A Novel Solid State Ultracapacitor

A Novel Solid State Ultracapacitor

<p>NASA/TM—2017–219686 </p><p><strong>A Novel Solid State Ultracapacitor </strong></p><p><em>A. Y . C ortés-Peña Johnson Space Center, Houston, Texas </em></p><p><em>T . D. Rolin and S.M. Strickland Marshall Space Flight Center, Huntsville, Alabama </em></p><p><em>C.W. Hill CK T e chnologies, Meridianville, Alabama </em></p><p><strong>August 2017 </strong></p><p><strong>The NASA STI Program…in Profile </strong></p><p>Since its founding, NASA has been dedicated to the </p><p>• CONFERENCE&nbsp;PUBLICATION. Collected papers from scientific and technical conferences, symposia, seminars, or other meetings sponsored or cosponsored by NASA. </p><p>advancement of aeronautics and space science. The </p><p>NASA Scientific and Technical Information (STI) Program Office plays a key part in helping NASA </p><p>maintain this important role. </p><p>• SPECIAL&nbsp;PUBLICATION. Scientific, technical, </p><p>or historical information from NASA programs, projects, and mission, often concerned with subjects having substantial public interest. </p><p>The NASA STI Program Office is operated by Langley Research Center, the lead center for NASA’s scientific and technical information. The NASA STI Program Office provides access to </p><p>the NASA STI Database, the largest collection of aeronautical and space science STI in the world. </p><p>The Program Office is also NASA’s institutional </p><p>mechanism for disseminating the results of its research and development activities. These results </p><p>are published by NASA in the NASA STI Report Series, which includes the following report types: <br>• TECHNICAL&nbsp;TRANSLATION. </p><p>English-language translations of foreign </p><p>scientific and technical material pertinent to </p><p>NASA’s mission. <br>Specialized services that complement the STI </p><p>Program Office’s diverse offerings include creating </p><p>custom thesauri, building customized databases, organizing and publishing research results…even providing videos. </p><p>• TECHNICAL&nbsp;PUBLICATION. Reports of completed research or a major significant </p><p>phase of research that present the results of NASA programs and include extensive data </p><p>or theoretical analysis. Includes compilations of significant scientific and technical data </p><p>and information deemed to be of continuing reference value. NASA’s counterpart of peerreviewed formal professional papers but has less stringent limitations on manuscript length and extent of graphic presentations. </p><p>For more information about the NASA STI Program Office, see the following: </p><p>• Access&nbsp;the NASA STI program home page at </p><p>&lt;http://www.sti.nasa.gov&gt; <br>• E-mail&nbsp;your question via the Internet to <br>&lt;[email protected]&gt; </p><p>• TECHNICAL&nbsp;MEMORANDUM. Scientific and technical findings that are preliminary or of specialized interest, e.g., quick release reports, working papers, and bibliographies that contain </p><p>minimal annotation. Does not contain extensive </p><p>analysis. <br>• Phone&nbsp;the NASA STI Help Desk at </p><p>757–864–9658 </p><p>• Write&nbsp;to: <br>NASA STI Information Desk </p><p>Mail Stop 148 </p><p>NASA Langley Research Center </p><ul style="display: flex;"><li style="flex:1">Hampton, VA 23681–2199, USA </li><li style="flex:1">• CONTRACTOR&nbsp;REPORT. Scientific and </li></ul><p>technical findings by NASA-sponsored </p><p>contractors and grantees. </p><p>NASA/TM—2017–219686 </p><p><strong>A Novel Solid State Ultracapacitor </strong></p><p><em>A. Y . C ortés-Peña Johnson Space Center, Houston, Texas </em></p><p><em>T . D. Rolin and S.M. Strickland Marshall Space Flight Center, Huntsville, Alabama </em></p><p><em>C.W. Hill CK T e chnologies, Meridianville, Alabama </em></p><p>National Aeronautics and Space Administration </p><p>Marshall Space Flight Center • Huntsville, Alabama&nbsp;35812 </p><p><strong>August 2017 </strong></p><p>i</p><p><strong>Acknowledgments </strong></p><p>A.Y. Cortés-Peña thanks Terry D. Rolin for his invaluable guidance and insight into this project as