CN115133146B - Self-protection gel electrolyte applied to zinc ion battery and preparation method thereof - Google Patents
Self-protection gel electrolyte applied to zinc ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of zinc ion batteries, and provides a self-protection gel electrolyte applied to a zinc ion battery and a preparation method thereof, aiming at the problem that a hydrogel electrolyte of the zinc ion battery promotes side reaction of water and an electrode from electrolysis at high temperature and greatly reduces the service life.
Description
Technical Field
The invention belongs to the technical field of zinc ion batteries, and particularly relates to a self-protection gel electrolyte applied to a zinc ion battery and a preparation method thereof.
Background
The water system zinc ion battery is the most potential lithium ion battery substitute due to the advantages of low price, high safety performance, easy assembly, high ionic conductivity, high theoretical specific capacity, environmental protection and the like. However, in the meantime, the aqueous zinc ion battery has many problems such as dissolution of the positive electrode, generation of by-products, and zinc dendrite growth, corrosion, and passivation of the negative electrode. Recently, a number of strategies have been employed to improve the reversibility of the zinc dissolution/deposition process and to extend the cycle life of zinc metal electrodes.
At present, the types of hydrogel electrolytes which are researched more in the field of water-based zinc ion batteries comprise polyvinyl alcohol, polyacrylamide, polyethylene glycol, polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride and the like, water molecules in the hydrogel electrolytes enhance the contact of a solid-solid interface between an electrode and the electrolyte, but the existing hydrogel electrolytes in the hydrogel zinc ion batteries are easy to cause local high temperature in the quick charge/discharge process, if the batteries are still in quick operation, the high temperature promotes the water and the electrode to generate side reaction from electrolysis in the long-term circulation process, so that the permanent reduction rate of the performance of the batteries is accelerated, and the service life is greatly shortened. Therefore, the development of the self-protection gel electrolyte which can adapt to the change of the charging and discharging temperature of the zinc ion battery has important significance for prolonging the service life of the zinc ions.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a self-protection gel electrolyte applied to a zinc ion battery and a preparation method thereof, and solves the problems that the hydrogel electrolyte of the zinc ion battery promotes side reactions of water and electrodes from electrolysis at high temperature, and the service life is greatly shortened.
(II) technical scheme
In order to solve the problems, the invention provides a self-protection gel electrolyte applied to a zinc ion battery, which is prepared by modifying bamboo fibers by siloxane, promoting the modified bamboo fibers to be crosslinked with N-isopropyl acrylamide by using a photoinitiator to obtain porous gel, soaking the porous gel into deionized water at 25-30 ℃ to wash and remove residual monomers and polymers, drying the porous gel in a drying oven at 30 ℃ to obtain dehydrated porous gel, and soaking the dehydrated porous gel into a mixed emulsion of zinc chloride and silicone oil to perform cyclic temperature control expansion to obtain the self-protection gel electrolyte.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of a self-protection gel electrolyte applied to a zinc ion battery comprises the following steps:
s1, placing holocellulose in a potassium hydroxide solution at the temperature of 75-80 ℃ for 2-3h, washing with deionized water, filtering, and drying to obtain bamboo fibers;
s2, preparing a mixture of ethanol and water, adjusting the pH of the mixture to a target pH value with acetic acid, adding methyltriethoxysilane, hydrolyzing for 3 hours to obtain a silane solution, and soaking the bamboo fibers in the silane solution for 3 hours. Then, washing the fiber with distilled water to remove unreacted silane molecules, and finally drying to obtain modified bamboo fiber;
s3, immersing the modified bamboo fibers in a benzophenone solution for 3-5min, thoroughly washing the modified bamboo fibers with ethanol and water, and then adding N-isopropylacrylamide and NaIO 4 Preparing a mixed solution from benzyl alcohol and deionized water, immersing the modified bamboo fiber absorbed with benzophenone into the mixed solution, applying strong ultraviolet irradiation for reaction to obtain porous gel, immersing the porous gel into deionized water at 25-30 ℃ for washing to remove residual monomers and polymers, and drying in an oven at 30 ℃ for 18-24 hours to obtain dehydrated porous gel;
and S4, mixing the zinc chloride solution and the silicone oil, uniformly dispersing by using ultrasonic waves to prepare emulsion, immersing the dehydrated porous gel into the emulsion, ultrasonically dispersing in an ultrasonic dispersion machine, and carrying out circulating temperature control until the porous gel is completely expanded to obtain the self-protection gel electrolyte.
