CN114335709A - Preparation method of polymer-based solid electrolyte membrane and battery - Google Patents
Preparation method of polymer-based solid electrolyte membrane and battery Download PDFInfo
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- CN114335709A CN114335709A CN202111529865.3A CN202111529865A CN114335709A CN 114335709 A CN114335709 A CN 114335709A CN 202111529865 A CN202111529865 A CN 202111529865A CN 114335709 A CN114335709 A CN 114335709A
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Abstract
The present application provides a method of manufacturing a polymer-based solid electrolyte membrane, which includes: preparing a precursor solution of a ferroelectric material; providing a stencil with holes and a substrate connected to the stencil; filling the precursor solution into the holes of the template and carrying out heat treatment to prepare the ferroelectric nano-pillars formed on the substrate; and (3) extending the ferroelectric nano column into polymer electrolyte liquid and drying to prepare the polymer-based solid electrolyte membrane. The ferroelectric nano-pillar structure reduces the crystallinity of a polymer matrix, greatly promotes the motion of a polymer chain segment, forms a highly stable and continuous phase interface, improves the contact area of a filler and the polymer matrix, and provides more lithium ion transmission paths. On the other hand, the high dielectric constant of the ferroelectric material also promotes the dissociation of lithium salt and enhances the solvation effect, so as to form more free lithium ions, further increase the number of carriers and further enhance the ion conduction.
Description
Technical Field
The invention relates to the technical field of new energy materials, in particular to a preparation method of a polymer-based solid electrolyte membrane and a battery.
Background
In the research of solid electrolyte, it is found that the solid electrolyte adopting a single system is difficult to meet the requirement of the battery in daily use.
In the current development process of composite solid electrolytes, a mode of adding inorganic fillers into a polymer matrix is generally adopted. However, the ionic conductivity of the composite electrolyte is greatly reduced (percolation effect) after the content of the inorganic filler exceeds the percolation threshold, and the ionic conductivity is difficult to be obviously improved even if the content is too low, so that the electrochemical performance of the battery is seriously influenced.
Therefore, how to solve the above problems is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
It is an object of embodiments of the present application to provide a method of producing a polymer-based solid electrolyte membrane and a battery, which can solve at least the above-described problems.
A first aspect of embodiments of the present application provides a method of producing a polymer-based solid electrolyte membrane, including: preparing a precursor solution of a ferroelectric material;
providing a stencil with holes and a substrate connected to the stencil;
filling the precursor solution into the holes of the template and carrying out heat treatment to prepare the ferroelectric nano-pillars formed on the substrate;
and (3) extending the ferroelectric nano column into polymer electrolyte liquid and drying to prepare the polymer-based solid electrolyte membrane.
In some embodiments, the filling the precursor solution into the pores of the template comprises:
placing the connected template and the substrate in a precursor solution of the ferroelectric material;
and carrying out ultrasonic oscillation treatment on the precursor solution so as to enable the precursor solution to be filled into the holes of the template.
In some embodiments, after the subjecting the precursor solution to the ultrasonic oscillation treatment, the method further includes:
and carrying out spin coating treatment on the template and the substrate covered with the precursor solution.
In some embodiments, the spin coating process is performed on the template and the substrate covered with the precursor solution at a rotation speed of 3000r/min to 4000r/min for a spin coating duration of 30s to 45 s.
In some embodiments, the filling the precursor solution into the pores of the template and performing the heat treatment includes:
and carrying out drying treatment, pyrolysis treatment and annealing treatment on the template and the substrate filled with the precursor solution.
In some embodiments, the temperature of the drying treatment in the heat treatment is 150 ℃ to 190 ℃ for 60s to 300 s;
the temperature of pyrolysis treatment in the heat treatment is 350-400 ℃, and the duration is 300-400 s;
the temperature of the annealing treatment in the heat treatment is 600-700 ℃, and the duration time is 500-600 s.
In some embodiments, the providing a stencil with apertures and a substrate coupled to the stencil includes:
coating silver paste on the contact part of the template and the substrate;
and heating the template and the substrate coated with the silver paste.
In some embodiments, when the template and the substrate after being coated with the silver paste are heated, the heating temperature is 120 ℃, and the heating duration is 4min to 6 min.
In some embodiments, said extending said ferroelectric nanopillar into a polymer electrolyte fluid comprises:
and extending the ferroelectric nano column into the polymer electrolyte liquid along the direction vertical to the liquid level of the polymer electrolyte liquid.
