Printed Batteries E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 405

Veröffentlichungsjahr: 2018

Beschreibung

Offers the first comprehensive account of this interesting and growing research field Printed Batteries: Materials, Technologies and Applications reviews the current state of the art for printed batteries, discussing the different types and materials, and describing the printing techniques. It addresses the main applications that are being developed for printed batteries as well as the major advantages and remaining challenges that exist in this rapidly evolving area of research. It is the first book on printed batteries that seeks to promote a deeper understanding of this increasingly relevant research and application area. It is written in a way so as to interest and motivate readers to tackle the many challenges that lie ahead so that the entire research community can provide the world with a bright, innovative future in the area of printed batteries. Topics covered in Printed Batteries include, Printed Batteries: Definition, Types and Advantages; Printing Techniques for Batteries, Including 3D Printing; Inks Formulation and Properties for Printing Techniques; Rheological Properties for Electrode Slurry; Solid Polymer Electrolytes for Printed Batteries; Printed Battery Design; and Printed Battery Applications. * Covers everything readers need to know about the materials and techniques required for printed batteries * Informs on the applications for printed batteries and what the benefits are * Discusses the challenges that lie ahead as innovators continue with their research Printed Batteries: Materials, Technologies and Applications is a unique and informative book that will appeal to academic researchers, industrial scientists, and engineers working in the areas of sensors, actuators, energy storage, and printed electronics.

Leseprobe

Table of Contents

Cover

Title Page

List of Contributors

Preface & Acknowledgements

1 Printed Batteries

1.1 Introduction

1.2 Types of Printed Batteries

1.3 Design of Printed Batteries

1.4 Main Advantages and Disadvantages of Printed Batteries

1.5 Application Areas

1.6 Commercial Printed Batteries

1.7 Summary and Outlook

Acknowledgements

References

2 Printing Techniques for Batteries

2.1 Introduction/Abstract

2.2 Materials and Substrates

2.3 Printing Techniques

2.4 Conclusions

Acknowledgements

References

3 The Influence of Slurry Rheology on Lithium-ion Electrode Processing

3.1 Introduction

3.2 Slurry Formulation

3.3 Rheological Characteristics of Electrode Slurry

3.4 Effects of Rheology on Electrode Processing

3.5 Conclusion

List of Symbols and Abbreviations

References

4 Polymer Electrolytes for Printed Batteries

4.1 Electrolytes for Conventional Batteries

4.2 Electrolytes for Printed Batteries

4.3 Summary

References

5 Design of Printed Batteries

5.1 Introduction

5.2 Design of Printed Battery Components

5.3 Aesthetic Versatility of Printed Battery Systems

5.4 Summary and Prospects

Acknowledgements

References

6 Applications of Printed Batteries

6.1 Printed Microbatteries

6.2 Printed Primary Batteries

6.3 Printed Rechargeable Batteries

6.4 High-Performance Printed Structured Batteries

6.5 Power Electronics and Energy Harvesting

References

7 Industrial Perspective on Printed Batteries

7.1 Introduction

7.2 Printing Technologies for Functional Printing

7.3 Comparison of Conventional Battery Manufacturing Methods with Screen Printing Technology

7.4 Industrial Aspects of Screen-printed Thin Film Batteries

7.5 Industrial Applications and Combination With Other Flexible Electronic Devices

7.6 Industrial Perspective on Printed Batteries

7.7 Conclusion

References

8 Open Questions, Challenges and Outlook

Acknowledgements

References

Index

End User License Agreement

List of Tables

Chapter 02

Table 2.1 Main components and properties of different printed battery types.

Table 2.2 Selection of important parameters for screen printing [33].

Table 2.3 Main advantages and disadvantages of the doctor blade and spray-coating techniques.

Table 2.4 Printing techniques applied to printed batteries.

Chapter 03

Table 3.1 The main ingredients in electrode slurries.

Table 3.2 Rheological analyses of various lithium-ion battery slurries.

Chapter 04

Table 4.1 Summary of candidate flexible battery technologies.

Table 4.2 Dependency of room temperature ionic conductivity on the size of ceramic particulates (barium titanium oxide) added [54].

Chapter 05

Table 5.1 Materials and formulations of electrode slurries/inks for various printed batteries.

Table 5.2 Commercially available metallic inks.

Table 5.3 Types, components, printing techniques, and electrochemical characteristics of various printed power sources.

Chapter 06

Table 6.1 Differences between printed and conventional batteries.

Chapter 07

Table 7.1 Major quality aspects in the fields of graphical printing and functional printing.

Table 7.2 Comparison of selected parameters of the common printing technologies. Adapted from [2], Table 1. Reproduced with permission of John Wiley and Sons, Ltd.

Table 7.3 Presentation of selected electrochemical systems that can be realized by screen printing technologies at ambient environment and their specifications for carrier substrates.

Table 7.4 Evaluation matrix of the technology-readiness levels of the individual components of printed NiMH and zinc-based batteries.

List of Illustrations

Chapter 01

Figure 1.1 Research articles published related to inks and printed electronics. Search performed in Scopus database with the keywords “inks” and “printed electronics” on 19 June 2017.

Figure 1.2 An overview of printed batteries and main applications.

Figure 1.3 An overview of the functional inks and relevant requirements in the area of printed battery research.

Figure 1.4 Main features and attributes of printed batteries.

Figure 1.5 Schematic illustration of the main constituents and representation of the charge and discharge modes of a battery.

Figure 1.6 Schematic representation of a printed battery in the stack or sandwich cell architecture.

Figure 1.7 Schematic representation of a printed battery in the coplanar or parallel cell architecture.

Figure 1.8 Schematic representation of the interdigitated battery architecture.

Figure 1.9 Schematic representation of the gear architecture.

