CN112670565B - Amino-containing MOF-based composite gel solid electrolyte with high specific surface area, and preparation method and application thereof - Google Patents
Amino-containing MOF-based composite gel solid electrolyte with high specific surface area, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an amino-containing MOF-based composite gel solid electrolyte with a high specific surface area, and a preparation method and application thereof. Firstly, preparing high specific surface area NH containing amino2MIL-101(Cr), then mixing with lithium-containing Ionic Liquid (ILE), fully grinding in a ball mill to enable the ILE to enter pores of the MOF to form a gel-like substance with certain viscosity, and applying the gel-like substance to an electrolyte of a lithium air battery, wherein the cycling stability of the battery is remarkably improved. The composite gel solid electrolyte prepared by the invention not only keeps the high lithium ion conductivity of the ILE, but also greatly reduces the fluidity of the ILE due to the existence of polar group amino, and is beneficial to effectively regulating and controlling ionic liquid TFSI-ions and realizing uniform Li+The ion is transmitted, so that other polymer matrix materials are not required to be added, the preparation method is simpler, and the conductivity and the cycling stability are better.
Description
Technical Field
The invention relates to the technical field of solid lithium batteries, in particular to an amino-containing MOF-based composite gel solid electrolyte with a high specific surface area, and a preparation method and application thereof.
Background
In the 21 st century, energy problems are one of the biggest challenges facing human society. With the growth of population and the development of industrialization, the world demand for energy will grow irreversibly. Therefore, the development of new energy storage systems with high energy density is urgent and necessary. The lithium-air battery is a new generation of high-performance green secondary battery which takes metal lithium or alloy thereof as an anode and takes oxygen in the air as a cathode active material, and is between a fuel battery and a lithium battery. Because oxygen is not stored in the battery and the chemical equivalent (3860mAh/g) of the metal lithium is very high, the theoretical specific energy of the lithium-air battery is up to 11140Wh/kg, which is 6-9 times that of the lithium ion battery. Lithium air batteries have received attention from numerous researchers throughout the world due to their high energy density, but still suffer from a number of problems, including the development of electrolytes.
At present, the electrolyte used for the lithium air battery is mainly a liquid electrolyte, which is divided into two types: aqueous and nonaqueous electrolytes. The aqueous electrolyte is the electrolyte which has been studied for the first time, and its development is limited due to the generation of hydrogen gas by the contact of water with the anode, poor stability during intermittent circulation, and the like. The organic electrolyte is volatile, cannot ensure the stability of the air cathode chemical reaction and the electrochemical process, is difficult to provide lithium oxide solubility and enough high oxygen transmission capacity in practical significance, and has potential safety hazards. Ionic liquid electrolytes have been the focus of recent research due to their low volatility, low flammability, and wide electrochemical window, but have limited oxygen solubility, low reactant mobility, and no means to prevent leakage.
To address the deficiencies of liquid electrolytes, solid electrolytes have been developed in recent years. The solid electrolyte is non-volatile, can prevent the interference of external factors through two-phase close contact, and certain mechanical strength can avoid the penetration of dendrites, thereby greatly improving the safety performance of the battery. Therefore, it is of great importance to research solid electrolytes having high ionic conductivity, high stability and good interfacial contact. Currently, most of the solid gel electrolytes studied are ionic liquids, polymer gel electrolytes, small molecule gel electrolytes and the like. The metal organogel is a potential carrier for preparing the gel electrolyte due to the advantages of a special network structure, simple preparation, low cost and the like.
Patent publication No. CN108878970A provides a composite polymer solid electrolyte, which is prepared by absorbing lithium-containing ionic liquid in a metal organic frame, and mixing the lithium-containing ionic liquid with polyoxyethylene, thereby improving the conductivity of a solid lithium battery. However, the patent uses polyethylene oxide as a polymer, is only suitable for lithium ion batteries to a certain extent, and cannot be applied to lithium air batteries because the product lithium peroxide in the lithium air batteries reacts with polyethylene oxide, thereby causing polyethylene oxide failure. Patent publication No. CN111180790A provides a polymer electrolyte, a method for preparing the same, and a solid-state lithium-air battery, in which a metal-organic framework absorbs lithium-containing ionic liquid, and then the lithium-containing ionic liquid is mixed with a polyether polyurethane elastomer, and the properties of the polymer electrolyte are comprehensively improved by using the soft segment and the hard segment of the polyether polyurethane elastomer. The battery cycle performance of the patent still needs to be improved.
