CN114292484A - Interpenetrating network structure layer, in-situ preparation method and application thereof - Google Patents
Interpenetrating network structure layer, in-situ preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an interpenetrating network structure layer, an in-situ preparation method and application thereof. This layer may serve as an interfacial buffer layer between the inorganic solid electrolyte and the lithium metal negative electrode, or a polymer electrolyte. Obtaining a polyion liquid (PIL) polymer molecular chain network through ultraviolet irradiation polymerization, then mixing an alkylene oxide monomer with the network to uniformly disperse the alkylene oxide monomer in the network, carrying out ring-opening polymerization reaction to generate a polyether molecular chain network with high molecular weight, and obtaining the polymer electrolyte membrane with an interpenetrating network structure in situ. The interface layer can effectively avoid side reaction caused by contact of inorganic solid electrolyte and lithium metal, and improves the cycle performance of the all-solid-state battery. The in-situ formation of the electrolyte can also obviously improve the compatibility of the electrolyte and the electrode, reduce the interface impedance of the electrolyte and improve the conductivity and mechanical strength of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis and batteries, and particularly relates to an interpenetrating network structure electrolyte interface layer, an in-situ preparation method and application thereof.
Background
In recent years, lithium batteries have attracted much attention because of their advantages such as high energy density, high open circuit voltage, long cycle life, and low self-discharge. At present, the traditional lithium battery uses volatile, easily combustible and easily leaked organic liquid electrolyte, and has larger potential safety hazard. Therefore, the improvement of the safety of the battery is a problem to be solved urgently, and the Solid Electrolyte (SE) has the advantages of thermal stability, nonflammability, no leakage, no volatilization and the like, has a higher thermal runaway starting temperature, and greatly improves the stability and the safety of the battery in the using process.
Development of all-solid-state lithium ion batteries is crucial to the full-force promotion of the development of lithium ion batteries, and solid electrolytes are mainly divided into polymer solid electrolytes and inorganic solid electrolytes, wherein the inorganic solid electrolytes can be divided into oxide solid electrolytes and sulfide solid electrolytes. The polymer electrolyte can replace the traditional organic electrolyte because of the characteristics of high flexibility, light weight, easy processing, low cost and the like, and improves the safety performance of the battery. Meanwhile, the polymer electrolyte can be matched with a lithium metal negative electrode to construct a high-energy-density lithium battery. Inorganic solid electrolytes, particularly sulfide electrolytes, have high ionic conductivity, wide electrochemical window and good stability and are receiving wide attention. However, the inorganic solid electrolyte has poor air stability and interface stability, and has interface problems between the positive electrode and the negative electrode, which limits the development and application of the inorganic solid electrolyte. Interpenetrating network (IPN) is one of the structures commonly used for gel polymer electrolytes and is generally prepared by swelling a second monomer, together with a crosslinking agent and an initiator (or activator), into an already crosslinked polymer i, polymerizing the second monomer in situ and crosslinking to form a polymer ii, which is then interpenetrated in the network of the polymer i. The three-dimensional interpenetrating structure can break the crystallization area of the polymer, improve the mechanical property and the thermal stability of the polymer electrolyte and have good application prospect as an interface material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an interpenetrating network structure electrolyte interface layer, an in-situ preparation method and a battery thereof, and solves the problems in the background art.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the interpenetrating network structure layer is formed by interpenetrating a PIL molecular chain network prepared by ionic liquid polymerization and a polyether molecular chain network with high molecular weight generated by ring-opening polymerization reaction of alkylene oxide monomers.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the application of the interpenetrating network structure layer is provided, and the interpenetrating network structure layer is used as an electrolyte of a solid-state battery or an interface layer between electrodes.
