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Printing Nanostructured Carbon for Energy Storage and Conversion Applications CARBON 92 (2015) 150– 176 Available at www.sciencedirect.com ScienceDirect journal homepage: www.elsevier.com/locate/carbon Printing nanostructured carbon for energy storage and conversion applications Stephen Lawes, Adam Riese, Qian Sun, Niancai Cheng, Xueliang Sun * Department of Mechanical and Materials Engineering, University of Western Ontario, London, ON N6A 3K7, Canada ARTICLE INFO ABSTRACT Article history: Printing is rapidly emerging as a novel fabrication technique for energy storage and Received 16 January 2015 conversion technologies. As nanostructured carbons replace traditional materials in energy Accepted 4 April 2015 devices due to their unique structures and properties, intensive research efforts have Available online 8 April 2015 focused on developing methods to print these new materials. Inkjet printing, screen print- ing, transfer printing, and 3D printing are increasingly used to print carbon nanomaterials. After a brief introduction of the basic operating principles of each of these techniques, methods for printing fullerenes, graphene, carbon nanotubes, carbon black, and activated carbon are reviewed. Subsequently, the applications of printing techniques for fabricating batteries, supercapacitors, fuel cells, and solar cells are discussed, followed by a perspective on the current challenges and future outlook of printing nanostructured carbon materials for these devices. Ó 2015 Elsevier Ltd. All rights reserved. 1. Introduction further advancements. Similarly, computers and controlled machinery mean super-fast and precise printing is available Printing techniques have existed in a variety of forms for mil- at low costs. Now techniques exist for printing nanoparticle lennia. The invention of the printing press was one of the dispersions, conductive polymers, biological molecules, and most significant advances in history and it transformed the nanostructured carbons. Using these techniques, printing way information was distributed, having widespread social has become much more than the transfer of words onto implications. Since then, many printing techniques have been pages. Functional printing technology has been used to fabri- developed, enabling faster throughput and higher quality cate displays, biological tissue scaffolds, battery electrodes, prints on a multitude of different substrates. Some of these supercapacitors, fuel cell catalysts, and solar cells. techniques include screen printing, lithography, inkjet Carbon exists in many forms including nanostructures printing, transfer printing, and recently, 3D printing. such as graphene, carbon nanotubes (CNTs), and fullerenes, The most common use of printing is the reproduction of which are some of the most fervently and widely studied text with ink on paper, however recently there has been a nanomaterials today. These three materials are similar in noteworthy rise in the development of printable functional their atomic bonding structure, comprised of sp2 bonded car- materials. Most printing inks have evolved considerably since bon, but are manifest as sheets, tubes, and spheres in 2, 1, the earliest printing, and the blossoming of nanotechnology and 0 dimensions, respectively. Both graphene and CNTs in recent decades has brought with it an opportunity for exhibit highly attractive properties such as good thermal * Corresponding author. E-mail address: [email protected] (X. Sun). http://dx.doi.org/10.1016/j.carbon.2015.04.008 0008-6223/Ó 2015 Elsevier Ltd. All rights reserved. CARBON 92 (2015) 150– 176 151 Fig. 1 – Schematic representing the printing process of nanostructured carbon materials for solar cells, batteries, fuel cells, and supercapacitors. (A color version of this figure can be viewed online.) and electrical conductivity, mechanical strength, and chemi- 2.1. Inkjet printing cal stability. Fullerenes also possess unique optical and elec- tronic properties, especially when functionalized. As a Inkjet printing is an additive technique for patterning two-di- result, nanostructured carbons are being used in a growing mensional structures onto a substrate. It precisely deposits number of established and emerging applications. Printing ink droplets at desired locations without pre-patterning the these materials has been recognized as an excellent approach substrate, making it simple to use while minimizing wasted for preparing functional structures and films with precise material. It has been widely adopted in industry as a rapid thickness control, patternability, and minimal wasted fabrication technique, ranging from advertising to material material. tagging to printed circuit boards. Here we review printing of carbon nanomaterials and the Inkjet printing has also been successfully applied to application