CN109796716B - Self-repairable polymer electrolyte and preparation method and application thereof - Google Patents
Self-repairable polymer electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a self-repairing polymer electrolyte, a preparation method and application thereof, wherein the polymer electrolyte comprises poly (2-acrylamido-2-methyl-1-propanesulfonic acid) and a water-soluble polymer capable of forming hydrogen bonds with sulfonic acid groups and/or amide groups. The polymer electrolyte provided by the invention has high self-repairing efficiency, good flexibility, stretchability and good mechanical property, and when the polymer electrolyte is applied to a double electric layer super capacitor, the flexible super capacitor with excellent self-repairing capability can be obtained.
Description
Technical Field
The invention belongs to the technical field of electrolytes, and relates to a self-repairable polymer electrolyte, and a preparation method and application thereof.
Background
The rapid development of flexible electronic products has led to an increasing demand for portable energy storage devices with good flexibility and high reliability. Flexible and stretchable supercapacitors and lithium ion batteries have become a focus of research in recent years. Among them, a flexible super capacitor having high power density and ultra-fast charge and discharge performance has attracted special attention.
Hydrogel materials are of increasing interest to researchers because of their interesting structure, the interstitial spaces of the crosslinked network consisting of polymer chains are filled with solvent moisture. This structure imparts the material with the characteristic of being soft and wet, and is an ideal candidate material for use as an electrolyte material for flexible energy storage devices. Hydrogel electrolytes crosslinked by covalent bonding have excellent electrochemical and mechanical properties, and after the electrodes are assembled into a complete supercapacitor, the device is difficult to recover because it is difficult to remove both electrodes in contact with the hydrogel electrolyte. Furthermore, hydrogel electrolytes crosslinked by covalent bonds are too difficult to process. Furthermore, covalent crosslinking is irreversible and therefore the mechanical properties are greatly reduced once a crack occurs in the hydrogel, and these problems will greatly limit the application prospects of flexible supercapacitors.
Flexible supercapacitors may break or even fail in some components or assemblies during use of the device due to repeated bending, twisting or stretching. In view of this, imparting self-healing properties to flexible supercapacitors would be an effective way to improve the stability and extend the lifetime of the devices. The components of the hydrogel material are various and adjustable in performance, and various practical functions such as self-repairing function, shape memory function and stretchability can be endowed through the design of a chemical structure. The multifunctional hydrogel is used as an electrolyte material of a flexible supercapacitor to obtain a stretchable self-repairing supercapacitor or a rechargeable battery, and is an effective way for rapidly developing the field of portable energy storage devices with good flexibility and high reliability.
Polyvinyl alcohol (PVA) is commonly used as an electrolyte polymer substrate for supercapacitors due to its chemical stability, electrochemical inertness and ready availability. In order to achieve effective ion conduction, an acid (H) is generally added to the PVA-based electrolyte2SO4And H3PO4) Alkali (KOH) or inorganic salts (KCl and Li)2SO4) An aqueous solution. Although it is rich in hydroxyl groups, most PVA-based electrolytes rarely exhibit self-healing behavior based on hydrogen bonding. In practice most are brittle or have low mechanical strength. One of the reasons for the poor self-healing properties is that inorganic ions (neutral salts and inorganic acids or bases) disrupt intermolecular hydrogen bonds between PVA chains and water molecules. This disruption causes dehydration of the PVA chains and agglomeration in water through intramolecular hydrogen bonding interactions. Agglomeration significantly reduces the PVA chain mobility necessary for the molecular level self-repair process. Furthermore, the chain aggregation degrades the mechanical properties and salt resistance of the PVA-based electrolyte. The present PVA-based electrolytes are caused by inorganic ionsThe problems of low self-repairing efficiency, poor mechanical property, limited salt content and the like still need to be solved urgently.
