CN111934007A - Crosslinked organic nano material modified all-solid-state polymer electrolyte and preparation method thereof - Google Patents
Crosslinked organic nano material modified all-solid-state polymer electrolyte and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of lithium ion batteries, and particularly relates to a crosslinked organic nano-material modified all-solid-state polymer electrolyte and a preparation method thereof. The invention provides an all-solid-state polymer electrolyte, which comprises the following components in percentage by weight: the lithium ion battery comprises a polymer with lithium ion transmission performance, lithium salt and an organic filler, wherein the organic filler is a cross-linked organic nano material obtained by template-free self-assembly of two-block copolymers through Friedel-crafts reaction. The obtained polymer electrolyte has higher ionic conductivity and other excellent electrochemical properties, and has good dimensional stability at the temperature of up to 200 ℃ compared with the common all-solid-state polymer electrolyte.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a crosslinked organic nano-material modified all-solid-state polymer electrolyte and a preparation method thereof.
Background
Commercial lithium ion batteries generally have four key components: a positive electrode material, a negative electrode material, an electrolyte, and a separator. The positive and negative electrode materials determine the capacity, the service voltage range and the charge and discharge rate of the battery to a great extent, but the performance of the battery has an inseparable relationship with a diaphragm and an electrolyte system in the aspects of long-range cycle stability, safety and the like. Problems such as thermal shrinkage of the separator, leakage of electrolyte, etc. can cause significant safety hazards such as combustion, explosion, etc. when the battery is subjected to thermal or mechanical abuse. Aiming at the problems, the commercialized market selects to coat a layer of ceramic material with mechanical enhancement and high temperature resistance on the surface of the polyolefin diaphragm with micron-sized pore diameter, or to modify the surface by adopting a multilayer composite membrane and other methods. The methods indeed reduce the hot air risk of the lithium ion battery to a certain extent, but cannot solve the problems fundamentally, and the flammable and explosive carbonate organic electrolyte still threatens the safe use of the lithium battery. The occurrence of the polymer electrolyte solves the problem of leakage of the lithium ion battery to a great extent, and improves the safety performance of the lithium ion battery.
Currently, All-Solid Polymer Electrolytes (SPEs) are widely studied due to their intrinsic advantages of being lightweight, good mechanical stability and processability, and not containing any liquid. The all-solid-state lithium ion battery having the possibility of use needs to satisfy three basic conditions: the ionic conductivity is more than 10 at the use temperature-4S·cm-1(ii) a Interface impedance between the all-solid electrolyte and the electrode is small, and interface stability is good; ③ the all-solid-state electrolyte should have a certain mechanical strength and flexibility to inhibit the growth of lithium dendrites and to buffer the volume change of the electrode material during the discharge process. The research which can basically meet the requirements at the present stage mainly focuses on polymer-based composite solid electrolytes taking ceramic materials with different morphologies as additives, and the flexibility of the polymer-based composite solid electrolytes also need to be improvedFor further improvement, the quality is different from that of the organic additive. Therefore, the organic filler which has excellent ion transmission capability and high thermal stability and has good compatibility with the polymer matrix and the anode and cathode materials and is used for the all-solid-state electrolyte has wide development prospect.
Disclosure of Invention
Aiming at the defects, the invention provides a crosslinked organic nano material modified all-solid-state polymer electrolyte, and the obtained polymer electrolyte has higher ionic conductivity and other excellent electrochemical properties.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the present invention is to provide an all-solid polymer electrolyte, which comprises the following components: the lithium ion battery comprises a polymer with lithium ion transmission performance, lithium salt and an organic filler, wherein the organic filler is a cross-linked organic nano material obtained by template-free self-assembly of two-block copolymers through Friedel-crafts reaction.
Further, the first component of the diblock copolymer is one of polyethylene oxide (PEO), polypropylene oxide (PPOX), polyphenylene oxide (PPO) or poly (methoxypolyethylene glycol methacrylate) (p (pegma)); the second component is polystyrene or a polymer of styrene derived monomers that does not contain strongly electron withdrawing groups.
Further, in the all-solid-state polymer electrolyte, the molar ratio of the polymer having lithium ion transport properties to the lithium salt satisfies: m is Li (10-20), and the mass fraction of the organic filler in the electrolyte is 5-30%; wherein M is a structural unit (e.g., EO in PEO) that reacts with (i.e., plays a practical role in) a lithium salt in the polymer having lithium ion transport properties.
Further, the method for preparing the cross-linked organic nano material by the template-free self-assembly of the two-block copolymer through the Friedel-crafts reaction comprises the following steps: under the anhydrous and anaerobic condition, taking a diblock copolymer (such as PEO-PS) as a raw material, and obtaining the organic crosslinking nano filler through Friedel-crafts alkylation reaction under the action of a catalyst, a crosslinking agent and a solvent; wherein the volume fraction of the cross-linking agent in the total volume of the cross-linking agent and the solvent is as follows: 0 to 90 percent.
Preferably, the volume fraction of the cross-linking agent in the total volume of the cross-linking agent and the solvent is 50-90%.
Further, the crosslinking agent is selected from: dimethoxymethane or ethylene glycol dimethyl ether.
Further, the catalyst is selected from: FeCl3、AlCl3、BF3、H2SO4、SnCl4Or ZnCl2At least one of (1).
Further, the solvent is selected from: at least one of 1, 2-Dichloroethane (DCE) or dichloromethane.
