CN110994020B - Dual-functional self-healing polymer electrolyte and preparation method thereof - Google Patents
Dual-functional self-healing polymer electrolyte and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a difunctional self-healing polymer electrolyte, which comprises polyethylene glycol with double bonds, a cross-linking agent with disulfide bonds, an initiator and a chain transfer agent; wherein the disulfide-bonded cross-linking agent has both disulfide bonds and hydrogen bonds. The invention also provides a preparation method of the difunctional self-healing polymer electrolyte, which comprises the following steps: s1: reacting a monomer with double bonds with a monomer with disulfide bonds in a first solution to obtain a crosslinking agent with disulfide bonds; s2: dissolving the cross-linking agent with the disulfide bond and polyethylene glycol with double bonds in a second solvent, adding an initiator and a chain transfer reagent, deoxidizing, and heating to react to obtain a PEG-SS copolymer; s3: and dissolving the PEG-SS copolymer in a third solvent, adding lithium salt, uniformly stirring, pouring the mixed solution into a film, and drying to obtain the bifunctional self-healing polymer electrolyte. The cross-linking agent with the disulfide bond simultaneously has the disulfide bond and the hydrogen bond, and realizes the self-healing of the electrolyte material at room temperature.
Description
Technical Field
The invention belongs to the technical field of polymer electrolytes, and particularly relates to a bifunctional self-healing polymer electrolyte and a preparation method thereof.
Background
Since the end of the 20 th century, the first commercial release of lithium ion batteries began to rapidly evolve over the twenty years. The energy-saving battery has the advantages of high energy density, low discharge rate and the like, and is widely used in daily electronic equipment such as computers, mobile phones and the like. However, the conventional lithium ion battery may cause damage and damage to the electrodes and the electrolyte during collision and bending due to external force, which may seriously affect the electrochemical performance of the battery itself, and even cause great safety hazard. Therefore, the solid electrolyte replaces the liquid electrolyte, and the self-healing function is introduced, so that a series of potential safety hazards caused by the liquid electrolyte can be effectively solved, and the service cycle of the lithium ion battery is prolonged.
The dynamic cross-linking effect of hydrogen bonds is introduced into the polymer, so that excellent mechanical properties and self-healing effect can be realized. The introduction of the hydrogen bond can lead the polymer to form the hydrogen bond again through the self interface functional group when the polymer is damaged or destroyed, thereby realizing the rapid self-healing function. However, the function of the hydrogen bonding system at room temperature is difficult to be expected, and the bonding force at room temperature is weak, and the function of the hydrogen bonding system at high temperature is destroyed, so that the mechanical property and the self-healing capability of the polymer electrolyte are seriously affected, and the performance of the lithium ion battery is poor.
Disclosure of Invention
In view of the above drawbacks or needs for improvement in the prior art, the present invention provides a method for introducing disulfide bonds into a polymer, wherein a disulfide-bonded cross-linking agent has both disulfide bonds and hydrogen bonds, and self-healing of an electrolyte material at room temperature is achieved.
In order to achieve the above object, the present invention provides a bifunctional self-healing polymer electrolyte comprising polyethylene glycol with double bonds, a cross-linking agent with disulfide bonds, an initiator, and a chain transfer agent; wherein the cross-linking agent with the disulfide bond simultaneously has the disulfide bond and the hydrogen bond, and the disulfide bond and the hydrogen bond have a self-healing function.
Further, the disulfide bond is self-healed by a dynamic exchange reaction having the following structural formula:
according to another aspect of the present invention, there is provided a method for preparing the bifunctional self-healing polymer electrolyte, comprising the steps of:
s1: reacting a monomer with double bonds with a monomer with disulfide bonds in a first solution, and obtaining a cross-linking agent with disulfide bonds through a nucleophilic addition reaction;
s2: dissolving the cross-linking agent with the disulfide bond and the polyethylene glycol with the double bond obtained in the step S1 in a second solvent, adding an initiator and a chain transfer reagent, removing oxygen, and heating to react to obtain a PEG-SS copolymer;
s3: and (3) dissolving the PEG-SS copolymer obtained in the S2 in a third solvent, adding lithium salt, uniformly stirring, pouring the mixed solution into a film, and drying to obtain the bifunctional self-healing polymer electrolyte.
Further, in step S1, the double-bond monomer is 2-isocyanoethyl acrylate or isocyanoethyl methacrylate, and the molecular structural formulas are:
further, in step S1, the monomer with disulfide bond is one or more of cystamine dihydrochloride, bis (2-hydroxyethyl) disulfide, 4 '-diaminodiphenyl disulfide, and 4,4' -dihydroxydiphenyl disulfide, and the molecular structural formulas are respectively:
further, in step S1, the molar ratio of the double bond-containing monomer to the disulfide bond-containing monomer is 1:6 to 1: 2.
Further, in step S2, the double-bonded polyethylene glycol is methoxypolyethylene glycol acrylate PEGA or polyethylene glycol methyl ether methacrylate PEGMA, and the structural formulas are respectively:
wherein n is 7-45.
