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DOI: 10.1002/adma.200600295

Photonic Crystal Structures as a Basis for a Three-Dimensionally Interpenetrating Electrochemical-Cell System**

By Nicholas S. Ergang, Justin C. Lytle, Kyu T. Lee, Seung M. Oh, William H. Smyrl, and Andreas Stein*
Templating with colloidal crystals, arrays of close-packed polymer or silica spheres,[1] is a general method of forming three-dimensionally ordered macroporous (3DOM) materials or inverse opals composed of metals, oxides, polymers, and other compositions.[2] The resulting structures consist of nanometer thick walls that surround interconnected close-packed spherical voids with sub-micrometer diameters. Because of their periodic features with unit-cell dimensions of the order of the wavelengths of UV-visible-IR light, inverse opals have generated significant interest as photonic crystals.[3] Other applications, such as those involving reactivity of the skeleton (e.g., catalysis, biomaterials)[2] can also benefit from the 3DOM structure. To enhance functionality of an inverse opal, pore surfaces can be modified, not merely with small organic groups, but also with polymer films and nanoparticles.[4] Here, we employ a strategy involving multiple surface-modification steps to create a threefold interpenetrating functional structure based on a conducting, monolithic inverse opal, an ultrathin polymer coating, and a second conducting phase that permeates the remaining pore space. In the example provided here the resulting composite material forms an electrochemical cell in which the interpenetrating electrode materials are electronically isolated. We demonstrate the ability to shuttle an intercalant between electrodes in this nano-/microstructured cell, whose design may be adaptable to battery, capacitor, or sensor applications.[514] It was recently demonstrated that the 3DOM architecture can lead to improved rate performance of individual electrodes.[1518] For example, monolithic 3DOM carbon anodes have several advantages that facilitate rapid intercalation and deintercalation of Li ions: 1) nanometer-scale solid-state diffusion lengths, 2) high ionic conductivity of a suitable electrolyte in the porous matrix, 3) reasonable electrical conductivity and 4) no need for a binder and/or a conducting agent. Furthermore, the bicontinuous pore and wall structure of the inverse-opal architecture permits facile access and sufficient void space to accommodate a second electrode throughout the monolithic macropore system. Challenges in synthesizing such an interpenetrating electrode structure on a sub-micrometer length scale include the need to isolate electrodes from each other to prevent shorts, the ability to make electrical contact to each individual electrode,[19] and the assembly of such a functional composite under reaction conditions that maintain the integrity of the underlying structure. We developed a strategy that can achieve these requirements by combining colloidal crystal templating with electrochemical thin-film growth and soft solgel chemistry. Monolithic 3DOM carbon was coated with a conformal layer of poly(phenylene oxide) (PPO) or sulfonated PPO (SPPO) by electro-oxidative deposition of phenolic monomers. The remaining void space was infiltrated with a vanadium alkoxide gel. The complete electrode structure, which is shown in Figure 1, was electrochemically lithiated and cycled multiple times. This composite system is an example of a truly 3D electrochemical cell with critical feature sizes on the scale of tens to hundreds of nanometers. 3DOM carbon monoliths were synthesized as described previously[16] and affixed to nickel mesh (X-met) currentcollector strips. The resulting working-electrode (WE) assemblies were electropolymerized multiple times with PPO under potentiostatic conditions. Alternatively, SPPO was used to increase the polarity and ionic conductivity of the PPO backbone. This cell design requires pinhole-free polymer films with nanometer-sized thicknesses, excellent electronic insulation, reasonable ionic conductivities, and dielectric breakdown potentials that can withstand the voltage between electrodes (e.g., 34 V when Li ions are employed). Previous research by Rolison and co-workers demonstrated that PPO has a high dielectric strength (170 kV mm1) and that it can be deposited within mesoporous solids as conformal coatings tens of nanometer thick.[2022] The polymerization can be selflimiting, due to the insulating nature of the deposited polymer coating.[2325] The 3DOM carbon electrode was considered

