CN114335709B - 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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- CN114335709B CN114335709B CN202111529865.3A CN202111529865A CN114335709B CN 114335709 B CN114335709 B CN 114335709B CN 202111529865 A CN202111529865 A CN 202111529865A CN 114335709 B CN114335709 B CN 114335709B
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Abstract
The application provides a preparation method of a polymer-based solid electrolyte membrane and a battery, wherein the preparation method of the polymer-based solid electrolyte membrane comprises the following steps: preparing a precursor solution of the ferroelectric material; providing a template with holes and a substrate connected with the template; filling the precursor solution into the holes of the template and performing heat treatment to prepare ferroelectric nano-pillars formed on the substrate; the ferroelectric nano-pillars are stretched into a polymer electrolyte solution and dried to prepare a polymer-based solid electrolyte membrane. The ferroelectric nano-pillar structure reduces the crystallinity of the polymer matrix, greatly promotes the movement of the polymer chain segment, forms a highly stable and continuous phase interface, improves the contact area of the filler and the polymer matrix, and provides more lithium ion transmission paths. On the other hand, the ferroelectric material has high dielectric constant, which can promote the dissociation of lithium salt and enhance the solvation effect, so as to form more free lithium ions, further improve 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 was found that the solid electrolyte using a single system is difficult to satisfy the requirement of the battery during the daily use.
In the current development of composite solid electrolytes, the addition of inorganic fillers to polymeric matrices is common. However, after the content of the inorganic filler exceeds the percolation threshold, the ion conductivity of the composite electrolyte is greatly reduced (percolation effect), and the ion conductivity is difficult to be obviously improved even if the content is too low, so that the electrochemical performance of the battery is seriously affected.
Therefore, how to solve the above-mentioned problems is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
It is an object of embodiments of the present application to provide a method of manufacturing a polymer-based solid electrolyte membrane and a battery, which can solve at least the above problems.
An embodiment of the present application provides, in a first aspect, a method for preparing a polymer-based solid electrolyte membrane, including: preparing a precursor solution of the ferroelectric material;
providing a template with holes and a substrate connected with the template;
filling the precursor solution into the holes of the template and performing heat treatment to prepare ferroelectric nano-pillars formed on the substrate;
and stretching the ferroelectric nano-column into polymer electrolyte solution 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 template and the substrate in a precursor solution of the ferroelectric material;
and carrying out ultrasonic vibration treatment on the precursor solution so that the precursor solution is filled into the holes of the template.
In some embodiments, after the precursor solution is subjected to ultrasonic oscillation treatment, the method further includes:
and carrying out spin coating treatment on the template covered with the precursor solution and the substrate.
In some embodiments, when the template and the substrate covered with the precursor solution are spin-coated, the spin-coating duration is 30s-45s, and the rotation speed is 3000r/min-4000 r/min.
In some embodiments, the filling the precursor solution into the pores of the template and heat treating comprises:
and 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 ℃ and the duration is 60s to 300s;
the pyrolysis treatment temperature in the heat treatment is 350-400 ℃ and the duration time 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 perforated template and a substrate coupled to the template includes:
coating silver paste on the contact part of the template and the substrate;
and carrying out heating treatment on the template and the substrate after silver paste is smeared.
In some embodiments, when the template and the substrate after silver paste application are subjected to heat treatment, the heating temperature is 120 ℃, and the heating duration is 4-6 min.
In some embodiments, the extending the ferroelectric nanopillars into the polymer electrolyte solution comprises:
the ferroelectric nano-pillars are extended into the polymer electrolyte solution along the direction perpendicular to the liquid level of the polymer electrolyte solution.
A second aspect of embodiments of the present application provides a battery comprising the polymer-based solid electrolyte membrane prepared by any of the methods described above.
