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CN118136938A - A polymer composite solid electrolyte, preparation method and application thereof - Google Patents

A polymer composite solid electrolyte, preparation method and application thereof Download PDF

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Publication number
CN118136938A
CN118136938A CN202410108804.7A CN202410108804A CN118136938A CN 118136938 A CN118136938 A CN 118136938A CN 202410108804 A CN202410108804 A CN 202410108804A CN 118136938 A CN118136938 A CN 118136938A
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glass fiber
uio
lithium
fiber cloth
acid
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王泽茹
王珂
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Southern University of Science and Technology
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Southern University of Science and Technology
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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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention provides a preparation method and application of a polymer composite solid electrolyte. In the preparation step of the polymer composite electrolyte provided by the invention, the surface of the glass fiber cloth is subjected to activation treatment, and then a Metal Organic Framework (MOF) is loaded on the activated glass fiber cloth in an in-situ nucleation mode. Such crystalline porous materials composed of metal ions or clusters and organic ligands can form dense, high loading MOF films on glass fibers. The solid electrolyte prepared by the method has excellent electrochemical performance and mechanical performance, and can be well applied to lithium metal and lithium ion structure batteries.

Description

Polymer composite solid electrolyte, preparation method and application thereof
Technical Field
The invention relates to the technical field of novel energy storage, in particular to a polymer composite solid electrolyte, a preparation method and application thereof.
Background
In the field of new energy automobiles, one of the development trends of technology is to integrate a composite material providing structural load-bearing capacity with a battery providing energy storage, and develop a structural energy storage device having both structural load-bearing and energy storage functions. One of the challenges in the development of this technology is to develop a composite electrode material and a composite solid electrolyte material that have both excellent electrochemical properties and mechanical properties. For this reason, scientists and engineers are doing a lot of effort. Among them, polymer-based composite solid electrolytes have great potential for development due to the designability of their overall properties. However, at present, as a main component of a high-performance battery, the room temperature ion conductivity and the lithium ion migration number of a polymer matrix composite solid electrolyte also need to be greatly improved. In addition, the polymer material has lower strength and modulus, and the growth of lithium dendrites can be effectively inhibited by greatly improving the method, so that the safety of the lithium battery is improved.
Typically, the polymer electrolyte or filled polymer composite electrolyte, when combined with the fiber reinforced composite material, behaves like a defect due to its lower strength and modulus, compromising the strength and reliability of the overall structure. It is therefore necessary to introduce reinforcing materials into the solid electrolyte. The existing solid electrolyte has the following problems: 1) The polymer solid electrolyte has low ionic conductivity (usually less than 1X10 -5 S/cm) at room temperature, small ionic migration number (usually less than 0.2) and very low tensile strength (usually less than 5 MPa); 2) The inorganic solid electrolyte has poor contact with the interface between electrodes and low fracture toughness. Although the existing additive polymer-based composite electrolyte can remarkably improve ion conductivity, ion migration number and fracture toughness and improve the interface between the electrolyte and an electrode, the electrolyte used as a high-performance lithium battery is still insufficient, and the strength and the modulus of the electrolyte are far lower than those of a common fiber reinforced composite material, so that the requirements of a structural battery cannot be met. Meanwhile, by adding a reinforcing material such as unmodified glass fiber and the like into the solid electrolyte, the strength and the modulus of the electrolyte can be greatly improved, but the electrochemical performance is often degraded, so that the performance of the assembled battery is reduced.
Therefore, how to further improve the electrochemical performance and the strength performance of the solid electrolyte so that the solid electrolyte better meets the performance requirement of the structural battery is a problem to be solved at present.
Disclosure of Invention
To achieve the above object, in a first aspect, the present invention discloses a method for preparing a polymer composite solid electrolyte based on a Metal Organic Framework (MOF) three-dimensional framework, comprising the steps of:
1) Cleaning and presintering the glass fiber cloth, and then carrying out surface activation treatment;
2) Coating the activated glass fiber cloth by a Metal Organic Framework (MOF) to obtain an MOF three-dimensional framework;
3) And compositing the MOF three-dimensional framework with a polymer/lithium salt mixture to obtain the polymer composite solid electrolyte.
The surface activation treatment method of the glass fiber cloth can adopt a surface treatment agent to treat the glass fiber cloth. In one embodiment of the present invention, the surface treatment agent may employ at least one of the group including, but not limited to, a silane coupling agent and dopamine. The silane coupling agent includes, but is not limited to, at least one of isobutyl triethoxysilane, gamma- (methacryloyloxy) propyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane, 3-aminopropyl triethoxysilane, vinyl trimethoxysilane, vinyl tris (beta-methoxyethoxy) silane, or vinyl triethoxysilane.
The surface activation treatment step includes: the surface treating agent was used in an amount of 1: 200-1: 5, dissolving the glass fiber cloth in the deionized water to obtain a surface treating agent solution, immersing the glass fiber cloth in the surface treating agent solution, and taking out and drying. Specifically, the glass fiber cloth is immersed in the surface treating agent solution for 0.01 to 24 hours, taken out, washed clean by deionized water and/or ethanol, and dried at 80 to 120 ℃.
The glass fiber cloth adopted in the preparation method comprises at least one of glass fiber woven cloth, glass fiber non-woven cloth and glass fiber filter membrane. In one embodiment of the invention, the glass fiber cloth has a specification of 10g/m 2～200g/m2 and a thickness of 10um to 100um.
The MOFs described above in the present invention include MOF-5 ((Zn 4O(BDC)3, bdc=1, 4-benzenedicarboxylate )、MIL-53(Al)(AlO4(OH)(BDC))、HKUST-1(Cu3(BTC)2、MIL-101(M3O(BTC)2OH(H2O)2,M＝Al,Cr,or Fe,BTC＝1,3,5- benzene tricarboxylate), zirconium (Zr) based MOF, hafnium (Hf) based MOF. Wherein the Zr/Hf based MOF comprises UiO-66 (Zr 6O4(OH)4(BDC)6 or Hf6O4(OH)4(BDC)6)、UiO-67(Zr6O4(OH)4(BPDC)6 or Hf 6O4(OH)4(BPDC)6, BPDC=dimethyl phthalate), uiO-68 (Zr 6O4(OH)4(TPDC)6 or Hf 6O4(OH)4(TPDC)6, TPDC =terphenyl-4, 4 "-dicarboxylic acid ester), uiO-66-OH (Zr or Hf), uiO-67-OH (Zr or Hf), uiO-68-OH (Zr or Hf), uiO-66-NH 2 (Zr or Hf), uiO-67-NH 2 (Zr or Hf), At least one of UiO-68-NH 2 (Zr or Hf), uiO-66-4F (Zr or Hf), uiO-66-2F (Zr or Hf), uiO-66-CF 3 (Zr or Hf), uiO-66-SO 3 (Zr or Hf), uiO-67-SO 3 (Zr or Hf), uiO-68-SO 3 (Zr or Hf). In a specific embodiment of the present invention, the MOFs described above employ UiO-66-NH 2 (Zr), uiO-66 (Hf), HKUST-1, MIL-53 and MOF-5, respectively.
