CN119627185B - Three-dimensional structure ceramic-polymer composite solid electrolyte and preparation method thereof - Google Patents
Three-dimensional structure ceramic-polymer composite solid electrolyte and preparation method thereofInfo
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- CN119627185B CN119627185B CN202411811426.5A CN202411811426A CN119627185B CN 119627185 B CN119627185 B CN 119627185B CN 202411811426 A CN202411811426 A CN 202411811426A CN 119627185 B CN119627185 B CN 119627185B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a three-dimensional structure ceramic-polymer composite solid electrolyte and a preparation method thereof, belonging to the technical field of solid electrolytes of lithium ion batteries. The solid electrolyte comprises a three-dimensional structural ceramic and a polymer compound, wherein the three-dimensional structural ceramic is an oxide ceramic electrolyte with a three-dimensional structure and is one of LLTO, LLZO and LATP, and the polymer compound comprises a polymer, a lithium salt, nitriles and phenoxy resin in a mass ratio of (30-50): (10-25): (10-20): (1-5). By compounding the three-dimensional structural ceramic with the polymer compound, the ceramic-based or polymer-based solid electrolyte can be regulated and controlled very simply and effectively, the interface contact state of inorganic matters and polymers is obviously improved, the ionic conductivity is high, the toughness of the material can be obviously improved by the phenoxy resin, and the mechanical stability is high.
Description
Technical Field
The invention belongs to the technical field of solid electrolytes of lithium ion batteries, and particularly relates to a three-dimensional structure ceramic-polymer composite solid electrolyte and a preparation method thereof.
Background
With the arrival of human energy crisis and the improvement of environmental protection consciousness, new energy automobiles are paid unprecedented importance, but the danger of fire explosion is easy to occur in the existing liquid lithium ion battery due to the adoption of liquid organic electrolyte, so that the safety is not thoroughly solved, and meanwhile, the problem of the endurance mileage of the new energy automobiles is not solved because the energy density of the existing liquid lithium ion battery reaches the upper limit. The solid-state battery has no liquid electrolyte, so that the safety is obviously improved, the energy density is greatly improved, and the solid-state battery is the main stream direction of the development of the secondary lithium ion battery in the future.
The existing solid electrolyte is mainly divided into polymer solid electrolyte and inorganic solid electrolyte. The polymer solid electrolyte has the advantages of good flexibility, low cost and easy large-scale processing and forming, but the application of the polymer solid electrolyte is limited by very low ionic conductivity at room temperature. The inorganic solid electrolyte includes an oxide solid electrolyte, a sulfide solid electrolyte, and a halide electrolyte. Wherein the oxide solid electrolyte has high chemical stability, high electrochemical stability, good mechanical strength and high electrochemical oxidation potential. However, the contact between the inorganic solid electrolyte and the pole piece is solid-solid contact, especially the oxide has very high rigidity, the contact state with the anode and the cathode is very poor, the surface contact is easy to be changed into point contact in the charge and discharge process, and the charge and discharge performance of the battery is seriously affected. Meanwhile, due to the rigid structure of the oxide, the electrolyte membrane cannot be prepared on a large scale, and the electrolyte membrane can be applied only by compounding. Therefore, there is a great deal of attention to compounding a polymer solid electrolyte with an inorganic solid electrolyte. The composite of the two can solve the problem of low ionic conductivity of the polymer solid electrolyte and the problem of insufficient structural toughness of the inorganic solid electrolyte, and remarkably improve the interface contact problem.
Disclosure of Invention
The invention aims to provide a three-dimensional structure ceramic-polymer composite solid electrolyte to solve the problem of low ionic conductivity of the solid electrolyte;
the second object of the present invention is to provide a method for preparing a three-dimensional structure ceramic-polymer composite solid electrolyte, so as to solve the problem of interface contact between the polymer solid electrolyte and the inorganic solid electrolyte.
The aim of the invention can be achieved by the following technical scheme:
In a first aspect, a three-dimensional structural ceramic-polymer composite solid electrolyte includes a three-dimensional structural ceramic and a polymer composite;
The three-dimensional structure ceramic is an oxide type ceramic electrolyte with a three-dimensional structure, and the ceramic electrolyte is one of LLTO (lithium lanthanum titanium oxide) ceramic, LLZO (lithium lanthanum zirconium oxide) ceramic and LATP (lithium aluminum titanium phosphate) ceramic;
the polymer composite comprises a polymer, a lithium salt, nitriles and phenoxy resin.