[*] Prof. A. Stein, N. S. Ergang, Dr. J. C. Lytle Department of Chemistry, University of Minnesota Minneapolis, MN 55455 (USA) E-mail: stein@chem.umn.edu K. T. Lee, Prof. S. M. Oh Research Center for Energy Conversion and Storage and School of Chemical and Biological Engineering Seoul National University Seoul 151-744 (South Korea) Prof. W. H. Smyrl Department of Chemical Engineering and Materials Science University of Minnesota Minneapolis, MN 55455 (USA) [**] N.S.E. and J.C.L. contributed equally to this work. This research was supported by the Office of Naval Research (grant number N0001401-1-0810, subcontracted from NWU), the Petroleum Research Foundation administered by the American Chemical Society (ACSPRF grant number 42751-AC10), the Brain-Korea 21 program between Seoul National University and the University of Minnesota, and in part by the MRSEC program of the NSF (DMR-0212302) which supports the University of Minnesota Characterization Facility. We thank Dr. Chris Rhodes for helpful discussions.

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Figure 1. A) Photograph of a 3DOM carbon electrode attached to nickel mesh. B) Cross-sectional representation of the interpenetrating electrode and electrolyte layers in the cell. C) Diagram of the assembled three-dimensionally interpenetrated electrochemical cell. Electrical contact was made to the vanadia gel cathode using an Al-foil current collector.

passivated when only a small residual oxidation current (less than 500 lA) was observed. A small residual oxidation current on the last potentiostatic step has been related to monomer diffusion through the thin PPO film to the electrode surface.[21] The X-met3DOM carbonPPO composite electrode was immersed in 1 M LiClO4acetonitrile to introduce Li ions, and then annealed to seal any pinholes in the polymer coating. Scanning electron microscopy (SEM) images taken before and after electropolymerization (EP) revealed small morphological differences (Fig. 2A and B). Unmodified 3DOM carbon monoliths showed smooth pore wall surfaces, crisp edges on the nanometer-sized structural features, and open pore windows approximately 110 nm in diameter. After polymer coating, the surface of the 3DOM carbon foundation appeared more textured, with previously crisp features looking softened and slightly rounded. Wall thicknesses were also increased, and pore windows were now significantly smaller (ca. 85 nm). Similar observations were made with SPPO coatings.

Figure 2. SEM images of A) 3DOM carbon before and B) after potentiostatic EP with PPO. C) SEM image of the sample shown in (B) after multiple infiltrations with vanadia, lithiation, and cycling. D) SEM image of uncoated 3DOM carbon after multiple infiltrations with vanadia.

PPO-coated 3DOM carbon electrodes were lithiated at various rates. As shown in Figure 3, the specific capacities of the PPO-coated electrode at given specific currents were significantly reduced compared to the uncoated 3DOM carbon monolith. Even though the polymer coatings were thin and lithiated, they presented a resistance for the diffusion of Li ions. Nonetheless, at specific currents below 50 mA g1, capacities for Li ions were significantly higher than in nonporous carbon monoliths with similar dimensions.[16] The PPO-coated or SPPO-coated 3DOM carbon anode was filled with triisopropoxide vanadium(V) oxide (TIVO) as the precursor material for the cathode, using a vacuum-infiltration process. Multiple vacuum infiltrations were employed to increase the solid-volume filling fraction of the vanadia gel that formed within the interconnected macropores. SEM images of cross-sectioned electrodes showed vanadia gel spheroids that occupied the macropore space (Fig. 2C and D). In PPO-coated samples many vanadia spheres were hollow, while more of the macropore space appeared to be filled in uncoated 3DOM monoliths. The difference in surface coating versus volume filling may be related to different surface interactions between TIVO, the carbon, and PPO. Interconnectivity between the spheroids, which is essential for good electronic contact throughout the infiltrated cathode, is observed in Figure 2D. After successive solvent extractions to remove water byproducts of condensation,[26] and completing the dried cell with an Al foil cathode current collector, carbon was galvanostatically lithiated through the infiltrated V2O5 and PPO coating in 1 M LiClO4 in propylene carbonate (PC) using Li foil as the reference electrode (RE) and counter electrode (CE). Electrochemical lithiation of the carbon anode was carried out by decreasing the anode voltage to 0.01 V (versus Li+/Li) at a cathodic current of 20 lA. The need for this low current is apparent from the rate data for the vanadia-infiltrated structure shown in Figure 3 (triangles). Faster currents caused polarization of the electrochemical cell and significantly reduced the specific capacity, because in the first charging cycle, Li ions had to pass through the vanadia-filled macropores and the PPO layer before reaching the carbon phase. The revers-