In step S2, the molar ratio of the double-bond polyethylene glycol to the disulfide bond-containing cross-linking agent is 100 (10-40).
Further, in step S3, the lithium salt is selected from one or more of lithium perchlorate, lithium bis (trifluoromethyl) sulfonyl imide, lithium bis (fluoro) sulfonyl imide, lithium tetrafluoroborate and lithium hexafluorophosphate; the molar ratio of the lithium salt to the Ethylene Oxide (EO) chain segment in the PEG-SS copolymer is 1: 8-1: 25.
Further, the first solvent, the second solvent and the third solvent are one or more of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) according to the bifunctional self-healing polymer electrolyte, the disulfide bonds are introduced into the polymer, and the cross-linking agent with the disulfide bonds simultaneously has the disulfide bonds and the hydrogen bonds, so that on one hand, the disulfide bonds have low bond energy and can perform reversible exchange dynamic equilibrium reaction under a mild condition, on the other hand, external stimulation is not needed, translocation of disulfide can also occur, and self-healing of the electrolyte material at room temperature is realized.
(2) The difunctional self-healing polymer electrolyte not only solves the problem of battery damage caused by collision or external force bending of the lithium ion battery, but also enables the lithium ion battery to be self-healed at room temperature without external stimulation.
(3) The preparation method of the bifunctional self-healing polymer electrolyte provided by the invention comprises the step of crosslinking the prepared crosslinking agent with the disulfide bond with PEGA or PEGMA to obtain the PEG-SS copolymer. Compared with the prior art, the copolymer PEG-SS has better self-healing effect, and the mechanical property, the self-healing effect and the electrochemical property of the polymer electrolyte are improved.
(4) The preparation method of the bifunctional self-healing polymer electrolyte selects PEGA or PEGMA with different molecular weights to react with different cross-linking agents with disulfide bonds, then pre-polymers with different molecular weights and cross-linking agents with different structures with disulfide bonds are cross-linked to form a polymer cross-linking network, and then the molar ratio, the reaction temperature and the reaction time among substances in the reaction process are optimized, so that the reaction activity is maximized, and the reaction yield is maximized.
Drawings
Fig. 1 is a graph of the conductivity of a bifunctional self-healing polymer electrolyte membrane according to example 1 of the present invention as a function of temperature;
fig. 2 is a diagram of an electrochemical stability window of the bifunctional self-healing polymer electrolyte membrane according to example 1 of the present invention;
fig. 3 is a battery cycle performance diagram of the bifunctional self-healing polymer electrolyte membrane according to example 1 of the present invention;
fig. 4 is a diagram of a self-healing process after the cut of the bifunctional self-healing polymer electrolyte membrane according to example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a bifunctional self-healing polymer electrolyte which is characterized by comprising polyethylene glycol with double bonds, a cross-linking agent with disulfide bonds, an initiator and a chain transfer reagent; the cross-linking agent with the disulfide bond has the disulfide bond and a hydrogen bond simultaneously, and the disulfide bond and the hydrogen bond have a self-healing function. The disulfide bonds self-heal by dynamic exchange reactions, the structural formula of which is as follows:
the invention also provides a preparation method of the difunctional self-healing polymer electrolyte, which comprises the following steps:
s1: reacting a monomer with double bonds with a monomer with disulfide bonds in a first solution, and obtaining a cross-linking agent with disulfide bonds through a nucleophilic addition reaction;
s2: dissolving the cross-linking agent with the disulfide bond and the polyethylene glycol with the double bond obtained in the step S1 in a second solvent, adding an initiator and a chain transfer reagent, removing oxygen, and heating to react to obtain a PEG-SS copolymer;
s3: and (3) dissolving the PEG-SS copolymer obtained in the S2 in a third solvent, adding lithium salt, uniformly stirring, pouring the mixed solution into a film, and drying to obtain the bifunctional self-healing polymer electrolyte.
Wherein the first solvent is one or more of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone, the second solvent is one or more of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone, and the third solvent is one or more of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the solvents are all aprotic solvents and have good solubility and proton binding capacity.
Specifically, in step S1, the double-bond monomer is 2-isocyanoethyl acrylate or isocyanoethyl methacrylate, and the molecular structural formulas are respectively:
the two isocyanates differ in their reactivity with respect to the reaction by the presence of a methyl group.
Further, the monomer with disulfide bond is cystamine dihydrochloride, bis (2-hydroxyethyl) disulfide, 4 '-diaminodiphenyl disulfide, 4' -dihydroxydiphenyl disulfide, and the molecular structural formulas are respectively:
wherein, 2-isocyano ethyl acrylate or isocyano ethyl methacrylate is isocyanate, cystamine dihydrochloride and 4,4' -diamino diphenyl disulfide are monomers containing amino, ureido generated by the reaction of amino and isocyanate has hydrogen bond function, and the reaction of the monomers with amino and isocyanate does not need to use a catalyst; in addition, bis (2-hydroxyethyl) disulfide and 4,4' -dihydroxydiphenyl disulfide are hydroxyl group-containing monomers, the urethane group formed by the reaction of hydroxyl groups with isocyanate has a hydrogen bonding effect, and a catalyst is required for the reaction of the hydroxyl group-containing monomers with isocyanate, and the catalyst is preferably dibutyltin dilaurate. Monomers with disulfide bonds affect their mechanical properties due to their presence or absence of a benzene ring and further affect self-healing properties.
