CN114142099A - Preparation method of composite solid electrolyte membrane and electrochemical energy storage device - Google Patents
Preparation method of composite solid electrolyte membrane and electrochemical energy storage device Download PDFInfo
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Abstract
The invention provides a preparation method of a composite solid electrolyte membrane and an electrochemical energy storage device. The preparation method comprises the following steps: and mixing the liquid monomer, the inorganic solid electrolyte, the lithium salt and the initiator, and then carrying out a curing reaction to obtain the composite solid electrolyte membrane. The invention provides a preparation method of a solvent-free composite solid electrolyte membrane, which can effectively avoid the problem of the conductivity reduction of the composite solid electrolyte membrane caused by contacting with a solvent, has simple preparation process, can easily realize large-area production, and has high ionic conductivity and excellent mechanical property.
Description
Technical Field
The invention belongs to the field of electrolytes, and particularly relates to a preparation method of a composite solid electrolyte membrane and an electrochemical energy storage device.
Background
With the increasing severity of energy crisis, the development of new energy resources is more and more emphasized in China, and lithium ion batteries are particularly important as green energy technologies and devices with the greatest development prospect. The lithium ion battery gradually occupies the mainstream market of the electric automobile due to the characteristics of high energy density, long service life and the like, and the rapid development of the electric automobile puts higher and higher requirements on the lithium ion battery. However, the lithium ion battery is greatly limited in use condition due to the influence of various problems such as technology and cost, and the development and application of the lithium ion battery are seriously influenced.
Most of lithium ion batteries produced in mass production in the industry at present are liquid batteries, the liquid batteries are influenced by more environmental factors, and the insertion and the separation of lithium ions are seriously influenced in a low-temperature environment, so that the endurance mileage and the service life of the batteries are shortened, and the temperature of the batteries is more seriously increased and side reactions are increased in the charging and discharging processes in a high-temperature environment, so that the conditions of gas generation, swelling, package and the like of the battery core are more serious, and the application range of the batteries is greatly limited.
Therefore, the solid-state battery is widely concerned in the industry in consideration of factors such as higher safety and stability, the solid-state battery well avoids potential safety hazards caused by leakage of electrolyte and the like due to the fact that the solid-state electrolyte is adopted to replace the organic electrolyte, the safety performance of the battery is greatly improved, the solid-state battery can be better adapted to the positive electrode and the negative electrode with high energy density, the requirement of the high energy density of the battery is met, and in addition, the solid-state battery has the advantages of being wide in electrochemical window, free of memory effect, good in thermal stability and the like.
Therefore, in the art, it is desirable to develop an organic cathode material that can be used in a solid-state lithium battery, while the preparation method is simple, and the prepared lithium ion battery has good electrochemical properties.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of a composite solid electrolyte membrane and an electrochemical energy storage device. The invention provides a preparation method of a solvent-free composite solid electrolyte membrane, which can effectively avoid the problem of the conductivity reduction of the composite solid electrolyte membrane caused by contacting with a solvent, has simple preparation process, can easily realize large-area production, and has high ionic conductivity and excellent mechanical property.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for producing a composite solid electrolyte membrane, the method comprising the steps of:
and mixing the liquid monomer, the inorganic solid electrolyte, the lithium salt and the initiator, and then carrying out a curing reaction to obtain the composite solid electrolyte membrane.
The composite solid electrolyte prepared by compounding the inorganic solid electrolyte and the polymer in situ by utilizing the characteristics of the liquid monomer and adopting a solvent-free method ensures that the inorganic solid electrolyte can be well dispersed into the polymer, avoids the addition of a solvent, and prevents the problems of side reaction of the residual solvent in the use process of the composite solid electrolyte and the reduction of the conductivity of the composite solid electrolyte.
Preferably, the liquid monomer includes any one or a combination of at least two of methyl ethylene carbonate, vinylene carbonate, vinylidene fluoride-hexafluoropropylene, acrylonitrile, ethylene glycol (diol) diacrylate, ethylene glycol dimethacrylate, ethylene glycol methyl ether acrylate, methyl methacrylate or ethylene glycol, for example, methyl ethylene carbonate and vinylene carbonate, vinylidene fluoride and vinylidene fluoride-hexafluoropropylene, acrylonitrile, methyl methacrylate or ethylene glycol, but is not limited to the enumerated species, and other species not enumerated within the liquid monomer range are also applicable.