The third technical scheme adopted by the invention for solving the technical problems is as follows: the in-situ preparation method of the interpenetrating network structure layer comprises the following steps:
s1: under the atmosphere of protective gas, mixing ionic liquid, lithium salt and an organic solvent, then adding a photoinitiator, uniformly mixing, carrying out ultraviolet illumination polymerization, and heating to remove the organic solvent to obtain a PIL molecular chain network polymer; adding a mixed solution of an alkylene oxide monomer and a ring-opening polymerization initiator into the PIL molecular chain network polymer, and absorbing the mixed solution to obtain interface layer precursor gel; or the like, or, alternatively,
under the atmosphere of protective gas, uniformly mixing an alkylene oxide monomer and a ring-opening polymerization initiator, standing at room temperature for 20min-20h to obtain polyether molecular chain network gel, and then adding a mixed solution of an ionic liquid, a lithium salt, a photoinitiator and an organic solvent into the gel to absorb the gel to obtain interface layer precursor gel;
s2: and in the protective gas atmosphere, obtaining an inorganic solid electrolyte sheet by a tabletting method, placing the precursor gel on the surface of the inorganic electrolyte sheet, and in-situ preparing the electrolyte interface layer with the interpenetrating network structure by ring-opening polymerization of the precursor.
In a preferred embodiment of the present invention, the ionic liquid is one of 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-vinyl-3-ethylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-vinyl-3-butylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-allyl-3-ethylimidazolium bis (trifluoromethanesulfonyl) imide salt, and 1-allyl-3-butylimidazolium bis (trifluoromethanesulfonyl) imide salt).
In a preferred embodiment of the present invention, the lithium salt includes one of lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluoro-oxalato-borate, and lithium bis-oxalato-borate.
In a preferred embodiment of the present invention, the photoinitiator comprises one of 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexane phenyl ketone, ethyl 4- (N, N-dimethylamino) benzoate, benzophenone, and 4-chlorobenzophenone.
In a preferred embodiment of the present invention, the content of the lithium salt is 2 to 100 mol% of the ionic liquid monomer, and the molar ratio of the lithium salt to the photoinitiator is 1 to 100: 1.
In a preferred embodiment of the present invention, the alkylene oxide monomer comprises at least one of 1, 3-dioxolane, ethylene oxide, propylene oxide, butylene oxide, trimethylolpropane triglycidyl ether, benzyl glycidyl ether, diglycidyl ether, and 1, 4-butanediol diglycidyl ether.
In a preferred embodiment of the present invention, the ring-opening polymerization initiator comprises LiPF6、HF、BF3、PF5、LiFSI、LiBF4One of (1) and (b).
In a preferred embodiment of the present invention, the solid electrolyte of the solid electrolyte layer is selected from at least one of LGPS type inorganic solid electrolyte, garnet type inorganic solid electrolyte, perovskite type inorganic solid electrolyte, LISICON type inorganic solid electrolyte, digermorite type inorganic solid electrolyte, or anti-perovskite type inorganic solid electrolyte.
In a preferred embodiment of the present invention, the organic solvent is one or more of tetrahydrofuran, acetonitrile, acetone, N-dimethylformamide, N-methylpyrrolidone, and the like, and the mass fraction of the organic solvent is 0 to 90%.
The fourth technical scheme adopted by the invention for solving the technical problems is as follows: the all-solid-state battery is assembled by a lamination process according to the sequence of a positive pole piece, an inorganic solid electrolyte piece and a negative pole piece; wherein the interpenetrating network structure layer of claim 1 is applied as an interfacial layer on the surface of the inorganic solid electrolyte sheet.
The fifth technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the button cell is provided, and comprises the following steps:
s1: under the atmosphere of protective gas, mixing ionic liquid, lithium salt and an organic solvent, then adding a photoinitiator, uniformly mixing, introducing into a cellulose membrane, carrying out ultraviolet illumination polymerization, and heating to remove the organic solvent to obtain a PIL molecular chain network polymer; adding a mixed solution of an alkylene oxide monomer and a ring-opening polymerization initiator into the PIL molecular chain network polymer supported by the cellulose membrane, and absorbing the mixed solution to obtain precursor gel;
s2: and assembling the precursor gel into a button cell in the atmosphere of protective gas, placing the assembled button cell at room temperature, and carrying out ring-opening polymerization on the precursor gel to form the electrolyte with an interpenetrating network structure in situ in the button cell.
In a preferred embodiment of the present invention, the ionic liquid is one of 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-vinyl-3-ethylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-vinyl-3-butylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-allyl-3-ethylimidazolium bis (trifluoromethanesulfonyl) imide salt, and 1-allyl-3-butylimidazolium bis (trifluoromethanesulfonyl) imide salt).
