CN115954539A - Self-healing mesh polymer electrolyte, preparation method and application thereof, and polymer lithium battery - Google Patents
Self-healing mesh polymer electrolyte, preparation method and application thereof, and polymer lithium battery Download PDFInfo
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Abstract
The invention relates to the technical field of polymer lithium batteries, in particular to a self-healing reticular polymer electrolyte, a preparation method and application thereof, and a polymer lithium battery. The invention provides a self-healing reticular polymer electrolyte which comprises the following preparation raw materials in parts by mass: 3-10 parts of ionic liquid, 40-70 parts of polyethylene glycol diacrylate, 1-10 parts of disulfide diacrylate, 1-5 parts of cross-linking agent, 3-10 parts of chain extender, 1-5 parts of alkali, 20-30 parts of lithium salt, 1-10 parts of photoinitiator and 90-110 parts of solvent; the cross-linking agent and the chain extender both comprise sulfydryl. The self-healing reticular polymer electrolyte has high conductivity at room temperature, stable interface contact and can realize self-healing without external stimulation.
Description
Technical Field
The invention relates to the technical field of polymer lithium batteries, in particular to a self-healing reticular polymer electrolyte, a preparation method and application thereof, and a polymer lithium battery.
Background
Wearable electronic devices such as smart bracelets and smart glasses are increasingly popular with people, however, conventional lithium batteries are difficult to use in wearable devices due to poor flexibility and low energy density. Therefore, researchers have extensively studied flexible solid-state lithium batteries with high energy density and good flexibility to meet consumer demands for wearable devices. The solid electrolyte is used as a key part of the flexible lithium battery, and is inevitably subjected to external forces such as stretching, twisting and bending in practical application, so that microcracks and fractures are caused, transmission of lithium ions in the solid electrolyte is hindered, and the performance and the cycle performance of the solid electrolyte battery are seriously influenced.
Disclosure of Invention
The invention aims to provide a self-healing reticular polymer electrolyte, a preparation method and application thereof, and a polymer lithium battery.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a self-healing reticular polymer electrolyte which comprises the following preparation raw materials in parts by mass: 3-10 parts of ionic liquid, 40-70 parts of polyethylene glycol diacrylate, 1-10 parts of disulfide diacrylate, 1-5 parts of cross-linking agent, 3-10 parts of chain extender, 1-5 parts of alkali, 20-30 parts of lithium salt, 1-10 parts of photoinitiator and 90-110 parts of solvent;
the cross-linking agent and the chain extender both comprise sulfydryl.
Preferably, the ionic liquid comprises one or more of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 2, 3-dimethyl-1-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidinium bis (trifluoromethanesulfonyl) imide salt and 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt.
Preferably, the disulfide diacrylates comprise bis (4-vinylphenyl) disulfide and/or disulfide dimethacrylate.
Preferably, the cross-linking agent comprises one or more of pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), and trimethylolpropane tris (3-mercaptopropionate).
Preferably, the chain extender comprises one or more of 3, 6-dioxa-1, 8-octanedithiol, 1, 10-decanedithiol, 1, 4-butanedithiol, 1, 2-ethanedithiol, 1, 16-hexadecanedithiol, 1, 5-pentanethiol and 1, 6-hexanedithiol;
the photoinitiator comprises one or more of 2, 2-dimethoxy-2-phenylacetophenone, 4-methylbenzophenone and 1-hydroxycyclohexyl phenyl ketone.
Preferably, the base comprises one or more of n-butylamine, t-butylamine, n-propylamine, t-pentylamine, and isobutylamine;
the lithium salt comprises LiPF 6 、LiClO 4 One or more of LiTFSI, liFSI, liBOB and lidpob.
The invention also provides a preparation method of the self-healing reticular polymer electrolyte, which comprises the following steps:
mixing ionic liquid, polyethylene glycol diacrylate, disulfide diacrylate, a cross-linking agent, a chain extender, lithium salt and a solvent, and then mixing the ionic liquid, the polyethylene glycol diacrylate, the disulfide diacrylate, the cross-linking agent, the chain extender, the lithium salt and the solvent with a photoinitiator and alkali to obtain a precursor solution;
and carrying out UV curing on the precursor solution to obtain the self-healing reticular polymer electrolyte.
Preferably, the irradiation wavelength of the UV curing is 100 to 380nm, and the irradiation light intensity is 10 to 200mW cm -2 The time is 0.5 to 10 hours.
The invention also provides the self-healing reticular polymer electrolyte prepared by the technical scheme or the self-healing reticular polymer prepared by the preparation method in the technical scheme, and the application of the self-healing reticular polymer electrolyte in a polymer lithium battery.
The invention also provides a polymer lithium battery which comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the self-healing reticular polymer electrolyte prepared by the technical scheme or the preparation method of the technical scheme.
