CN111276662A - Organic metal frame poly rotaxane type diaphragm and application in battery - Google Patents
Organic metal frame poly rotaxane type diaphragm and application in battery Download PDFInfo
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- CN111276662A CN111276662A CN202010085905.9A CN202010085905A CN111276662A CN 111276662 A CN111276662 A CN 111276662A CN 202010085905 A CN202010085905 A CN 202010085905A CN 111276662 A CN111276662 A CN 111276662A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- 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
Abstract
The invention relates to an organic metal frame polyrotaxane type diaphragm and application thereof in a battery, which is characterized in that: the organic metal framework polyrotaxane type diaphragm is composed of linear polymers, cyclodextrin type group molecules, end-capped polymers and metal ions capable of forming an organic metal framework with hydroxyl. The organic metal framework polyrotaxane type electrolyte membrane is composed of linear polymers, molecules of cyclodextrin type groups, end-capped polymers, lithium salts and metal ions capable of forming an organic metal framework with hydroxyl. The invention can obviously improve the liquid absorption and retention capability and the high temperature resistance of the diaphragm, and reduce the impedance of the diaphragm in a battery system, thereby improving the electrochemical performance and the safety performance of the battery.
Description
Technical Field
The invention relates to an organic metal frame polyrotaxane type diaphragm and application thereof in batteries, in particular to a liquid battery diaphragm and a solid battery electrolyte diaphragm which can be used for lithium batteries, lithium ion batteries, sodium batteries and sodium ion batteries, belonging to the technical field of battery diaphragms.
Technical Field
The quality of the diaphragm directly influences the discharge capacity, the cycle life and the safety of the lithium ion battery. Power plantBatteries and energy storage batteries are mostly large batteries. The energy of an energy storage battery system is often on the order of megawatts. In the process of using a large battery, the requirement on the safety of the battery is higher. The use of a high temperature resistant separator in a liquid lithium ion battery or a high temperature resistant polymer electrolyte in a solid battery is considered to improve the safety of a large battery. Polymer electrolytes of solid-state batteries that have been studied include polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polypropylene oxide, polyvinylidene chloride, and the like. However, the polymer electrolyte currently studied still has the problems of large side reaction in a battery system, low conductivity, large interfacial resistance of the electrolyte, no high temperature resistance and easy generation of battery safety due to precipitation of negative electrode metal lithium, so that the current solid-state battery is difficult to study and is difficult to apply. In order to further increase the energy density of the battery, the research of lithium-sulfur batteries has also attracted great attention in the battery industry in recent years. The energy density of the lithium-sulfur battery is very high, the theoretical specific discharge capacity of elemental lithium is 3860mAh/g, the theoretical discharge voltage of the lithium-sulfur battery is 2.287V, and when sulfur and lithium completely react to generate lithium sulfide (Li)2S) is selected. The theoretical discharge mass specific energy of the corresponding lithium-sulfur battery was 2600 Wh/kg. Other advantages of lithium sulfur batteries include: low production cost, less influence on the environment after use, energy consumption for recovery and the like. However, the lithium sulfur battery has problems that the electron conductivity and the ion conductivity of elemental sulfur are poor, intermediate discharge products are dissolved in an organic electrolyte, and the like. In particular, during charging and discharging, polysulfide ions migrate between the positive and negative electrodes (the Shuttle effect) to cause loss of active material and destruction of the interfacial film of the negative electrode solid electrolyte. The metal-organic framework materials are considered to have the following particular advantages: the organic ligand-metal ions or clusters of different coordination metal ions have different internal pore selectivity, and can play a role in inhibiting the shuttling effect of polysulfide ions on positive and negative electrodes in the charging and discharging process of the lithium-sulfur battery, so that the battery diaphragm prepared from the metal-organic framework material can play a significant role in improving the charging and discharging performance of the lithium-sulfur battery. Dissolved in the charge and discharge process of other battery systems, such as lithium manganate batteries and ternary batteriesThe shuttling problem of metal ions (such as manganese ions) on the positive electrode and the negative electrode influences the charge and discharge performance of the battery. The metal-organic framework material can inhibit the shuttling effect, so that the charge and discharge performance of the battery is improved. Meanwhile, the diaphragm of the invention can bear the impact of the temperature above 220 ℃ without obvious shrinkage, so that the safety of the lithium ion battery using the diaphragm or the electrolyte can be obviously improved. In addition, the polyrotaxane type diaphragm or the polyrotaxane type electrolyte diaphragm has the advantages of green preparation process, simple operation, low internal resistance in a solid battery system, good high temperature resistance, good compatibility with an electrolyte system and the like, and can be suitable for industrial production.
Disclosure of Invention
The organic metal frame polyrotaxane type diaphragm and the application thereof in the battery are characterized in that:
the organic metal frame poly rotaxane type diaphragm is a poly rotaxane type liquid battery diaphragm and a poly rotaxane type electrolyte diaphragm.
The organic metal framework polyrotaxane type diaphragm is composed of a linear polymer, cyclodextrin type group molecules and an end-capped polymer, and the linear polymer penetrates through a hydrophobic part of an inner cavity of the cyclodextrin type group.
The organic metal framework polyrotaxane type diaphragm simultaneously meets the following requirements: the melting point is in the range of 185-290 ℃, the porosity is in the range of 30-82%, the liquid absorption rate is in the range of 10-95%, and the maximum tensile strength is in the range of 6.33-15 MPa.
The organic metal framework polyrotaxane type diaphragm simultaneously meets the following requirements: in LiPF6The concentration is 1.0 mol L-1The mixed electrolyte of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate with the weight ratio of 1:1:1 has the conductivity of 2 multiplied by 10-4～6×10-3S cm-1In the range of (1), the electrochemical stability window is 2 to 5.1V (vs. Li)+/Li).
