Patent Description:
Lithium-ion batteries are widely used due to their high energy density and working voltage, long cycle life, low self-discharge rate, no memory effect, fast charging and discharging, and environmental friendliness. However, traditional liquid lithium secondary batteries contain a large amount of organic electrolytes, and are easily volatile, flammable, and explosive, thus posing a major safety hazard. Compared with organic electrolytes, polymer electrolytes can avoid the leakage of traditional lithium batteries and improve the safety performance of batteries. Moreover, the polymer electrolytes show better compatibility with electrodes and inhibit the growth of lithium dendrites. Furthermore, desirable mechanical processing properties of the polymer electrolytes make thin-film, miniaturized, flexible, and bendable lithium batteries possible. At present, a commonly used electrolyte for polymer electrolyte batteries is polyethylene oxide. However, polyethylene oxide electrolytes have high interfacial impedance and low ionic conductivity at room temperature.

To address these issues, researchers have proposed a variety of modification schemes, such as preparation of random copolymers, block copolymers, network polymers, or comb polymers. These polymers can enhance a lithium-conducting function to a certain extent, but still need to improve their rate and cycle performances.

<NPL>) disclose a process to prepare microporous poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) copolymer based gel electrolyte with polyethylene glycol dimethacrylate (PEGDMA) network without the need for extraction process, where the microporous structure in polymer matrix is achieved by solvent controlled evaporation from solution containing a copolymer in a mixture of volatile solvent and nonsolvent.

<NPL>) disclose a PVdF-HFP based gel polymer electrolytes synthesized by UV-curing method, where the PEGMA and PEGDA are employed to enhance the mechanical properties of the electrolyte by forming 3D semi-interpenetrating polymer network.

<NPL>) disclose a method for preparing semi-interpenetrating polymer networks of PVDF-HFP based electrolytes with crosslinked diepoxy polyethylene glycol (DIEPEG). In the method, impurities are avoided because of a moderate reaction temperature at <NUM> and poly(ethylenimine)(PEI) as the crosslinking agent.

An objective of the present disclosure is to provide an SIPN electrolyte and a preparation method and use thereof. The SIPN electrolyte has an excellent rate performance and a stable cycle performance.

To achieve the above objective of the present disclosure, the present disclosure provides the following technical solutions.

The present disclosure provides a semi-interpenetrating polymer network (SIPN) electrolyte, including the following raw materials: poly(vinylidene fluoride-co-hexafluoropropylene), a diallyl compound, a crosslinking agent, a plasticizer, a photoinitiator , and a lithium salt; where.

Preferably, the N,N'-carbonyldiimidazole, the N,N'-diisopropylethylamine, and the polyethylene glycol monomethyl ether are at a mass ratio of (<NUM>-<NUM>):(<NUM>-<NUM>):<NUM>; and
the terminal methylimidazole-based polyethylene oxide and the <NUM>,<NUM>-bis(allyloxymethyl)-<NUM>-butanol (containing mono- and tri-substituted products) are at a mass ratio of <NUM>:(<NUM>-<NUM>).

Preferably, the first organic solvent and the second organic solvent are independently selected from the group consisting of dichloromethane, chloroform, methanol, ethanol, acetone, acetonitrile, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA).

Preferably, the first elimination and the second elimination each are conducted under stirring; and
the first elimination and the second elimination are conducted at a room temperature for independently <NUM> to <NUM>.

Preferably, the plasticizer is one or more selected from the group consisting of propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, fluorovinyl hydrochloride, and ethyl methyl carbonate.

Preferably, the photoinitiator is one or more selected from the group consisting of benzoylbenzene, phenylbenzophenone, <NUM>-methylbenzophenone, <NUM>-hydroxycyclohexyl phenyl ketone, and <NUM>,<NUM>-dimethoxy-<NUM>-phenylacetophenone; and
the lithium salt is one or more selected from the group consisting of LiPF<NUM>, LiClO<NUM>, LiTFSI, LiFSI, LiBOB, and LiDFOB.