In a preferred embodiment of the present invention, the lithium salt includes one of lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluoro-oxalato-borate, and lithium bis-oxalato-borate.
In a preferred embodiment of the present invention, the photoinitiator comprises one of 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexane phenyl ketone, ethyl 4- (N, N-dimethylamino) benzoate, benzophenone, and 4-chlorobenzophenone.
In a preferred embodiment of the present invention, the content of the lithium salt is 2 to 100 mol% of the ionic liquid monomer, and the molar ratio of the lithium salt to the photoinitiator is 1 to 100: 1.
In a preferred embodiment of the present invention, the alkylene oxide monomer comprises at least one of 1, 3-dioxolane, ethylene oxide, propylene oxide, butylene oxide, trimethylolpropane triglycidyl ether, benzyl glycidyl ether, diglycidyl ether, and 1, 4-butanediol diglycidyl ether.
In a preferred embodiment of the present invention, the ring-opening polymerization initiator comprises LiPF6、HF、BF3、PF5、LiFSI、LiBF4One of (1) and (b).
In a preferred embodiment of the present invention, the organic solvent is one or more of tetrahydrofuran, acetonitrile, acetone, N-dimethylformamide, N-methylpyrrolidone, and the like, and the mass fraction of the organic solvent is 0 to 90%.
The sixth technical scheme adopted by the invention for solving the technical problems is as follows: the button cell is prepared by the method, a cellulose membrane is arranged in the cell, and an electrolyte is arranged on the surface layer of the cellulose membrane; the electrolyte comprises an interpenetrating PIL molecular chain network and a polyether molecular chain network.
Compared with the background technology, the technical scheme has the following advantages:
the invention provides an in-situ preparation method of an interpenetrating network structure electrolyte interface layer of polyion liquid and an all-solid-state battery. The amount of solvent in the first network can control the degree of crosslinking of the PIL first network and the mechanical properties of the product and is removed by heating. The all-solid-state battery comprises an inorganic solid electrolyte and an interface buffer layer, strong Lewis acid can be formed in a precursor solution by adding lithium salt, DOL ring-opening polymerization is initiated in situ through a cation mechanism, and the polyionic liquid and the DOL of the ring-opening polymerization are crosslinked with each other to reduce the crystallinity of a polymer and ensure high ionic conductivity. The high ionic conductivity remarkably improves the lithium ion conduction performance of the interface, the interface buffer layer has high mechanical strength, side reactions caused by contact between the inorganic solid electrolyte and the electrode can be effectively inhibited, the growth of lithium dendrites is inhibited, and the cycle performance of the battery is effectively improved.
The organic liquid ether monomer is polymerized in an in-situ mode, so that a continuous and stable interface can be formed between the organic liquid ether monomer and an electrode material, a solvent volatilization step in process production can be avoided, the production cost and complexity are reduced, and the method is suitable for large-scale production.
Drawings
Fig. 1 is a schematic view of the structure of an all-solid-state battery according to example 1; in the figure: 1-metallic lithium cathode, 2-interface layer, 3-inorganic solid electrolyte sheet, and 4-lithium metal anode.
FIG. 2 is a schematic view of the structure of an electrolyte interface layer in example 1.
FIG. 3 shows the results of the example 1 in which the total solid-state battery is operated at 0.2mA/cm2Charge and discharge curves at current density.
FIG. 4 depicts the gel polymer electrolyte and LiFePO of the interpenetrating network of example 44And lithium metal assembled button half cell cycling profiles.
FIG. 5 is an optical photograph of an interpenetrating network gel polymer electrolyte.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following will describe the contents of the present invention in more detail by way of examples, but the scope of the present invention is not limited to these examples.