The invention provides a self-healing reticular polymer electrolyte which comprises the following preparation raw materials in parts by mass: 3-10 parts of ionic liquid, 40-70 parts of polyethylene glycol diacrylate, 1-10 parts of disulfide diacrylate, 1-5 parts of cross-linking agent, 3-10 parts of chain extender, 1-5 parts of alkali, 20-30 parts of lithium salt, 1-10 parts of photoinitiator and 90-110 parts of solvent; the cross-linking agent and the chain extender both comprise sulfydryl. Thiol-ene click reaction can occur between carbon-carbon double bonds in the disulfide diacrylate and the polyethylene glycol diacrylate and sulfydryl of the cross-linking agent and the chain extender, so that the self-healing reticular polymer electrolyte has a disulfide bond network structure, and the dynamic disulfide bonds can enable the electrolyte membrane to realize self-healing without external stimulation at room temperature. The ionic liquid has good ion transmission performance and flame retardance, not only accelerates the transmission of lithium ions, but also has good flame retardance, improves the conductivity of the electrolyte membrane at room temperature, has good interface compatibility with a lithium metal cathode, and reduces the interface impedance, thereby improving the cycle performance and the rate performance of the battery. According to the description of the embodiment, the self-healing reticular polymer electrolyte reaches the ionic conductivity of 1.13 multiplied by 10 at room temperature -4 S·cm -1 (ii) a The lithium iron phosphate battery assembled by using the self-healing reticular polymer electrolyte as the electrolyte has a specific discharge capacity of 160 mAh.g under the multiplying power of 0.1C -1 。
The invention also provides a preparation method of the self-healing reticular polymer electrolyte, which comprises the following steps: mixing ionic liquid, polyethylene glycol diacrylate, disulfide diacrylate, a cross-linking agent, a chain extender, lithium salt and a solvent, and then mixing the ionic liquid, the polyethylene glycol diacrylate, the disulfide diacrylate, the cross-linking agent, the chain extender, the lithium salt and the solvent with a photoinitiator and alkali to obtain a precursor solution; and carrying out UV curing on the precursor solution to obtain the self-healing reticular polymer electrolyte. The UV curing may promote the occurrence of thiol-ene click reactions; meanwhile, the preparation method is simple to operate, mild in condition and low in cost.
Drawings
FIG. 1 is an infrared spectrum of a self-healing network polymer electrolyte, pentaerythritol tetrakis (3-mercaptopropionate), polyethylene glycol diacrylate, diphenyl disulfide bis (2-methacrylamide), and 3, 6-dioxa-1, 8-octanedithiol obtained in example 1;
FIG. 2 is a physical representation and SEM photograph of a self-healing reticulated polymer electrolyte prepared in example 1;
FIG. 3 is a graph showing the change of ion conductivity with temperature of the self-healing reticulated polymer electrolyte membrane prepared in example 1 and the self-healing reticulated polymer electrolyte membrane after self-healing after standing for 24 hours;
fig. 4 is a room temperature cycle test plot of a button cell assembled with the self-healing reticulated polymer electrolyte prepared in example 1;
fig. 5 is a room temperature rate cycle test chart of the button cell of example 1;
fig. 6 is a cycle stability curve for a Li// Li symmetric button cell assembled with the self-healing network polymer electrolyte prepared in example 1;
FIG. 7 shows the self-healing process of the self-healing reticulated polymer electrolyte membrane prepared in example 1 at room temperature;
fig. 8 is a flame-retardant process of the self-healing mesh polymer electrolyte membrane prepared in example 1.
Detailed Description
The invention provides a self-healing reticular polymer electrolyte which comprises the following preparation raw materials in parts by mass: 3-10 parts of ionic liquid, 40-70 parts of polyethylene glycol diacrylate, 1-10 parts of disulfide diacrylate, 1-5 parts of cross-linking agent, 3-10 parts of chain extender, 1-5 parts of alkali, 20-30 parts of lithium salt, 1-10 parts of photoinitiator and 90-110 parts of solvent;
the cross-linking agent and the chain extender both comprise sulfydryl.
In the present invention, all the starting materials for the preparation are commercially available products well known to those skilled in the art, unless otherwise specified.
The self-healing reticular polymer electrolysis preparation raw material comprises 3-10 parts by mass of ionic liquid, preferably 4-8 parts by mass, and more preferably 5-6 parts by mass. In the present invention, the ionic liquid preferably comprises one or more of 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-hexyl-3-methylimidazole tetrafluoroboric acid, 1-ethyl-3-methylimidazole trifluoromethanesulfonate salt, 2, 3-dimethyl-1-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidine bis (trifluoromethanesulfonyl) imide salt and 1-octyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt; more preferably 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide salt; when the ionic liquid is more than two of the above specific choices, the invention has no special limitation on the proportion of the specific substances, and the specific substances can be mixed according to any proportion.
According to the invention, the ionic liquid not only accelerates the transmission of lithium ions, but also has good flame retardance, the conductivity of the electrolyte membrane at room temperature is improved on the premise of not reducing the mechanical performance of the membrane, the interface compatibility between the electrolyte membrane and the lithium metal cathode is good, and the impedance of the interface is reduced, so that the cycle performance and the rate capability of the battery are improved.