Further, the polymer comprises one or more of polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, polyvinylidene fluoride co-hexafluoropropylene, polyurethane acrylic ester and polyethylene glycol.
Further, the lithium salt includes one or two of lithium halide (LiX, x=f, cl, br, I), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium perchlorate (LiClO 4), lithium hexafluorophosphate (LiPF 6), lithium tetrafluoroborate (LiBF 4).
Further, the nitrile includes one or two of succinonitrile, adiponitrile and phenylacetonitrile.
In a second aspect, a method for preparing a three-dimensional structure ceramic-polymer composite solid electrolyte includes the steps of:
s1, preparing a glue film from composite slurry of ceramic electrolyte and epoxy resin through a coating process;
S2, embossing the adhesive film to obtain an embossed adhesive film;
s3, sintering the embossed adhesive film to obtain the ceramic with the three-dimensional structure;
And S4, preparing a polymer composite system solution, and blending with the three-dimensional structural ceramic to obtain the three-dimensional structural ceramic-polymer composite solid electrolyte.
Further, the mass ratio of the ceramic electrolyte to the epoxy resin in the step S1 is (5-15) (2.5-30).
Further, the epoxy resin in the S1 is a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, and the mass ratio is (2-20) (0.5-10).
Further, the epoxy value of the bisphenol A epoxy resin is 0.001 to 0.5, and preferably, the epoxy value of the bisphenol A epoxy resin is 0.02 to 0.09.
Further, the coating process in S1 specifically comprises the steps of taking PET with the thickness of 50 μm as a substrate (base film), coating composite slurry of ceramic electrolyte and epoxy resin on the substrate through a slit, drying to obtain a composite adhesive film, and stripping the substrate to obtain the adhesive film.
Further, the thickness of the adhesive film is 10-100 μm, preferably 20-50 μm.
Further, the step S1 further includes:
S1-1, preparing oxygen ceramic electrolyte slurry, namely dissolving ceramic electrolyte in a solvent, and crushing to obtain ceramic electrolyte slurry, wherein the crushing mode comprises but is not limited to high-energy ball milling or sand milling;
S1-2, preparing composite slurry of ceramic electrolyte and epoxy resin, namely uniformly mixing the ceramic electrolyte slurry and the epoxy resin to obtain the composite slurry of the ceramic electrolyte and the epoxy resin.
Further, in the step S2, the embossing template is a metal nickel template with regular-shaped bulges on the surface, and the bulges comprise but are not limited to hexagons, triangles, quadrilaterals or circles.
Further, the height of the protrusions is 10-50 μm, preferably 10-20 μm, and the pitch of the protrusions is 5-20 μm, preferably 5-10 μm.
Further, the embossing temperature in the S2 is 30-100 ℃, preferably 30-60 ℃, and the embossing speed is 1-20cm/min, preferably 1-5cm/min.
Further, in the step S3, the sintering temperature is 500-950 ℃ and the sintering time is 1-10h.
Further, in the step S4, the polymer composite system solution is prepared by dissolving the polymer, the lithium salt, the nitrile and the phenoxy resin in a solvent according to the mass ratio of (30-50): (10-25): (10-20): (1-5) and uniformly mixing to obtain the polymer composite system solution.
Compared with the prior art, the invention has the beneficial effects that:
1. The invention provides a three-dimensional structure ceramic-polymer composite solid electrolyte and a preparation method thereof, wherein the three-dimensional structure ceramic and polymer composite is compounded, so that the ceramic-based or polymer-based solid electrolyte can be simply and effectively regulated and controlled, the interface contact state of inorganic matters and polymers is remarkably improved, the ionic conductivity is high, the toughness of the material can be remarkably improved by using phenoxy resin, and the mechanical stability is high.
2. According to the invention, the ceramic electrolyte is ground into micro-nano particles, then mixed with epoxy resin and coated, so that the ceramic electrolyte/epoxy resin adhesive film with controllable thickness can be obtained, the type of bisphenol A epoxy resin in the epoxy resin and the proportion of bisphenol F epoxy resin are regulated, the adhesive film is in a solid structure at room temperature (25-30 ℃), winding and unwinding can be smoothly realized, meanwhile, the epoxy resin can infiltrate inorganic particles very well, and the epoxy resin and the ceramic particles in the dried adhesive film can be fully mutually wrapped.