The polyrotaxane type liquid battery diaphragm is composed of linear polymers, cyclodextrin type group molecules, end-capped polymers and metal ions capable of forming an organic metal framework with hydroxyl, wherein:
(1) the linear polymer is polyethylene glycol, polyvinyl alcohol and polypropylene glycol, or the substitutes of sulfur, chlorine or fluorine of the polyethylene glycol, the polyvinyl alcohol and the polypropylene glycol;
(2) the molar ratio of the linear polymer, the cyclodextrin group molecule, the end-capping polymer and the metal ions capable of forming an organic metal framework with hydroxyl is within the range of 1 (0.1-5): 0.001-1;
(3) the molecule of the cyclodextrin type group is α, β or gamma-type cyclodextrin, or reaction products of etherification, esterification, oxidation, crosslinking and the like of alcoholic hydroxyl on the surface of the cyclodextrin, or chlorine and fluorine substitutes of the cyclodextrin;
(4) the end-capped polymer is polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene or polymethyl methacrylate;
(5) the molecular weight of the linear polymer is within the range of 3000-100000. The molecular weight of the end-capped polymer is 50000-2000000;
(6) the preparation method of the polyrotaxane type liquid battery diaphragm comprises the following steps:
under the condition of heating and stirring, respectively dissolving the linear polymer, the molecules of the cyclodextrin type group and the end-capped polymer in a liquid solvent to respectively prepare liquid solutions of the linear polymer, the molecules of the cyclodextrin type group and the end-capped polymer. And mixing the liquid solution of the linear polymer with the liquid solution of the molecules of the cyclodextrin type group, and heating and stirring for 5-48 h. The linear polymer passes through the inner hydrophobic part of the cyclodextrin-type group. Adding a liquid solution of metal ions capable of forming an organic metal framework with hydroxyl, refluxing for 1-100 h at the temperature of 90-180 ℃, and cooling to room temperature. Adding a liquid solution of the end-capped polymer, and heating and stirring for 5-48 h. Then adding pore-forming agent. Heating and stirring for 5-48 h. Until the solution became transparent, a casting solution was obtained. The casting solution was cast on a glass plate to form a film. Vacuum drying to obtain primary film. And soaking the primary film in deionized water, performing ultrasonic treatment to form holes on the primary film, and performing vacuum drying again to obtain the polyrotaxane type liquid battery diaphragm. Assembling the prepared polyrotaxane type liquid battery diaphragm into a liquid battery;
(7) the preparation steps of the liquid battery are as follows: soaking the prepared polyrotaxane type liquid battery diaphragm in electrolyte for 2-10 h, sucking the electrolyte on the surface of the diaphragm, and assembling the liquid battery. Or the poly rotaxane type liquid battery diaphragm, the battery anode, the battery cathode and the aluminum plastic film are made into an unsealed quasi-battery cell, the inside of the unsealed quasi-battery cell is vacuumized, so that the electrolyte is rapidly gasified in vacuum, the unsealed quasi-battery cell is sealed, and the liquid battery is assembled.
The polyrotaxane type electrolyte membrane consists of a linear polymer, cyclodextrin type group molecules, a terminated polymer, lithium salt and metal ions capable of forming an organic metal framework with hydroxyl, wherein:
(1) the linear polymer is polyethylene glycol, polyvinyl alcohol and polypropylene glycol, or the substitutes of sulfur, chlorine or fluorine of the polyethylene glycol, the polyvinyl alcohol and the polypropylene glycol;
(2) the molar ratio of the linear polymer, the cyclodextrin group molecule, the end-capping polymer and the metal ions capable of forming an organic metal framework with hydroxyl is within the range of 1 (0.1-5): 0.001-1;
(3) the cyclodextrin type group molecule is α, β or gamma-type cyclodextrin, or reaction products of etherification, esterification, oxidation, crosslinking and the like of alcohol hydroxyl on the surface of cyclodextrin, or chlorine and fluorine substitutes of cyclodextrin;
(4) the end-capped polymer is polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene or polymethyl methacrylate;
(5) the molecular weight of the linear polymer is within the range of 3000-100000; the molecular weight of the end-capped polymer is 50000-2000000;
(6) the preparation steps of the polyrotaxane electrolyte membrane are as follows:
under the condition of heating and stirring, respectively dissolving the linear polymer, the molecules of the cyclodextrin type group and the end-capped polymer in a liquid solvent to respectively prepare liquid solutions of the linear polymer, the molecules of the cyclodextrin type group and the end-capped polymer. And mixing the liquid solution of the linear polymer with the liquid solution of the molecules of the cyclodextrin type group, and heating and stirring for 5-48 h. The linear polymer passes through the inner hydrophobic part of the cyclodextrin-type group. Adding a liquid solution of metal ions capable of forming an organic metal framework with hydroxyl, refluxing for 1-100 h at the temperature of 90-180 ℃, and cooling to room temperature. Adding a liquid solution of the end-capped polymer, and heating and stirring for 5-48 h. And then adding lithium salt. Heating and stirring for 5-48 h. Until the solution became transparent, a casting solution was obtained. The casting solution was cast on a glass plate to form a film. And (4) drying in vacuum to obtain the polyrotaxane type electrolyte membrane. Assembling the prepared poly rotaxane type electrolyte membrane into a solid-state battery;
(7) the preparation steps of the solid-state battery are as follows: soaking the prepared poly rotaxane type electrolyte diaphragm in electrolyte for 2-10 h, sucking the electrolyte on the surface of the diaphragm, and assembling the solid battery. Or the poly rotaxane type electrolyte membrane, the positive electrode, the negative electrode and the aluminum plastic film of the battery are made into an unsealed quasi-battery cell, the inside of the unsealed quasi-battery cell is vacuumized, so that the electrolyte is rapidly gasified in vacuum, the unsealed quasi-battery cell is sealed, and the solid-state battery is assembled.