Based on the mass part of the ionic liquid, the self-healing reticular polymer electrolysis preparation raw material comprises 40-70 parts of polyethylene glycol diacrylate, preferably 45-65 parts, and more preferably 50-60 parts. In the present invention, the molecular weight of the polyethylene glycol diacrylate is preferably 400 to 4000g/mol, more preferably 1000 to 3000g/mol. In the present invention, the polyethylene glycol diacrylate functions to transport lithium ions and to improve the mechanical properties of the self-healing network polymer electrolysis.
The self-healing reticular polymer electrolysis preparation raw material comprises 1-10 parts of disulfide diacrylate ester, preferably 2-8 parts, and more preferably 4-6 parts by mass based on the mass part of the ionic liquid. In the present invention, the disulfide diacrylate preferably includes bis (4-vinylphenyl) disulfide and/or disulfide dimethacrylate, more preferably disulfide dimethacrylate.
In the present invention, the method for producing the disulfide dimethacrylate preferably comprises the steps of:
under the nitrogen atmosphere, disulfide, methacrylic ester isocyano ethyl ester and an organic solvent are mixed and reacted to obtain the disulfide dimethacrylate.
In the present invention, the nitrogen atmosphere is preferably realized by bubbling nitrogen gas.
In the present invention, the disulfide preferably includes one or more of 4, 4-diaminodiphenyl disulfide, bis (4-hydroxyphenyl) disulfide and bis (2-hydroxyethyl) disulfide and bis (2-diaminoethyl) disulfide; when the disulfide is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances can be mixed according to any proportion. In the present invention, the organic solvent preferably comprises one or more of benzene, toluene, dichloromethane, methanol, ethanol, acetone, acetonitrile, dimethyl sulfoxide and N, N-dimethylformamide; when the organic solvent is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances can be mixed according to any proportion. In the present invention, when the disulfide is 4, 4-diaminodiphenyl disulfide, bis (2-diaminoethyl) disulfide, the reaction does not require the addition of a catalyst; when the disulfide is bis (4-hydroxyphenyl) disulfide, bis (2-hydroxyethyl) disulfide, the reaction requires the addition of a catalyst, preferably dibutyltin dilaurate; the mass ratio of the disulfide to the dibutyltin dilaurate was 2.5g.
In the present invention, the mass ratio of the disulfide, the isocyanatoethyl methacrylate, and the organic solvent is preferably (3 to 10): (5-10): (5-15).
The mixing is not subject to any particular restriction by the present invention, and can be carried out by procedures known to those skilled in the art and ensuring that the disulfide and the isocyanatoethyl methacrylate are sufficiently soluble in the organic solvent.
In the present invention, the temperature of the reaction is preferably 20 to 80 ℃, more preferably 30 to 60 ℃, and most preferably 40 to 50 ℃; the time is preferably 10 to 30 hours, more preferably 15 to 25 hours. In the present invention, the reaction is preferably carried out under stirring conditions, and the stirring conditions in the present invention are not particularly limited, and those well known to those skilled in the art may be used.
In the present invention, the disulfide diacrylate functions such that it contains dynamic disulfide bonds that allow the electrolyte membrane to self-heal at room temperature without external stimulus.
Based on the mass part of the ionic liquid, the preparation raw material for the self-healing reticular polymer electrolysis comprises 1-5 parts of cross-linking agent, preferably 2-4 parts, and more preferably 2.5-3.5 parts. In the present invention, the crosslinking agent preferably includes one or more of pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), and trimethylolpropane tris (3-mercaptopropionate); when the cross-linking agent is more than two of the above specific choices, the present invention does not have any special limitation on the proportion of the specific substances, and the specific substances can be mixed according to any proportion.
In the invention, the cross-linking agent has the function of generating a self-healing reticular polymer through thiol-ene click reaction between the carbon-carbon double bonds of the disulfide diacrylate and the polyethylene glycol diacrylate and the sulfydryl of the cross-linking agent, thereby improving the mechanical property of the polymer.
Based on the mass portion of the ionic liquid, the self-healing reticular polymer electrolysis preparation raw material comprises 3-10 parts of chain extender, preferably 4-8 parts, and more preferably 5-6 parts. In the present invention, the chain extender preferably includes one or more of 3, 6-dioxa-1, 8-octanedithiol, 1, 10-decanedithiol, 1, 4-butanedithiol, 1, 2-ethanedithiol, 1, 16-hexadecanedithiol, 1, 5-pentanedithiol, and 1, 6-hexanedithiol; when the chain extenders are more than two of the above specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances are mixed according to any proportion.
In the invention, the chain extender has the function of polymerizing the disulfide diacrylate, the polyethylene glycol diacrylate and the chain extender by generating thiol-ene click reaction between the carbon-carbon double bond of the disulfide diacrylate and the carbon-carbon double bond of the polyethylene glycol diacrylate and the sulfydryl of the chain extender, so that the length of a molecular chain is increased, and the flexibility of the polymer is improved.