3. The controllable imprinting of the ceramic electrolyte/epoxy resin adhesive film is realized by an imprinting means, and the surface of the adhesive film can be duplicated to form regular controllable holes according to the pattern of the template. By combining the sintering process, a three-dimensional ceramic electrolyte skeleton with regular holes can be formed, and the abundant three-dimensional skeleton is favorable for filling polymer solution subsequently to form a ceramic/polymer composite electrolyte with tight contact.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a process flow for preparing a three-dimensional structured ceramic-polymer composite solid electrolyte according to the present invention;
FIG. 2 is an impedance spectrum of a three-dimensional structure ceramic-polymer composite solid electrolyte prepared by example 1 according to the present invention;
FIG. 3 is a linear sweep voltammogram of a three-dimensional structured ceramic-polymer composite solid electrolyte prepared from example 1 of the present invention;
fig. 4 is a stress strain graph of a three-dimensional structure ceramic-polymer composite solid electrolyte prepared from example 1 according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the present application, there is no particular requirement for the drying process of the coating process, and any known drying process can be used in the present application without departing from the inventive concept. It may be performed by means of electric heating, infrared heating, blast heating, etc. It is understood that the related process parameters such as the drying temperature, the drying time and the like are not particularly limited, and any technical scheme obtained by adjusting parameters without performing creative labor is within the protection scope of the application on the basis of not departing from the concept of the application.
The schematic process flow of the preparation process of the ceramic-polymer composite solid electrolyte with three-dimensional structure in the following examples is shown in fig. 1.
Example 1
The preparation method of the three-dimensional structure ceramic-polymer composite solid electrolyte comprises the following steps:
S1, preparing a glue film:
S1-1, dissolving 10g of LLTO into 20g of dimethylbenzene in a ball milling mode, and performing ball milling for 5 hours at a rotating speed of 500rpm to obtain LLTO slurry with a D50 of 500 nm;
S1-2, adding 2g of bisphenol A epoxy resin E-06 and 0.5g of bisphenol F epoxy resin 830 into LLTO slurry, and stirring at a high speed for 0.5h at a rotating speed of 1000rpm to obtain composite slurry of ceramic electrolyte and epoxy resin;
s1-3, taking PET with the thickness of 50 mu m as a substrate (base film), coating composite slurry of ceramic electrolyte and epoxy resin on the substrate through a slit at the coating speed of 3m/min, drying at 100 ℃ to obtain a composite adhesive film, and stripping the substrate to obtain the adhesive film with the thickness of 20 mu m;
s2, designing a hexagonal protruding shape on a metal nickel template, wherein the height of the protruding shape of the template is 50 mu m, the distance between the protruding shapes is 5 mu m, imprinting the adhesive film, wherein the imprinting temperature is 30 ℃, the imprinting speed is 20cm/min, and stripping the template to obtain an imprinting adhesive film;
S3, placing the imprinting adhesive film in a muffle furnace for sintering, wherein the sintering temperature is 500 ℃, and the sintering time is 10 hours, so that the three-dimensional structural ceramic is obtained;
S4, weighing polyethylene oxide, liTFSI, succinonitrile and phenyl resin PKHH according to the mass ratio of 50:25:10:1, dissolving the polyethylene oxide, liTFSI and succinonitrile in 30g of dimethylbenzene, dissolving the phenyl resin PKHH in 15g of butanone in advance, uniformly mixing the two to obtain a polymer composite system solution, fully immersing 2g of three-dimensional structural ceramic in the polymer composite system solution, taking out after 5h, sucking the superfluous surface solution by using filter paper, standing for 24h at room temperature, and continuously drying in an oven at 50 ℃ for 24h to obtain the three-dimensional structural ceramic-polymer composite solid electrolyte.
The mass ratio of the three-dimensional structure ceramic to the polymer composite is calculated to be 2:10, and the material is a typical three-dimensional structure ceramic-polymer composite solid electrolyte.