Generally, a supercapacitor consists of a current collector, electrodes, and a liquid electrolyte (electrolyte). However, rigid energy storage devices encapsulated by an electrolyte and a stainless steel housing have limited their application in flexible electronic devices. Thereafter, PVA/H2SO4、PVA/H3PO4The emergence of gel electrolytes such as PVA/KOH, PVA/LiCl, etc. led to a breakthrough, and thus wearable supercapacitors having excellent mechanical strength and flexibility were developed. While the theoretical feasibility of flexible wearable supercapacitors has been demonstrated using gel electrolytes, the lack of self-healing properties limits their reliability, preventing their practical application in smart wearable electronics. To this end, some research teams developed self-healing polymer electrolytes for high performance supercapacitors. For example, Y.Guo et al report an iron ion crosslinked supramolecular PAA hydrogel electrolyte that shows comparable mechanical properties to the original hydrogel after 24 hours of repair (stress: 295kPa, strain: 342%). Then the hydrogel electrolyte and the polypyrrole supported by the graphene sponge are assembled into a super capacitor, and the rate performance (the current density is 10 A.g) equivalent to that of the electrolyte super capacitor is shown-1Then the specific capacitance is 80% of the liquid supercapacitor) (DOI:10.1039/c6ta01441 k). Wang et al prepared a polyacrylic acid grafted polyvinyl alcohol based borax/KCl hydrogel electrolyte that recovered its mechanical properties (stress: 5.82kPa, strain: 630%) spontaneously (within 20 minutes) and multiple times (15 times) under mild conditions. Then the hydrogel electrolyte is clamped between two active carbon film electrodes to assemble a capacitor prototype which is still at 1.0 A.g after the cutting-repairing process-1Has a current density of 84.8 F.g-1Specific capacitance of (1.0A · g for the original capacitor)-1Has a specific capacitance of 85.4 F.g at a current density of-1) (DOI:10.1039/c6ta08018 a). Wang et al also used 2, 3-epoxypropyltrimethylammonium chloride grafted polyvinyl alcohol to synthesize hydrogels that were crosslinked by diol-borate linkages in the presence of KCl and borax. The self-repaired super capacitor can bear15 cycles of fracture/repair (DOI: 10.1002/adfm.201700690). Wang designs a low-temperature self-repairing and renewable hydrogel electrolyte through vinyl imidazole and hydroxypropyl acrylate copolymerization. A supercapacitor manufactured by coating activated carbon electrodes on opposite sides of the above polymer electrolyte can recover its electrochemical properties in a temperature range of 25 to-15 c, and can undergo a regeneration process of 5 dry bathing-wetting cycles (DOI: 10.1021/acsami.7b07836). Liu et al by combining polyaniline with H2SO4The solution was integrated in situ into a single network copolymer comprising vinyl imidazole and hydroxypropyl acrylate (stress: 30kPa, strain: 370%) to produce an integrated self-healing capacitor. The capacitor has high specific capacitance (at 0.5mA cm)-2718 mF-cm at current density-2) Rate capability (at 5mA cm)-2514.0mF cm at current density-2) And still longer cycle life after 10 breaks/repairs (capacity retention 96% after 13000 charge-discharge cycles) (DOI:10.1039/c7ta10323 a). However, the current self-repairing polymer electrolyte still has the problems of complex preparation process, limited mechanical and self-repairing performance and the like.
Recently, poly (2-acrylamido-2-methyl-1-propanesulfonic acid) (pampss) hydrogels with good self-healing capabilities have been reported. The hydrogel is simple to prepare, low in monomer price and capable of self-repairing. However, pampss hydrogels can only achieve high healing efficiency at high solids (specific gravity up to 91 wt%), but are less stretchable (strain at break at 90 wt% solids 47%). While drawability is better when the solids content is lower, the self-healing efficiency is limited (about 30% healing efficiency at 50 wt% content).
Therefore, it is important to develop a polymer electrolyte having both excellent self-repairing efficiency and mechanical properties.
Disclosure of Invention
The polymer electrolyte provided by the invention has high self-repairing efficiency, good flexibility, stretchability and good mechanical property, and when the polymer electrolyte is applied to a double electric layer super capacitor, a flexible super capacitor with excellent self-repairing capability can be obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a self-healing polymer electrolyte comprising poly (2-acrylamido-2-methyl-1-propanesulfonic acid) and a water-soluble polymer that can form hydrogen bonds with sulfonic acid and/or amide groups.
The poly (2-acrylamido-2-methyl-1-propanesulfonic acid) in the polymer electrolyte provided by the invention has the advantages that dynamic hydrogen bonds formed between sulfonic acid groups and amide groups in a polymer chain endow the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) with self-repairing capability, and simultaneously, a water-soluble polymer capable of forming hydrogen bonds with the sulfonic acid groups and/or the amide groups is added, so that the hydrogen bond density of the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) is further improved, and the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) also has higher self-repairing efficiency under the condition of relatively low solid content, and at the moment, the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) also has better stretchability, therefore, the polymer electrolyte provided by the invention has better mechanical property and excellent self-repairing capability.