The pore-forming agent is polyethylene glycol, polyvinyl alcohol or polypropylene glycol with the molecular weight of 100-1000, or is a sulfur, chlorine or fluorine substitute of the polyethylene glycol, the polyvinyl alcohol or the polypropylene glycol.
The liquid solvent is dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide, cyclohexanone or butanone.
The lithium salt is lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate or lithium tetrafluoroborate.
The metal ions capable of forming an organic metal framework with hydroxyl are titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, tin, silver or rare earth ions.
The invention can obviously improve the liquid absorption and retention capability and the high temperature resistance of the diaphragm, and reduce the impedance of the diaphragm in a battery system, thereby improving the electrochemical performance and the safety performance of the battery.
Drawings
FIG. 1 is an infrared spectrum of a sample of alumina polyrotaxane prepared in example 1 of the present invention;
FIG. 2 shows Al as a raw material in example 1 of the present invention2O3An infrared spectrum of (1).
Detailed Description
The present invention will be further described with reference to the following examples. The examples are merely further additions and illustrations of the present invention, and are not intended to limit the invention.
Example 1
The organometallic framework polyrotaxane type membrane described in this example has the following characteristics:
the organic metal frame poly rotaxane type diaphragm is composed of polyethylene glycol with the molecular weight of 18000, α -cyclodextrin, polyvinylidene fluoride-hexafluoropropylene end-capped molecules with the molecular weight of 150000 and zinc ions, and linear polyethylene glycol penetrates through the inner cavity hydrophobic part of the cyclodextrin type group.
The polyrotaxane type diaphragm simultaneously meets the following requirements: the melting point is 260 ℃, the porosity is 62%, the liquid absorption rate is 37%, and the maximum tensile strength is 10.5 MPa; in LiPF6Concentration 1.0 mol L-1The electric conductivity of the mixed electrolyte of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (weight ratio is 1:1: 1) is 8.2 multiplied by 10-4S cm-1The electrochemical stability window is 2-4.5V (vs. Li)+/Li).
The preparation steps of the organic metal framework polyrotaxane type diaphragm and the application in the battery are as follows:
the molar ratio of the polyethylene glycol, the cyclodextrin group molecule, the polyvinylidene fluoride-hexafluoropropylene end-capped polymer and the zinc ions is 1:1: 1: 0.1.
Under the condition of heating and stirring, respectively dissolving 1 mol of 18000 polyethylene glycol, 1 mol of α -cyclodextrin and 1 mol of 150000 polyvinylidene fluoride-hexafluoropropylene end-capped molecules in N, N-dimethylacetamide solutions to respectively prepare polyethylene glycol, α -cyclodextrin and polyvinylidene fluoride-hexafluoropropylene N, N-dimethylacetamide solutions, mixing the polyethylene glycol N, N-dimethylacetamide solutions and α -cyclodextrin N, N-dimethylacetamide solutions, heating and stirring for 28h, enabling linear polyethylene glycol to penetrate through the inner cavity hydrophobic part of a cyclodextrin group, adding 0.1 mol of zinc ion N, N-dimethylacetamide solution, refluxing at 100 ℃ for 50h, cooling to room temperature, adding the vinylidene fluoride-hexafluoropropylene N, N-dimethylacetamide solution end-capped, heating and stirring for 5h, adding 1 mol of 400 polyethylene glycol, heating and stirring for 18h, enabling organic metal to be in a transparent solution to obtain an organic metal solution, forming a film on a glass plate, carrying out vacuum drying to obtain a film, carrying out initial film formation, carrying out annular rolling treatment in a wheel, carrying out vacuum treatment, carrying out film casting, and preparing a poly-alkyl membrane by using an ultrasonic casting to obtain a casting frame to prepare a poly-alkyl organic metal film.
The liquid battery is assembled by soaking the prepared organic metal frame polyrotaxane type diaphragm in electrolyte for 10h, and sucking the electrolyte on the surface of the diaphragm.
The organic metal frame polyrotaxane type diaphragm can obviously improve the liquid absorption and retention capacity and the high temperature resistance of the diaphragm, and reduce the impedance of the diaphragm in a battery system, so that the electrochemical performance and the safety performance of the battery are improved.
Example 2
The characteristics of the organometallic framework polyrotaxane type separator and the application thereof in the battery are as follows:
the organic metal framework polyrotaxane type diaphragm is composed of polyvinyl alcohol with the molecular weight of 100000, β -cyclodextrin, polyvinylidene fluoride-hexafluoropropylene end-capped molecules with the molecular weight of 2000000 and cerium ions.
The polyrotaxane type diaphragm simultaneously meets the following requirements: the melting point is 185 ℃, the porosity is 72%, the liquid absorption rate is 75%, and the maximum tensile strength is 6.33 MPa; in LiPF6Concentration 1.0 mol L-1The mixed electrolyte of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (weight ratio is 1:1: 1) has the conductivity of 2 multiplied by 10-4S cm-1The electrochemical stability window is 2-4.3V: (vs. Li+/Li).
The preparation method of the organic metal framework polyrotaxane type diaphragm comprises the following steps:
the molar ratio of the polyvinyl alcohol to the cyclodextrin group molecule to the polyvinylidene fluoride-hexafluoropropylene end-capped polymer to the cerium ions is 1:0.1:0.1: 0.001.