The method for coating the activated glass fiber cloth by MOF comprises the following steps: the glass fiber cloth after the activation treatment is immersed in precursor solution of MOF, reacts for 4 to 48 hours at the temperature of 25 to 120 ℃, is taken out for washing, is dried at the temperature of 120 ℃ and is activated for 24 hours at the temperature of 150 ℃. The precursor solution is prepared from metal salt and organic ligand in an organic solvent through a solvothermal synthesis method. In one embodiment of the present invention, the metal salts employed include, but are not limited to, copper nitrate hydrate, copper chloride, zinc perchlorate, zinc nitrate, zinc acetate, iron (III) nitrate nonahydrate, cadmium nitrate, zirconium tetrachloride, zirconium acetate, zirconium acetylacetonate, zirconium phosphate, hafnium acetylacetonate, hafnium chloride, hafnium sulfate, zinc acetylacetonate monohydrate, and aluminum nitrate, and specifically one or more of the metal salts exemplified above may be employed. The organic ligand includes, but is not limited to, at least one of terephthalic acid, 2-hydroxyterephthalic acid, tetrafluoroterephthalic acid, 2, 5-difluoroterephthalic acid, 2- (trifluoromethyl) terephthalic acid, 2-bromoterephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 1,3, 5-trimesic acid, diphenic acid, 4' -biphenyl-dicarboxylic acid, and terphenyl-4, 4 "-dicarboxylic acid, and the organic solvent includes, but is not limited to, at least one of N, N-dimethylformamide DMF, methylacetamide DMA, ethanol, isopropanol, acetone, or methanol. Further, in the above-mentioned solvothermal synthesis method, it is preferable to further include a regulator, and in the embodiment of the present invention, the regulator includes at least one of water, hydrochloric acid, formic acid, acetic acid, propionic acid, or methanol, for example, when DMF alone is used, it is preferable to use the regulator hydrochloric acid, formic acid, acetic acid in combination. When methylacetamide is used, the regulators ethanol, isopropanol, methanol are preferably used in combination. The person skilled in the art can choose whether to adjust the addition of the regulator according to the actual use of the organic solvent. The molar concentration of the metal salt and the organic ligand in the organic solvent is 0.1M-5M, and the molar concentration ratio between the metal salt and the organic ligand can be 1: 0.75-2M. The heating mode in the solvent thermal synthesis method is at least one of oven heating, oil bath heating, water bath heating, microwave heating or ultrasonic heating. The washing step is respectively cleaned by at least one of methanol, isopropanol, acetone or diethyl ether and DMF.
The polymer/lithium salt mixture suitable for the invention is one or a mixture of a plurality of homopolymers or copolymers of Polyoxyethylene (PEO), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polycarbonate (PC), polyurethane (PU) and the like. The lithium salt is one or a combination of lithium salts such as lithium bis (trifluoromethanesulfonyl) imide, lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium difluoroborate, lithium difluorooxalato borate, lithium difluorophosphate, lithium oxalato phosphate and the like.
The specific form of the mixture of the polymer and the lithium salt in the preparation process can be a mixture solution containing a solvent, or a liquid mixture or a solid film without the solvent. In one embodiment of the invention, the method of mixing the liquid polymer/lithium salt mixture comprises adding an organic solvent to dissolve the polymer and lithium salt and stirring to obtain a solvent-containing mixture solution. Further, the solvent-containing mixture solution may be subjected to film coating and drying to obtain a solvent-free liquid mixture or solid film.
The method of complexing the MOF three-dimensional framework with the polymer/lithium salt mixture includes: one or a combination of several methods of dipping, in situ polymerization, lamination, coating, etc. It should be understood that the compounding may be a compounding of a solvent-containing polymer/lithium salt mixture and a three-dimensional skeleton, i.e., one or more of impregnation, in-situ polymerization, coating, etc., followed by drying to obtain a polymer composite solid electrolyte. Meanwhile, the polymer composite solid electrolyte can be obtained by laminating a dry polymer/lithium salt mixture solid film and a three-dimensional framework.
In one embodiment of the invention, the loading rate of the MOF on the MOF three-dimensional framework is 5-30%.
In a second aspect, the invention provides a polymer composite solid electrolyte prepared by the method and application of the solid electrolyte in the field of batteries.
In one embodiment of the invention, the thickness of the polymer composite solid electrolyte based on the MOF three-dimensional skeleton is 30-250 um.
The invention has the beneficial effects that: in the preparation step of the polymer composite electrolyte provided by the invention, through surface activation treatment of the glass fiber cloth, and then loading MOF on the activated glass fiber cloth, a compact MOF film layer with high loading capacity can be formed, on one hand, the MOF film layer can inhibit migration of anions, so that the ion conductivity and ion migration number are improved, and the charge-discharge stability is improved. The solid electrolyte has excellent electrochemical performance and thermal stability, the ionic conductivity at room temperature can reach 1.5x10 -3 S cm-1, the ionic migration number reaches 0.56, and the thermal decomposition temperature exceeds 400 ℃. Meanwhile, the polymer composite electrolyte also has excellent mechanical properties, the tensile strength of the polymer composite electrolyte can reach 48.5MPa, and the Young modulus of the polymer composite electrolyte can reach 1.66GPa.
Drawings
FIG. 1 is a schematic diagram of a sample preparation flow;
FIG. 2 is a schematic diagram of a mechanism for lithium ion transport in an electrolyte;
FIG. 3 is an SEM image of a framework material supporting a metal-organic framework material;
FIG. 4 is a graph showing the comparison of the ionic conductivities of the solid electrolytes of examples 9 to 15 and comparative example 5;
FIG. 5 is a graph showing the comparison of the ion migration numbers of the solid electrolytes in example 9 and comparative example 5;
FIG. 6 is a graph comparing electrochemical stability windows of solid state electrolytes in example 9 and comparative example 5;
fig. 7 is a graph of the rate performance of the solid electrolyte of example 9;
FIG. 8 is a plot of lithium iron phosphate versus lithium charge and discharge for example 9;
Fig. 9 is a graph showing a comparison of the tensile curves of the three-dimensional skeletons in examples 1 and 2, the polymer composite solid electrolytes in examples 9 and 10, and the polymer composite solid electrolytes in comparative examples.
Detailed Description
In view of the foregoing prior art, an object of the present invention is to provide a solid electrolyte applicable to lithium metal and lithium ion structural batteries, which can be used as an important component of structural batteries, and which can be used as a solid electrolyte material with excellent electrochemical properties and mechanical properties.
Through repeated research and exploration, the invention discovers that the design and preparation of the composite solid electrolyte based on the MOF three-dimensional framework support with excellent electrochemical performance and mechanical performance have several key technical problems to be solved:
1) The functional potential on the surface of the glass fiber is deficient, which is unfavorable for nucleation and efficient growth of MOF crystallization, and the loading capacity of the MOF is lower. While lower MOF loadings are detrimental and electrochemical performance improves;
2) The MOF has weak adhesive force with the surface of the glass fiber, and has negative influence on the mechanical property of the composite material;
3) The physical and chemical structure of MOFs is crucial for the dissociation of lithium salts and the transport of lithium ions and for the regulation of anion movement, requiring rational design and screening.