Preferably, the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) is present in an amount of from 90 to 98% by mass, for example 91%, 92%, 93%, 94%, 95%, 96%, 97%, etc., based on 100% by mass of the total of the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) and the water-soluble polymer.
Preferably, the solid content of the polymer electrolyte is 20-60 wt%, such as 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, etc.
The polymer electrolyte provided by the invention is a hydrogel material, and the interstitial spaces of the crosslinked network of the hydrogel material are filled with solvent water, so that the solid content of the polymer electrolyte needs to be limited.
Preferably, the water-soluble polymer comprises any one of polyvinyl alcohol, polyethyleneimine, sodium alginate, chitosan or carboxymethyl chitosan or a combination of at least two of the two.
Preferably, the polymerized monomer of the water-soluble polymer is a vinyl monomer.
Preferably, the vinyl monomer has any one of a hydroxyl group, a carboxyl group, an amide group, an imino group, or a sulfonic acid group, or a combination of at least two thereof.
Preferably, the vinyl monomer is selected from any one of hydroxyethyl acrylate, hydroxypropyl acrylate, 3-allyloxy-1, 2-propanediol, N-methylolacrylamide, dimethylaminoethyl methacrylate or vinylimidazole or a combination of at least two thereof.
In the preparation of the polymer electrolyte of the present invention, a water-soluble polymer (e.g., polyvinyl alcohol, polyethyleneimine, sodium alginate, chitosan, carboxymethyl chitosan, etc.) capable of forming a hydrogen bond with a sulfonic acid group and/or an amide group may be directly used, or a vinyl monomer (e.g., hydroxyethyl acrylate, hydroxypropyl acrylate, 3-allyloxy-1, 2-propanediol, N-methylolacrylamide, dimethylaminoethyl methacrylate, vinyl imidazole, etc.) may be added to perform polymerization to obtain a water-soluble polymer capable of forming a hydrogen bond with a sulfonic acid group and/or an amide group.
Preferably, the electrolyte further comprises lithium chloride.
The ionic conductivity of the polymer electrolyte can be further improved by adding lithium chloride into the system.
Preferably, in the self-repairable polymer electrolyte, the concentration of the lithium chloride is 0.5 to 3M, such as 1.0M, 1.5M, 2.0M, 2.5M, and the like.
In a second aspect, the present invention provides a method for preparing the self-repairable polymer electrolyte according to the first aspect, comprising the following steps:
mixing 2-acrylamido-2-methyl-1-propanesulfonic acid with an aqueous solution of a water-soluble polymer, and then adding an initiator and a cross-linking agent to carry out a polymerization reaction to obtain the self-repairable polymer electrolyte;
or mixing 2-acrylamido-2-methyl-1-propanesulfonic acid with an aqueous solution of a vinyl monomer, and then adding an initiator and a crosslinking agent to carry out polymerization reaction, thereby obtaining the self-repairable polymer electrolyte.
The preparation method provided by the invention is simple and feasible, has few steps, short time and high efficiency; the used preparation raw materials are wide in source, cheap and easily available, environment-friendly and low in manufacturing cost, and meanwhile, inorganic acid or alkali is not needed, so that the safety is higher.
When the polymer electrolyte is prepared, the water-soluble polymer can be directly mixed with the 2-acrylamido-2-methyl-1-propanesulfonic acid, and then the 2-acrylamido-2-methyl-1-propanesulfonic acid is polymerized to obtain the polymer electrolyte. 2-acrylamido-2-methyl-1-propanesulfonic acid and a vinyl monomer may be added to the electrolyte to polymerize the same, thereby obtaining poly-2-acrylamido-2-methyl-1-propanesulfonic acid and a water-soluble polymer, and in this case, a copolymer of 2-acrylamido-2-methyl-1-propanesulfonic acid and a vinyl monomer may be contained in the electrolyte.
Preferably, the concentration of the aqueous solution of the water-soluble polymer is 1 to 10 wt%, such as 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, etc.
Preferably, the water-soluble polymer comprises any one of polyvinyl alcohol, polyethyleneimine, sodium alginate, chitosan or carboxymethyl chitosan or a combination of at least two of the two.
Preferably, the concentration of the aqueous solution of the vinyl monomer is 1 to 10 wt%, such as 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, etc.