Further, the holocellulose in the step S1 is extracted from the moso bamboos of 3-4 years, and the extraction method comprises the following steps:
(a) Grinding bamboo splints into particles, sequentially sieving with a 30-mesh sieve and a 60-mesh sieve, collecting the particles with the 30-60-mesh sieve, putting the particles into distilled water with the weight 4-6 times of that of the bamboo splints, stirring, standing for 3-5h, suspending parenchyma cells on the surface, sinking fiber cells into the bottom due to large density difference, and collecting the fiber cells at the bottom;
(b) Completely soaking the fiber cell particles in a 2:1 (v/v) benzyl/ethanol mixture to dewax the fiber cell particles for 6 hours at 78-82 ℃, then cooling the fiber cell particles to dewax the fiber cell particles for 1 hour at 72-75 ℃, repeating the dewaxing step for 5 times, washing the particles with deionized water until the water becomes neutral, filtering the particles, and drying the particles in an oven at 40 ℃ for 6-8 hours to obtain holocellulose.
Further, the concentration of the potassium hydroxide solution in the step S1 is 2-3wt%, the mass ratio of the holocellulose to the potassium hydroxide solution is 15-20:100-150, and the drying condition is drying in an oven at 40 ℃ for 6-8h.
Further, the volume ratio of ethanol to water in the mixture in the step S2 is 4:1, the target pH is 4-5, and the mixture is stored in a drying cabinet driven by a constant temperature blower at 80 ℃ for 12h under the drying condition.
Further, the mass ratio of the methyltriethoxysilane to the mixture in the step S2 is 3:15-20, the ratio of the weight of the bamboo fiber to the volume of the silane solution is 6-9:100 (g/mL or kg/L), and the drying condition is drying in an oven at 50 ℃ for 6-8h.
Further, the concentration of the benzophenone solution in the step S3 is 20wt%, and the balance is acetone.
Further, the mass percentages of the N-isopropylacrylamide, the NaIO4 and the benzyl alcohol in the mixed solution in the step S3 are respectively 10-12wt%,0.5-0.7wt%,0.6-0.8wt%, and the balance of deionized water, and the mass ratio of the modified bamboo fiber to the mixed solution is 8-10:50-60.
Further, in the step S3, the ultraviolet light parameter is 200-220W,365nm, and the irradiation time is 15-20min.
Further, the concentration of the zinc chloride solution in the step S4 is 5.5-7.5mol/L, the mass ratio of the zinc chloride solution to the silicone oil is 10:13, and the circulating temperature control condition is that the temperature is raised from 25 ℃ to 40 ℃ at the speed of 1 ℃/5min, and then is lowered to 25 ℃ at the speed of 1 ℃/5min, so as to circulate.
The obtained self-protection gel electrolyte assembly is applied to a zinc ion battery, is suitable for the use condition of temperature change, and has the effects of self-protection and service life prolonging on the zinc ion battery.