A second aspect of embodiments of the present application provides a battery including the polymer-based solid electrolyte membrane prepared by any one of the above-described methods.
The technical scheme of the application has the following beneficial technical effects:
(1) the method optimizes the ion conduction performance of the polymer-based solid electrolyte membrane from two aspects of introducing the inorganic filler and designing the dimension of the filler, and fully combines the advantages of the inorganic solid electrolyte and the polymer-based solid electrolyte, so that the mechanical property and the electrochemical property are simultaneously improved;
(2) when the ferroelectric nano-column designed and prepared by the application is used as a filler and is introduced into a polymer matrix; on one hand, the ferroelectric nano-pillar structure reduces the crystallinity of a polymer matrix, greatly promotes the motion of a polymer chain segment, forms a highly stable and continuous phase interface, improves the contact area of a filler and the polymer matrix, and provides more lithium ion transmission paths. On the other hand, the high dielectric constant of the ferroelectric material also promotes the dissociation of lithium salt and enhances the solvation effect, so as to form more free lithium ions, further increase the number of carriers and further enhance the ion conduction. This is a new way to increase the ionic conductivity of polymer-based solid-state electrolytes.
Drawings
FIG. 1 is a schematic flow diagram of a method of making a polymer-based solid electrolyte membrane according to one embodiment of the present application;
FIG. 2 is a flow chart illustrating the preparation of a lead zirconate titanate precursor solution according to an embodiment of the present disclosure;
fig. 3 is a flow chart of a process for preparing a one-dimensional ferroelectric nanorod according to an embodiment of the present disclosure;
FIG. 4 is a flow chart of the preparation of a precursor solution of neodymium bismuth titanate according to an embodiment of the present disclosure;
FIG. 5 is a flow chart illustrating the preparation of a precursor solution of barium titanate according to an embodiment of the present disclosure;
fig. 6 is a view of the hysteresis loop (i.e., PE) of lead zirconate titanate according to an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings in conjunction with the detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
The structure schematic diagram according to the embodiment of the application is shown in the attached drawings. The figures are not drawn to scale, wherein certain details may be omitted for clarity. The various regions, shapes, and relative sizes and positional relationships therebetween shown in the drawings are merely exemplary, and deviations may occur in practice due to manufacturing tolerances or technical limitations, and those skilled in the art may additionally design regions having different shapes, sizes, relative positions, as the actual requirements may dictate.
It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In addition, the technical features mentioned in the different embodiments of the present application described below may be combined with each other as long as they do not conflict with each other.
The present application will be described in more detail below with reference to the accompanying drawings. Like elements in the various figures are denoted by like reference numerals. For purposes of clarity, the various features in the drawings are not necessarily drawn to scale.
In an embodiment of the present application, referring to fig. 1, a first aspect of the embodiment of the present application provides a method of manufacturing a polymer-based solid electrolyte membrane, including: s101, preparing a precursor solution of a ferroelectric material; wherein, the ferroelectric material is inorganic filler;
s102, providing a template with holes and a substrate connected with the template;
s103, filling the precursor solution into the holes of the template and carrying out heat treatment to prepare the ferroelectric nano-pillars formed on the substrate;
and S104, extending the ferroelectric nano-column into polymer electrolyte liquid and drying to prepare the polymer-based solid electrolyte membrane.
In the embodiment of the application, firstly, the ion conduction performance of the polymer-based solid electrolyte is optimized from two aspects of introducing the inorganic filler and designing the dimension of the filler, and the advantages of the inorganic solid electrolyte and the advantages of the polymer-based solid electrolyte are fully combined, so that the mechanical property and the electrochemical property are simultaneously improved; secondly, when the ferroelectric nano-column designed and prepared by the application is used as a filler to be introduced into a polymer matrix; on one hand, the ferroelectric nano-pillar structure reduces the crystallinity of a polymer matrix, greatly promotes the motion of a polymer chain segment, forms a highly stable and continuous phase interface, improves the contact area of a filler and the polymer matrix, and provides more lithium ion transmission paths. On the other hand, the high dielectric constant of the ferroelectric material also promotes the dissociation of lithium salt and enhances the solvation effect, so as to form more free lithium ions, further increase the number of carriers and further enhance the ion conduction. This is a new way to increase the ionic conductivity of polymer-based solid-state electrolytes.
In some embodiments, the step S103 of filling the precursor solution into the holes of the template includes:
s1031, placing the connected template and the substrate in a precursor solution of the ferroelectric material;
s1032, performing ultrasonic oscillation treatment on the precursor solution to enable the precursor solution to be filled into the holes of the template.
