Self-Healing Polymer Gel Electrolyte with Zwitterionic Agent

Abstract

The invention relates to a self-healing polymer gel electrolyte with high ionic conductivity, doped with a zwitterionic agent, and its production method. The invention specifically concerns a polymer gel electrolyte developed for use in supercapacitor-type energy storage systems, which enables the self-repair of damage resulting from fatigue deformation in electrolytes, while maintaining high ionic conductivity after repair.

Description

1 TARIFF Self-Healing Polymer Gel Electrolyte with Zwitterionic Agent Technical Area The invention is a Zwitterionic Agent with high ionic conductivity that can instantly self-heal. This relates to additive polymer gel electrolytes and their production method. 5 The invention is intended for use particularly in supercapacitor-type energy storage systems. improved, occurring as a result of fatigue deformation in electrolytes allowing for self-repair of damage, resulting in high ionic output. This relates to the polymer gel electrolyte that makes it possible to maintain conductivity. State of the Art With the rapid development of energy storage technologies, especially flexible, bendable and The increasing prevalence of wearable electronic systems necessitates the use of safe, durable materials in these applications. This has increased the need for durable and high-performance electrolyte materials. Flexible 15 The electrolytes used in these systems should not only offer high ionic conductivity, also when subjected to mechanical deformation, they lose their structural integrity It must be able to protect, demonstrate stability in long-term cycles, and not compromise device safety. should not be discarded. These requirements apply to polymer matrices with self-healing capabilities. This has placed the design of modern energy storage technologies at the heart of modern technology. However, 20 Existing solutions are comprehensive due to both synthesis costs and structural limitations. It does not offer a solution; it offers a more environmentally friendly, economical, natural and high-quality solution. There is a need to develop new electrolyte systems that offer mechanical / electrochemical stability. It continues. In recent years, new generation energy storage devices with flexible structures have been attracting increasing attention. The polymer gel electrolytes used in these devices are designed to prevent repetitive fatigue deformation and Cracking, splitting, puncturing, and surface damage due to electrochemical depletion processes. It can be subjected to various damages such as scaling. Such damages affect the electrode-electrolyte relationship. This leads to the disruption of the interface and interruption of ion transport pathways. 30 This leads to significant decreases in device performance. Furthermore, these damages can cause some... These situations also present safety risks such as short circuits, electrolyte leakage, and thermal instability. This brings with it both high flexibility. Therefore, energy storage systems require both flexibility and flexibility. 2 Furthermore, the development of polymer gel electrolytes that offer self-healing properties is critical. It is important. Zwitterionic additives offer high ionic conductivity, wide temperature resistance, and chemical resistance. Due to its properties such as stability, it holds an important place in polymer electrolyte development studies. 5 However, many studies in the literature have shown that synthetic zwitterionic polymers... the focus is on designing these systems, which are often expensive, complex, and environmentally friendly. This requires synthesis steps that are not sustainable in terms of these polymers. Furthermore, these polymers... In various studies, their mechanical strength was limited and their flexibility remained low. It has been reported. 10 A study in the literature compared a gel with zwitterionic soy sauce with hydroxyethyl cellulose. By using these two methods together, an edible and ingestible supercapacitor has been designed. However, the statement... The self-healing mechanism was not evaluated in the study in question, and soy... 15 studies on the interaction of natural zwitterionic ions in the sauce with repairable polymer bonds. No discovery has been made. Literature reviews indicate that commercial soy sauce is a... It is used as a source of zwitterionic ions and also promotes self-healing. any study that incorporates a polymer gel electrolyte design exhibiting this property None have been encountered. Self-healing PVA matrices are mostly described in the literature as boronate ester or borate. Shape-recovery and elastic behavior thanks to the dynamic structures of the cross-links. It has been examined through systems that show [this]. For example, patent number US10507399B2, found in the literature, is based on a PVA / Borax matrix. This patent relates to a safe playdough (slime) activator composition for children. 25 The viscoelastic properties of the material are attributed to dynamic borate cross-linking; however Here, self-healing is not a directly targeted characteristic, and in the composition... No cellulose nanofibers or plasticizers are present. Soft contact lens. In patent number US4559186A, which relates to the application, the dynamic properties of a PVA-based hydrogel are discussed. The ability to regain structure through bonding has been explained, but energy storage 30 No emphasis has been placed on its applications. Zn-ion in patent number US11075406B2. Device performance can be improved by adding borax to PVA-based gel polymer electrolytes for batteries. It has been shown that it can be enhanced; however, the system's self-healing mechanism has not been addressed. It has not been received. 