Compared with the prior art, the method of the invention has the following beneficial effects:
(1) The invention provides a self-protection gel electrolyte applied to a zinc ion battery and a preparation method thereof.A methyltriethoxysilane is used as a bridge for connecting bamboo fibers and N-isopropylacrylamide, benzophenone is used as a photoinitiator, strong ultraviolet rays are applied to start the methyl on the modified bamboo fibers and the N-isopropylacrylamide to carry out cross linking and polymerization to obtain porous gel, the porous gel is washed clean and dried at low temperature, the dehydrated porous gel is immersed into a mixed emulsion of zinc chloride and silicone oil under ultrasonic dispersion, the fine emulsion droplets are subjected to circulating temperature control at the same time, when the temperature of the porous gel is higher than 32 ℃, the pore walls of the porous gel are hydrophobic, the water-in-oil emulsion droplets are promoted to enter pore channels, and when the temperature of the porous gel is lower than 32 ℃, the pore walls of the porous gel are rendered hydrophilic, the oil-in-water emulsion droplets are promoted to enter the pore channels, so that the porous gel is completely expanded to obtain the self-protection gel electrolyte;
(2) The self-protection gel electrolyte applied to the zinc ion battery is assembled and applied to the zinc ion battery, when local high temperature is caused by heat generated in the rapid charging/discharging process, N-isopropylacrylamide in the self-protection gel electrolyte has a temperature-sensitive induction effect, when the temperature is higher than 32 ℃, the inner surface of a pore channel becomes hydrophobic, so that an emulsion in the pore channel forms a water-in-oil form, the ion transmission is reduced but cannot be cut off, the rapid charging/discharging rate is reduced to achieve the self-protection effect, when the temperature is reduced below 32 ℃, the inner surface of a hollow sleeve becomes hydrophilic, the emulsion in the pore channel is promoted to form an oil-in-water form, a smooth ion transmission channel is kept, the zinc ion battery can efficiently run at low temperature, the high-temperature self-protection is realized, the loss is reduced, and the service life is prolonged;
(3) The self-protection gel electrolyte applied to the zinc ion battery utilizes a small amount of silicone oil and zinc chloride solution emulsion as electrolyte, can achieve the high-temperature self-protection effect by matching with the heat-sensitive induction of the porous gel in the form of oil-in-water and water-in-oil, and can block the aging speed of the electrolyte and further prolong the service life of the battery.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
A preparation method of a self-protection gel electrolyte applied to a zinc ion battery comprises the following specific steps:
extracting holocellulose:
(a) Cutting 3-year-old moso bamboos into strips, weighing 100g of bamboo strips, grinding into particles, sequentially passing through a 30-mesh sieve and a 60-mesh sieve, collecting the particles between the 30-60-mesh sieve, putting the particles into distilled water, wherein the weight of the distilled water is 4 times that of the bamboo strips, stirring, standing for 3 hours, suspending parenchyma cells on the surface, sinking the fiber cells to the bottom due to large density difference, and collecting the fiber cells at the bottom;
(b) Dewaxing the fiber cells by using a 2:1 (v/v) benzyl/ethanol mixture at 78 ℃ for 6 hours by completely immersing the fiber cells in the benzyl/ethanol mixture, then dewaxing at 72 ℃ for 1 hour by cooling, repeating the dewaxing step for 5 times, washing the particles by using deionized water until the water becomes neutral, filtering, and drying in an oven at 40 ℃ for 6 hours to obtain holocellulose;
s1, placing 15g of holocellulose in 100g of potassium hydroxide solution at 75 ℃ for 2h, washing with deionized water, filtering, and drying in an oven at 40 ℃ for 8h to obtain bamboo fibers;
s2, preparing ethanol and water according to the volume ratio of 4:1 to obtain 15g of a mixture, adjusting the pH of the mixture to 5 by using acetic acid, adding 3g of methyltriethoxysilane for hydrolysis for 3 hours to obtain a silane solution, soaking 6g of bamboo fibers into 100ml of the silane solution for 3 hours, then washing the fibers by using distilled water to remove unreacted silane molecules, and finally drying in a 50 ℃ drying oven for 6 hours to obtain modified bamboo fibers;
s3, soaking 8g of modified bamboo fiber into a benzophenone solution mixed by 10g of benzophenone and 40g of acetone for 3min, thoroughly washing the modified bamboo fiber with ethanol and water, and then, adding N-isopropylacrylamide and NaIO 4 Preparing a mixed solution by using benzyl alcohol and deionized water, wherein the mass percentages of N-isopropylacrylamide, naIO4 and benzyl alcohol are respectively 10wt%,0.5wt% and 0.6wt%, and the balance is deionized water, immersing the modified bamboo fiber absorbed with benzophenone into the mixed solution, applying strong ultraviolet light for irradiation reaction, wherein the ultraviolet light parameter is 200W,365nm, the irradiation time is 15min, obtaining porous gel, immersing the porous gel into deionized water at 25 ℃ for washing to remove residual monomers and polymers, and then drying the porous gel in an oven at 30 ℃ for 18h to obtain dehydrated porous gel;
s4, mixing 10g of zinc chloride solution with the concentration of 5.5mol/L and 13g of silicone oil, uniformly performing ultrasonic dispersion to prepare emulsion, immersing the dehydrated porous gel into the emulsion, performing ultrasonic dispersion in an ultrasonic dispersion machine, and performing circulating temperature control under the condition that the temperature is increased from 25 ℃ to 40 ℃ at the speed of 1 ℃/5min, and then the temperature is decreased to 25 ℃ at the speed of 1 ℃/5min, so that the circulation is performed until the porous gel is completely expanded to obtain the self-protection gel electrolyte.