Based on the problems found in the research, the novel preparation method of the polymer composite electrolyte based on the MOF three-dimensional framework is obtained through repeated experiments, specifically, the method is characterized in that the surface of glass fiber is subjected to activation treatment, the nucleation capacity of MOF on the original inert surface of the MOF and the affinity between the MOF and the surface of the glass fiber are obviously improved, so that a uniform, compact MOF film with strong bonding force with the surface of the glass fiber is generated on the glass fiber, and the highest MOF loading rate in the specific embodiment of the invention can reach more than 30%. The activation treatment of glass fiber cloth, especially in combination with the preferred surface treatment agent and treatment process, makes MOFs more prone to nucleate on the fiber surface and form a dense, high loading MOF film layer, as shown in the sample preparation flow schematic of fig. 1.
Furthermore, the invention selects MOF to coat the glass fiber cloth to form a three-dimensional framework. A plurality of metal organic frameworks regularly coated on glass fibers provide rapid channels for lithium ion transport through their porous structure, and in one embodiment of the invention, amino modified UiO-66 (UiO-66-NH 2) is preferred, the amino groups on the surface of which promote dissociation of lithium salts and regulate movement of anions. Regarding the selection of MOFs, the amino group contained in the UiO-66-NH 2 type MOFs used in the examples of the present invention can promote dissociation of only lithium salts and inhibit migration of anions, thereby improving ion conductivity and ion migration number and improving charge-discharge stability. The UiO-66-NH 2 material has rich amino functional groups, meanwhile, the-NH 2 has strong interaction on lithium ions, and meanwhile, the C-F group in the PVDF-based polymer also has strong interaction on lithium ions, so that the two interactions compete, the lithium ions are promoted to be rapidly transmitted, and the migration number of the polymer electrolyte is improved, as shown in a schematic diagram of a lithium ion transmission mechanism in the electrolyte of FIG. 2.
The solid electrolyte obtained by compounding the MOF coated glass fiber cloth with the PVDF-HFP and the lithium salt mixture obtained by the preparation method provided by the invention has excellent electrochemical performance and thermal stability, the ionic conductivity at room temperature reaches 1.5x10 -3 S cm-1, the ion migration number reaches 0.56, and the thermal decomposition temperature exceeds 400 ℃. Meanwhile, the polymer composite electrolyte also has excellent mechanical properties, the tensile strength of the polymer composite electrolyte reaches 48.5MPa, the Young modulus of the polymer composite electrolyte reaches 1.66GPa, and the polymer composite electrolyte is equivalent to a normal glass fiber reinforced polymer composite material. The electrolyte not only can be used as a solid electrolyte of a high-performance lithium battery, but also can be used as an effective component of a structural battery, for example, the electrolyte can be combined with a composite electrode to prepare the composite structural battery.
The invention will be described in further detail below with reference to the drawings by means of specific embodiments.
In the following embodiments, the calculation method of the MOF load factor adopts the following formula:
MOF load factor= (mass of MOF@GF-original mass of GF)/mass of MOF@GF
Wherein MOF@GF is glass fiber cloth loaded with MOF, and GF is glass fiber cloth.
Example 1: three-dimensional skeleton 1
The preparation of the three-dimensional skeleton 1 in this example includes the steps of:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour.
(2) Preparing a silane coupling agent solution: the silane coupling agent is 1wt% of the glass fiber cloth, and is dissolved in deionized water in a proportion of 1:100.
(3) Surface treatment of glass fiber cloth: immersing glass fiber cloth in a silane coupling agent solution for 15min, taking out, and drying at 80 ℃ for later use;
(4) A solvent-thermal synthesis method is adopted to put 0.70 g of zirconium tetrachloride and 0.54 g of 2-amino terephthalic acid into a mixed solution of acetone and DMF, and ultrasonic dissolution is carried out for 10 minutes, so as to obtain a UiO-66-NH 2 (Zr) precursor solution.
(5) Immersing the glass fiber cloth subjected to surface treatment into a UiO-66-NH 2 (Zr) precursor solution, and filling the glass fiber cloth into a polytetrafluoroethylene reaction kettle, and heating the glass fiber cloth at 120 ℃ for 24 hours.
(6) The product was washed three times with DMF and methanol, dried at 120℃under vacuum for 24 hours, and activated at 150℃for 24 hours to give a three-dimensional framework 1 of MOF having a loading rate of 25.1%.
As shown in Table 1 and FIG. 9, the tensile strength of the three-dimensional skeleton 1 obtained by the tensile test reached 90.3MPa, and the modulus was 2.22GPa.
Note that: not for a clearer explanation, the present application compares the three-dimensional skeleton load amount, the tensile strength of the polymer composite solid electrolyte and the modulus of the related examples with those of the comparative examples at the end of the examples and makes table 1. FIG. 9 is a graph showing a comparison of the tensile curves of the three-dimensional skeleton (three-dimensional skeleton 1-2) in examples 1 and 2, the polymer composite solid electrolyte (polymer composite solid electrolyte 1-2) in examples 9 and 10, and the polymer composite solid electrolyte of comparative example 5
Example 2: three-dimensional skeleton 2
The preparation of the three-dimensional skeleton 2 in this example includes the steps of:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour.
(2) Preparing a silane coupling agent solution: the silane coupling agent is 1wt% of the glass fiber cloth, and is dissolved in deionized water in a proportion of 1:100.
(3) Surface treatment of glass fiber cloth: immersing glass fiber cloth in a silane coupling agent solution for 15min, taking out, and drying at 80 ℃ for later use;
(4) 0.70 g zirconium tetrachloride and 0.54 g 2-amino terephthalic acid were put into 200ml DMF by solvothermal synthesis, 120uL hydrochloric acid was added, and ultrasonic dissolution was carried out for 10 minutes to obtain UiO-66-NH 2 (Zr) precursor solution.
(5) Immersing the glass fiber cloth subjected to surface treatment into a UiO-66-NH 2 (Zr) precursor solution, and filling the glass fiber cloth into a polytetrafluoroethylene reaction kettle, and heating the glass fiber cloth at 120 ℃ for 24 hours.
(6) The product is washed three times by DMF and methanol respectively, dried for 24 hours at the temperature of 120 ℃ in vacuum and activated for 24 hours at the temperature of 150 ℃ to obtain the MOF three-dimensional framework 2 with the loading rate of 19.9 percent.
As shown in Table 1 and FIG. 9, the tensile strength of the three-dimensional skeleton 2 obtained by the tensile test reaches 90.1MPa, and the modulus is 2.05GPa.
Example 3: three-dimensional skeleton 3
The preparation of the three-dimensional skeleton 3 in this example includes the steps of:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour.
(2) Preparing a dopamine solution: 0.4g of dopamine was dissolved in 400ml of RO water and 100ml of Tri-HCl buffer, and magnetically stirred for 30 minutes.
(3) Surface treatment of glass fiber cloth: the glass cloth was immersed in the prepared solution at room temperature and left to stand for 24 hours.
(4) And taking out the dopamine-modified glass fiber cloth, washing with water for three times, and washing with ethanol for three times. Until the wash filtrate became colorless.