35 3 Most current research focuses on lithium-ion battery technologies, Regarding self-healing gel electrolytes that can be used in supercapacitors. This shows that the literature remains extremely limited. In the current state of the art, high... a high-performance and self-healing polymer gel electrolyte solution is needed It is heard 5 In conclusion, due to the negative aspects described above and the current solutions, the subject matter... Due to its shortcomings, an improvement is needed in the relevant technical field. It has been made. Purpose of the Invention The present invention meets the aforementioned requirements while eliminating all disadvantages. a self-healing polymer gel electrolyte that removes and offers some additional benefits. It is related to the method of preparation. 15 The primary purpose of the invention is to prevent mechanical deformation, cracking, and in energy storage devices. overcoming performance-limiting damage mechanisms such as interface degradation The goal is to create a gel electrolyte structure that can heal itself. The aim of the invention is to create a dynamic zwitterionic commercial soy sauce additive based on boronate ester. Thanks to its binding mechanism, it has high ionic conductivity (approximately 65 mS / cm). The goal is to develop a rapidly healing PVA-based gel electrolyte. One aim of the invention is to improve traditional synthetic and costly zwitterionic polymer designs. conversely, by using commercially available soy sauce, which is a protein-based product that is naturally zwitterionic. The goal is to make the production process practical, economical, and environmentally friendly. Another objective of the invention is to improve the performance of PVA-Borax based gel structures. The effect of cellulose nanofiber in increasing mechanical strength and the plasticizer in improving flexibility By synergistically combining their contributions, self-healing and ion transport 30 The goal is to ensure it is optimized. Another purpose of the invention is to prevent electrolyte leakage and safety risks thanks to its non-fluid gel form. and a safer alternative that eliminates disadvantages associated with liquid electrolytes, such as thermal instability. to offer an energy storage system. 35 4 Another aim of the invention is to achieve high capacitance and long cycle life in supercapacitor applications. The device's lifespan is extended by ensuring good electrode / electrolyte interface contact and reversible redox behavior. The goal is to develop an electrolyte system that enhances performance. Another aim of the invention is to automatically restore the structural integrity of the electrolyte after physical damage. By enabling it to recover its properties, the device's durability, service life, and reliability are improved. to increase. Another objective of the invention is to combine PVA, soy sauce, cellulose nanofiber, and plasticizer for the first time. An innovative approach to the field of self-healing gel electrolytes through their use. 10 to win To achieve the purposes described above, the invention is capable of self-healing. The polymer gel electrolyte consists of polyvinyl alcohol, cellulose nanofiber, and the plasticizer sodium tetraborate. Soy sauce contains decahydrate and zwitterionic and a natural ionic conductor additive 15 is doing. To achieve the purposes described above, the invention is capable of self-healing. The polymer gel electrolyte production method involves the following steps: i. Dissolving polyvinyl alcohol in a water bath, 20 ii. Adding and mixing cellulose nanofibers into molten polyvinyl alcohol, iii. Soy sauce, being a zwitterionic and natural ionic conductor additive, affects the pH. adjustment, iv. Adding pH-adjusted soy sauce to the PVA / cellulose nanofiber mixture. v. Addition of plasticizer to the mixture, 25 vi. Next, sodium tetraborate decahydrate is added to the mixture to obtain the gel electrolyte. to be done The structural and characteristic features and all the advantages of the invention are given in the figures below. Thanks to the detailed explanation written with references to the figures, 30 is clearer. This will be understood, and therefore the evaluation should also take these figures and detailed explanations into account. It must be done by taking it. 35 Figures that will help understand the invention. Figure 1. Pure gel electrolyte in a supercapacitor cell and six repeated recovery cycles. electrochemical impedance spectroscopy as a result. Figure 2. Pure gel electrolyte in a supercapacitor cell and six repeated recovery cycles. The resulting cyclic voltmeter curves 5 Detailed Description of the Invention This detailed explanation describes the product and method of invention only to provide a better understanding of the subject. 10 for the purpose of understanding and without creating any limiting effect It is explained. The invention is an instantaneous self-healing polymer gel electrolyte made of polyvinyl alcohol and cellulose. nanofiber, plasticizer, sodium tetraborate decahydrate and zwitterionic and a natural ionic It contains soy sauce as a conductive additive. 