CN115588778A - Self-healing polymer electrolyte based on dynamic borate bond and preparation and application thereof - Google Patents

Self-healing polymer electrolyte based on dynamic borate bond and preparation and application thereof Download PDF

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CN115588778A
CN115588778A CN202211479024.0A CN202211479024A CN115588778A CN 115588778 A CN115588778 A CN 115588778A CN 202211479024 A CN202211479024 A CN 202211479024A CN 115588778 A CN115588778 A CN 115588778A
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borate
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CN115588778B (en
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周炳华
杨超龙
刘欢欢
邓婷枝
王淑琴
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Jiangxi Normal University
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Abstract

The invention belongs to the technical field of polymer electrolytes, and discloses a self-healing polymer electrolyte based on dynamic borate bonds, and preparation and application thereof. According to the invention, by improving the key chemical structure of the polymer, the proportion between the polymer monomer and the cross-linking agent, the design of the whole process flow of the preparation method and the like, on one hand, the rearrangement of the polymer network can be realized by the dynamic borate ester bond cross-linked network through exchange reaction to endow the electrolyte material with self-healing performance, and the service life of the lithium battery is prolonged; the construction of the chemical crosslinking network can also obviously enhance the mechanical property of the material; on the other hand, by means of the interaction between boron atoms and anions in the boric acid ester bond, lithium ions are promoted to be uniformly distributed on the surface of the lithium metal, and the interface stability of the lithium metal is improved.

Description

Self-healing polymer electrolyte based on dynamic borate bond and preparation and application thereof
Technical Field
The invention relates to the technical field of polymer electrolytes, in particular to a self-healing polymer electrolyte based on dynamic borate bonds, and preparation and application thereof.
Background
The lithium ion battery has the advantages of high energy density, large output power, long cycle life, environmental friendliness and the like, and becomes a main energy storage component of a flexible electronic device. The commercialized lithium ion battery mainly adopts combustible carbonate organic liquid as an electrolyte material, and brings huge potential safety hazards to the manufacturing, transportation and use of the lithium ion battery. The polymer electrolyte is mainly composed of a polymer matrix and lithium salt, and has the advantages that the system does not contain a liquid organic solvent, has good thermal stability and a wider electrochemical window, and is expected to fundamentally improve the safety performance of the lithium ion battery. However, polymer electrolytes have problems of insufficient toughness and easy embrittlement, which seriously affect the electrochemical performance and service life of lithium ion batteries after rupture during battery assembly and cycling, and even cause safety problems.
If the self-healing function can be introduced into the polymer electrolyte, the service life of the lithium ion battery can be obviously prolonged by self-healing after the electrolyte material is broken. The electrolyte can be endowed with self-healing performance by constructing a quadruple hydrogen bond network, but the hydrogen bonds are non-covalent bonds with weak intermolecular acting force, and the mechanical property of the self-healing polymer electrolyte is low due to the low bonds, so that the formation of lithium dendrites is difficult to inhibit, and the cycle stability of the polymer electrolyte is further reduced. In addition, the problem that the stability of the interface between the self-healing polymer electrolyte and lithium metal is reduced due to the uneven distribution of lithium ions in the self-healing polymer electrolyte and the surface of the lithium metal in the lithium deposition process is not solved, and the problem is also an important factor influencing the electrochemical performance of the lithium ion battery.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention aims to provide a self-healing polymer electrolyte based on dynamic borate bonds, and a preparation method and an application thereof, wherein the self-healing polymer electrolyte based on dynamic borate bonds is formed by improving the key structure, related components (especially the key chemical structural formula, cross-linked network structure, etc. of the polymer electrolyte), route design of the corresponding preparation method, and reaction conditions of each step. Compared with the prior art, on one hand, the self-healing polymer electrolyte has a cross-linked network structure, and on the other hand, the dynamic borate ester bond cross-linked network can realize rearrangement of the polymer network through exchange reaction to endow the electrolyte material with self-healing performance, and can carry out efficient repair when the material is subjected to external force or self stress and cracks appear, thereby preventing internal short circuit and prolonging the service life of a lithium battery; the construction of the chemical crosslinking network can also obviously enhance the mechanical property of the material and improve the safety of the polymer electrolyte; on the other hand, by means of the interaction of boron atoms and anions in the boric acid ester bond, lithium ions are promoted to be uniformly distributed in the electrolyte and on the surface of lithium metal, and the interface stability of the electrolyte material and the lithium metal is improved.