her mentor. She also thanks NASA’s Motivating Undergraduates in Science Technology Program and the Hispanic Scholarship Fund for making her internship possible. She also thanks Mark Strickland, Patrick Mcmanus, Curtis Hill, Kathy Pressnell, Lee Allen, David Geist, Furman Thompson, Ron Hodge, Angela Shields, Angie Thoren, and staff in ES43 for supporting her project. This work has been paid in part by the Electrical, Electronic, and Electromechanical Parts, Packaging, and Fabrication Branch (ES43), the Center Innovation Fund, several NASA Marshall Space Flight Center Project Offices and has been funded by the NASA Georgia Space Grant. </p><p><strong>TRADEMARKS </strong></p><p>Trade names and trademarks are used in this report for identification only. This usage does not constitute an official endorsement, either expressed or implied, by the National Aeronautics and Space Administration. </p><p>Available from: <br>NASA STI Information Desk <br>Mail Stop 148 <br>NASA Langley Research Center Hampton, VA 23681–2199, USA <br>757–864–9658 </p><p>This report is also available in electronic form at <br><a href="/goto?url=http://www." target="_blank">&lt;http://ww</a><a href="/goto?url=http://www." target="_blank">w</a><a href="/goto?url=http://www." target="_blank">.</a>sti.nasa.gov&gt; </p><p>ii </p><p><strong>TABLE OF CONTENTS </strong></p><p>1. INTRODUCTION ............................................................................................................. 2. BACKGROUND&nbsp;................................................................................................................ <br>12<br>2.1 Conventional&nbsp;Capacitors .............................................................................................. 2.2 Electrochemical&nbsp;Double-Layer Capacitor ..................................................................... 2.3 Internal&nbsp;Barrier Layer Capacitor&nbsp;.................................................................................. <br>246</p><p></p><ul style="display: flex;"><li style="flex:1">3. METHODOLOGY ............................................................................................................ </li><li style="flex:1">8</li></ul><p>3.1 Atomic&nbsp;Layer Deposition-Coated Ceramic Barium Titanate Nanoparticles ................. 3.2 High-Temperature&nbsp;and Reduced Forming Gas Sintering&nbsp;.............................................. <br>89<br>3.3 Pellet&nbsp;Electrical Characterization ..................................................................................&nbsp;11 3.4 Dielectric&nbsp;Ink Formulation&nbsp;........................................................................................... 12 3.5 3D&nbsp;Additive Thick Film Deposition&nbsp;............................................................................. 12 3.6 Thick&nbsp;Film Electrical Characterization .........................................................................&nbsp;14 </p><p>4. ANALYSIS .........................................................................................................................&nbsp;15 <br>4.1 Pellet&nbsp;Electrical Characterization ..................................................................................&nbsp;15 4.2 Thick&nbsp;Film Electrical Characterization .........................................................................&nbsp;20 </p><p>5. CONCLUSIONS ................................................................................................................&nbsp;26 REFERENCES .......................................................................................................................&nbsp;28 </p><p>iii </p><p><strong>LIST OF FIGURES </strong></p><p>1. 2. </p><ul style="display: flex;"><li style="flex:1">Schematic of a conventional capacitor ....................................................................... </li><li style="flex:1">2</li></ul><p>Ragone chart of energy storage devices. Source: Defense Logistics Agency Land </p><ul style="display: flex;"><li style="flex:1">and Maritime ............................................................................................................. </li><li style="flex:1">5</li></ul><p>679<br>3. 