Further, the molar ratio of the monomer with the double bond to the monomer with the disulfide bond is 1: 6-1: 2; the temperature of the reaction of the monomer with the double bond and the monomer with the disulfide bond in the first solvent is 25-80 ℃, and the reaction lasts for 1-18 h under the stirring action. At the above molar ratio and reaction range, the reaction activity is maximized and the yield is maximized.
In addition, in step S1, the initiator is azobisisobutyronitrile; the chain transfer reagent is 2-cyano-2-propylbenzene disulfide.
Further, in step S2, the double-bonded polyethylene glycol is methoxypolyethylene glycol acrylate PEGA or methoxypolyethylene glycol methacrylate PEGMA, and the structural formulas are respectively:
wherein n is 7-45; polyethylene glycols with double bonds are different in reactivity depending on whether they carry a methyl group or not. The molecular weight of the polyethylene glycol with double bonds is 500-2000.
Further, the molar ratio of the polyethylene glycol with double bonds to the cross-linking agent with disulfide bonds is 100 (10-40); the conditions for the reaction of the two in the second solvent are as follows: stirring and reacting for 14-24 h at 60-120 ℃, wherein the reaction activity is the largest and the yield is the highest under the condition of the above molar ratio and reaction range.
In addition, in step S2, the introduced protective gas is argon or nitrogen.
In step S3, the lithium salt is selected from one or more of lithium perchlorate, lithium bis (trifluoromethyl) sulfonyl imide, lithium bis (fluoro) sulfonyl imide, lithium tetrafluoroborate and lithium hexafluorophosphate; the molar ratio of the lithium salt to the Ethylene Oxide (EO) chain segment in the PEG-SS copolymer is 1: 8-1: 25. The addition of the lithium salt can electrolyze lithium ions in the solution, and the lithium ions can be continuously combined and dissociated with the ethylene oxide EO chain segment.
The difunctional self-healing polymer electrolyte provided by the invention has the advantages that the disulfide bonds are introduced into the polymer to prepare the self-healing electrolyte material, and the introduction of the disulfide bonds is an effective method for prolonging the service life and improving the stability of the material. It offers the possibility for the self-healing properties of the material, firstly because the bond energy of the disulfide bonds is low and it can undergo reversible exchange dynamic equilibrium reactions under mild conditions, and secondly, without external stimuli, metathesis of the disulfide can also occur, which offers the possibility for the self-healing of the electrolyte material at room temperature. It can be seen that self-healing materials with reversible covalent bonds are prepared by introducing disulfide bonds into the material through its reversible dynamic equilibrium. The service life of the material is prolonged better, and the safety of the material is improved.
The difunctional self-healing polymer electrolyte not only solves the problem of battery damage caused by collision or external force bending of the lithium ion battery, but also enables the lithium ion battery to be self-healed at room temperature without external stimulation. The method emphasizes self-healing and repairing of damaged lithium ion batteries, and translocation can also occur without external stimulation by utilizing dynamic exchange reaction of disulfide bonds, thereby providing possibility for self-healing.
The preparation method of the bifunctional self-healing polymer electrolyte comprises the step of crosslinking the prepared crosslinking agent with the disulfide bond with PEGA or PEGMA to obtain the PEG-SS copolymer. Compared with the prior art, the copolymer PEG-SS has better self-healing effect, and the mechanical property, the self-healing effect and the electrochemical property of the polymer electrolyte are improved.
In the preparation process of the difunctional self-healing polymer electrolyte, PEGA or PEGMA with different molecular weights and different cross-linking agents with disulfide bonds are cross-linked with the prepolymers with different molecular weights and the cross-linking agents with different structures and disulfide bonds to form a polymer cross-linking network, so that on one hand, the prepolymers with different molecular weights have great influence on the conductivity and the mechanical property of a polymer material; on the other hand, among different cross-linking agents with disulfide bonds, cystamine dihydrochloride, bis (2-hydroxyethyl) disulfide, 4 '-diaminodiphenyl disulfide, or 4,4' -dihydroxydiphenyl disulfide also have different self-healing properties with respect to self-healing materials, so that the optimum self-healing electrolyte material was studied, and the amount of experimental chemicals in the reaction was adjusted to control the experiment.