The purpose of the invention is realized based on the following technical scheme:
1. in a first aspect of the invention, a self-healing polymer electrolyte based on dynamic borate bonds is provided, which comprises a borate bond-based cross-linked polymer and a lithium salt component, wherein the borate bond-based cross-linked polymer is prepared by a mercapto-epoxy ring-opening reaction of a boron-based single-ion conductor polymer and a mercapto-functionalized borate bond cross-linking agent; the electrolyte is of a three-dimensional cross-linked network structure, and the structural formula of the electrolyte is as follows:
Figure DEST_PATH_IMAGE001
。
as a further preferred aspect of the present invention, the boron-based single ion conductor polymer is obtained by copolymerizing a borate-containing reactive monomer and poly (ethylene glycol) methacrylate, and has the following chemical structural formula:
Figure 63268DEST_PATH_IMAGE002
。
the mercapto-functionalized borate ester bond crosslinking agent is a mercapto-crosslinking agent with a mercapto group at the tail end and a boric acid ester structure at the middle chain segment, and the chemical structural formula of the mercapto-functionalized borate ester bond crosslinking agent is as follows:
Figure 192898DEST_PATH_IMAGE003
。
in a second aspect, the invention provides a method for preparing a self-healing polymer electrolyte based on dynamic borate ester bonds, which comprises the following steps:
1) Dissolving 2, 5-dimethyl-2, 5-hexanediol and trimethyl borate in a first solvent, and reacting under stirring; adding poly (ethylene glycol) methacrylate for continuous reaction, and filtering, washing and drying a reaction product to obtain a reaction monomer containing borate;
2) Dissolving a reaction monomer containing borate, a reaction monomer of glycidyl methacrylate and an initiator in a second solvent, stirring to dissolve the reaction monomer, removing oxygen and water, and reacting under stirring to obtain a boron-based single-ion conductor polymer;
3) Dissolving boron-based single-ion conductor polymer, sulfydryl-functionalized borate bond cross-linking agent, catalyst and lithium salt in a third solvent, uniformly mixing, and reacting under a heating condition to obtain the self-healing polymer electrolyte with a cross-linked network structure and based on the dynamic borate bond.
Preferably, in the step 1), the relative molecular mass of the poly (ethylene glycol) methacrylate is 200 to 1000; the first solvent comprises at least one of tetrahydrofuran, acetonitrile, dimethyl sulfoxide and N, N-dimethylformamide; the reaction temperature is 30-100 DEG C o C, the reaction time is 1 to 12 hours;
preferably, in the step 2), the amount of the glycidyl methacrylate reaction monomer is 5 to 100 mol% of the borate-containing reaction monomer; the initiator is an oil-soluble free radical polymerization initiator, preferably azobisisobutyronitrileOne of azodiisoheptonitrile and dimethyl azodiisobutyrate; the amount of the initiator is 1 to 20 mol% of the reaction monomer containing the borate; the second solvent comprises at least one of ethanol, N-dimethylformamide, acetonitrile and dimethyl sulfoxide; the reaction temperature is 50 to 100 o And C, the reaction time is 8 to 24 hours.
Preferably, in the step 3), the mass ratio of the boron-based single-ion conductor polymer to the mercapto-functionalized borate ester bond crosslinking agent is 100 to 5; the catalyst is at least one of sodium methoxide, sodium ethoxide and sodium tert-butoxide, and the amount of the catalyst is 0.1 to 10 wt% of the boron-based single-ion conductor polymer; the third solvent comprises at least one of N, N-dimethylformamide, ethanol, tetrahydrofuran and dimethyl sulfoxide; the reaction temperature is 60 to 100 DEG C o C; the reaction time is 12 to 48 hours.