Respectively dissolving polyvinyl alcohol with a molecular weight of 100000, β -cyclodextrin with a molecular weight of 0.1 and polyvinylidene fluoride-hexafluoropropylene with a molecular weight of 2000000 with a molecular weight of 0.1 in N-methylpyrrolidone to respectively prepare N-methylpyrrolidone solutions of polyvinyl alcohol, β -cyclodextrin and polyvinylidene fluoride-hexafluoropropylene end-capped molecules, mixing the N-methylpyrrolidone solution of polyvinyl alcohol with the N-methylpyrrolidone solution of β -cyclodextrin, heating and stirring for 48 hours, allowing linear polyvinyl alcohol to pass through the inner cavity hydrophobic part of a cyclodextrin fine group, adding the N-methylpyrrolidone solution of cerium ions with a molecular weight of 0.001, refluxing at 100 ℃ for 20 hours, cooling to room temperature, adding the N-methylpyrrolidone solution of polyvinylidene fluoride-hexafluoropropylene, heating and stirring for 48 hours, adding a polyethylene glycol pore forming agent with a molecular weight of 100, heating and stirring for 48 hours, allowing the pore solution to be transparent to obtain a casting solution, forming a film on a glass plate, performing vacuum drying to obtain a film, performing primary treatment, performing ultrasonic treatment, performing secondary vacuum drying on the film forming, and assembling a diaphragm by tape casting to obtain a casting battery.
The liquid battery is prepared by soaking the prepared organic metal frame polyrotaxane type diaphragm in electrolyte for 8h, sucking the electrolyte on the surface of the diaphragm, and assembling the battery.
The organic metal frame polyrotaxane type diaphragm can obviously improve the liquid absorption and retention capacity and the high temperature resistance of the diaphragm, and reduces the impedance of the diaphragm in a battery system, so that the electrochemical performance and the safety performance of the battery are improved.
Example 3
The characteristics of the organometallic framework polyrotaxane type separator and the application thereof in the battery described in the embodiment are as follows:
the organic metal frame polyrotaxane type diaphragm consists of polypropylene glycol with the molecular weight of 8000, gamma-cyclodextrin, end-capped molecules of polyvinylidene fluoride-hexafluoropropylene with the molecular weight of 100000 and nickel ions.
The polyrotaxane type diaphragm simultaneously meets the following requirements: the melting point is 230 ℃, the porosity is 40%, the liquid absorption rate is 95%, and the maximum tensile strength is 8.2 MPa; in LiPF6Concentration 1.0 mol L-1The mixed electrolyte of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (weight ratio is 1:1: 1) has the conductivity of 1 x 10-3S cm-1The electrochemical stability window is 2-4.8V (vs. Li)+/Li）。
The molar ratio of the polypropylene glycol, the cyclodextrin group molecules, the vinylidene fluoride-hexafluoropropylene end-capped polymer and the nickel ions is 1: 5: 5: 1.
The preparation steps of the organic metal framework polyrotaxane type diaphragm are as follows:
1 mole of polypropylene glycol with a molecular weight of 8000, 5 moles of gamma-cyclodextrin and 5 moles of polyvinylidene fluoride-hexafluoropropylene end-capped molecules with a molecular weight of 100000 are dissolved in N-methylpyrrolidone solvent respectively under the condition of heating and stirring. Respectively preparing N-methyl pyrrolidone solutions of polypropylene glycol, gamma-cyclodextrin and polyvinylidene fluoride-hexafluoropropylene. Mixing the N-methylpyrrolidone solution of polypropylene glycol with the N-methylpyrrolidone solution of gamma-cyclodextrin, heating and stirring for 48 hours; the linear polypropylene glycol penetrates through the inner cavity hydrophobic part of the cyclodextrin group; adding 1 mol of nickel ion N-methyl pyrrolidone solution, refluxing at 180 ℃ for 100h, and cooling to room temperature; then adding an N-methyl pyrrolidone solution of polyvinylidene fluoride-hexafluoropropylene, heating and stirring for 5 hours; adding 1 mol of polyethylene glycol pore-forming agent with the molecular weight of 1000; heating and stirring for 10 h; until the solution became transparent, a casting solution was obtained. Casting the casting solution on a glass plate to form a film; vacuum drying to obtain a primary film; soaking the primary film in deionized water, performing ultrasonic treatment to make the diaphragm generate holes, and performing vacuum drying again to obtain an organic metal frame polyrotaxane type diaphragm; assembling the prepared organic metal frame polyrotaxane type diaphragm into a liquid battery.
The liquid battery is a quasi-battery cell which is not sealed and is prepared by the prepared organic metal frame poly rotaxane type diaphragm, a battery anode, a battery cathode and an aluminum plastic film. And vacuumizing the inside of the unsealed quasi-electric core to quickly gasify the electrolyte in vacuum, and sealing the unsealed quasi-electric core to obtain the liquid battery.
The organic metal frame polyrotaxane type diaphragm can obviously improve the liquid absorption and retention capacity and the high temperature resistance of the diaphragm, and reduces the impedance of the diaphragm in a battery system, so that the electrochemical performance and the safety performance of the battery are improved.
Example 4
The characteristics of the organometallic framework polyrotaxane type separator and the application thereof in the battery described in the embodiment are as follows:
the organic metal frame polyrotaxane type diaphragm is composed of polyvinyl alcohol with molecular weight of 200000, an etherified product of alcohol hydroxyl of α type cyclodextrin, polymethyl methacrylate end-capped molecules with molecular weight of 50000 and zinc ions.