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 inorganic filler and dimension design of the filler, fully combines the advantages of the inorganic solid electrolyte and the polymer-based solid electrolyte, and improves the mechanical property and the electrochemical property at the same time;
(2) The ferroelectric nano column designed and prepared by the application is introduced into a polymer matrix as a filler; on one hand, the ferroelectric nano-pillar structure reduces the crystallinity of the polymer matrix, greatly promotes the movement of the polymer chain segment, forms a highly stable and continuous phase interface, improves the contact area of the filler and the polymer matrix, and provides more lithium ion transmission paths. On the other hand, the ferroelectric material has high dielectric constant, which can promote the dissociation of lithium salt and enhance the solvation effect, so as to form more free lithium ions, further improve 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 chart of a method for preparing a polymer-based solid electrolyte membrane according to one embodiment of the present application;
FIG. 2 is a flow chart of the preparation of a precursor solution of lead zirconate titanate provided in an embodiment of the present application;
FIG. 3 is a flow chart of a one-dimensional ferroelectric nanopillar according to one embodiment of the present application;
FIG. 4 is a flow chart of the preparation of a precursor solution of bismuth neodymium titanate provided in an embodiment of the present application;
FIG. 5 is a flow chart of the preparation of a precursor solution of barium titanate according to an embodiment of the present application;
fig. 6 is a graph of a hysteresis loop (i.e., PE) of lead zirconate titanate provided in an embodiment of the present application.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the present application more apparent, the present invention will be further described in detail below with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
In the accompanying drawings, a schematic structural diagram according to an embodiment of the present application is shown. The figures are not drawn to scale, wherein certain details may be omitted for the sake of clarity. The various regions, shapes and relative sizes and positional relationships between them shown in the drawings are merely exemplary, may in practice deviate due to manufacturing tolerances or technical limitations, and one skilled in the art may additionally design regions having different shapes, sizes and relative positions as actually required.
It will be apparent that the embodiments described are some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on the embodiments of the present invention, are intended to be within the scope of the present application.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not collide with each other.
The present application will be described in more detail below with reference to the accompanying drawings. Like elements are denoted by like reference numerals throughout the various figures. For clarity, the various features of the drawings are not drawn to scale.
In an embodiment of the present application, referring to fig. 1, a first aspect of an embodiment of the present application provides a method for preparing a polymer-based solid electrolyte membrane, including: s101, preparing a precursor solution of a ferroelectric material; wherein the ferroelectric material is an 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 performing heat treatment to prepare ferroelectric nano-columns formed on the substrate;
s104, stretching the ferroelectric nano-column into polymer electrolyte solution and drying to prepare the polymer-based solid electrolyte membrane.
In the embodiment of the application, the first aspect and the design aspect of introducing inorganic filler and filler dimension simultaneously optimize the ion conduction performance of the polymer-based solid electrolyte, fully combine the advantages of the inorganic solid electrolyte and the polymer-based solid electrolyte, and simultaneously improve the mechanical property and the electrochemical property; secondly, the ferroelectric nano column prepared by the design of the application is introduced into a polymer matrix as a filler; on one hand, the ferroelectric nano-pillar structure reduces the crystallinity of the polymer matrix, greatly promotes the movement of the polymer chain segment, forms a highly stable and continuous phase interface, improves the contact area of the filler and the polymer matrix, and provides more lithium ion transmission paths. On the other hand, the ferroelectric material has high dielectric constant, which can promote the dissociation of lithium salt and enhance the solvation effect, so as to form more free lithium ions, further improve 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, in step S103, filling the precursor solution into the pores of the template comprises:
s1031, placing the connected template and substrate in a precursor solution of the ferroelectric material;
s1032, carrying out ultrasonic vibration treatment on the precursor solution so as to fill the precursor solution 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, so that the preparation of the high-quality ferroelectric nano-pillars is facilitated.
In some embodiments, in step S1032, after the precursor solution is subjected to ultrasonic oscillation treatment, the method further includes:
s1033, spin coating is carried out 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 column and ensure the product quality of a finished product.