The present disclosure further provides a preparation method of the SIPN electrolyte, including the following steps:.

Preferably, the ultraviolet irradiation is conducted at a wavelength of <NUM> to <NUM> and a light intensity of (<NUM>-<NUM>) mW·cm-<NUM> for <NUM> to <NUM>.

The present disclosure further provides use of the SIPN electrolyte in a polymer lithium battery.

The present disclosure provides a semi-interpenetrating polymer network (SIPN) electrolyte, including the following raw materials: poly(vinylidene fluoride-co-hexafluoropropylene), a diallyl compound, a crosslinking agent, a plasticizer, a photoinitiator , and a lithium salt; where the poly(vinylidene fluoride-co-hexafluoropropylene), the diallyl compound, the crosslinking agent, the plasticizer, and the photoinitiator are at a mass ratio of (<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>); and the lithium salt and oxirane groups in the SIPN electrolyte are at a mass ratio of <NUM>:(<NUM>-<NUM>). In the present disclosure, the SIPN electrolyte can undergo a thiol-ene click reaction under ultraviolet irradiation to form a solid electrolyte containing a semi-interpenetrating network structure. The poly(vinylidene fluoride-co-hexafluoropropylene) not only enhances mechanical properties of the semi-interpenetrating network structure, but also improves an ionic conductivity of a film of the SIPN electrolyte at room temperature. In this way, an obtained polymer lithium battery can obtain an excellent rate performance and a cycle stability. According to the description of examples, the SIPN electrolyte has an ion conductivity of <NUM>×<NUM>-<NUM> S·cm-<NUM> at room temperature; a lithium iron phosphate-based lithium battery assembled with the film of the SIPN electrolyte has a specific discharge capacity of up to <NUM> mA·h·g-<NUM> at a rate of <NUM> C.

The present disclosure further provides a preparation method of the SIPN electrolyte, including the following steps: mixing the poly(vinylidene fluoride-co-hexafluoropropylene), the lithium salt, the diallyl compound, the crosslinking agent, the plasticizer, and the photoinitiator with an organic solvent to obtain a precursor solution; and forming a film from the precursor solution, and subjecting the film to ultraviolet irradiation to obtain the SIPN electrolyte. The preparation method has simple operation, mild conditions, and low cost.

In the present disclosure, unless otherwise specified, all raw materials for preparation are commercially available products well known to those skilled in the art.

In the present disclosure, N,N'-carbonyldiimidazole, N,N'-diisopropylethylamine, and polyethylene glycol monomethyl ether are mixed with a first organic solvent to allow first elimination to obtain a terminal methylimidazole-based polyethylene oxide.

In the present disclosure, the first organic solvent is preferably one or more of dichloromethane, chloroform, methanol, ethanol, acetone, acetonitrile, DMSO, DMF, and DMA. When the first organic solvent includes two or more of the above specific options, there is no special limitation on a proportion of the above specific substances, which can be mixed according to any proportion.

In the present disclosure, the N,N'-carbonyldiimidazole, the N,N'-diisopropylethylamine, and the polyethylene glycol monomethyl ether are at a mass ratio of preferably (<NUM>-<NUM>):(<NUM>-<NUM>):<NUM>, more preferably (<NUM>-<NUM>):(<NUM>-<NUM>):<NUM>, and most preferably (<NUM>-<NUM>):(<NUM>-<NUM>):<NUM>.

In the present disclosure, the N,N'-carbonyldiimidazole and the first organic solvent are at a mass-to-volume ratio of preferably <NUM>: (<NUM>-<NUM>) mL, more preferably <NUM>: (<NUM>-<NUM>) mL, most preferably <NUM>: (<NUM>-<NUM>) mL.