In the embodiment of the application, the precursor solution fully enters the holes of the template through ultrasonic oscillation, and the preparation of the high-quality ferroelectric nano column is facilitated.
In some embodiments, in step S1032, after the ultrasonic oscillation process is performed on the precursor solution, the method further includes:
and S1033, carrying out spin coating treatment on the template and the substrate covered with the precursor solution.
In the embodiment of the application, the purpose of spin coating is to improve the continuity and the length-diameter ratio of the prepared ferroelectric nano-pillar and ensure the product quality of a finished product.
In some embodiments, the template and the substrate covered with the precursor solution are subjected to spin coating at a rotation speed of 3000r/min to 4000r/min for a spin coating duration of 30s to 45 s. After spin coating treatment, a ferroelectric film is formed, and the purpose of preparing the ferroelectric film is to verify whether the precursor solution is successfully prepared in the later period.
Too fast speed of spin coating or too long time of spin coating can cause the nano-column to be excessively tightly attached to the hole wall, so that the process of forming the hollow nano-tube by the nano-column is easy to occur, and the brittleness of the nano-tube is large, so that the strength required by the application cannot be achieved. Too slow a spin coating speed or too short a spin coating time may prevent the solution from spreading tightly against the pore walls, which may deteriorate the continuity of the nano-pillars after the post annealing treatment. In the embodiment of the application, after the spin coating treatment with the rotating speed of 3000r/min-4000r/min and the duration of 35s-45s is configured, the continuity and the length-diameter ratio of the prepared ferroelectric nano column can be improved, and the product quality of a finished product is ensured.
In some embodiments, the step S103 of filling the precursor solution into the holes of the template and performing the heat treatment includes:
s1034, drying, pyrolyzing and annealing the template and the substrate filled with the precursor solution.
In some embodiments, the temperature of the drying treatment in the heat treatment is 150 ℃ to 190 ℃ for 60s to 350 s;
the temperature of the pyrolysis treatment in the heat treatment is 350-400 ℃, and the duration is 300-400 s;
the temperature of the annealing treatment in the heat treatment is 600-700 ℃, and the duration time is 500-600 s.
Further, the drying process in step S1034 includes: s10341, after the spin coating in the step S1033 is finished, placing the spin-coated products of the substrate and the template on a heating table for first drying; the temperature of the first drying treatment was 150 ℃ for 60 s.
In some embodiments, step S1032, step S1033, and step S10341 are repeated a plurality of times to prepare ferroelectric nanopillars. It should be noted that the repetition times of step S1032, step S1033 and step S10341 can be configured as required to prepare ferroelectric nano-pillars meeting the use requirements.
In some embodiments, step S1032, step S1033, and step S10341 are repeated five times.
In some embodiments, providing a stencil with apertures and a substrate coupled to the stencil includes:
coating silver paste on the contact part of the template and the substrate;
and heating the template and the substrate coated with the silver paste.
In the embodiment of the application, silver paste is smeared and heat treatment is carried out through the contact position of template and base plate, the connection fastening performance of template and base plate can be obviously promoted, the template and the base plate are effectively prevented from being separated in the spin coating treatment, and the preparation reliability of the ferroelectric nano column is ensured.
In some embodiments, silver paste may be uniformly applied at the peripheral edge of the stencil.
In the embodiment of the application, silver paste is evenly smeared at the peripheral edge of the template, so that the peripheral edge of the template is tightly connected with the substrate, and the connection reliability of the substrate and the template is ensured.
In some embodiments, the template and the substrate after being coated with the silver paste are heated at 120 ℃ for 4-6 min.
In the embodiment of the application, in the heating of silver paste, the time that the silver paste solidified becomes very long due to too low temperature, although the silver paste solidified very fast due to the heating at too high temperature, the template has the possibility of bending, and in order not to damage the template, the temperature cannot be too high. The heating temperature is limited to 120 ℃, and when the heating duration is 4-6 min, the silver paste can be effectively solidified, and the template is not deformed.
In some embodiments, extending the ferroelectric nanopillar into the polymer electrolyte fluid comprises:
and extending the ferroelectric nano column into the polymer electrolyte liquid along the direction vertical to the liquid level of the polymer electrolyte liquid.
In the embodiment of the application, the ferroelectric nano column extends into the polymer electrolyte liquid along the direction vertical to the liquid level of the polymer electrolyte liquid, so that the product yield of the prepared ferroelectric nano column can be effectively ensured.