4. 5. 6. <br>Schematic of an EDLC .............................................................................................. IBLC effect&nbsp;................................................................................................................ BaTiO nanoparticle&nbsp;with 5 nm of SiO&nbsp;coating ........................................................ </p><p></p><ul style="display: flex;"><li style="flex:1">3</li><li style="flex:1">2</li></ul><p></p><p>The BaTiO&nbsp;crystal structure. The green, red, and blue atoms are titanium, </p><p>3</p><p>oxygen, and barium, respectively. Source: &lt;www.crystalmaker.com&gt;&nbsp;........................ 10 </p><ul style="display: flex;"><li style="flex:1">7. </li><li style="flex:1">Dielectric Test Fixture 1645-1B (bottom) and Agilent E4980A precision LCR </li></ul><p>meter (top) .................................................................................................................&nbsp;11 </p><p>8. 9. <br>Top and side views of the ultracapacitor module layers&nbsp;............................................. 13 Eight-zone belt furnace temperature settings&nbsp;............................................................. 13 Belt furnace temperature profile .................................................................................&nbsp;14 SEM images of BaTiO&nbsp;(a) uncoated from TPL, (b) coated with Al O , <br>10. 11. </p><p></p><ul style="display: flex;"><li style="flex:1">3</li><li style="flex:1">2</li><li style="flex:1">3</li></ul><p></p><p>and (c) Al&nbsp;O -coated treated at 750 °C for 30 hr ........................................................&nbsp;15 </p><p></p><ul style="display: flex;"><li style="flex:1">2</li><li style="flex:1">3</li></ul><p></p><p>12. 13. 14. 15. <br>Optical microscopy photographs of untreated (a) uncoated, (b) SiO -coated, </p><p>2</p><p>and (c) Al&nbsp;O -coated BaTiO&nbsp;pellets ..........................................................................&nbsp;15 </p><p></p><ul style="display: flex;"><li style="flex:1">2</li><li style="flex:1">3</li><li style="flex:1">3</li></ul><p></p><p>Optical microscopy photographs of (a) uncoated, (b) SiO -coated, </p><p>2</p><p>and (c) Al&nbsp;O -coated BaTiO&nbsp;pellets treated at 900 °C for 1 hr ..................................&nbsp;16 </p><p></p><ul style="display: flex;"><li style="flex:1">2</li><li style="flex:1">3</li><li style="flex:1">3</li></ul><p></p><p>Optical microscopy photographs of (a) uncoated, (b) SiO -coated, </p><p>2</p><p>and (c) Al&nbsp;O -coated BaTiO&nbsp;pellets treated at 1,100 °C for 1 hr&nbsp;............................... 16 </p><p></p><ul style="display: flex;"><li style="flex:1">2</li><li style="flex:1">3</li><li style="flex:1">3</li></ul><p></p><p>Plots of (a) permittivity, (b) DF, and (c) ESR samples treated at 900 °C for 15 hr and 1,100 °C for 1 hr compared to the untreated powders&nbsp;......................................... 17 </p><p>iv </p><p><strong>LIST OF FIGURES (Continued) </strong></p><p>16. 17. 18. 19. <br>Plots of (a) permittivity, (b) DF, and (c) ESR samples treated at 900 °C for 1 hr compared to the untreated powders ...............................................................&nbsp;19 </p><p>Ultracapacitor test cell made from SiO&nbsp;-coated BaTiO&nbsp;deposited by screen </p><p></p><ul style="display: flex;"><li style="flex:1">2</li><li style="flex:1">3</li></ul><p></p><p>printing ......................................................................................................................&nbsp;20 Plots of (a) permittivity, (b) DF, and (c) ESR plots of powdered samples treated at 900 °C for 1 hr before and after furnace sintering&nbsp;.................................................. 21 </p><p>SEM image showing a 75% densification and the porosity of SiO -coated BaTiO </p><p></p><ul style="display: flex;"><li style="flex:1">2</li><li style="flex:1">3</li></ul><p></p><p>test cell with 184 nF of capacitance&nbsp;........................................................................... 