In view of the above, there is a need for an improved solid electrolyte to solve the above problems.
Disclosure of Invention
The invention aims to provide an amino-containing MOF-based composite gel solid electrolyte with a high specific surface area, and a preparation method and application thereof. The invention adopts the MOF with high specific surface area of amino as a matrix, and the functionalized lithium ion-containing Ionic Liquid (ILE) enters the pores of the MOF by repeated ball milling, thereby obviously improving the lithium ion conductivity of electrolyte and the cycling stability of the battery.
In order to achieve the above purpose, the invention provides a preparation method of an amino-containing MOF-based composite gel solid electrolyte with high specific surface area, which comprises the following steps:
s1, preparing amino-containing high-specific-surface-area metal organic framework NH2-MIL-101(Cr)；
S2, dissolving lithium salt in the ionic liquid, and stirring to dissolve the lithium salt to obtain lithium-containing ionic liquid with the concentration of 1-3 mol/L;
s3, the NH prepared in the step S12MIL-101(Cr) and the lithium-containing ionic liquid obtained in the step S2 are mixed according to the mass-volume ratio of 4g to 5ml, and then the mixture is put into a ball mill for full grinding to obtain a green gel block-shaped object in a flour shape; and pressing the flour-shaped green gel block-shaped object into a sheet by using a roller press to obtain the amino-containing MOF-based composite gel solid electrolyte with high specific surface area.
As a further development of the invention, in step S1 the amino-containing high specific surface area metal-organic framework NH2The preparation method of MIL-101(Cr) comprises:
s11, adding chromium nitrate nonahydrate, 2-aminoterephthalic acid and sodium hydroxide into deionized water according to the molar ratio of 0.9:1: 2.1-1.3: 1:2.8, stirring and mixing uniformly, pouring the mixture into a reaction kettle, keeping the mixture for 12-48 hours at 373-423K, and centrifuging to obtain a green precipitate;
s12, washing the green precipitate obtained in the step S11 with DMF three times at room temperature, washing with methanol twice, and placing at 253KDrying, and grinding into powder to obtain the NH2-MIL-101(Cr)。
As a further development of the invention, the amino group-containing high specific surface area metal-organic framework NH2The pore diameter of the-MIL-101 (Cr) is 2-6 nm, and the specific surface area is 1500-2500 m2/g。
As a further improvement of the present invention, in step S2, the lithium salt is lithium bistrifluoromethanesulfonylimide, lithium iron hexafluorophosphate, lithium bistrifluoromethanesulfonylimidazole, or lithium trifluoromethanesulfonate; the ionic liquid is 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imine.
As a further improvement of the invention, the lithium salt is lithium bistrifluoromethanesulfonylimide, and the concentration of the lithium-containing ionic liquid is 2 mol/L.
In a further improvement of the present invention, in step S3, the sheet has a thickness of 20 to 80 μm and a diameter of 16 to 20 mm.
In a further improvement of the present invention, in step S3, the grinding time is 1-6 hours.
An amino-containing MOF-based composite gel solid electrolyte with a high specific surface area is prepared by the preparation method.
The application of the amino-containing high specific surface area MOF-based composite gel solid electrolyte prepared by the preparation method is used for preparing battery materials.
As a further improvement of the invention, the amino-containing high specific surface area MOF-based composite gel solid electrolyte is used for preparing a lithium air battery, and comprises the following steps: mixing graphene serving as a catalyst with Super P, polyvinylidene fluoride and N-methyl pyrrolidone to prepare slurry, and spraying the slurry on a foamed nickel current collector to serve as an air positive electrode; and (3) taking a metal lithium sheet as a negative electrode, and then assembling the metal lithium sheet, the air positive electrode and the amino-containing MOF-based composite gel solid electrolyte to obtain the lithium-air battery.