Example 2
The preparation method of the three-dimensional structure ceramic-polymer composite solid electrolyte comprises the following steps:
S1, preparing a glue film:
S1-1, dissolving 15g of LLTO in 25g of dimethylbenzene in a ball milling mode, and performing ball milling for 5 hours at a rotating speed of 1000rpm to obtain LLTO slurry with a D50 of 300 nm;
S1-2, adding 5g of bisphenol A epoxy resin E-06 and 1g of bisphenol F epoxy resin 830 into LLTO slurry, and stirring at a high speed for 0.5h at a rotating speed of 1000rpm to obtain composite slurry of ceramic electrolyte and epoxy resin;
S1-3, taking PET with the thickness of 50 mu m as a substrate (base film), coating composite slurry of ceramic electrolyte and epoxy resin on the substrate through a slit at the coating speed of 1m/min, drying at 80 ℃ to obtain a composite adhesive film, and stripping the substrate to obtain the adhesive film with the thickness of 50 mu m;
S2, designing a hexagonal protruding shape on a metal nickel template, wherein the protruding height of the template is 40 mu m, the protruding distance is 10 mu m, imprinting the adhesive film, wherein the imprinting temperature is 50 ℃, the imprinting speed is 10cm/min, and stripping the template to obtain an imprinting adhesive film;
S3, placing the imprinting adhesive film in a muffle furnace for sintering, wherein the sintering temperature is 950 ℃ and the sintering time is 1h, so as to obtain the three-dimensional structural ceramic;
and S4, weighing polyvinylidene fluoride, liTFSI, succinonitrile and phenyl resin PKHB according to the mass ratio of 30:20:10:5, dissolving the polyvinylidene fluoride, liTFSI and succinonitrile in 25g of dimethylbenzene, dissolving phenyl resin PKHB in 10g of butanone in advance, uniformly mixing the two to obtain a polymer composite object system solution, fully immersing 5g of three-dimensional structural ceramic into the polymer composite object system solution, taking out after 10h, sucking the superfluous surface solution by using filter paper, standing for 24h at room temperature, and continuously drying in an oven at 50 ℃ for 24h to obtain the three-dimensional structural ceramic-polymer composite solid electrolyte.
The mass ratio of the three-dimensional structure ceramic to the polymer composite is calculated to be 7:3, and the material is a typical three-dimensional structure ceramic-polymer composite solid electrolyte.
Example 3
The preparation method of the three-dimensional structure ceramic-polymer composite solid electrolyte comprises the following steps:
S1, preparing a glue film:
s1-1, dissolving 10g of LLTO in 15g of toluene by a sand grinding mode, ball-milling for 15h at a rotating speed of 1500rpm to obtain LLTO slurry with a D50 of 150 nm;
s1-2, adding 20g of bisphenol A epoxy resin E-06 and 10g of bisphenol F epoxy resin 830 into LLTO slurry, and stirring at a high speed for 0.5h at a rotating speed of 1000rpm to obtain composite slurry of ceramic electrolyte and epoxy resin;
S1-3, taking PET with the thickness of 50 mu m as a substrate (base film), coating composite slurry of ceramic electrolyte and epoxy resin on the substrate through a slit at the coating speed of 3m/min, drying at 60 ℃ to obtain a composite adhesive film, and stripping the substrate to obtain the adhesive film with the thickness of 50 mu m;
s2, designing a quadrangle shape of protrusions on the metal nickel template, wherein the heights of the protrusions of the template are 50 mu m, the distances between the protrusions are 15 mu m, imprinting the adhesive film, wherein the imprinting temperature is 80 ℃, the imprinting speed is 10cm/min, and stripping the template to obtain an imprinted adhesive film;
S3, placing the imprinting adhesive film in a muffle furnace for sintering, wherein the sintering temperature is 750 ℃, and the sintering time is 5 hours, so that the three-dimensional structural ceramic is obtained;
And S4, weighing polymethyl methacrylate, lithium perchlorate, succinonitrile and phenyl resin PKHH according to the mass ratio of 50:10:25:5, dissolving the polymethyl methacrylate, the lithium perchlorate and the succinonitrile in 45g of dimethylbenzene, dissolving the phenyl resin PKHH in 25g of butanone in advance, uniformly mixing the two to obtain a polymer composite object system solution, fully immersing 5g of three-dimensional structural ceramic into the polymer composite object system solution, taking out after 5h, sucking the superfluous solution on the surface by using filter paper, standing for 24h at room temperature, and continuously drying in an oven at 50 ℃ for 24h to obtain the three-dimensional structural ceramic-polymer composite solid electrolyte.