Preferably, in the step 3), the lithium salt is one or more of lithium tetrafluoroborate, lithium bistrifluoromethylsulfonyl imide, lithium perchlorate and lithium hexafluorophosphate; 5 to 30 wt% of the lithium salt and the boron-based single ion conductor polymer; the thickness of the polymer electrolyte membrane is preferably 30 to 300 μm.
The invention also can further improve the self-healing and electrochemical properties of the polymer electrolyte based on the dynamic borate bond by optimally controlling the parameter conditions (including the molecular weight control of the poly (ethylene glycol) methacrylate, the mixture ratio of different monomers, the reaction time, the temperature and the like) of each process step of the preparation method.
In a third aspect of the invention, the invention provides an application of a self-healing polymer electrolyte based on a dynamic borate bond in a lithium ion battery.
Overall, the present invention can achieve the following advantageous effects:
(1) The invention firstly synthesizes a copolymer containing borate and an epoxy group side chain, and then adopts a sulfydryl-epoxy group ring-opening reaction between a thermal initiation copolymer and a sulfydryl functional borate bond cross-linking agent to efficiently prepare the self-healing polymer electrolyte based on the dynamic borate bond. At present, no report is found on a method for synchronously improving the self-healing and the interface stability of the polymer electrolyte by utilizing the polymer matrix containing a large number of borate bond groups.
(2) The self-healing polymer electrolyte based on the dynamic borate bonds has a network structure containing borate cross-linking agents, and the mechanical property and the thermal stability of the polymer electrolyte are guaranteed. On one hand, the rearrangement of the polymer network can be realized by the dynamic borate ester bond crosslinking network through exchange reaction to endow the electrolyte material with self-healing performance, and the electrolyte material can be efficiently repaired when the material is cracked under external force or self stress, so that the internal short circuit is prevented, and the service life of the lithium battery is prolonged; the construction of the chemical crosslinking network can also obviously enhance the mechanical property of the material and improve the safety of the polymer electrolyte; on the other hand, by means of the interaction of boron atoms and anions in the borate bond, lithium ions are promoted to be uniformly distributed in the electrolyte and on the surface of lithium metal, and the interface stability of the electrolyte material and the lithium metal is improved. The unique structural design can solve the problems of low mechanical property and poor interface stability of the existing self-healing electrolyte, namely, the polymer electrolyte with a cross-linking structure and containing a large number of dynamic borate bond groups inside is formed through thermal initiation, wherein the borate bond can simultaneously realize the improvement of the mechanical property and the interface stability of the self-healing polymer electrolyte.
(3) The synthesized copolymer containing the borate and the epoxy group side chain aims at introducing the borate-containing side chain and the epoxy group into the copolymer, wherein the borate bond can promote the rapid conduction of lithium ions in electrolyte and promote the lithium ions to be more uniformly distributed on the surface of lithium metal; the introduction of the epoxy group provides a reaction group for the next step of thermally-initiated sulfydryl-epoxy ring-opening reaction, and the self-healing polymer electrolyte with a cross-linking structure can be efficiently prepared. At present, no method for obtaining the self-healing polymer electrolyte based on the dynamic borate bond by adopting the method is reported.
(4) According to the invention, a borate ester bond group is introduced into a polymer network, and the polymer network can be used as Lewis acid to play a role in fixing anions through the interaction of the Lewis acid and lithium salt anions, so that the interface stability of an electrolyte system is improved. The preparation method of the self-healing polymer electrolyte based on the dynamic borate bond provided by the invention adopts the thermally-initiated mercapto-epoxy ring-opening reaction, and can efficiently prepare the electrolyte material. The polymer skeleton with stable structure and excellent mechanical property is formed by controlling the proportion of the mercapto-containing cross-linking agent and the copolymer containing the side chain of the boric acid ester and the epoxy group in the structure, and the electrochemical property of the polymer electrolyte can be effectively controlled by regulating and controlling the content of the boric acid ester in the polymer matrix.