Further, the Friedel-crafts alkylation reaction process is as follows: adding the two-block copolymer and the catalyst into a solvent and a crosslinking agent, and stirring to uniformly disperse the components; then carrying out reflux reaction at 25-80 ℃ for 24-25 h; after the reaction, adding ethanol, performing ultrasonic dispersion and suction filtration to obtain a product; and then washing the product with methanol and dilute hydrochloric acid in sequence, finally carrying out soxhlet extraction with methanol for 48-72 h, collecting and carrying out vacuum drying to obtain the crosslinked organic nano filler.
Furthermore, the electrochemical window of the all-solid-state polymer electrolyte reaches 4.8-5.0V.
Further, the polymer having lithium ion transport properties is selected from the group consisting of: polyether polymer, polyacrylate, polyacrylonitrile or polyvinylidene fluoride.
Still further, the polymer having lithium ion transport properties is selected from the group consisting of: at least one of polyethylene oxide (PEO), polymethyl methacrylate (PMMA), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), or polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP).
Further, the lithium salt is selected from: at least one of lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis fluorosulfonylimide, lithium trifluoromethanesulfonate, lithium bis (oxalato) borate, or lithium difluoro (oxalato) borate.
The second technical problem to be solved by the present invention is to provide a method for preparing the above all-solid polymer electrolyte, which comprises a solution casting method or a melt hot-pressing method.
Further, the solution casting method comprises the following steps: firstly, uniformly stirring and mixing a polymer with lithium ion transmission performance, a lithium salt, a solvent and an organic filler to obtain electrolyte slurry; and then casting, molding and drying the obtained electrolyte slurry to obtain the all-solid-state polymer electrolyte.
Further, the solution casting method includes the steps of:
1) preparing electrolyte slurry: in an argon-filled glove box (H)2O<0.1ppm,O2<0.1ppm), adding a polymer with lithium ion transmission performance and a lithium salt into a solvent, and stirring at room temperature; then adding an organic filler and continuously stirring until the organic filler is uniformly dispersed to obtain electrolyte slurry;
2) casting and molding of electrolyte slurry: under the anhydrous and anaerobic conditions, casting the electrolyte slurry by using a Teflon mold after defoaming the electrolyte slurry, and then drying to obtain a polymer electrolyte membrane; and is placed in a glove box for standby.
Further, in step 1), the solvent is selected from: at least one of acetonitrile, N-dimethylformamide, acetone, dichloromethane, or tetrahydrofuran.
Preferably, the solvent is a mixed solvent of acetonitrile and tetrahydrofuran mixed according to a volume ratio of 1: 8-1: 4, and more preferably 1: 5.
Further, in the step 1), the molar ratio of the polymer with lithium ion transmission performance to the lithium salt satisfies the following conditions: m is Li (10-20), and the mass fraction of the organic filler in the electrolyte is 5-30%; wherein M is a structural unit which reacts with (i.e. plays a practical role in) a lithium salt in the polymer having lithium ion transport properties.
Further, in the step 1), after adding a polymer with lithium ion transmission performance and a lithium salt, stirring at a speed of 300-400 rpm; stirring for 12-18 h to obtain a uniform mixed solution.
Further, in the step 1), grinding the organic filler for 1-2 h (5-30 wt%) before adding the organic filler; after adding, the stirring speed is 300-400 rpm; stirring for 48-72 h to obtain uniform electrolyte slurry.
Further, in the step 2), the electrolyte slurry is subjected to defoaming treatment after standing for 20-30 min.
Further, in step 2), the drying conditions are as follows: and drying the membrane for 24-30 hours at the temperature of 20-30 ℃ and 50-70 ℃ respectively to obtain the polymer electrolyte membrane. In the invention, the aim of drying in two steps is as follows: firstly, the drying at room temperature is to slowly volatilize the solvent, so as to avoid the influence on the electrolyte form, the physical property and the like in the process; the subsequent drying at high temperature is to further remove the residual solvent after the electrolyte is formed.
The third technical problem to be solved by the invention is to provide the application of the two-block copolymer in the all-solid-state polymer electrolyte, the two-block copolymer is subjected to template-free self-assembly through Friedel-crafts reaction to obtain a cross-linked organic nano material, and the obtained cross-linked organic nano filler is then subjected to solution casting or melting hot pressing with a polymer with lithium ion transmission performance and lithium salt to obtain the all-solid-state polymer electrolyte.
Further, the molar ratio of the polymer having lithium ion transport properties to the lithium salt satisfies: m is Li (10-20), and the mass fraction of the crosslinked organic nano material in the electrolyte is 5-30%; wherein M is a structural unit (e.g., EO in PEO) that reacts with (i.e., plays a practical role in) a lithium salt in the polymer having lithium ion transport properties.
Further, the first component of the diblock copolymer is one of polyethylene oxide (PEO), polypropylene oxide (PPOX), polyphenylene oxide (PPO) or poly (methoxypolyethylene glycol methacrylate) (p (pegma)); the second component is polystyrene or a polymer of styrene derived monomers that does not contain strongly electron withdrawing groups.
The invention has the beneficial effects that:
1. the thermal stability and the mechanical property of the all-solid-state polymer electrolyte are improved through the cross-linked structure; the compatibility between the nano-filler and the polymer matrix and the anode and cathode materials is improved through a flexible chain segment such as PEO; the transport of lithium ions is accelerated by the nanostructure and the elevated specific surface.
2. Compared with the common all-solid-state polymer electrolyte, the cross-linked organic nano-material modified all-solid-state polymer electrolyte prepared by the invention still has good dimensional stability at the temperature of 200 ℃, thereby ensuring that the electrolyte membrane can not shrink greatly when the battery is used at high temperature, and avoiding the occurrence of internal short circuit caused by the contact of the anode and the cathode of the battery; in addition, the electrochemical performance of the electrolyte can be further improved along with the increase of the use temperature.