In some embodiments, as shown in fig. 2, the ferroelectric material comprises lead zirconate titanate.
In some embodiments, the content of zirconium and titanium in the precursor solution of the ferroelectric material is as follows: the ratio of Zr to Ti was 52: 48.
Further, in the examples of the present application, Zr: the ratio of Ti is 52:48 of lead zirconate titanate is used as a precursor solution for preparing the ferroelectric nano column. When Zr: the preparation ratio of Ti is 52:48, the lead zirconate titanate is positioned at the boundary of the ferroelectric tetragonal phase and the ferroelectric trigonal phase, and the electrochemical property and the mechanical property of the lead zirconate titanate configured based on the proportion are optimized.
In some embodiments, the lead element in the lead zirconate titanate precursor solution volatilizes when subjected to a high temperature annealing process. In this case, the molar ratio of the elements which has been set in advance is no longer exact. In this example, when the precursor solution of lead zirconate titanate was prepared, the lead content was prepared so as to be 10% excess. Specifically, the molar ratio of lead, zirconium and titanium in the precursor solution is as follows: the precursor solution prepared according to the molar ratio is lead zirconate titanate sol, the concentration of the prepared lead zirconate titanate sol is 0.4mol/L, and the volume of the prepared lead zirconate titanate sol can be limited to 20 ml.
In the embodiment of the application, the molar ratio Pb to Zr to Ti is 1.1 to 0.52 to 0.48, so that the lead zirconate titanate sol is prepared, the loss of lead volatilization during high-temperature annealing of drying treatment can be effectively offset, and the accuracy of the molar ratio of lead to zirconium to titanium in the lead zirconate titanate sol is ensured.
Referring specifically to fig. 2, in some embodiments, lead acetate is used as the lead source in the lead zirconate titanate sol. The preparation method comprises the following steps: 3.338g of lead acetate solid is weighed in a beaker, 5ml of glacial acetic acid is added, the beaker is sealed by a preservative film, and the solid is fully dissolved by magnetic stirring to prepare a lead source solution.
In some embodiments, zirconium nitrate is selected as the zirconium source in the lead zirconate titanate sol. The preparation method comprises the following steps: 1.786g of zirconium nitrate powder was weighed into a flask, 7ml of ethylene glycol monomethyl ether was added thereto, and then a stopper was plugged, and heated in a constant temperature oil bath at 60 ℃ and dissolved by magnetic stirring to prepare a zirconium source solution.
In some embodiments, tetrabutyl titanate is selected as the titanium source in the lead zirconate titanate sol. The preparation method comprises the following steps: weighing 1.333g of tetrabutyl titanate in a flask (tetrabutyl titanate is easy to absorb water, the weighing process is quick), adding 6ml of ethylene glycol monomethyl ether as a solvent, adding a few drops of acetylacetone as a stabilizer, sealing by a silicone grease-coated rubber plug, heating in a constant-temperature oil area at 60 ℃, and dissolving by magnetic stirring to prepare a titanium source solution.
In some embodiments, the concentration of the precursor solution is configured to be between 0.1mol/L and 0.4 mol/L.
In the embodiment of the application, a precipitate is generated when the concentration of the precursor solution is too high, the continuity of the nano-column is reduced when the concentration of the precursor solution is too low, the concentration of the precursor solution is configured to be between 0.1 and 0.4mol/L, and the continuity of the prepared ferroelectric nano-column can be effectively ensured.
Further, after the lead source solution, the zirconium source solution and the titanium source solution are fully dissolved, slowly dripping the lead source solution into the titanium source solution under the magnetic stirring state, sealing by using a rubber plug coated with silicone grease, and stirring for 20min to fully and uniformly mix the lead source solution, the zirconium source solution and the titanium source solution. After mixing, slowly dropwise adding a zirconium source solution under a magnetic stirring state, and then adding a few drops of formamide to adjust the pH value of the solution to be 2-4 and to fix the volume. The formamide has the main function of preventing the film from cracking during the preparation of the ferroelectric film, and finally, the solution is magnetically stirred for 12 hours at room temperature and is kept stand for more than 3 days to obtain the lead zirconate titanate precursor solution.
Further, after the precursor solution of the ferroelectric material is successfully prepared, one part of the precursor solution is used for filling the template to prepare the nano-column, and the other part of the precursor solution can be prepared into the ferroelectric film. The ferroelectric film is used for subsequent film test to detect whether the precursor solution is successfully prepared, and can be used as a reference for eliminating the factor of poor performance of the electrolyte membrane caused by the unsuccessfully prepared precursor solution when the performance of the polymer-based solid electrolyte membrane is analyzed.
