CN109585931B - Wide-working-voltage flexible self-repairing salt hydrogel electrolyte and preparation method thereof - Google Patents
Wide-working-voltage flexible self-repairing salt hydrogel electrolyte and preparation method thereof Download PDFInfo
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Abstract
A salt hydrogel electrolyte with wide working voltage and flexible self-repairing and a preparation method thereof belong to the technical field of electrolyte preparation. According to the invention, an ion absorbent chitosan and inorganic functional network silicon dioxide with high mechanical property are introduced into a hydrophilic monomer, self-repairing hydrogel with ultrahigh hydrophilic capability and water retention capability is prepared by thermal polymerization, and then lithium salt with ultrahigh concentration is introduced into a gel network by a simple impregnation method, so that the problems of low ionic conductivity, easy liquid leakage, low power density caused by highly solvated lithium salt and the like of the existing water-in-salt electrolyte are solved, the electrolyte is endowed with high mechanical property, and a novel salt-in-salt hydrogel electrolyte with wide working voltage and flexible self-repairing property is prepared. The experimental result shows that the product of the invention has 50mS cm at room temperature‑1The ionic conductivity of the electrolyte is 5 times higher than that of water-in-salt electrolyte and is superior to most hydrogel electrolytes.
Description
Technical Field
The invention belongs to the technical field of electrolyte preparation, and particularly relates to a flexible self-repairing salt hydrogel electrolyte with wide working voltage and a preparation method thereof.
Background
The excessive consumption of fossil energy promotes the appearance and development of new energy. Meanwhile, lithium batteries, solar batteries and super capacitors as energy storage devices are important devices for realizing storage and conversion of new energy, and more attention is paid to the devices. As an important component of an energy storage device, the electrolyte needs to ensure rapid transmission of ions between the positive electrode and the negative electrode, is cheap and easily available, has high safety, no toxicity, no volatilization, low flammability, and most importantly has stable and wide working voltage.
Most commercial electrolytes on the market are liquid electrolytes, including organic electrolytes (2.7V), ionic liquids (2-4V) and aqueous electrolytes. Organic electrolytes can provide large operating voltages, but they still suffer from a number of disadvantages including liquid leakage, high flammability, toxicity and corrosiveness. Ionic liquids have higher viscosity and lower ionic conductivity. In contrast, aqueous electrolytes are more attractive due to their high ionic conductivity, low flammability, abundant sources, low cost, and environmental friendliness. The aqueous electrolyte is limited to a narrow operating voltage (1.23V) and cannot provide a sufficient energy density. The appearance of the Water-in-salt electrolyte solves the problem of narrow working voltage of the Water system electrolyte to a certain extent, the potential window can reach 3V, and the Water-in-salt electrolyte has good chemical stability and thermal stability. However, the water-in-salt electrolyte reported at the present stage is a highly concentrated salt solution, which often results in lower ionic conductivity and lower power density, and meanwhile, the nature of the water-in-salt liquid electrolyte still has the problems of easy leakage, larger volume of the assembled device, and the like.
Therefore, under the condition of not reducing the working voltage of the water-in-salt electrolyte, the preparation of the electrolyte with high ionic conductivity and easy leakage of the liquid electrolyte has very important significance.
Disclosure of Invention
In order to overcome the technical defects of the prior water-in-salt electrolyte and meet the improvement requirements, the invention provides a novel wide-working-voltage flexible self-repairing hydrogel-in-salt electrolyte and a preparation method thereof, wherein an ion absorbent chitosan and inorganic functional network silicon dioxide with high mechanical property are introduced into a hydrophilic monomer, and thermal polymerization is carried out to prepare the self-repairing hydrogel with ultrahigh hydrophilic capability and water retention capability, then, the lithium salt with ultrahigh concentration is introduced into the gel network by a simple impregnation method, thereby solving the problems of low ionic conductivity, easy liquid leakage, low power density caused by the highly solvated lithium salt and the like of the existing water-in-salt electrolyte, and endows the electrolyte with high mechanical property, and prepares novel flexible self-repairing 'salt hydrogel' electrolyte with wide working voltage.