Figure 1.10 Main advantages of printed batteries.

Figure 1.11 Main disadvantages of printed batteries.

Figure 1.12 Main application areas of printed batteries.

Chapter 02

Figure 2.1 There are a number of established printing and patterning technologies; some can be employed for printing battery materials.

Figure 2.2 Schematic representation of the main components of a battery.

Figure 2.3 Principle of the flatbed screen printing process.

Figure 2.4 Principle of a rotary screen printing process.

Figure 2.5 Left – plain (PW) and right – twill (TW) 1:2 weave: black: side view of thread.

Figure 2.6 Screen properties in transferring ink [39].

Figure 2.7 Schematic of stencil printing. The top view is given in the upper part of the sketch.

Figure 2.8 The principle of the letterpress printing process.

Figure 2.9 The principle of the flexography printing process.

Figure 2.10 The principle of the gravure printing process.

Figure 2.11 Cross cut of a gravure cylinder.

Figure 2.12 Lithographic/offset printing setup.

Figure 2.13 Schematic illustration of: a) doctor blade and b) spray-coating techniques.

Figure 2.14 Scheme showing the basic principles of (a) CIJ technology, DoD-based (b) TIJ and (c) PIJ technology.

Figure 2.15 Scheme showing the basic principle of SIJ based on electro-hydrodynamic inkjet technology.

Figure 2.16 Images of printers (a) Primefire 106 + L from Heidelberg AG and (b) Heidelberg AG Gallus Labelfire 340 [86, 88].

Figure 2.17 SIJ inkjet printer SIJ-S050 from SIJTechnology Inc. (a) full machine, (b) inside view [70, 71].

Figure 2.18 Image of application illustrating the potential for printing of graphics on three-dimensional products using inkjet technology, e.g. the Omnifire from Heidelberg AG.

Figure 2.19 Main procedures for printed batteries.

Chapter 03

Figure 3.1 The viscosity data of mixtures with different concentrations of carbon black dispersed in the PVDF solution.

Figure 3.2 Viscoelastic data of a cathode slurry. The storage modulus (G’) is greater than the loss modulus (G”) for the cathode slurry, which has 56wt% active material, 1.3wt% Super-P, 2.5wt% KS-6, 3.2wt% PVDF and 37wt% NMP.

Figure 3.3 Comparison of viscosity curves obtained with different mixing devices.

Chapter 04

Figure 4.1 Cross-sectional SEM images of fully printed cells with thick and thin GPEs. Left: fully printed thick GPE cell; right: fully printed thin GPE cell .

Figure 4.2 Cross-sectional SEM micrograph of a spray-painted full cell showing its multilayer structure, with interfaces between successive layers indicated by dashed lines for clarity (scale bar is 100 mm) [22].

Figure 4.3 Charge–discharge curves for 1st, 2nd, 20th and 30th cycles (a) Specific capacity vs cycle numbers for the spray-painted full cell (LCO/MGE/LTO) cycled at a rate of C/8 between 2.72 and 1.5 V, (b) capacity of the different printed cells, showing 10% variation of the absolute capacity values (c) [20, 22].

Figure 4.4 Viscosity behavior of the representative electrode, gel electrolyte and ionic liquid inks as a function of the applied shear rate [30–32].

Figure 4.5 Electrochemical potential stability windows of ionic-liquid electrolytes with 0–0.75 M zinc salt concentrations [32].

Figure 4.6 Electrochemical impedance plots of a cell after assembly [32].

Figure 4.7 (a) High-discharge-rate data from printed 350-µm-thick zinc polymer battery with more than 5C-rate discharge capability. (b) Discharge curves at continuous currents (0.2, 0.5, 1, 2, 5, 10, 20 mA/cm

2

(blue through gray) from printed zinc polymer cell (the data in (a) and (b) are obtained from different cells) [35].

Figure 4.8 Ionic conductivity of PVDF/ionic-liquid mixtures [18].

Figure 4.9 Galvanostatic cycling of tape-cast LiFePO

4

-based porous composite electrode with printed ionogel in half-cell with lithium-metal counter electrode from 2.0 to 4.1 V at C/30 rate and at room temperature [41].

Figure 4.10 3D-printed miniature cell. Digital images of the 3D-printed electrodes (a) and (b), and arrays (c). Charge and discharge profiles of the 3D-printed full cell (d) [44].

Figure 4.11 Optical micrographs showing the strength and flexibility of the nanocomposite solid-state electrolyte membranes laser printed on a glass slide. (a) Membrane laser printed on a glass slide, (b) membrane partially lifted off from glass slide, and (c) membrane held using tweezers [52].

Figure 4.12 SEM micrographs of laser-printed solid-state electrolyte onto porous LiCoO

2

cathodes. The inks of various viscosities (DBE concentrations) are: (a) 91 wt.% DBE, (b) 90 wt.% DBE, (c) 89 wt.% DBE, (d) 88 wt.% DBE, and (e) 87 wt.% DBE [52].

Figure 4.13 The temperature dependence of ionic conductivity of the laser-printed nanocomposite solid-state electrolyte membrane. The inset figure is the complex resistivity plot for the same membrane [52].

Figure 4.14 (a) Representative cross-section and cutout schematic of an embedded lithium-ion microbattery fabricated by laser direct-write (LDW) printing using a nanocomposite solid-polymer ionic-liquid (nc-SPIL) electrolyte. (b) Scanning-electron-microscopy (SEM) cross-section showing the layer structures. The numbers 1 through 4 correspond to the metal current collector, the carbon anode, the nc-SPIL electrolyte, and the lithium cobalt oxide cathode, respectively. Layers 2, 3, and 4 are deposited sequentially by LDW. (c) SEM images of the nc-SPIL separator with the cathode and anode removed, showing the structural integrity of the nc-SPIL after cleaving. (d) Actual LDW microbattery in a polyimide substrate shown against a US dime for scale. The black square (3 mm

2

) indicates the active battery portion of the system [54].