Example 2
A preparation method of a self-protection gel electrolyte applied to a zinc ion battery comprises the following specific steps:
extracting holocellulose:
(a) Cutting moso bamboos growing for 3 years into strips, weighing 100g of bamboo strips, grinding into particles, sequentially passing through a 30-mesh sieve and a 60-mesh sieve, collecting the particles between the 30-60-mesh sieve, putting the particles into distilled water, wherein the weight of the distilled water is 5 times that of the bamboo strips, stirring, standing for 3 hours, suspending parenchyma cells on the surface, sinking the fiber cells into the bottom due to large density difference, and collecting the fiber cells at the bottom;
(b) Completely immersing the fiber cells in a 2:1 (v/v) benzyl/ethanol mixture to dewax the fiber cells for 6 hours at 80 ℃, then cooling to dewax the fiber cells for 1 hour at 74 ℃, repeating the dewaxing step for 5 times, washing the particles with deionized water until the water becomes neutral, filtering, and drying in an oven at 40 ℃ for 6 hours to obtain holocellulose;
s1, placing 16g of holocellulose in 120g of potassium hydroxide solution at 76 ℃ for 2.5h, washing with deionized water, filtering, and drying in an oven at 40 ℃ for 7h to obtain bamboo fibers;
s2, preparing ethanol and water according to the volume ratio of 4:1 to obtain 17g of mixture, adjusting the pH of the mixture to 4.5 by using acetic acid, adding 3g of methyltriethoxysilane for hydrolysis for 3 hours to obtain a silane solution, soaking 7g of bamboo fiber into 100ml of the silane solution for 3 hours, then washing the fiber by using distilled water to remove unreacted silane molecules, and finally drying in a 50 ℃ drying oven for 6 hours to obtain modified bamboo fiber;
s3, soaking 8g of modified bamboo fibers in a benzophenone solution mixed by 10g of benzophenone and 40g of acetone for 4min, thoroughly washing the modified bamboo fibers with ethanol and water, and then, adding N-isopropylacrylamide and NaIO 4 Preparing a mixed solution by using benzyl alcohol and deionized water, wherein the mass percentages of N-isopropylacrylamide, naIO4 and benzyl alcohol are respectively 11wt%,0.6wt% and 0.7wt%, and the balance is deionized water, immersing the modified bamboo fibers absorbing benzophenone into the mixed solution, applying strong ultraviolet light to irradiate for reaction, wherein the ultraviolet light parameters are 210W and 365nm, the irradiation time is 16min, obtaining porous gel, immersing the porous gel into deionized water at the temperature of 28 ℃, washing and removing residual monomers and polymers,then drying in an oven at 30 ℃ for 20h to obtain dehydrated porous gel;
and S4, mixing 10g of zinc chloride solution with the concentration of 6mol/L and 13g of silicone oil, uniformly performing ultrasonic dispersion to prepare emulsion, immersing the dehydrated porous gel into the emulsion, performing ultrasonic dispersion in an ultrasonic dispersion machine, and performing circulating temperature control under the condition that the temperature is raised to 40 ℃ from 25 ℃ at the speed of 1 ℃/5min, and then, the temperature is lowered to 25 ℃ at the speed of 1 ℃/5min, so that circulation is performed until the porous gel is completely expanded to obtain the self-protection gel electrolyte.