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between the two electrodes in the early cycles, creating a 3D interpenetrating galvanic cell on a sub-micrometer length scale. In later cycles the composite behaved more like a pseudocapacitor with rapid polarization during each charge and discharge cycle. Pseudocapacitive electrode materials store faradaic charge at their surface, behavior that can be expected for a vanadia gel cathode, which has relatively low electrical conductivity in its undoped state.[27] This pseudocapacitive behavior confirmed that the carbon and vanadia gel electrodes were sufficiently isolated from each other by the conformal PPO thin film so that no hard electronic short circuits existed. One can expect to enhance the capacity of the electrochemical cell significantly by improved matching of electrode capacities and optimization Figure 3. Rate performances for lithiation of a 3DOM carbon monolith ( ), a 3DOM of materials properties. More complete filling of carbon monolith coated with PPO ( ), and a PPO-coated 3DOM carbon that was the pores with vanadia would increase the overall subsequently infiltrated with vanadia (~). Lines are intended merely to guide the eye. capacity for intercalation and release of Li ions by matching electrode capacities more closely, while additional ible specific charge capacity of the carbon anode was calcuincreases in the electronic conductivity of the vanadia by doplated to be approximately 750 C g1 after multiple lithiation ing[27] and increases in the ionic conductivity of the polymer steps. The open-circuit voltage (OCV) of the lithiated anode electrolyte are expected to increase the rate at which Li ions was measured to be 0.25 V, while the OCV of the cathode was or other intercalants may be transported between electrodes. 3.0 V. We are currently investigating all of these approaches toward The cell was cycled 100 times in 1 M LiClO4PC solution uncapacity enhancement. der Ar between voltage limits of 0.4 and 3.3 V versus carbon. In summary, this work has demonstrated the feasibility of A portion of the cycling profile is shown in Figure 4. In order fabricating electrochemical cells from nanostructured materito avoid polarization, the charge and discharge currents were als around an inverse opal electrode foundation. It has been set at 1 lA. The first specific discharge capacity was calcushown that it is possible to assemble the necessary solid-state lated to be approximately 250 C g1, but dropped to 59 C g1 components in a 3D interpenetrating design, using a combinain the second cycle and decreased to approximately 2.6 C g1 tion of colloidal-crystal templating, EP, and solgel chemistry. by the 100th cycle. Based on these data, Li ions were shuttled With appropriate optimization of materials and synthesis conditions, assembly strategies like the one presented here may be of interest for designs of novel nanostructured batteries, supercapacitors, or sensors.

Experimental
3DOM Carbon WEs: The 3DOM carbon products were wet-polished using 600 grit sandpaper and water to remove surface layers of dense carbon. Loose carbon particles were removed by sonication in water. Polished carbon pieces were dried at 85 C for 12 h. WE assemblies were constructed by gluing polished 3DOM carbon to a strip of X-met nickel mesh as a current collector using resorcinol formaldehyde (RF) adhesive. Nanometer-Scale Polymer Electrolyte Coatings: The PPO monomer solution was air sensitive, thus requiring that reagents and WE assemblies were handled within an Arfilled glovebox. WE assemblies were vacu-

Figure 4. Cycling profile of the 3D interpenetrating electrochemical cell. The voltage limits were readjusted during the first four cycles to attempt to increase the observed capacity. After each charge and discharge cycle, the voltage relaxed back to values of approximately 2.3 and 2.0 V versus carbon, respectively.