Preferably, the weight average molecular weight of the liquid monomer is 500 to 5000, and may be, for example, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500 or 5000.
According to the invention, the film forming effect and the curing effect of the electrolyte film are improved by adjusting the weight average molecular weight of the liquid monomer to a specific range, and if the weight average molecular weight is too low, the film forming stability of the electrolyte film is influenced and the curing time is increased, so that the film forming effect is influenced, otherwise, if the weight average molecular weight is too high, the monomer is changed into a solid state.
Preferably, the liquid monomer is contained in an amount of 1% to 50% by mass, for example, 1%, 3%, 6%, 8%, 11%, 13%, 16%, 18%, 21%, 23%, 26%, 28%, 31%, 33%, 36%, 38%, 41%, 43%, 46%, 48% or 50% by mass based on 100% by mass of the total of the liquid monomer and the inorganic solid electrolyte.
Preferably, the inorganic solid electrolyte is an oxide solid electrolyte.
Preferably, the oxide solid electrolyte includes any one or a combination of at least two of perovskite type, NASICON type, LISICON type, garnet type or LiPON type, and may be, for example, perovskite type and NASICON type, LISICON type, garnet type or LiPON type, but is not limited to the listed species, and other species not listed within the scope of oxide solid electrolyte are equally applicable.
Preferably, the inorganic solid electrolyte is present in an amount of 50% to 99% by mass, for example 50%, 52%, 55%, 57%, 60%, 62%, 65%, 67%, 70%, 72%, 75%, 77%, 80%, 82%, 85%, 87%, 90%, 92%, 95%, 97% or 99% by mass, based on 100% by mass of the total of the liquid monomer and the inorganic solid electrolyte.
According to the invention, by adjusting the mass percentage of the liquid monomer and the inorganic solid electrolyte, the electrolyte has different film forming states and the conductivity is improved, and the mass ratio of the liquid monomer to the inorganic solid electrolyte is too low, so that the resistivity is reduced, otherwise, the film forming is difficult.
Preferably, the lithium salt includes any one or a combination of at least two of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium bis (difluorosulfonylimide) or lithium bis (trifluoromethylsulfonylimide), for example, lithium perchlorate and lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate and lithium bis (oxalato) borate, lithium difluorooxalato borate, lithium bis (difluorosulfonylimide) or lithium bis (trifluoromethylsulfonylimide) may be used, but not limited to the listed species, and other species not listed in the lithium salt range may be equally suitable.
Preferably, the mass ratio of the lithium salt to the liquid monomer is 1 (1-5), and may be, for example, 1:1, 1:2, 1:3, 1:4 or 1: 5.
According to the invention, the mass ratio of the lithium salt to the liquid monomer is adjusted, so that the liquid monomer has the ion conduction performance, and the ion conductivity is too low due to too low mass ratio, otherwise, the cost is increased.
Preferably, the initiator includes any one or a combination of at least two of a, a-dimethoxy-a-phenylacetophenone, benzophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide or azobisisobutyronitrile, such as a, a-dimethoxy-a-phenylacetophenone and benzophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide or azobisisobutyronitrile, but is not limited to the enumerated species, and other species not enumerated within the initiator range are equally applicable.
Preferably, the initiator is present in an amount of 1% to 5% by mass, for example 1%, 2%, 3%, 4% or 5% by mass, based on 100% by mass of the total liquid monomer.
Preferably, the curing reaction is any one of a thermal curing reaction or a photo-curing reaction or a combination of both.
Preferably, the curing reaction time is 10min to 60min, for example, 10min, 12min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60 min.
In a second aspect, the present invention provides a composite solid electrolyte membrane produced by the production method according to the first aspect.
Preferably, the thickness of the composite solid electrolyte membrane is 50 μm to 200 μm, and may be, for example, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm or 200 μm.
In a third aspect, the present invention provides an electrochemical energy storage device comprising a positive electrode, a negative electrode and an electrolyte, the electrolyte being the composite solid electrolyte membrane of the second aspect.
In the present invention, the electrochemical energy storage device comprises an all-solid-state battery or a gel-state battery.