The mass ratio of the three-dimensional structure ceramic to the polymer composite is calculated to be 0.5:10, and the material is a typical three-dimensional structure ceramic-polymer composite solid electrolyte.
Example 4
The preparation method of the three-dimensional structure ceramic-polymer composite solid electrolyte comprises the following steps:
S1, preparing a glue film:
S1-1, dissolving 10g of LATP in 30g of dimethylbenzene by a ball milling mode, and ball milling for 5 hours at a rotating speed of 2000rpm to obtain LATP slurry with a D50 of 800 nm;
S1-2, adding 10g of bisphenol A epoxy resin E-06 and 0.5g of bisphenol F epoxy resin 830 into the LATP slurry, and stirring at a high speed for 0.5h at a rotating speed of 1000rpm to obtain composite slurry of ceramic electrolyte and epoxy resin;
s1-3, taking PET with the thickness of 50 mu m as a substrate (base film), coating composite slurry of ceramic electrolyte and epoxy resin on the substrate through a slit at the coating speed of 3m/min, drying at 100 ℃ to obtain a composite adhesive film, and stripping the substrate to obtain the adhesive film with the thickness of 30 mu m;
s2, designing a hexagonal protruding shape on a metal nickel template, wherein the protruding height of the template is 25 mu m, the protruding distance is 5 mu m, imprinting the adhesive film, wherein the imprinting temperature is 100 ℃, the imprinting speed is 20cm/min, and stripping the template to obtain an imprinting adhesive film;
S3, placing the imprinting adhesive film in a muffle furnace for sintering, wherein the sintering temperature is 750 ℃, and the sintering time is 5 hours, so that the three-dimensional structural ceramic is obtained;
And S4, weighing polyvinylidene fluoride co-hexafluoropropylene, lithium hexafluorophosphate, benzyl cyanide and phenyl resin PKHB according to the mass ratio of 30:10:10:3, dissolving the polyvinylidene fluoride co-hexafluoropropylene, lithium hexafluorophosphate and benzyl cyanide in 40g of dimethylbenzene, dissolving phenyl resin PKHB in 25g of butanone in advance, uniformly mixing the two to obtain a polymer composite object system solution, fully immersing 10g of three-dimensional structural ceramic in the polymer composite object system solution, taking out after 1h, sucking the superfluous solution on the surface by using filter paper, standing for 24h at room temperature, and continuously drying in an oven at 50 ℃ for 24h to obtain the three-dimensional structural ceramic-polymer composite solid electrolyte.
The mass of the three-dimensional structure ceramic-polymer composite solid electrolyte obtained after weighing and drying is 12+/-0.01 g, and the mass ratio of the three-dimensional structure ceramic to the polymer composite is calculated to be 10:2, so that the three-dimensional structure ceramic-polymer composite solid electrolyte is typical.
Example 5
The preparation method of the three-dimensional structure ceramic-polymer composite solid electrolyte comprises the following steps:
S1, preparing a glue film:
S1-1, dissolving 5g of LLTO into 20g of dimethylbenzene in a sand milling mode, and ball milling for 5h at a rotating speed of 500rpm to obtain LLTO slurry with a D50 of 500 nm;
S1-2, adding 2g of bisphenol A epoxy resin E-51 and 1g of bisphenol F epoxy resin 830 into LLTO slurry, and stirring at a high speed for 0.5h at a rotating speed of 1000rpm to obtain composite slurry of ceramic electrolyte and epoxy resin;
s1-3, taking PET with the thickness of 50 mu m as a substrate (base film), coating composite slurry of ceramic electrolyte and epoxy resin on the substrate through a slit at the coating speed of 2.5m/min, drying at 40 ℃ to obtain a composite adhesive film, and stripping the substrate to obtain the adhesive film with the thickness of 30 mu m;
S2, designing a hexagonal protruding shape on a metal nickel template, wherein the height of the protruding shape of the template is 30 mu m, the distance between the protruding shapes is 20 mu m, imprinting the adhesive film, wherein the imprinting temperature is 30 ℃, the imprinting speed is 15cm/min, and stripping the template to obtain an imprinting adhesive film;
S3, placing the imprinting adhesive film in a muffle furnace for sintering, wherein the sintering temperature is 650 ℃, and the sintering time is 3 hours, so as to obtain the three-dimensional structural ceramic;
And S4, weighing polyethylene oxide, lithium fluoride, benzyl cyanide and phenyl resin PKHH according to the mass ratio of 45:25:10:5, dissolving the polyethylene oxide, the lithium fluoride and the benzyl cyanide in 25g of tetrahydrofuran, dissolving the phenyl resin PKHH in 25g of butanone in advance, uniformly mixing the two to obtain a polymer composite object system solution, fully immersing 1g of three-dimensional structural ceramic into the polymer composite object system solution, taking out the polymer composite object system solution after 15h, sucking the superfluous solution on the surface by using filter paper, standing the solution at room temperature for 24h, and continuously drying the solution in an oven at 50 ℃ for 24h to obtain the three-dimensional structural ceramic-polymer composite solid electrolyte.