In some embodiments, the spin-coating process is performed on the template and the substrate covered with the precursor solution at a spin speed of 3000r/min to 4000r/min for a spin duration of 30s to 45s. Wherein, 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.
The speed of spin coating is too fast or the time of spin coating is too long, so that the nano-pillars are excessively clung to the hole wall, the hollow nano-tube process formed by the nano-pillars is easy to occur, and the brittleness of the nano-tubes is large and cannot reach the strength required by the application. Too slow spin coating or too short spin coating time can cause the solution to be unable to spread against the pore walls, which can degrade the continuity of the nanopillar after the post-annealing treatment. In the embodiment of the application, after spin coating treatment with the configuration rotating speed of 3000r/min-4000r/min and the duration of 35s-45s, 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, in step S103, filling the precursor solution into the pores of the template and performing a heat treatment, including:
s1034, drying, pyrolysis 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 ℃ and the duration is 60s to 350s;
the pyrolysis treatment temperature in the heat treatment is 350-400 ℃ and the duration time is 300-400 s;
the annealing treatment temperature 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 spin coating in the step S1033 is completed, placing 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℃and the duration was 60s.
In some embodiments, step S1032, step S1033, and step S10341 are repeated multiple times to produce ferroelectric nanopillars. It should be noted that the number of repetitions of steps S1032, S1033 and S10341 may be configured as needed to prepare ferroelectric nanopillars that meet the use requirements.
In some embodiments, step S1032, step S1033, and step S10341 are repeated five times.
In some embodiments, providing a perforated template and a substrate coupled 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.
According to the embodiment of the application, the silver paste is smeared at the contact position of the template and the substrate and is subjected to heating treatment, so that the connection tightness of the template and the substrate can be remarkably improved, the template and the substrate are effectively prevented from being separated in spin coating treatment, and the preparation reliability of the ferroelectric nano-column is ensured.
In some embodiments, the silver paste may be uniformly spread at the peripheral edge of the template.
In this embodiment of the application, through evenly scribbling silver thick liquid in the peripheral edge department of template for the peripheral edge and the base plate zonulae occludens of template, guarantees the connection reliability of base plate and template.
In some embodiments, the template and the substrate coated with the silver paste are heated at 120 ℃ for 4-6 min.
In this embodiment of the present application, in heating the silver paste, the time for the silver paste to solidify becomes long when the temperature is too low, and although the heating is performed at too high a temperature, the template may be bent, so that the temperature cannot be too high in order not to damage the template. When the heating temperature is limited to 120 ℃ and 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 nanopillars into the polymer electrolyte solution comprises:
the ferroelectric nano-pillars are extended into the polymer electrolyte solution in a direction perpendicular to the liquid surface of the polymer electrolyte solution.
In the embodiment of the application, the ferroelectric nano-column extends into the polymer electrolyte along the direction perpendicular to the liquid level of the polymer electrolyte, so that the product yield of the prepared ferroelectric nano-column can be effectively ensured.
In some embodiments, as 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: zr: ti=52:48.
Further, in the examples herein, zr is prepared: the Ti ratio is 52:48 as a precursor solution for preparing ferroelectric nanopillars. When Zr: the arrangement ratio of Ti is 52:48, lead zirconate titanate is positioned at the junction of the ferroelectric tetragonal phase and the ferroelectric triphasic phase, and the electrochemical property and the mechanical property of the lead zirconate titanate prepared based on the proportion are optimized.
In some embodiments, lead element in the precursor solution of lead zirconate titanate is volatilized when subjected to high temperature annealing treatment. In this case, the element molar ratio set in advance is no longer accurate. In this example, when the precursor solution of lead zirconate titanate was prepared, the lead content was 10% excessive. Specifically, the molar ratio of lead, zirconium and titanium in the precursor solution is as follows: pb: zr: ti=1.1:0.52:0.48, and the precursor solution prepared in this molar ratio was lead zirconate titanate sol, so that the concentration of the prepared lead zirconate titanate sol was 0.4mol/L, and the volume was limited to 20ml.