In conclusion, the dynamic borate ester bond crosslinking network can realize rearrangement of the polymer network through exchange reaction and endow the electrolyte material with self-healing performance; by introducing the boric acid ester bond group, the lithium ion deposition is promoted to be more uniform by utilizing the action of the boric acid ester bond group and the Lewis acid base of lithium salt anions, and the interface stability of the polymer electrolyte and lithium metal is improved. The self-healing polymer electrolyte based on the dynamic borate bond has good mechanical property and interface stability, and can provide a new method for preparing a novel polymer electrolyte.
Drawings
FIG. 1 is a physical representation of a self-healing polymer electrolyte based on dynamic borate bonds under different bending conditions.
Fig. 2 is a graph of conductivity versus temperature for a self-healing polymer electrolyte based on dynamic borate bonds.
Fig. 3 is a self-healing experiment of a self-healing polymer electrolyte based on dynamic borate bonds.
Fig. 4 is a lithium deposition experiment of a self-healing polymer electrolyte based on dynamic borate bonds.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The self-healing polymer electrolyte based on the dynamic borate bond comprises a cross-linked polymer based on the borate bond and a lithium salt component, wherein the cross-linked polymer based on the borate bond is prepared by a mercapto-epoxy ring-opening reaction of a boron-based single-ion conductor polymer and a mercapto-functionalized borate bond cross-linking agent, and the molar ratio of the boron-based single-ion conductor polymer to the mercapto-functionalized borate bond cross-linking agent is 10 to 1; the amount of the catalyst is 0.1 to 10 wt% of the boron-based single ion conductor polymer. The crosslinking compound is formed by thermally-initiated mercapto-epoxy ring-opening reaction, and the boric acid ester bond in the structure can promote the rapid conduction of lithium ions in electrolyte and promote the lithium ions to be more uniformly distributed on the surface of lithium metal; the introduction of the epoxy group provides a reaction group for the next step of thermally-initiated sulfydryl-epoxy group ring-opening reaction, and the self-healing polymer electrolyte with a cross-linking structure can be efficiently prepared.
The preparation method of the self-healing polymer electrolyte based on the dynamic borate bond comprises the following steps:
(1) Dissolving 2, 5-dimethyl-2, 5-hexanediol and trimethyl borate in a first solvent, and reacting under the condition of stirring; adding poly (ethylene glycol) methacrylate for continuous reaction, and filtering, washing and drying a reaction product to obtain a reaction monomer containing borate;
(2) Dissolving a reaction monomer containing borate, a reaction monomer of glycidyl methacrylate and an initiator in a second solvent, stirring to dissolve the reaction monomer, deoxidizing and reacting under stirring to obtain a boron-based single-ion conductor polymer;
(3) Dissolving a boron-based single-ion conductor polymer, a sulfydryl-functionalized borate bond crosslinking agent, a catalyst and lithium salt in a third solvent, uniformly mixing, and reacting under a heating condition to obtain the self-healing polymer electrolyte with a crosslinking network structure based on the dynamic borate bond.
The following are specific examples.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments and accompanying drawings further illustrate the present invention in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
Example 1
1.46 g of 2, 5-dimethyl-2, 5-hexanediol and 1.3 mL of trimethyl borate are added to 30 mL of tetrahydrofuran, stirred until dissolved, blanketed with nitrogen and stirred at 30 DEG o And C, stirring and reacting for 0.5 hour, adding the poly (ethylene glycol) methacrylate with the molecular weight of 200 into the reaction liquid, and continuously reacting for 0.5 hour to obtain the reaction monomer containing the borate.
1.02 g of reaction monomer containing borate and 14.2 mg of glycidyl methacrylate, removing water and oxygen in the system by 3 times of freezing-vacuumizing-argon filling circulation in 3.2 mg of 2, 2-azobisisobutyronitrile and 30 mL of ethanol, and heating to 50 DEG o C, reacting for 8 hours to obtain the boron-based single-ion conductor polymer.
