Large-Scale Colour-Changing Thin Film Energy Storage Device with

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Large-Scale Colour-Changing Thin Film Energy Storage Device with High Optical Contrast and Energy Storage Capacity Xuesong Yin, James Robert Jennings, Wei Tang, Tang Jiao Huang, Chunhua Tang, Hao Gong, and Guangyuan Wesley Zheng ACS Appl. Energy Mater., Just Accepted Manuscript • DOI: 10.1021/acsaem.8b00120 • Publication Date (Web): 03 Apr 2018 Downloaded from http://pubs.acs.org on April 3, 2018

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ACS Applied Energy Materials

Large-Scale Colour-Changing Thin Film Energy Storage Device with High Optical Contrast and Energy Storage Capacity Xuesong Yin,†,‡ James Robert Jennings,§ Wei Tang,† Tang Jiao Huang,‡ Chunhua Tang,‡ Hao Gong,*,‡ and Guangyuan Wesley Zheng*,†,∥ †

Institute of Materials Research and Engineering, A*STAR, 2 Fusionopolis Way, Innovis, 138634 Singapore. ‡

Department of Materials Science and Engineering, National University of Singapore, 117576, Singapore. §

Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, Gadong BE1410, Brunei Darussalam ∥Department

of Chemical and Biomolecular Engineering, National University of Singapore, 117585, Singapore

ABSTRACT: Thin film energy storage technology has great potential in emerging applications. The concept of integrating smart window and energy storage provides an ideally large area for thin film battery and a structural power backup for energy efficient building. However, due to the limited number of candidate materials, there is still significant challenge in optimizing the electrochemical energy storage and electrochromic properties. Here we demonstrate a novel nickel-carbonate-hydroxide (NCH) nanowire thin film based colourchanging energy storage device that possesses a high optical contrast of ~85% at 500 nm and a superior capacitance of more than 170 mF/cm2 at 10mV/s, as well as good cycling performance and controllability. Its versatility as a smart energy-storage and display device are successfully demonstrated. In addition, the scalable and cost-efficient method for fabricating the NCH material and its compatibility with flexible substrates are also expected to expand its horizon for future applications. KEYWORDS: electrochromism, energy storage, large-scale, nickel carbonate hydroxide nanowire, flexibility, thin film

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The shift towards distributed renewable energy generation requires the concurrent deployment of localized energy storage systems to balance the energy production and demand.1-3 While stationary energy systems are attractive options, structural batteries could also play an important role in providing energy storage.4 Thin film energy storage technology holds great potential in emerging flexible/wearable electronics5-6 and integrated energy storage devices,7-9 but the low areal capacity has limited its utilization. The advent of the smart home/building concept has driven materials research to enable new applications that could fundamentally change the ways we interact with the surrounding environment. The large coverage of windows in a smart building could allow thin film batteries to provide significant energy storage capacity. As electrochemical energy storage and electrochromism share similar chemical reaction pathways and device structures, electrochromic energy storage (EES) device could combine the two functions in one system and lead to costsaving.10-12 This will enable the smart windows in an energy-efficient building to serve as structural energy storage systems.13-15 However, such functional integration also brings new challenges in material selection and device construction. One important consideration in developing EES devices is to balance the requirements of coloration efficiency and energy storage capacity.12 Coloration efficiency (η) is defined as,

η=

∆OD log ( / ) = ∆ ∆

(1)

where ∆OD is the change in optical density, Tb and Tc are the transmittance in the bleached and colored states, respectively, and ∆Q is the electronic charge delivered per unit area.16 When two materials are of equivalent coloration ability (∆OD), the one with lower charge density (∆Q), i.e. higher η, is preferable for electrochromic applications. However, in an electrochromic energy storage device, a high charge density is an important requirement for high energy-storage capacity, so η is no longer a determining factor. Therefore, among


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materials with the same coloration ability, the one with the highest charge density would be chosen for EES applications. In addition to performance evaluation, another difference between energy storage and electrochromic devices lies in the microstructure of the functional materials. In energy storage devices, the demand for a large electrode–electrolyte interface makes nano-structured porous materials on a large area substrate more promising for achieving high performance.1718