In order to achieve the purposes, the invention provides a novel wide-working-voltage flexible self-repairing hydrogel-in-salt electrolyte, and the final product comprises the following components in percentage by mass:
a preparation method of a novel wide-working-voltage flexible self-repairing hydrogel-in-salt electrolyte comprises the following steps:
1) dissolving 300-500 mg of hydrophilic monomer into 2-5 mL of water-soluble polyhydroxy high molecular polysaccharide ion absorption solution (30-50 mg/mL), adding 100-400 mg of inorganic reinforcing agent, adding 15-30 mg of initiator, degassing for 30-60 min by using nitrogen to remove oxygen, uniformly stirring at 300-600 rpm in the nitrogen atmosphere, pouring the product into a cylindrical mold with the diameter of 5-10 cm, and heating at 50-80 ℃ for 8-15 h to prepare hydrogel;
2) swelling the hydrogel prepared in the step 1) to remove unreacted monomers, and drying the hydrogel under vacuum for 20-30 hours to constant weight;
3) soaking the dried gel dry sample obtained in the step 2) in 1-10M lithium salt aqueous solution for 10-20 h to obtain the flexible self-repairing 'saline gel' electrolyte with wide working voltage.
The hydrophilic monomer of the present invention may be any one or a mixture of two or more of acrylamide (AAm), Acrylic Acid (AA), hydroxyethyl methacrylate (HEMA), N-dimethyl methacrylamide (DMMA), N-dimethyl acrylamide (DMA), and N-vinyl-2-pyrrolidone (NVP), but is not limited to these monomers.
The lithium salt is one or two of lithium bis (trifluoromethyl) sulfonyl imide (LiTFSI) or lithium bis (pentafluoroethylsulfonyl) imide (LiBETI), but is not limited to the substances.
The water-soluble polyhydroxy high molecular polysaccharide used as the ion absorbent can be one or two of Chitosan (CS) or Sodium Alginate (SA), but is not limited to the above substances.
The initiator is one of ammonium persulfate or potassium persulfate.
The inorganic reinforcing agent is tetraethyl orthosilicate and generates silicon dioxide after reaction;
taking example 3 as an example, the invention was prepared by a one-pot method and a simple dipping method by immersing polyacrylamide-chitosan/silica in a high concentration lithium salt solution for 12 hours with a water content of 163.3mmol g in the hydrogel-1And the content of lithium salt was 53.3mmol g-1Obtaining highly concentrated hydrogel, wherein the mass ratio of the gel components is as follows: water: lithium salt 1: 2.9: 15.3, ensuring that the water in the gel is all bound water and has 50mS cm at room temperature-1The ionic conductivity of the electrolyte is 5 times higher than that of water-in-salt electrolyte and is superior to most hydrogel electrolytes.
Drawings
FIG. 1 is a graph showing infrared analysis curves of hydrogels obtained in example 1 (curve 1) and example 2 (curve 2) of the present invention.
FIG. 2 is a diagram of novel high-stretchability flexible self-repairing hydrogel polyacrylamide-chitosan/silica (PACH/SiO) prepared in example 2 of the present invention2) FE-SEM photograph of (1). Panel a (50um) and panel b (100um) are PACH/SiO, respectively2After water absorption and swelling, electron microscope pictures with different dimensions show that PACH/SiO2Has good water retention property, and the large aperture inside the gel is beneficial to ensuring the storage and transportation of ions.
FIG. 3 is a graph showing the ratio of salt to water after swelling of the novel wide-working-voltage, flexible, self-repairing hydrogel-in-salt electrolyte prepared in example 3 of the present invention in LiTFSI solutions of different concentrations. Panel a illustrates the change in the mass concentration of LiTFSI and water in hydrogel-in-salt electrolyte as the LiTFSI ion concentration increases; panel b illustrates the change in molar concentrations of LiTFSI and water in hydrogel-in-salt electrolyte with increasing ion concentration of LiTFSI.
FIG. 4 is a water loss curve at 40 ℃ after the novel wide-working-voltage flexible self-repairing hydrogel-in-salt electrolyte of example 3 of the present invention is soaked in LiTFSI solutions of different concentrations. Panel a illustrates the change in mass of fully dried hydrogel-in-salt electrolyte at 40 ℃ and 40% humidity as the LiTFSI ion concentration increases; panel b illustrates the change in mass of hydrogel-in-salt electrolyte at 40 ℃ and 40% humidity as the LiTFSI ion concentration increases.
FIG. 5 example 2 of the present invention is a novel high tensile flexible self-healing hydrogel polyacrylamide-chitosan/silica (PACH/SiO)2) Stress strain curve. In the figure, curve 1 corresponds to polyacrylamide-chitosan hydrogel, and curve 2 corresponds to polyacrylamide-chitosan/100 mg silicon dioxide (PACH-100 mgSiO)2) Curve 3 corresponds to polyacrylamide-chitosan/100 mg silica (PACH-200 mgSiO)2) Curve 4 corresponds to polyacrylamide-chitosan/100 mg silica (PACH-400 mgSiO)2) Curve 5 corresponds to polyacrylamide-chitosan/100 mg silica (PACH-600 mgSiO)2)。
FIG. 6 example 6 of the present invention provides a novel wide-working-voltage, flexible, self-repairing hydrogel-in-salt electrolyte PACH/SiO2-10 ion conductivity as a function of temperature.