The following description is given with reference to specific examples:
example 1
The bifunctional self-healing polymer electrolyte comprises a cross-linking agent with a disulfide bond, polyethylene glycol with a double bond, an initiator and a chain transfer reagent, wherein the cross-linking agent with the disulfide bond is obtained by reacting 2-isocyanoethyl acrylate with cystamine dihydrochloride, and the molar ratio of the two is 1: 6; the double-bond polyethylene glycol is polyethylene glycol methyl ether methacrylate, the molecular weight of the polyethylene glycol methyl ether methacrylate is 2000, the molar ratio of the polyethylene glycol methyl ether methacrylate to the cross-linking agent with the disulfide bond is 100:10, lithium perchlorate is added into the self-healing polymer, and the addition amount is 25:1 according to the molar ratio of an ethoxy chain segment in the self-healing polymer to Li ions; the preparation method of the bifunctional self-healing polymer electrolyte in the embodiment is concretely as follows;
s1: reacting 5.5g of 2-isocyanoethyl acrylate with 1.0g of cystamine dihydrochloride in a tetrahydrofuran solvent, stirring for 16 hours at 25 ℃, and performing suction filtration and vacuum drying on a reaction product to obtain a cross-linking agent monomer with a disulfide bond;
s2: dissolving 0.5g of the cross-linking agent with the disulfide bond obtained in the step S1 and 21.6g of polyethylene glycol methyl ether methacrylate with the molecular weight of 2000 in tetrahydrofuran, adding an initiator and a chain transfer reagent, removing oxygen, heating to 60 ℃ under the condition that protective gas is argon, reacting for 18 hours, and drying to obtain a PEG-SS copolymer;
s3: and (3) dissolving the PEG-SS copolymer obtained in the step (S2) in a dimethyl sulfoxide solvent, adding lithium perchlorate, and adding an ethoxy chain segment in the polymer: the molar ratio of Li is 25:1, the mixture is evenly stirred, cast into a film in a mould, dried for 12 hours at room temperature and then dried for 24 hours at 60 ℃, the thickness of the polymer electrolyte film prepared by the method is 50 microns, and the self-healing polymer electrolyte with double functions is obtained.
Fig. 1 shows the lithium ion conductivity of the polymer electrolyte obtained in example 1, where the conductivity is 23 to 100 ℃ with temperature, and the lithium ion conductivity of the polymer electrolyte is calculated to be 7.51 × 10 "5S/cm at 60 ℃ according to a calculation formula of the ionic conductivity, where σ is L/R × a, L is the thickness of the self-healing polymer electrolyte, R is the measured resistance value, and a is the area of the self-healing polymer electrolyte.
FIG. 2 is an electrochemical stability window of the polymer electrolyte obtained in example 1, and the applied voltage was in the range of 0 to 6V, and the most positive potential of the polymer electrolyte was about 5.1V at a scan rate of 1mV/s, indicating that the polymer electrolyte of this example is very stable at high voltages.
Fig. 3 shows that the polymer electrolyte prepared in example 1 is subjected to charge and discharge tests, and according to the present invention, a positive electrode sheet is prepared from a positive electrode material of LiFePO4 according to LiFePO4, carbon black, polyvinylidene fluoride (pvdf) 8:1:1, and the positive electrode sheet is assembled into a Li/polymer electrolyte membrane/LiFePO 4 half cell in a glove box; the cut-off voltage range is 2.5V-4.2V, after standing for 10 hours, the charge and discharge performance is tested under the current density of 0.1C at 60 ℃, and the result is as follows: the specific discharge capacity of the first circle is 142.3mAh/g, and the specific discharge capacity of the first circle reaches 138.3mAh/g after 100 circles, which shows that the battery assembled by using the polymer electrolyte provided by the embodiment has the coulombic efficiency of more than 99%.
FIG. 4 shows that the self-healing property of the polymer electrolyte prepared in example 1 was measured, and the polymer electrolyte was cut into two segments and completely healed after 30 minutes at room temperature.
Example 2
The bifunctional self-healing polymer electrolyte comprises a cross-linking agent with a disulfide bond, polyethylene glycol, an initiator and a chain transfer reagent, wherein the cross-linking agent with the disulfide bond is obtained by reacting isocyanoethyl methacrylate with 4,4 '-diaminodiphenyl disulfide, and the molar ratio of the isocyanoethyl methacrylate to the 4,4' -diaminodiphenyl disulfide is 1: 5; the polyethylene glycol with double bonds is methoxy polyethylene glycol acrylate, the molecular weight of the methoxy polyethylene glycol acrylate is 2000, and the molar ratio of the methoxy polyethylene glycol acrylate to the cross-linking agent with disulfide bonds is 100: 15; adding lithium bis (trifluoromethyl) sulfonyl imide into the self-healing polymer, wherein the addition amount of the lithium bis (trifluoromethyl) sulfonyl imide is 20:1 according to the molar ratio of an ethoxy chain segment to Li ions in the self-healing polymer; the preparation method of the bifunctional self-healing polymer electrolyte in the embodiment is concretely as follows;
s1: 3.1g of isocyano ethyl methacrylate and 1.0g of 4,4' -diaminodiphenyl disulfide react in an N, N-dimethylformamide solvent, the mixture is stirred for 14 hours at the temperature of 30 ℃, and a cross-linking agent monomer with a disulfide bond is obtained after a reaction product is filtered and dried in vacuum;
s2: dissolving 0.5g of the cross-linking agent with the disulfide bond obtained in the step S1 and 9.9g of methoxy polyethylene glycol acrylate with the molecular weight of 2000 in N, N-dimethylformamide, adding an initiator and a chain transfer reagent, removing oxygen, heating to 70 ℃ under the condition that protective gas is argon, reacting for 16 hours, and drying to obtain a PEG-SS copolymer;
s3: dissolving the PEG-SS copolymer obtained in the step S2 in a tetrahydrofuran solvent, adding lithium bis (trifluoromethyl) sulfonyl imide, and adding an ethoxy chain segment: the molar ratio of Li is 20:1, the mixture is evenly stirred, cast into a film in a mould, dried for 12 hours at room temperature and then dried for 24 hours at 60 ℃, the thickness of the polymer electrolyte film prepared by the method is 100 microns, and the self-healing polymer electrolyte with double functions is obtained.