Example 3
A preparation method of a self-protection gel electrolyte applied to a zinc ion battery comprises the following specific steps:
extracting holocellulose:
(a) Cutting 4-year-old moso bamboos into strips, weighing 100g of bamboo strips, grinding into particles, sequentially passing through a 30-mesh sieve and a 60-mesh sieve, collecting the particles between the 30-60-mesh sieve, putting the particles into distilled water, wherein the weight of the distilled water is 6 times that of the bamboo strips, standing for 4 hours after stirring, suspending parenchyma cells on the surface, sinking the fiber cells into the bottom due to large density difference, and collecting the fiber cells at the bottom;
(b) Completely immersing the fiber cells into a benzyl/ethanol mixture of 2:1 (v/v) to dewax for 6 hours at 79 ℃, then cooling to dewax for 1 hour at 73 ℃, repeating the dewaxing step for 5 times, washing particles with deionized water until the water becomes neutral, filtering, and drying in an oven at 40 ℃ for 8 hours to obtain holocellulose;
s1, placing 15g of holocellulose in 140g of potassium hydroxide solution at 78 ℃ for 3h, washing with deionized water, filtering, and drying in an oven at 40 ℃ for 7.5h to obtain bamboo fibers;
s2, preparing ethanol and water according to the volume ratio of 4:1 to obtain 18g of mixture, adjusting the pH of the mixture to 4 by using acetic acid, adding 3g of methyltriethoxysilane for hydrolysis for 3 hours to obtain a silane solution, soaking 8g of bamboo fiber into 100ml of the silane solution for 3 hours, then washing the fiber by using distilled water to remove unreacted silane molecules, and finally drying in a 50 ℃ drying oven for 6.5 hours to obtain modified bamboo fiber;
s3, soaking 9g of modified bamboo fiber into a benzophenone solution mixed by 11g of benzophenone and 44g of acetone for 5min, thoroughly washing the modified bamboo fiber with ethanol and water, and then, adding N-isopropylacrylamide and NaIO 4 Preparing a mixed solution by using benzyl alcohol and deionized water, wherein the mass percentages of N-isopropylacrylamide, naIO4 and benzyl alcohol are respectively 12wt%,0.7wt% and 0.7wt%, and the balance is deionized water, immersing the modified bamboo fiber absorbed with benzophenone into the mixed solution, applying strong ultraviolet light for irradiation reaction, wherein the ultraviolet light parameters are 220W and 365nm, the irradiation time is 18min, obtaining porous gel, immersing the porous gel into deionized water at 26 ℃ for washing to remove residual monomers and polymers, and then drying the porous gel in an oven at 30 ℃ for 22h to obtain dehydrated porous gel;
and S4, mixing 10g of zinc chloride solution with the concentration of 6mol/L and 13g of silicone oil, uniformly performing ultrasonic dispersion to prepare emulsion, immersing the dehydrated porous gel into the emulsion, performing ultrasonic dispersion in an ultrasonic dispersion machine, and performing circulating temperature control under the condition that the temperature is raised to 40 ℃ from 25 ℃ at the speed of 1 ℃/5min, and then, the temperature is lowered to 25 ℃ at the speed of 1 ℃/5min, so that circulation is performed until the porous gel is completely expanded to obtain the self-protection gel electrolyte.
Example 4
A preparation method of a self-protection gel electrolyte applied to a zinc ion battery comprises the following specific steps:
extracting holocellulose:
(a) Cutting 4-year-old moso bamboos into strips, weighing 100g of bamboo strips, grinding into particles, sequentially passing through a 30-mesh sieve and a 60-mesh sieve, collecting the particles between the 30-60-mesh sieve, putting the particles into distilled water, wherein the weight of the distilled water is 6 times that of the bamboo strips, stirring, standing for 5 hours, suspending parenchyma cells on the surface, sinking the fiber cells into the bottom due to large density difference, and collecting the fiber cells at the bottom;
(b) Completely immersing the fiber cells in a 2:1 (v/v) benzyl/ethanol mixture to dewax the fiber cells for 6 hours at 82 ℃, then cooling to dewax the fiber cells for 1 hour at 75 ℃, repeating the dewaxing step for 5 times, washing the particles with deionized water until the water becomes neutral, filtering, and drying in an oven at 40 ℃ for 8 hours to obtain holocellulose;
s1, placing 15g of holocellulose in 150g of potassium hydroxide solution at 80 ℃ for 3h, washing with deionized water, filtering, and drying in an oven at 40 ℃ for 8h to obtain bamboo fibers;