Example 1
The in-situ preparation method of the interpenetrating network structure electrolyte interface layer comprises the following steps:
(1) preparing an interface layer precursor: under the atmosphere of protective gas, 1g of 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide) (VMImTFSI) and LiTFSI (20 mol%) are mixed firstly, then a photoinitiator 2-hydroxy-2-methyl propiophenone is added and mixed uniformly, the mixture is polymerized by ultraviolet irradiation to obtain polyion liquid (PIL), and then 2mL of 1,3 Dioxolane (DOL) and LiPF6Uniformly mixing the initiator and adding the initiator into the PIL to enable the initiator to be absorbed to obtain interface layer precursor gel;
(2) 200mg of inorganic solid electrolyte Li10GeP2S12Pressing into ceramic sheet with diameter of 12mm, placing the precursor solution on the surface of inorganic electrolyte sheet, standing at room temperature, and passing through LiPF6And (3) initiating cationic polymerization to obtain an electrolyte interface layer with an interpenetrating network structure.
The all-solid-state battery of this example is a lithium symmetrical battery assembled from the above-mentioned inorganic solid-state electrolyte with an electrolyte interface layer and lithium metal.
Fig. 1 is a schematic structural diagram of a lithium symmetric battery of the present embodiment, in which: 1-metallic lithium cathode, 2-interface layer, 3-inorganic solid electrolyte sheet, and 4-lithium metal anode. The inorganic solid electrolyte sheet 3 is Li10GeP2S12The interface layer 2 is arranged between the electrolyte sheet 3 and the lithium metal cathode 1 and between the electrolyte sheet 3 and the lithium metal anode 4, and the interface layer is in a viscous gel state and has better contact with the electrode and the inorganic solid electrolyte sheet.
FIG. 2 is a schematic view of the structure of the electrolyte interface layer in this embodiment.
FIG. 3 shows that the interfacial layer lithium symmetric battery prepared in the embodiment 1 is at 0.2mA/cm2Charge and discharge curves at current density. The initial interface impedance of a symmetrical lithium battery comprising the interface layer is about 85 Ω · cm2In the circulation process, the constant-current electroplating/stripping curve of the interface layer symmetrical lithium battery shows smallerThe polarization voltage (about 45mV) indicates that the interface layer material has good electrochemical stability for lithium metal and better ability to inhibit lithium dendrite growth.
Example 2
This example differs from example 1 in that:
(1) preparing an interface layer precursor: under the atmosphere of protective gas, 1g of 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide) (VMImTFSI) and LiTFSI (60 mol%) are mixed firstly, then a photoinitiator 2-hydroxy-2-methyl propiophenone is added and mixed uniformly, the mixture is polymerized by ultraviolet irradiation to obtain polyion liquid (PIL), and then 2mL of 1,3 Dioxolane (DOL) and LiPF6Uniformly mixing the initiator and adding the initiator into the PIL to enable the initiator to be absorbed to obtain interface layer precursor gel;
(2) 200mg of inorganic solid electrolyte Li10GeP2S12Pressing into ceramic sheet with diameter of 12mm, placing the precursor on the surface of inorganic electrolyte sheet, standing at room temperature, and passing through LiPF6And (3) ring-opening polymerization is initiated to obtain an electrolyte interface layer with an interpenetrating network structure.
(3) The inorganic solid-state electrolyte and lithium metal are assembled into a lithium symmetric battery with an interface layer.
Example 3
This example differs from example 1 in that:
(1) preparing an interface layer precursor: under an atmosphere of protective gas, first 2mL of 1,3 Dioxolane (DOL) and LiPF6Uniformly mixing, standing for 6h, carrying out ring-opening polymerization to obtain a polyether molecular network polymer, uniformly mixing 1g of 1-vinyl-3-butylimidazole bis (trifluoromethanesulfonyl) imide) (VBImTFSI) and LiTFSI (80 mol%), and adding a photoinitiator 2-hydroxy-2-methyl propiophenone into the molecular network polymer, and absorbing to obtain an interface layer precursor gel;
(2) 200mg of inorganic solid electrolyte Li10GeP2S12Pressing into a ceramic wafer with the diameter of 12mm, placing the precursor on the surface of an inorganic electrolyte sheet, and irradiating by ultraviolet light to obtain an electrolyte interface layer with an interpenetrating network structure.
(3) The inorganic solid-state electrolyte and lithium metal are assembled into a lithium symmetric battery with an interface layer.