The lithium ion conductivity of the polymer electrolyte provided by the embodiment is 7.13X 10-5S/cm at 60 ℃; the most positive potential of the electrochemical stability window is 5.03V; the specific discharge capacity of the first circle of the battery is 140.1 mAh/g.
Example 3
The bifunctional self-healing polymer electrolyte comprises a cross-linking agent with a disulfide bond, polyethylene glycol with a double bond, an initiator and a chain transfer reagent, wherein the cross-linking agent with the disulfide bond is obtained by reacting isocyanoethyl methacrylate with cystamine dihydrochloride, and the molar ratio of the isocyanoethyl methacrylate to the cystamine dihydrochloride is 1: 4; the polyethylene glycol with double bonds is polyethylene glycol methyl ether methacrylate, the molecular weight of the polyethylene glycol methyl ether methacrylate is 1000, and the molar ratio of the polyethylene glycol methyl ether methacrylate to the cross-linking agent with disulfide bonds is 100: 20; adding lithium bis (fluorosulfonyl) imide into the self-healing polymer, wherein the addition amount of the lithium bis (fluorosulfonyl) imide is 16:1 according to the molar ratio of an ethoxy chain segment to Li ions in the self-healing polymer; the preparation method of the bifunctional self-healing polymer electrolyte in the embodiment is specifically as follows;
s1: reacting 3.6g of isocyano ethyl methacrylate with 1.0g of cystamine dihydrochloride in a tetrahydrofuran solvent, stirring for 16 hours at 30 ℃, filtering and vacuum-drying a reaction product to obtain a cross-linking agent monomer with a disulfide bond;
s2: dissolving 0.5g of the cross-linking agent with the disulfide bond obtained in the step S1 and 5.4g of polyethylene glycol methyl ether methacrylate with the molecular weight of 1000 in N, N-dimethylformamide, adding an initiator and a chain transfer reagent, removing oxygen, heating to 80 ℃ under the condition that protective gas is argon, reacting for 18 hours, and drying to obtain a PEG-SS copolymer;
s3: dissolving the PEG-SS copolymer obtained in the step S2 in a dimethyl sulfoxide solvent, adding lithium bis (fluorosulfonyl) imide, and adding an ethoxy chain segment in the polymer: the molar ratio of Li is 16:1, the mixture is evenly stirred, cast into a film in a mould, dried for 12 hours at room temperature and then dried for 24 hours at 60 ℃, the thickness of the polymer electrolyte membrane prepared by the method is 200 microns, and the self-healing polymer electrolyte with double functions is obtained.
The lithium ion conductivity of the polymer electrolyte provided by the embodiment is 5.74X 10-5S/cm at 60 ℃; the most positive potential of the electrochemical stability window is 4.93V; the specific discharge capacity of the first circle of the battery is 138.5 mAh/g.
Example 4
The bifunctional self-healing polymer electrolyte comprises a cross-linking agent with a disulfide bond, polyethylene glycol with a double bond, an initiator and a chain transfer reagent, wherein the cross-linking agent with the disulfide bond is obtained by reacting 2-isocyanoethyl acrylate and 4,4' -diaminodiphenyl disulfide, and the molar ratio of the two is 1: 3; the polyethylene glycol with double bonds is methoxy polyethylene glycol acrylate, the molecular weight of the methoxy polyethylene glycol acrylate is 1000, and the molar ratio of the methoxy polyethylene glycol acrylate to the cross-linking agent with disulfide bonds is 100: 25; adding lithium tetrafluoroborate into the self-healing polymer, wherein the addition amount of the lithium tetrafluoroborate is 12:1 according to the molar ratio of the ethoxy chain segment to the Li ions in the self-healing polymer; the preparation method of the bifunctional self-healing polymer electrolyte in the embodiment is specifically as follows;
s1: reacting 1.9g of 2-isocyano ethyl acrylate with 1.0g of 4,4' -diaminodiphenyl disulfide in an N-methylpyrrolidone solvent, stirring for 14 hours at 45 ℃, and performing suction filtration and vacuum drying on a reaction product to obtain a cross-linking agent monomer with a disulfide bond;
s2: dissolving 0.5g of the cross-linking agent with the disulfide bond obtained in the step S1 and 3.6g of methoxy polyethylene glycol acrylate with the molecular weight of 1000 in N, N-dimethylformamide, adding an initiator and a chain transfer reagent, removing oxygen, heating to 90 ℃ under the condition that protective gas is argon, reacting for 20 hours, and drying to obtain a PEG-SS copolymer;
s3: and (3) dissolving the PEG-SS copolymer obtained in the step S2 in a tetrahydrofuran solvent, adding lithium tetrafluoroborate, and adding an ethoxy chain segment in the polymer: the molar ratio of Li is 12:1, the mixture is evenly stirred, cast into a film in a mould, and then dried for 12 hours at room temperature and then dried for 24 hours at 60 ℃, the thickness of the polymer electrolyte film prepared by the method is 100 microns, and the self-healing polymer electrolyte with double functions is obtained.