The self-healing reticular polymer electrolysis preparation raw material comprises 1-5 parts of alkali, preferably 2-5 parts of alkali, and more preferably 3-4 parts of alkali based on the mass part of the ionic liquid. In the present invention, the base preferably includes one or more of n-butylamine, tert-butylamine, n-propylamine, tert-pentylamine, and isobutylamine; when the alkali is more than two of the above specific choices, the present invention does not have any special limitation on the proportion of the above specific substances, and the specific substances can be mixed according to any proportion.
In the present invention, the base functions to accelerate the reaction of the carbon-carbon double bond and the mercapto group.
Based on the mass portion of the ionic liquid, the preparation raw material for electrolyzing the self-healing reticular polymer comprises 20-30 parts of lithium salt, preferably 22-28 parts, and more preferably 23-26 parts. In the present invention, the lithium salt preferably includes LiPF 6 、LiClO 4 One or more of LiTFSI, liFSI, liBOB and lidpob; when the lithium salt is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances are mixed according to any proportion.
In the present invention, the lithium salt functions to supply lithium ions and to lower the glass transition temperature of the polymer electrolyte.
Based on the mass portion of the ionic liquid, the preparation raw material for the self-healing reticular polymer electrolysis comprises 1-10 parts of photoinitiator, preferably 2-8 parts, and more preferably 3-6 parts. In the present invention, the photoinitiator preferably comprises one or more of 2, 2-dimethoxy-2-phenylacetophenone, 4-methylbenzophenone and 1-hydroxycyclohexyl phenyl ketone; when the photoinitiator is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion.
The self-healing reticular polymer electrolysis preparation raw material comprises 90-110 parts of solvent, preferably 95-105 parts of solvent, and more preferably 98-102 parts of solvent based on the mass parts of the ionic liquid. In the present invention, the solvent is preferably anhydrous acetonitrile.
In the present invention, the self-healing mesh polymer electrolyte membrane is preferably in a shape of a self-healing mesh polymer electrolyte membrane, and the thickness of the self-healing mesh polymer electrolyte membrane is preferably 100 to 120 μm.
The invention also provides a preparation method of the self-healing reticular polymer electrolyte, which comprises the following steps:
mixing ionic liquid, polyethylene glycol diacrylate, disulfide diacrylate, a cross-linking agent, a chain extender, lithium salt and a solvent, and then mixing the ionic liquid, the polyethylene glycol diacrylate, the disulfide diacrylate, the cross-linking agent, the chain extender, the lithium salt and the solvent with a photoinitiator and alkali to obtain a precursor solution;
and carrying out UV curing on the precursor solution to obtain the self-healing reticular polymer electrolyte.
Mixing ionic liquid, polyethylene glycol diacrylate, disulfide diacrylate, a cross-linking agent, a chain extender, lithium salt and a solvent, and then mixing the mixture with a photoinitiator and alkali to obtain a precursor solution.
In the present invention, the mixing of the ionic liquid, polyethylene glycol diacrylate, disulfide diacrylate, the crosslinking agent, the chain extender, the lithium salt and the solvent is preferably performed under stirring conditions; the stirring time is preferably 5 to 12 hours, the rotation speed of the stirring is not limited in the invention, and the rotation speed well known to those skilled in the art is adopted and the ionic liquid, the polyethylene glycol diacrylate, the disulfide diacrylate, the cross-linking agent, the chain extender and the lithium salt are fully dissolved in the solvent under the stirring time.
In the present invention, the mixing with the photoinitiator and the base is preferably performed under stirring conditions; the stirring time is preferably 2 to 5 hours, the rotating speed of the stirring is not limited in any way, and the rotating speed is known to those skilled in the art and the photoinitiator and the alkali are fully dissolved in the solvent under the stirring time.
After the precursor solution is obtained, the self-healing reticular polymer electrolyte is obtained by carrying out UV curing on the precursor solution.
After the precursor solution is obtained, the invention also preferably carries out ultrasonic treatment on the precursor solution for 1-10 min; the conditions of the ultrasound are not particularly limited in the present invention, and may be performed by using conditions known to those skilled in the art.
After the ultrasonic treatment is completed, the invention also preferably comprises the step of blade coating the precursor solution on the surface of the polytetrafluoroethylene plate and then pre-curing. In the invention, the scraping and coating preferably adopts a scraper with a 750-micron groove; the pre-curing mode is preferably drying, the drying temperature is preferably 20-40 ℃, and the drying time is preferably 20-40 h.
In the present invention, the irradiation wavelength of the UV curing is preferably 100 to 380nm, more preferably 300 to 380nm; the irradiation intensity is preferably 10-200 mW cm -2 More preferably 100 to 200 mW/cm -2 (ii) a The time is preferably from 0.5 to 10 hours, more preferably from 0.5 to 1.5 hours.