3. The all-solid-state polymer electrolyte obtained by the invention can be used for: (1) household daily small-sized electric appliances such as mobile phones, computers, cameras and the like; (2) some industries that need to operate in high temperature environments, such as the electric automobile industry, the underground oil production industry, and the aerospace industry. That is, the all-solid polymer electrolyte obtained by the present invention can be used in a wide temperature range.
Description of the drawings:
FIG. 1 is a scanning electron microscope characterization result of the crosslinked organic nanomaterial of the present invention: (a-b) is a scanning electron microscope image of the added cross-linked organic nano-material HCPs-1 in the embodiment 1 and the embodiment 6 of the invention under different magnifications; (c-d) is a scanning electron microscope image of the added cross-linked organic nano-material HCPs-2 in the embodiment 2 and the embodiment 7 of the invention under different magnifications; (e-f) is a scanning electron microscope image of the added cross-linked organic nano-material HCPs-3 in the embodiment 3 and the embodiment 8 of the invention under different magnifications; (g-h) is a scanning electron microscope image of the added cross-linked organic nano-materials HCPs-4 in the embodiment 4 and the embodiment 9 of the invention under different magnifications; as can be seen from fig. 1: the prepared organic materials HCPs-1, HCPs-2, HCPs-3 and HCPs-4 are all nano materials.
FIG. 2 is a digital image of all-solid polymer electrolytes of examples 1 to 3 and 5 of the present invention after heat treatment at different temperatures; as can be seen from fig. 2: the electrolyte prepared by the method has smooth, uniform and defect-free surface, and can ensure good interface contact in the battery; furthermore, the reference polymer electrolyte SPE-PEO in example 5 showed a significant increase in viscosity from 120 ℃ and was completely melted at 160 ℃, while the polymer electrolytes in examples 1-3 still ensured superior dimensional stability at elevated temperatures.
Fig. 3 is an electrochemical ac impedance spectrum of the all-solid polymer electrolyte of example 2 and example 5 at different test temperatures: FIG. 3(a) is the electrochemical AC impedance spectrum of the cross-linked organic nanomaterial modified all-solid polymer electrolyte MSPE-2 of example 2 at different test temperatures; FIG. 3(b) is the electrochemical AC impedance spectrum of SPE-PEO as a reference sample in example 5 at different test temperatures; as can be seen from fig. 3: under different temperatures, the interface impedance (the diameter of a semi-circular arc is the size of the interface impedance value) of the cross-linked organic nano-material modified all-solid-state polymer electrolyte is hardly changed compared with that of a reference SPE-PEO sample; the cross-linked organic nano material is well dispersed in the electrolyte and has good compatibility with the electrodes.
FIG. 4 is a linear sweep voltammogram of an all-solid polymer electrolyte in examples 1 to 5; as can be seen from fig. 4: the electrolyte prepared by the invention has an excellent electrochemical window, and can meet the requirements of different batteries on voltage ranges.
FIG. 5 shows Li/MSPE-2/LiFePO assembled by using MSPE-2 as an all-solid polymer electrolyte in example 2 of the present invention4The multiplying power and the cycle performance of the button cell at 50 ℃ are tested; as can be seen from fig. 5: the electrolyte prepared by the invention has good charge and discharge performance at the temperature, and meets the requirements of practical application.
Detailed Description
The following are some specific examples of the present invention, but the present invention is not limited to the following examples, and many modifications are possible.
Example 1
Crosslinked organic nanomaterials HCPs-1 modified and EO: the preparation of an all-solid polymer electrolyte of Li-16, comprising the steps of:
1) preparation of mPEO-Br macroinitiator:
under the argon atmosphere with water and oxygen removed, 8g of polyethylene glycol monomethyl ether (mPEG) and 0.12g of 4-dimethylaminopyridine are added into 130mL of dichloromethane, stirred until the mPEG is dissolved, and then 4.22mL of Triethylamine (TEA) is added; adding 20 into another anhydrous oxygen-free container3.76mL of 2-bromoisobutyryl bromide (BIBB) is dissolved in the dichloromethane which is used for preparing the active ingredient at the temperature of about 0 ℃; slowly adding a dichloromethane solution of BIBB into a first container at about 0 ℃, then heating to 25-35 ℃, and stirring for 15-20 h; after the reaction is finished, triethylamine bromate generated by triethylamine is filtered, and then saturated NaHCO is respectively used3Washing with water for multiple times to remove unreacted BIBB in the system; then adding a large amount of anhydrous Na2SO4Drying to remove residual water in the system; filtering to remove Na2SO4And evaporating to remove a large amount of DCM solvent, then settling in ether to obtain a white solid, washing with ether for multiple times, and drying to obtain the mPEO-Br macroinitiator.
2) Preparation of PEO-PS diblock copolymer:
under the anhydrous and oxygen-free conditions, adding 2g of mPEO-Br prepared in the step 1), 0.14g of CuBr and 20mL of dioxane, stirring to dissolve, then adding 8.57mL of St, then adding 0.31mL of N, N, N' -pentamethyl diethylene triamine (PMDETA), and stirring at the temperature of 100-120 ℃ for 12-36 h; after the reaction is completed, the reaction mixture is diluted with THF, preferably basic Al2O3Copper salt is removed by a short column, a large amount of THF solvent is removed by evaporation, and the PEO-PS diblock copolymer is obtained by settling and separating out in normal hexane and drying.
