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Ion gel

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An Ion gel (or Ionogel) is a composite material consisting of an ionic liquid immobilized by an inorganic or a polymer matrix.[1][2][3] The material has the quality of maintaining high ionic conductivity while in the solid state. To create an ion gel, the solid matrix is mixed or synthesized in-situ with an ionic liquid. A common practice is to utilize a block copolymer which is polymerized in solution with an ionic liquid so that a self-assembled nanostructure is generated where the ions are selectively soluble. Ion gels can also be made using non-copolymer polymers such as cellulose, oxides such as silicon dioxide or refractory materials such as boron nitride.

Types of Ion Gels

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Ion gels can be divided in two broad classes based on the major component of the matrix in the composite: polymeric and inorganic.[1] These broad classes can be further subdivided based on the chemical class of the matrix. Across typical ion gel applications, it is desired that the matrix components be electrically insulating to separate contacts within a device and supply ionic conductivity alone. The matrix selection of a material has ramifications on the ionic conductivity as well as the mechanical properties of the final composite material.

Inorganic Classes:[1]

Polymeric Classes:[3]

Although these subtypes of ion gels can classify many materials in this broad class, there are yet still hybrid materials that fall outside these categorizations. Examples have been demonstrated of ion gels with both polymeric and inorganic materials to provide both flexibility and strength in the final composite.[4]

Applications

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Ion gels have been utilized in many electrical device systems such as in capacitors as dielectrics,[5] as insulators for field effect transistors,[6] and as electrolytes for lithium-ion batteries.[1] The solid state and yet flexible form of ion gels are attractive for modern mobile devices such as formable screens, health monitoring systems, and solid state batteries.[7] Especially for solid state battery applications, the high viscosity of ion gels provides sufficient strength to serve as both an electrolyte and separator between the anode and cathode.[1] In addition, ion gels are sought after in battery applications as the viscoelastic flow of the gel under stress creates a high quality electrode/electrolyte contact compared to other solid state electrolytes.[8]

Thermal Stability

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Ion gels have been known to be able to sustain upwards of 300 °C before onset of degradation.[9] The high temperature capability is typically limited by the underlying ionic liquid, which can have a wide range of thermal stability, but are typically stable to at least 250 °C.[10] This high temperature stability has been exploited to operate lithium-ion battery cells at lab scale up to 175 °C, which is well beyond the capabilities of current commercial electrolytes.[11]

Mechanical Properties

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Given the variety of ion gels, the mechanical properties of this broad class of materials spans a wide range. Often mechanical properties are tailored towards the desired application. Applications that require high flexibility target a highly elastic matrix material such as a cross-linked polymer.[7][9] These types of elastomeric materials offer high degree of elastic strain with full recovery, which is desirable in wearable devices that will undergo many stress cycles during their lifetime. Additionally, these types of materials can achieve up to 135% strain at failure indicating a degree of ductility.[12] Applications that require higher strength ion gel will often use a refractory matrix to generate composite strengthening. This is particularly desirable in lithium-ion battery applications, which seek to deter the growth of lithium dendrites in the cell that can result in an internal short-circuit. A relationship has been established in lithium-ion batteries between high modulus, strong, solid electrolytes and a reduction in lithium dendrite growth.[13] Thereby, a strong ion gel composite can improve the longevity of lithium-ion batteries through reduced internal short circuit failures.

The elastic resistance to flow of ion gels is often measure via Dynamic Mechanical Spectroscopy. This method reveals the storage modulus as well as the loss modulus, which define the stress-strain response of the gel. All ion gels are in the quasi-solid to solid state regime indicating that the storage modulus is higher than the loss modulus (i.e. elastic behavior prevails over the energy dissipating liquid-like behavior).[14] The magnitude of the storage modulus and its ratio to the loss modulus dictate the strength and the toughness of composite material.[9] Storage modulus values for ion gels can vary from approximately 1.0 kPa for typical polymeric-based matrices[15] up to approximately 1.0 MPa for refractory-based matrices.[11]

The structure of the composite matrix can play a large role in the outcome of the final bulk mechanical properties. This is especially true for inorganic based matrix materials. Several lab-scale examples have demonstrated a general trend that smaller matrix particle sizes can result in orders of magnitude increase in storage modulus.[11][13] This has been attributed to higher surface area to volume ratio of the matrix particles and the higher concentration of nanoscale interactions between the particle and the immobilized ionic liquid.[11] The higher the interaction forces between the components in the ion gel composite results in a higher force required for plastic deformation and an overall stiffer material.

Another degree of freedom in ion gel design lies in the ratio of matrix to ionic liquid in the final composite. As the concentration of ionic liquid in the matrix increases, the material will become more liquid-like in general corresponding to a decrease in storage modulus.[16] Conversely, a decrease in concentration will generally strengthen the material and depending on the matrix material can generate a more elastomeric or brittle stress-strain response.[17] The general tradeoff in a reduced concentration in ionic liquid is a subsequent decrease in ionic conductivity of the overall composite making optimization necessary for the specific application.[16]