The invention has the beneficial effects that:
1、the invention adopts the MOF with high specific surface area and amino as a matrix material, and makes the functionalized lithium ion-containing Ionic Liquid (ILE) enter the MOF pores through repeated ball milling, thereby obviously improving the lithium ion conductivity of the electrolyte; due to the existence of polar group amino, the acting force between the MOF and the ILE is enhanced, so that the MOF is changed into a dough-like MOF/ILE from a powder state to form a gel-like substance with certain viscosity, and on one hand, the ILE is favorably locked in the MOF holes to be prevented from flowing out; on the other hand, it contributes to the formation of a dense electrolyte layer. The material not only retains the high lithium ion conductivity of the ILE, but also greatly reduces the fluidity of the ILE. Compared with disordered transmission of anions and cations in a common electrolyte and uneven lithium deposition, on one hand, the MOF can serve as a cage to limit a large amount of ILEs in pores, and is beneficial to uniform transfer and deposition of lithium ion liquid; on the other hand, the porous characteristic and the surface functional group of the MOF are beneficial to the effective regulation and control of TFSI-ion of the ionic liquid and the realization of uniform Li+And (4) ion transmission. Meanwhile, the porous structure of the MOF is beneficial to the protection of the lithium cathode, and the growth of lithium dendrites is limited. According to the invention, the MOF with high specific surface area and amino groups is used as the matrix material, and other polymer matrix materials are not required to be added, so that the preparation method is simple, and the conductivity and the cycling stability are better.
2. The invention prepares a compound with-NH2High specific area NH of2MIL-101 (Cr). Compared with other small-pore MOFs, the MOFs with high specific area can allow a larger amount of Li-IL to be inserted into the pores, and can also reduce the resistance caused by the MOFs, so that the lithium ion conductivity of the electrolyte is remarkably improved.
3. The prepared amino-containing MOF-based composite gel solid electrolyte with high specific surface area is used as the electrolyte of the lithium air battery, and the cycling stability of the battery is obviously improved. Such a gel-like electrolyte can effectively solve various problems of a liquid electrolyte and has advantages in ion conductivity, stability and interfacial contact compared to other solid electrolytes. The material can promote the application of the solid electrolyte in the lithium air battery, and has important significance for the practical application development of the lithium air battery.
Drawings
In FIG. 1, (a), (b) and (c) are each NH2Structural schematic of MIL-101(Cr), ILE in NH2-a schematic diagram of single particles within MIL-101(Cr) pores and a schematic diagram of MOF/ILE gel structure;
FIG. 2 (a) shows NH after drying2-an optical image of MIL-101(Cr) powder; (b) an optical image of the gel electrolyte cut into 19mm disks;
in FIG. 3, (a) is NH2SEM picture of MIL-101(Cr)/ILE gel; (b) for NH after roll-forming2SEM picture of MIL-101(Cr)/ILE gel solid electrolyte;
FIG. 4 is NH2N of MIL-101(Cr)2An isothermal adsorption curve;
FIG. 5 is NH2N of MIL-101(Cr)2An aperture volume profile;
FIG. 6 is NH2MIL-101(Cr) and NH2-XRD pattern of MIL-101(Cr)/ILE gel;
FIG. 7 is based on NH2-a cycle diagram for a lithium air battery with gel solid state electrolyte of MIL-101 (Cr)/ILE;
FIG. 8 is based on NH2-charge-discharge curves for different cycles of lithium air battery with gel solid electrolyte of MIL-101 (Cr)/ILE;
FIG. 9 is based on NH2Coulombic efficiency curve of lithium-air battery with gel solid electrolyte of MIL-101 (Cr)/ILE.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that 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.