Preferably, the vinyl monomer is selected from any one of hydroxyethyl acrylate, hydroxypropyl acrylate, 3-allyloxy-1, 2-propanediol, N-methylolacrylamide, dimethylaminoethyl methacrylate or vinylimidazole or a combination of at least two thereof.
Preferably, the content of the vinyl monomer is 4 to 40% by mass, for example, 5%, 10%, 15%, 20%, 25%, 30%, 35%, etc., based on 100% by mass of the total mass of the vinyl monomer and 2-acrylamido-2-methyl-1-propanesulfonic acid.
Preferably, lithium chloride is further included in the reaction system.
Preferably, the initiator is ammonium persulfate.
Preferably, the initiator is added in an amount of 0.1 to 0.4 wt%, such as 0.15 wt%, 0.20 wt%, 0.25 wt%, 0.30 wt%, 0.35 wt%, etc., of the mass of polymerized monomer.
When the water-soluble polymer is directly added, the polymerized monomers are 2-acrylamido-2-methyl-1-propanesulfonic acid, and when the water-soluble polymer is prepared by adding a vinyl monomer, the polymerized monomers are 2-acrylamido-2-methyl-1-propanesulfonic acid and the vinyl monomer.
Preferably, the polymerized monomer comprises 2-acrylamido-2-methyl-1-propanesulfonic acid.
Preferably, the polymerized monomers include 2-acrylamido-2-methyl-1-propanesulfonic acid and vinyl monomers.
Preferably, the crosslinking agent is N, N' -dimethylbisacrylamide.
Preferably, the crosslinking agent is added in an amount of 0.2 to 0.8 wt%, such as 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, etc., of the polymerized monomer.
Preferably, the polymerization reaction is carried out in a closed environment.
Preferably, the polymerization reaction is carried out in a closed environment under inert gas conditions.
Preferably, the inert gas is nitrogen and/or argon.
Preferably, the polymerization reaction is carried out at a temperature of 80-90 deg.C, such as 82 deg.C, 85 deg.C, 87 deg.C, etc., for a period of 2-3 hours, such as 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, etc.
Preferably, the preparation method comprises the following steps:
(1) mixing 2-acrylamido-2-methyl-1-propanesulfonic acid with 1-10 wt% water soluble polymer or 1-10 wt% water soluble vinyl monomer solution, adding initiator, cross-linking agent and lithium chloride, and mixing;
(2) and (3) placing the reaction system in a vacuum environment for 10-15min to remove air, and then carrying out polymerization reaction in a closed environment filled with inert gas, wherein the reaction temperature is 80-90 ℃, and the reaction time is 2-3h, so as to obtain the self-repairable polymer electrolyte.
In a third aspect, the present invention provides a polymer electrolyte membrane comprising the self-repairable polymer electrolyte of the first aspect.
In a fourth aspect, the self-repairable polymer electrolyte according to the first aspect is used in a capacitor.
Preferably, the capacitor is a flexible supercapacitor.
Compared with the prior art, the invention has the following beneficial effects:
the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) in the polymer electrolyte provided by the invention has the advantages that dynamic hydrogen bonds formed between sulfonic acid groups and amide groups in a polymer chain endow the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) with self-repairing capability, and simultaneously, a water-soluble polymer capable of forming hydrogen bonds with the sulfonic acid groups and/or the amide groups is added, so that the hydrogen bond density of the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) is further improved, and the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) also has higher self-repairing efficiency under the condition of relatively low solid content, and at the moment, the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) also has better stretchability, therefore, the polymer electrolyte provided by the invention has better mechanical property and excellent self-repairing capability.
Drawings
Fig. 1 is a stress-strain curve of the polymer electrolyte provided in example 1 before fracture and after self-repair.
FIG. 2 is a cyclic voltammogram of a capacitor prepared from the polymer electrolyte provided in example 1 before fracture and after self-repair.
FIG. 3 shows the constant current charge-discharge curve (current density 1 mA/cm) before and after self-repairing of the capacitor made of the polymer electrolyte provided in example 12)。
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A self-repairable polymer electrolyte has a solid content of 50 wt%, and is prepared by the following steps:
(1) mixing 1.76g of 2-acrylamido-2-methyl-1-propanesulfonic acid with 2g of a 6 wt% polyvinyl alcohol aqueous solution, adding 1.76mg of ammonium persulfate, 14.08mg of N, N' -dimethyl bisacrylamide and 79.69mg of lithium chloride, and uniformly mixing;
(2) and (3) placing the reaction system in a vacuum environment for 15min to remove air, and then carrying out polymerization reaction in a closed environment filled with argon, wherein the reaction temperature is 80 ℃, and the reaction time is 3h, so as to obtain the self-repairable polymer electrolyte.