After the UV curing is completed, the present invention also preferably includes vacuum drying; the vacuum drying process is not particularly limited, and may be performed by a method known to those skilled in the art. After the vacuum drying is finished, the invention also preferably comprises film uncovering; the process of the film uncovering is not limited in any way, and can be carried out by adopting a process well known to those skilled in the art.
The invention also provides the self-healing reticular polymer electrolyte prepared by the technical scheme or the self-healing reticular polymer prepared by the preparation method in the technical scheme, and the application of the self-healing reticular polymer electrolyte in a polymer lithium battery.
The invention also provides a polymer lithium battery which comprises a positive electrode, a negative electrode and an electrolyte, and is characterized in that the electrolyte is the self-healing reticular polymer electrolyte in the technical scheme or the self-healing reticular polymer prepared by the preparation method in the technical scheme.
The present invention does not particularly require the positive electrode and the negative electrode, and a positive electrode and a negative electrode for a lithium electrode well known to those skilled in the art may be used. In a specific embodiment of the present invention, the positive electrode includes a positive electrode active material, a current collector, a conductive agent, and a binder, and the mass ratio of the positive electrode active material, the conductive agent, and the binder is preferably 8; the positive active material comprises one or more of lithium cobaltate, lithium manganate, lithium iron phosphate and lithium iron manganese phosphate; the current collector preferably comprises a copper foil or an aluminum foil; the conductive agent preferably comprises one or more of acetylene black, ketjen black and carbon nanotubes; the binder preferably comprises one or more of polytetrafluoroethylene, polyurethane and polyvinylidene fluoride. In the present invention, the negative electrode is preferably metallic lithium. The invention has no special requirements on the assembly mode of the polymer lithium battery, and the assembly mode which is well known by the technical personnel in the field can be adopted.
The self-healing reticular polymer electrolyte is used as the electrolyte of the polymer lithium battery provided by the invention, and the polymer lithium battery has excellent rate capability.
The self-healing polymer electrolyte, the preparation method and the application thereof, and the polymer lithium battery provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dissolving 2.5g of 4, 4-diaminodiphenyl disulfide in acetone, bubbling nitrogen for 30min, adding 2.9mL of methacrylic ester isocyanoethyl ester, and stirring at room temperature for 20h to obtain diphenyl disulfide bis (2-methacrylamide);
dissolving 0.55g of lithium salt (LiTFSI), 0.08g of ionic liquid (1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt), 1.25g of polyethylene glycol diacrylate with the molecular weight of 1000g/mol, 0.077g of diphenyl disulfide bis (2-methacrylamide), 0.0305g of pentaerythritol tetrakis (3-mercaptopropionate) and 0.23g of 3, 6-dioxa-1, 8-octane dithiol in anhydrous acetonitrile, stirring for 12 hours, adding 20mg of photoinitiator and 10 mu L of n-butylamine after stirring uniformly, and continuing stirring for 1 hour to obtain a uniform precursor solution;
subjecting the uniform precursor solution to ultrafiltrationApplying the slurry onto a 10 × 20cm rectangular polytetrafluoroethylene plate by blade coating for 3min, precuring in a drier for 24h, and irradiating with ultraviolet light for 1h (wavelength of 365nm and light intensity of 150mW cm) -2 ) Drying at 60 deg.C for 4h in a vacuum oven after curing, and stripping the membrane to obtain healing mesh polymer electrolyte;
FIG. 1 is an infrared spectrum of 2560cm of a self-healing network polymer electrolyte, pentaerythritol tetrakis (3-mercaptopropionate), polyethylene glycol diacrylate, diphenyl disulfide bis (2-methacrylamide) and 3, 6-dioxa-1, 8-octanedithiol obtained in example 1 -1 Absorption band V S-H Peak sum 1620cm -1 Absorption band V C＝C Disappearance indicates that the pentaerythritol tetra (3-mercaptopropionate), the polyethylene glycol diacrylate, the diphenyl disulfide bis (2-methacrylamide) and the 3, 6-dioxa-1, 8-octane dithiol have thiol-ene click reaction to generate a reticular polymer;
fig. 2 is a pictorial view and SEM image of the self-healing reticulated polymer electrolyte prepared in example 1, wherein (a) is a photograph of the electrolyte folded in half, (b) is a photograph of the electrolyte laid flat, and (c) is a SEM image of the self-healing reticulated polymer electrolyte; as can be seen from fig. 2, the self-healing reticulated polymer electrolyte prepared in example 1 is a transparent self-supporting electrolyte membrane and can be recovered after folding and rolling, and the overall morphology indicates that the electrolyte membrane has excellent mechanical flexibility and is microscopically compact and non-porous; interface contact with the electrode is facilitated;
FIG. 3 is a graph showing the change of ion conductivity with temperature of the self-healing mesh-shaped polymer electrolyte membrane prepared in example 1 and the self-healing mesh-shaped polymer electrolyte membrane after self-healing after leaving for 24 hours, the membrane thickness being about 110 μm, and the original ion conductivity at 28 ℃ being 1.13X 10 -4 S·cm -1 The self-healing reticular polymer electrolyte membrane after self-healing has the ionic conductivity of 0.569 multiplied by 10 -4 S·cm -1 . The ion conductivity of the self-healing reticular polymer electrolyte membrane after self-healing is slightly lower than the original ion conductivity;