The invention provides a preparation method of an amino-containing MOF-based composite gel solid electrolyte with high specific surface area, which comprises the following steps:
s1, preparing amino-containing high-specific-surface-area metal organic framework NH2-MIL-101(Cr)；
The amino-containing metal organic framework NH with high specific surface area2The preparation method of MIL-101(Cr) comprises:
s11, adding chromium nitrate nonahydrate, 2-amino terephthalic acid and sodium hydroxide into deionized water according to the molar ratio of 0.9:1: 2.1-1.3: 1:2.8, stirring and mixing uniformly, pouring the mixture into a reaction kettle, keeping the mixture for 12-48 hours at 373-423K, and then centrifuging to obtain a green precipitate;
s12, washing the green precipitate obtained in the step S11 with DMF three times at room temperature, washing with methanol twice, drying at 253K, and grinding into powder to obtain the NH2-MIL-101(Cr)。
By adopting the technical scheme, the prepared amino-containing metal organic framework NH with high specific surface area2The pore diameter of the-MIL-101 (Cr) is 2-6 nm, and the specific surface area is 1500-2500 m2(iv) g. The specific surface area is far superior to the prior art, a larger amount of Li-IL can be allowed to be inserted into pores, the resistance caused by MOF can be reduced, and the lithium ion conductivity of the electrolyte is obviously improved.
S2, dissolving lithium salt in the ionic liquid, and stirring to dissolve the lithium salt to obtain lithium-containing ionic liquid with the concentration of 1-3 mol/L;
the lithium salt is bis (trifluoromethanesulfonyl) imide lithium, lithium iron hexafluorophosphate, bis (trifluoromethanesulfonyl) imidazole lithium or lithium trifluoromethanesulfonate; the ionic liquid is 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imine. The lithium salt is preferably lithium bistrifluoromethanesulfonimide, and the concentration of the lithium-containing ionic liquid is preferably 2 mol/L.
S3, the NH prepared in the step S12MIL-101(Cr) and the lithium-containing ionic liquid obtained in the step S2 are mixed according to the mass-volume ratio of 4g to 5ml, and then the mixture is put into a ball mill for full grinding to obtain a green gel block-shaped object in a flour shape; and pressing the flour-shaped green gel block-shaped object into a sheet by using a roller press to obtain the amino-containing MOF-based composite gel solid electrolyte with high specific surface area.
The thickness of the thin slice is 20-80 μm, and the diameter is 16-20 mm. The grinding time is preferably 1-6 h.
According to the invention, the MOF containing amino groups is selected, and the existence of polar group amino groups enhances the mutual acting force between the MOF and the ILE, so that the MOF is changed into dough-shaped MOF/ILE from a powder state, a gel substance with certain viscosity is formed, and the formation of a compact electrolyte layer is facilitated.
The invention also provides an amino-containing MOF-based composite gel solid electrolyte with high specific surface area, which is prepared by the preparation method.
The invention also provides application of the amino-containing MOF-based composite gel solid electrolyte with high specific surface area prepared by the preparation method in preparation of battery materials.
As a further improvement of the invention, the amino-containing MOF-based composite gel solid electrolyte with high specific surface area is used for preparing a lithium air battery, and comprises the following steps: mixing graphene serving as a catalyst with Super P (conductive carbon black), polyvinylidene fluoride and N-methyl pyrrolidone to prepare a sizing material, and spraying the sizing material on a foamed nickel current collector to serve as an air positive electrode; and (3) taking a metal lithium sheet as a negative electrode, and then assembling the metal lithium sheet, the air positive electrode and the amino-containing MOF-based composite gel solid electrolyte to obtain the lithium-air battery.
Example 1
An amino-containing high specific surface area MOF-based composite gel solid electrolyte prepared by the following steps:
s1, preparing amino-containing high-specific-surface-area metal organic framework NH2-MIL-101 (Cr): 25.6g of chromium (III) nitrate nonahydrate and 11.52g of 2-amino-p-phenylene-bisFormic acid and 6.4g sodium hydroxide were added to 480mL deionized water and stirred at ambient temperature for 10 minutes; the mixture was poured into the reaction kettle and then held at 423K for 12 h. Centrifuging the resulting mixture and collecting the green precipitate; washing the green precipitate with DMF three times at ambient temperature and then with methanol twice; finally, the sample is placed at 253K and dried, and then ground into powder to obtain the required NH2-MIL-101(Cr)。
Referring to FIG. 2 (a), it can be seen that NH2-MIL-101(Cr) is a grey-green powder.