On the other hand, in electrochromic devices, a dense and continuous layer is normally

needed to facilitate effective light transmission and shielding during operation, so dense thin films are often adopted to prepare high-performance electrochromic devices.19-21 The EES device, a functional combination of electrochromism and energy storage, appears to require a structural combination of a dense film and a porous layer in its active material. Previously, some attempts have been made to develop such bi-functional devices, but the results are not satisfying.12 Organic electrochromic candidates such as polyaniline13, 22 and Prussian blue11 exhibit relatively low capacitive performance compared with inorganic transition metal oxides/hydroxides.23-25 WOx-based electrochromic devices have received the most research interest and achieved considerable commercial success, partly due to their high η values (around 50 cm2/C).26 However, when applied to EES, the highest capacitance reported for a WOx-based material was only 102.4 mF/cm2 (measured at a scan rate of 10 mV/s).14 The challenge in increasing the energy storage capability of current EES devices makes it necessary to explore alternative electrochromic materials with higher capacitive performance. In this work, we developed a novel nano-structured nickel-carbonate-hydroxide (NCH) film, comprising a dense seed layer under a porous nanowire layer. This NCH film delivered a superior capacitance of more than 170 mF/cm2 (10 mV/s), which is 66% higher than the best WOx-based EES device reported. At the same time, we can achieve a high optical



contrast of ~85% (at 500 nm) with good controllability. A 13 cm × 13 cm prototype was built on glass substrate to demonstrate the bi-functional performance of the EES device. Furthermore, the facile fabrication process allows the NCH film to be compatible with different substrates and easily scalable.

Figure 1. (a) Top-view and cross-sectional SEM images, (b) TEM image and SAED pattern, (c) TG and MS curves of the NCH material. (d) XRD patterns of the NCH and annealed NCH


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samples. (e) TEM image and SAED pattern of the annealed NCH material. (f) Magnified image of the area enclosed by a red square in (e).

The NCH film is fabricated through a simple hydrothermal process. Fluorine-doped tin oxide (FTO) substrate is heated in an aqueous precursor (0.2 M nickel sulphate and 0.4 M urea) at 120-140 °C for 5 hours (see details in the supporting information). The top-view and cross-sectional SEM images of the as-prepared nickel carbonate-hydroxide (NCH) film (Figure 1a) show a 3D nanowire structure (~350 nm) and a compact layer (~400 nm) on the FTO-coated glass substrate. The SAED pattern of the nanowire material (Figure 1b) reveals two broad bands, which correspond to the (201) and (002) planes of the Ni2(CO3)(OH)2 phase (PDF #35-0501). The Thermal Gravimetric Mass Spectroscopy (TG-MS) profiles in Figure 1c reveal a major mass loss from 300°C to 400°C in the form of CO2 and H2O gases. The overall weight loss (~40 %) is larger than the theoretical value for NCH (29.3 %), indicating that the NCH may contain crystalline water.27 The FTIR spectra of the precursor material (NCH) and the annealed product (NCH-annealed) also indicate CO2 and H2O loss during heat treatment in Figure S1 (See Supporting Information). These results are consistent with the thermal analysis of nickel carbonate-hydroxide materials in the literature.27-28 No characteristic XRD peaks, except for peaks belonging to the FTO substrate, are observed in Figure 1d, indicating a weak crystalline nature of the NCH nanowire film.27 The XRD pattern of the annealed NCH sample contains a peak attributable to NiO, and the diffraction rings in Figure 1e can be assigned to the (111), (200), (222), and (311) plans of the NiO phase (PDF #47-1049). Correspondingly, clear fringes with spacing values of 0.241 nm for the (111) planes of the NiO phase are demonstrated in the high resolution TEM image (Figure 1f). Therefore, it can be concluded that a bi-layered nickel-carbonate-hydroxide (NCH) nanowire film was fabricated on the transparent and conducting FTO glass substrate.