In the embodiment of the application, the lead zirconate titanate sol is prepared by selecting the molar ratio Pb/Zr/Ti=1.1:0.52:0.48, so that the loss of lead volatilization during high-temperature annealing in the drying treatment can be effectively counteracted, and the accuracy of the molar ratio of lead, zirconium and titanium in the lead zirconate titanate sol is ensured.
The formulation process referring specifically to fig. 2, in some embodiments, lead acetate is selected 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 into a beaker, 5ml of glacial acetic acid is added, the beaker is sealed by a preservative film, and the lead acetate 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 methyl ether was added thereto, and then a plug was plugged, and heated in an oil bath at a constant temperature of 60℃and magnetically stirred to dissolve it, to prepare a zirconium source solution.
In some embodiments, tetrabutyl titanate is selected as the titanium source in lead zirconate titanate sol. The preparation method comprises the following steps: 1.333g of tetrabutyl titanate was weighed into a flask (tetrabutyl titanate was easily absorbed in water, the weighing process was faster), 6ml of ethylene glycol methyl ether was added as a solvent, a few drops of acetylacetone was added as a stabilizer, and the mixture was sealed with a rubber stopper coated with silicone grease, and heated in an oil field at a constant temperature of 60℃and magnetically stirred to dissolve the mixture, to prepare a titanium source solution.
In some embodiments, the precursor solution concentration is configured to be between 0.1 and 0.4 mol/L.
In the embodiment of the application, precipitation 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, and the concentration of the precursor solution is configured to be between 0.1 and 0.4mol/L, so that 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 dropwise adding the lead source solution into the titanium source solution under a 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 and the zirconium source solution. After mixing, slowly dripping zirconium source solution under the magnetic stirring state, and then adding a few drops of formamide to adjust the PH value of the solution to be 2-4 and fix the volume. The main function of the formamide is to prevent the membrane from cracking when preparing the ferroelectric film, and finally, magnetically stirring at room temperature for 12 hours, and standing for more than 3 days to obtain 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-pillars, and the other part of the precursor solution is prepared into the ferroelectric film. The ferroelectric thin film is used for the subsequent thin film test to detect whether the precursor solution is successfully formulated, and can be used as a reference for excluding the factor of "the precursor solution is not successfully formulated and the electrolyte membrane is poor in performance" when analyzing the performance of the polymer-based solid electrolyte membrane.
In this application embodiment, the too little PH value of acetic acid can lead to zirconium source solution to produce the sediment immediately when adding plumbous, titanium mixed solution, and the too big PH of acetic acid can lead to the hydrolysis rate too fast, makes holistic each item performance of solution take place very big degree reduction, and adds the back when placing one section, still can precipitate, causes the reduction of solution life. The consumption of acetic acid is required to ensure that the PH of the solution is between 2 and 4, so that the stability of the zirconium source solution when the lead and titanium mixed solution is added can be effectively ensured, and the quality of the prepared ferroelectric nano-column is ensured.
In some embodiments, the substrate is a mica sheet. Specifically, a rectangular smooth and crack-free natural mica sheet with the thickness of 1.35cm is taken as a substrate.
Further, the template is an anodic aluminum oxide template. Specifically, the anodized aluminum template had a thickness of 60 μm, which was circular, and a template diameter of 1.3cm.
In some embodiments, the template includes holes arranged at a pitch, the center-to-center pitch of the holes of the template being 450nm and the diameter of the holes of the template being 350nm.
In some embodiments, the ferroelectric nanopillars are treated with a polymer electrolyte solution and dried to produce a polymer solid electrolyte membrane comprising:
inserting a substrate having ferroelectric nanopillars into a polymer electrolyte solution; the polymer electrolyte solution comprises polyethylene oxide electrolyte glue solution;
drying the substrate covered with the ferroelectric nano-pillars of the polymer electrolyte;
and removing the template to obtain the polymer-based solid electrolyte membrane.