(5) A solvent-thermal synthesis method is adopted to put 0.70 g of zirconium tetrachloride and 0.54 g of 2-amino terephthalic acid into a mixed solution of acetone and DMF, and ultrasonic dissolution is carried out for 10 minutes, so as to obtain a UiO-66-NH 2 (Zr) precursor solution.
(6) Immersing the glass fiber cloth subjected to surface treatment into a UiO-66-NH 2 (Zr) precursor solution, and filling the glass fiber cloth into a polytetrafluoroethylene reaction kettle, and heating the glass fiber cloth at 120 ℃ for 24 hours.
(7) The product is washed three times by DMF and methanol respectively, dried for 24 hours at the temperature of 120 ℃ in vacuum and activated for 24 hours at the temperature of 150 ℃ to obtain the MOF three-dimensional framework 3 with the loading rate of 34.4 percent.
Example 4: three-dimensional skeleton 4
The preparation of the three-dimensional skeleton 4 in this example includes the steps of:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour.
(2) Preparing a dopamine solution: 0.4g of dopamine was dissolved in 400ml of RO water and 100ml of Tri-HCl buffer, and magnetically stirred for 30 minutes.
(3) Surface treatment of glass fiber cloth: the glass cloth was immersed in the prepared solution at room temperature and left to stand for 24 hours.
(4) And taking out the dopamine-modified glass fiber cloth, washing with water for three times, and washing with ethanol for three times. Until the wash filtrate became colorless.
(5) 0.70 G zirconium tetrachloride and 0.54 g 2-amino terephthalic acid were put into 200ml DMF by solvothermal synthesis, 120uL hydrochloric acid was added, and ultrasonic dissolution was carried out for 10 minutes to obtain UiO-66-NH 2 (Zr) precursor solution.
(6) Immersing the glass fiber cloth subjected to surface treatment into a UiO-66-NH 2 (Zr) precursor solution, and filling the glass fiber cloth into a polytetrafluoroethylene reaction kettle, and heating the glass fiber cloth at 120 ℃ for 24 hours.
(7) The product is washed three times by DMF and methanol respectively, dried for 24 hours at the temperature of 120 ℃ in vacuum and activated for 24 hours at the temperature of 150 ℃ to obtain the MOF three-dimensional framework 4 with the loading rate of 34.4 percent.
To further compare the three-dimensional skeletons 1 to 4 in examples 1 to 4 described above, comparative examples 1, 2, 3, 4 (corresponding to three-dimensional skeletons 5 to 8, respectively) were established. Among these, the glass fiber cloth without surface treatment was used in comparative examples 1 and 2 to prepare a three-dimensional skeleton, which includes the following steps.
Comparative example 1: three-dimensional skeleton 5
The preparation of the three-dimensional skeleton 5 in this example comprises the following steps:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour, and taken out for use.
(2) A solvent-thermal synthesis method is adopted to put 0.70 g of zirconium tetrachloride and 0.54 g of 2-amino terephthalic acid into a mixed solution of acetone and DMF, and ultrasonic dissolution is carried out for 10 minutes, so as to obtain a UiO-66-NH 2 (Zr) precursor solution.
(3) Immersing the commercial glass fiber cloth in the step (1) into a UiO-66-NH 2 (Zr) precursor solution, and filling the solution into a polytetrafluoroethylene reaction kettle, and heating the solution at 120 ℃ for 24 hours.
(4) The product was washed three times with DMF and methanol, dried at 120℃under vacuum for 24 hours, and activated at 150℃for 24 hours to give a three-dimensional framework 5 of MOF having a loading rate of 8.7%.
Comparative example 2: three-dimensional skeleton 6
The preparation of the three-dimensional skeleton 6 in this example includes the steps of:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour, and taken out for use.
(2) 0.70 G zirconium tetrachloride and 0.54 g 2-amino terephthalic acid were put into 200ml DMF by solvothermal synthesis, 120uL hydrochloric acid was added, and ultrasonic dissolution was carried out for 10 minutes to obtain UiO-66-NH 2 (Zr) precursor solution.
(3) Immersing the commercial glass fiber cloth in the step (1) into a UiO-66-NH 2 (Zr) precursor solution, and filling the solution into a polytetrafluoroethylene reaction kettle, and heating the solution at 120 ℃ for 24 hours.
(4) The product is washed three times by DMF and methanol respectively, dried for 24 hours at the temperature of 120 ℃ in vacuum and activated for 24 hours at the temperature of 150 ℃ to obtain the MOF three-dimensional framework 6 with the loading rate of 7.6 percent.
The preparation of the three-dimensional skeleton was carried out in comparative examples 3, 4, using surface-treated glass fiber cloth but adjusting the use of regulator HCl in the solvothermal synthesis step, comprising the steps of:
Comparative example 3: three-dimensional skeleton 7
The preparation of the three-dimensional skeleton 7 in this example includes the steps of:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour.
(2) Preparing a silane coupling agent solution: the silane coupling agent is 1wt% of the glass fiber cloth, and is dissolved in deionized water in a proportion of 1:100.
(3) Surface treatment of glass fiber cloth: immersing glass fiber cloth in a silane coupling agent solution for 15min, taking out, and drying at 80 ℃ for later use;
(4) 0.70 g zirconium tetrachloride and 0.54 g 2-amino terephthalic acid are put into a mixed solution of acetone and DMF by a solvothermal synthesis method, 120uL of hydrochloric acid is added, and ultrasonic dissolution is carried out for 10 minutes, so as to obtain a UiO-66-NH 2 (Zr) precursor solution.
(5) Immersing the glass fiber cloth subjected to surface treatment into a UiO-66-NH 2 (Zr) precursor solution, and filling the glass fiber cloth into a polytetrafluoroethylene reaction kettle, and heating the glass fiber cloth at 120 ℃ for 24 hours.
(6) The product is washed three times by DMF and methanol respectively, dried for 24 hours at the temperature of 120 ℃ in vacuum and activated for 24 hours at the temperature of 150 ℃ to obtain the MOF three-dimensional framework 7 with the loading rate of 9.0 percent.
Comparative example 4: three-dimensional skeleton 8
The preparation of the three-dimensional skeleton 8 in this example includes the steps of:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour.
(2) Preparing a silane coupling agent solution: the silane coupling agent is 1wt% of the glass fiber cloth, and is dissolved in deionized water in a proportion of 1:100.
(3) Surface treatment of glass fiber cloth: immersing glass fiber cloth in a silane coupling agent solution for 15min, taking out, and drying at 80 ℃ for later use;
(4) 0.70 g zirconium tetrachloride and 0.54 g 2-amino terephthalic acid were put into 200ml DMF by solvothermal synthesis, and dissolved by ultrasonic for 10 minutes to obtain UiO-66-NH 2 (Zr) precursor solution.
(5) Immersing the glass fiber cloth subjected to surface treatment into a UiO-66-NH 2 (Zr) precursor solution, and filling the glass fiber cloth into a polytetrafluoroethylene reaction kettle, and heating the glass fiber cloth at 120 ℃ for 24 hours.