15 Table 1. Usable and preferred quantities by weight of the gel electrolyte subject to the invention. Components Preferred by Weight amount (%) By weight Available amount (%) Polyvinyl alcohol (PVA) 40 30-50 Cellulose nanofiber 30 20-40 Plasticizer 5 3-5 Soy sauce 20 10-30 Sodium tetraborate decahydrate (borax, Na₂B₄O₇ ) 3-5 The subject of the invention is a gel electrolyte containing 30-50% polyvinyl alcohol by weight, and 20-40% by weight. Cellulose nanofiber, 3-5% plasticizer, 10-30% soy sauce, 3-5% It contains sodium tetraborate decahydrate within this range. The subject of the invention is a preferred application of gel electrolyte; 40% polyvinyl alcohol by weight, 25% Cellulose nanofiber, 5% plasticizer, 20% soy sauce, 5% sodium tetraborate decahydrate. It includes. 6 The subject of this invention is the use of plasticizers, including but not limited to, glycerin, in the gel electrolyte. Polyethylene glycol, propylene glycol, sorbitol, and ionic liquids can be used. The invention concerns a gel electrolyte containing preferably glycerin as a plasticizer. 5 The invention describes polyvinyl alcohol as a thin, flexible, and high-performance self-healing material. For creating hydrogel electrolytes, chemical stability, environmental friendliness, and cost-effectiveness are important considerations. and because of its advantages such as easy availability, light weight and ease of shaping Polymer substrates were used. PVA gel electrolytes, a wide range of electrolyte solutions such as aqueous electrolyte solutions were used. having a pH value range and preventing the structure of the electrode materials from deteriorating. to prevent, it acts as an elastic coating with a certain mechanical strength It ensures that the electrolytes perform perfectly. Cellulose nanofibers are a type of polysaccharide that is biodegradable at the nanoscale, and consist of 15 Characterized by a network structure formed by the physical entanglement of nanofibers. Well-dispersed complexes are used as nanofillers in hydrogels. To prepare them, these fibers, which contain a large number of hydroxyl groups, form a chemical bond with borax. alongside the gel electrolyte, it forms a physical cross-link, creating an ionic conductive hydrogel. It improves its stability and mechanical properties. 20 Sodium tetraborate decahydrate (Borax, Na₂B₄O₇), dynamic boronate in gel electrolyte. by enabling the formation of ester bonds, dynamic covalent bonds within the electrolyte. It causes it to break and reform. High ionic properties can be achieved by incorporating ions, salts, or ionic suspended groups into hydrogel structures. Gel electrolytes with conductivity can be obtained. In their monomeric formulas, both anionic and conductive can be obtained. Zwitterions, a well-known type of molecule with cationic counterparts, exhibit ionic conductivity. It has been observed that the donor ion could be an alternative to salt or ionic suspended groups. Zwitterionic structures, ion migration of cationic and anionic counterions of polyswitterions 30 It provides high ionic conductivity, allowing for easy separation during use. Environmentally harmful chemical reagents used in the formation of zwitterionic structures Apart from these, proteins with zwitterionic groups have ionic conductivity at the molecular level. This has been proven. 35 7 Plasticizers increase segmental mobility within the gel electrolyte matrix, thereby enhancing ion mobility. It increases the transport rate. It also improves the electrode / electrolyte interface, thereby increasing mechanical strength. It allows it to increase. Invention 5: A manufacturing method for obtaining a self-healing polymer gel electrolyte. It is related to the invention. The method described in the invention includes the following steps; i. Dissolving polyvinyl alcohol in a water bath, ii. Adding and mixing cellulose nanofibers into molten polyvinyl alcohol, iii. Adjusting the pH of soy sauce, which is a zwitterionic and natural ionic conductor additive, iv. Adding pH-adjusted soy sauce to the PVA / cellulose nanofiber mixture, 10 v. Adding a plasticizer to the mixture, vi. Next, sodium tetraborate decahydrate is added to the mixture to obtain the gel electrolyte. to be done An application of the method described in the invention; in process step i, polyvinyl alcohol at 90 °C for 15 minutes. melting in a water bath and then magnetically heating the melted PVA gel at 1500 rpm at 90°C It involves mixing in a blender for 15 minutes. An application of the method described in the invention involves dissolving cellulose in PVA in process step 2. Nanofibers are added and the process is carried out at a speed of 1000-1500 rpm, preferably 1500 rpm, with a heater at 90°C. This involves stirring the mixture in a magnetic stirrer for 15 minutes. An application of the method described in the invention involves adjusting the pH of the soy sauce to 4.5-8 in step iii of the process. adjustment within the range with a 1% NaOH basic solution or a 1% H2SO4 solution. It includes. 25 An application of the method described in the invention involves adjusting the pH to the range of 4.5-8 in step 4 of the process. Soy sauce is added to the PVA / cellulose nanofiber mixture. An application of the method described in the invention; in step v, the plasticizer is added to the mixture 30 and stirred in a heated magnetic stirrer at 90°C for 20 minutes at 1500 rpm. It involves mixing. An application of the method described in the invention is in process step vi with 20 mmol / L Sodium tetraborate. Preparation of the decahydrate aqueous solution and adding 35 drops to the mixture prepared in the previous step. 8 It involves adding drops of 20 mmol / L sodium tetraborate decahydrate aqueous. The pH of the solution was found to vary between 8.8 and 9.5. A sample application of the production of the gel electrolyte that is the subject of the invention is described below;  1g of PVA was dissolved in 10ml of water at 90 degrees Celsius in a water bath, 5  The melted gel was left to be stirred at 90°C and 1500 rpm for 15 minutes,  0.1 g of cellulose nanofibers are added to the PVA gel and magnetically heated at 90°C and 1500 rpm. The mixture was continuously stirred with the mixer for 15 minutes.  