Specifically, referring to fig. 3, the preparation process specifically refers to placing the template above the substrate, uniformly coating the uniformly oscillated silver paste on the connection part of the template and the substrate on the premise of ensuring sufficient effective area, and immediately heating at 120 ℃ for 5min on a heating table after coating is finished, so that the silver paste is solidified. It should be noted that, too short heating time may cause incomplete solidification of the silver paste, too long heating time may cause easy peeling of the silver paste by ultrasonic oscillation, and cause tight adhesion of the template and the substrate. Further, the closely connected template and substrate were placed in a beaker containing the precursor solution of the lead zirconate titanate after the preparation, and the precursor solution was allowed to enter the pores of the anodized aluminum template sufficiently by ultrasonic vibration 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 coating machine for spin coating, wherein the purpose of spin coating is to improve the continuity and the length-diameter ratio of the ferroelectric nano-pillars. Further, the spin-coating speed was 4000rmp and the duration time was 40s. After spin coating was completed, the substrate and the template were placed on a heating table to perform a first drying process at a temperature of 150 ℃ for a duration of 60s.
Still further, the above-mentioned ultrasonic vibration treatment, spin coating treatment and first drying treatment were repeated 5 times. After repeating the step 5 times, placing the substrate and the template subjected to the first drying treatment in a rapid annealing furnace for carrying out second drying treatment, pyrolysis treatment and annealing treatment, wherein the temperature of the second drying treatment is 190 ℃, and the heating time is 20s and is continuously 300s; the pyrolysis treatment temperature is 400 ℃, the heating time is 20s, the duration is 400s, the annealing treatment is connected with the second drying treatment and the pyrolysis treatment process, the annealing treatment temperature is 650 ℃, and the heating time is 25s, and the duration is 600s. Through the treatment, the one-dimensional lead zirconate titanate ferroelectric nano-column which is uniformly filled in the anodic aluminum oxide template is finally obtained.
Specifically, the method comprises the following steps: template removal: and (3) placing the template filled with the one-dimensional lead zirconate titanate nano-pillars and the substrate in a sodium hydroxide solution with the concentration of 1.8mol/L, soaking for 43min to enable the template to be corroded fully, taking out the template after the template is corroded, slowly dripping absolute ethyl alcohol into the template to wash the residual sodium hydroxide solution clean, and simultaneously wiping the residual silver paste with the absolute ethyl alcohol to obtain the one-dimensional lead zirconate titanate nano-pillars connected with the substrate.
In the embodiment of the application, the soaking time is too long, so that the sodium hydroxide can further corrode the prepared nano-pillars, and the nano-pillars are damaged; the etching time is too short to ensure complete removal of the anodized aluminum template, and soaking for 43min generally ensures complete removal of the template, but at the same time, it should be noted that the specific soaking time should be properly prolonged or shortened in combination with specific etching conditions.
Preparing polyethylene oxide electrolyte glue solution: weighing 0.35-0.55 mg of lithium bistrifluoromethane sulfonyl imide (lithium salt), and determining the mass of polyethylene oxide according to the mass of the weighed lithium salt by the molar ratio of lithium bistrifluoromethane sulfonyl imide to polyethylene oxide=1:10; polyethylene oxide: acetonitrile=1:19 by mass ratio to determine the amount of acetonitrile. Further, after the dosage calculation is completed, the lithium salt is weighed and added into a small flask (the lithium salt is easy to absorb water, the weighing process is quick), acetonitrile is added, after the magnetic stirring is carried out for 2 hours to enable the lithium salt to be fully dissolved in the acetonitrile, polyethylene oxide is added, stirring is continued for 12 hours, and standing is carried out for 6 hours, so that the polyethylene oxide electrolyte glue solution is obtained.