button assembly with self-healing reticulated polymer electrolyte prepared in example 1 as electrolyteThe battery comprises a positive electrode active material, a current collector, a conductive agent and a binder, wherein the positive electrode active material is lithium iron phosphate, the current collector is aluminum foil, the conductive agent is acetylene black, and the binder is polytetrafluoroethylene; the negative electrode is metallic lithium. FIG. 4 is a room temperature cycle test chart of the button cell, and it can be seen from FIG. 4 that the initial discharge capacity of the original self-healing polymer electrolyte cell is 146.9mAh g at 0.1C rate for the button cell assembled by the original self-healing polymer electrolyte cell and the self-healing polymer electrolyte cell -1 And after 19 cycles, the concentration of the active ingredient is kept at 161mAh g -1 The coulomb efficiency was 99.8%. The initial discharge capacity of the self-healing reticular polymer electrolytically assembled battery after self-healing is 140.9 mAh.g -1 And kept at 161mAh g after 19 cycles -1 The coulomb efficiency is 99.9%, and the current cell (146.9 mAh g) -1 ) Very close to that, the specific capacity reaches 161mAh g after 19 times of circulation -1 . However, the self-healing reticular polymer electrolysis assembled battery after self-healing shows higher specific discharge capacity than the original battery after 11 cycles, which indicates that the electrolyte membrane after repairing can still be effectively applied to the lithium ion battery;
fig. 5 is a room temperature rate cycle test chart of the button cell, and it can be seen from fig. 5 that the specific discharge capacity of the lithium iron phosphate at room temperature under 0.1C rate is 160mAh g -1 (ii) a The specific discharge capacity at 0.2C rate is 150mAh g -1 (ii) a The specific discharge capacity at 0.5C rate is 130mAh g -1 (ii) a The specific discharge capacity at 1C rate is 100mAh g -1 The specific capacity of the lithium iron phosphate under the 2C multiplying power is 80 mAh.g -1 And when the current multiplying power is recovered to the initial 0.1C, the discharge specific capacity is almost completely recovered. Therefore, the button cell has excellent rate performance;
fig. 6 is a cycle stability curve for a Li// Li symmetric button cell assembled from the self-healing reticulated polymer electrolyte prepared in example 1. Using a lithium foil having a diameter of 12mm at 0.05 mA-cm -2 At a current density of (3), the symmetric cell has a Li content of one hour + Electroplating and one hour Li + The cycle was run under stripping, with negative and positive voltages representing plated and stripped lithium ions, respectively. After 120 hours of cycling, the positive voltage was still constant at 0.15V, indicating that between the Li negative electrode and the electrolyte membraneThe interface is relatively stable and has excellent interface compatibility with a lithium negative electrode;
fig. 7 shows the self-healing process of the self-healing reticulated polymer electrolyte membrane prepared in example 1 at room temperature. The thickness of the electrolyte membrane is about 800 μm, and the use of a thicker membrane is intended to improve the operability of the self-healing test. The film was cut into two pieces with a scalpel, the two separated portions were brought into contact, and after standing for 24 hours, the cut film was healed, and although the gap was not completely disappeared, the healed film could withstand a weight of 100g without breaking. The self-healing performance is good, and the self-healing capability is attributed to the action of urea groups and dynamic disulfide bonds in the polymer;
fig. 8 is a flame-retardant process of the self-healing mesh polymer electrolyte membrane prepared in example 1. When no igniter is arranged after the film is burnt, no further burning is observed, the flame can be automatically extinguished, and the flame retardant property is good.
Example 2
The self-healing reticular polymer electrolyte is prepared by the following steps:
dissolving 2.5g of bis (4-hydroxyphenyl) disulfide in dichloromethane, bubbling nitrogen for 30min, heating at 60 ℃, stirring for 30min, adding 1mL of dibutyltin dilaurate and 2.9mL of methacrylic ester isocyanoethyl ester when the temperature is reduced to 40 ℃, and stirring for 20h at 40 ℃ to obtain diphenyl disulfide bis (2-methacrylate);
dissolving 0.55g of lithium salt (LiTFSI), 0.08g of ionic liquid (1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt), 1.25g of polyethylene glycol diacrylate with the molecular weight of 1000g/mol, 0.077g of diphenyl disulfide bis (2-methacrylate), 0.0305g of pentaerythritol tetrakis (3-mercaptopropionate) and 0.23g of 3, 6-dioxa-1, 8-octane dithiol in anhydrous acetonitrile, stirring for 12 hours, adding 20mg of photoinitiator and 10 mu L of n-butylamine after stirring uniformly, and continuing stirring for 1 hour to obtain a uniform precursor solution;
subjecting the uniform precursor solution to ultrasound for 3min to obtain slurry, blade-coating the slurry on a 10 × 20cm rectangular polytetrafluoroethylene plate, precuring in a drier for 24h, and irradiating with ultraviolet light for 1h (wavelength of 365nm and light intensity of 150mW cm) -2 ) Curing and then putting in a vacuum ovenDrying at 60 deg.C for 4h, and stripping to obtain healing network polymer electrolyte.