Figure 4.15 50th to 53rd charge–discharge cycle of an LiCoO

2

-based microbattery made by LDW [54].

Chapter 05

Figure 5.1 Schematic of printed battery architecture and printing technologies. Examples and features of printed battery electronics integration are also described [4].

Figure 5.2 Printed electrodes with mixed electron/ion conduction. (a) Rheological properties (viscosity and viscoelasticity represented by storage modulus (G’) and loss modulus (G”)) of the electrode slurry, which consisted of LiFePO

4

(as cathode material), or Li

4

Ti

5

O

12

(as anode material), carbon black additives, and ionically conductive matrix (= UV-crosslinkable ETPTA monomer + 1 M LiPF

6

in EC/PC) without NMP solvent. (b) Photographs showing mechanical flexibility (upper image) and printability (represented by word “UNIST”, lower image) of the electrode slurry. (c) Schematic illustration of the UV-IL technique-driven micropatterning procedure and an SEM image showing the printed electrode with an inverse replica of the finely defined microscale stripe pattern.

Figure 5.3 Inkjet-printed cellulose nanomat on commercial A4 paper. (a) Effect of substrates on the resolution of the inkjet printing process: the wetting substrate (left upper side, random spreading of ink droplets), the non-wetting substrate (left lower side, coffee-ring formation), and the CNF nanomat on A4 paper (right side, high-resolution print pattern). (b) Variation in the water-contact angles of different substrates with time. (c) SEM images (surface view) of the inkjet-printed ((SWNT/AC) + Ag NWs) electrodes on different substrates. (d) Electric resistances of the inkjet-printed ((SWNT/AC) + Ag NWs) electrodes on different substrates.

Figure 5.4 Printed, UV-cured gel separator membrane. (a) Polymerization scheme of polyacrylic gel electrolyte, where R is the water-soluble photoinitiator, 4-(2-hydroxyethoxy) phenyl(2-hydroxyl-2-propyl) ketone. (b) Photolysis of the photoinitiator after exposure to UV light. (c) Photograph of the polymerized gel separator.

Figure 5.5 Spray-printed separator membranes. (a) SEM image showing the layered and fibrous structure. (b) Nyquist plot of the spray-printed separator membrane. The separator shows an ionic conductivity of ~ 1.24 mS cm

−1

.

Figure 5.6 Printed, flexible solid-state electrolyte. (a) Conceptual illustration of the printed, flexible solid-state electrolyte. (b) Dripping characteristic of a liquid electrolyte (F-solution) containing no Al

2

O

3

nanoparticles. (c) Non-dripping behavior of UV-curable electrolyte mixture (V-solution) containing Al

2

O

3

nanoparticles before UV-crosslinking reaction. (d) Comparison of viscosity between the F- and V-solution as a function of shear rate. (e) SEM images (surface) of the printed solid-state electrolyte. (f) Photographs showing the highly bendable and twistable features of the printed solid-state electrolyte. (g) FT-IR spectra depicting acrylic C = C double bonds of the printed solid-state electrolyte before/after UV irradiation.

Figure 5.7 Schematic illustration of batteries with different component configurations: (a) in series (b) in parallel.

Figure 5.8 Printed, flexible Zn/MnO

2

batteries based on Nylon mesh-containing electrodes. (a) SEM image (cross-section) of the mesh-embedded Zn electrode and (b) high-resolution SEM image of the Zn-silver interface. (c) Schematic diagram of the assembled Zn/MnO

2

alkaline battery with in-series configuration. (d) Photograph of the flexible Zn/MnO

2

battery laminated inside a polyethylene pouch. (e) Discharge profiles of the flexible Zn/MnO

2

battery at a constant current of 1 mA under the bent state (bending diameter = 0.95–3.81 cm).

Figure 5.9 (a) Schematic illustration of the Zn-MnO

2

battery with 10 series-connected cells, which was printed on a fibrous substrate. The printed silver electrodes served as the current collectors and interconnects. Amorphous fluoropolymer solution printed inbetween the Zn and MnO

2

electrodes segregated the electrolyte in individual cells. The resultant printed membrane was cut into two sheets (sheets A and B). Each electrode in sheets A and B was soaked in KOH/ZnO electrolyte and stacked together to complete the battery. (b) Photograph of sheets A and B after printing Zn, MnO

2

electrodes, silver current collectors and interconnects (scale bar = 2 cm). (c) Discharge profile of the battery under the load of a 100 kΩ resistor. (d) Output from the printed 5-stage ring oscillator when powered with a 14 V printed battery (blue line: oscillator output, red line: battery output).

Figure 5.10 Schematic representation of textile supercapacitors based on knitted carbon fibers and activated carbon inks.

Figure 5.11 All-inkjet-printed, solid-state flexible supercapacitors (SCs) on A4 paper. (a) Photograph of the inkjet-printed SCs. (b) Photograph of the inkjet-printed, letter-shaped SC that was seamlessly connected with the inkjet-printed electrical circuits and an LED lamp. (c) Photograph of the inkjet-printed, traditional Korean “Taegeuk” symbol-like SC that was seamlessly connected with the inkjet-printed electrical circuits and an LED lamp. (d) Photograph of the inkjet-printed Korea map, wherein the inkjet-printed SCs were seamlessly connected to LED lamps via the inkjet-printed electrical circuits. (e) SEM image of the LED lamp connected to the inkjet-printed electric circuits. (f) CV profile (scan rate = 1.0 mV s

−1

) of the inkjet-printed SC in the map. (g) Photograph depicting the operation of the blue LED lamp in the smart cup (with cold water (~10 °C)), wherein the inset is a photograph of a temperature sensor assembled with an Arduino board. (h) Photograph depicting the operation of the red LED lamp in the smart cup (with hot water (~80 °C)).