s2, preparing ethanol and water according to the volume ratio of 4:1 to obtain 20g of mixture, adjusting the pH of the mixture to 5 by using acetic acid, adding 3g of methyltriethoxysilane for hydrolysis for 3 hours to obtain a silane solution, soaking 9g of bamboo fiber into 100ml of silane solution for 3 hours, then washing the fiber by using distilled water to remove unreacted silane molecules, and finally drying in a 50 ℃ drying oven for 8 hours to obtain the modified bamboo fiber;
s3, immersing 10g of modified bamboo fibers in a benzophenone solution mixed by 12g of benzophenone and 48g of acetone for 4min, thoroughly washing the modified bamboo fibers with ethanol and water, and then, adding N-isopropylacrylamide and NaIO 4 Preparing a mixed solution by using benzyl alcohol and deionized water, wherein the mass percentages of N-isopropylacrylamide, naIO4 and benzyl alcohol are respectively 12wt%,0.6wt% and 0.8wt%, and the balance is deionized water, immersing the modified bamboo fibers absorbing benzophenone into the mixed solution, applying strong ultraviolet light for irradiation to perform reaction, wherein the ultraviolet light parameter is 220W and 365nm, the irradiation time is 20min, obtaining porous gel, immersing the porous gel into deionized water at the temperature of 30 ℃ for washing to remove residual monomers and polymers, and drying the porous gel in an oven at the temperature of 30 ℃ for 24h to obtain dehydrated porous gel;
s4, mixing 10g of zinc chloride solution with the concentration of 7.5mol/L and 13g of silicone oil, uniformly performing ultrasonic dispersion to prepare emulsion, immersing the dehydrated porous gel into the emulsion, performing ultrasonic dispersion in an ultrasonic dispersion machine, and performing circulating temperature control under the condition that the temperature is increased from 25 ℃ to 40 ℃ at the speed of 1 ℃/5min, and then the temperature is decreased to 25 ℃ at the speed of 1 ℃/5min, so that the circulation is performed until the porous gel is completely expanded to obtain the self-protection gel electrolyte.
Comparative example 1
A preparation method of a gel electrolyte applied to a zinc ion battery comprises the following specific steps:
extracting holocellulose:
(a) Cutting moso bamboos growing for 3 years into strips, weighing 100g of bamboo strips, grinding into particles, sequentially passing through a 30-mesh sieve and a 60-mesh sieve, collecting the particles between the 30-60-mesh sieve, putting the particles into distilled water, wherein the weight of the distilled water is 4 times that of the bamboo strips, stirring, standing for 3 hours, suspending parenchyma cells on the surface, sinking the fiber cells into the bottom due to large density difference, and collecting the fiber cells at the bottom;
(b) Dewaxing fiber cells by using a 2:1 (v/v) benzyl/ethanol mixture at 78 ℃ for 6 hours by completely immersing the fiber cells in the benzyl/ethanol mixture, then dewaxing at 72 ℃ for 1 hour by cooling, repeating the dewaxing step for 5 times, washing particles by using deionized water until the water becomes neutral, filtering, and drying in an oven at 40 ℃ for 7 hours to obtain holocellulose;
s1, placing 15g of holocellulose in 100g of potassium hydroxide solution at 76 ℃ for 3h, washing with deionized water, filtering, and drying in an oven at 40 ℃ for 7h to obtain bamboo fibers;
s2, preparing ethanol and water according to the volume ratio of 4:1 to obtain 15g of a mixture, adjusting the pH of the mixture to 4 by using acetic acid, adding 3g of methyltriethoxysilane for hydrolysis for 3 hours to obtain a silane solution, soaking 6g of bamboo fibers into 100ml of the silane solution for 3 hours, then washing the fibers by using distilled water to remove unreacted silane molecules, and finally drying in a 50 ℃ drying oven for 6-8 hours to obtain modified bamboo fibers;
s3, soaking 8g of modified bamboo fiber into 20g of silicate sol, uniformly mixing by ultrasonic waves, and drying in an oven at the temperature of 30 ℃ for 18h to obtain dehydrated gel;
and S4, mixing 10g of zinc chloride solution with the concentration of 6.5mol/L and 13g of silicone oil, then carrying out ultrasonic dispersion on the mixture uniformly to prepare emulsion, immersing the dehydrated porous gel into the emulsion, and carrying out ultrasonic dispersion on the emulsion uniformly in an ultrasonic dispersion machine to obtain the gel electrolyte.