3) Preparation of crosslinked organic nanomaterials HCPs-1:
0.2775g of PEO-PS and 2.925g of FeCl are taken under the anhydrous and oxygen-free conditions3Adding the mixture into 30mL of DCE, and stirring for about five minutes to uniformly disperse the components; then carrying out reflux reaction at 25-80 ℃ for 24-25 h; after the reaction, adding a large amount of ethanol, performing ultrasonic dispersion and suction filtration to obtain a product; washing the product with methanol and dilute hydrochloric acid, collecting after methanol extraction for two days, and vacuum drying to obtain the cross-linked organic nano material HCPs-1.
4) Preparation of crosslinked organic nanomaterial modified all-solid-state polymer electrolyte 1:
preparing electrolyte slurry: in an argon-filled glove box (H)2O<0.1ppm,O2<0.5ppm), 1.225g of PEO and 0.5g of PEO were takenDissolving LiTFSI in a mixed solvent of 25mL tetrahydrofuran and 5mL acetonitrile, and stirring at 300-400 rpm at room temperature for 12-18 h; then 0.192g of cross-linked organic nano material HCPs-1 (accounting for 10 wt% of all solid components) ground for 1-2 h is added, and the mixture is stirred at 300-400 rpm for 48-72 h to obtain uniform electrolyte slurry.
Casting and molding of electrolyte slurry: under the anhydrous and anaerobic conditions, firstly, standing and defoaming the electrolyte slurry for 20-30 min, then, casting the electrolyte slurry by adopting a Teflon mold, and drying at 20-30 ℃ and 50-70 ℃ for at least 24h respectively; the obtained polymer electrolyte is called MSPE-1 for short.
Example 2
Preparation of all-solid polymer electrolytes modified with crosslinked organic nanomaterials HCPs-2 and EO: Li ═ 16, comprising the steps of:
1) preparation of mPEO-Br macroinitiator: the concrete method is the same as the step 1) of the example 1;
2) preparation of PEO-PS diblock copolymer: the concrete method is the same as the step 2) of the example 1;
3) preparation of crosslinked organic nanomaterials HCPs-2:
0.2775g of PEO-PS and 2.925g of FeCl are taken under the anhydrous and oxygen-free conditions3Adding the mixture into 15mL of DCE, adding 15mL of FDA, and stirring for five minutes to uniformly disperse the components; then carrying out reflux reaction at 25-80 ℃ for 24-25 h; after the reaction, adding a large amount of ethanol, performing ultrasonic dispersion and suction filtration to obtain a product; washing the product with methanol and dilute hydrochloric acid, collecting after methanol extraction for two days, and vacuum drying to obtain the cross-linked organic nano material HCPs-2.
4) Preparation of crosslinked organic nanomaterial modified all-solid-state polymer electrolyte 2:
preparing electrolyte slurry: in an argon-filled glove box (H)2O<0.1ppm,O2<0.5ppm), dissolving 1.225g of PEO and 0.5g of LiTFSI in a mixed solvent of 25mL of tetrahydrofuran and 5mL of acetonitrile, and stirring at 300-400 rpm at room temperature for 12-18 h; then adding 0.192g of cross-linked organic nano material HCPs-2 (accounting for 10 wt% of all solid components) ground for 1-2 h, and stirring at 300-400 rpm for 48-72 h to obtain the nano-composite materialTo a homogeneous electrolyte slurry.
Casting and molding of electrolyte slurry: under the anhydrous and anaerobic conditions, firstly, standing and defoaming the electrolyte slurry for 20-30 min, then, casting the electrolyte slurry by adopting a Teflon mold, and drying at 20-30 ℃ and 50-70 ℃ for at least 24h respectively; the obtained polymer electrolyte is called MSPE-2 for short.
Example 3
Preparation of all-solid polymer electrolytes modified with crosslinked organic nanomaterials HCPs-3 and EO: Li ═ 16, comprising the steps of:
1) preparation of mPEO-Br macroinitiator: the concrete method is the same as the step 1) of the example 1;
2) preparation of PEO-PS diblock copolymer: the concrete method is the same as the step 2) of the example 1;
3) preparing cross-linked organic nano-material HCPs-3:
0.2775g of PEO-PS and 2.925g of FeCl are taken under the anhydrous and oxygen-free conditions3Adding the mixture into 6mL of liquid crystal gel, adding 24mL of FDA, and stirring for five minutes to uniformly disperse the components; then carrying out reflux reaction at 25-80 ℃ for 24-25 h; after the reaction, adding a large amount of ethanol, performing ultrasonic dispersion and suction filtration to obtain a product; washing the product with methanol and dilute hydrochloric acid, collecting and vacuum drying after methanol extraction for two days to obtain crosslinked organic nano material HCPs-3;
4) preparation of crosslinked organic nanomaterial modified all-solid-state polymer electrolyte 3:
preparing electrolyte slurry: in an argon-filled glove box (H)2O<0.1ppm,O2<0.5ppm), dissolving 1.225g of PEO and 0.5g of LiTFSI in a mixed solvent of 25mL of tetrahydrofuran and 5mL of acetonitrile, and stirring at 300-400 rpm at room temperature for 12-18 h; then 0.192g of cross-linked organic nano material HCPs-3 which is ground for 1-2 h and accounts for 10 wt% of all solid components is added, and the mixture is stirred at 300-400 rpm for 48-72 h to obtain uniform electrolyte slurry.
Casting and molding of electrolyte slurry: under the anhydrous and anaerobic conditions, firstly, standing and defoaming the electrolyte slurry for 20-30 min, then, casting the electrolyte slurry by adopting a Teflon mold, and drying at 20-30 ℃ and 50-70 ℃ for at least 24h respectively; the obtained polymer electrolyte is called MSPE-3 for short.