Referring to FIGS. 3 and 4, it can be seen that NH was prepared in this example2MIL-101(Cr) having an ultra-high specific surface area (1563 m)2(iv)/g); FIG. 4 shows the NH prepared2The pore size of MIL-101(Cr) is about 2.2 nm.
S2, dissolving LiTFSI (lithium bis (trifluoromethanesulfonylimide)) in [ EMIM ] [ TFSI ] (1-ethyl-3-methylimidazoline bis (trifluoromethanesulfonyl) imide), and stirring to dissolve the solution to obtain lithium-containing Ionic Liquid (ILE) with the concentration of 2 mol/L.
S3, adding 8g of NH2MIL-101(Cr) and 10mL of ILE were mixed, and the mixture was ground in a ball mill for 2 hours to obtain a green gel block in the form of flour, and then the green gel thus obtained was placed between two polypropylene (PP) diaphragms, pressed into 50 μm thin pieces using a roll press, and cut into circular pieces having a diameter of 19mm using a cutter.
Referring to fig. 5, it can be seen that the crystalline structure of MOF and ILE addition retain the framework structure.
Referring to FIG. 2, it can be seen that in NH2In the gel formed by milling MIL-101(Cr)/ILE, the MOF basically retains the original morphological structure and has uniform particle size. After roll forming, the particles were seen to be tightly connected to each other to form an integral mass, which helped to form a dense electrolyte layer. Under the mutual material characteristics and chemical forces of the MOF and the ILE, the MOF is changed into a 'dough' shaped MOF/ILE from a powder state, has certain viscosity, and can act as a cage to limit a large amount of ILE in holes, so that the uniform transfer and deposition of lithium ion liquid are facilitated.Meanwhile, the porous structure of the MOF is beneficial to the protection of the lithium cathode, and the growth of lithium dendrites is limited.
As can be seen from FIG. 1, 2-amino terephthalic acid molecule is used as a connecting bridge to link Cr3+The metal ions are connected by strong coordination bonds to form a stable metal organic structure with high specific surface area. FIG. 1 (b) shows the insertion of NH2Li-IL in the pores of MIL-101(Cr) is locked in the pores by its linkage to the organic skeleton, losing fluidity. FIG. 1 (c) shows Li-IL intercalation into NH2Overall structure within MIL-101(Cr) pores, showing a uniform distribution of Li-IL. It can be seen that the high specific surface area MOFs are able to encapsulate large amounts of Li-IL without hindering the conduction of lithium ions.
Using the amino-containing high specific surface area MOF-based composite gel solid electrolyte for the preparation of a lithium air battery: mixing graphene serving as a catalyst with Super P, polyvinylidene fluoride (PVDF) and N-methyl pyrrolidone (NMP) to prepare a sizing material, and spraying the sizing material on a foamed nickel current collector to serve as an air positive electrode; and (3) taking a metal lithium sheet as a negative electrode, and then assembling the metal lithium sheet, the air positive electrode and the amino-containing MOF-based composite gel solid electrolyte to obtain the lithium-air battery.
Referring now to FIGS. 6 through 9, it can be seen that for NH2For the lithium air battery with MIL-101(Cr)/ILE gel solid electrolyte, when the lithium air battery is circulated in an oxygen atmosphere (the current density is 1000mA/g, the limited capacity is 1000mAh/g), the polarization of the battery is very small along with the circulation, the circulation number can reach 158 circles, and 100 percent of coulombic efficiency is kept before 158 circles, which indicates that the battery has good circulation stability. The test result shows that the conductivity of the conductive material is 16.8 multiplied by 10-4S/cm, indicating the NH2The MIL-101(Cr)/ILE gel solid electrolyte has excellent conductive performance.
