvent at room temperature. (c)
28 Shear viscosity of the TiO2 ink measured at room temperature under shear rate between 100-1000 s-1.
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30 (inset: optical image of the well-dispersed TiO2 ink). (d) Electron diffraction pattern of TiO2 nanoparticles.
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(e). High resolution TEM image showing TiO2 crystal lattice.
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37 The fabrication process of the multilayered TiO2 electrode is depicted in Scheme 1. The effective
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39 footprint area was defined to be 1.51.5 cm2. To do this, a bilayer of Ti/Au (5 nm/50 nm)
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current collector was e-beam evaporated onto the silicon dioxide wafer through a shadow mask
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44 (Figure S1). The current collector is connected to the contact pad by a thin trace of gold, the
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46 dimensions of which are negligible relative to the current collection area. The imprinting
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48 followed a typical spin coating-molding-demolding process. The patterned TiO2 structure
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51 solidifies as excessive solvent permeates through poly (dimethyl siloxane) (PDMS) stamp upon
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53 heating. The structure is robust even before calcination due to the strong cohesive forces between
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55 TiO2 particles. This allowed quick demolding in less than 5 min. In order to make multilayered
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3 structures, we introduced the planarization step. A commercial thiol-ene based acrylate
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6 photoresist (NOA60, Norland, Inc) is selected as the planarization material. During spin coating,
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8 it fills the trenches between TiO2 line patterns, forming a solid, planar surface upon UV exposure,
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10 which then acts as the new substrate. By repeating steps of imprinting and planarization,
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additional layers can be readily stacked onto previous ones in an orthogonal orientation.
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15 Conceivably, as the structure volume increases with the number of stacked layers, a nearly
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17 constant surface-to-volume ratio is maintained. The woodpile architecture was obtained after a
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short time calcination in air at 750 ℃ for 5 min, during which the organic planarization layer was
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22 completely removed, as verified by thermal gravimetric analysis (TGA) (Figure S2). The neck
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24 formation and ripening of particles enhance the mechanical strength of the architecture and
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26 create nanoscale voids within TiO2 lines, which favors ion transfer.31 The porosity is estimated to
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29 be 31.3% based on the difference of refractive index from bulk TiO2 (Figure S3, Supplementary
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31 Information).
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53 Scheme 1. Schematic illustration of the TiO2 woodpile fabrication process. (i) Single layer imprinting.
54 TiO2 ink spin coated on gold charge collector followed by PDMS stamp molding-drying-demolding
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3 process. (ii) Planarization with cross-linkable thiol-ene based acrylate resin. (iii) Multilayer structure
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5 fabrication by repeating (i) and (ii). (iv) Woodpile electrode obtained after calcination.
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10 Scanning electron microscopy (SEM) and atomic force microscopy (AFM) of the attained single
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layer imprint show that well-defined line pattern of approximately 200 nm in width and height
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15 (Figure 2a, 2b) is obtained, generating an aspect ratio of 1. Barely any residual layer was
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17 observed. The deviation from stamp dimension results from the shrinkage caused by solvent
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19 evaporation and calcination. The dimensions remained consistent in the multilayered woodpile
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22 structure (Figure 2c to 2g). Consequently, stacking up to 2, 3, 4 and 6 layers resulted in effective
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24 aspect ratios of 2, 3, 4 and 6 respectively. Notably, the line shapes were well maintained even
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26 though they spanned wide gaps over the underlying layers. A larger area view of the defect-free
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imprint (Figure S4) demonstrates the robustness of the imprinting. X-ray diffraction (XRD)
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31 indicates that after calcination, the sub-10 nm TiO2 particles merged into bigger crystallites
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33 confirmed by the sharper (101) peak (Figure 2h). The crystallite size is calculated to increase
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from 3.8 nm to 23.6 nm. In addition, we noticed that small amount of TiO2 converted from
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38 anatase to rutile phase. Note that both phases are electroactive, and possess similar theoretical
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40 specific capacities (~335 mAhg-1) when nanoscale materials are used,32,33 no extra effort on
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42 crystal phase refinement was offered. To demonstrate the readiness of scaled fabrication, an
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45 inch-scale imprint was made (Figure 2i). The optical color results from the light interaction with
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47 the periodic patterns on the substrate.