Examples 2 to 3
The difference from example 1 is that the solid content of the polymer electrolyte obtained finally was 20 wt% (example 2) and 60 wt% (example 3) by adjusting the amount of water used.
At this time, it is necessary to ensure that the concentration of lithium chloride is constant.
Examples 4 to 5
The difference from example 1 is that the amount of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) was changed to 90% and 98% by weight (example 4) and 98% by weight (example 5) with respect to the amount of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) while maintaining the amount of 2-acrylamido-2-methyl-1-propanesulfonic acid.
The mass percentage of the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) is based on 100% of the total mass of the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) and the water-soluble polymer.
Example 6
A self-repairable polymer electrolyte has a solid content of 50 wt%, and is prepared by the following steps:
(1)2g of deionized water 1.81g of 2-acrylamido-2-methyl-1-propanesulfonic acid were mixed with 0.19g of polyethyleneimine (M)w10000), then adding 1.81mg of ammonium persulfate, 14.48mg of N, N' -dimethyl bisacrylamide and 85mg of lithium chloride, and uniformly mixing;
(2) and (3) placing the reaction system in a vacuum environment for 15min to remove air, and then carrying out polymerization reaction in a closed environment filled with nitrogen, wherein the reaction temperature is 90 ℃, and the reaction time is 2h, so as to obtain the self-repairable polymer electrolyte.
Example 7
A self-repairable polymer electrolyte has a solid content of 50 wt%, and is prepared by the following steps:
(1)2g of deionized water, 1.89g of 2-acrylamido-2-methyl-1-propanesulfonic acid and 0.11g of hydroxyethyl acrylate are mixed, and then 2mg of ammonium persulfate, 16mg of N, N' -dimethyl bisacrylamide and 85mg of lithium chloride are added and uniformly mixed;
(2) and (3) placing the reaction system in a vacuum environment for 15min to remove air, and then carrying out polymerization reaction in a closed environment filled with nitrogen, wherein the reaction temperature is 80 ℃, and the reaction time is 3h, so as to obtain the self-repairable polymer electrolyte.
Example 8
A self-repairable polymer electrolyte has a solid content of 50 wt%, and is prepared by the following steps:
(1)2g of deionized water, 1.91g of 2-acrylamido-2-methyl-1-propanesulfonic acid and 0.09g N-hydroxymethyl acrylamide are mixed, and then 2mg of ammonium persulfate, 16mg of N, N' -dimethyl bisacrylamide and 85mg of lithium chloride are added and uniformly mixed;
(2) and (3) placing the reaction system in a vacuum environment for 15min to remove air, and then carrying out polymerization reaction in a closed environment filled with argon, wherein the reaction temperature is 80 ℃, and the reaction time is 3h, so as to obtain the self-repairable polymer electrolyte.
Comparative example 1
The only difference from example 1 is that in this comparative example, poly (2-acrylamido-2-methyl-1-propanesulfonic acid) electrolyte was obtained with a solids content of 50% by weight, without the addition of polyvinyl alcohol.
Comparative example 2
The only difference from example 1 is that this comparative example provides an electrolyte consisting of polyvinyl alcohol and lithium chloride, added in the same amount as in example 1, with a solid content of 50 wt%.
Performance testing
The electrolytes provided in examples 1 to 8 and comparative examples 1 to 2 were subjected to performance tests as follows:
(1) tensile strength and elongation at break: the sample was cut into small strips of 30 mm. times.5 mm. times.3 mm, and then subjected to a tensile tester (Shimadzu AG-X Plus100N, Japan) at room temperature at 1 mm. s-1The speed of the polymer electrolyte is measured by a uniaxial tension test, and the polymer electrolyte strip is continuously elongated until the fracture machine records the fracture stress and the fracture strain of the sample.