Figure 2. (a) Transmittance spectra of the NCH films in the bleached and coloured states. The insets show photographs of a 13 cm × 13 cm film. (b) Raman spectra of the NCH films in the bleached and coloured states. (c) Voltage dependence of the faradaic capacitance (green circles) extracted by fitting EIS data using the equivalent circuit model shown in Figure S3 and the voltage dependent transmittance at 500 nm (brown squares). As reference, the transmittance spectra are shown in Figure S4. (d) Comparison of areal specific capacitance and optical contrast (∆T) of EES devices in the literature and this work. The symbols (square, circle, triangle and star) denote the different measurement parameters used for capacitance evaluation in different works, and the ∆T values are the highest transmittance contrast values obtained in the visible wavelength range.


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The transmittance spectra of the NCH film in Figure 2a show a high transparency of ~90% throughout the visible wavelength range in the bleached state and an effective light modulating ability (∆T ~ 85% at 500 nm) in the coloured state. The photographs in the insets show the coloration and bleaching effects of the NCH film with a dimension of 13 cm × 13 cm. The electrochromic properties of the nickel-based materials arises from alternation of the optical band gap between NiOOH (~1.7 eV) and NiO/Ni(OH)2 (~3.8 eV) in the charged and discharged states, respectively.15 In Figure 2b, the change of Raman shifts at 474 cm-1 and 556 cm-1 for the NCH film confirm the formation and disappearance of NiOOH in the colored and bleached states.29-30 To demonstrate the charge storage ability of the NCH films, their capacitive performance was evaluated (Figure S2). The CV curves, charge-discharge profiles and cycling ability of the NCH films exhibit the characteristics of a nickel-based energy storage material.27, 31 Comparing with the reported NCH-based materials,27, 32 the areal capacitance of the NCH film (0.22 F/cm2 at a scan rate of 5 mV/s) is smaller due to the lower mass loading to achieve transparency, but it delivers a higher gravimetric capacitance of 917 F/g. To gain further insight into the capacitive characteristics of the NCH material, EIS measurements were performed at potentials ranging from 0 V (bleached state) to 0.6 V (coloured state). A comprehensive discussion of the EIS analysis is presented in the Supporting Information (Figure S3 and Table S1). Essentially, a model-based analysis of the impedance data shows that the critical parameter, the faradaic capacitance (Cf), increases as the electrode potential increases (Figure 2c), which is attributed to the electrode potential moving into the vicinity of the redox potential for the faradic reaction. Once the potential becomes positive enough for the redox reaction to take place, the faradic capacitance sharply increases. For reference, the voltage-dependent transmittance (at 500 nm) of a NCH film is also plotted in Figure 2c,



which shows that the sharp increase in capacitance coincides with the drop in transmittance. It is worth noting that the EIS-, CV-, and charge–discharge-derived capacitance values are not identical in value, because EIS extracts the differential capacitance at a single potential, whereas the capacitances shown in Figure S2 and Figure 3 are integral capacitances that indicate the total capacitance averaged over a given potential range. The transmittance spectra at different voltages are presented in Figure S4. In Figure S5, the transmittance spectra at bleached and coloured states are also tested after various cycles. The results demonstrate good optical responses of the sample with respect to the operating voltage and cycles. Areal capacitance values of the NCH films calculated from both the charge-discharge and CV measurements are plotted in Figure S2b,e. A comparison of the performance between EES devices in the literature11, 13-14, 22, 33-34 and in this work is shown in Figure S3d and Table S2. Since diverse current densities and/or scan rates were employed in the different papers published, we carried out experiments under various conditions to obtain comparable data with the literature. It was found that our NCH-based device delivers much higher specific capacitance as well as larger transmittance contrast (∆T) than the other reported EES devices. This is attributed to the intrinsically high capacitive performance, good visible-light modulation ability and ideal microstructure of the NCH nanowire film.


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Figure 3. (a) Discharge profiles at different current densities, (b) CV curve at a scan rate of 10mV/s, (c) Areal specific capacitance and capacity at different current densities and (d) Ragone plot of the NCH films.