The lithium ion conductivity of the polymer electrolyte provided by the embodiment is 3.64 multiplied by 10 < -5 > S/cm at 60 ℃; the most positive potential of the electrochemically stable window is 4.7V; the specific discharge capacity of the first circle of the battery is 133.1 mAh/g.
Example 5
The bifunctional self-healing polymer electrolyte comprises a cross-linking agent with a disulfide bond, polyethylene glycol with a double bond, an initiator and a chain transfer reagent, wherein the cross-linking agent with the disulfide bond is obtained by reacting 2-isocyanoethyl acrylate and bis (2-hydroxyethyl) disulfide, and the molar ratio of the two is 1: 4; the polyethylene glycol with double bonds is methoxy polyethylene glycol acrylate, the molecular weight of the methoxy polyethylene glycol acrylate is 500, and the molar ratio of the methoxy polyethylene glycol acrylate to the cross-linking agent with disulfide bonds is 100: 30; adding lithium hexafluorophosphate into the self-healing polymer, wherein the addition amount of the lithium hexafluorophosphate is 20:1 according to the molar ratio of the ethoxy chain segment to the Li ions in the self-healing polymer; the preparation method of the bifunctional self-healing polymer electrolyte in the embodiment is specifically as follows;
s1: reacting 3.7g of 2-isocyanoethyl acrylate, 1.0g of bis (2-hydroxyethyl) disulfide and 0.01g of dibutyltin dilaurate catalyst in a tetrahydrofuran solvent, stirring at 60 ℃ for 4 hours, and performing suction filtration and vacuum drying on a reaction product to obtain a cross-linking agent monomer with a disulfide bond;
s2: dissolving 0.5g of the cross-linking agent with the disulfide bond obtained in the step S1 and 2.1g of methoxy polyethylene glycol acrylate with the molecular weight of 500 in dimethyl sulfoxide, adding an initiator and a chain transfer reagent, removing oxygen, heating to 90 ℃ under the condition that protective gas is nitrogen, reacting for 20 hours, and drying to obtain a PEG-SS copolymer;
s3: dissolving the PEG-SS copolymer obtained in the step S2 in an N-methyl pyrrolidone solvent, adding lithium hexafluorophosphate, and adding the polymer with the following ethoxy chain segment: the molar ratio of Li is 12:1, the mixture is evenly stirred, cast into a film in a mould, dried for 12 hours at room temperature and then dried for 24 hours at 60 ℃, the thickness of the polymer electrolyte film prepared by the method is 150 microns, and the self-healing polymer electrolyte with double functions is obtained.
The lithium ion conductivity of the polymer electrolyte provided by the embodiment is 2.89X 10-5S/cm at 60 ℃; the most positive potential of the electrochemically stable window is 4.61V; the specific discharge capacity of the first circle of the battery is 139.1 mAh/g.
Example 6
The bifunctional self-healing polymer electrolyte comprises a cross-linking agent with a disulfide bond, polyethylene glycol with a double bond, an initiator and a chain transfer reagent, wherein the cross-linking agent with the disulfide bond is obtained by reacting isocyanoethyl methacrylate with 4,4 '-dihydroxy diphenyl disulfide, the molar ratio of the isocyanoethyl methacrylate to the 4,4' -dihydroxy diphenyl disulfide is 1:4, the polyethylene glycol with the double bond is polyethylene glycol methyl ether methacrylate, the molecular weight of the polyethylene glycol methyl ether methacrylate is 1000, and the molar ratio of the polyethylene glycol methyl ether methacrylate to the cross-linking agent with the disulfide bond is 100: 35; adding lithium perchlorate into the self-healing polymer, wherein the addition amount of the lithium perchlorate is 16:1 according to the molar ratio of an ethoxy chain segment to Li ions in the self-healing polymer; the embodiment provides a bifunctional self-healing polymer electrolyte and a preparation method thereof, which are specifically as follows;
s1: reacting 2.5g of isocyano ethyl methacrylate, 1.0g of 4,4' -dihydroxy diphenyl disulfide and 0.01g of dibutyltin dilaurate catalyst in a tetrahydrofuran solvent, stirring at 70 ℃ for 3 hours, and performing suction filtration and vacuum drying on a reaction product to obtain a cross-linking agent monomer with a disulfide bond;
s2: dissolving 0.5g of the cross-linking agent with the disulfide bond obtained in the step S1 and 2.6g of methoxy polyethylene glycol acrylate with the molecular weight of 1000 in dimethyl sulfoxide, adding an initiator and a chain transfer reagent, removing oxygen, heating to 100 ℃ under the condition that protective gas is nitrogen, reacting for 22 hours, and drying to obtain a PEG-SS copolymer;
s3: and (3) dissolving the PEG-SS copolymer obtained in the step (S2) in an N-methylpyrrolidone solvent, adding lithium perchlorate, and adding an ethyoxyl chain segment in the polymer: the molar ratio of Li is 16:1, the mixture is evenly stirred, cast into a film in a mould, dried for 12 hours at room temperature and then dried for 24 hours at 60 ℃, the thickness of the polymer electrolyte membrane prepared by the method is 250 micrometers, and the self-healing polymer electrolyte with double functions is obtained.