To ensure homogeneous distribution after magnetic stirring, the mixture should be left for 10 minutes. The process continued with mixing in the sonicator, 10  During this process, the pH value of the soy sauce is adjusted to suit gelling, resulting in a 1% form. Gelation from the prepared NaOH basic solution or 1% H2SO4 solution The appropriate pH value at which this can occur has been found.  pH value between 4.5-8, preferably 6.24, for the solution mixed with soy sauce. 2.5ml added, 15  Then 0.02g of plasticizer was added and-  Mixing for 20 minutes at 90°C and 1500 rpm for a homogeneous mixture. It has been accomplished.  The pH of the solution mixed at 90°C and 600 rpm is between 8.8 and 9.5. preferably a borax / water solution prepared at 20 mmol / L with a pH of 9, added drop by drop 20 2.5ml has been added.  The resulting liquid-gel consistency structure was allowed to cool to room temperature and  A self-healing gel electrolyte is obtained by the gel solidifying at room temperature. It has been done. Testing of the electrolyte prepared here on a supercapacitor using activated carbon-PVDF-carbon. It is made using an electrode made of black. For this, a ratio of 8:1:1 or 7:2:1 is used. The slurry was prepared using the formulation. (Active ingredient: PVDF: Carbon black) 0.05 g of PVDF as a binder and 1 g of N- organic solvent used to prepare the mud. It was dissolved in methyl pyrrolidone (NMP) and left to stand for 1 hour under magnetic stirring. 30 0.025g of carbon black was added to the dissolved PVDF and stirred on a magnetic stirrer for 300 minutes. Mixing was continued at rpm. Then the suspension was transferred to an ultrasonic mixer. It was transferred and left to the ultrasonic mixture at 50% power for 30 minutes. Finally, activated carbon. This is added to the suspension and mixed with a magnetic stirrer for 45 minutes. It was dispersed. The resulting mixture was stirred for 1 hour on a magnetic stirrer at 500 rpm and 35 9 The resulting electrode was subjected to electrochemical tests using soybeans with a pH range of 4.5-8. It was left to marinate in the sauce for 3 hours. Analysis Results Assessment of electrolyte self-healing status 5 The gel electrolyte obtained in the studies conducted for the invention has a self-healing effect. Two different cutting procedures were applied to the electrolyte for evaluation. Recovery status. In the evaluation, during the first cutting procedure, the gel electrolyte was cut in half and left for 5 seconds. They were reconnected at intervals. After 5 seconds, the gel was momentarily pulled into the electrolyte. An elongation test was performed. As a result, it was observed that immediate improvement occurred in the gels. It has been observed. In another cutting procedure to assess healing, a square-shaped electrolyte is used. The process involved cutting one of its four equal parts and reassembling it. According to the instructions, the reassembly was performed 5 seconds after cutting. Then, immediately pulling... An extension test was performed. The test result showed that effective immediate improvement occurred at 15. It has been observed. The self-healing status of the gel electrolyte was examined under a digital microscope. The immediate recovery of electrolyte in the discontinuation area is shown in microscopic images. It has been confirmed. Evaluation of healing with ionic conductivity 20 A supercapacitor device consisting of a gel electrolyte with added soy sauce and an activated carbon electrode. According to electrochemical impedance spectroscopy (EIS) test, six replicates self-test The improvement assessment was performed in the graph in Figure 1. The original and derived values ​​from the graph were used. The equivalent series resistance values ​​after recovery are shown in Table 2. Accordingly, Resistance values ​​after repeated recovery tests and ionic 25 obtained as a result of calculation It has been observed that conductivity values ​​are maintained within a certain range. Table 2 Equivalent series resistance of the original sample and the samples showing improvement. ionic conductivity values. Recovery repetitions Equivalent Series resistance (RESR, ohm) Ionic Conductivity Values (mS / cm) Original sample 3.44 65 1. Self-healing 2.97 75 2. Self-healing 3.30 68 3. Self-healing 3.22 69 4. Self-healing 3.42 65 5. Self-healing 3.22 69 6. Self-healing 3.25 69 Assessment of improvement with cyclic voltammetry. Created with original gel electrolyte and repeated self-healing gel electrolyte. The cyclic voltameter curves of the supercapacitor are given in Figure 2. Accordingly, the resulting gel electrolyte has a wide potential window range of 0-1V. It has been observed that the study showed improvement. In addition, six repeated improvements with the original gel electrolyte and electrolyte. The resulting cyclic voltmeter curves are preserved, giving similar curves to each other. It has been observed. In conclusion, the self-healing status of soy sauce was evaluated through various tests. Successful restoration of electrolyte gel containing zwitterionic agent in performance loss 10 It was found that it was carried out without.