The self-healing network polymer electrolyte prepared in example 2 has a room temperature conductivity of 8.76X 10 -5 S·cm -1 。
Example 3
The self-healing reticular polymer electrolyte is prepared by the following steps:
dissolving 0.31g of bis (2-hydroxyethyl) disulfide in dichloromethane, bubbling nitrogen for 30min, heating and stirring at 60 ℃ for 30min, adding 0.2mL of dibutyltin dilaurate and 0.58mL of methacrylic ester isocyanoethyl ester when the temperature is reduced to 40 ℃, and stirring at 40 ℃ for 20h to obtain disulfide bis (2-methacrylate);
dissolving 0.55g of lithium salt (LiTFSI), 0.08g of ionic liquid (1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide salt), 1.25g of polyethylene glycol diacrylate with the molecular weight of 1000g/mol, 0.077g of disulfide bis (2-methacrylate), 0.0305g of pentaerythritol tetrakis (3-mercaptopropionate) and 0.23g of 3, 6-dioxa-1, 8-octane dithiol in anhydrous acetonitrile, stirring for 12 hours, adding 20mg of photoinitiator and 10 mu L of n-butylamine after stirring uniformly, and continuing stirring for 1 hour to obtain a uniform precursor solution;
subjecting the uniform precursor solution to ultrasound for 3min to obtain slurry, knife-coating the slurry on a rectangular polytetrafluoroethylene plate of 10 × 20cm, precuring in a drier for 24h, and irradiating with ultraviolet light for 1h (wavelength of 365nm, light intensity of 150mW cm) -2 ) After curing, drying at 60 ℃ for 4h in a vacuum oven, stripping the film, and obtaining the healing reticular polymer electrolyte.
The self-healing network polymer electrolyte prepared in example 3 had a room temperature conductivity of 8.56X 10 -5 S·cm -1 。
Example 4
The self-healing reticular polymer electrolyte is prepared by the following steps:
dissolving 2.5g of 4, 4-diaminodiphenyl disulfide in acetone, bubbling nitrogen for 30min, adding 2.9mL of methacrylic ester isocyanoethyl ester, and stirring at room temperature for 20h to obtain diphenyl disulfide bis (2-methacrylamide);
dissolving 0.6063g of lithium salt (LiTFSI), 0.1586g of ionic liquid (1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt), 1.25g of polyethylene glycol diacrylate with the molecular weight of 1000g/mol, 0.077g of diphenyl disulfide bis (2-methacrylamide), 0.0305g of pentaerythritol tetrakis (3-mercaptopropionate) and 0.23g of 3, 6-dioxa-1, 8-octane dithiol in anhydrous acetonitrile, stirring for 12 hours, adding 20mg of photoinitiator and 10 mu L of n-butylamine after stirring uniformly, and continuing stirring for 1 hour to obtain a uniform precursor solution;
subjecting the uniform precursor solution to ultrasound for 3min to obtain slurry, blade-coating the slurry on a 10 × 20cm rectangular polytetrafluoroethylene plate, precuring in a drier for 24h, and irradiating with ultraviolet light for 1h (wavelength of 365nm and light intensity of 150mW cm) -2 ) After curing, drying at 60 ℃ for 4h in a vacuum oven, film stripping, and self healing of the reticulated polymer electrolyte.
The self-healing network polymer electrolyte prepared in example 4 has a room temperature conductivity of 1.24X 10 -4 S·cm -1 。
Example 5
The self-healing reticular polymer electrolyte is prepared by the following steps:
dissolving 2.5g of 4, 4-diaminodiphenyl disulfide in acetone, bubbling nitrogen for 30min, adding 2.9mL of methacrylic ester isocyanoethyl ester, and stirring at room temperature for 20h to obtain diphenyl disulfide bis (2-methacrylamide);
0.6650g of lithium salt (LiTFSI), 0.2379g of ionic liquid (1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide salt), 1.25g of polyethylene glycol diacrylate with the molecular weight of 1000g/mol, 0.077g of diphenyl disulfide bis (2-methacrylamide), 0.0305g of pentaerythritol tetrakis (3-mercaptopropionate) and 0.23g of 3, 6-dioxa-1, 8-octane dithiol are dissolved in anhydrous acetonitrile and stirred for 12h, after the mixture is stirred uniformly, 20mg of photoinitiator and 10 μ L of n-butylamine are added, and the mixture is stirred continuously for 1h to obtain a uniform precursor solution;
subjecting the uniform precursor solution to ultrasound for 3min to obtain slurry, knife-coating the slurry on a rectangular polytetrafluoroethylene plate of 10 × 20cm, precuring in a drier for 24h, and irradiating with ultraviolet light for 1h (wavelength of 365nm, light intensity of 150mW cm) -2 ) After curing, under vacuumDrying in an oven at 60 deg.C for 4h, stripping the membrane, and obtaining a healed network polymer electrolyte.