The gel electrolyte assemblies obtained in examples 1 to 4 and comparative example 1 were applied to zinc ion batteries (manganese dioxide as a positive electrode and zinc foil as a negative electrode) and tested for performance at 20 ℃, 30 ℃, 35 ℃, 40 ℃ and 42 ℃ at a current density of 0.2Ag -1 The initial specific capacity is measured, the ionic conductivity of the gel electrolyte is tested through an electrochemical alternating current impedance test, and the results are shown in the following tables 1 and 2:
table 1:
table 2:
as can be seen from tables 1 and 2, in the embodiment, methyltriethoxysilane is used as a bridge for connecting bamboo fibers and N-isopropylacrylamide, due to the temperature sensing effect, when the temperature is higher than 32 ℃, the inner surface of the pore becomes hydrophobic, so that the emulsion in the pore forms a water-in-oil form, ion transmission is reduced but not cut off, the rapid charge/discharge rate is reduced to achieve the self-protection effect, when the temperature is reduced below 32 ℃, the inner surface of the hollow sleeve becomes hydrophilic, the emulsion in the pore forms an oil-in-water form, a smooth ion transmission channel is maintained, the rapid charge/discharge rate is reduced to achieve the self-protection effect, the specific discharge capacity reduction range of the zinc ion battery operated at high temperature is small, and the zinc ion battery can still operate efficiently, while the gel electrolyte of comparative example 1 is influenced by external temperature and internal local high temperature, the specific discharge capacity of the gel electrolyte rapidly decreases with the increase of the cycle number, and examples 1 to 4 can adapt to the use situation of temperature change, thereby achieving the effects of protecting the zinc ion battery and prolonging the service life.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A self-protection gel electrolyte applied to a zinc ion battery is characterized in that bamboo fibers are modified by siloxane, a photoinitiator is used for promoting the modified bamboo fibers to be crosslinked with N-isopropyl acrylamide to obtain porous gel, the porous gel is immersed into deionized water at 25-30 ℃ to wash and remove residual monomers and polymers, then the porous gel is dried in a drying oven at 30 ℃ to obtain dehydrated porous gel, and the dehydrated porous gel is immersed into a mixed emulsion of zinc chloride and silicone oil to carry out circulating temperature control expansion to obtain the self-protection gel electrolyte.
2. A method for preparing the self-protecting gel electrolyte for zinc ion batteries according to claim 1, comprising the following steps:
s1, placing holocellulose in a potassium hydroxide solution at the temperature of 75-80 ℃ for 2-3h, washing with deionized water, filtering, and drying to obtain bamboo fibers;
s2, preparing a mixture of ethanol and water, adjusting the pH of the mixture to a target pH value with acetic acid, adding methyltriethoxysilane, hydrolyzing for 3 hours to obtain a silane solution, and soaking the bamboo fibers in the silane solution for 3 hours; then, washing the fiber with distilled water to remove unreacted silane molecules, and finally drying to obtain the modified bamboo fiber;
s3, immersing the modified bamboo fibers in a benzophenone solution for 3-5min, thoroughly washing the modified bamboo fibers with ethanol and water, and then, adding N-isopropylacrylamide and NaIO 4 Preparing benzyl alcohol and deionized water into mixed solution, and absorbing benzophenone modified bamboo fiberImmersing in the mixed solution, applying strong ultraviolet irradiation for reaction to obtain porous gel, immersing in deionized water at 25-30 ℃ for washing to remove residual monomers and polymers, and then drying in an oven at 30 ℃ for 18-24h to obtain dehydrated porous gel;
and S4, mixing the zinc chloride solution and the silicone oil, uniformly dispersing by using ultrasonic waves to prepare emulsion, immersing the dehydrated porous gel into the emulsion, ultrasonically dispersing in an ultrasonic dispersion machine, and carrying out circulating temperature control until the porous gel is completely expanded to obtain the self-protection gel electrolyte.