In the present disclosure, the mixing includes preferably: mixing the N,N'-carbonyldiimidazole, the N,N'-diisopropylethylamine, and a part of the first organic solvent, and discharging air to obtain a first solution; mixing the polyethylene glycol monomethyl ether and a remaining part of the first organic solvent to obtain a second solution; adding the second solution to the first solution. There is no special limitation on a ratio of the part of the first organic solvent and the remaining part of the first organic solvent, and a ratio well known to those skilled in the art can be used to ensure that the first solution and the second solution are fully dissolved.

In the present disclosure, the first elimination is preferably conducted under stirring. There is no special limitation on a stirring process, and a process well known to those skilled in the art can be used. The first elimination is conducted at preferably a room temperature for preferably <NUM> to <NUM>.

In the present disclosure, the terminal methylimidazole-based polyethylene oxide and <NUM>,<NUM>-bis(allyloxymethyl)-<NUM>-butanol (containing mono- and tri-substituted products) are mixed with a second organic solvent to allow second elimination to obtain the diallyl compound.

In the present disclosure, the second organic solvent is preferably one or more of dichloromethane, chloroform, methanol, ethanol, acetone, acetonitrile, DMSO, DMF, and DMA. When the second organic solvent includes two or more of the above specific options, there is no special limitation on a proportion of the above specific substances, which can be mixed according to any proportion.

In the present disclosure, the terminal methylimidazole-based polyethylene oxide and the <NUM>,<NUM>-bis(allyloxymethyl)-<NUM>-butanol (containing mono- and tri-substituted products) are at a mass ratio of preferably <NUM>:(<NUM>-<NUM>), more preferably <NUM>:(<NUM>-<NUM>), and most preferably <NUM>:(<NUM>-<NUM>).

In the present invention, the terminal methylimidazole-based polyethylene oxide and the second organic solvent are at a mass-to-volume ratio of preferably <NUM>: (<NUM>-<NUM>) mL, more preferably <NUM>: (<NUM>-<NUM>) mL, and most preferably <NUM>: (<NUM>-<NUM>) mL.

In the present disclosure, there is no special limitation on a mixing process, which can be conducted by adopting a process well known to those skilled in the art.

In the present disclosure, the second elimination is preferably conducted under stirring. There is no special limitation on a stirring process, and a process well known to those skilled in the art can be used. The second elimination is conducted at preferably a room temperature for preferably <NUM> to <NUM>.

In the present disclosure, the crosslinking agent is one or more selected from the group consisting of pentaerythritol tetrakis(<NUM>-mercaptopropionate), dipentaerythritol hexakis(<NUM>-mercaptopropionate), trimethylolpropane tris(<NUM>-mercaptopropionate), and pentaerythritol tetrakis(<NUM>-mercaptoacetate). When the crosslinking agent includes two or more of the above specific options, there is no special limitation on a proportion of the above specific substances, which can be mixed according to any proportion.

In the present disclosure, the plasticizer is one or more selected from the group consisting of propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, fluorovinyl hydrochloride, and ethyl methyl carbonate. When the plasticizer includes two or more of the above specific options, there is no special limitation on a proportion of the above specific substances, which can be mixed according to any proportion.

In the present disclosure, the photoinitiator is one or more selected from the group consisting of benzoylbenzene, phenylbenzophenone, <NUM>-methylbenzophenone, <NUM>-hydroxycyclohexyl phenyl ketone, and <NUM>,<NUM>-dimethoxy-<NUM>-phenylacetophenone. When the photoinitiator includes two or more of the above specific options, there is no special limitation on a proportion of the above specific substances, which can be mixed according to any proportion.

In the present disclosure, the lithium salt is one or more selected from the group consisting of LiPF<NUM>, LiClO<NUM>, LiTFSI, LiFSI, LiBOB, and LiDFOB. When the lithium salt includes two or more of the above specific options, there is no special limitation on a proportion of the above specific substances, which can be mixed according to any proportion.