Figure 5.12 Spray-printed lithium-ion batteries. (a) (Left) Glazed ceramic tile with spray-printed lithium-ion cell (area = 5 × 5 cm

2

, capacity = 30 mAh) before packaging. (Right) Similar cell packaged with laminated PE-Al-PET sheets after electrolyte addition and heat sealing. (b) Mass distribution of components in the spray-printed lithium-ion battery. (c) Cross-sectional SEM image of the spray-printed full cell showing its multilayered structure, with interfaces between successive layers indicated by dashed lines for clarity (Scale bar is 100 µm). (d) Charge/discharge curves for 1st and 30th cycles. (e) Specific capacity vs. cycle numbers for the spray-printed full cell (LiCoO

2

/Li

4

Ti

5

O

12

) cycled at a rate of C/8 between 2.7 and 1.5 V. (f) Capacities of 8 out of 9 cells fall within 10% of the targeted capacity of 30 mAh, suggesting good process control over a complex device even with manual spray printing.

Figure 5.13 3D-printed microbatteries based on high-aspect-ratio electrode arrays that were interdigitated on a sub-millimeter scale. (a) Photograph of the 3D-printed battery after packaging. (b) SEM image of the 3D-printed, 16-layer interdigitated electrode. (c) Discharge profiles of the 3D-printed microbattery as a function of areal capacity. (d, e) Digital images of a miniaturized version of the 3D-printed graphene electrodes. (f) Charge/discharge profiles of the 3D-printed full cell.

Figure 5.14 Printed, solid-state lithium-ion batteries. (a) Photograph showing direct fabrication and operation of the printed lithium-ion cell on paper-made eyeglasses. (b) Photograph showing direct fabrication of the printed lithium-ion cell on a transparent glass cup with curvilinear surface. The printed lithium-ion cell, having being mounted on the round glass cup, delivered normal charge/discharge behavior (at charge/discharge current density of 0.05 C/0.05 C under a voltage range of 1.0 − 2.5 V). (c) Photograph of “PRISS” letters-shaped, printed lithium-ion cell (left side) and its charge/discharge profiles at charge/discharge current density of 0.05 C/0.05 C under voltage range of 1.0 − 2.5 V (right side), which were measured having being completely wound along rods with different diameters (=5, 10, 15 mm).

Figure 5.15 Rechargeable, skin-worn Ag-Zn tattoo battery. (a) Schematic illustration depicting the fabrication steps of the Zn/Ag tattoo cell. (b) Photograph of the Zn/Ag tattoo cell on a temporary transfer tattoo support. (c) Charge/discharge profile of the Zn/Ag tattoo cell. (d) Application of the Zn/Ag tattoo cell onto the skin.

Figure 5.16 Stencil-printed, Ag2O-Zn battery. (a) Schematic representation depicting the stencil printing of the electrode slurry. (b) Cross-sectional illustration of the stencil-printed Ag2O-Zn battery. (c) Top-down view of the stencil-printed Ag2O-Zn battery stack. (d) SEM image of the stencil-printed Ag2O-Zn battery stack.

Chapter 06

Figure 6.1 (a) Schematic of cross-section of the thin film battery and (b) discharge curve of the battery at various C-rates [17].

Figure 6.2 Schematic of dispenser-printer head with ink deposited in form of continuous line and drops [1].

Figure 6.3 (a) Optical images of a dispenser-printed lithium ion polymer battery after the deposition of graphite, PVDF separator and LCO layer [2]. (b) Schematic of the fabrication process of Zn-MnO

2

battery. (c) SEM micrograph Zn-MnO

2

battery. (d) Discharge characteristics [3].

Figure 6.4 (a–d) Schematic of the fabrication process of three-dimensional interdigitated microbattery. The process starts with patterning the gold current collector, followed by depositing the slurry for the anode and cathode, followed by encapsulation and soaking of the electrode with electrolyte. (e, f) SEM micrographs of the microbattery. (g) Rate performance of the microbattery with 8 and 16 layers of electrodes. (h) Photograph of the encapsulated microbattery [16].

Figure 6.5 (a) Schematic of the P-80 Polaroid battery and (b) discharge curve of the battery pack at various C-rates.

Figure 6.6 (a) Schematic of a printed battery laminated with a printed electronic device. (b) Demonstration of a printed temperature sensor with printed electronics powered by two-printed batteries connected in series. (c) Demonstration of printed batteries integrated with a hybrid sensor.

Figure 6.7 (a) Schematic of the Zn-MnO

2

flexible battery, (b) optical images of the battery, (c) discharge curves of the battery with varying diameter of carbon fiber and (d) discharge curves of the battery when flexed at various bending radii [30].

Figure 6.8 (a) Process flow of fabricating a mesh-embedded flexible alkaline battery. Discharge curves at the mesh-battery at various C-rates (b) and discharge curves of the battery when flexed to various bending radii (c). (d) Mesh-battery powering a green-LED under flat and bend conditions [11]. (e) A flexible alkaline battery with reinforced electrode structure powering an interactive display and microcontroller. The display shows FLAT when the battery is flat and the display shows BEND (f) when the battery is bent [31].

Figure 6.9 (a) Schematic showing the integration of a high voltage battery with a printed sensor. (b) Schematic of an all-printed high voltage Zn-MnO

2

battery. The battery consists of ten Zn-MnO

2

cells connected in series. (c) Optical image of a printed ring oscillator and (d) output from a five-stage ring oscillator powered with a high voltage printed battery [18].