In the embodiment of the application, the pH value undersize of acetic acid can lead to zirconium source solution to produce the sediment when adding plumbous, titanium mixed solution at once, and the PH of acetic acid is too big can lead to the rate of hydrolysis too fast, makes holistic each item performance of solution take place very big degree's reduction, and when placing one section after adding, still can appear the sediment, causes the reduction of solution life-span. The use amount of acetic acid is required to ensure that the pH value of the solution is between 2 and 4, so that the stability of the zirconium source solution in the process of adding the lead-titanium mixed solution can be effectively ensured, and the quality of the prepared ferroelectric nanocolumn is ensured.
In some embodiments, the substrate is a mica sheet. Specifically, a rectangular smooth crack-free natural mica sheet of 1.35 × 1.35cm can be used as the substrate.
Further, the template is an anodic aluminum oxide template. Specifically, the anodized aluminum template was 60 μm thick, circular in shape, and 1.3cm in diameter.
In some embodiments, the template comprises spaced apart holes, the holes of the template having a center to center spacing of 450nm and a diameter of 350 nm.
In some embodiments, the ferroelectric nanocolumn is dried with a polymer electrolyte solution to prepare a polymer solid electrolyte membrane, comprising:
inserting the substrate having the ferroelectric nanopillars into a polymer electrolyte solution; the polymer electrolyte liquid comprises polyethylene oxide-based electrolyte liquid;
drying the substrate of the ferroelectric nano column covered with the polymer electrolyte liquid;
and removing the template to obtain the polymer-based solid electrolyte membrane.
Specifically, in the preparation process, referring to fig. 3 specifically, the template is flatly placed above the substrate, the uniformly vibrated silver paste is uniformly coated on the joint of the template and the substrate on the premise of ensuring that the template has a sufficient effective area, and after the coating is finished, the template is immediately heated on a heating table at 120 ℃ for 5min to solidify the silver paste. It should be noted that, too short heating time may result in incomplete solidification of the silver paste, and too long heating time may result in easy peeling of the silver paste during ultrasonic oscillation, resulting in tight adhesion of the template and the substrate. Further, the template and the substrate which are tightly connected are placed in a beaker filled with the prepared lead zirconate titanate precursor solution, and the precursor solution is fully filled into the holes of the anodic alumina template through ultrasonic oscillation for 20 minutes. And taking out the substrate and the template after the oscillation is finished, and wiping off redundant solution on the surfaces of the substrate and the template by using propanol. Further, the template and the substrate are placed on a spin coater for spin coating, wherein the purpose of spin coating is to improve the continuity and the aspect ratio of the ferroelectric nano-pillar. Further, the spin speed was 4000rmp and the duration was 40 s. After the spin coating was completed, the substrate and the template were placed on a heating stage to perform a first drying process at a temperature of 150 ℃ for a duration of 60 seconds.
Further, the ultrasonic oscillation treatment, the spin coating treatment, and the first drying treatment were repeated 5 times. After repeating the step for 5 times, placing the substrate and the template which are subjected to the first drying treatment in a rapid annealing furnace for second drying treatment, pyrolysis treatment and annealing treatment, wherein the temperature of the second drying treatment is 190 ℃, the temperature rise time is 20s, and the duration is 300 s; the temperature of the pyrolysis treatment is 400 ℃, the temperature rise time is 20s, the duration is 400s, the annealing treatment is connected with the second drying treatment and the pyrolysis treatment, the temperature of the annealing treatment is 650 ℃, the temperature rise time is 25s, and the duration is 600 s. Through the treatment, the one-dimensional lead zirconate titanate ferroelectric nano column which is uniformly filled in the anodic alumina template is finally obtained.
Specifically, the method comprises the following steps: removing the template: and (3) placing the template filled with the one-dimensional lead zirconate titanate nano column and the substrate in a 1.8mol/L sodium hydroxide solution for soaking for 43min to fully corrode the template, carefully taking out the template by using a pair of tweezers after the template is corroded, slowly dropwise adding absolute ethyl alcohol to wash the residual sodium hydroxide solution clean, and simultaneously wiping off residual silver paste by using the absolute ethyl alcohol to obtain the one-dimensional lead zirconate titanate nano column connected with the substrate.