Dissolving 3.0 g boron-based single ion conductor polymer, 30.0 mg sulfhydryl functionalized borate ester bond crosslinking agent, 3.0 mg sodium methoxide and 0.15 g lithium perchlorate in N, N-dimethylformamide, stirring to dissolve completely, casting the solution in a mold, and 60 g o After 12 hours of reaction at C. Then, after completely removing the solvent in the electrolyte at high temperature, the self-healing polymer electrolyte based on the dynamic borate bond is obtained. The thickness of the polymer electrolyte membrane obtained in this example was 30 μm. The appearance of the polymer electrolyte membrane prepared by the implementation is as shown in fig. 1, and the polymer electrolyte membrane can keep good structural stability under different bending conditions and shows good flexibility and mechanical properties.
Example 2
1.46 g of 2, 5-dimethyl-2, 5-hexanediol and 1.3 mL of trimethyl borate are added to 30 mL of acetonitrile, stirred until dissolved, purged with nitrogen, and then the mixture is stirred at 50 ℃ under reduced pressure o And C, stirring and reacting for 2 hours, adding the poly (ethylene glycol) methacrylate with the molecular weight of 400 into the reaction liquid, and continuously reacting for 4 hours to obtain the reaction monomer containing the borate.
1.02 g of monomers containing borate reaction monomers and 28.42 mg of glycidyl methacrylate, 6.4 mg of azobisisoheptonitrile and 30 mL of acetonitrile, removing water and oxygen in the system by freezing, vacuumizing and filling argon for 3 times, and heating to 60% o And C, reacting for 10 hours to obtain the boron-based single-ion conductor polymer.
Dissolving 3.0 g of boron-based single ion conductor polymer, 60.0 mg of sulfydryl-functionalized borate ester bond crosslinking agent, 6.0 mg of sodium ethoxide and 0.3 g of lithium tetrafluoroborate in ethanol, stirring to completely dissolve, casting the solution in a mold, and pouring 80 g of the solution o After 15 hours of reaction under C. Then, after completely removing the solvent in the electrolyte at high temperature, the self-healing polymer electrolyte based on the dynamic borate bond is obtained.
Example 3
Adding 1.46 g of 2, 5-dimethyl-2, 5-hexanediol and 1.3 mL of trimethyl borate into 30 mL of dimethyl sulfoxide, stirring until the materials are dissolved, introducing nitrogen for protection, and reacting at 60 DEG o And C, stirring and reacting for 2 hours, adding poly (ethylene glycol) methacrylate with the molecular weight of 500 into the reaction liquid, and continuing to react for 3 hours to obtain the reaction monomer containing the borate.
1.02 g of a reaction monomer containing borate ester and 56.8 mg of glycidyl methacrylate as monomers, 16.0 mg of dimethyl azodiisobutyrate and 30 mL of dimethyl sulfoxide, removing water and oxygen from the system by a cycle of freezing, vacuumizing, and filling argon for 3 times, and heating to 50 deg.C o C, reacting for 8 hours to obtain the boron-based single-ion conductor polymer.
Dissolving 3.0 g boron-based single ion conductor polymer, 180.0 mg sulfhydryl-functionalized borate ester bond crosslinking agent, 30.0 mg sodium tert-butoxide and 0.6 g lithium bis (trifluoromethyl) sulfonyl imide in tetrahydrofuran, stirring to dissolve completely, casting the solution in a mold, and 60 g o After 16 hours of reaction under C. Then, after the solvent in the electrolyte is completely removed at high temperature, the self-healing polymer electrolyte based on the dynamic borate bond is obtained. The ionic conductivity of the polymer electrolyte membrane produced in this example is shown in FIG. 2. To examine the effect of the thiol-functionalized borate ester linkage crosslinker on the ionic conductivity of the polymer electrolyte, a control polymer electrolyte was prepared using 3, 6-dioxa-1, 8-octanedithiol instead of the thiol-functionalized borate ester linkage crosslinker. It was found by testing that electrolytes prepared using thiol-functionalized borate ester bond crosslinkers were at 30 deg.f o The ionic conductivity of C was 4.65X 10 -5 S cm -1 To is in pairAs a polymer electrolyte at 30 o The ionic conductivity of C was 1.86X 10 -5 S cm -1 The method shows that the mercapto-functionalized borate bond crosslinking agent has a promotion effect on the ionic conductivity, and the borate bond in the structure of the mercapto-functionalized borate bond crosslinking agent can play a role of a bridge for conducting lithium ions, so that the method is favorable for the rapid conduction of the lithium ions in the electrolyte. In addition, the self-healing polymer electrolyte based on dynamic borate bonds prepared in this example exhibited good self-healing properties. As shown in FIG. 3, the cut polymer electrolyte membrane is brought into contact and lightly pressed, 60 o Cracks substantially disappeared after two hours at C. The electrolyte membrane after healing can bear a weight of 500 g, and shows excellent self-healing performance and mechanical property.