Figure 6.10 (a, b) Schematic of the flexible lithium ion battery with carbon nanotube-based current collector. The electrodes are attached to a Xerox paper with PVDF binder. (c) Photograph of the battery under flexed state, (d) cross-section SEM micrograph of the battery, (e) charge–discharge curve of the battery and (f) photograph of the battery powering a red-LED under flexed state [38].

Figure 6.11 (a) Schematic of the nickel-coated textile fabric and EDS mapping showing the distribution of carbon, nickel, and iron. (b) Optical image showing the plain textile before and after electroless deposition of nickel and deposition of the slurry. (c) SEM micrograph showing the polyester textile with the nickel metal on the yarn. (d) and (e) Electrochemical characterization of the LFP- and LTO-based batteries when folding and unfolding the batteries with textile and metal foils as the current collector [39].

Figure 6.12 Demonstration of the textile battery attached to a shirt (a) and watch (b) [39].

Figure 6.13 (a) Illustration of the unrolling the textile-based flexible lithium ion battery. (b) Schematic of the battery module containing 16 batteries in series to increase the potential to 29 V with a capacity of 25 mAh. Photographs of the textile battery module integrated in a tent (c) and roller blind (d) [40].

Figure 6.14 Optical image (a) and schematic illustration (b) of the coplanar flexible battery. The battery is composed of two cells connected in series. The electrodes have an interdigitated design. The cross-section at the bottom shows the curved shape of the current collector foil. The curved design helps to prevent shorting of the electrode during flexing [41].

Figure 6.15 Examples of devices powered with a flexible coplanar battery. (a) A cosmetic patch with iontophoresis function powered with a flexible battery, (b) smart bank card to provide additional security for transactions powered with a battery, and (c) smart watch with flexible batteries embedded inside the band of the watch to provide additional capacity [41].

Figure 6.16 (a) Schematic of Zn-MnO

2

stretchable battery, (b) discharge capacities of the stretchable battery with cycle number with the battery held at various state of stretching, and (c, d) demonstration of the battery retaining its voltage even after stretching of the battery by 50% [47].

Figure 6.17 Photograph of the Kirigami battery in compressed (a) and stretched (b) state. (c, d) Photograph of the Kirigami battery continuously powering a Samsung Galaxy Gear watch even under stretched state. Discharge curves at a slow rate (e) representing standby mode and at a high rate (f) representing watching a video on the watch [48].

Figure 6.18 (a) Schematic of structured electrode with density gradient along its thickness. The electrode near the current collector is denser as compared to the electrode away from the current collector. (b) Schematic of structured electrode with gaps between islands of active material.

Figure 6.19 (a) Schematic of the co-extrusion printing process developed by researchers at Palo Alto Research Center. (b) Schematic of structured electrode with alternating patterns of high-density and low-density regions to improve Li Ion diffusion through the electrode [56].

Figure 6.20 Power electronics commonly used in battery charging. (a) The bridge rectifier circuit converts from AC to DC power. (b) The boost converter converts from a lower DC voltage to a higher DC voltage. The two transistors in the boost converter are switched on and off at opposite times; the conversion ratio V

in

/V

out

is controlled by the duty cycle of the switching.

Figure 6.21 Flexible thin film system using PV module and Li Ion battery. (a) Illustration and (b) photograph of the system. (c) Current-voltage characteristics of the PV module under three illumination conditions, corresponding to sunlight (green), and indoor light with high brightness (red) and moderate brightness (blue). (d) Battery voltage curves when charged by the PV module under the same illumination conditions [37].

Figure 6.22 Battery charging using printed organic photovoltaic module. (a) Photograph of the photovoltaic module demonstrating its flexibility. (b) Circuit schematic of battery charging. The components in the blue shaded box are contained in a BMS integrated circuit. (c) Voltage profile of a printed Li Ion battery during solar charging. The BMS prevents the battery voltage from increasing beyond 4.1 V, by turning on the transistor labeled “1” to shunt away excess current from the PV module, around the 3.6-hour mark.

Figure 6.23 Wearable system with triboelectric generator and Li Ion battery. (a) Illustration of the working mechanism of a textile triboelectric generator using fibers coated with nickel (blue) and parylene (yellow) in contact-separation (C-S) mode. (b–c) Photographs of wearable system including textile triboelectric nanogenerator (TENG) and belt containing flexible Li Ion batteries (LIB), used to power a heartbeat meter and transmit heart rate data to a smartphone. (d) Circuit schematic of the system. (e) Voltage profiles of the Li Ion battery during three cycles of charging by the triboelectric nanogenerator and galvanostatic discharging (GD) [23].

Figure 6.24 Printed thermoelectric device charging a printed battery. (a) Photograph of the system, consisting of thermoelectric generator, battery, and DC-DC converter. (b) Voltage and (c) current as the battery is charged by the thermoelectric device and discharged through an Ardustat [21].

Chapter 07

Figure 7.1 Construction principle of a flexographic printing unit.

Figure 7.2 Example of a nyloflex® digital photopolymer printing plate manufactured and distributed by Flint Group with detailed view of the raised printing elements. Reproduced with permission of Flint Group Germany GmbH (Stuttgart, Germany).

Figure 7.3 Construction principle of a rotogravure printing unit.

Figure 7.4 Detail view of a chromium-plated rotogravure printing cylinder with recessed printing elements.

Figure 7.5 Basic construction of a conventional offset printing unit.

Figure 7.6 Detail view of an offset printing plate with the printing elements (green colored) virtually located on the same layer as the non-printing elements (white area).

Figure 7.7 Main elements of a flatbed screen printing unit.

Figure 7.8 Geometrical parameters of screen printing meshes.

Figure 7.9 Detail view of a screen printing form with a thick film stencil (printing side). Printing elements are characterized as open mesh areas allowing the printing paste to be transferred onto the substrate.