Pouring the prepared polymer-based solid electrolyte glue solution (polyethylene oxide-based electrolyte glue solution) into a mold plate, inserting the substrate with the one-dimensional ferroelectric nano-pillars grown into the electrolyte glue solution in the downward direction of the ferroelectric nano-pillars, standing for a period of time to enable the electrolyte glue solution to be fully filled into the gaps of the nano-pillars, placing into a baking oven, vacuumizing and drying at 60 ℃ for 12 hours, taking out and tearing off the substrate after the glue solution is completely dried; dropping the polymer-based solid electrolyte glue again, putting the polymer-based solid electrolyte glue into an oven with the dimension of 60 ℃ again after the polymer-based solid electrolyte glue reaches a certain thickness, vacuumizing and drying for 12 hours to obtain the one-dimensional ferroelectric nano-pillar composite polymer-based solid electrolyte membrane. And finally, tearing the one-dimensional ferroelectric nano-column composite polymer-based solid electrolyte membrane from the mold plate, and placing the solid electrolyte membrane in a glove box to obtain a solid electrolyte, namely a one-dimensional lead zirconate titanate nano-column composite polyethylene oxide composite solid electrolyte membrane finished product.
In another embodiment of the present application, referring to fig. 4, bismuth neodymium titanate is selected as the ferroelectric material. Preparing bismuth neodymium titanate precursor solution: the use amount of bismuth element, neodymium element and titanium element in the solution is determined according to the proportion of Bi to Nd to Ti=3.15 to 0.85 to 3, and the bismuth ions are easy to volatilize under the high temperature condition, so that the added bismuth ions need to be excessive by 10% to compensate the volatilization loss, and the concentration of the bismuth neodymium titanate solution is 0.1mol/L, and the volume is 20ml.
Bismuth nitrate is selected as a bismuth source: 2.488g bismuth nitrate solid is weighed into a beaker, 5ml ethylene glycol methyl ether is added, the beaker is sealed by a preservative film, and the bismuth source solution is prepared by fully dissolving the bismuth nitrate solid through magnetic stirring.
Tetrabutyl titanate is selected as a titanium source: 2.041g of tetrabutyl titanate is weighed into a flask (note that tetrabutyl titanate is easy to absorb water and the weighing process is quick), 6ml of ethylene glycol methyl ether is added as a solvent, a few drops of acetylacetone are added as a stabilizer, the mixture is sealed by a rubber plug coated with silicone grease, and the mixture is heated in an oil field with constant temperature of 60 ℃ and is magnetically stirred to be dissolved. And preparing a titanium source solution.
Neodymium nitrate is selected as a neodymium source: weighing 0.561g of neodymium nitrate solid and a beaker, adding 7ml of ethylene glycol methyl ether, sealing with a preservative film, and magnetically stirring to fully dissolve the neodymium nitrate solid and the beaker to prepare a neodymium source solution.
After all three solutions are fully dissolved, adding a bismuth source solution into a neodymium source solution under a magnetic stirring state, magnetically stirring for 20 minutes to fully mix the bismuth source solution, dripping a 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.
The procedure for preparing bismuth neodymium titanate nanopillars in example 2 was completely identical to that of preparing lead zirconate titanate nanopillars in example 1, except that the spin-coating rotation speed for preparing bismuth neodymium titanate nanopillars was 3000rmp and the duration time was 30s. Wherein, when the material is placed in a rapid annealing furnace and subjected to second drying treatment, pyrolysis treatment and annealing treatment, the temperature of the second drying treatment is 180 ℃, the heating time is 20s, and the time lasts for 350s; the pyrolysis treatment temperature is 400 ℃, the heating time is 20s, and the duration is 300s; the annealing treatment is connected with the final drying treatment and the pyrolysis treatment and is carried out under the oxygen atmosphere, the annealing temperature is 700 ℃, and the heating time is 30s and lasts 500s.
In another embodiment of the present application, referring to fig. 5, barium titanate is selected as the ferroelectric material. Preparation of 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 dosages of the barium acetate, the tetrabutyl titanate and the acetylacetone are as follows according to the mass ratio: barium acetate: tetrabutyl titanate: acetylacetone=1:1:1. The concentration of the prepared barium titanate solution is 0.5mol/L and the volume is 20ml.