Examples 2 to 3 and comparative examples 1 to 2
Examples 2 to 3 and comparative examples 1 to 2 were compared with example 1 except for the concentration of the lithium-containing ionic liquid and NH2The mass-to-volume ratio of-MIL-101 (Cr) to the lithium-containing ionic liquid is shown in table 1. The rest is substantially the same as embodiment 1, and will not be described herein.
TABLE 1 preparation conditions and Performance test results of examples 2 to 3 and comparative examples 1 to 2
As can be seen from table 1, as the concentration of the lithium-containing ionic liquid increases, the conductivity gradually increases, and the cycle stability first increases and then decreases, indicating that appropriately increasing the concentration of the lithium-containing ionic liquid contributes to improving the conductivity of the electrolyte and the cycle stability of the battery. When NH is present2When the mass-to-volume ratio of-MIL-101 (Cr) to the lithium-containing ionic liquid is too low or too high, both the conductivity and the cycle stability tend to be reduced, which indicates that NH is generated2Mass-to-volume ratios of MIL-101(Cr) to the lithium-containing ionic liquid have a significant impact on the performance of the resulting composite solid electrolyte.
Comparative example 3
Comparative example 3 is compared to example 1 with the difference that the metal organic framework does not comprise amino groups, i.e. in step S1 the 2-amino terephthalic acid is replaced by terephthalic acid. The rest is substantially the same as that of embodiment 1, and will not be described herein.
The solid electrolyte prepared in comparative example 3 had a conductivity of 10.8X 10-4S/cm, the coulombic efficiency of the lithium-air battery is only 81.2 percent when the lithium-air battery circulates for 150 circles. It is demonstrated that when MOFs without amino groups were selected as the matrix, both the conductivity of the electrolyte and the cycling stability of the cell were significantly reduced. This is probably because the interaction of common MOFs with lithium-containing ionic liquids is weak, resulting in easy loss of ILE in the solid electrolyte; and since no other polymer matrix is added, the mechanical strength of the dielectric layer is relatively high, and thus the conductivity cyclability stability is significantly reduced.
In conclusion, the invention adopts the MOF with high specific surface area and amino groups as a matrix material, and the functionalized lithium ion-containing Ionic Liquid (ILE) enters the pores of the MOF through repeated ball milling, thereby obviously improving the lithium ion conductivity of the electrolyte; due to the existence of polar group amino, the interaction force between the MOF and the ILE is enhanced, so that the MOF is changed into a 'dough' shaped MOF/ILE from a powder state, a gel-like substance with certain viscosity is formed, and the dense electrolyte layer is formed. The invention does not need to add other polymer matrix materials, has simple preparation method and better conductivity and cycling stability. The lithium air battery electrolyte can remarkably improve the cycle stability of the lithium air battery.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (9)
1. A preparation method of an amino-containing MOF-based composite gel solid electrolyte with high specific surface area is characterized by comprising the following steps:
s1, preparing amino-containing high-specific-surface-area chromium-based metal organic framework NH2-MIL-101；
S2, dissolving lithium salt in the ionic liquid, and stirring to dissolve the lithium salt to obtain lithium-containing ionic liquid with the concentration of 2-3 mol/L;
s3, preparing the chromium-based metal organic framework NH prepared in the step S12MIL-101 and the lithium-containing ionic liquid obtained in step S2 are mixed according to the mass-volume ratio of 4g to 5ml, and then the mixture is put into a ball mill for full grinding to obtain a green gel block-shaped object in a flour shape; pressing the flour-shaped green gel block-shaped object into a sheet by using a roller press to obtain the amino-containing MOF-based composite gel solid electrolyte with high specific surface area, which is used as an electrolyte of a lithium air battery;
the chromium-based metal organic framework NH2The preparation method of MIL-101 comprises the following steps:
s11, adding chromium nitrate nonahydrate, 2-amino terephthalic acid and sodium hydroxide into deionized water according to the molar ratio of 0.9:1: 2.1-1.3: 1:2.8, stirring and mixing uniformly, pouring the mixture into a reaction kettle, keeping the mixture for 12-48 hours at 373-423K, and then centrifuging to obtain a green precipitate;
s12, at room temperature, using DMF to treat the green color obtained in the step S11Washing the precipitate for three times, washing the precipitate with methanol for two times, then putting the precipitate at 253K for drying, and then grinding the precipitate into powder to obtain the chromium-based metal organic framework NH2-MIL-101。
2. The method for preparing the amino-containing high specific surface area MOF-based composite gel solid electrolyte of claim 1, wherein the amino-containing high specific surface area metal organic framework comprises a chromium-based metal organic framework comprising NH2The aperture of the-MIL-101 is 2-6 nm, and the specific surface area is 1500-2500 m2/g。
3. The method for preparing the MOF-based composite gel solid electrolyte with high specific surface area containing amino group according to claim 1, wherein in step S2, the lithium salt is lithium bistrifluoromethanesulfonylimide, lithium iron hexafluorophosphate, lithium bistrifluoromethanesulfonylimidazolium or lithium trifluoromethanesulfonate; the ionic liquid is 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imine.