Example 4
The preparation method of the button cell of the embodiment includes the following steps:
(1) preparing an electrolyte precursor: under the atmosphere of protective gas, 1g of 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide) (VMImTFSI) and LiTFSI (20 mol%) are mixed firstly, then a photoinitiator 2-hydroxy-2-methyl propiophenone is added and mixed uniformly, the solution is introduced onto a cellulose membrane, ultraviolet irradiation polymerization is carried out to obtain polyion liquid (PIL), and then 2mL of 1,3 Dioxolane (DOL) and LiPF (lithium ion exchange resin) are added6Uniformly mixing and adding the mixture into PIL supported by a cellulose membrane, and absorbing the mixture to obtain an electrolyte precursor;
(2) placing the precursor in LiFePO under the atmosphere of protective gas4And (3) assembling the electrode sheet and a lithium metal cathode into a button cell, placing the assembled button cell at room temperature, and preparing the interpenetrating network gel polymer electrolyte in situ by ring-opening polymerization of the precursor.
FIG. 4 depicts the gel polymer electrolyte and LiFePO of the interpenetrating network of example 44And lithium metal assembled button half cell cycle curve chart and previous several circles of charge and discharge curve chart.
Example 5
This example differs from example 2 in that:
(1) preparing an electrolyte precursor: under the atmosphere of protective gas, firstly, mixing 1g of 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide) (VMImTFSI) and LiTFSI (60mol percent), then adding a photoinitiator 2-hydroxy-2-methyl propiophenone, uniformly mixing, introducing the solution onto a cellulose membrane, polymerizing by ultraviolet irradiation to obtain polyion liquid (PIL), then uniformly mixing 2mL of 1,3 Dioxolane (DOL) and LiPF6 initiator, adding the mixture into the PIL supported by cellulose, and absorbing the mixture to obtain an electrolyte precursor;
(2) and (2) placing the precursor on a positive electrode LiFePO4 pole piece in the atmosphere of protective gas, assembling the precursor and a lithium metal negative electrode into a button cell, placing the assembled button cell at room temperature, and performing ring-opening polymerization on the precursor to obtain the interpenetrating network polymer electrolyte in situ.
Example 6
This example differs from example 1 in that:
(1) preparing an interface layer precursor: under the atmosphere of protective gas, 1g of 1-vinyl-3-ethylimidazole bis (trifluoromethanesulfonyl) imide) (VEImTFSI) and LiFSI (60 mol%) are mixed firstly, then a photoinitiator 2-hydroxy-2-methyl propiophenone is added and mixed uniformly, the mixture is polymerized by ultraviolet irradiation to obtain polyion liquid (PIL), and then 2mL of 1,3 Dioxolane (DOL) and LiPF (lithium ion exchange resin)6Uniformly mixing the initiator and adding the initiator into the PIL to enable the initiator to be absorbed to obtain interface layer precursor gel;
(2) 200mg of inorganic solid electrolyte Li10GeP2S12Pressing into a ceramic wafer with the diameter of 12mm, placing the precursor on the surface of an inorganic electrolyte wafer, and standing at room temperature to obtain an electrolyte interface layer with an interpenetrating network structure;
(3) the inorganic solid-state electrolyte and lithium metal are assembled into a lithium symmetric battery with an interface layer.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (21)
1. An interpenetrating network structure layer, characterized in that: the high molecular weight polyether is formed by interpenetrating PIL molecular chain network prepared by ionic liquid polymerization and polyether molecular chain network with high molecular weight generated by ring-opening polymerization reaction of alkylene oxide monomers.
2. The use of an interpenetrating network structure of claim 1 wherein: as an electrolyte for solid-state batteries or as an interfacial layer between electrodes.
3. The method of in situ preparation of an interpenetrating network structure layer according to claim 1, wherein: the method comprises the following steps:
s1: under the atmosphere of protective gas, mixing ionic liquid, lithium salt and an organic solvent, then adding a photoinitiator, uniformly mixing, carrying out ultraviolet illumination polymerization, and heating to remove the organic solvent to obtain a PIL molecular chain network polymer; adding a mixed solution of an alkylene oxide monomer and a ring-opening polymerization initiator into the PIL molecular chain network polymer, and absorbing the mixed solution to obtain interface layer precursor gel; or the like, or, alternatively,
under the atmosphere of protective gas, uniformly mixing an alkylene oxide monomer and a ring-opening polymerization initiator, standing at room temperature for 20min-20h to obtain polyether molecular chain network gel, and then adding a mixed solution of an ionic liquid, a lithium salt, a photoinitiator and an organic solvent into the gel to absorb the gel to obtain interface layer precursor gel;
s2: and in the protective gas atmosphere, obtaining an inorganic solid electrolyte sheet by a tabletting method, placing the precursor gel on the surface of the inorganic electrolyte sheet, and in-situ preparing the electrolyte interface layer with the interpenetrating network structure by ring-opening polymerization of the precursor.