Example 4
1.46 g of 2, 5-dimethyl-2, 5-hexanediol and 1.3 mL of trimethyl borate are added to 30 mL of acetonitrile, stirred until dissolved, protected by nitrogen, and the mixture is stirred at 80 ℃ under stirring o And C, stirring and reacting for 5 hours, adding the poly (ethylene glycol) methacrylate with the molecular weight of 800 into the reaction liquid, and continuously reacting for 3 hours to obtain the reaction monomer containing the borate.
1.02 g comprising boric acid ester reaction monomer and 71.05 mg of glycidyl methacrylate as monomers, removing water and oxygen in the system by freezing, vacuumizing and filling argon in 64.0 mg of azobisisobutyronitrile and 30 mL of N, N-dimethylformamide for 3 times, and heating to 70 DEG C o C, reacting for 16 hours to obtain the boron-based single-ion conductor polymer.
Dissolving 3.0 g boron-based single ion conductor polymer, 300.0 mg sulfhydryl functionalized borate ester bond crosslinking agent, 150.0 mg sodium methoxide and 0.9 g lithium bis (trifluoromethyl) sulfonyl imide in N, N-dimethylformamide, stirring to dissolve completely, casting the solution in a mold, and 100 g o After 12 hours of reaction at C. Then, after completely removing the solvent in the electrolyte at high temperature, the self-healing polymer electrolyte based on the dynamic borate bond is obtained. The thickness of the polymer electrolyte membrane prepared in this example was 150. Mu.m.
Example 5
1.46 g of 2, 5-dimethyl-2, 5-hexanediol, 1.3 mL of trimethylborateThe ester was added to 30 mL of N, N-dimethylformamide, stirred until dissolved, blanketed with nitrogen, at 80 deg.C o And C, stirring and reacting for 6 hours, adding poly (ethylene glycol) methacrylate with the molecular weight of 1000 into the reaction liquid, and continuing to react for 6 hours to obtain the reaction monomer containing the borate.
1.02 g of monomers containing borate ester and 284.2 mg of glycidyl methacrylate, 142.1 mg of dimethyl azodiisobutyrate and 30 mL of acetonitrile, removing water and oxygen from the system by 3 cycles of freezing, vacuumizing and filling argon, and heating to 70% o And C, reacting for 12 hours to obtain the boron-based single-ion conductor polymer.
Dissolving 3.0 g boron-based single ion conductor polymer, 600.0 mg mercapto-functionalized borate ester bond crosslinking agent, 300.0 mg sodium methoxide, and 0.6 g lithium hexafluorophosphate in dimethyl sulfoxide, stirring to dissolve completely, casting the solution in a mold, and 60 g lithium hexafluorophosphate o After 16 hours at C. Then, after the solvent in the electrolyte is completely removed at high temperature, the self-healing polymer electrolyte based on the dynamic borate bond is obtained.
Example 6
1.46 g of 2, 5-dimethyl-2, 5-hexanediol and 1.3 mL of trimethyl borate are added to 30 mL of tetrahydrofuran, stirred until dissolved, blanketed with nitrogen and stirred at 60 ℃ under nitrogen o And C, stirring for reaction for 2 hours, adding the poly (ethylene glycol) methacrylate with the molecular weight of 400 into the reaction liquid, and continuing to react for 4 hours to obtain the reaction monomer containing the borate.