22 Voltage versus time plot used for the discharge method&nbsp;............................................. 23 Breakdown curves for a device exhibiting breakdown &gt;500 V&nbsp;................................... 24 <br>20. 21. </p><ul style="display: flex;"><li style="flex:1">22. </li><li style="flex:1">Plots of (a) capacitance, (b) DF, and (c) ESR the capacitor test cells, made from </li></ul><p>the dielectric material treated at 900 °C for 1 hr before and after furnace sintering&nbsp;........................................................................................................ 25 </p><p>23. 24. <br>Ultracapacitor cells in parallel ....................................................................................&nbsp;27 Ultracapacitor package...............................................................................................&nbsp;27 </p><p>v</p><p><strong>LIST OF TABLES </strong></p><p>1. 2. 3. 4. 5. 6. 7. <br>Model for corresponding capacitance ranges&nbsp;.............................................................. Ultracapacitor/Battery comparison ............................................................................. <br>36</p><ul style="display: flex;"><li style="flex:1">8</li><li style="flex:1">BaTiO materials&nbsp;........................................................................................................ </li></ul><p></p><p>3</p><p>Dielectric ink formulation ...........................................................................................&nbsp;12 Furnace nitrogen flow profile&nbsp;...................................................................................... 14 Synthesis profile effect on dielectric permittivity&nbsp;......................................................... 18 SiO -coated BaTiO&nbsp;capacitor test cell characteristics .................................................&nbsp;23 </p><p></p><ul style="display: flex;"><li style="flex:1">2</li><li style="flex:1">3</li></ul><p></p><p>vi </p><p><strong>LIST OF ACRONYMS, SYMBOLS, AND ABBREVIATIONS </strong></p><p></p><ul style="display: flex;"><li style="flex:1">AC </li><li style="flex:1">alternating current </li></ul><p>AgZn Al O silver zinc alumina </p><p></p><ul style="display: flex;"><li style="flex:1">2</li><li style="flex:1">3</li></ul><p></p><p></p><ul style="display: flex;"><li style="flex:1">ALD </li><li style="flex:1">atomic layer deposition </li></ul><p></p><ul style="display: flex;"><li style="flex:1">barium titanate </li><li style="flex:1">BaTiO </li></ul><p>DC </p><p>3</p><p>direct current </p><ul style="display: flex;"><li style="flex:1">DF </li><li style="flex:1">dissipation factor </li></ul><p>EEE EDLC ESR electrical, electronic, and electromechanical electrochemical double-layer capacitor equivalent series resistance </p><ul style="display: flex;"><li style="flex:1">hydrogen gas </li><li style="flex:1">H</li></ul><p></p><p>2</p><p>HESSCap IBLC high energy solid state capacitor internal barrier layer capacitor inductance, capacitance, resistance lithium-ion <br>LCR Li-ion </p><ul style="display: flex;"><li style="flex:1">N</li><li style="flex:1">nitrogen gas </li></ul><p></p><p>2</p><p></p><ul style="display: flex;"><li style="flex:1">O</li><li style="flex:1">oxygen </li></ul><p>PdAg SEM palladium silver scanning electron microscopy </p><p>vii </p><p><strong>LIST OF ACRONYMS, SYMBOLS, AND ABBREVIATIONS (Continued) </strong></p><p></p><ul style="display: flex;"><li style="flex:1">Si </li><li style="flex:1">silicon </li></ul><p></p><ul style="display: flex;"><li style="flex:1">SiO </li><li style="flex:1">silica </li></ul><p></p><p>2</p><p>SPS Ti spark plasma sintering titanium </p><p>viii </p><p><strong>NOMENCLATURE </strong></p><p><em>A C D E e</em></p><p>surface area capacitance distance energy electron </p><p><em>f</em></p><p>frequency current </p><p><em>I j</em></p><p>imaginary part of impedance power </p><p><em>P P</em></p><p>maximum power stored charge resistance, resistor time </p><p>max </p><p><em>Q R t</em></p><p>tan δ loss tangent delta </p><p>voltage </p><p><em>V V</em></p><p>final voltage initial voltage reactance </p><p><em>f</em></p><p><em>V</em></p><p><em>i</em></p><p><em>X Z</em></p><p>impedance ix </p><p><strong>NOMENCLATURE (Continued) </strong></p><p>εεε</p><p>vacuum permittivity effective permittivity relative permittivity </p><p>0eff </p><p><em>r</em></p><p>x<br>TECHNICAL MEMORANDUM </p><p><strong>A NOVEL SOLID STATE ULTRACAPACITOR </strong><br><strong>1. INTRODUCTION </strong></p><p>NASA analyzes, tests, packages, and fabricates electrical, electronic, and electromechanical (EEE) parts used in space vehicles. One area that NASA wishes to advance is energy storage and delivery. Currently, space vehicles use rechargeable batteries that utilize silver zinc (AgZn) or lithium ion (Li-ion) electrochemical processes. These current state-of-the-art rechargeable batteries cannot be rapidly charged, contain harmful chemicals, and suffer from early wear-out mechanisms. A solid state ultracapacitor is an EEE part that offers significant advantages over current electrochemical and electrolytic devices. The objective of this research is to develop an internal barrier layer capacitor (IBLC) using novel dielectric materials as a battery replacement with a focus on such advantages as longer life, lower mass-to-weight ratio, rapid charging, on-demand pulse power, improved on-pad standby time without maintenance, and environmental friendliness. </p><p>Ultracapacitor behavior has been reported in a number of oxides including reduced barium titanate (BaTiO ) ferroelectric ceramics. BaTiO&nbsp;is a ceramic material in the perovskite family that </p><p></p><ul style="display: flex;"><li style="flex:1">3</li><li style="flex:1">3</li></ul><p></p><p>possesses a high dielectric constant. Individual coating of ferroelectric BaTiO&nbsp;grains with a silica </p><p>3</p><p>(SiO ) shell followed by spark plasma sintering (SPS) in reducing conditions has been shown to </p><p>2<br>5</p><p>lead to stable ultracapacitor behavior. The permittivity values have been reported to be ≈10&nbsp;in electroceramics. It&nbsp;has also been shown that treating oxidized BaTiO&nbsp;at high temperatures in reduc- </p><p>1<br>3</p><p>ing forming gas atmosphere (96% nitrogen gas (N ), 4% hydrogen gas (H )) produces an N-type </p><p></p><ul style="display: flex;"><li style="flex:1">2</li><li style="flex:1">2</li></ul><p>2</p><p>semiconducting material.&nbsp;The outer coating, which remains an insulating shell, combines with this semiconducting internal layer, resulting in millions of nanocapacitors in parallel. The combination of a semiconducting grain with an insulating boundary leads to the IBLC effect. </p><p>These so-called giant ultracapacitor properties are not easily controlled. The American <br>Piezo Ceramics International reports a relative dielectric constant of 1,550 and a dielectric dis- </p><p>3</p><p>sipation factor (DF) of 0.5 for single crystal BaTiO .&nbsp;High permittivity values such as relative </p><p>3</p><p>permittivity ε ≈10,000 are reported in polycrystalline ferroelectric BaTiO . Reduced BaTiO&nbsp;of </p><p><em>r</em></p><p></p><ul style="display: flex;"><li style="flex:1">3</li><li style="flex:1">3</li></ul><p>5 4 </p><p>grain sizes between 70 and 300 nm have yielded colossal permittivity values in the order of 10 . The purpose of this study is to evaluate shell-coated BaTiO&nbsp;processed under reducing conditions </p><p>3</p><p>to produce the IBLC effect. <br>1</p><p><strong>2. BACKGROUND </strong><br><strong>2.1 Conventional&nbsp;Capacitors </strong></p><p>A capacitor is an electrical component consisting of two conducting electrodes separated by an insulating dielectric material. When voltage is applied across the capacitor, opposite charges accumulate on the surface of each electrode, developing a static electric field. This field causes atoms in the insulator to polarize, producing an internal electric field. Capacitors are able to store energy in this overall electric field. This is illustrated in figure 1. </p><p>Dielectric </p><p>+++++++++</p><p>–––––––––<br>– + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + – + </p><p>Positive Electrode <br>Negative Electrode </p><p>Load <br>Resistance <br>Electric Field </p><p>–</p><p>+</p><p>Applied Voltage </p><p>5</p><p>Figure 1.