4. The method of claim 1, wherein the interpenetrating network structure layer is prepared in situ, and the method comprises the following steps: the ionic liquid is one of 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-vinyl-3-ethylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-vinyl-3-butylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-allyl-3-ethylimidazolium bis (trifluoromethanesulfonyl) imide salt and 1-allyl-3-butylimidazolium bis (trifluoromethanesulfonyl) imide salt).
5. The method of claim 1, wherein the interpenetrating network structure layer is prepared in situ, and the method comprises the following steps: the lithium salt comprises one of lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluoro-oxalato-borate and lithium bis-oxalato-borate.
6. The method of claim 1, wherein the interpenetrating network structure layer is prepared in situ, and the method comprises the following steps: the photoinitiator comprises one of 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexane phenyl ketone, 4- (N, N-dimethylamino) ethyl benzoate, benzophenone and 4-chlorobenzophenone.
7. The method of claim 1, wherein the interpenetrating network structure layer is prepared in situ, and the method comprises the following steps: the content of the lithium salt is 2-100 mol% of the ionic liquid monomer, and the molar ratio of the lithium salt to the photoinitiator is 1-100: 1.
8. The method of claim 1, wherein the interpenetrating network structure layer is prepared in situ, and the method comprises the following steps: the alkylene oxide monomer comprises at least one of 1, 3-dioxolane, ethylene oxide, propylene oxide, butylene oxide, trimethylolpropane triglycidyl ether, benzyl glycidyl ether, diglycidyl ether and 1, 4-butanediol diglycidyl ether.
9. The method of claim 1, wherein the interpenetrating network structure layer is prepared in situ, and the method comprises the following steps: the ring-opening polymerization initiator includes LiPF6、HF、BF3、PF5、LiFSI、LiBF4One of (1) and (b).
10. The method of claim 1, wherein the interpenetrating network structure layer is prepared in situ, and the method comprises the following steps: the solid electrolyte of the solid electrolyte layer is selected from at least one of LGPS type inorganic solid electrolyte, garnet type inorganic solid electrolyte, perovskite type inorganic solid electrolyte, LISICON type inorganic solid electrolyte, Geranite type inorganic solid electrolyte or anti-perovskite type inorganic solid electrolyte.
11. The method of claim 1, wherein the interpenetrating network structure layer is prepared in situ, and the method comprises the following steps: the organic solvent is one or more of tetrahydrofuran, acetonitrile, acetone, N-dimethylformamide, N-methylpyrrolidone and the like, and the mass fraction of the organic solvent is 0-90%.
12. An all-solid-state battery characterized by: the electrolyte is formed by assembling a positive pole piece, an inorganic solid electrolyte piece and a negative pole piece through a lamination process in sequence; wherein the interpenetrating network structure layer of claim 1 is applied as an interfacial layer on the surface of the inorganic solid electrolyte sheet.
13. A preparation method of button cell is characterized in that: the method comprises the following steps:
s1: under the atmosphere of protective gas, mixing ionic liquid, lithium salt and an organic solvent, then adding a photoinitiator, uniformly mixing, introducing into a cellulose membrane, carrying out ultraviolet illumination polymerization, and heating to remove the organic solvent to obtain a PIL molecular chain network polymer; adding a mixed solution of an alkylene oxide monomer and a ring-opening polymerization initiator into the PIL molecular chain network polymer supported by the cellulose membrane, and absorbing the mixed solution to obtain precursor gel;
s2: and assembling the precursor gel into a button cell in the atmosphere of protective gas, placing the assembled button cell at room temperature, and carrying out ring-opening polymerization on the precursor gel to form the electrolyte with an interpenetrating network structure in situ in the button cell.