Example 4
Preparation of all-solid polymer electrolytes modified with crosslinked organic nanomaterials HCPs-4 and EO: Li ═ 16, comprising the steps of:
1) preparation of mPEO-Br macroinitiator: the concrete method is the same as the step 1) of the example 1;
2) preparation of PEO-PS diblock copolymer: the concrete method is the same as the step 2) of the example 1;
3) preparing cross-linked organic nano-material HCPs-4:
0.2775g of PEO-PS and 2.925g of FeCl are taken under the anhydrous and oxygen-free conditions3Adding the mixture into 3mL of liquid crystal gel, adding 27mL of FDA, and stirring for five minutes to uniformly disperse the components; then carrying out reflux reaction at 25-80 ℃ for 24-25 h; after the reaction, adding a large amount of ethanol, performing ultrasonic dispersion and suction filtration to obtain a product; washing the product with methanol and dilute hydrochloric acid, collecting after methanol extraction for two days, and vacuum drying to obtain the cross-linked organic nano material HCPs-4.
4) Preparation of crosslinked organic nanomaterial modified all-solid-state polymer electrolyte 4:
preparing electrolyte slurry: in an argon-filled glove box (H)2O<0.1ppm,O2<0.5ppm), dissolving 1.225g of PEO and 0.5g of LiTFSI in a mixed solvent of 25mL of tetrahydrofuran and 5mL of acetonitrile, and stirring at 300-400 rpm at room temperature for 12-18 h; then 0.192g of crosslinked organic nano material HCPs-4 (accounting for 10 wt% of all solid components) ground for 1-2 h is added, and the mixture is stirred at 300-400 rpm for 48-72 h to obtain uniform electrolyte slurry.
Casting and molding of electrolyte slurry: under the anhydrous and anaerobic conditions, firstly, standing and defoaming the electrolyte slurry for 20-30 min, then, casting the electrolyte slurry by adopting a Teflon mold, and drying at 20-30 ℃ and 50-70 ℃ for at least 24h respectively; the obtained polymer electrolyte is called MSPE-4 for short.
Example 5
As a reference, we prepared an unmodified PEO all-solid polymer electrolyte with EO Li ═ 16; the specific implementation process is as follows:
1) in an argon-filled glove box (H)2O<0.1ppm,O2<0.5ppm), 1.361g of PEO and 0.556g of LiTFSI are dissolved in a mixed solvent of 25mL of tetrahydrofuran and 5mL of acetonitrile, and the mixture is stirred at the room temperature of 300-400 rpm for 12-18 h to obtain uniform electrolyte slurry.
2) Casting and molding of electrolyte slurry: under the anhydrous and anaerobic conditions, firstly, standing and defoaming the electrolyte slurry for 20-30 min, then, casting the electrolyte slurry by adopting a Teflon mold, and drying at 20-30 ℃ and 50-70 ℃ for at least 24h respectively; the obtained polymer electrolyte is called SPE-PEO for short.
Example 6
Preparation of all-solid polymer electrolyte modified by cross-linked organic nanomaterial HCPs-1 and EO: Li ═ 20, comprising the following steps:
1) preparation of mPEO-Br macroinitiator: the concrete method is the same as the step 1) of the example 1;
2) preparation of PEO-PS diblock copolymer: the concrete method is the same as the step 2) of the example 1;
3) preparation of crosslinked organic nanomaterials HCPs-1: the concrete method is the same as the step 3) of the example 1;
4) preparation of crosslinked organic nanomaterial modified all-solid-state polymer electrolyte 5:
preparing electrolyte slurry: in an argon-filled glove box (H)2O<0.1ppm,O2<0.5ppm), dissolving 1.3g of PEO and 0.425g of LiTFSI in a mixed solvent of 25mL of tetrahydrofuran and 5mL of acetonitrile, and stirring at 300-400 rpm at room temperature for 12-18 h; then adding 0.192g of cross-linked organic nano material HCPs-1 (accounting for 10 wt% of all solid components) ground for 1-2 h, and stirring at 300-400 rpm for 48-72 h to obtain uniform electrolyte slurry;
casting and molding of electrolyte slurry: under the anhydrous and anaerobic conditions, firstly, standing and defoaming the electrolyte slurry for 20-30 min, then, casting the electrolyte slurry by adopting a Teflon mold, and drying at 20-30 ℃ and 50-70 ℃ for at least 24h respectively; the obtained polymer electrolyte is called MSPE-5 for short.
Example 7
Preparation of all-solid polymer electrolytes modified with crosslinked organic nanomaterials of HCPs-2 and EO: Li ═ 20, comprising the steps of:
1) preparation of mPEO-Br macroinitiator: the concrete method is the same as the step 1) of the example 1;
2) preparation of PEO-PS diblock copolymer: the concrete method is the same as the step 2) of the example 1;
3) preparation of crosslinked organic nanomaterials HCPs-2: the concrete method is the same as the step 3) of the example 2;
4) preparation of crosslinked organic nanomaterial modified all-solid-state polymer electrolyte 6:
preparing electrolyte slurry: in an argon-filled glove box (H)2O<0.1ppm,O2<0.5ppm), dissolving 1.3g of PEO and 0.425g of LiTFSI in a mixed solvent of 25mL of tetrahydrofuran and 5mL of acetonitrile, and stirring at 300-400 rpm at room temperature for 12-18 h; then adding 0.192g of cross-linked organic nano material HCPs-2 (accounting for 10 wt% of all solid components) ground for 1-2 h, and stirring at 300-400 rpm for 48-72 h to obtain uniform electrolyte slurry;
casting and molding of electrolyte slurry: under the anhydrous and anaerobic conditions, firstly, standing and defoaming the electrolyte slurry for 20-30 min, then, casting the electrolyte slurry by adopting a Teflon mold, and drying at 20-30 ℃ and 50-70 ℃ for at least 24h respectively; the obtained polymer electrolyte is called MSPE-6 for short.