(6) The product is washed three times by DMF and methanol respectively, dried for 24 hours at the temperature of 120 ℃ in vacuum and activated for 24 hours at the temperature of 150 ℃ to obtain the MOF three-dimensional framework 8 with the loading rate of 5.6 percent.
Comparing the three-dimensional frameworks 1-2 prepared in the above examples 1-2 with the three-dimensional frameworks 5,6 prepared in comparative examples 1, 2, the SEM images of which are shown in fig. 3, it can be found that the step of activating the surface of the glass fiber is important for producing a uniform, dense and high-load MOF film. The reason is that after the glass fiber is subjected to surface activation, the nucleation capacity of the MOF on the original inert surface and the affinity between the MOF and the surface of the glass fiber are obviously improved, so that a uniform, compact MOF film with strong bonding force with the surface of the glass is generated on the glass fiber. Examples 3 and 4 demonstrate that the use of different surface activation techniques has a certain effect on the generation of MOFs. Comparative example 3 was based on example 1 with the addition of the MOF growth regulator HCl, which indicated that the addition of HCl affected the nucleation growth of MOFs on the glass fibers, resulting in a MOF loading of the three-dimensional framework 7 of only 9.0%. Comparative example 4 is based on example 2 without addition of MOF growth regulator HCl, which shows that no addition of HCl affects the nucleation growth of MOFs on glass fibers. Therefore, when two organic solvents, DMF and acetone, are used simultaneously in the solvothermal synthesis, no regulator is needed. The use of a modifier will facilitate the nucleation growth of MOFs on glass fibers when DMF alone is used. The use of modulators in different solvent schemes will have an impact on the MOF loading rate. As can be seen from the SEM image of fig. 3, the loading of the MOFs with the surface-activated glass fibers in the comparative examples (comparative examples 3, 4 versus comparative examples 1, 2) was more uniform.
Example 5: three-dimensional skeleton 9
The preparation of the three-dimensional skeleton 9 in this example includes the steps of:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour.
(2) Preparing a dopamine solution: 0.4g of dopamine was dissolved in 400ml of RO water and 100ml of Tri-HCl buffer, and magnetically stirred for 30 minutes.
(3) Surface treatment of glass fiber cloth: the glass cloth was immersed in the prepared solution at room temperature and left to stand for 24 hours.
(4) And taking out the dopamine-modified glass fiber cloth, washing with water for three times, and washing with ethanol for three times. Until the wash filtrate became colorless.
(5) 0.81 G of hafnium tetrachloride and 0.41 g of terephthalic acid were introduced into 200ml of DMF by solvothermal synthesis, 120uL of hydrochloric acid was added, and ultrasonic dissolution was performed for 10 minutes to obtain a UiO-66 (Hf) precursor solution.
(6) Immersing the glass fiber cloth subjected to surface treatment into a UiO-66 (Hf) precursor solution, and filling the solution into a polytetrafluoroethylene reaction kettle, and heating the solution at 120 ℃ for 24 hours.
(7) The product is washed three times by DMF and methanol respectively, dried for 24 hours at the temperature of 120 ℃ in vacuum and activated for 24 hours at the temperature of 150 ℃ to obtain the MOF three-dimensional framework 9 with the loading rate of 18.2 percent.
Example 6: three-dimensional skeleton 10
The preparation of the three-dimensional skeleton 10 in this example includes the steps of:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour.
(2) Preparing a dopamine solution: 0.4g of dopamine was dissolved in 400ml of RO water and 100ml of Tri-HCl buffer, and magnetically stirred for 30 minutes.
(3) Surface treatment of glass fiber cloth: the glass cloth was immersed in the prepared solution at room temperature and left to stand for 24 hours.
(4) And taking out the dopamine-modified glass fiber cloth, washing with water for three times, and washing with ethanol for three times. Until the wash filtrate became colorless.
(5) And adding 0.875 g of hydrated copper nitrate and 0.42 g of trimesic acid into a mixed solvent of 20ml of water and ethanol by adopting a solvothermal synthesis method, and carrying out ultrasonic dissolution for 10 minutes to obtain the HKUST-1 precursor solution.
(6) Immersing the glass fiber cloth subjected to surface treatment into the HKUST-1 precursor solution, and filling the glass fiber cloth into a polytetrafluoroethylene reaction kettle, and heating the glass fiber cloth at 100 ℃ for 24 hours.
(7) The product is washed three times by DMF and methanol respectively, dried for 24 hours at the temperature of 120 ℃ in vacuum and activated for 24 hours at the temperature of 150 ℃ to obtain the MOF three-dimensional framework 10 with the loading rate of 17.9 percent.
Example 7: three-dimensional skeleton 11
The preparation of the three-dimensional skeleton 11 in this example includes the steps of:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour.
(2) Preparing a dopamine solution: 0.4g of dopamine was dissolved in 400ml of RO water and 100ml of Tri-HCl buffer, and magnetically stirred for 30 minutes.
(3) Surface treatment of glass fiber cloth: the glass cloth was immersed in the prepared solution at room temperature and left to stand for 24 hours.
(4) And taking out the dopamine-modified glass fiber cloth, washing with water for three times, and washing with ethanol for three times. Until the wash filtrate became colorless.
(5) 0.23 G of aluminum nitrate nonahydrate and 0.50 g of terephthalic acid are put into 20ml of DMF by a solvothermal synthesis method, 120uL of hydrochloric acid is added, and ultrasonic dissolution is carried out for 10 minutes, so as to obtain MIL-53 (AL) precursor solution.
(6) Immersing the glass fiber cloth subjected to surface treatment into MIL-53 (AL) precursor solution, and filling the glass fiber cloth into a polytetrafluoroethylene reaction kettle, and heating the glass fiber cloth at 120 ℃ for 24 hours.
(7) The product is washed three times by DMF and methanol respectively, dried for 24 hours at the temperature of 120 ℃ in vacuum and activated for 24 hours at the temperature of 150 ℃ to obtain the MOF three-dimensional framework 11 with the loading rate of 20.5 percent.
Example 8: three-dimensional skeleton 12
The preparation of the three-dimensional bone 12 in this example comprises the steps of:
(1) 10 g of commercial glass cloth (electronic glass cloth 106) was pre-burned at 500℃and incubated for 1 hour.
(2) Preparing a dopamine solution: 0.4g of dopamine was dissolved in 400ml of RO water and 100ml of Tri-HCl buffer, and magnetically stirred for 30 minutes.
(3) Surface treatment of glass fiber cloth: the glass cloth was immersed in the prepared solution at room temperature and left to stand for 24 hours.
(4) And taking out the dopamine-modified glass fiber cloth, washing with water for three times, and washing with ethanol for three times. Until the wash filtrate became colorless.
(5) 1.48 G of zinc acetylacetonate monohydrate and 0.38 g of 2-aminoterephthalic acid were put into 200ml of DMF by solvothermal synthesis, 120uL of hydrochloric acid was added, and the mixture was sonicated for 10 minutes to obtain a precursor solution of MOF-5.
(6) Immersing the glass fiber cloth subjected to surface treatment into MOF-5 precursor solution, and filling the glass fiber cloth into a polytetrafluoroethylene reaction kettle to be heated for 4 hours at 130 ℃.