Figure 7.10 Fully automated production line for the production and assembly of lithium-ion batteries. Reproduced with permission of Harro Hoefliger Verpackungsmaschinen GmbH (Allmersbach im Tal, Germany).

Figure 7.11 Exemplary presentation of two rotary screen printing lines and a sealing unit for the manufacture of zinc-based batteries in stack configuration.

Figure 7.12 Schematic drawing of the layered construction principle of a printed sandwich-type battery in stack configuration (single cell).

Figure 7.13 Printed electrodes of an NiMH battery (single cell) in stack configuration. The battery is finished after the separator is placed on one electrode followed by defined insertion of the electrolyte, the folding procedure and contact heat sealing of the printed adhesive layer (structured framing).

Figure 7.14 Schematic drawing of the layered construction principle of a printed coplanar battery with parallel architecture (single cell).

Figure 7.15 Fully printed coplanar zinc-carbon battery (single-cell, ZnCl electrolyte) with an overall thickness of 0.5 mm and the corresponding discharge curve. A capacity of 135.4 mAh was determined during discharge from the open-circuit voltage (OCV) to the cut-off voltage of 1.0 V.

Figure 7.16 Construction of a multilayered and paper-based composite substrate (p_e: smart paper type 4) developed and manufactured by Schoeller Technocell GmbH & Co. KG. GSM: Gram per square meter.

Figure 7.17 Delamination and electrolytic corrosion of the terminals of a printed NiMH battery with alkaline electrolyte (KOH).

Figure 7.18 Confocal laser scanning microscope image of a printed zinc anode layer with the different surface morphologies of the zinc particles clearly visible.

Figure 7.19 Manually realized encapsulation of a printed zinc-based battery with a handsealer.

Figure 7.20 (a) Ultrasonic welding of two PET films with printed silver tracks being crossed by the seam. Partial damage to the printed silver tracks simulating lead-outs of printed batteries in variable line widths is clearly visible in (b).

Figure 7.21 Layout variations of temperature loggers with individual positioning of the antenna and battery to optimize area usage.

Figure 7.22 Exemplary data protocol of a functional test of a temperature logger with a printegrated zinc-carbon battery (ZnCl, single cell) which was stored in a freezer.

Figure 7.23 Exemplary data protocol of a printed zinc-carbon battery-powered temperature logger (ZnCl, single cell) which was stored in a heating cabinet at elevated temperatures for functional performance testing.

Figure 7.24 Battery demonstration of a screen-printed series connection of a primary zinc-carbon battery (alkaline) with a nominal voltage of 30 V consisting of 20 cells. Manufacturing took place during the term of the EU-funded project “Flexibility”, contract number: FP7 – 287568.

Chapter 08

Figure 8.1 Main characteristics of printed batteries.

Figure 8.2 Current and future applications of printed batteries.

Guide

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Table of Contents

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Printed Batteries

Materials, Technologies and Applications

Edited by

Senentxu Lanceros-Méndez

BCMaterials, Basque Center for Materials, Applications and Nanostructures, Spain and Center of Physics, University of Minho, Gualtar campus, Braga, Portugal

and

Carlos Miguel Costa

Centers of Physics and Chemistry, University of Minho, Gualtar campus, Braga, Portugal

This edition first published 2018© 2018 John Wiley & Sons Ltd

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions.

The right of Senentxu Lanceros-Méndez and Carlos Miguel Costa be identified as the authors of the editorial material in this work has been asserted in accordance with law.

Registered Office(s)John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USAJohn Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, UK

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Limit of Liability/Disclaimer of WarrantyThe contents of this work are intended to further general scientific research, understanding, and discussion only and are not intended and should not be relied upon as recommending or promoting scientific method, diagnosis, or treatment by physicians for any particular patient. In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of medicines, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each medicine, equipment, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. While the publisher and authors have used their best efforts in preparing this work, they make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives, written sales materials or promotional statements for this work. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further information does not mean that the publisher and authors endorse the information or services the organization, website, or product may provide or recommendations it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.

Library of Congress Cataloging-in-Publication Data

Names: Lanceros-Méndez, Senentxu, 1968– editor. | Costa, Carlos Miguel, 1991– editor.Title: Printed batteries : materials, technologies and applications / edited by Senentxu Lanceros-Méndez, Carlos Miguel Costa.Description: Hoboken, NJ : John Wiley & Sons, 2018. | Includes bibliographical references and index. |Identifiers: LCCN 2017054470 (print) | LCCN 2018000676 (ebook) | ISBN 9781119287889 (pdf) | ISBN 9781119287896 (epub) | ISBN 9781119287421 (cloth)Subjects: LCSH: Electric batteries. | Three-dimensional printing.Classification: LCC TK2896 (ebook) | LCC TK2896 .P755 2018 (print) | DDC 621.31/2424–dc23LC record available at https://lccn.loc.gov/2017054470

Cover design by WileyCover image: © D3Damon/Getty Images

List of Contributors

Ana Claudia AriasElectrical Engineering and Computer Sciences DepartmentUniversity of California,BerkeleyUSA

Reinhard BaumannDepartment of Printed FunctionalitiesFraunhofer ENASChemnitzGermanyandDepartment of Digital Printing and Imaging TechnologyChemnitz University of TechnologyGermany

Li-Chun ChenDepartment of Chemical EngineeringNational Tsing Hua UniversityHsinchuTaiwanandMaterial and Chemical Research LaboratoriesIndustrial Technology Research InstituteHsinchuTaiwan

Keun-Ho ChoiDepartment of Energy EngineeringSchool of Energy and Chemical EngineeringUlsan National Institute of Science and Technology (UNIST)Korea