(2) Resistance: testing the resistance values of the electrolyte before fracture and after self-repairing by using an electrochemical impedance spectrum testing method;
the method comprises the steps of taking small polyelectrolyte strips with the size of 30mm multiplied by 5mm multiplied by 3mm, attaching gold-plated PET films to the upper surface and the lower surface of each small polyelectrolyte strip as extraction electrodes, and then carrying out a double-electrode mode electrochemical impedance spectroscopy test in a CHI 660e electrochemical workstation, wherein the frequency range is 1Hz-100kHz, the potential amplitude is 5mV, and the intercept value of a curve in a complex plane of an impedance spectroscopy on a real axis is the resistance value of the polyelectrolyte.
A sample with dimensions of 30mm × 5mm × 3mm was assembled with PPy @ SWCNT films attached to the top and bottom sides of the sample, and the following tests were performed:
(3) resistance: testing the resistance of the capacitor before breaking and the resistance after self-repairing;
the upper surface and the lower surface of the capacitor are tightly attached to gold-plated PET electrodes, and then a double-electrode mode electrochemical impedance spectroscopy test is carried out on a CHI 660e electrochemical workstation, wherein the frequency range is 10mHz-100kHz, and the potential amplitude is 5 mV. And the intercept of the curve in the impedance spectrogram complex plane on a real axis is the equivalent resistance value of the capacitor under high frequency.
(4) Cyclic charge and discharge performance: testing cyclic voltammetry curves of the capacitor before breakage and after repair;
the test method comprises the following steps: and (2) closely attaching the upper surface and the lower surface of the capacitor to gold-plated PET electrodes, then carrying out a double-electrode mode cyclic voltammetry characteristic test in a CHI 660e electrochemical workstation, setting electrode potential between-0.5V and 0.5V to make symmetrical triangular wave change along with time (the electrode potential change rate range is 5-200mV/s), and recording a curve of current changing along with the electrode potential to obtain a cyclic voltammetry curve of the capacitor.
Fig. 2 is a cyclic voltammetry curve before rupture and after self-repair of the capacitor prepared from the polymer electrolyte provided in example 1, and it can be seen from the graph that the cyclic voltammetry curves before and after self-repair are both close to a rectangle, showing the characteristic of a symmetric supercapacitor, and the two curves are almost coincident, showing the excellent self-repair capability of the supercapacitor; more importantly, the integral area of the curve after the repair is almost the same as that of the original curve, namely the capacity of the repaired supercapacitor is basically kept unchanged, which shows that the polymer electrolyte provided by the invention has excellent self-repairing performance.
(5) Area specific capacitance and coulombic efficiency: and (3) calculating the area specific capacitance and coulombic efficiency of the original sample and the repaired sample by testing constant current charge-discharge curves before breaking and after repairing the capacitor.
The constant current charging and discharging curve test method comprises the following steps: the upper and lower surfaces of the capacitor are tightly attached to gold-plated PET electrodes, and then a double-electrode mode constant current charge and discharge test is carried out at a CHI 660e electrochemical workstation. Charging at constant current density in the range of-0.5V to 0.5V of electrode potential, and then discharging at the same constant current density (current density in the range of 0.1-5.0mA/cm is used)2). And recording the change curve of the electrode potential along with time to obtain the constant current charge-discharge curve of the capacitor.
Single electrode area specific capacitance (C)s，mF cm-2) The calculation of (2): cs＝2(I×td) V (V × A), where I is the discharge current in the constant-current charge-discharge test, tdIs the discharge time in the constant current charge-discharge test, V is the electrode potential range, and a is the electrode area.
Calculation of coulombic efficiency (CE,%): CE ═ td/tcWherein t isdIs the discharge time, t, in a constant current charge-discharge testcIs the charging time in the constant current charging and discharging test.
FIG. 3 shows the constant current charge-discharge curve (current density 1 mA/cm) before and after self-repairing of the capacitor made of the polymer electrolyte provided in example 12) It can be known from the figure that the curve shapes of constant current charging and discharging before and after the repair are close to isosceles triangles, and the curve shows that the super capacitor has high voltage before and after the repairCoulomb efficiency. Through calculation, the area specific capacitance of the polymer electrolyte provided by the example 1 before self-repairing is 350mF/cm2The coulomb efficiency is 97.3 percent, and the area specific capacitance after self-repairing is 328mF/cm2The coulombic efficiency was 93.7% (current density was 1 mA/cm)2) Therefore, the self-repairing efficiency of the polymer electrolyte provided by the invention is very high.
The data for the other examples and comparative examples are shown in table 1.