The mass ratio of the three-dimensional structure ceramic to the polymer composite is calculated to be 1:10, and the material is a typical three-dimensional structure ceramic-polymer composite solid electrolyte.
Comparative example 1
The comparative example is different from example 1 in that the adhesive film obtained in S1-3 is directly sintered without the S2 imprinting process, and the rest steps and parameters remain consistent.
Comparative example 2
This comparative example differs from example 1 in that the polymer composite system in S4 was not added with the phenyl resin PKHH, and the remaining steps and parameters remained identical.
Performance tests were performed on the solid electrolytes prepared in examples 1 to 5 and comparative examples 1 to 2:
And (I) testing ion conductivity, namely testing alternating current impedance spectrum of a sample by adopting a Autolab PGSTAR N electrochemical workstation, and calculating corresponding particle conductivity according to a formula. In a glove box, the electrolyte impedance R is indirectly obtained according to the stainless steel/composite solid electrolyte/stainless steel assembled blocking electrode, and the ion conductivity at 25 ℃ is tested, the frequency range is 0.1-1MHz, and the voltage is 10mV. The ionic conductivity of the electrolyte film can be calculated by the formula σ=l/(s×r), where L is the thickness of the electrolyte film in cm, S is the effective contact area of the electrolyte film with the stainless steel sheet in cm 2, and R is the impedance of the electrolyte film in Ω.
And (II) electrochemical stability window the electrochemical stability window of the sample was tested using Autolab PGSTAR N electrochemical workstation. In a glove box, assembling a button cell according to the sequence of a negative electrode shell, a stainless steel sheet, a lithium sheet, a composite solid electrolyte, the stainless steel sheet, a metal elastic sheet and a positive electrode shell, recording a linear scanning voltammogram of an electrolyte film in a 2.5-5V interval, wherein the scanning speed is 1mV/s, and the testing temperature is 25 ℃.
And (III) mechanical property test, namely testing the mechanical property of the electrolyte film by adopting a CMT4104 type electronic universal measuring instrument. The testing method comprises the steps of cutting the polymer film into long strips, fixing the long strips between clamps of a tensile machine, and stretching at a speed of 5mm/min.
The results of the performance test are shown in Table 1.
TABLE 1
Wherein the impedance spectrum of the three-dimensional structure ceramic-polymer composite solid electrolyte prepared in the example 1 is shown in fig. 2, the linear sweep voltammetry curve is shown in fig. 3, and the stress strain curve is shown in fig. 4.
From the above test results, it can be seen that the ionic conductivity, electrochemical window, and mechanical strength-based elongation at break of the composite polymer electrolyte can be further improved by using the imprinting process in comparative example 1 and comparative example 1. Comparative examples 1 and 2 illustrate that the addition of phenoxy resin can improve the mechanical strength and elongation at break of the material. Example 2-example 5 demonstrate that the electrochemical and mechanical properties of the composite solid electrolyte can be adjusted over a wide range by optimization of experimental conditions.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
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| JP2005255850A (en) * | 2004-03-11 | 2005-09-22 | Jsr Corp | Polymer composition and composite membrane |
| CN111244536A (en) * | 2020-01-15 | 2020-06-05 | 浙江大学 | Three-dimensional framework structure ceramic-polymer composite solid electrolyte and preparation method and application thereof |
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