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35 Figure 2. Characterizations of the calcined imprinted structures. (a, b) SEM top view and AFM height
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37 profile of the single layer imprint. (c, d) SEM top views of 2-layer and 3-layer woodpile structure. (e)
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39 Zoom-out view of the 3-layer woodpile structure. (f) SEM top view of 4-layer woodpile structure (inset:
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cross sectional view). (g) SEM cross section of the 6-layer woodpile structure. (h) XRD measurement of
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44 TiO2 before and after calcination. (i) Photograph of a larger area, 1.5’’ 2.5’’ imprint.
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To evaluate the electrochemical performance of the imprinted electrodes, a Li-TiO2 half-cell was
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52 assembled by immersing the TiO2 woodpile into liquid electrolyte and using lithium foil as
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54 counter electrode (Figure 3a). Figure 3b shows the cyclic voltammogram (CV) of a 6-layer TiO2
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3 woodpile electrode at different scan rates. At 0.1 mVs-1, characteristic cathodic peak at 1.74V
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6 and anodic peak at 2.04V were observed, corresponding to Li+ insertion and extraction (xLi
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8 TiO ↔ Li TiO ). By correlating peak current (i) to scan rates (v) (Figure 3c), we find that
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10 i ∝ v . , indicating diffusion controlled kinetics. 34
As scan rate increased to 10 mVs-1, cathodic
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13 and anodic peak shifted slightly to1.65 V and 2.1 V. This scan rate-dependence is indicative of
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15 the deviation from Nernstian system in the fast scan region. Note that the woodpile architecture
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17 provides sufficient pathways for ion transport. We believe the kinetic limitation arises from
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20 either electron transport across electrode or from the relatively slow ion diffusion within TiO2
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25 To demonstrate sequential imprinting as an efficient way to enhance areal capacity, a series of
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27 un-patterned TiO2 film electrodes with comparable loading and porosity were fabricated as
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control samples. For example, a TiO2 film made by 6 spin coating-calcination cycles is used to
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32 compare with the 6-layer woodpile. As shown in Figure 3d, areal capacity of woodpile electrodes
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34 increases linearly with the stacking of layers. The imprinted electrodes exhibit areal capacities of
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36 3.6, 7.1, 11.4, 15.5 and 21.3 μAhcm-2 for 1-, 2-, 3-, 4- and 6-layer electrode respectively under
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39 discharge current density of 500 mAg-1. This confirms that the woodpile stacking is effective
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41 towards multiplied capacity. Conceivably, when normalized to the mass loading of TiO2,
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43 woodpile electrodes with one to six layers possess identical specific capacity of approximately
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46 250.9 mAhg-1, corresponding to 0.74 Li uptake per formula unit. This value is larger than the
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48 bulk anatase TiO2 lattice, which at most accommodates 0.5 Li per formula unit, but it is not
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50 unexpected. Prior literature has revealed that decreasing particle size to the nanoscale induces
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size-dependent expansion Li uptake capacity and that the maximum Li uptake was reported to
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55 approach 1.0 per formula unit for particle sizes approaching 11 nm.32 Differential capacity curves
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3 of charge and discharge (Figure 3e) of woodpile electrode shows sharp and single peaks at 1.74
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6 V and 2.10 V. This corresponds well with the CV measurement, indicating the redox reaction
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8 occurs predominantly at these two potentials. In contrast, for planar TiO2 electrodes, increasing
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10 film thickness failed to achieve proportional enhancement of areal capacity (Figure 3f). A 6-layer
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film generates less than quadruple amount of capacity of a single layer. This indicates a
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15 significant waste of TiO2 due to inefficient material packing. The difference can be explained in
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the impact of which may not be evident when
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structure dimensions are small, as shown by the overlap of discharging profiles of patterned and
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22 un-patterned single layers. Nevertheless, when thickness increases, the slow diffusion rate of Li-
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24 ion across the electrode becomes significant. As a result, ion insertion into the inner regions of
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26 the TiO2 film is impeded and only the top layer is effective. On the contrary, woodpile
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29 architecture circumvents this limitation by maintaining a constant surface-to-volume ratio and
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31 providing an infiltrated ionic pathway into the structure. This finding demonstrates the potential
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33 of using TiO2 woodpile as a high-performance on-chip nanoelectrode.