The polyrotaxane type diaphragm simultaneously meets the following requirements: the melting point is 290 ℃, the porosity is 30%, the liquid absorption rate is 39%, and the maximum tensile strength is 6.33 MPa; in LiPF6Concentration 1.0 mol L-1The mixed electrolyte of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (weight ratio 1:1: 1) has an electric conductivity of 9.6X 10-4S cm-1The electrochemical stability window is 2-5.0V (vs. Li)+/Li).
The preparation method of the organic metal framework polyrotaxane type diaphragm comprises the following steps:
the molar ratio of the polyvinyl alcohol to the cyclodextrin group molecule to the polymethyl methacrylate end-capped polymer to the zinc ions is 1:1: 0.5: 0.2.
Under the condition of heating and stirring, respectively dissolving 1 mol of 200000 polyvinyl alcohol, 1 mol of α type cyclodextrin alcoholic hydroxyl ethylated product and 0.5 mol of 50000 type polymethyl methacrylate end-capped molecules in cyclohexanone to respectively prepare polyvinyl alcohol, α type cyclodextrin alcoholic hydroxyl ethylated product and polymethyl methacrylate cyclohexanone solution, mixing the polyvinyl alcohol cyclohexanone solution and α type cyclodextrin alcoholic hydroxyl ethylated product cyclohexanone solution, heating and stirring for 8 hours, enabling linear polyvinyl alcohol to pass through the hydrophobic part of the inner cavity of a cyclodextrin fine group, adding 0.2 mol of zinc ion cyclohexanone solution, refluxing for 1 hour at 90 ℃, cooling to room temperature, adding polymethyl methacrylate cyclohexanone solution, heating and stirring for 5-48 hours, adding 0.1 mol of 300 molecular weight polypropylene glycol pore-forming agent, heating and stirring for 20 hours to obtain a casting hole transparent solution, forming a film by using the casting solution, forming a film on a glass plate, vacuum drying to obtain a primary film, soaking the film in deionized water, performing ultrasonic treatment again, and drying to obtain a casting organic metal film diaphragm, and assembling a casting frame to obtain a casting organic metal diaphragm.
The liquid battery is prepared by preparing the prepared organic metal frame poly rotaxane type diaphragm, a battery anode, a battery cathode and an aluminum plastic film into an unsealed quasi-battery cell, vacuumizing the inside of the unsealed quasi-battery cell to rapidly gasify electrolyte in vacuum, and sealing the unsealed quasi-battery cell.
The organic metal frame polyrotaxane type diaphragm can obviously improve the liquid absorption and retention capacity and the high temperature resistance of the diaphragm, and reduces the impedance of the diaphragm in a battery system, so that the electrochemical performance and the safety performance of the battery are improved.
Example 5
The characteristics of the organometallic framework polyrotaxane type separator and the application thereof in the battery described in the embodiment are as follows:
the organic metal frame polyrotaxane type diaphragm consists of fluorine substitution products of polyethylene glycol with molecular weight of 20000, cross-linking products of alcohol hydroxyl on the surface of α -cyclodextrin and ethylene, polyvinylidene fluoride end-capped molecules with molecular weight of 100000 and cobalt ions.
The polyrotaxane type diaphragm simultaneously meets the following requirements: the melting point is 230 ℃, the porosity is 82%, the liquid absorption rate is 95%, and the maximum tensile strength is 6.33 MPa; in LiPF6Concentration 1.0 mol L-1In the mixed electrolyte of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (weight)Conductivity ratio 1:1: 1) of 6X 10-3S cm-1The electrochemical stability window is 2-5.1V (vs. Li)+/Li).
The preparation method of the organic metal framework polyrotaxane type diaphragm comprises the following steps:
the molar ratio of fluorine substitutes of the polyethylene glycol, cyclodextrin type group molecules, polyvinylidene fluoride and cobalt ions is 1:1.2: 2: 0.5.
Respectively dissolving 1 mol of polyethylene glycol fluoro-substitute with the molecular weight of 20000, 1.2 mol of α -cyclodextrin surface alcoholic hydroxyl and ethylene crosslinked product and 2 mol of polyvinylidene fluoride end-capping molecule with the molecular weight of 100000 in N, N-dimethylacetamide solvent to respectively prepare the polyethylene glycol fluoro-substitute, α -cyclodextrin surface alcoholic hydroxyl and ethylene crosslinked product and polyvinylidene fluoride N, N-dimethylacetamide solution, mixing the polyethylene glycol N, N-dimethylacetamide solution with α -cyclodextrin surface alcoholic hydroxyl and ethylene crosslinked product N, N-dimethylacetamide solution, heating and stirring for 48h, allowing linear polyethylene glycol fluoro-substitute to pass through the hydrophobic part in the inner cavity of the cyclodextrin fine group, adding 0.5 mol of cobalt ion N, N-dimethylacetamide solution, refluxing at 120 ℃ for 90 h, cooling to room temperature, adding polyvinylidene fluoride end-capping molecule N, N-dimethylacetamide solution, heating and stirring for 5h, adding 1 mol of cobalt ion N, N-dimethylacetamide solution, stirring for 90 h, vacuum drying to obtain a film, coating, drying the organic metal ion film, and forming a film, and drying to obtain a film, and vacuum casting the film forming.
The liquid battery is prepared by preparing the prepared poly rotaxane type porous film, a battery anode, a battery cathode and an aluminum plastic film into an unsealed quasi-battery cell, vacuumizing the inside of the unsealed quasi-battery cell to rapidly gasify electrolyte in vacuum, and sealing the unsealed quasi-battery cell.