1.02 g of reaction monomer containing borate and 42.6 mg of glycidyl methacrylate, removing water and oxygen in the system by freezing, vacuumizing and argon filling circulation for 3 times in 25.6 mg of azobisisobutyronitrile and 30 mL of N, N-dimethylformamide, and heating to 60% o And C, reacting for 12 hours to obtain the boron-based single-ion conductor polymer.
Dissolving 3.0 g boron-based single ion conductor polymer, 180.0 mg sulfhydryl functionalized borate ester bond crosslinking agent, 12.0 mg sodium ethoxide and 0.3 g lithium perchlorate in tetrahydrofuran, stirring to dissolve completely, casting the solution in a mold, and 100 percent o After 18 hours at C. Then after completely removing the solvent in the electrolyte at a high temperature,obtaining the self-healing polymer electrolyte based on the dynamic borate bond. The electrolyte membrane prepared in the embodiment is assembled into a Li/Li symmetrical battery to be subjected to constant current charge and discharge tests, and the constant current charge and discharge tests show that the electrolyte membrane is 0.1 mA cm -2 The battery shows a stable polarization curve under current density, and the stable polarization voltage is still maintained after 1200-hour cycling (figure 4), which shows that the polymer electrolyte has good interface stability with lithium metal.
Example 7
1.46 g of 2, 5-dimethyl-2, 5-hexanediol and 1.3 mL of trimethyl borate are added to 30 mL of dimethyl sulfoxide, stirred until dissolved, purged with nitrogen, and stirred at 100 deg.C o And C, stirring and reacting for 6 hours, adding poly (ethylene glycol) methacrylate with the molecular weight of 600 into the reaction liquid, and continuously reacting for 6 hours to obtain the reaction monomer containing the borate.
1.02 g of reaction monomer containing borate and 213.0 mg of glycidyl methacrylate, 6.4 mg of azobisisobutyronitrile and 30 mL of ethanol, removing water and oxygen in the system by freezing, vacuumizing and filling argon for 3 times, and heating to 100% o And C, reacting for 24 hours to obtain the boron-based single-ion conductor polymer.
Dissolving 3.0 g of boron-based single ion conductor polymer, 240.0 mg of sulfhydryl functionalized borate ester bond crosslinking agent, 30.0 mg of sodium tert-butoxide and 0.6 g of lithium perchlorate in N, N-dimethylformamide, stirring to completely dissolve, casting the solution in a mold, and 80 percent of the solution o After 16 hours of reaction under C. Then, after completely removing the solvent in the electrolyte at high temperature, the self-healing polymer electrolyte based on the dynamic borate bond is obtained. The thickness of the polymer electrolyte membrane prepared in this example was 300. Mu.m.