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Figure 3. Electrochemical performance of TiO2 woodpiles and control samples. (a) Electrochemical test
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28 set-up and illustrative view of electrolyte permeation into woodpile structure. (b) CVs of a 6-layer TiO2
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30 woodpile electrode under scan rates of 0.1, 0.5, 1.0, 2.0, 5.0 and 10 mVs-1. (c) Plot of scan rate
31 dependence of anodic peak current. (d) Galvanostatic discharge profiles of imprinted architectures with 1,
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33 2, 3, 4 and 6 layers under current density 500 mAg-1. (e) Differential charge/discharge capacity curves of
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TiO2 woodpile electrode. (f) Comparison of capacity enhancement in TiO2 woodpiles and in planar films.
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40 The imprinted woodpile architecture becomes even more advantageous when performance under
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42 higher discharge rates is investigated. We define discharge current density of 1 C as 335 mAg-1.
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44 As shown in Figure 4a, at 3 C (~ 1000 mAg-1), the planar TiO2 electrode lost half of its capacity
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47 while the woodpile electrode demonstrated a capacity retention of 75%. From 1000 mAg-1 to
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49 higher discharge rates, the woodpile electrode consistently exhibited doubled to tripled capacity
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51 retention relative to the planar electrode. Even at rate as high as 15 C (5000 mAg-1), the
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woodpile electrode is able to deliver 25% of its initial capacity whereas the flat sample suffers
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56 almost complete capacity degradation. Notice that the absolute values of their initial capacities at
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3 500 mAg-1 are offset by a factor of 1.7 (Figure 3f), the woodpile exhibits 3-5 folds improvement
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6 of the actual areal capacity. Figure 4b compares the specific capacity and the discharge current
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8 density with TiO2 electrodes reported from recent literature.32,33, 36-43 The selected works mainly
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10 focus on nanostructured TiO2 (e.g. nanotube, nanocage, hollow shell, etc) or composites of TiO2
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and conductive additives including carbon nanotubes (CNTs) and graphene. It is worth noting
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15 that although we used commercially available particles and added no carbonaceous additives,
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17 these relatively simple and scalable woodpile structures achieved comparable-to-better
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electrochemical performance relative to the best-in-class reports. This comparison highlights the
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22 impact of nanoscale patterning on electrode’s performance.
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47 Figure 4. Rate capability and electrochemical performance comparison. (a) Capacity retention of 6-layer
48 woodpile electrode and control film sample under discharge rates from 1.5 C (500 mAg-1) to 15 C (5000
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50 mAg-1). (b) Comparison of specific capacity and cycling current density of the 6-layer woodpile electrode
51 with recently reported TiO2 electrodes. Voltage windows of all tests are between 1.0-3.0 V versus Li+/Li.
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3 Remarkably, the woodpile electrode demonstrated stable performance even during harsh testing
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6 conditions, such as the 15 C discharging. To further investigate the stability of the imprinted
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8 electrode, we extended the lower cut-off voltage to 0.4 V. As shown in Figure 5a, the woodpile
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10 electrodes still followed linear relationship as stacking of layers increased and demonstrated
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expanded capacity values. Areal capacity of 6-layer electrode increased from 21.3 μAhcm-2 to
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15 35.1 μAhcm-2, resulting in specific capacity as high as 413.4 mAhg-1, which is even larger than
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17 the theoretical value of 335 mAhg-1. The exact reason is not conclusive yet, but we propose that
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surface charge storage mechanisms may be involved. The randomly oriented small TiO2
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22 crystallites provide nanovoids to adsorb additional Li+, which is similar to the “house of cards”
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24 model used to explain larger Li+ storage capacity in amorphous carbon (relative to graphite).44-46
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In fact, Ferris et al recently reported that an anomalous extension of voltage window was also
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29 observed in nanosupercapacitors.47 The atypical electrochemical properties in nanodevices need
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31 more fundamental investigation. In this extended voltage window, TiO2 is likely to suffer over-
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33 discharge and may go through irreversible structural changes. Surprisingly, the imprinted TiO2
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36 woodpile electrode could be stably cycled under current densities from 500-5000 mAg-1 (Figure
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38 5b). This may be attributed to the thermal treatment and the nanoscale line pattern for facile
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40 strain release.