of printed carbons for energy storage and conver- fabricating energy storage and conversion devices, such as sion (Fig. 1). This review begins with an introduction of basic battery electrodes [1–6], supercapacitors [7–11], and solar cells printing methods and principles, highlighting and comparing [12–16]. It can be used to fabricate thin films or patterns of several of the most important techniques. Subsequently, a uniform thickness, which can be controlled by the number detailed review of printed carbon nanomaterials is given. of layers printed on top of one another. Inkjet printing tech- Essential parameters for printing these materials such as nology has many advantages over other fabrication tech- functionalization, surface treatment, and ink preparation will niques, including cost-effectiveness, ease of use, minimal be discussed with specific examples from the literature given wasted material, scalability, and the ability to deposit throughout. Finally, applications of printed carbon nano- designed patterns. materials for energy storage and conversion are discussed, Principally, inkjet printing can be divided into continuous followed by an outlook on potential future trends in printing inkjet (CIJ) and drop-on-demand (DOD) methods. CIJ printing nanostructured carbon research and technology. involves pumping liquid ink through a nozzle where a con- tinuous stream of droplets is formed by a vibrating piezoelec- 2. Principles of printing technologies tric crystal. Some droplets are charged by passing them through an electric field, which can be varied to control the The fundamental principles of four major printing techniques degree of charging. The droplets then pass through another are introduced here. Inkjet printing, screen printing, and electric field, with the more highly charged droplets deflecting transfer printing are all commonly used techniques for more than those with a lesser charge. In this way an image depositing nanostructured carbon onto substrates of varying can be produced, with unused ink being collected in a gutter size, surface energy, and flexibility for energy applications. and recycled. On the other hand, DOD printers eject material 3D printing, on the other hand is an emerging technology, only when required. This involves forcing ink out of a series of with very few studies of its use for carbon nanomaterials nozzles mounted on a print head. Because DOD printers do reported. However, it is becoming a popular technique in both not recycle ink, which may result in degradation upon expo- academic research and industry, and is therefore discussed sure to atmosphere, they are the standard choice for printing briefly in this section. functional materials including graphene and carbon 152 CARBON 92 (2015) 150– 176 nanotubes. In addition, DOD printing generally wastes less material; it is therefore a more suitable technique for printing expensive materials. The three main stages of inkjet printing are illustrated in Fig. 3a: droplet ejection, droplet spreading, and droplet solidi- fication. The print head is first moved to the desired position, where droplets are ejected through the nozzle and travel to the substrate. Upon impact, they spread along the surface and join with other droplets, forming a thin film of liquid ink. Finally, the solvent evaporates, leaving the solid contents of the ink remaining on the substrate. To achieve droplet ejection in DOD printers, there are two main types of inkjet print heads: thermal and piezoelectric. Thermal print heads contain a resistor inside the ink chamber which, upon an applied voltage, will superheat the ink above the bubble nucleation temperature. The bubble expands, forc- ing ink out of the chamber and through the nozzle. Once the ink is ejected, the chamber rapidly cools, allowing more ink to refill the chamber. This entire process occurs within a few microseconds [17]. Piezoelectric inkjet print heads, on the other hand, contain a piezoelectric element that pulsates upon electrical excitation, which forms a pressure wave that forces ink out of the chamber. The vibration of the piezoelec- tric material can be precisely tuned to control droplet ejection from the nozzle. Typically, inkjet print heads comprise of hundreds of ink chambers and nozzles to achieve high throughput. A higher number of nozzles allows for printing of higher resolution patterns in shorter time frames, an important metric for large-scale production. Thermal print heads are generally cheaper and require less maintenance than piezoelectric print heads because they Fig. 2 – Influence of ink properties on (a) droplet formation contain no moving parts. The cartridge on which the print (Reprinted from [27]. Copyright 2010 Annual Reviews) and heads are mounted can simply be replaced by the user for (b) droplet spreading
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