Barium acetate is selected as a barium source: firstly, calculating the mass of the needed acetic acid according to the volume of the solution to be prepared, adding the solution into a flask by using a disposable dropper, putting the flask into a heat-collecting constant-temperature heating magnetic stirrer, heating and stirring for 10min at 70 ℃, and enabling the temperature of the acetic acid to reach the needed 70 ℃. 2.55g of barium acetate is weighed and added into hot acetic acid in stirring, and the mixture is fully stirred for 30min under the water bath heating at 70 ℃ to completely dissolve the barium acetate, so as 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 water bath heating of 70 ℃ so that the acetylacetone and the barium source solution are fully and uniformly mixed. 3.4036g of tetrabutyl titanate is weighed and added into a flask with fully mixed acetylacetone and barium source solution, and the mixture is fully stirred for 30min under the water bath heating of 70 ℃ to fully and uniformly mix the solution, and the ratio of the substances of barium acetate to water is 1:15 adding deionized water, fully stirring for 60min under the water bath heating at 70 ℃, finally stirring for 12 hours on a magnetic stirrer at normal temperature, taking down the seal, standing for 3 days, and fully chelating the solution to obtain 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 rotation speed for preparing the barium titanate nano-column is 4000rmp and the duration time is 45s. When the material is placed in a rapid annealing furnace to carry out second drying treatment, pyrolysis treatment and annealing treatment, the temperature of the second drying treatment is 150 ℃, and the heating time is 20s and lasts 300s; the pyrolysis treatment temperature is 350 ℃, the heating time is 20s, and the duration is 300s; and connecting the annealing treatment with the final drying treatment and the pyrolysis treatment, wherein the annealing treatment temperature is 600 ℃, and the heating time is 30s and lasts 500s.
Referring to fig. 6, the hysteresis loop (P-v line) of the lead zirconate titanate ferroelectric material of the present application is a typical curve for characterizing the ferroelectric performance of lead zirconate titanate, and it can be seen that lead zirconate titanate has a higher remnant polarization (Pr), a lower coercive electric field (Ec), and excellent ferroelectric performance and a higher dielectric constant. The ferroelectric properties were measured while also directly demonstrating the successful preparation of lead zirconate titanate precursor solutions.
The embodiment of the application also provides a preparation method of the lithium metal battery electrode positive plate, which comprises the following steps: the metal lithium is used as a negative electrode, and the positive electrode material comprises lithium iron phosphate, conductive carbon black and polyvinylidene fluoride binder. The preparation method comprises the following steps: 300mg of electrode slurry is prepared, wherein the mass ratio of all substances 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 binder are weighed, put into a mortar, ground for 20 minutes, the three raw materials are fully mixed, transferred into a beaker, and a proper amount of N-methylpyrrolidone is added dropwise to adjust the viscosity of the slurry. Further, after magnetic stirring for 8 hours, the electrode slurry is uniformly coated on an 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 mu m, the coated aluminum foil is transferred into an oven, and the aluminum foil is dried for 12 hours at the temperature of 60 ℃ after vacuum pumping, so that 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 of the methods described above. The battery is a one-dimensional lead zirconate titanate nano-pillar composite polyethylene oxide based solid electrolyte lithium metal battery.
In some embodiments, the present application provides a method of assembling a battery, comprising: the assembled 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, and the button battery is assembled by the positive electrode shell, the lithium iron phosphate positive electrode plate, the composite solid electrolyte membrane (one-dimensional lead zirconate titanate nano-pillar composite polyethylene oxide composite solid electrolyte membrane), the metal lithium negative electrode plate and the negative electrode shell in sequence, wherein the pressure is selected to be 60Mpa.
The invention has been described above with reference to the 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 made by those skilled in the art without departing from the scope of the invention, and such alternatives and modifications are intended to fall within the scope of the invention.