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22 Figure 5. Electrochemical tests of woodpile electrodes in extended voltage window from 0.4 V-3.0 V
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24 versus Li+/Li. (a) Expanded areal capacities of 1-layer to 6-layer structures. (b) Capacity retention of 6-
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layer woodpile electrode under discharge rates from 500-5000 mAg-1 in the extended voltage window.
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31 It can be clearly seen in Figure 6a that the woodpile remained intact after the test without evident
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33 cracks or delamination. It is noted however, that compared to the untested woodpiles, the surface
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35 structure of the tested samples became coarser and line width changed from 200 nm to 380 nm
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38 (Figure 6b). This results from the volume change of TiO2 and forming of the solid electrolyte
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40 interphase (SEI). It has been reported that SEI tends to form on TiO2 surface at lower potential.48
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42 To determine the surface elemental composition, electrodes after testing were rinsed in
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45 propylene carbonate (PC) to clean the residual liquid electrolyte and dried in an oven. Energy-
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47 dispersive X-ray spectroscopy (EDX) shows that besides Ti and O, Cl and C also existed (Figure
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49 6c). A more detailed X-ray photoelectron spectroscopy (XPS) elemental scan reveals that the
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atomic ratio of O: Li: Cl: C is 52.4%: 27.3%:17.0%: 3.1% (Figure 6d to 6g). As the penetration
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54 depth (less than 20 nm) of XPS is much smaller than EDX, barely any signal from Ti was
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56 collected, which is indicative of complete coverage of TiO2 under the surface SEI layer. In fact,
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58 16
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3 capacity fade can result from continuous cracking and reformation of the SEI. The stable
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6 performance of the woodpile electrodes confirms that the SEI was intact during the tests.
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29 Figure 6. SEM imaging and elemental analysis of the woodpile electrodes after electrochemical tests. (a)
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31 Cross-sectional view of a 3-layer woodpile after cycling. (b) Zoom-in view of a 3-layer woodpile showing
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33 the structure’s dimension and surface morphology changes. (c) EDX measurement of the woodpile. (d-g)
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35 XPS elemental scan of Li 1s, Cl 2p, O 1s and C 1s.
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41 4. Conclusions
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44 In summary, we fabricated the 3D TiO2 woodpile electrodes comprised designated numbers of
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stacked layers for lithium-ion nanobatteries using solvent-assisted NIL. This technique allows
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49 scalable fabrication of delicate electrode architectures with nanoscale resolution and yields
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51 specific capacities as high as 250.9 mAhg-1 and stable performance even over an extended
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53 voltage window. In addition, the sequential imprinting enabled the areal capacity to be readily
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56 multiplied while maintaining superior rate capability. In this work, we demonstrated up to 6
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3 layers of stackings. Conceivably, by using the method described, even thicker electrodes can be
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6 fabricated. The upper limit is determined by the mechanical strength and conductivity of the
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8 electroactive material. As a solution-based, additive manufacturing method, it is possible to
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10 avoid such limitations by formulating composite inks to improve rheological, mechanical and
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electrical properties. The method here is general and may inspire investigations into patterning a
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15 broad array of electroactive materials.
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21 Associated Content
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24 Supporting Information. Shadow mask design for depositing current collector, thermal
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26 gravimetric analysis (TGA) of NOA60 and TiO2 nanoparticles in air, ellipsometry of TiO2 films
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28 after thermal treatment, SEM image showing the larger area, defect-free imprinted 4-layer
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31 woodpile structure.
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34 This material is available free of charge via the internet at http://pubs.acs.org.
35
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37 Author Information
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40
Corresponding Author
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42
e-mail: watkins@polysci.umass.edu
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45
Author Contributions
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48
W. Li and Y. Zhou contributed equally to this work.
49
50
51 Notes
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54 The authors declare no competing financial interest.
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6 Acknowledgement
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9 W. L., Y. Z., I. R. H., Y. G., A. R. N., S. L., K. R. C., and J. J. W. were supported by the NSF
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Center of Hierarchical Manufacturing at the University of Massachusetts, Amherst (CMMI-
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14 1025020). The Materials Research Science and Engineering Center (MRSEC) at University of
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16 Massachusetts Amherst supported facilities used in this study. W. L. acknowledges J. Harris, K.
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Martin, A. Chang, L. Bartlett and A. Ribbe for their help with experimental procedures.
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