The organic metal frame polyrotaxane type diaphragm can obviously improve the liquid absorption and retention capacity and the high temperature resistance of the diaphragm, and reduces the impedance of the diaphragm in a battery system, so that the electrochemical performance and the safety performance of a battery are improved.
Example 6
The characteristics of the organometallic framework polyrotaxane type separator and the application thereof in the battery described in the embodiment are as follows:
the organic metal framework polyrotaxane type diaphragm consists of sulfur substitute of polyethylene glycol with molecular weight of 10000, β -cyclodextrin, polyvinylidene fluoride-hexafluoropropylene end-capped molecule with molecular weight of 2000000 and praseodymium ions.
The preparation method of the organic metal framework polyrotaxane type diaphragm comprises the following steps:
the molar ratio of the sulfur substitute of the polyethylene glycol, the cyclodextrin type group molecule, the polyvinylidene fluoride-hexafluoropropylene end-capped polymer and the praseodymium ions is 1:1: 3.5: 0.05.
Under the condition of heating and stirring, respectively dissolving 1 mol of 10000-molecular-weight polyethylene glycol sulfur substitute, 1 mol of β -cyclodextrin and 3.5 mol of 2000000-molecular-weight polyvinylidene fluoride-hexafluoropropylene end-capped molecules in an N-methyl pyrrolidone solvent to respectively prepare a polyethylene glycol sulfur substitute, β -cyclodextrin and a polyvinylidene fluoride-hexafluoropropylene N-methyl pyrrolidone solution, respectively mixing the polyethylene glycol sulfur substitute N-methyl pyrrolidone solution with a β -cyclodextrin N-methyl pyrrolidone solution, heating and stirring for 5 hours, allowing linear polyethylene glycol sulfur substitute to pass through an inner cavity hydrophobic part of a cyclodextrin fine group, adding 0.05 mol of praseodymium ion N-methyl pyrrolidone solution, refluxing for 100 hours at 90 ℃, cooling to room temperature, adding the polyvinylidene fluoride-hexafluoropropylene end-capped molecules in the N-methyl pyrrolidone solution, heating and stirring for 22 hours, adding 0.1 mol of polypropylene glycol molecular-weight 500, heating and stirring for 38 hours to obtain a transparent primary solution, drying the primary solution on a glass pore glass, coating, performing vacuum casting on the primary pore glass, and forming a film, and drying the battery to obtain a quasi-pore film, wherein the battery is prepared by vacuum casting, and the battery is prepared by a quasi-hole-sealing.
The invention can obviously improve the liquid absorption and retention capability and the high temperature resistance of the diaphragm, and reduce the impedance of the diaphragm in a battery system, thereby improving the electrochemical performance and the safety performance of the battery.
Example 7
The characteristics of the organic metal frame polyrotaxane electrolyte membrane and the application thereof in the battery are as follows:
the organic metal framework polyrotaxane type diaphragm consists of sulfur substitute of polyethylene glycol with molecular weight of 10000, β -cyclodextrin, polyvinylidene fluoride-hexafluoropropylene end-capped molecule with molecular weight of 2000000, silver ions and lithium hexafluorophosphate.
The polyrotaxane type diaphragm simultaneously meets the following requirements: the melting point is 290 ℃, the porosity is 30%, the liquid absorption rate is 10%, and the maximum tensile strength is 15 MPa; in LiPF6Concentration 1.0 mol L-1The mixed electrolyte of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (weight ratio is 1:1: 1) has the conductivity of 2 multiplied by 10-4S cm-1The electrochemical stability window is 2-4.6V (vs. Li)+/Li).
The preparation method of the organic metal framework polyrotaxane type diaphragm comprises the following steps:
the molar ratio of the sulfur substitute of the polyethylene glycol, the cyclodextrin group molecule, the polyvinylidene fluoride-hexafluoropropylene end-capped polymer and the silver ion is 1:1: 0.5: 0.03.
Respectively dissolving 1 mol of 10000-polyethylene glycol sulfur substitute with molecular weight, 1 mol of β -cyclodextrin and 0.5 mol of 2000000 polyvinylidene fluoride-hexafluoropropylene end capping molecules in an N-methyl pyrrolidone solvent under the conditions of heating and stirring to respectively prepare a polyethylene glycol sulfur substitute, β -cyclodextrin and a polyvinylidene fluoride-hexafluoropropylene N-methyl pyrrolidone solution, mixing the polyethylene glycol sulfur substitute N-methyl pyrrolidone solution with a β -cyclodextrin N-methyl pyrrolidone solution, heating and stirring for 5 hours, enabling the linear polyethylene glycol sulfur substitute to penetrate through an inner cavity hydrophobic part of a cyclodextrin type group, adding 0.03 mol of silver ion N-methyl pyrrolidone solution, refluxing for 1 hour at 180 ℃, cooling to room temperature, adding the polyvinylidene fluoride-hexafluoropropylene end capping molecules N-methyl pyrrolidone solution, heating and stirring for 22 hours, adding 1 mol of lithium hexafluorophosphate, heating and stirring for 38 hours until the solution is transparent to obtain a solution, placing the solution on a glass plate, drying a vacuum wheel casting frame, and assembling a solid electrolyte casting battery to obtain an organometallic lithium hexafluorophosphate diaphragm.
The solid-state battery is prepared by preparing an organic metal frame poly rotaxane electrolyte diaphragm, a battery anode, a battery cathode and an aluminum plastic film into an unsealed quasi-battery cell, vacuumizing the inside of the unsealed quasi-battery cell to rapidly gasify electrolyte in vacuum, and sealing the unsealed quasi-battery cell.