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um-dried at 60 C for at least 12 h. PPO electrochemical experiments were performed in three-electrode cells using a Pt gauze CE and a Pt foil RE. A KCl saturated calomel electrode (KSCE) was used as the RE for SPPO coatings. PPO: 0.471 g of phenol, 0.906 g of tetramethylammonium hydroxide pentahydrate, and 1.71 g of tetrabutylammonium perchlorate were dissolved in 50 mL of acetonitrile with stirring for at least 12 h. WE assemblies were immersed in the monomer solution for 1 h to fully infiltrate the porous architecture. Potentiostatic EP was accomplished by applying a potential of 1.2 V (versus Pt) for 30 min, followed by a period of rest for 30 min. In order to completely passivate each carbon electrode, PPO was electrodeposited in two sets of four potentiostatic steps, each set using fresh PPO solution. As-synthesized PPO-coated electrodes were immersed multiple times in 1 M LiClO4 acetonitrile for 3 days to introduce Li ions to the polymer film, then rinsed in fresh acetonitrile to extract excess LiClO4, and vacuum annealed at 85 C for 12 h. SPPO: 0.229 g of 2,6-dimethylphenol (99.5 + %), 0.145 g of 4-hydroxybenzene sulfonic acid, sodium salt dihydrate (98 %), and 0.599 g of NaOH were dissolved in 50 mL of methanol with stirring for at least 1 h. WE assemblies were immersed in the monomer solution for 1 h to fully infiltrate the porous architecture. Potentiostatic EP was accomplished by applying a potential of 1.5 V (versus KSCE) for 30 min, followed by a period of rest for at least 1 h. Cycling sweeps ranged from the OCV to 2.0 V over tens to hundreds of cycles at a scan rate of 10 mV s1. As-synthesized SPPO-coated electrodes were immersed multiple times in 1 M LiClO4PC for 3 days to displace methanol and to introduce Li ions to the polymer film, then rinsed in fresh PC and vacuum annealed at 140 C for 12 h. Infiltration with Vanadia Gel: Electrodes were filled with vanadia gel by vacuum infiltration of TIVO within the polymer-coated 3DOM carbon electrode in a dry room with relative humidity < 1 %. To avoid electronic short circuiting, infiltration was confined to the immediate vicinity of the carbon monolith by coating the outside areas with PlastiDip (a multipurpose rubber coating). Composite electrodes of current collector3DOM carbonpolymer were evacuated for 1 h in a vacuum flask. 2 mL of TIVO was injected using a syringe to completely cover the carbon electrode. Samples were removed after 30 min of immersion, and aged for 2472 h in ambient conditions. Multiple vacuum infiltrations were necessary to fully load the macroporous material with vanadia gel. After aging the gels for 3 days, the samples were immersed in acetone and hexane to extract residual water. Electrochemical Lithiation: Solvent-extracted pieces were dried under high-purity flowing Ar for several minutes. An Al foil current collector was placed on the V2O5 layer, and the interpenetrating cell was clipped together between two glass slides with a binder clip. The only contact between the two current collectors was through the cell. The electrode assembly and Li foil RE and CE were immersed in 1 M LiClO4PC to equilibrate. The carbon anode was lithiated by applying a reducing current of 20 lA from OCV to 0.01 V (versus Li+/Li). Electrochemical Cycling: The lithiated composite was immersed in a 1 M LiClO4PC electrolyte solution to enhance ionic conductivity across the PPO electrolyte layer. The V2O5 current collector was the WE and the carbon anode was used as the CE and RE. The electrochemical cell was cycled under an Ar purge for 100 cycles with a current of 1 lA. Received: February 13, 2006 Final version: March 25, 2006

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