FIG. 7 novel high tensile Flexible self-healing hydrogel Polyacrylamide-Chitosan/silica (PACH/SiO) in EXAMPLE 2 of the present invention2) Schematic diagram of the self-repairing process. FIG. a (5um) is PACH/SiO2A microscope picture after the incision, a microscope picture after the self-repair for 10 minutes in fig. b (5um), a microscope picture after the self-repair for 20 minutes in fig. c (5um), and a microscope picture after the self-repair for 20 minutes and 100um in fig. d.
FIG. 8 novel high tensile Flexible self-healing hydrogel Polyacrylamide-Chitosan/silica (PACH/SiO) in EXAMPLE 2 of the present invention2) Mechanical efficiency curve in the self-healing process.
FIG. 9 shows the novel embodiments 3 to 7 of the present inventionThe change curve of the working voltage of the wide-working-voltage flexible self-repairing hydrogel-in-salt electrolyte along with the concentration of the soaked lithium salt is shown, and when the concentration reaches 10M, PACH/SiO 210 has good temperature stability and can reach stable working voltage of 2.6V. In the figure, Curve 1 corresponds to PACH/SiO in example 32 Curve 2 corresponds to PACH/SiO in example 4-12 Curve 3 corresponds to PACH/SiO in example 52-5, Curve 4 corresponds to PACH/SiO in example 6210, corresponding to the linear sweep voltammetry test profiles, respectively.
FIG. 10 is a graph of the novel high tensile flexible self-healing hydrogel polyacrylamide-chitosan/silica (PACH/SiO) prepared in examples 2 and 6 of the present invention2) And a differential thermal scan schematic diagram of a novel wide-working-voltage, flexible self-repairing hydrogel-in-salt electrolyte, which can illustrate that the addition of the preparation of LITFSI can effectively increase the thermal stability.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
Example 1:
a preparation method of a novel high-stretchability flexible self-repairing hydrogel polyacrylamide-chitosan (PACH) comprises the following steps: dissolving 400mg of hydrophilic monomer acrylamide in 2mL of chitosan solution (40mg/mL), adding 20mg of initiator ammonium persulfate, degassing for 30min by using nitrogen to remove oxygen, uniformly stirring at 400rpm in the nitrogen atmosphere, pouring into a cylindrical polymethyl methacrylate mould with the diameter of 6cm, and heating at 60 ℃ for 10h to prepare the hydrogel.
Example 2:
novel high-stretchability flexible self-repairing hydrogel polyacrylamide-chitosan/silicon dioxide (PACH/SiO)2) The preparation method comprises the following steps: dissolving 400mg hydrophilic monomer acrylamide in 2mL chitosan solution (40mg/mL), adding tetraethyl orthosilicate (100 mg) as inorganic reinforcing agent, adding 20mg initiator ammonium persulfate, degassing with nitrogen for 30min to remove oxygen, stirring at 400rpm under nitrogen atmosphere, pouring cylindrical polymethacrylene with diameter of 6cmHeating the mixture in a methyl acid ester mould at 60 ℃ for 10h to prepare the hydrogel.