The organic metal frame polyrotaxane type diaphragm can obviously improve the liquid absorption and retention capacity and the high temperature resistance of the diaphragm, and reduces the impedance of the diaphragm in a battery system, so that the electrochemical performance and the safety performance of the battery are improved.
Example 8
The characteristics of the organometallic framework polyrotaxane electrolyte membrane and the application thereof in the battery described in the embodiment are as follows:
the poly rotaxane electrolyte membrane of the organic metal framework polyethylene glycol consists of polyvinyl alcohol with the molecular weight of 5000, α -cyclodextrin, polyvinylidene fluoride end-capped molecules with the molecular weight of 80000, cerium ions and lithium bis (fluorosulfonyl) imide.
The polyrotaxane type diaphragm simultaneously meets the following requirements: the melting point is 290 ℃, the porosity is 82%, the liquid absorption rate is 55%, and the maximum tensile strength is 11 MPa; in LiPF6Concentration 1.0 mol L-1The mixed electrolyte of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate (weight ratio 1:1: 1) has an electric conductivity of 1.9X 10-3S cm-1The electrochemical stability window is 2-5V (vs. Li)+/Li）。
The preparation method of the organic metal framework polyrotaxane type diaphragm comprises the following steps:
the molar ratio of the polyvinyl alcohol to the cyclodextrin group molecules to the polyvinylidene fluoride end-capped polymer to the cerium ions is 1:2:0.5: 0.22.
Under the condition of heating and stirring, 1 mol of polyvinyl alcohol with the molecular weight of 5000, 2 mol of α -cyclodextrin and 0.5 mol of polyvinylidene fluoride end-capped molecules with the molecular weight of 80000 are respectively dissolved in N, N-dimethylacetamide solution to respectively prepare polyvinyl alcohol, α -cyclodextrin and polyvinylidene fluoride end-capped N, N-dimethylacetamide solution, the N, N-dimethylacetamide solution of the polyvinyl alcohol and the N, N-dimethylacetamide solution of α -cyclodextrin are mixed and heated and stirred for 28h, linear polyvinyl alcohol penetrates through the inner cavity hydrophobic part of a cyclodextrin group, 0.22 mol of cerium ion is added in the N, N-dimethylacetamide solution, the mixture is refluxed for 100h at 120 ℃ and cooled to room temperature, the N, N-dimethylacetamide solution of the polyvinylidene fluoride is added for end capping, the mixture is heated and stirred for 5h, 1 mol of bis (fluorosulfonyl) imide lithium is added, the mixture is heated and stirred for 18h until organic metal is in a transparent solution to obtain a film, the film forming solution is formed on a glass plate, vacuum drying is carried out to obtain a poly rotaxane frame electrolyte membrane assembly and a solid flow casting electrolyte membrane is assembled.
The solid-state battery is assembled by soaking the prepared organic metal frame poly rotaxane type electrolyte diaphragm in electrolyte for 10 hours, and sucking the electrolyte on the surface of the diaphragm. The invention can obviously improve the liquid absorption and retention capability and the high temperature resistance of the diaphragm, and reduce the impedance of the diaphragm in a battery system, thereby improving the electrochemical performance and the safety performance of the battery.
Claims (8)
1. An organometallic framework polyrotaxane-type separator characterized in that:
the organic metal frame poly-rotaxane type diaphragm is a poly-rotaxane type liquid battery diaphragm and a poly-rotaxane type electrolyte diaphragm;
the organic metal framework polyrotaxane type diaphragm consists of a linear polymer, cyclodextrin type group molecules and an end-capped polymer, and the linear polymer penetrates through the hydrophobic part of the inner cavity of the cyclodextrin type group;
the organic metal framework polyrotaxane type diaphragm simultaneously meets the following requirements: the melting point is in the range of 185-290 ℃, the porosity is in the range of 30-82%, the liquid absorption rate is in the range of 10-95%, and the maximum tensile strength is in the range of 6.33-15 MPa;
the organic metal framework polyrotaxane type diaphragm simultaneously meets the following requirements: in LiPF6The concentration is 1.0 mol L-1The mixed electrolyte of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate with the weight ratio of 1:1:1 has the conductivity of 2 multiplied by 10-4～6×10-3S cm-1In the range of (1), the electrochemical stability window is 2 to 5.1V (vs. Li)+/Li).
2. The organic metal frame polyrotaxane type separator according to claim 1, wherein the polyrotaxane type liquid battery separator is composed of a linear polymer, a cyclodextrin type radical molecule, a terminal polymer, and a metal ion capable of forming an organic metal frame with a hydroxyl group, wherein:
(1) the linear polymer is polyethylene glycol, polyvinyl alcohol and polypropylene glycol, or the substitutes of sulfur, chlorine or fluorine of the polyethylene glycol, the polyvinyl alcohol and the polypropylene glycol;
(2) the molar ratio of the linear polymer, the cyclodextrin group molecule, the end-capping polymer and the metal ions capable of forming an organic metal framework with hydroxyl is within the range of 1 (0.1-5): 0.001-1;
(3) the molecule of the cyclodextrin type group is α, β or gamma-type cyclodextrin, or reaction products of etherification, esterification, oxidation, crosslinking and the like of alcoholic hydroxyl on the surface of the cyclodextrin, or chlorine and fluorine substitutes of the cyclodextrin;
(4) the end-capped polymer is polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene or polymethyl methacrylate;
(5) the molecular weight of the linear polymer is within the range of 3000-100000; the molecular weight of the end-capped polymer is 50000-2000000;
(6) the preparation method of the polyrotaxane type liquid battery diaphragm comprises the following steps:
respectively dissolving the linear polymer, the molecules of the cyclodextrin type group and the end-capped polymer in a liquid solvent under the conditions of heating and stirring to respectively prepare liquid solutions of the linear polymer, the molecules of the cyclodextrin type group and the end-capped polymer; mixing the liquid solution of the linear polymer with the liquid solution of the molecules of the cyclodextrin type group, and heating and stirring for 5-48 h; the linear polymer penetrates through the inner cavity hydrophobic part of the cyclodextrin group; adding a liquid solution of metal ions capable of forming an organic metal framework with hydroxyl, refluxing for 1-100 h at a temperature of 90-180 ℃, and cooling to room temperature; adding a liquid solution of the end-capped polymer, heating and stirring for 5-48 h; adding a pore-forming agent; heating and stirring for 5-48 h; until the solution is transparent, obtaining a casting solution; casting the casting solution on a glass plate to form a film; vacuum drying to obtain a primary film; soaking the primary film in deionized water, performing ultrasonic treatment to form a hole on the primary film, and performing vacuum drying again to obtain a polyrotaxane type liquid battery diaphragm; and assembling the prepared polyrotaxane type liquid battery diaphragm into a liquid battery.