4. The method for preparing the amino-containing high specific surface area MOF-based composite gel solid electrolyte according to claim 3, wherein the lithium salt is lithium bistrifluoromethanesulfonylimide.
5. The preparation method of the amino-containing high specific surface area MOF-based composite gel solid electrolyte according to claim 1, wherein in step S3, the thickness of the thin sheet is 20-80 μm, and the diameter is 16-20 mm.
6. The preparation method of the amino-containing high specific surface area MOF-based composite gel solid electrolyte according to claim 1, wherein in the step S3, the grinding time is 1-6 h.
7. An amino-containing high-specific-surface-area MOF-based composite gel solid electrolyte, which is prepared by the preparation method of any one of claims 1 to 6.
8. Use of the amino group-containing high specific surface area MOF-based composite gel solid-state electrolyte prepared by the preparation method according to any one of claims 1 to 6, wherein the amino group-containing high specific surface area MOF-based composite gel solid-state electrolyte is used for preparing a battery solid-state electrolyte.
9. Use of the amino group-containing high specific surface area MOF-based composite gel solid electrolyte according to claim 8, wherein the amino group-containing high specific surface area MOF-based composite gel solid electrolyte is used for the preparation of a lithium air battery, comprising the steps of: mixing graphene serving as a catalyst with Super P, polyvinylidene fluoride and N-methyl pyrrolidone to prepare slurry, and spraying the slurry on a foamed nickel current collector to serve as an air positive electrode; and (3) taking a metal lithium sheet as a negative electrode, and then assembling the metal lithium sheet, the air positive electrode and the amino-containing MOF-based composite gel solid electrolyte to obtain the lithium-air battery.
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| CN115960368A (en) * | 2022-12-29 | 2023-04-14 | 西安电子科技大学 | MOF-based porous liquid and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1941219A (en) * | 2006-09-14 | 2007-04-04 | 中国科学院等离子体物理研究所 | Quasi-solid nano-composite gel electrolyte, its production and use |
| KR20120031738A (en) * | 2010-09-27 | 2012-04-04 | 삼성전자주식회사 | Electrolyte membrane for lithium battery, lithium battery using the same, and method for preparing the same |
| CN102617646A (en) * | 2012-02-29 | 2012-08-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method of nanoscale metal organic framework materials |
| CN102738510A (en) * | 2012-06-25 | 2012-10-17 | 中南大学 | Solid electrolyte for lithium ion battery and application thereof |
| CN105070946A (en) * | 2015-09-15 | 2015-11-18 | 中南大学 | Nanostructured quasi-solid electrolyte applied to lithium ion batteries or lithium sulfur batteries and preparation method and application thereof |
| KR20160024610A (en) * | 2014-08-26 | 2016-03-07 | 삼성전자주식회사 | Electrolyte Membrane for energy storage device, energy storage device including the same, and method for preparing the lectrolyte membrane for energy storage device |
| CN105390744A (en) * | 2014-08-29 | 2016-03-09 | 三星电子株式会社 | Composite, method of preparing composite, electrolyte comprising composite, and lithium secondary battery comprising electrolyte |
| CN108878970A (en) * | 2018-06-29 | 2018-11-23 | 华中科技大学 | A kind of composition polymer solid electrolyte, solid state lithium battery and preparation method thereof |