In the present disclosure, the poly(vinylidene fluoride-co-hexafluoropropylene), the diallyl compound, the crosslinking agent, the plasticizer, and the photoinitiator are at a mass ratio of preferably (<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>), more preferably (<NUM>-<NUM>):(<NUM>-<NUM>):( <NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>), and most preferably (<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>).

In the present disclosure, the lithium salt and the SIPN electrolyte are at a mass ratio of <NUM>:(<NUM>-<NUM>), more preferably <NUM>:(<NUM>-<NUM>), and most preferably <NUM>:(<NUM>-<NUM>).

In the present disclosure, the poly(vinylidene fluoride-co-hexafluoropropylene), the lithium salt, the diallyl compound, the crosslinking agent, the plasticizer, and the photoinitiator are mixed with an organic solvent to obtain a precursor solution.

In the present disclosure, the organic solvent is preferably one or more of dichloromethane, chloroform, methanol, ethanol, acetone, acetonitrile, DMSO, DMF, and DMA. When the organic solvent includes two or more of the above specific options, there is no special limitation on a proportion of the above specific substances, which can be mixed according to any proportion.

In the present disclosure, the mixing includes preferably: mixing the poly(vinylidene fluoride-co-hexafluoropropylene) and the organic solvent, adding the lithium salt, the diallyl compound, the crosslinking agent, and the plasticizer in sequence, stirring for <NUM> to <NUM> until uniformly dispersed, adding the photoinitiator and continuing to stir for <NUM> to <NUM>.

In the present disclosure, a film is formed from the precursor solution, and the film is subjected to ultraviolet irradiation to obtain the SIPN electrolyte.

In the present disclosure, the precursor solution is preferably subjected to ultrasonic treatment for <NUM> to <NUM> before the film is formed. There is no special limitation on a frequency of the ultrasonic treatment, and a frequency well known to those skilled in the art can be used.

In the present disclosure, the film is preferably formed by: coating the precursor solution on a surface of a substrate, and then drying.

In the present disclosure, the coating includes preferably scraping the precursor solution onto the surface of the substrate with a doctor blade with a groove of <NUM>. The substrate is preferably a polytetrafluoroethylene substrate.

In the present disclosure, the drying is preferably vacuum drying; and the vacuum drying is conducted at preferably <NUM> to <NUM>, more preferably <NUM> to <NUM> for preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>.

In the present disclosure, the ultraviolet irradiation is conducted at a wavelength of preferably <NUM> to <NUM>, more preferably <NUM> to <NUM> and a light intensity of (<NUM>-<NUM>) mW·cm-<NUM>, more preferably (<NUM>-<NUM>) mW·cm-<NUM> for preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>.

The present disclosure further provides use of the SIPN electrolyte in a polymer lithium battery. In the present disclosure, there is no special limitation on a use method, and the SIPN electrolyte can be used as an electrolyte between a cathode and an anode in the polymer lithium battery by a method well known to those skilled in the art.

The SIPN electrolyte and the preparation method and the use thereof provided by the present disclosure will be described in detail below in conjunction with examples, but should not be construed as limiting the scope of the disclosure.

<NUM> of N,N'-carbonyldiimidazole and <NUM> of N,N'-diisopropylethylamine were dissolved in <NUM> of dichloromethane, and air in a device was removed to obtain a first solution; <NUM> of polyethylene glycol monomethyl ether with a molar mass of <NUM>,<NUM>/mol was dissolved in <NUM> of dichloromethane to obtain a second solution; the second solution was added to the first solution, and stirred at room temperature for <NUM> to obtain terminal methylimidazole-based polyethylene oxide.

<NUM> of the terminal methylimidazole-based polyethylene oxide and <NUM> of <NUM>,<NUM>-bis(allyloxymethyl)-<NUM>-butanol were dissolved in <NUM> of chloroform, and stirred at room temperature for <NUM> to obtain a diallyl compound.