Example 8
Preparation of all-solid polymer electrolyte modified by cross-linked organic nanomaterials HCPs-3 and EO: Li ═ 20, comprising the steps of:
1) preparation of mPEO-Br macroinitiator: the concrete method is the same as the step 1) of the example 1;
2) preparation of PEO-PS diblock copolymer: the concrete method is the same as the step 2) of the example 1;
3) preparing cross-linked organic nano-material HCPs-3: the concrete method is the same as the step 3) of the example 2;
4) preparation of crosslinked organic nanomaterial modified all-solid-state polymer electrolyte 7:
preparing electrolyte slurry: in an argon-filled glove box (H)2O<0.1ppm,O2<0.5ppm), dissolving 1.3g of PEO and 0.425g of LiTFSI in a mixed solvent of 25mL of tetrahydrofuran and 5mL of acetonitrile, and stirring at 300-400 rpm at room temperature for 12-18 h; then 0.192g of cross-linked organic nano material HCPs-3 (accounting for 10 wt% of all solid components) ground for 1-2 h is added, and the mixture is stirred at 300-400 rpm for 48-72 h to obtain uniform electrolyte slurry.
Casting and molding of electrolyte slurry: under the anhydrous and anaerobic conditions, firstly, standing and defoaming the electrolyte slurry for 20-30 min, then, casting the electrolyte slurry by adopting a Teflon mold, and drying at 20-30 ℃ and 50-70 ℃ for at least 24h respectively; the obtained polymer electrolyte is called MSPE-7 for short.
Example 9
Preparation of all-solid polymer electrolyte modified by cross-linked organic nanomaterials HCPs-4 and EO: Li ═ 20, comprising the steps of:
1) preparation of mPEO-Br macroinitiator: the concrete method is the same as the step 1) of the example 1;
2) preparation of PEO-PS diblock copolymer: the concrete method is the same as the step 2) of the example 1;
3) preparing cross-linked organic nano-material HCPs-4: the concrete method is the same as the step 3) of the example 2;
4) preparation of crosslinked organic nanomaterial modified all-solid-state polymer electrolyte 8:
preparing electrolyte slurry: in an argon-filled glove box (H)2O<0.1ppm,O2<0.5ppm), dissolving 1.3g of PEO and 0.425g of LiTFSI in a mixed solvent of 25mL of tetrahydrofuran and 5mL of acetonitrile, and stirring at 300-400 rpm at room temperature for 12-18 h; then adding 0.192g of cross-linked organic nano material HCPs-4 (accounting for 10 wt% of all solid components) ground for 1-2 h, and stirring at 300-400 rpm for 48-72 h to obtain uniform electrolyte slurry;
casting and molding of electrolyte slurry: under the anhydrous and anaerobic conditions, firstly, standing and defoaming the electrolyte slurry for 20-30 min, then, casting the electrolyte slurry by adopting a Teflon mold, and drying at 20-30 ℃ and 50-70 ℃ for at least 24h respectively; the obtained polymer electrolyte is called MSPE-8 for short.
Table 1 results of ionic conductivity test of polymer electrolytes of examples 1 to 5 groups at different temperatures
In addition, scanning electron microscope characterization was performed on the crosslinked organic nanomaterials used in examples 1-4 and 6-9, respectively, and the results are shown in fig. 1. a-f show that some adhesion occurred between the polymer nanoparticles due to the formation of the crosslinked network.
The electrochemical AC impedance spectra of examples 1-5 were tested at different test temperatures, respectively, wherein the results of testing MSPE-2 and the SPE-PEO of example 2 and example 5 are shown in FIG. 3; the ionic conductivity values in table 1 were obtained by calculation.
Linear Sweep Voltammograms (LSV) for examples 1-5 are shown in FIG. 4; it can be seen from the graph that the oxidative decomposition voltage values of examples 1-4 are all close to 5V, and have a wider electrochemical stability window, which is obviously improved compared with the comparative sample.
The all-solid polymer electrolyte MSPE-2 of example 2 was assembled into Li/MSPE-2/LiFePO4The test curve of the multiplying power and the cycle performance of the button cell at 50 ℃ is shown in figure 5; the curve analysis in the graph (a) shows that MSPE-2 shows good charge and discharge performance under different multiplying powers, and the curve analysis in the graph (b) shows that MSPE-2 has initial specific discharge capacity higher than 145mAh/g under 0.1C and shows good cycling stability.
Claims (10)
1. An all-solid polymer electrolyte, wherein the composition of the all-solid polymer electrolyte comprises: the lithium ion battery comprises a polymer with lithium ion transmission performance, lithium salt and an organic filler, wherein the organic filler is a cross-linked organic nano material obtained by template-free self-assembly of two-block copolymers through Friedel-crafts reaction.
2. The all-solid polymer electrolyte according to claim 1, wherein the first component of the diblock copolymer is one of polyethylene oxide, polypropylene oxide, polyphenylene oxide or poly (polyethylene glycol methyl ether methacrylate); the second component is polystyrene or a polymer of styrene derived monomers that does not contain strongly electron withdrawing groups.