In the embodiment of the application, the sodium hydroxide can further corrode the prepared nano-column due to too long soaking time, so that the nano-column is damaged; the short etching time can not ensure the complete removal of the anodized aluminum template, and the soaking for 43min can ensure the complete removal of the template under normal conditions, but it should be noted that the specific soaking time is properly prolonged or shortened in combination with the specific etching conditions.
Preparing a polyethylene oxide-based electrolyte glue solution: weighing 0.35-0.55 mg of lithium bistrifluoromethanesulfonylimide (lithium salt), and determining the mass of polyethylene oxide according to the mass of the weighed lithium salt and the molar ratio of lithium bistrifluoromethanesulfonylimide to polyethylene oxide of 1: 10; the mass ratio of polyethylene oxide to acetonitrile is 1:19, so as to determine the using amount of the acetonitrile. Further, after the amount is calculated, weighing lithium salt, adding the lithium salt into a small flask (the lithium salt is easy to absorb water, and the weighing process is quick), adding acetonitrile, magnetically stirring for 2 hours to fully dissolve the lithium salt in the acetonitrile, adding polyethylene oxide, continuously stirring for 12 hours, and standing for 6 hours to obtain polyethylene oxide-based electrolyte glue solution.
Further, pouring the prepared polymer-based solid electrolyte glue solution (polyethylene oxide-based electrolyte glue solution) into a mold plate, inserting the substrate on which the one-dimensional ferroelectric nano-pillars have grown into the electrolyte glue solution in the downward direction of the ferroelectric nano-pillars, standing for a period of time to fully fill the electrolyte glue solution into gaps of the nano-pillars, putting the substrate into an oven, vacuumizing and drying for 12 hours at the temperature of 60 ℃, taking out the substrate after the glue solution is completely dried, and tearing off the substrate; and dripping polymer-based solid electrolyte glue solution again, putting the solution into a drying oven with the dimension of 60 ℃ again after reaching a certain thickness, vacuumizing and drying for 12h to obtain the one-dimensional ferroelectric nano-column composite polymer-based solid electrolyte membrane. And finally, tearing off the one-dimensional ferroelectric nanorod composite polymer-based solid electrolyte membrane from the die plate, and placing the membrane in a glove box to obtain the solid electrolyte, namely the one-dimensional lead zirconate titanate nanorod composite polyethylene oxide-based composite solid electrolyte membrane finished product.
In another embodiment of the present application, referring to fig. 4, the ferroelectric material is bismuth neodymium titanate. Preparing a bismuth neodymium titanate precursor solution: the dosage of bismuth element, neodymium element and titanium element in the solution is determined according to the proportion Bi: Nd: Ti of 3.15:0.85:3, bismuth ions are easy to volatilize under the high temperature condition, so that the added bismuth ions need to be excessive by 10% to make up for the loss of volatilization, and the concentration of the prepared bismuth titanate neodymium solution is 0.1mol/L, and the volume is 20 ml.
Selecting bismuth nitrate as a bismuth source: weighing 2.488g of bismuth nitrate solid in a beaker, adding 5ml of ethylene glycol monomethyl ether, sealing with a preservative film, and magnetically stirring to fully dissolve the bismuth nitrate solid to prepare bismuth source solution.
Selecting tetrabutyl titanate as a titanium source: weighing 2.041g of tetrabutyl titanate in a flask (note that tetrabutyl titanate is easy to absorb water and the weighing process is fast), adding 6ml of ethylene glycol monomethyl ether as a solvent, adding a few drops of acetylacetone as a stabilizer, sealing with a silicone grease-coated rubber plug, heating in a constant temperature oil field at 60 ℃ and magnetically stirring to dissolve. To prepare a titanium source solution.
Neodymium nitrate was selected as the neodymium source: weighing 0.561g of neodymium nitrate solid and a beaker, adding 7ml of ethylene glycol monomethyl ether, sealing with a preservative film, and stirring by magnetic force to fully dissolve the neodymium nitrate solid to prepare a neodymium source solution.
After the three solutions are completely dissolved, adding the bismuth source solution into the neodymium source solution under the magnetic stirring state, stirring for 20 minutes under magnetic stirring to fully mix the solutions, dripping the titanium source solution into the bismuth and neodymium mixed solution to prepare a titanium, bismuth and neodymium mixed solution, stirring for 24 hours under a sealing state to obtain an orange yellow solution, standing the solution for 3 days, and filtering to obtain a bismuth neodymium titanate precursor solution.