Example 3:
novel wide-working-voltage flexible self-repairing hydrogel-in-salt electrolyte preparation process
The novel high-stretchability flexible self-repairing hydrogel polyacrylamide-chitosan/silicon dioxide (PACH/SiO) in example 22) And soaking the hydrogel in excessive deionized water to swell and remove unreacted monomers, and then drying the hydrogel in vacuum for 24 hours to constant weight. Soaking the dried gel dry sample in a highly concentrated 1M lithium salt solution for 12h, taking out and weighing to obtain a flexible self-repairing hydrogel-in-salt electrolyte with working voltage, which is recorded as PACH/SiO2-1。
Example 4:
novel wide-working-voltage flexible self-repairing hydrogel-in-salt electrolyte preparation process
The novel high-stretchability flexible self-repairing hydrogel polyacrylamide-chitosan/silicon dioxide (PACH/SiO) in example 22) And soaking the hydrogel in excessive deionized water to swell and remove unreacted monomers, and then drying the hydrogel in vacuum for 24 hours to constant weight. Soaking the dried gel dry sample in highly concentrated 2M lithium salt solution for 12h, taking out and weighing to obtain flexible self-repairing hydrogel-in-salt electrolyte with working voltage, which is recorded as PACH/SiO2-2。
Example 5:
preparation process of novel wide-working-voltage flexible self-repairing hydrogel-in-salt electrolyte, the novel high-stretchability flexible self-repairing hydrogel polyacrylamide-chitosan/silicon dioxide (PACH/SiO) in example 2 is prepared2) And soaking the hydrogel in excessive deionized water to swell and remove unreacted monomers, and then drying the hydrogel in vacuum for 24 hours to constant weight. Soaking the dried gel dry sample in a highly concentrated 5M lithium salt solution for 12h, taking out and weighing to obtain a flexible self-repairing hydrogel-in-salt electrolyte, PACH/SiO2-5。
Example 6:
a novel wide-working-voltage flexible self-repairing hydrogel-in-salt electrolyte preparation process described in example 2High-tensile flexible self-repairing hydrogel polyacrylamide-chitosan/silicon dioxide (PACH/SiO)2) And soaking the hydrogel in excessive deionized water to swell and remove unreacted monomers, and then drying the hydrogel in vacuum for 24 hours to constant weight. Soaking the dried gel dry sample in a highly concentrated 10M lithium salt solution for 12h, taking out and weighing to obtain a flexible self-repairing hydrogel-in-salt electrolyte with working voltage, which is recorded as PACH/SiO2-10。
Example 7:
performing component analysis on the materials in the examples 3 to 6, in order to confirm the contents of water and LiTFSI, drying the novel wide-working-voltage flexible self-repairing hydrogel-in-salt electrolyte in the examples 3 to 6 in vacuum, soaking the electrolyte in a LiTFSI solution (10M) to constant weight, and finally drying the electrolyte again, wherein the weight is marked as PACH/SiO2-10。PACH/SiO2-10 showed high electrolyte absorption (up to 400 wt% water, up to 1500 wt% LiTFSI). The electrolytes of examples 3 to 6 were tested by linear sweep voltammetry using an electrochemical workstation to determine the working voltage.
The novel wide-working-voltage flexible self-repairing hydrogel-in-salt electrolyte synthesized by the method is subjected to detailed performance characterization, and the specific characterization mode is as follows:
infrared spectroscopic analysis
The hydrogel was characterized by infrared spectroscopy (Spectrum FTIR 8400S spectrometer, Shimadzu). The prepared hydrogel was completely dried, pulverized with potassium bromide to powder, and tested.
Topography analysis
The morphology of the lyophilized gel was observed by using FE-SEM (Hitachi FE-SEM S-4800 instrument).
Component content test
The dried PACH/SiO2Sample (W)0G) immersion in aqueous LiTFSI (1M, 2M, 5M and 10M) solutions for 12 hours at room temperature. The hydrogel was then removed from the LiTFSI solution, excess water on the surface of the hydrogel was removed using an absorbent tissue, and the soaked PACH/SiO was measured2(W1And g) weight of the composition. Then drying the soaked hydrogel to constant weight as PACH/SiO2-LiTFSI(W2G). The water and lithium salt contents (wt%) in the electrolyte were calculated using the following equations (1-4):
and (3) testing mechanical properties:
prepared PACH/SiO2The hydrogel film samples were cut into standard sample strips (length. times. width. times. thickness-14 mm. times.l 0 mm. times.1 mm), centered on the universal material tensile tester plate so that they remained naturally vertical, and then clamped with a clamp at a constant rate (20mm min)-1) And slowly applying the load until the sample bar is broken, measuring the maximum tensile stress strength and the breaking elongation, and calculating corresponding stress and strain data according to the maximum tensile stress strength and the breaking elongation.
Self-repairing performance test:
splicing two hydrogel samples which are just cut together to ensure complete contact, and observing the self-repairing condition and the mechanical property recovery condition of the wound at room temperature.
Determination of the Ionic conductivity
Two platinum sheets were placed on both sides of the gel electrolyte, ac impedance measurement was performed on an electrochemical workstation, the change in resistance was observed, and the ionic conductivity (5) was calculated according to the following formula: (R is gel electrolyte resistance, S is gel electrolyte area, L is distance between two platinum sheets)
And (3) analyzing an experimental result:
FIG. 1 shows the infrared analysis of the hydrogels obtained in examples 1 and 2: in the figure, 3480 is the stretching vibration peak of-OH, 3380 is-NH2The absorption peak of 1658, the absorption peak of amido bond, and the absorption peaks of 1080 and 680, which are Si-O-Si, proves that the tetraethyl orthosilicate in the gel is completely converted into silicon dioxide, and the gel is non-covalently crosslinked without new bond formation.
The FE-SEM photograph of fig. 2 can clearly observe the porous network structure inside the novel wide-working-voltage, flexible self-repairing hydrogel-in-salt electrolyte prepared in example 2.