Maurice Clair3D- Micromac AGChemnitzGermany

Carlos Miguel CostaCenters of Physics and ChemistryUniversity of MinhoGualtar campusBragaPortugal

Abhinav M. GaikwadElectrical Engineering and Computer Sciences DepartmentUniversity of California,BerkeleyUSA

Diana GolodnitskySchool of Chemistry and Applied MaterialsTel Aviv UniversityIsrael

Martin KrebsVARTA Microbattery GmbHInnovative ProjectsEllwangenGermany

Senentxu Lanceros-MéndezBCMaterialsBasque Center for MaterialsApplications and NanostructuresSpainandCenter of PhysicsUniversity of MinhoGualtar campusBragaPortugal

Sang-Young LeeDepartment of Energy EngineeringSchool of Energy and Chemical EngineeringUlsan National Institute of Science and Technology (UNIST)Korea

Darjen LiuDepartment of Chemical EngineeringNational Tsing Hua UniversityHsinchuTaiwanandMaterial and Chemical Research LaboratoriesIndustrial Technology Research InstituteHsinchuTaiwan

Ta-Jo LiuDepartment of Chemical EngineeringNational Tsing Hua UniversityHsinchuTaiwan

Svetlana MenkinSchool of ChemistryTel Aviv UniversityIsrael

Kalyan Yoti MitraDepartment of Digital Printing and Imaging TechnologyChemnitz University of TechnologyGermany

Juliana OliveiraCenter of PhysicsUniversity of MinhoGualtar campusBragaPortugal

Aminy E. OstfeldElectrical Engineering and Computer Sciences DepartmentUniversity of California,BerkeleyUSA

Patrick RassekHochschule der Medien (HdM)Innovative Applications of the Printing Technologies (IAF/IAD)Stuttgart Media UniversityGermany

Ela StraussMinistry of Science, Spaceand TechnologyJerusalemIsrael

Carlos TiuDepartment of Chemical EngineeringMonash UniversityClaytonAustralia

Anh-Tuan Tran-LeDepartment of Digital Printing and Imaging TechnologyChemnitz University of TechnologyGermany

Michael WendlerELMERIC GmbHRangendingenGermany

Andreas WillertDepartment of Printed FunctionalitiesFraunhofer ENASChemnitzGermany

Preface & Acknowledgements

He who sees things grow from the beginningwill have the best view of them.

Aristotle (384 BC–c. 322 BC)

Printed batteries are an excellent alternative to conventional batteries for an increasing number of applications such as radio frequency sensing, interactive packaging, medical devices, sensors, and related consumer products. These batteries result from the combination of conventional battery technologies and printing technologies. Printed batteries are increasingly being explored for highly innovative energy storage systems, offering the possibility for better integration into devices and novel application areas.

In this context, the main motivation of the present book is to offer the first comprehensive account on this interesting and growing research field providing the main definitions, the present state of the art, the main research issues and challenges, and the main application areas. In this scope, this book summarizes the frontline research in this fascinating field of study, presented by selected authors with truly innovative and preponderant work.

The book provides an introduction to printed batteries and the current state of the art on the different types and materials, as well as the printing techniques for these batteries. Further, the main applications that are being developed for those printed batteries are addressed as well as the principal advantages and remaining challenges in this research field.

The first chapter provides a general overview of the area of printed batteries. It deals with definitions and the main printed batteries types such as lithium-ion, Zn/MnO2 and related systems. The advantages and disadvantages of printed batteries are discussed and the main applications summarized. Chapter 2 describes the printing techniques used for the production of printed batteries and gives a brief description of materials, substrates and the process chain used in printed batteries. Chapter 3 deals with the important issue of the influence of slurry rheology on electrode processing through its formulation, preparation technique, coating and drying systems. Moreover, the rheological characteristics of the electrode slurry are described.

Chapter 4 focuses on the polymer electrolytes used for the development of printed batteries. The state of the art on polymer electrolytes produced with different printing techniques is described in this chapter, as well as the electrolytes used in conventional and lithium-ion batteries.

The subject of Chapter 5 is the design of printed battery components. This chapter focuses on printed material layers for the electrodes used in Zn/MnO2 batteries, lithium-ion batteries, and related systems.

Chapter 6 presents the main applications of printed batteries. Power electronics, RFID, sensors and actuators, medical and energy-harvesting devices are presented and discussed.

Taking into account the different applications of printed batteries, Chapter 7 provides an industrial perspective on printed batteries considering relevant industrial aspects such as layout considerations, current collectors, carrier substrates and multifunctional substrates, among other topics.

Finally, Chapter 8 summarizes some of the main open questions and challenges and the outlook for this research field.

This book would have not been possible without the dedicated and insightful work of the authors of the different chapters. The editors truly thank them for agreeing to devote their precious time to this enterprise. We thank them for their kindness, dedication and excellence in providing high-quality chapters illustrating the main features, challenges and potential of the area of printed batteries. It has been a pleasure and an honor to work with you in this important landmark in the field!

Additionally, this book would not have been possible without the continuous dedication, support and understanding of our research group colleagues both at the Center of Physics, University of Minho, Portugal, and the BCMaterials, Basque Center for Materials, Applications and Nanostructures, Leioa, Spain. Thank you all for the beautiful and continuous endeavor of driving science and technology a step further together and for sharing this important part of our lives!

Last but not least, we truly thank the team from Wiley for their excellent support: from the first contacts with Rebecca Ralf and Sarah Higginbotham to the last with Shagun Chaudhary, Máire O’Dwyer, Emma Strickland, Rajitha Selvarajan and Lesley Jebaraj, passing through the different colleagues that supported this work; your kindness, patience, continuous support, technical expertise and insights were essential to make this book come true. It has been a real pleasure to work together with you!