<NUM> of poly(vinylidene fluoride-co-hexafluoropropylene) was dissolved in <NUM> of DMF; <NUM> of LiTFSI, <NUM> of the diallyl compound, <NUM> of pentaerythritol tetrakis(<NUM>-mercaptopropionate), and <NUM> of fluoroethylene carbonate were added, stirred for <NUM> to uniformity, then added with <NUM> of a photoinitiator (the photoinitiator was <NUM>,<NUM>-dimethoxy-<NUM>-phenylacetophenone) and then continuously stirred for <NUM> to obtain a homogeneous precursor solution. the precursor solution was subjected to ultrasonic treatment for <NUM>, scraped onto a rectangular polytetrafluoroethylene plate using a scraper with a groove of <NUM>, dried in vacuum at <NUM> for <NUM>, and subjected to ultraviolet irradiation for <NUM> (wavelength: <NUM>, light intensity: <NUM> mW cm-<NUM>) to obtain a film; the film was peeled off from the polytetrafluoroethylene plate for demolding to obtain an SIPN electrolyte (with a thickness of <NUM>).

The diallyl compound was subjected to a nuclear magnetic resonance test, and the test results were shown in <FIG> showed a proton nuclear magnetic resonance spectrogram of the diallyl compound. As shown in <FIG>, the diallyl compound had a structure consistent with that shown in Formula <NUM>.

<FIG> showed a curve that an ion conductivity of the SIPN electrolyte changed with temperature. As shown in <FIG>, an original ionic conductivity at <NUM> was <NUM>×<NUM>-<NUM> S·cm-<NUM>, and an ionic conductivity at <NUM> was <NUM>×<NUM>-<NUM> S·cm-<NUM>, indicating that the ionic conductivity increased with the increase of temperature.

The SIPN electrolyte prepared in Example <NUM> was used as an electrolyte to assemble a button cell, where a cathode active material was lithium iron phosphate, a current collector was aluminum foil, a conductive agent was acetylene black, and a binder was polytetrafluoroethylene; an anode was lithium metal. <FIG> showed a room-temperature cycle test result of a button cell assembled by the SIPN electrolyte. As shown in <FIG>, for the button cell assembled with the SIPN electrolyte: at a rate of <NUM> C, the SIPN electrolyte-based battery exhibited an initial discharge capacity of <NUM> mA·h·g-<NUM>, which maintained at <NUM> mA·h·g-<NUM> after <NUM> cycles; and the battery had a Coulombic efficiency consistently above <NUM>%.

<FIG> showed a cycle test result of a Li//Li symmetric button cell assembled by the SIPN electrolyte prepared in Example <NUM>. The symmetric cell was cycled for one hour of Li+ electroplating and one hour of Li+ stripping with a <NUM>-mm-diameter lithium foil at a current density of <NUM> mA cm-<NUM>; where a negative voltage and a positive voltage represented electroplated and stripped lithium ions, respectively. After <NUM> of cycling, the positive voltage was maintained at <NUM> V, indicating that an interface between the Li anode and the electrolyte film was relatively stable, while the electrolyte film and the lithium anode showed excellent interfacial compatibility.

<NUM> of poly(vinylidene fluoride-co-hexafluoropropylene) was dissolved in <NUM> of DMF; <NUM> of LiTFSI, <NUM> of the diallyl compound, <NUM> of pentaerythritol tetrakis(<NUM>-mercaptopropionate), and <NUM> of fluoroethylene carbonate were added, stirred for <NUM> to uniformity, then added with <NUM> of a photoinitiator (the photoinitiator was <NUM>,<NUM>-dimethoxy-<NUM>-phenylacetophenone) and then continuously stirred for <NUM> to obtain a homogeneous precursor solution.