3. The all-solid polymer electrolyte according to claim 1 or 2, wherein the molar ratio of the polymer having lithium ion transport properties to the lithium salt in the all-solid polymer electrolyte satisfies: m is Li (10-20), and the mass fraction of the organic filler in the electrolyte is 5-30%; wherein M is a structural unit which reacts with lithium salt in the polymer with lithium ion transmission performance.
4. The all-solid-state polymer electrolyte according to any one of claims 1 to 3, wherein the method for preparing the cross-linked organic nano-material by template-free self-assembly of the two-block copolymer through Friedel-crafts reaction comprises the following steps: under the anhydrous and anaerobic condition, taking two-block copolymer as raw material, and under the action of catalyst, cross-linking agent and solvent, obtaining cross-linked organic nano filler through Friedel-crafts alkylation reaction; wherein the volume fraction of the cross-linking agent in the total volume of the cross-linking agent and the solvent is as follows: 0% -90%; preferably, the volume fraction of the cross-linking agent in the total volume of the cross-linking agent and the solvent is 50-90%;
further, the crosslinking agent is selected from: dimethoxymethane or ethylene glycol dimethyl ether;
further, the catalyst is selected from: FeCl3、AlCl3、BF3、H2SO4、SnCl4Or ZnCl2At least one of;
further, the solvent is selected from: at least one of 1, 2-dichloroethane or dichloromethane;
further, the Friedel-crafts alkylation reaction process is as follows: adding the two-block copolymer and the catalyst into a solvent and a crosslinking agent, and stirring to uniformly disperse the components; then carrying out reflux reaction at 25-80 ℃ for 24-25 h; after the reaction, adding ethanol, performing ultrasonic dispersion and suction filtration to obtain a product; and then washing the product with methanol and dilute hydrochloric acid in sequence, finally carrying out soxhlet extraction with methanol for 48-72 h, collecting and carrying out vacuum drying to obtain the crosslinked organic nano filler.
5. The all-solid polymer electrolyte according to any one of claims 1 to 4, wherein the all-solid polymer electrolyte has an electrochemical window of 4.8 to 5.0V;
further, the polymer having lithium ion transport properties is selected from the group consisting of: one of polyether polymer, polyacrylate, polyacrylonitrile or polyvinylidene fluoride; still further, the polymer having lithium ion transport properties is selected from the group consisting of: at least one of polyethylene oxide, polymethyl methacrylate, polyacrylonitrile, polyvinylidene fluoride, or polyvinylidene fluoride-hexafluoropropylene copolymer;
further, the lithium salt is selected from: at least one of lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis (trifluoromethanesulfonyl) imide, lithium bis fluorosulfonylimide, lithium trifluoromethanesulfonate, lithium bis (oxalato) borate, or lithium difluoro (oxalato) borate.
6. The method for producing an all-solid polymer electrolyte according to any one of claims 1 to 5, wherein the production method comprises a solution casting method or a melt-hot-pressing method.
7. The method for producing an all-solid polymer electrolyte according to claim 6, wherein the solution casting method is: firstly, uniformly stirring and mixing a polymer with lithium ion transmission performance, a lithium salt, a solvent and an organic filler to obtain electrolyte slurry; then casting, molding and drying the obtained electrolyte slurry to obtain the all-solid-state polymer electrolyte;
further, the solution casting method includes the steps of:
1) preparing electrolyte slurry: adding a polymer with lithium ion transmission performance and a lithium salt into a solvent in an argon-filled glove box, and stirring at room temperature; then adding an organic filler and continuously stirring until the organic filler is uniformly dispersed to obtain electrolyte slurry;
2) casting and molding of electrolyte slurry: under the anhydrous and anaerobic conditions, casting the electrolyte slurry by using a Teflon mold after defoaming the electrolyte slurry, and then drying to obtain a polymer electrolyte membrane; placing in a glove box for later use;
further, in step 1), the solvent is selected from: at least one of acetonitrile, N-dimethylformamide, acetone, dichloromethane, or tetrahydrofuran; preferably, the solvent is a mixed solvent formed by mixing acetonitrile and tetrahydrofuran according to a volume ratio of 1: 8-1: 4, and more preferably 1: 5;
further, in the step 1), the molar ratio of the polymer with lithium ion transmission performance to the lithium salt satisfies the following conditions: and M is Li 10-20, wherein M is a structural unit which reacts with lithium salt in the polymer with lithium ion transmission performance.
8. The preparation method of the all-solid polymer electrolyte according to claim 7, wherein in the step 1), the organic filler is ground for 1-2 hours before being added; after adding, the stirring speed is 300-400 rpm; stirring for 48-72 h to obtain uniform electrolyte slurry;
further, in the step 2), defoaming the electrolyte slurry by standing for 20-30 min;
further, in step 2), the drying conditions are as follows: and drying the membrane for 24-30 hours at the temperature of 20-30 ℃ and 50-70 ℃ respectively to obtain the polymer electrolyte membrane.
9. The application of the diblock copolymer in the all-solid polymer electrolyte is characterized in that the application method comprises the following steps: the two-block copolymer is subjected to template-free self-assembly through Friedel-crafts reaction to obtain a crosslinked organic nano material, and the obtained crosslinked organic nano filler, the polymer with lithium ion transmission performance and lithium salt are subjected to a solution casting method or a melting hot pressing method to prepare the all-solid-state polymer electrolyte.