Claims

11 REQUESTS 1. It is a self-healing polymer gel electrolyte, composed of: Polyvinyl alcohol, Cellulose nanofiber, plasticizer Sodium tetraborate decahydrate and Zwitterionic and a natural ionic 5 It contains soy sauce as a conductive additive.

2. A gel electrolyte conforming to Claim 1, with the characteristic of containing 30-50% polyvinyl by weight. Alcohol, 20-40% Cellulose nanofiber, 3-5% plasticizer, 10-30% Soy sauce contains 3-5% sodium tetraborate decahydrate. 10 3. A gel electrolyte conforming to Claim 1, with the following composition: 40% polyvinyl alcohol, 30% cellulose by weight. Nanofiber, 5% plasticizer, 20% soy sauce, 5% sodium tetraborate decahydrate. It includes.

4. It is a method for producing a self-healing polymer gel electrolyte, the characteristic of which is; vii. Dissolving polyvinyl alcohol in a water bath, viii. Adding and mixing cellulose nanofibers into molten polyvinyl alcohol, ix. Soy sauce, being a zwitterionic and natural ionic conductor, increases pH. adjustment, 20 x. Addition of pH-adjusted soy sauce to a PVA / cellulose nanofiber mixture, xi. Addition of plasticizer to the mixture, xii. Next, sodium tetraborate decahydrate is added to the mixture to obtain the gel electrolyte. to be done It includes the steps of the process. 25 5. A method that complies with claim 4, the characteristic of which is that in process step i, polyvinyl alcohol is heated to 90 °C melting in a water bath at a certain temperature and then grinding the melted PVA gel at 90°C and 1500 rpm for 15 minutes. It involves mixing.

6. This is a method that complies with claim 4, and its characteristic is that cellulose is dissolved into PVA in step ii. nanofibers were added and the mixture was infused at 90°C, at a speed of 1000-1500 rpm for 15 minutes. It involves mixing.

7. This is a method that conforms to claim 4, and its characteristic is that in step iii, a 1% NaOH basic solution is used. Alternatively, the pH of soy sauce can be adjusted to 4.5-8 using a 1% H2SO4 solution. 12 8. A method that conforms to claim 4 or 5, with the characteristic of having the appropriate pH value in step 4 of the process. Soy sauce, adjusted to a PVA / cellulose nanofiber mixture with a concentration between 4.5 and 8, is added.

9. This is a method that complies with claim 5, and its characteristic feature is that the plasticizer is added to the mixture in step v of the process.

5. Adding and mixing at 90°C and 1500 rpm for 20 minutes. It includes.

10. This is a method that complies with claim 5, and its characteristic is that in step vi, 20 mmol / L Sodium Preparation of tetraborate decahydrate aqueous solution and the solution prepared in the previous step It involves adding it to the mixture drop by drop. 10