(7) The product is washed three times by DMF and methanol respectively, dried for 24 hours at the temperature of 120 ℃ in vacuum and activated for 24 hours at the temperature of 150 ℃ to obtain the MOF three-dimensional framework 12 with the loading rate of 15.9 percent.
Example 9: polymer composite solid electrolyte 1
In this example, using the three-dimensional framework 1 of example 1, PVDF-HFP and LiTFSI were selected to prepare a polymer composite solid electrolyte 1, comprising the steps of:
(1) PVDF-HFP, liTFSI and DMF were mixed according to 1:1:9, and stirring to transparent clear solution at 70 ℃.
(2) And (3) pouring the PVDF-HFP/LiTFSI mixed solution obtained in the step (1) on the three-dimensional framework 1 in the example 1, naturally drying at room temperature, and then drying at 70 ℃ in vacuum for 24 hours to obtain the composite polymer solid electrolyte 1 containing the UiO-66-NH 2 modified glass fibers.
(3) And cutting the solid electrolyte membrane into a circular sheet with the diameter of 16mm, and assembling the circular sheet with a lithium iron phosphate positive electrode sheet and a lithium metal negative electrode. And simultaneously assembling a lithium-to-lithium symmetrical battery.
Example 10: polymer composite solid electrolyte 2
In this example, using the three-dimensional framework 2 of example 2, PVDF-HFP and LiTFSI were selected to prepare a polymer composite solid electrolyte 2, comprising the steps of:
(1) PVDF-HFP, liTFSI and DMF were mixed according to 1:1:9, and stirring to transparent clear solution at 70 ℃.
(2) And (3) pouring the PVDF-HFP/LiTFSI mixed solution obtained in the step (1) on the three-dimensional framework 2 in the example 2, naturally drying at room temperature, and then drying at 70 ℃ in vacuum for 24 hours to obtain the composite polymer solid electrolyte 2 containing the UiO-66-NH 2 modified glass fibers.
(3) And cutting the solid electrolyte membrane into a circular sheet with the diameter of 16mm, and assembling the circular sheet with a lithium iron phosphate positive electrode sheet and a lithium metal negative electrode. And simultaneously assembling a lithium-to-lithium symmetrical battery.
Example 11: polymer composite solid electrolyte 3
In this example, using the three-dimensional framework 1 of example 1, PEO and LiTFSI were selected to prepare a polymer composite solid electrolyte 3 comprising the steps of:
(1) PEO and LiTFSI were prepared according to Li: EO is 1:15, and stirred at 30 ℃ until PEO is completely dissolved.
(2) The PEO solution was poured onto the three-dimensional skeleton 1 of example 1, and after natural drying at room temperature, it was dried under vacuum at 70℃for 24 hours to obtain a composite polymer solid electrolyte 3 containing UiO-66-NH 2 modified glass fibers.
(3) And cutting the solid electrolyte membrane into a circular sheet with the diameter of 16mm, and assembling the circular sheet with a lithium iron phosphate positive electrode sheet and a lithium metal negative electrode. And simultaneously assembling a lithium-to-lithium symmetrical battery.
Example 12: polymer composite solid electrolyte 4
In this example, using three-dimensional framework 9 of example 5, PEO and LiTFSI were selected to prepare polymer composite solid electrolyte 4 comprising the steps of:
(1) PEO and LiTFSI were prepared according to Li: EO is 1:15, and stirred at 30 ℃ until PEO is completely dissolved.
(2) The PEO solution was poured onto the three-dimensional skeleton 9 of example 5, naturally dried at room temperature, and then vacuum dried at 70℃for 24 hours to obtain a composite polymer solid electrolyte 4 containing UiO-66 (Hf) modified glass fibers.
(3) And cutting the solid electrolyte membrane into a circular sheet with the diameter of 16mm, and assembling the circular sheet with a lithium iron phosphate positive electrode sheet and a lithium metal negative electrode. And simultaneously assembling a lithium-to-lithium symmetrical battery.
Example 13: polymer composite solid electrolyte 5
In this example, using the three-dimensional framework 10 of example 6, PEO and LiTFSI were selected to prepare a polymer composite solid electrolyte 5 comprising the steps of:
(1) PEO and LiTFSI were prepared according to Li: EO is 1:15, and stirred at 30 ℃ until PEO is completely dissolved.
(2) The PEO solution was poured onto the three-dimensional skeleton 10 of example 6, and after natural drying at room temperature, it was dried under vacuum at 70℃for 24 hours, to obtain a composite polymer solid electrolyte 5 containing HKUST-1 modified glass fibers.
(3) And cutting the solid electrolyte membrane into a circular sheet with the diameter of 16mm, and assembling the circular sheet with a lithium iron phosphate positive electrode sheet and a lithium metal negative electrode. And simultaneously assembling a lithium-to-lithium symmetrical battery.
Example 14: polymer composite solid electrolyte 6
In this example, the three-dimensional skeleton 11 in example 7 was used to prepare a polymer composite solid electrolyte 6 by selecting PEO and LiTFSI, comprising the steps of:
(1) PEO and LiTFSI were prepared according to Li: EO is 1:15, and stirred at 30 ℃ until PEO is completely dissolved.
(2) The PEO solution was poured onto the three-dimensional skeleton 11 of example 7, and after natural drying at room temperature, it was dried under vacuum at 70℃for 24 hours to obtain a composite polymer solid electrolyte 6 containing MIL-53 modified glass fibers.
(3) And cutting the solid electrolyte membrane into a circular sheet with the diameter of 16mm, and assembling the circular sheet with a lithium iron phosphate positive electrode sheet and a lithium metal negative electrode. And simultaneously assembling a lithium-to-lithium symmetrical battery.
Example 15: polymer composite solid electrolyte 7
In this example, the three-dimensional skeleton 12 in example 8 was used to prepare a polymer composite solid electrolyte 7 by selecting PEO and LiTFSI, comprising the steps of:
(1) PEO and LiTFSI were prepared according to Li: EO is 1:15, and stirred at 30 ℃ until PEO is completely dissolved.
(2) The PEO solution was poured onto the three-dimensional skeleton 12 of example 8, naturally dried at room temperature, and then vacuum dried at 70℃for 24 hours to obtain a composite polymer solid electrolyte 7 containing MOF-5 modified glass fibers.
(3) And cutting the solid electrolyte membrane into a circular sheet with the diameter of 16mm, and assembling the circular sheet with a lithium iron phosphate positive electrode sheet and a lithium metal negative electrode. And simultaneously assembling a lithium-to-lithium symmetrical battery.
To further compare the above polymer composite solid state electrolysis, comparative example 5 was set up.
The polymer solid electrolyte was prepared in comparative example 5 using the same PVDF-HFP and LiTFSI as in example 9, comprising the steps of:
(1) PVDF-HFP, liTFSI and DMF were mixed according to 1:1:9, and stirring to transparent clear solution at 70 ℃.
(2) And pouring the PVDF-HFP solution on a blank glass substrate, naturally drying at room temperature, and then drying at 70 ℃ in vacuum for 24 hours to obtain the polymer solid electrolyte.