FIG. 3 examples 3-6 change in salt to water ratio after swelling of novel wide-working-voltage, flexible, self-healing hydrogel-in-salt electrolytes in LiTFSI solutions of different concentrations.
FIG. 4 shows the dehydration condition of the novel wide-working-voltage, flexible and self-repairing hydrogel-in-salt electrolyte in the embodiment 3-6 at 40 ℃ after soaking in LiTFSI solutions with different concentrations.
FIG. 5 is a stress-strain curve of a novel wide-working-voltage, flexible and self-repairing hydrogel-in-salt electrolyte in example 2, and it can be seen from the graph that the elongation at break of the material reaches 3000%, the tensile stress reaches 250kPa, and the mechanical properties are obviously improved compared with those of the conventional hydrogel.
FIG. 6 example 7 shows the relationship curve of the ion conductivity of the novel wide-operating-voltage flexible self-repairing hydrogel-in-salt electrolyte with temperature change, when the concentration reaches 10M, PACH/SiO2-10 has good temperature stability, and conforms to the Arrhenius formula, and at-20 ℃, 17.3mS cm is still present-1Has an ionic conductivity of 53mS cm at 25 DEG C-1The ionic conductivity of (a).
FIG. 7 novel high tensile Flexible self-healing hydrogel Polyacrylamide-Chitosan/silica (PACH/SiO) in example 22) The self-healing process of (1).
FIG. 8 novel high tensile Flexible self-healing hydrogel Polymer in example 2acrylamide-Chitosan/silica (PACH/SiO)2) The self-repairing process of (2) has mechanical property recovery efficiency.
FIG. 9 is a graph showing the change of the operating voltage of the novel wide-operating-voltage flexible self-repairing hydrogel-in-salt electrolyte according to the concentration of lithium salt in the soaking solution in example 7, wherein when the concentration reaches 10M, PACH/SiO2-10 has good temperature stability and can reach a stable operating voltage of 2.6V.
FIG. 10 is a graph of the novel high-stretch flexible self-healing hydrogel polyacrylamide-chitosan/silica (PACH/SiO) prepared in examples 2, 3 and 7 of the present invention2) And a differential thermal scan schematic diagram of a novel wide-working-voltage, flexible self-repairing hydrogel-in-salt electrolyte, which can illustrate that the addition of the preparation of LITFSI can effectively increase the thermal stability.
Claims (5)
1. A preparation method of a flexible self-repairing salt hydrogel electrolyte with wide working voltage comprises the following steps:
1) dissolving 300-500 mg of hydrophilic monomer into 2-5 mL of water-soluble polyhydroxy high molecular polysaccharide ion absorbent chitosan aqueous solution, adding 100-400 mg of inorganic reinforcing agent silicon dioxide, adding 15-30 mg of initiator, degassing for 30-60 min by using nitrogen to remove oxygen, uniformly stirring at 300-600 rpm under the nitrogen atmosphere, pouring the product into a cylindrical mold with the diameter of 5-10 cm, and heating at 50-80 ℃ for 8-15 h to prepare hydrogel;
2) swelling the hydrogel prepared in the step 1) to remove unreacted monomers, and drying the hydrogel under vacuum for 20-30 hours to constant weight;
3) soaking the dry gel sample obtained in the step 2) in 1-10M lithium salt aqueous solution for 10-20 h to obtain the flexible self-repairing 'water gel in salt' electrolyte with wide working voltage.
2. The preparation method of the salt hydrogel electrolyte with wide working voltage and flexible self-repair function as claimed in claim 1, wherein: the hydrophilic monomer is one or two of acrylamide, acrylic acid, hydroxyethyl methacrylate, N-dimethyl methacrylamide, N-dimethyl acrylamide or N-vinyl-2-pyrrolidone.
3. The preparation method of the salt hydrogel electrolyte with wide working voltage and flexible self-repair function as claimed in claim 1, wherein: the lithium salt is one or two of lithium bistrifluoromethylsulfonyl imide or lithium bis (pentafluoroethylsulfonyl) imide.
4. The preparation method of the salt hydrogel electrolyte with wide working voltage and flexible self-repair function as claimed in claim 1, wherein: the initiator is one or two of ammonium persulfate or potassium persulfate.
5. A salt hydrogel electrolyte with wide working voltage and flexible self-repairing is characterized in that: is prepared by any one of the methods of claims 1 to 4.
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| CN112510255A (en) * | 2020-12-23 | 2021-03-16 | 长春工业大学 | Gel electrolyte of zinc-based battery and preparation and application thereof |
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