The self-healing network polymer electrolyte prepared in example 5 had a room temperature conductivity of 1.31X 10 -4 S·cm -1 。
Comparative example 1
The self-healing reticular polymer electrolyte is prepared by the following steps:
dissolving 2.5g of 4, 4-diaminodiphenyl disulfide in acetone, bubbling nitrogen for 30min, adding 2.9mL of methacrylate isocyanate, and stirring at room temperature for 20h to obtain diphenyl disulfide bis (2-methacrylamide);
dissolving 0.489g of lithium salt (LiTFSI), 1.25g of polyethylene glycol diacrylate with the molecular weight of 1000g/mol, 0.077g of diphenyl disulfide bis (2-methacrylamide), 0.0305g of tetra (3-mercaptopropionic acid) pentaerythritol ester and 0.23g of 3, 6-dioxa-1, 8-octane dithiol in anhydrous acetonitrile, stirring for 12 hours, adding 20mg of photoinitiator and 10 mu L of n-butylamine after stirring uniformly, and continuing stirring for 1 hour to obtain a uniform precursor solution;
subjecting the uniform precursor solution to ultrasound for 3min to obtain slurry, blade-coating the slurry on a 10 × 20cm rectangular polytetrafluoroethylene plate, precuring in a drier for 24h, and irradiating with ultraviolet light for 1h (wavelength of 365nm and light intensity of 150mW cm) -2 ) After curing, drying at 60 ℃ for 4h in a vacuum oven, film stripping, and self healing of the reticulated polymer electrolyte.
The self-healing network polymer electrolyte prepared in comparative example 1 had a room temperature conductivity of 9.7X 10 -5 S·cm -1 。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The self-healing reticular polymer electrolyte is characterized by comprising the following preparation raw materials in parts by mass: 3-10 parts of ionic liquid, 40-70 parts of polyethylene glycol diacrylate, 1-10 parts of disulfide diacrylate, 1-5 parts of cross-linking agent, 3-10 parts of chain extender, 1-5 parts of alkali, 20-30 parts of lithium salt, 1-10 parts of photoinitiator and 90-110 parts of solvent;
the cross-linking agent and the chain extender both comprise sulfydryl.
2. A self-healing network polymer electrolyte according to claim 1, wherein the ionic liquid comprises one or more of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 2, 3-dimethyl-1-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidine bis (trifluoromethanesulfonyl) imide salt, and 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt.
3. A self-healing reticulated polymer electrolyte according to claim 1, wherein the disulfide diacrylates comprise bis (4-vinylphenyl) disulfide and/or disulfide dimethacrylates.
4. A self-healing network polymer electrolyte according to claim 1, wherein the cross-linking agent includes one or more of pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), and trimethylolpropane tris (3-mercaptopropionate).
5. A self-healing reticulated polymer electrolyte according to claim 1, wherein the chain extender comprises one or more of 3, 6-dioxa-1, 8-octanedithiol, 1, 10-decanedithiol, 1, 4-butanedithiol, 1, 2-ethanedithiol, 1, 16-hexadecanedithiol, 1, 5-pentanedithiol, and 1, 6-hexanedithiol;
the photoinitiator comprises one or more of 2, 2-dimethoxy-2-phenylacetophenone, 4-methylbenzophenone and 1-hydroxycyclohexyl phenyl ketone.
6. A self-healing reticulated polymer electrolyte according to claim 1, wherein the base comprises one or more of n-butylamine, t-butylamine, n-propylamine, t-pentylamine, and isobutylamine;
the lithium salt comprises LiPF 6 、LiClO 4 One or more of LiTFSI, liFSI, liBOB and lidpob.
7. A method for preparing a self-healing reticulated polymer electrolyte according to any one of claims 1 to 6, comprising the following steps:
mixing ionic liquid, polyethylene glycol diacrylate, disulfide diacrylate, a cross-linking agent, a chain extender, lithium salt and a solvent, and then mixing the ionic liquid, the polyethylene glycol diacrylate, the disulfide diacrylate, the cross-linking agent, the chain extender, the lithium salt and the solvent with a photoinitiator and alkali to obtain a precursor solution;
and carrying out UV curing on the precursor solution to obtain the self-healing reticular polymer electrolyte.
8. The method according to claim 7, wherein the UV-curing is performed at an irradiation wavelength of 100 to 380nm and an irradiation intensity of 10 to 200 mW-cm -2 The time is 0.5 to 10 hours.
9. Use of the self-healing reticulated polymer electrolyte according to any one of claims 1 to 6 or the self-healing reticulated polymer obtained by the preparation method according to claim 7 or 8 in a lithium polymer battery.
10. A polymer lithium battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the self-healing network polymer electrolyte according to any one of claims 1 to 6 or the self-healing network polymer prepared by the preparation method according to claim 7 or 8.
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