The self-healing polymer electrolyte based on the dynamic borate bonds, prepared by the preferred embodiment of the invention, can not only endow the electrolyte material with self-healing performance, but also promote the uniform deposition of lithium ions by constructing a cross-linking network and the action of Lewis acid and base, thereby improving the mechanical property and the interface stability of the polymer electrolyte and providing a new method for preparing the high-performance self-healing polymer electrolyte.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims (10)

1. A self-healing polymer electrolyte based on dynamic borate bonds is characterized by comprising a cross-linked polymer based on borate bonds and a lithium salt component, wherein the cross-linked polymer based on borate bonds is prepared by a sulfydryl-epoxy group ring opening reaction of a boron-based single-ion conductor polymer and a sulfydryl-functionalized borate bond cross-linking agent; the electrolyte is of a three-dimensional cross-linked network structure, and the structural formula of the electrolyte is as follows:
Figure DEST_PATH_IMAGE002
。
2. a self-healing polymer electrolyte based on dynamic borate bonds according to claim 1, wherein the boron-based single ion conductor polymer is obtained by copolymerizing a borate-containing reactive monomer with poly (ethylene glycol) methacrylate and has the following chemical formula:
Figure DEST_PATH_IMAGE004
。
3. a self-healing polymer electrolyte based on dynamic borate bonds according to claim 1, wherein the thiol-functionalized borate bond crosslinker is a thiol crosslinker having a terminal thiol group and an intermediate segment having a borate structure, and has the following chemical formula:
Figure DEST_PATH_IMAGE006
。
4. a preparation method of a self-healing polymer electrolyte based on a dynamic borate bond is characterized by comprising the following steps:
dissolving 2, 5-dimethyl-2, 5-hexanediol and trimethyl borate in a first solvent, and reacting under the condition of stirring; adding poly (ethylene glycol) methacrylate for continuous reaction, and filtering, washing and drying a reaction product to obtain a reaction monomer containing borate;
dissolving the reaction monomer containing the borate, the reaction monomer containing the glycidyl methacrylate and the initiator obtained in the step 1) in a second solvent, stirring to dissolve the reaction monomer, and reacting under stirring to obtain the boron-based single-ion conductor polymer after removing oxygen and water;
dissolving the boron-based single-ion conductor polymer obtained in the step 2), a sulfydryl-functionalized borate bond crosslinking agent, a catalyst and lithium salt in a third solvent, uniformly mixing, and reacting under a heating condition to obtain the self-healing polymer electrolyte with a crosslinking network structure based on the dynamic borate bond.
5. The method for preparing a self-healing polymer electrolyte based on dynamic borate bonds according to claim 1, wherein in the step 1), the relative molecular mass of the poly (ethylene glycol) methacrylate is 200 to 1000; the first solvent comprises at least one of tetrahydrofuran, acetonitrile, dimethyl sulfoxide and N, N-dimethylformamide; the reaction temperature is 30-100 DEG C o C, the reaction time is 1 to 12 hours.
6. The method for preparing a self-healing polymer electrolyte based on dynamic borate bonds as claimed in claim 1, wherein in step 2),
the content of the glycidyl methacrylate reaction monomer is 5 to 100 mol percent of the reaction monomer containing the boric acid ester; the initiator is an oil-soluble free radical polymerization initiator, and specifically is azobisisobutyric acidOne of nitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate; the amount of the initiator is 1 to 20 mol% of the reaction monomer containing the borate; the second solvent comprises at least one of ethanol, N-dimethylformamide, acetonitrile and dimethyl sulfoxide; the reaction temperature is 50 to 100 o And C, the reaction time is 8 to 24 hours.
7. The method for preparing a self-healing polymer electrolyte based on a dynamic borate bond according to claim 1, wherein in the step 3), the mass ratio of the boron-based single-ion conductor polymer to the mercapto-functionalized borate bond crosslinking agent is 100 to 5; the catalyst is at least one of sodium methoxide, sodium ethoxide and sodium tert-butoxide, and the amount of the catalyst is 0.1 to 10 wt% of the boron-based single-ion conductor polymer; the third solvent comprises at least one of N, N-dimethylformamide, ethanol, tetrahydrofuran and dimethyl sulfoxide; the reaction temperature is 60 to 100 DEG C o C; the reaction time is 12 to 48 hours.
8. The method for preparing a self-healing polymer electrolyte based on dynamic borate bonds according to claim 1, wherein in step 3), the lithium salt is one or more of lithium tetrafluoroborate, lithium bistrifluoromethylsulfonyl imide, lithium perchlorate and lithium hexafluorophosphate; 5 to 30 wt% of the lithium salt and the boron-based single ion conductor polymer.
9. The method for preparing a self-healing polymer electrolyte based on dynamic borate bonds according to claim 1, wherein in step 3), the mixed solution is poured in a mold, and is subjected to reaction and drying to form a film, so as to obtain the self-healing polymer electrolyte film based on dynamic borate bonds; specifically, the thickness of the polymer electrolyte membrane is 30 to 300 micrometers.
10. Use of the dynamic borate bond-based self-healing polymer electrolyte according to any one of claims 1 to 9 in a lithium ion battery.
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