In order to prepare the bismuth neodymium titanate nanorod, the preparation steps of the embodiment 2 are completely the same as the preparation process of the lead zirconate titanate nanorod in the embodiment 1, and the difference is that the spin coating rotating speed for preparing the bismuth neodymium titanate nanorod is 3000rmp, and the duration is 30 s. When the glass is placed in a rapid annealing furnace for second drying treatment, pyrolysis treatment and annealing treatment, the temperature of the second drying treatment is 180 ℃, the temperature rise time is 20s, and the duration is 350 s; the temperature of the pyrolysis treatment is 400 ℃, the temperature rise time is 20s, and the duration is 300 s; and connecting the annealing treatment with the final drying treatment and the pyrolysis treatment, and performing annealing at 700 ℃ for 30s and 500s in an oxygen atmosphere.
In another embodiment of the present application, referring to fig. 5, the ferroelectric material is barium titanate. Preparing a barium titanate precursor solution: respectively selecting barium acetate as a barium source, tetrabutyl titanate as a titanium source, simultaneously selecting acetic acid as a solvent, and acetylacetone as a chelating agent, wherein the dosage of the barium acetate, the tetrabutyl titanate and the acetylacetone is as follows according to the ratio of the dosage of the materials: barium acetate: tetrabutyl titanate: acetylacetone 1:1: 1. The prepared barium titanate solution has the concentration of 0.5mol/L and the volume of 20 ml.
Barium acetate is selected as a barium source: firstly, calculating the mass of the required acetic acid according to the volume of the solution required to be prepared, adding the mass into a flask by using a disposable dropper, putting the flask into a heat collection type constant temperature heating magnetic stirrer, heating and stirring at 70 ℃ for 10min, and enabling the temperature of the acetic acid to reach the required 70 ℃. Weighing 2.55g of barium acetate, adding into hot acetic acid while stirring, and fully stirring for 30min under the condition of heating in a water bath at 70 ℃ to completely dissolve the barium acetate to prepare a barium source solution.
1.0011g of acetylacetone is weighed and added into the barium source solution, and the mixture is fully stirred for 30min under the heating of water bath at 70 ℃, so that the acetylacetone and the barium source solution are fully and uniformly mixed. Weighing 3.4036g of tetrabutyl titanate, adding into a flask in which acetylacetone and barium source solution are fully mixed, fully stirring for 30min under the heating of water bath at 70 ℃ to fully mix the solution uniformly, wherein the mass ratio of barium acetate to water is 1: 15 adding deionized water, heating in 70 deg.C water bath, stirring for 60min, stirring at room temperature for 12 hr, sealing, standing for 3 days to chelate the solution, and collecting the stable yellow transparent barium titanate precursor solution.
In order to prepare the barium titanate nano-column, the preparation steps of the barium titanate nano-column are completely consistent with the preparation process of the lead zirconate titanate nano-column, and the difference is that the spin coating rotating speed for preparing the barium titanate nano-column is 4000rmp, and the duration is 45 s. When the glass is placed in a rapid annealing furnace for second drying treatment, pyrolysis treatment and annealing treatment, the temperature of the second drying treatment is 150 ℃, the temperature rise time is 20s, and the duration is 300 s; the temperature of the pyrolysis treatment is 350 ℃, the temperature rise time is 20s, and the duration is 300 s; and connecting the annealing treatment with the final drying treatment and the pyrolysis treatment, wherein the annealing treatment temperature is 600 ℃, the temperature rise time is 30s, and the duration is 500 s.
Referring to fig. 6, the hysteresis loop (P-v line) of the lead zirconate titanate ferroelectric material of the present application is a general curve for characterizing the ferroelectric performance of lead zirconate titanate, and it can be seen that lead zirconate titanate has higher remanent polarization (Pr) and lower coercive electric field (Ec), indicating that the ferroelectric performance is excellent and has higher dielectric constant. The ferroelectric property of the lead zirconate titanate precursor solution is measured, and the successful preparation of the lead zirconate titanate precursor solution is directly proved.