3. The method for preparing the self-protective gel electrolyte applied to the zinc ion battery as claimed in claim 2, wherein the holocellulose in the step S1 is extracted from moso bamboos of 3-4 years, and the extraction method comprises the following steps:
(a) Grinding the bamboo strips into particles, sequentially passing through a 30-mesh sieve and a 60-mesh sieve, collecting the particles among the 30-60-mesh sieves, putting the particles into distilled water, wherein the weight of the distilled water is 4-6 times of that of the bamboo strips, stirring, standing for 3-5h, suspending parenchyma cells on the surface, sinking fiber cells into the bottom due to large density difference, and collecting the fiber cells at the bottom;
(b) Fully immersing the fiber cell particles in a benzyl/ethanol mixture of 2 (v/v) and 1 (v/v) to dewax the fiber cells for 6 hours at 78-82 ℃, then cooling the fiber cell particles to dewax the fiber cell particles for 1 hour at 72-75 ℃, repeating the dewaxing step for 5 times, washing the particles by deionized water until the water becomes neutral, and drying the particles in an oven at 40 ℃ for 6-8 hours after filtering to obtain holocellulose.
4. The preparation method of the self-protective gel electrolyte applied to the zinc ion battery, according to claim 2, is characterized in that the concentration of the potassium hydroxide solution in the step S1 is 2-3wt%, the mass ratio of the holocellulose to the potassium hydroxide solution is 15-20.
5. The method for preparing a self-protective gel electrolyte for a zinc ion battery according to claim 2, wherein the volume ratio of ethanol to water in the mixture in the step S2 is 4.
6. The preparation method of the self-protective gel electrolyte applied to the zinc ion battery, according to claim 2, wherein the mass ratio of the methyltriethoxysilane to the mixture in the step S2 is 3 to 20, the ratio of the weight of the bamboo fiber to the volume of the silane solution is 6 to 9 (g/mL or kg/L), and the drying condition is drying in an oven at 50 ℃ for 6 to 8 hours.
7. The method for preparing the self-protecting gel electrolyte applied to the zinc ion battery according to claim 2, wherein the concentration of the benzophenone solution in the step S3 is 20wt%, and the balance is acetone.
8. The method for preparing the self-protecting gel electrolyte applied to the zinc ion battery according to claim 2, wherein the N-isopropylacrylamide and the NaIO in the solution are mixed in the step S3 4 And the benzyl alcohol is 10-12wt%,0.5-0.7wt%,0.6-0.8wt% and the balance is deionized water, wherein the mass ratio of the modified bamboo fiber to the mixed solution is 8-10.
9. The preparation method of the self-protection gel electrolyte applied to the zinc ion battery, according to the claim 2, characterized in that in the step S3, the ultraviolet light parameter is 200-220W,365nm, and the irradiation time is 15-20min.
10. The method for preparing the self-protective gel electrolyte applied to the zinc ion battery according to claim 2, wherein the concentration of the zinc chloride solution in the step S4 is 5.5-7.5mol/L, the mass ratio of the zinc chloride solution to the silicone oil is 10/13, and the circulating temperature control condition is that after the temperature is increased from 25 ℃ to 40 ℃ at the rate of 1 ℃/5min, the temperature is decreased to 25 ℃ at the rate of 1 ℃/5min, so as to circulate the solution.
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| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
| JP2014029818A (en) * | 2011-08-23 | 2014-02-13 | Nippon Shokubai Co Ltd | Gel electrolyte or negative electrode mixture, and battery using the gel electrolyte or the negative electrode mixture |
| CN110336081A (en) * | 2019-06-27 | 2019-10-15 | 武汉工程大学 | Gel electrolyte of zinc ion battery and preparation method and application thereof |
| CN114497721A (en) * | 2022-01-07 | 2022-05-13 | 哈尔滨工业大学 | Composite electrolyte film, preparation method thereof and application thereof in solid-state lithium battery |
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| JP2014029818A (en) * | 2011-08-23 | 2014-02-13 | Nippon Shokubai Co Ltd | Gel electrolyte or negative electrode mixture, and battery using the gel electrolyte or the negative electrode mixture |
| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
| CN110336081A (en) * | 2019-06-27 | 2019-10-15 | 武汉工程大学 | Gel electrolyte of zinc ion battery and preparation method and application thereof |
| CN114497721A (en) * | 2022-01-07 | 2022-05-13 | 哈尔滨工业大学 | Composite electrolyte film, preparation method thereof and application thereof in solid-state lithium battery |
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