The lithium ion conductivity of the polymer electrolyte provided by the embodiment is 5.32X 10-5S/cm at 60 ℃; the most positive potential of the electrochemical stability window is 4.52V; the specific discharge capacity of the first circle of the battery is 131.7 mAh/g.
Example 7
The bifunctional self-healing polymer electrolyte comprises a cross-linking agent with a disulfide bond, polyethylene glycol with a double bond, an initiator and a chain transfer reagent, wherein the cross-linking agent with the disulfide bond is obtained by reacting isocyanoethyl methacrylate with bis (2-hydroxyethyl) disulfide, and the molar ratio of the isocyanoethyl methacrylate to the bis (2-hydroxyethyl) disulfide is 1/2.5; the polyethylene glycol with double bonds is methoxy polyethylene glycol acrylate, the molecular weight of the methoxy polyethylene glycol acrylate is 500, and the molar ratio of the methoxy polyethylene glycol acrylate to the cross-linking agent with disulfide bonds is 100: 40; adding lithium perchlorate into the self-healing polymer, wherein the addition amount of the lithium perchlorate is 12:1 according to the molar ratio of an ethoxy chain segment to Li ions in the self-healing polymer; the preparation method of the bifunctional self-healing polymer electrolyte in the embodiment is specifically as follows;
s1: reacting 2.5g of isocyano ethyl methacrylate, 1.0g of bis (2-hydroxyethyl) disulfide and 0.01g of dibutyltin dilaurate catalyst in a dimethyl sulfoxide solvent, stirring at 80 ℃ for 2 hours, and performing suction filtration and vacuum drying on a reaction product to obtain a cross-linking agent monomer with a disulfide bond;
s2: dissolving 0.5g of the cross-linking agent with the disulfide bond obtained in the step S1 and 1.4g of methoxy polyethylene glycol acrylate with the molecular weight of 500 in dimethyl sulfoxide, adding an initiator and a chain transfer reagent, removing oxygen, heating to 110 ℃ under the condition that protective gas is nitrogen, reacting for 23 hours, and drying to obtain a PEG-SS copolymer;
s3: and (3) dissolving the PEG-SS copolymer obtained in the step (S2) in an N-methylpyrrolidone solvent, adding lithium perchlorate, and adding an ethyoxyl chain segment in the polymer: the molar ratio of Li is 12:1, the mixture is evenly stirred, cast into a film in a mould, and then dried for 12 hours at room temperature and then dried for 24 hours at 60 ℃, the thickness of the polymer electrolyte film prepared by the method is 250 micrometers, and the self-healing polymer electrolyte with double functions is obtained.
The lithium ion conductivity of the polymer electrolyte provided by the embodiment is 1.94 multiplied by 10 < -5 > S/cm at 60 ℃; the most positive potential of the electrochemical stability window is 4.21V; the specific discharge capacity of the first circle of the battery is 129.7 mAh/g.
Example 8
A bifunctional self-healing polymer electrolyte comprises a cross-linking agent with a disulfide bond, polyethylene glycol with a double bond, an initiator and a chain transfer reagent, wherein the cross-linking agent with the disulfide bond is obtained by reacting 2-isocyanoethyl acrylate with 4,4' -dihydroxy diphenyl disulfide, and the molar ratio of the two is 1: 2; the polyethylene glycol with double bonds is polyethylene glycol methyl ether methacrylate, the molecular weight of the polyethylene glycol methyl ether methacrylate is 1000, and the molar ratio of the polyethylene glycol methyl ether methacrylate to the cross-linking agent with disulfide bonds is 100: 35; adding lithium bis (fluorosulfonyl) imide into the self-healing polymer, wherein the addition amount of the lithium bis (fluorosulfonyl) imide is 8:1 according to the molar ratio of an ethoxy chain segment to Li ions in the self-healing polymer; the preparation method of the bifunctional self-healing polymer electrolyte in the embodiment is specifically as follows;
s1: reacting 1.2g of 2-isocyanoethyl acrylate, 1.0g of 4,4' -dihydroxy diphenyl disulfide and 0.01g of dibutyltin dilaurate catalyst in an N, N-dimethylformamide solvent, stirring for 1 hour at 80 ℃, filtering and vacuum drying a reaction product to obtain a crosslinking agent monomer with a disulfide bond;
s2: dissolving 0.5g of the cross-linking agent with the disulfide bond obtained in the step S1 and 2.6g of polyethylene glycol methyl ether methacrylate with the molecular weight of 1000 in dimethyl sulfoxide, adding an initiator and a chain transfer reagent, removing oxygen, heating to 120 ℃ under the condition that protective gas is nitrogen, reacting for 24 hours, and drying to obtain a PEG-SS copolymer;
s3: dissolving the PEG-SS copolymer obtained in the step S2 in an N-methylpyrrolidone solvent, adding lithium bis (fluorosulfonyl) imide, and adding an ethylene oxide segment: the molar ratio of Li is 8:1, the mixture is evenly stirred, cast into a film in a mould, dried for 12 hours at room temperature and then dried for 24 hours at 60 ℃, the thickness of the polymer electrolyte membrane prepared by the method is 200 microns, and the self-healing polymer electrolyte with double functions is obtained.