(3) And cutting the solid electrolyte membrane into a circular sheet with the diameter of 16mm, and assembling the circular sheet with a lithium iron phosphate positive electrode sheet and a lithium metal negative electrode. And simultaneously assembling a lithium-to-lithium symmetrical battery.
Pairs of ion conductivity, lithium ion migration number, and electrochemical stability window of the solid state electrolytes of example 9 and comparative example 5 such as shown in fig. 4,5, and 6, the rate performance and charge and discharge curves of the polymer composite solid state electrolyte 1 of example 9 after assembled into a half cell of lithium iron phosphate to lithium metal are shown in fig. 7 and 8, respectively. Fig. 4 shows that example 9 has a higher room temperature ion conductivity (1.5x10 -3 S cm-1) than comparative example 5 has only 2.1x10 -4 S cm-1, and that the room temperature ion conductivity in examples 9-15 is also significantly higher than comparative example 5. And fig. 5 and 6 show that the polymer composite solid electrolyte of example 9 has higher ion conductivity and lithium ion migration number. Fig. 7 and 8 demonstrate the excellent rate performance and cycle performance of the polymer composite solid electrolyte of example 9 after being assembled into a battery. These are all attributed to the large number of UiO-66-NH 2 regularly coated on the glass fiber, the porous structure of which provides a rapid channel for lithium ion transport, and the amino-modified surface amino groups of UiO-66 promote dissociation of lithium salt and regulate and control the movement of anions, thereby improving ion conductivity and lithium ion migration number and improving charge and discharge stability.
As shown in fig. 9, the tensile strength of the polymer composite solid electrolyte 1 obtained by the tensile test reaches 48.5MPa, and the modulus is 1.66GPa. And compared with the polymer solid electrolyte in proportion 5, the tensile strength obtained by the tensile test is only 0.57MPa, and the modulus is 0.5GPa. The difference between the two is obvious.
The small knot: the results of comparing the above examples with comparative examples are shown in Table 1. From this table it can be found that: glass fiber surface activation is critical to the uniformity of MOF growth in situ of the glass fiber. The loading rate of the MOF can be properly adjusted by adjusting the solution composition in the MOF in-situ synthesis process so as to meet the requirements. After MOF is added by adopting the preparation method provided by the invention, the electrochemical performance and mechanical performance of the solid electrolyte are obviously improved.
Table 1 comparison of three-dimensional skeletal loading and tensile Strength and modulus of Polymer composite solid electrolyte in examples and comparative examples
The foregoing description of the invention has been presented for purposes of illustration and description, and is not intended to be limiting. Several simple deductions, modifications or substitutions may also be made by a person skilled in the art to which the invention pertains, based on the idea of the invention.

Claims (10)

1.一种聚合物复合固态电解质的制备方法，包括：1. A method for preparing a polymer composite solid electrolyte, comprising: 1)将玻璃纤维布清洗预烧结后进行表面活化处理；1) Clean and pre-sinter the glass fiber cloth and then perform surface activation treatment; 2)以金属有机框架对活化后的玻璃纤维布进行原位成核包覆，得到MOF三维骨架；2) In-situ nucleation and coating of the activated glass fiber cloth with a metal organic framework to obtain a MOF three-dimensional skeleton; 3)将所述金属有机框架三维骨架与聚合物/锂盐混合物复合，得到聚合物复合固态电解质。3) Compounding the metal organic framework three-dimensional skeleton with a polymer/lithium salt mixture to obtain a polymer composite solid electrolyte. 2.如权利要求1所述的制备方法，其特征在于，所述表面活化处理包括：采用表面处理剂对玻璃纤维布进行处理；2. The preparation method according to claim 1, characterized in that the surface activation treatment comprises: treating the glass fiber cloth with a surface treatment agent; 优选的，所述表面处理剂包括硅烷偶联剂和/或多巴胺；Preferably, the surface treatment agent includes a silane coupling agent and/or dopamine; 优选的，所述硅烷偶联剂包括异丁基三乙氧基硅、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷或乙烯基三乙氧基硅烷中的至少一种；Preferably, the silane coupling agent includes at least one of isobutyl triethoxysilane, γ-(methacryloyloxy)propyl trimethoxysilane, γ-glycidyloxypropyl trimethoxysilane, 3-aminopropyl triethoxysilane, vinyl trimethoxysilane, vinyl tri(β-methoxyethoxy) silane or vinyl triethoxysilane; 优选的，所述表面活化处理的步骤包括：将表面处理剂以1：200～1：5的比例溶解在去离子水中得到表面处理剂溶液，再将玻璃纤维布浸入所述表面处理剂溶液中，后取出烘干；Preferably, the step of surface activation treatment comprises: dissolving the surface treatment agent in deionized water at a ratio of 1:200 to 1:5 to obtain a surface treatment agent solution, then immersing the glass fiber cloth in the surface treatment agent solution, and then taking it out and drying it; 优选的，将玻璃纤维布浸入表面处理剂溶液0.01～24小时后，取出并用去离子水和/或乙醇冲洗干净，在80～120℃烘干。Preferably, after the glass fiber cloth is immersed in the surface treatment agent solution for 0.01 to 24 hours, it is taken out and rinsed with deionized water and/or ethanol, and dried at 80 to 120°C. 3.如权利要求1所述的制备方法，其特征在于，所述玻璃纤维布为玻璃纤维编织布、玻璃纤维无纺布或玻璃纤维滤膜中的至少一种；3. The preparation method according to claim 1, characterized in that the glass fiber cloth is at least one of glass fiber woven cloth, glass fiber non-woven cloth or glass fiber filter membrane; 优选的，所述玻璃纤维布规格为10g/m2～200g/m2，其厚度为10um～100um。Preferably, the glass fiber cloth has a specification of 10 g/m 2 to 200 g/m 2 and a thickness of 10 um to 100 um. 4.