&nbsp;Schematic of a conventional capacitor. <br>Capacitance is a measure of the ability to store charge, and it is the ratio of the stored charge <em>Q </em>to the applied voltage <em>V</em>: </p><p><em>Q V</em></p><p>.</p><p>(1) </p><p><em>C </em>= </p><p>The capacitance can be improved by increasing the electrode surface area <em>A </em>and decreasing the distance between the plates. It is also proportional to the ε , which measures how much electric flux </p><p><em>r</em></p><p>is generated per unit charge, and it is directly related to how easily a specific material polarizes in response to an electric field. The vacuum permittivity ε is a constant due to free space vacuum and </p><p>0</p><p>2</p><p>–12 </p><p>is 8.854187…× 10 F/m.&nbsp;The relative permittivity multiplied by the vacuum permittivity is usually called the effective permittivity ε : </p><p>eff </p><p><em>A D</em></p><p></p><ul style="display: flex;"><li style="flex:1">.</li><li style="flex:1">(2) </li></ul><p></p><p><em>C </em>= ε ε </p><p>0 <em>r </em></p><p>Capacitive loads oppose the change of voltage. Impedance <em>Z </em>is a measure of the effect of capacitive loads. When reactance <em>X </em>is zero, the load is purely resistive; when resistance <em>R </em>is zero, the load is purely reactive. Ideal capacitors consist entirely of reactance, having infinite resistance: </p><p><em>Z </em>= <em>R</em>+ꢀ<em>jX </em></p><p>(3) and </p><p>1</p><p><em>X </em>= </p><p><em>C</em></p><p>.</p><p>(4) </p><p>2π<em>fC </em></p><p>Loads are modeled as either series or parallel combination of a resistive and a reactive load. <br>The parallel resistance is typically larger than the series resistance. To measure small reactive values, such as high-valued capacitors, it is preferable to use the series model because the series resistance is more significant than the parallel resistance. When measuring large reactive values, such as high-valued inductors or low-valued capacitors, it is preferable to use the parallel model. Table 1 </p><p>6</p><p>shows the capacitance ranges and which model should be used. <br>Table 1.&nbsp;Model for corresponding capacitance ranges. </p><p><strong>Range </strong></p><p>&gt;100 µF </p><p><strong>Impedance (</strong>Ω<strong>) </strong></p><p>&lt;10 </p><p><strong>Model </strong></p><p>Series <br>10–10,000 <br>10,000 <br>Series or parallel <br>Parallel <br>10 nF–100 µF <br>&lt;10 nF </p><p>At low frequencies, a capacitor is an open circuit, as no current flows in the dielectric. <br>A direct current (DC) voltage applied across a capacitor causes positive charge to accumulate on one side and negative charge to accumulate on the other side; due to the accumulated charge, the electric field is the source of the opposition to the current. When the potential associated with the charge exactly balances the applied voltage, the current goes to zero. Driven by an alternating current (AC) supply, a capacitor will only accumulate a limited amount of charge before the potential difference changes polarity and the charge dissipates. The higher the frequency, the less charge will </p>

View Full Text

Details

  • File Type
    pdf
  • Upload Time
    -
  • Content Languages
    English
  • Upload User
    Anonymous/Not logged-in
  • File Pages
    44 Page
  • File Size
    -

Download

Channel Download Status
Express Download Enable

Copyright

We respect the copyrights and intellectual property rights of all users. All uploaded documents are either original works of the uploader or authorized works of the rightful owners.

  • Not to be reproduced or distributed without explicit permission.
  • Not used for commercial purposes outside of approved use cases.
  • Not used to infringe on the rights of the original creators.
  • If you believe any content infringes your copyright, please contact us immediately.

Support

For help with questions, suggestions, or problems, please contact us