Claims (5)
1. A method for preparing a polymer-based solid electrolyte membrane, comprising:
preparing a precursor solution of a ferroelectric material, wherein the ferroelectric material comprises any one of lead zirconate titanate, bismuth neodymium titanate and barium titanate;
providing a template with holes and a substrate connected with the template;
filling the precursor solution into the holes of the template and performing heat treatment to prepare ferroelectric nano-pillars formed on the substrate;
the filling of the precursor solution into the pores of the template specifically comprises: placing the template and the substrate in a precursor solution of the ferroelectric material; performing ultrasonic vibration treatment on the precursor solution to fill the precursor solution into the holes of the template; spin-coating the template and the substrate covered with the precursor solution, wherein the rotating speed is 3000r/min-4000r/min during spin-coating, and the spin-coating duration is 30s-45 s;
the step of filling the precursor solution into the holes of the template and performing heat treatment specifically comprises the following steps: drying, pyrolyzing and annealing the template and the substrate filled with the precursor solution, wherein the drying temperature in the heat treatment is 150-190 ℃ and the duration time is 60-300 s; the pyrolysis treatment temperature in the heat treatment is 350-400 ℃ and the duration time 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;
removing the template;
the removing the template specifically comprises the following steps: placing the template filled with the one-dimensional ferroelectric nano-pillars and the substrate in a sodium hydroxide solution with the concentration of 1.8mol/L for soaking for 43min, fully corroding the template, taking out the template after the template is corroded, slowly dripping absolute ethyl alcohol into the template to wash the residual sodium hydroxide solution clean, and simultaneously wiping the residual silver paste with the absolute ethyl alcohol to obtain the one-dimensional ferroelectric nano-pillars connected with the substrate; extending the ferroelectric nano-pillars into a polymer electrolyte solution and drying the polymer electrolyte solution to prepare the polymer-based solid electrolyte membrane;
the method for extending the ferroelectric nano-column into the polymer electrolyte comprises the following steps: pouring the prepared polymer-based solid electrolyte glue solution into a mold plate, inserting a substrate on which one-dimensional ferroelectric nano columns are grown into the polymer-based solid electrolyte glue solution in a direction of the ferroelectric nano columns downwards, standing for a period of time to enable the polymer-based solid electrolyte glue solution to be fully filled into gaps of the ferroelectric nano columns, placing the gaps into a baking oven, vacuumizing and drying for 12 hours at the temperature of 60 ℃, taking out the substrate after the polymer-based solid electrolyte glue solution is completely dried, and tearing off the substrate; dropping the polymer-based solid electrolyte glue solution again, putting the polymer-based solid electrolyte glue solution into a baking oven with the temperature of 60 ℃ again after reaching a certain thickness, and vacuumizing and baking for 12 hours to obtain the one-dimensional ferroelectric nano-pillar composite polymer-based solid electrolyte membrane; finally, tearing the one-dimensional ferroelectric nano-column composite polymer-based solid electrolyte membrane from the mold plate, and placing the solid electrolyte membrane in a glove box to obtain a solid electrolyte;
wherein the substrate is a mica sheet, and the template is an anodic aluminum oxide template.
2. The method for producing a polymer-based solid electrolyte membrane according to claim 1, wherein the providing a template with holes and a substrate connected to the template comprises:
coating silver paste on the contact part of the template and the substrate;
and carrying out heating treatment on the template and the substrate after silver paste is smeared.
3. The method for producing a polymer-based solid electrolyte membrane according to claim 2, wherein,
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.
4. The method for preparing a polymer-based solid electrolyte membrane according to claim 1, wherein the extending the ferroelectric nanopillars into a polymer electrolyte solution comprises:
the ferroelectric nano-pillars are extended into the polymer electrolyte solution along the direction perpendicular to the liquid level of the polymer electrolyte solution.
5. A battery comprising the polymer-based solid electrolyte membrane produced by the method according to any one of claims 1 to 4.
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