如权利要求1所述的制备方法，其特征在于，所述金属有机框架包括MOF-5、MIL-53、HKUST-1、锆基MOF或铪基MOF中的至少一种；4. The preparation method according to claim 1, characterized in that the metal organic framework comprises at least one of MOF-5, MIL-53, HKUST-1, zirconium-based MOF or hafnium-based MOF; 优选的，所述锆/铪基MOF包括UiO-66、UiO-67、UiO-68、UiO-66-OH、、UiO-67-OH、UiO-68-OH、UiO-66-NH2、UiO-67-NH2、UiO-68-NH2、UiO-66-4F、UiO-66-2F、UiO-66-CF3、UiO-66-SO3、UiO-67-SO3或UiO-68-SO3中的至少一种。Preferably, the zirconium/hafnium-based MOF includes at least one of UiO-66, UiO-67, UiO-68, UiO-66-OH, UiO-67-OH, UiO-68-OH, UiO-66-NH 2 , UiO-67-NH 2 , UiO-68-NH 2 , UiO-66-4F, UiO-66-2F, UiO-66-CF 3 , UiO-66-SO 3 , UiO-67-SO 3 or UiO-68-SO 3 . 5.如权利要求1所述的制备方法，其特征在于，所述金属有机框架对活化后的玻璃纤维布进行包覆的方法包括：将经过活化处理的玻璃纤维布浸渍在金属有机框架的前驱体溶液中，在25～120℃温度下反应4～48小时，取出洗涤并在120℃下烘干及150℃下活化24小时；5. The preparation method according to claim 1, characterized in that the method of coating the activated glass fiber cloth with the metal organic framework comprises: immersing the activated glass fiber cloth in a precursor solution of the metal organic framework, reacting at a temperature of 25 to 120° C. for 4 to 48 hours, taking out, washing, drying at 120° C., and activating at 150° C. for 24 hours; 优选的，所述洗涤采用甲醇、异丙醇、丙酮或乙醚中的至少一种以及DMF各进行至少一次洗涤。Preferably, the washing is performed at least once with at least one of methanol, isopropanol, acetone or ether and DMF. 6.如权利要求5所述的制备方法，其特征在于，所述前驱体溶液由金属盐与有机配体在有机溶剂中通过溶剂热合成法制备得到；6. The preparation method according to claim 5, characterized in that the precursor solution is prepared by a solvothermal synthesis method of a metal salt and an organic ligand in an organic solvent; 优选的，所述金属盐包括硝酸铜水合物、氯化铜、高氯酸锌、硝酸锌、醋酸锌、硝酸铁(III)九水合物、硝酸镉、四氯化锆、乙酸锆、乙酰丙酮锆、磷酸锆、乙酰丙酮铪、氯化铪、硫酸铪、乙酰丙酮锌一水合物和硝酸铝中的至少一种；Preferably, the metal salt comprises at least one of copper nitrate hydrate, copper chloride, zinc perchlorate, zinc nitrate, zinc acetate, iron (III) nitrate nonahydrate, cadmium nitrate, zirconium tetrachloride, zirconium acetate, zirconium acetylacetonate, zirconium phosphate, hafnium acetylacetonate, hafnium chloride, hafnium sulfate, zinc acetylacetonate monohydrate and aluminum nitrate; 优选的，所述有机配体为对苯二甲酸、2-羟基对苯二甲酸、四氟对苯二甲酸、2,5-二氟对苯二甲酸、2-(三氟甲基)对苯二甲酸、2-溴对苯二甲酸、2-氨基对苯二甲酸、2-硝基对苯二甲酸、1,3,5-均苯三甲酸、联苯甲酸、4,4'-联苯二甲酸和三联苯-4,4“-二羧酸中的至少一种，所述有机溶剂为N,N-二甲基甲酰胺DMF、甲基乙酰胺DMA、乙醇、异丙醇、丙酮或甲醇中的至少一种；Preferably, the organic ligand is at least one of terephthalic acid, 2-hydroxyterephthalic acid, tetrafluoroterephthalic acid, 2,5-difluoroterephthalic acid, 2-(trifluoromethyl)terephthalic acid, 2-bromoterephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 1,3,5-trimethylenedicarboxylic acid, biphenylcarboxylic acid, 4,4'-biphenyldicarboxylic acid and terphenyl-4,4"-dicarboxylic acid, and the organic solvent is at least one of N,N-dimethylformamide DMF, methylacetamide DMA, ethanol, isopropanol, acetone or methanol; 优选的，所述溶剂热合成法中还包括调节剂，所述调节剂为水、盐酸、甲酸、乙酸、丙酸或甲醇中的至少一种；Preferably, the solvent thermal synthesis method further comprises a regulator, and the regulator is at least one of water, hydrochloric acid, formic acid, acetic acid, propionic acid or methanol; 优选的，所述金属盐与有机配体在有机溶剂中的摩尔浓度为0.1M～5M，金属盐与有机配体之间的摩尔浓度比为1：0.75～2M。Preferably, the molar concentration of the metal salt and the organic ligand in the organic solvent is 0.1M-5M, and the molar concentration ratio of the metal salt to the organic ligand is 1:0.75-2M. 优选的，所述溶剂热合成法中的加热方式为烘箱加热、油浴加热、水浴加热、微波加热或超声加热中的至少一种。Preferably, the heating method in the solvent thermal synthesis method is at least one of oven heating, oil bath heating, water bath heating, microwave heating or ultrasonic heating. 7.如权利要求1所述的制备方法，其特征在于，所述聚合物/锂盐混合物中，所述聚合物为聚氧乙烯、聚偏氟乙烯、聚甲基丙烯酸甲酯、聚丙烯腈、聚碳酸酯和聚氨酯的均聚物或共聚物中的一种或是几种的共混物；7. The preparation method according to claim 1, characterized in that in the polymer/lithium salt mixture, the polymer is one or a blend of homopolymers or copolymers of polyoxyethylene, polyvinylidene fluoride, polymethyl methacrylate, polyacrylonitrile, polycarbonate and polyurethane; 和/或，所述的锂盐为双三氟甲烷磺酰亚胺锂、高氯酸锂、六氟磷酸锂、四氟硼酸锂、六氟砷酸锂﹑二氟硼酸锂、二氟草酸硼酸锂、二氟磷酸锂和草酸磷酸锂中的至少一种；And/or, the lithium salt is at least one of lithium bis(trifluoromethanesulfonyl)imide, lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium difluoroborate, lithium difluorooxalatoborate, lithium difluorophosphate and lithium oxalatephosphate; 和/或，所述聚合物/锂盐的混合物为含有溶剂的混合物溶液或不含溶剂的液态混合物或固态薄膜；and/or, the polymer/lithium salt mixture is a mixture solution containing a solvent or a liquid mixture or a solid film without a solvent; 优选的，所述聚合物/锂盐混合物的混合方法包括添加有机溶剂溶解聚合物和锂盐，并搅拌均匀得到含有溶剂的混合物溶液；Preferably, the mixing method of the polymer/lithium salt mixture comprises adding an organic solvent to dissolve the polymer and the lithium salt, and stirring to obtain a mixture solution containing the solvent; 和/或，所述金属有机框架三维骨架与聚合物/锂盐混合物复合的方法包括浸渍、原位聚合、压合和涂布方法中的一种或几种的结合。And/or, the method of compounding the metal organic framework three-dimensional skeleton with the polymer/lithium salt mixture includes one or a combination of impregnation, in-situ polymerization, pressing and coating methods. 8.如权利要求1所述的制备方法，其特征在于，所述金属有机框架三维骨架上金属有机框架的负载率为5～30％。8 . The preparation method according to claim 1 , wherein the loading rate of the metal organic framework on the metal organic framework three-dimensional skeleton is 5 to 30%. 9.一种如权利要求1-8任一项所述的制备方法得到聚合物复合固态电解质；9. A polymer composite solid electrolyte obtained by the preparation method according to any one of claims 1 to 8; 优选的，所述聚合物固态电解质的厚度为30～250um。Preferably, the thickness of the polymer solid electrolyte is 30 to 250 um. 10.如权利要求9所述的聚合物复合固态电解质在电池领域的应用。10. Use of the polymer composite solid electrolyte as claimed in claim 9 in the field of batteries.
CN202410108804.7A 2024-01-24 2024-01-24 A polymer composite solid electrolyte, preparation method and application thereof Pending CN118136938A (en)

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