| CN109888380A (en) * | 2019-03-07 | 2019-06-14 | 苏州大学 | A kind of solid polymer electrolyte and its application in lithium metal battery |
| CN109904519A (en) * | 2019-01-18 | 2019-06-18 | 北京理工大学 | A kind of all solid state electrolyte material and its preparation method and application |
| CN110724277A (en) * | 2019-11-28 | 2020-01-24 | 河南理工大学 | Cr-based metal-organic framework material and preparation method thereof |
| CN111313089A (en) * | 2020-01-03 | 2020-06-19 | 武汉理工大学 | Preparation method of ion conductor/polyethylene oxide composite solid electrolyte based on ultraviolet crosslinking |
| CN111443544A (en) * | 2020-03-13 | 2020-07-24 | 东华大学 | MOFs-based gel electrolyte and preparation and application thereof |
| CN111446497A (en) * | 2020-04-03 | 2020-07-24 | 上海电气集团股份有限公司 | Solid electrolyte and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10751694B2 (en) * | 2018-01-26 | 2020-08-25 | GM Global Technology Operations LLC | Metal organic framework (MOF) structured object and method |
-
2020
- 2020-09-07 CN CN202010929557.9A patent/CN112670565B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1941219A (en) * | 2006-09-14 | 2007-04-04 | 中国科学院等离子体物理研究所 | Quasi-solid nano-composite gel electrolyte, its production and use |
| KR20120031738A (en) * | 2010-09-27 | 2012-04-04 | 삼성전자주식회사 | Electrolyte membrane for lithium battery, lithium battery using the same, and method for preparing the same |
| CN102617646A (en) * | 2012-02-29 | 2012-08-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method of nanoscale metal organic framework materials |
| CN102738510A (en) * | 2012-06-25 | 2012-10-17 | 中南大学 | Solid electrolyte for lithium ion battery and application thereof |
| KR20160024610A (en) * | 2014-08-26 | 2016-03-07 | 삼성전자주식회사 | Electrolyte Membrane for energy storage device, energy storage device including the same, and method for preparing the lectrolyte membrane for energy storage device |
| CN105390744A (en) * | 2014-08-29 | 2016-03-09 | 三星电子株式会社 | Composite, method of preparing composite, electrolyte comprising composite, and lithium secondary battery comprising electrolyte |
| CN105070946A (en) * | 2015-09-15 | 2015-11-18 | 中南大学 | Nanostructured quasi-solid electrolyte applied to lithium ion batteries or lithium sulfur batteries and preparation method and application thereof |
| CN108878970A (en) * | 2018-06-29 | 2018-11-23 | 华中科技大学 | A kind of composition polymer solid electrolyte, solid state lithium battery and preparation method thereof |
| CN109904519A (en) * | 2019-01-18 | 2019-06-18 | 北京理工大学 | A kind of all solid state electrolyte material and its preparation method and application |
| CN109888380A (en) * | 2019-03-07 | 2019-06-14 | 苏州大学 | A kind of solid polymer electrolyte and its application in lithium metal battery |
| CN110724277A (en) * | 2019-11-28 | 2020-01-24 | 河南理工大学 | Cr-based metal-organic framework material and preparation method thereof |
| CN111313089A (en) * | 2020-01-03 | 2020-06-19 | 武汉理工大学 | Preparation method of ion conductor/polyethylene oxide composite solid electrolyte based on ultraviolet crosslinking |
| CN111443544A (en) * | 2020-03-13 | 2020-07-24 | 东华大学 | MOFs-based gel electrolyte and preparation and application thereof |
| CN111446497A (en) * | 2020-04-03 | 2020-07-24 | 上海电气集团股份有限公司 | Solid electrolyte and application thereof |
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