The embodiment of the application also provides a preparation method of the lithium metal battery electrode positive plate, which comprises the following steps: the lithium metal is used as a negative electrode, and the positive electrode material comprises lithium iron phosphate, conductive carbon black and a polyvinylidene fluoride adhesive. The preparation method comprises the following steps: preparing 300mg of electrode slurry, wherein the mass ratio of each substance in the electrode slurry is as follows: conductive carbon black: polyvinylidene fluoride binder 8: 1: 1. further, 240mg of lithium iron phosphate, 30mg of conductive carbon black and 30mg of polyvinylidene fluoride adhesive are weighed and put into a mortar, and are ground for 20 minutes, so that the three raw materials are fully mixed and then transferred into a beaker, and a proper amount of N-methyl pyrrolidone is dripped, and the viscosity of the slurry is adjusted. Further, after magnetic stirring for 8 hours, the electrode slurry is uniformly coated on the aluminum foil by a scraper (the coating process is as fast as possible, the electrode slurry is easy to absorb water), the thickness is 150 μm, after the coating is finished, the electrode slurry is transferred into a drying oven, and after the drying for 12 hours at 60 ℃ in a vacuumizing manner, the positive plate is prepared.
A second aspect of embodiments of the present application provides a battery comprising a solid-state electrolyte prepared by any one of the methods described above. The battery is a one-dimensional lead zirconate titanate nano-column composite polyethylene oxide solid electrolyte lithium metal battery.
In some embodiments, the present application provides a method of assembling a battery, comprising: the assembly of the battery is carried out in a glove box, the oxygen content and the water content are required to be ensured to be less than 0.01ppm, the button battery is assembled according to the sequence of a positive electrode shell, a lithium iron phosphate positive plate, a composite solid electrolyte membrane (one-dimensional lead zirconate titanate nano-column composite polyethylene oxide composite solid electrolyte membrane), a lithium metal negative plate and a negative electrode shell, and the pressure is selected to be 60 Mpa.
The invention has been described above with reference to embodiments thereof. However, these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The scope of the invention is defined by the appended claims and equivalents thereof. Various alternatives and modifications can be devised by those skilled in the art without departing from the scope of the invention, and these alternatives and modifications are intended to be within the scope of the invention.
Claims (10)
1. A method for producing a polymer-based solid electrolyte membrane, comprising:
preparing a precursor solution of a ferroelectric material;
providing a stencil with holes and a substrate connected to the stencil;
filling the precursor solution into the holes of the template and carrying out heat treatment to prepare the ferroelectric nano-pillars formed on the substrate;
and (3) extending the ferroelectric nano column into polymer electrolyte liquid and drying to prepare the polymer-based solid electrolyte membrane.
2. The method for producing a polymer-based solid electrolyte membrane according to claim 1, wherein the filling of the precursor solution into the pores of the template includes:
placing the connected template and the substrate in a precursor solution of the ferroelectric material;
and carrying out ultrasonic oscillation treatment on the precursor solution so as to enable the precursor solution to be filled into the holes of the template.
3. The method for producing a polymer-based solid electrolyte membrane according to claim 2, further comprising, after subjecting the precursor solution to ultrasonic oscillation treatment:
and carrying out spin coating treatment on the template and the substrate covered with the precursor solution.
4. The method for producing a polymer-based solid electrolyte membrane according to claim 3,
and when the template and the substrate covered with the precursor solution are subjected to spin coating treatment, the rotating speed is 3000r/min-4000r/min, and the spin coating duration is 30s-45 s.
5. The method for producing a polymer-based solid electrolyte membrane according to claim 1, wherein the filling of the precursor solution into the pores of the template and the heat treatment include:
and carrying out drying treatment, pyrolysis treatment and annealing treatment on the template and the substrate filled with the precursor solution.
6. The method for producing a polymer-based solid electrolyte membrane according to claim 5,
the temperature of drying treatment in the heat treatment is 150-190 ℃, and the duration is 60-300 s;
the temperature of pyrolysis treatment in the heat treatment is 350-400 ℃, and the duration is 300-400 s;
the temperature of the annealing treatment in the heat treatment is 600-700 ℃, and the duration time is 500-600 s.
7. The method for producing a polymer-based solid electrolyte membrane according to claim 1, wherein the providing of the perforated template and the substrate attached to the template includes:
coating silver paste on the contact part of the template and the substrate;
and heating the template and the substrate coated with the silver paste.
8. The method for producing a polymer-based solid electrolyte membrane according to claim 5,
and when the template and the substrate coated with the silver paste are subjected to heating treatment, the heating temperature is 120 ℃, and the heating duration is 4-6 min.
9. The method for producing a polymer-based solid electrolyte membrane according to claim 5, wherein the extending the ferroelectric nanocolumn into a polymer electrolyte liquid comprises:
and extending the ferroelectric nano column into the polymer electrolyte liquid along the direction vertical to the liquid level of the polymer electrolyte liquid.
10. A battery comprising the polymer-based solid electrolyte membrane prepared by the method according to any one of claims 1 to 9.
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