Finally, let us hope this first book on printed batteries will promote not only a deeper understanding of this increasingly relevant research and application area but also the interest and motivation to tackle the main challenges, so that we all together contribute to a bright and innovative future in the area of printed batteries!

Carlos Miguel Costa and Senentxu Lanceros-Méndez

1Printed Batteries: An Overview

Juliana Oliveira1, Carlos Miguel Costa1,2 and Senentxu Lanceros-Méndez1,3

1Center of Physics, University of Minho, Gualtar campus, Braga, Portugal

2Center of Chemistry, University of Minho, Gualtar campus, Braga, Portugal

3BCMaterials, Basque Center for Materials, Applications and Nanostructures, Spain

1.1 Introduction

Increasing technological development leads to the question of how to efficiently store energy for devices in the fields of mobile applications and transport that need power supply [1, 2]. Energy storage is thus not only essential but also one of the main challenges that it is necessary to solve in this century [2, 3].

Further, energy storage systems are also increasingly needed, among others, to suitably manage the energy generated by environmentally friendly energy sources, such as photovoltaic, wind and geothermal [4, 5].

Batteries are the most-used energy storage systems for powering portable electronic devices due to the larger amounts of energy stored in comparison to related systems [2, 6]. Among them, the most widely used battery type is lithium-ion batteries, with a market share of 75% [7].

Anode, cathode and separator/electrolyte are the basic components of a battery, the cathode (positive electrode) being responsible for the cell capacity and cycle life. The anode (negative electrode) should show a low potential in order to provide a high cell voltage with the cathode [8–10].

The separator/electrolyte is placed between the electrodes as a medium for the transfer of lithium ions and also to control the number of lithium ions and their mobility [11].

Advances in the area of batteries in relation to printed technologies is expected to have a large impact in the growing area of small portable and wearable electronic devices for applications such as smart cards, RFID tags, remote sensors and medical devices, among others. This in fact originated in the development and proliferation of smart and functional materials and microelectromechanical systems (MEMS) needing on-board power supply to provide capacities of 5 to 10 mAh.cm−2 with overall dimension of < 10 mm3 [12–14].

The technological advances of the past years and the need for low-cost and simple processing leads to the potential replacement, in some areas, of conventional processing technologies by printed technologies, as evidenced in applications such as sensors, light-emitting devices, transistors (TFT), photodiodes, flat panel display solar cells and batteries, among others. Printed technology characteristics such as low cost, large area, high volume, light weight, and the processing of multilayered functional structures on rugged and flexible substrates, pave the way for new production paradigms for specific application areas [15–17].

In fact, it is expected that the global market for printed electronics will reach $45 billion in 2017 and is estimated to exceed $300 billion over the next 20 years [15, 16, 18].

This fact is also evidenced by the many articles published in scientific journal about inks and printed electronics, as shown in Figure 1.1.

Figure 1.1 Research articles published related to inks and printed electronics. Search performed in Scopus database with the keywords “inks” and “printed electronics” on 19 June 2017.

Printed materials for electronics can be applied on different substrates such as paper, plastics and textiles, giving origin to the term “flexible electronics”. Typically, the most frequently used printing techniques for printed electronics are ink-jet and screen-printing [19], but related cost-efficient and high-throughput production techniques such as solution-processing techniques including spin, spray, dip, blade and slot-die have been used, as well as gravure, flexographic and offset printing technologies [20, 21].

The different printing techniques require the use of specific inks with accurate control of viscosity and surface tension, among other things [22, 23]. Further, for specific printing techniques, the ink properties should be adjusted taking into account the specific pattern to be printed [24].

Printed electronics requires the use of different types of inks such as dielectric, semi-conductive or conductive, which are used to print the different active layers of the devices. Further, inks with piezoelectric [25], piezoresistive [26], and photosensitive [27] properties, among others, have been developed for the fabrication of sensor devices. Typically, inks can be defined as colloidal solutions as the result of a dispersion of organic and/or inorganic particles with specific size into a polymer solution [28]. Moreover, these inks must be cheap, reliable, safe to human health, and processable at temperatures below 50 °C. Further, the inks should preferentially show mechanical robustness, flexibility and recyclability [29].

Independent of the printing process, the ink should be distributed on the substrate with a specific pattern in a reproducible way, which strongly depends on its rheological properties [30].

The rheological properties (flow behavior, flow time and tack) of the ink can be evaluated by using the rotational viscosimeter to measure the viscosity as a function of shear rate, as the material is subjected to multiple shear rates during material processing.

In particular, it is important to prevent the agglomeration or sedimentation of the particles through attractive/repulsive forces, which depends on processing shear rate, as this will strongly affect the final properties of the printed layer [31].

At low shear rate, the viscosity of the inks is higher due to the attraction between particles, which induces their flocculation and immobility. At higher shear rates, the viscosity of the inks decreases through the low flocculation and higher mobility of solvent entrapped between particles [32, 33]. However, the viscosity of printing inks is not only a function of the shear stress but also of time, which plays an important role in the flow process of the ink for each printed element [30].

Further, the physical and chemical stability of the inks is affected by the different fabrication steps (stirring, dispersion, etc.), in which the energy input and mixing time influence both particle stability and degree of dispersion [34].

The combination of printing and battery technologies gives rise to printed batteries; for this at least one of the components should be processed and deposited through printing techniques in order to keep that designation [12, 35].

Figure 1.2 shows the origin of the denomination and the main applications of printed batteries.

Figure 1.2 An overview of printed batteries and main applications.

Further, flexible/stretchable batteries [36, 37] and solid-state microbatteries [38] can be included within the printed battery area when one or more components are produced by printing technologies. In addition, there are usually non-printed components such as the current collector, which also serves as support for the printed structure.