TABLE 1
TABLE 2
As can be seen from the examples and performance tests, the polymer electrolyte provided by the invention has better mechanical properties and excellent self-repairing capability. The breaking elongation of the polymer electrolyte is more than 135 +/-10 percent and as high as 795 +/-20 percent, the maximum repairing efficiency can reach about 92.68 percent, the maximum repairing efficiency on the tensile strength can reach more than 89.92 percent, and the maximum repairing efficiency on the electrolyte resistance can reach 99.90 percent.
After the capacitor is prepared by the polymer electrolyte, the highest repair efficiency of the capacitor on the internal resistance can reach 98.02 percent; the area specific capacitance can reach 358mF/cm at most before the capacitor breaks2About, the maximum after fracture repair can reach 328mF/cm2About, the repair efficiency can reach more than 94%; the coulombic efficiency of the capacitor is inThe highest rate before fracture can reach 99%, the fracture is still more than 90% after fracture repair, and the repair efficiency is more than 95%.
As is apparent from a comparison of example 1 and comparative examples 1 to 2, the polymer electrolyte of the present invention can achieve optimum overall performance only when it comprises poly (2-acrylamido-2-methyl-1-propanesulfonic acid) and a water-soluble polymer capable of forming a hydrogen bond with a sulfonic acid group and/or an amide group.
The applicant states that the self-repairable polymer electrolyte of the present invention and the preparation method and application thereof are illustrated by the above examples, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (27)
1. A self-repairable polymer electrolyte, which comprises poly (2-acrylamido-2-methyl-1-propanesulfonic acid) and a water-soluble polymer capable of forming a hydrogen bond with a sulfonic acid group and/or an amide group, and lithium chloride;
the mass percentage of the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) is 90-98% based on 100% of the total mass of the poly (2-acrylamido-2-methyl-1-propanesulfonic acid) and the water-soluble polymer;
the solid content of the polymer electrolyte is 20-60 wt%;
the preparation method of the self-repairable polymer electrolyte comprises the following steps:
mixing 2-acrylamido-2-methyl-1-propanesulfonic acid with an aqueous solution of a water-soluble polymer, and then adding an initiator and a cross-linking agent to carry out a polymerization reaction to obtain the self-repairable polymer electrolyte;
or mixing 2-acrylamido-2-methyl-1-propanesulfonic acid with an aqueous solution of a vinyl monomer, and then adding an initiator and a crosslinking agent to carry out polymerization reaction, thereby obtaining the self-repairable polymer electrolyte.
2. The self-repairable polymer electrolyte according to claim 1, wherein the water-soluble polymer comprises any one or a combination of at least two of polyvinyl alcohol, polyethyleneimine, sodium alginate, chitosan or carboxymethyl chitosan.
3. The self-repairable polymer electrolyte according to claim 1, wherein the polymerized monomer of the water-soluble polymer is a vinyl monomer.
4. The self-repairable polymer electrolyte according to claim 3, wherein the vinyl monomer has any one or a combination of at least two of a hydroxyl group, a carboxyl group, an amide group, an imino group, or a sulfonic acid group.
5. The self-repairable polymer electrolyte according to claim 4, wherein the vinyl monomer is selected from any one of or a combination of at least two of hydroxyethyl acrylate, hydroxypropyl acrylate, 3-allyloxy-1, 2-propanediol, N-methylolacrylamide, dimethylaminoethyl methacrylate, or vinylimidazole.
6. The self-repairable polymer electrolyte according to claim 1, wherein the concentration of the lithium chloride in the self-repairable polymer electrolyte is 0.5 to 3M.
7. The preparation method of the self-repairable polymer electrolyte according to claim 1, comprising the following steps:
mixing 2-acrylamido-2-methyl-1-propanesulfonic acid with an aqueous solution of a water-soluble polymer, and then adding an initiator and a cross-linking agent to carry out a polymerization reaction to obtain the self-repairable polymer electrolyte;
or mixing 2-acrylamido-2-methyl-1-propanesulfonic acid with an aqueous solution of a vinyl monomer, and then adding an initiator and a crosslinking agent to carry out polymerization reaction, thereby obtaining the self-repairable polymer electrolyte.
8. The method according to claim 7, wherein the concentration of the aqueous solution of the water-soluble polymer is 1 to 10 wt%.
9. The method according to claim 7, wherein the water-soluble polymer comprises any one of polyvinyl alcohol, polyethyleneimine, sodium alginate, chitosan or carboxymethyl chitosan or a combination of at least two thereof.