The lithium ion conductivity of the polymer electrolyte provided by the embodiment is 9.66X 10-6S/cm at 60 ℃; the most positive potential of the electrochemical stability window is 4.45V; the specific discharge capacity of the first circle of the battery is 135.8 mAh/g.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The bifunctional self-healing polymer electrolyte is characterized by comprising polyethylene glycol with double bonds, a cross-linking agent with disulfide bonds, an initiator and a chain transfer agent; wherein the cross-linking agent with the disulfide bond simultaneously has the disulfide bond and the hydrogen bond, and the disulfide bond and the hydrogen bond have a self-healing function.
2. A bifunctional self-healing polymer electrolyte according to claim 1, wherein the disulfide bonds are self-healing via a dynamic exchange reaction having the following structural formula:
3. a method for preparing a bifunctional self-healing polymer electrolyte according to claim 1 or 2, comprising the steps of:
s1: reacting a monomer with double bonds with a monomer with disulfide bonds in a first solution, and obtaining a cross-linking agent with disulfide bonds through a nucleophilic addition reaction;
s2: dissolving the cross-linking agent with the disulfide bond and the polyethylene glycol with the double bond obtained in the step S1 in a second solvent, adding an initiator and a chain transfer reagent, removing oxygen, and heating to react to obtain a PEG-SS copolymer;
s3: and (3) dissolving the PEG-SS copolymer obtained in the S2 in a third solvent, adding lithium salt, uniformly stirring, pouring the obtained mixed solution into a film, and drying to obtain the bifunctional self-healing polymer electrolyte.
4. The method according to claim 3, wherein in step S1, the double-bonded monomer is 2-isocyanoethyl acrylate or isocyanoethyl methacrylate, and the molecular structural formulas are respectively:
5. the method according to claim 3, wherein in step S1, the monomer with disulfide bond is one or more of cystamine dihydrochloride, bis (2-hydroxyethyl) disulfide, 4 '-diaminodiphenyl disulfide, and 4,4' -dihydroxydiphenyl disulfide, and the molecular structural formulas are as follows:
6. the method according to claim 3, wherein in step S1, the molar ratio of the double-bond monomer to the disulfide-bond monomer is 1:6 to 1: 2.
7. The method according to claim 3, wherein in step S2, the double-bonded polyethylene glycol is methoxypolyethylene glycol acrylate PEGA or polyethylene glycol methyl ether methacrylate PEGMA, and the structural formulas are respectively:
wherein n is 7-45.
8. The method according to claim 3, wherein in step S2, the molar ratio of the double-bonded polyethylene glycol to the cross-linking agent with disulfide bonds is 100 (10-40).
9. A method according to claim 3, wherein in step S3, the lithium salt is selected from one or more of lithium perchlorate, lithium bis (trifluoromethyl) sulfonyl imide, lithium bis (fluoro) sulfonyl imide, lithium tetrafluoroborate and lithium hexafluorophosphate.
10. The method for preparing a bifunctional self-healing polymer electrolyte according to any one of claims 3 to 8, wherein the first solvent, the second solvent, and the third solvent are one or more of tetrahydrofuran, dimethylsulfoxide, N-dimethylformamide, and N-methylpyrrolidone.
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| CN113583208A (en) * | 2021-07-14 | 2021-11-02 | 华中科技大学 | Polycaprolactone-based polymer electrolyte with self-repairing and shape memory characteristics and preparation thereof |
| CN113745652B (en) * | 2021-08-17 | 2023-04-04 | 华中科技大学 | Polymer electrolyte based on disulfide bond exchange reaction, preparation and application thereof |
| CN113921822A (en) * | 2021-10-08 | 2022-01-11 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Flexible self-healing deep sea solid-state battery |
| CN113964380A (en) * | 2021-10-15 | 2022-01-21 | 常州大学 | Self-repairing polymer electrolyte capable of being thermally polymerized in situ and preparation method thereof |
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| CN115472910B (en) * | 2022-01-20 | 2023-06-20 | 长虹三杰新能源有限公司 | Overcharge-preventing electrolyte containing electropolymerization crosslinking auxiliary agent and lithium ion battery |
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