References

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  1. ^ a b c d e Chen, Nan; Zhang, Haiqin; Li, Li; Chen, Renjie; Guo, Shaojun (April 2018). "Ionogel Electrolytes for High-Performance Lithium Batteries: A Review". Advanced Energy Materials. 8 (12): 1702675. doi:10.1002/aenm.201702675. S2CID 102749351.
  2. ^ Tripathi, Alok Kumar (2021). "Ionic liquid–based solid electrolytes (ionogels) for application in rechargeable lithium battery". Materials Today Energy. 20: 100643. doi:10.1016/j.mtener.2021.100643. S2CID 233581904.
  3. ^ a b Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano (2016). "Ionic-Liquid-Based Polymer Electrolytes for Battery Applications". Angewandte Chemie International Edition. 55 (2): 500–513. doi:10.1002/anie.201504971. ISSN 1521-3773. PMID 26783056.
  4. ^ Guyomard-Lack, Aurélie; Abusleme, Julio; Soudan, Patrick; Lestriez, Bernard; Guyomard, Dominique; Bideau, Jean Le (June 2014). "Hybrid Silica-Polymer Ionogel Solid Electrolyte with Tunable Properties". Advanced Energy Materials. 4 (8): 1301570. doi:10.1002/aenm.201301570. S2CID 94800401.
  5. ^ Yong, Hansol; Park, Habin; Jung, Cheolsoo (2020-01-31). "Quasi-solid-state gel polymer electrolyte for a wide temperature range application of acetonitrile-based supercapacitors". Journal of Power Sources. 447: 227390. doi:10.1016/j.jpowsour.2019.227390. ISSN 0378-7753. S2CID 209710082.
  6. ^ Lodge, T. P. (2008-07-04). "MATERIALS SCIENCE: A Unique Platform for Materials Design". Science. 321 (5885): 50–51. doi:10.1126/science.1159652. ISSN 0036-8075. PMID 18599764. S2CID 206513712.
  7. ^ a b Palchoudhury, Soubantika; Ramasamy, Karthik; Gupta, Ram K.; Gupta, Arunava (2019). "Flexible Supercapacitors: A Materials Perspective". Frontiers in Materials. 5. doi:10.3389/fmats.2018.00083. ISSN 2296-8016.
  8. ^ Wang, Ziqi; Tan, Rui; Wang, Hongbin; Yang, Luyi; Hu, Jiangtao; Chen, Haibiao; Pan, Feng (January 2018). "A Metal-Organic-Framework-Based Electrolyte with Nanowetted Interfaces for High-Energy-Density Solid-State Lithium Battery". Advanced Materials. 30 (2): 1704436. doi:10.1002/adma.201704436. PMID 29178151. S2CID 25616925.
  9. ^ a b c Zhao, Kang; Song, Hongzan; Duan, Xiaoli; Wang, Zihao; Liu, Jiahang; Ba, Xinwu (March 2019). "Novel Chemical Cross-Linked Ionogel Based on Acrylate Terminated Hyperbranched Polymer with Superior Ionic Conductivity for High Performance Lithium-Ion Batteries". Polymers. 11 (3): 444. doi:10.3390/polym11030444. PMC 6473542. PMID 30960428.
  10. ^ Lewandowski, Andrzej; Świderska-Mocek, Agnieszka (December 2009). "Ionic liquids as electrolytes for Li-ion batteries—An overview of electrochemical studies". Journal of Power Sources. 194 (2): 601–609. doi:10.1016/j.jpowsour.2009.06.089.
  11. ^ a b c d Hyun, Woo Jin; de Moraes, Ana C. M.; Lim, Jin-Myoung; Downing, Julia R.; Park, Kyu-Young; Tan, Mark Tian Zhi; Hersam, Mark C. (2019-08-27). "High-Modulus Hexagonal Boron Nitride Nanoplatelet Gel Electrolytes for Solid-State Rechargeable Lithium-Ion Batteries". ACS Nano. 13 (8): 9664–9672. doi:10.1021/acsnano.9b04989. ISSN 1936-0851. PMID 31318524. S2CID 197665200.
  12. ^ Guo, Panlong; Su, Anyu; Wei, Yingjin; Liu, Xiaokong; Li, Yang; Guo, Feifan; Li, Jian; Hu, Zhenyuan; Sun, Junqi (2019-05-29). "Healable, Highly Conductive, Flexible, and Nonflammable Supramolecular Ionogel Electrolytes for Lithium-Ion Batteries". ACS Applied Materials & Interfaces. 11 (21): 19413–19420. doi:10.1021/acsami.9b02182. ISSN 1944-8244. PMID 31058482. S2CID 145822146.
  13. ^ a b Lu, Yingying; Korf, Kevin; Kambe, Yu; Tu, Zhengyuan; Archer, Lynden A. (2014-01-07). "Ionic-Liquid-Nanoparticle Hybrid Electrolytes: Applications in Lithium Metal Batteries". Angewandte Chemie International Edition. 53 (2): 488–492. doi:10.1002/anie.201307137. PMID 24282090.
  14. ^ Franck, A. "Viscoelasticity and dynamic mechanical testing" (PDF). TA Instruments.
  15. ^ Patel, Monalisa; Gnanavel, M.; Bhattacharyya, Aninda J. (2011). "Utilizing an ionic liquid for synthesizing a soft matter polymer "gel" electrolyte for high rate capability lithium-ion batteries". Journal of Materials Chemistry. 21 (43): 17419. doi:10.1039/c1jm12269j. ISSN 0959-9428.
  16. ^ a b Lu, Yingying; Moganty, Surya S.; Schaefer, Jennifer L.; Archer, Lynden A. (2012). "Ionic liquid-nanoparticle hybrid electrolytes". Journal of Materials Chemistry. 22 (9): 4066. doi:10.1039/c2jm15345a. hdl:1813/33452. ISSN 0959-9428.
  17. ^ Wu, Feng; Chen, Nan; Chen, Renjie; Zhu, Qizhen; Tan, Guoqiang; Li, Li (January 2016). "Self-Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery". Advanced Science. 3 (1): 1500306. doi:10.1002/advs.201500306. PMC 5063194. PMID 27774385.
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