The electrochromic energy storage device is constructed with Zn foil as the anode and a NCH film as the cathode. The discharge plateaus at around 1.70–1.90 V at various current densities (Figure 3a) and the redox reaction peaks at around 1.6–1.7 V and 1.9–2.1 V in the CV curves (Figure 3b) are consistent with the electrochemical reactions of Ni3+/Ni2+ and Zn/Zn2+ in Ni–Zn batteries.35-36 From the discharge curves, areal capacitance and capacity values were calculated (Figure 3c). The small capacitance decay of less than 4% from 0.1 mA/cm2 (259 mF/cm2) to 1.5 mA/cm2 (249 mF/cm2) confirms the good rate performance of this EES device. The Ragone plot in Figure 3d shows an areal energy density of 4.4 µWh/cm2 at a power density of 17.5 µW/cm2, and the energy density remains at 4.1 µWh/cm2 even



when the power density is increased to 262.55 µW/cm2. These results show that our EES device has one of the best energy storage performances as reported in the literature.

Figure 4. (a) Schematic illustration of a sustainable energy system incorporating an EES device, and photographs of a prototype EES device in (State I) bleached and (State II) coloured states, and a strip of LED lights being powered by the EES device. A movie showing this prototype system in operation is provided in Video S1. (b) Photographs of a NCH display panel showing a contrast change from State I to State II. A movie ACS Paragon Plus Environment

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demonstrating this function is provided in Video S2. (c) Photographs of bleached (State I) and coloured (State II) flexible NCH-coated films under flat, bent and twisted conditions.

As a demonstration of the EES system application, electricity generated from the solar cells during the day time can be used to darken the EES device, attenuating the passage of sunlight and at the same time storing the electricity (Figure 4a). At night, the stored energy can be released to power electrical appliances (e.g. LED lights). During this process, the EES device returns to the discharged and clear state, improving the passage of light. The high transmittance of the NCH film in the bleached state (State I) can be distinguished from the colored state (State II) with the flower photo at the back. A video of the coloration of the EES device powered by a solar cell and the bleaching process through powering a fan is provided in Video S1. In addition, the as-grown NCH film can be easily modified to achieve different patterns, while maintaining the electrochromic properties (Figure 4b and Video S2). A pattern with the word “NICKEL” is printed on the EES device, which shows stable electrochromic performance. Furthermore, the facile synthesis process also allows us to grow the NCH film onto a polymer substrate to realize a highly flexible device. The bending and twisting tests of the NCH-coated ITO/PET films in bleached (State I) and coloured (State II) states in shown Figure 4c indicate their potential applications for flexible devices. In conclusion, we developed a colour-changing energy storage device based on a novel nanostructured nickel-carbonate-hydroxide film that delivers a high areal capacitance and large optical contrast, together with excellent cycling performance and controllability. The potential application of this device in multifunctional energy storage system was clearly demonstrated. Furthermore, the scalable, low-cost and environmentally friendly fabrication



process reported here makes our proposed design compatible with various substrates and makes it easier for scale up production.

ASSOCIATED CONTENT Supporting information The Supporting Information is available free of charge on the ACS Publications website at DOI: Experimental methods, additional figures, tables and discussion (PDF) A prototype EES device working with a solar cell and an electrical fan (AVI) Display function of a NCH-based device (AVI)

AUTHOR INFORMATION Corresponding Authors *Email: [email protected] *Email: [email protected] Author Contributions X.Y. conceived the project, conducted the experiments and wrote the manuscript. J.R.J conducted EIS analysis and helped on manuscript development. W.T. helped on TEM characterization and manuscript writing. T.H. and C.T. helped on optical characterizations. H.G. and G.Z. supervised the project and revised the manuscript. Notes The authors declare no competing financial interest.

ACKNOWLEDGEMENT


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G.Z., W.T. and X.Y. acknowledge support from Guangdong Dynavolt Renewable Energy Technology Co. Ltd. X. Y. thanks Xue Qi Koh for technical supports. H.G. acknowledges support from the Singapore Ministry of Education Academic Research Fund Tier 2 MOE2016-T2-1-049 Grant R284-000-157-112.

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Fig. 1 177x180mm (300 x 300 DPI)


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Fig. 2 177x138mm (300 x 300 DPI)



Fig. 3 177x118mm (300 x 300 DPI)


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Fig. 4 177x175mm (300 x 300 DPI)



Table of Content 35x23mm (300 x 300 DPI)


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Large-Scale Colour-Changing Thin Film Energy Storage Device with

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