10. The production method according to claim 7, wherein the concentration of the aqueous solution of the vinyl monomer is 1 to 10 wt%.
11. The method according to claim 10, wherein the vinyl monomer is selected from any one of hydroxyethyl acrylate, hydroxypropyl acrylate, 3-allyloxy-1, 2-propanediol, N-methylolacrylamide, dimethylaminoethyl methacrylate, and vinylimidazole, or a combination of at least two thereof.
12. The production method according to claim 7, wherein the mass percentage of the vinyl monomer is 4 to 40% based on 100% of the total mass of the vinyl monomer and 2-acrylamido-2-methyl-1-propanesulfonic acid.
13. The method according to claim 7, wherein lithium chloride is further contained in the reaction system.
14. The method according to claim 7, wherein the initiator is ammonium persulfate.
15. The method according to claim 7, wherein the initiator is added in an amount of 0.1 to 0.4 wt% based on the mass of the monomer to be polymerized.
16. The method of claim 7, wherein the polymerized monomer comprises 2-acrylamido-2-methyl-1-propanesulfonic acid.
17. The method of claim 7, wherein the polymerized monomers comprise 2-acrylamido-2-methyl-1-propanesulfonic acid and a vinyl monomer.
18. The method according to claim 7, wherein the crosslinking agent is N, N' -dimethylbisacrylamide.
19. The method according to claim 7, wherein the crosslinking agent is added in an amount of 0.2 to 0.8 wt% based on the polymerized monomer.
20. The method of claim 7, wherein the polymerization is performed in a closed environment.
21. The method of claim 7, wherein the polymerization is carried out in a closed environment under protective gas conditions.
22. The method according to claim 7, wherein the protective gas is preferably nitrogen and/or argon.
23. The process according to claim 7, wherein the polymerization is carried out at a temperature of 80 to 90 ℃ for 2 to 3 hours.
24. The method of claim 7, comprising the steps of:
(1) mixing 2-acrylamido-2-methyl-1-propanesulfonic acid with 1-10 wt% water solution of water soluble polymer or 1-10 wt% water solution of water soluble vinyl monomer, adding initiator, cross-linking agent and lithium chloride and mixing;
(2) and (3) placing the reaction system in a vacuum environment for 10-15min to remove air, and then carrying out polymerization reaction in a closed environment filled with inert gas, wherein the reaction temperature is 80-90 ℃, and the reaction time is 2-3h, so as to obtain the self-repairable polymer electrolyte.
25. A polymer electrolyte membrane comprising the self-repairable polymer electrolyte of any one of claims 1 to 6.
26. Use of the self-repairable polymer electrolyte of any one of claims 1-6 in a capacitor.
27. The use according to claim 26, wherein the capacitor is a flexible supercapacitor.
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| CN110600279B (en) * | 2019-10-28 | 2021-10-12 | 锦州凯美能源有限公司 | Gel electrolyte precursor and application thereof in preparing quasi-solid supercapacitor |
| CN110600280B (en) * | 2019-10-28 | 2022-03-08 | 锦州凯美能源有限公司 | Gel electrolyte precursor and application thereof in preparation of supercapacitor |
| CN110746640B (en) * | 2019-11-11 | 2020-07-07 | 浙江农林大学 | Capacitive sensor material and preparation method and application thereof |
| CN110867536A (en) * | 2019-11-19 | 2020-03-06 | 电子科技大学 | Multilayer nano film, preparation method thereof and lithium battery |
| CN111019041B (en) * | 2019-12-24 | 2021-05-25 | 齐鲁工业大学 | High-conductivity, stretchable, compressible and repairable zwitterionic gel polymer electrolyte and preparation and application thereof |
| CN111162314B (en) * | 2019-12-25 | 2023-05-09 | 中国科学院青岛生物能源与过程研究所 | Self-repairing polymer electrolyte based on dynamic chemical bond and application of self-repairing polymer electrolyte in secondary lithium battery |
| CN112768255B (en) * | 2020-12-06 | 2023-01-24 | 齐鲁工业大学 | Anti-freezing zwitterion hydrogel electrolyte and application thereof |
| CN113527714B (en) * | 2021-06-03 | 2022-05-31 | 湖南工业大学 | Anti-freezing conductive hydrogel, preparation method thereof and force response sensing application |
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