3. The organic metal framework polyrotaxane-type separator according to claim 1, wherein the polyrotaxane-type electrolyte membrane is composed of a linear polymer, a cyclodextrin-type radical molecule, a capping polymer, a lithium salt and a metal ion capable of forming an organic metal framework with a hydroxyl group, wherein:
(1) the linear polymer is polyethylene glycol, polyvinyl alcohol and polypropylene glycol, or the substitutes of sulfur, chlorine or fluorine of the polyethylene glycol, the polyvinyl alcohol and the polypropylene glycol;
(2) the molar ratio of the linear polymer, the cyclodextrin group molecule, the end-capping polymer and the metal ions capable of forming an organic metal framework with hydroxyl is within the range of 1 (0.1-5): 0.001-1;
(3) the cyclodextrin type group molecule is α, β or gamma-type cyclodextrin, or reaction products of etherification, esterification, oxidation, crosslinking and the like of alcohol hydroxyl on the surface of cyclodextrin, or chlorine and fluorine substitutes of cyclodextrin;
(4) the end-capped polymer is polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene or polymethyl methacrylate;
(5) the molecular weight of the linear polymer is within the range of 3000-100000; the molecular weight of the end-capped polymer is 50000-2000000;
(6) the preparation steps of the polyrotaxane electrolyte membrane are as follows:
respectively dissolving the linear polymer, the molecules of the cyclodextrin type group and the end-capped polymer in a liquid solvent under the conditions of heating and stirring to respectively prepare liquid solutions of the linear polymer, the molecules of the cyclodextrin type group and the end-capped polymer; mixing the liquid solution of the linear polymer with the liquid solution of the molecules of the cyclodextrin type group, and heating and stirring for 5-48 h; the linear polymer penetrates through the inner cavity hydrophobic part of the cyclodextrin group; adding a liquid solution of metal ions capable of forming an organic metal framework with hydroxyl, refluxing for 1-100 h at a temperature of 90-180 ℃, and cooling to room temperature; adding a liquid solution of the end-capped polymer, heating and stirring for 5-48 h; adding lithium salt; heating and stirring for 5-48 h; until the solution is transparent, obtaining a casting solution; casting the casting solution on a glass plate to form a film; vacuum drying to obtain a polyrotaxane type electrolyte diaphragm; and assembling the prepared poly rotaxane type electrolyte diaphragm into a solid-state battery.
4. The organic metal frame polyrotaxane type membrane according to claim 2, wherein the pore-forming agent is polyethylene glycol, polyvinyl alcohol, polypropylene glycol having a molecular weight of 100 to 1000, or a sulfur, chlorine or fluorine substituent of polyethylene glycol, polyvinyl alcohol, polypropylene glycol.
5. The organic metal frame polyrotaxane type separator according to claim 2 or 3, wherein the liquid solvent is dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide, cyclohexanone, or butanone.
6. The organic metal framework polyrotaxane type separator according to claim 3, wherein the lithium salt is lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate or lithium tetrafluoroborate.
7. The organic metal frame polyrotaxane type separator according to claim 2 or 3, wherein the metal ion capable of forming an organic metal frame with a hydroxyl group is titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, tin, silver or a rare earth ion.
8. Use of the inorganic additive polyrotaxane-type separator according to claim 1 in battery assembly, characterized in that:
(1) the preparation steps of the liquid battery are as follows: soaking the prepared poly rotaxane type liquid battery diaphragm in electrolyte for 2-10 h, sucking the electrolyte on the surface of the diaphragm, assembling the liquid battery, or preparing the poly rotaxane type liquid battery diaphragm, a battery anode, a battery cathode and an aluminum plastic film into an unsealed quasi-battery cell, vacuumizing the inside of the unsealed quasi-battery cell to quickly gasify the electrolyte in vacuum, sealing the unsealed quasi-battery cell, and assembling the liquid battery;
(2) the preparation steps of the solid-state battery are as follows: soaking the prepared poly-rotaxane type electrolyte membrane in electrolyte for 2-10 h, sucking the electrolyte on the surface of the membrane, assembling a solid-state battery, or preparing the poly-rotaxane type electrolyte membrane, a battery anode, a battery cathode and an aluminum plastic membrane into an unsealed quasi-battery cell, vacuumizing the inside of the unsealed quasi-battery cell, rapidly gasifying the electrolyte in vacuum, sealing the unsealed quasi-battery cell, and assembling the solid-state battery.
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