The precursor solution was subjected to ultrasonic treatment for <NUM>, scraped onto a rectangular polytetrafluoroethylene plate using a scraper with a groove of <NUM>, dried in vacuum at <NUM> for <NUM>, and subjected to ultraviolet irradiation for <NUM> (wavelength: <NUM>, light intensity: <NUM> mW cm-<NUM>) to obtain a film; the film was peeled off from the polytetrafluoroethylene plate for demolding to obtain an SIPN electrolyte (with a thickness of <NUM>).

<FIG> showed a room-temperature rate cycle test result of a Li//Li symmetric button cell assembled by the SIPN electrolyte. As shown in <FIG>, the lithium iron phosphate had a specific discharge capacity of <NUM> mAh·g-<NUM> at a rate of <NUM> C under room temperature; the specific discharge capacity at <NUM> C rate was <NUM> mAh g-<NUM>; the specific discharge capacity at <NUM> C rate was <NUM> mAh g-<NUM>; the specific discharge capacity at <NUM> C rate was <NUM> mAh·g-<NUM>. Moreover, when the current rate was restored to the initial <NUM> C, the specific discharge capacity was almost completely restored, indicating that the button cell had excellent rate performance.

<NUM> of N,N'-carbonyldiimidazole and <NUM> of N,N'-diisopropylethylamine were dissolved in <NUM> of dichloromethane, and air in a device was removed to obtain a first solution; <NUM> of polyethylene glycol monomethyl ether with a molar mass of <NUM>/mol was dissolved in <NUM> of dichloromethane to obtain a second solution; the second solution was added to the first solution, and stirred at room temperature for <NUM> to obtain terminal methylimidazole-based polyethylene oxide.

<NUM> of the terminal methylimidazole-based polyethylene oxide and <NUM> of <NUM>,<NUM>-bis(allyloxymethyl)-<NUM>-butanol (containing mono- and tri-substituted products) were dissolved in <NUM> of chloroform, and stirred at room temperature for <NUM> to obtain a diallyl compound.

Claim 1:
A semi-interpenetrating polymer network (SIPN) electrolyte, comprising the following raw materials: poly(vinylidene fluoride-co-hexafluoropropylene), a diallyl compound, a crosslinking agent, a plasticizer, a photoinitiator , and a lithium salt; wherein
the poly(vinylidene fluoride-co-hexafluoropropylene), the diallyl compound, the crosslinking agent, the plasticizer, and the photoinitiator are at a mass ratio of (<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>):(<NUM>-<NUM>);
the lithium salt and the SIPN electrolyte are at a mass ratio of <NUM>:(<NUM>-<NUM>);
the diallyl compound has a structure shown in Formula <NUM>:
<CHM>
wherein
n is a positive integer;a preparation method of the diallyl compound comprises the following steps:
mixing N,N'-carbonyldiimidazole, N,N'-diisopropylethylamine, and polyethylene glycol monomethyl ether with a first organic solvent to allow first elimination to obtain a terminal methylimidazole-based polyethylene oxide; and
mixing the terminal methylimidazole-based polyethylene oxide and <NUM>,<NUM>-bis(allyloxymethyl)-<NUM>-butanol (containing mono- and tri-substituted products) with a second organic solvent to allow second elimination to obtain the diallyl compound; wherein
the crosslinking agent is one or more selected from the group consisting of pentaerythritol tetrakis(<NUM>-mercaptopropionate), dipentaerythritol hexakis(<NUM>-mercaptopropionate), trimethylolpropane tris(<NUM>-mercaptopropionate), and pentaerythritol tetrakis(<NUM>-mercaptoacetate); and
a preparation method of the SIPN electrolyte comprises the following steps:
mixing the poly(vinylidene fluoride-co-hexafluoropropylene), the lithium salt, the diallyl compound, the crosslinking agent, the plasticizer, and the photoinitiator with an organic solvent to obtain a precursor solution; and
forming a film from the precursor solution, and subjecting the film to ultraviolet irradiation to obtain the SIPN electrolyte.