10. Use of a diblock copolymer according to claim 9 in an all solid state polymer electrolyte, wherein the molar ratio of the polymer having lithium ion transport properties to the lithium salt satisfies: m is Li (10-20), and the mass fraction of the crosslinked organic nano material in the electrolyte is 5-30%; wherein M is a structural unit which reacts with lithium salt in the polymer with lithium ion transmission performance;
further, the first component of the diblock copolymer is one of polyoxyethylene, polyoxypropylene, polyphenylene oxide or poly (methoxy polyethylene glycol methacrylate); the second component is polystyrene or a polymer of styrene derived monomers that does not contain strongly electron withdrawing groups.
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| CN113258133A (en) * | 2021-05-12 | 2021-08-13 | 宁波怡乐新材料科技有限公司 | Preparation method of lithium ion battery gel polymer electrolyte |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7135254B2 (en) * | 2001-01-31 | 2006-11-14 | Korea Institute Of Science And Technologies | Multi-layered, UV-cured polymer electrolyte and lithium secondary battery comprising the same |
| WO2012025542A1 (en) * | 2010-08-24 | 2012-03-01 | Basf Se | Electrolyte materials for use in electrochemical cells |
| CN105470569A (en) * | 2014-09-26 | 2016-04-06 | 三星电子株式会社 | Electrolyte, method of preparing electrolyte, and secondary battery including electrolyte |
| CN105591154A (en) * | 2015-02-13 | 2016-05-18 | 中国科学院青岛生物能源与过程研究所 | Polycarbonate all-solid-state polymer electrolyte, all-solid-state secondary lithium battery made of same and preparation and application thereof |
| US20170092983A1 (en) * | 2015-09-30 | 2017-03-30 | Seeo, Inc | Block copolymer electrolytes containing polymeric additives |
| CN106654363A (en) * | 2017-01-17 | 2017-05-10 | 北京科技大学 | Composite solid-state polymer electrolyte and all-solid-state lithium battery |
| US20170373300A1 (en) * | 2015-03-25 | 2017-12-28 | Ngk Insulators, Ltd. | All solid state lithium battery |
| CN107706427A (en) * | 2016-08-08 | 2018-02-16 | 三星电子株式会社 | For the positive pole of metal-air battery including its metal-air battery and the method for preparing the positive pole for metal-air battery |
| CN108701506A (en) * | 2016-03-05 | 2018-10-23 | 西奥公司 | Crosslinking interpenetrating networks block copolymer electrolyte matter for lithium battery |
| CN109735915A (en) * | 2019-01-09 | 2019-05-10 | 四川大学 | Super crosslinking organic nano particle and preparation method thereof, modifying polymer film and preparation method thereof and gel polymer electrolyte |
| CN110010853A (en) * | 2017-12-12 | 2019-07-12 | 三星电子株式会社 | The method of composite electrolyte, protective film, protected cathode, lithium metal battery and the protected cathode of manufacture |
-
2020
- 2020-08-10 CN CN202010793333.XA patent/CN111934007B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7135254B2 (en) * | 2001-01-31 | 2006-11-14 | Korea Institute Of Science And Technologies | Multi-layered, UV-cured polymer electrolyte and lithium secondary battery comprising the same |
| WO2012025542A1 (en) * | 2010-08-24 | 2012-03-01 | Basf Se | Electrolyte materials for use in electrochemical cells |
| CN103283064A (en) * | 2010-08-24 | 2013-09-04 | 巴斯夫欧洲公司 | Electrolyte materials for use in electrochemical cells |
| CN105470569A (en) * | 2014-09-26 | 2016-04-06 | 三星电子株式会社 | Electrolyte, method of preparing electrolyte, and secondary battery including electrolyte |
| CN105591154A (en) * | 2015-02-13 | 2016-05-18 | 中国科学院青岛生物能源与过程研究所 | Polycarbonate all-solid-state polymer electrolyte, all-solid-state secondary lithium battery made of same and preparation and application thereof |
| US20170373300A1 (en) * | 2015-03-25 | 2017-12-28 | Ngk Insulators, Ltd. | All solid state lithium battery |
| US20170092983A1 (en) * | 2015-09-30 | 2017-03-30 | Seeo, Inc | Block copolymer electrolytes containing polymeric additives |
| CN108701506A (en) * | 2016-03-05 | 2018-10-23 | 西奥公司 | Crosslinking interpenetrating networks block copolymer electrolyte matter for lithium battery |
| CN107706427A (en) * | 2016-08-08 | 2018-02-16 | 三星电子株式会社 | For the positive pole of metal-air battery including its metal-air battery and the method for preparing the positive pole for metal-air battery |
| CN106654363A (en) * | 2017-01-17 | 2017-05-10 | 北京科技大学 | Composite solid-state polymer electrolyte and all-solid-state lithium battery |
| CN110010853A (en) * | 2017-12-12 | 2019-07-12 | 三星电子株式会社 | The method of composite electrolyte, protective film, protected cathode, lithium metal battery and the protected cathode of manufacture |
| CN109735915A (en) * | 2019-01-09 | 2019-05-10 | 四川大学 | Super crosslinking organic nano particle and preparation method thereof, modifying polymer film and preparation method thereof and gel polymer electrolyte |
Non-Patent Citations (1)
| Title |
|---|
| TU-NAN GAO,TAO WANG,WEI WU,QISHENG HUO,ZHEN-AN QIAO AND ETAL: "Solvent-Induced Self-Assembly Strategy to Synthesize Well-Defined Hierarchically Porous Polymers", 《ADVANCED MATERIALS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113258133A (en) * | 2021-05-12 | 2021-08-13 | 宁波怡乐新材料科技有限公司 | Preparation method of lithium ion battery gel polymer electrolyte |
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