14. The method for preparing button cell battery according to claim 13, wherein: the ionic liquid is one of 1-vinyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-vinyl-3-ethylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-vinyl-3-butylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-allyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt), 1-allyl-3-ethylimidazolium bis (trifluoromethanesulfonyl) imide salt and 1-allyl-3-butylimidazolium bis (trifluoromethanesulfonyl) imide salt).
15. The method for preparing button cell battery according to claim 13, wherein: the lithium salt comprises one of lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium difluoro-oxalato-borate and lithium bis-oxalato-borate.
16. The method for preparing button cell battery according to claim 13, wherein: the photoinitiator comprises one of 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexane phenyl ketone, 4- (N, N-dimethylamino) ethyl benzoate, benzophenone and 4-chlorobenzophenone.
17. The method for preparing button cell battery according to claim 13, wherein: the content of the lithium salt is 2-100 mol% of the ionic liquid monomer, and the molar ratio of the lithium salt to the photoinitiator is 1-100: 1.
18. The method for preparing button cell battery according to claim 13, wherein: the alkylene oxide monomer comprises at least one of 1, 3-dioxolane, ethylene oxide, propylene oxide, butylene oxide, trimethylolpropane triglycidyl ether, benzyl glycidyl ether, diglycidyl ether and 1, 4-butanediol diglycidyl ether.
19. The method for preparing button cell battery according to claim 13, wherein: the ring-opening polymerization initiator includes LiPF6、HF、BF3、PF5、LiFSI、LiBF4One of (1) and (b).
20. The method for preparing button cell battery according to claim 12, wherein: the organic solvent is one or more of tetrahydrofuran, acetonitrile, acetone, N-dimethylformamide, N-methylpyrrolidone and the like, and the mass fraction of the organic solvent is 0-90%.
21. A button cell battery, characterized in that: the preparation method is characterized in that a cellulose membrane is arranged in the battery, and an electrolyte is arranged on the surface layer of the cellulose membrane; the electrolyte comprises an interpenetrating PIL molecular chain network and a polyether molecular chain network.
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Cited By (3)
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| CN114583258A (en) * | 2022-04-24 | 2022-06-03 | 浙江金羽新能源科技有限公司 | Solid polymer electrolyte membrane and preparation method and application thereof |
| CN116759639A (en) * | 2023-08-17 | 2023-09-15 | 上海瑞浦青创新能源有限公司 | Semi-solid battery and preparation method thereof |
| CN117430832A (en) * | 2023-12-19 | 2024-01-23 | 北京科技大学 | Multilayer potassium ion gel electrolyte and preparation method thereof |
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| CN110148781A (en) * | 2019-04-22 | 2019-08-20 | 华中科技大学 | A kind of ionic liquid gel electrolyte, preparation method and application |
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| WO2021157278A1 (en) * | 2020-02-07 | 2021-08-12 | 富士フイルム株式会社 | Inorganic-solid-electrolyte-containing composition, sheet for all-solid-state secondary battery, all-solid-state secondary battery, and methods for manufacturing sheet for all-solid-state secondary battery and all-solid-state secondary battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114583258A (en) * | 2022-04-24 | 2022-06-03 | 浙江金羽新能源科技有限公司 | Solid polymer electrolyte membrane and preparation method and application thereof |
| CN114583258B (en) * | 2022-04-24 | 2022-07-29 | 浙江金羽新能源科技有限公司 | Polymer electrolyte membrane and preparation method and application thereof |
| CN116759639A (en) * | 2023-08-17 | 2023-09-15 | 上海瑞浦青创新能源有限公司 | Semi-solid battery and preparation method thereof |
| CN116759639B (en) * | 2023-08-17 | 2023-11-28 | 上海瑞浦青创新能源有限公司 | Semi-solid battery and preparation method thereof |
| CN117430832A (en) * | 2023-12-19 | 2024-01-23 | 北京科技大学 | Multilayer potassium ion gel electrolyte and preparation method thereof |
| CN117430832B (en) * | 2023-12-19 | 2024-03-05 | 北京科技大学 | Multilayer potassium ion gel electrolyte and preparation method thereof |
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| CN114292484B (en) | 2023-04-07 |
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