In the invention, the cathode material includes but is not limited to one or more of a lithium iron phosphate cathode, a ternary cathode or a cobalt-free cathode.
In the present invention, the mass ratio of the positive electrode material to the electrolyte is preferably (99%: 1%) to (90%: 10%), and may be, for example, 98%: 2%.
In the present invention, the mass ratio of the positive electrode material to the binder is preferably (95%: 5%) to (98%: 2%), and may be, for example, 96%: 4%.
In the present invention, the negative electrode material includes, but is not limited to, one or more of a lithium metal negative electrode, a graphite negative electrode, or a graphite-blended silica negative electrode.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a solvent-free preparation process for performing blend coating by using a liquid monomer, an inorganic solid electrolyte, a lithium salt and an initiator, and then performing photocuring or thermocuring reaction to enable the liquid monomer to generate crosslinking reaction so as to form a composite solid electrolyte membrane. The preparation method provided by the invention can effectively avoid the influence of the organic solvent on the conductivity of the composite electrolyte membrane, is simple in preparation process and easy to realize mass production, can effectively solve the problem of internal short circuit of the battery caused by the growth of lithium dendrites, further prolongs the cycle life of the battery, and has the characteristic of stability to lithium metal.
Drawings
Fig. 1 is a graph of cycle performance of the lithium ion batteries provided in application examples 1-3 and comparative application example 1.
Detailed Description
The technical solution of the present invention is further explained by combining the drawings and the detailed description. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Lithium lanthanum titanium oxide inorganic solid electrolyte (Li) used in examples 1 to 7 and comparative examples 1 to 2 of the present invention0.34La0.56TiO3Written as LLTO) as follows:
(1) adding polyvinylpyrrolidone into dimethylformamide as a solvent, and stirring to obtain a polyvinylpyrrolidone solution;
(2) adding tetra-n-butyl titanate, lanthanum nitrate hexahydrate, lithium nitrate and acetic acid into the polyvinylpyrrolidone solution in the step (1), and mechanically stirring for 12 hours in a water bath kettle at 50 ℃ to obtain a uniform solution;
(3) preparing the solution in the step (2) into a spinning fiber precursor by adopting an electrostatic spinning method, calcining the spinning fiber precursor at 850 ℃ for 2h at the heating rate of 1.5 ℃/min, and then cooling the spinning fiber precursor to room temperature to obtain a sample, namely the lithium lanthanum titanium oxide inorganic solid electrolyte.
The raw materials in the examples and comparative examples of the present invention were purchased from Shanghai Aladdin Biotechnology Ltd and the purity was 99.99%.
Example 1
The present embodiment provides a method for producing a composite solid electrolyte membrane, including the steps of:
stirring ethylene glycol (glycol) diacrylate with the weight-average molecular weight of 800 and lithium bistrifluoromethanesulfonimide according to the proportion of 3:1 for 2 hours, adding an a, a-dimethoxy-a-phenylacetophenone initiator with the mass percentage of 2% of the total mass of the monomers, and stirring and dissolving in a dark place. And (2) taking the total mass of the liquid monomer and the inorganic solid electrolyte as 100%, adding the LLTO inorganic solid electrolyte with the mass percentage of 90% into the solution after the dissolution is finished, stirring the solution for about 12 hours in a dark place to obtain uniformly dispersed white slurry, coating the slurry on lithium metal in a drying room by using a scraper, and then carrying out light curing reaction by using an ultraviolet lamp for 30 minutes to obtain the composite solid electrolyte membrane with the thickness of 150 microns.
Example 2
The present embodiment provides a composite solid electrolyte membrane, the preparation method including the steps of:
stirring ethylene glycol (glycol) diacrylate with the weight-average molecular weight of 800 and lithium bistrifluoromethanesulfonimide according to the proportion of 3:1 for 2 hours, adding an a, a-dimethoxy-a-phenylacetophenone initiator with the mass percentage of 2% of the total mass of the monomers, and stirring and dissolving in a dark place. And (2) taking the total mass of the liquid monomer and the inorganic solid electrolyte as 100%, adding the LLTO inorganic solid electrolyte with the mass percentage of 95% into the solution after the dissolution is finished, stirring the solution for about 12 hours in a dark place to obtain uniformly dispersed white slurry, coating the slurry on lithium metal in a drying room by using a scraper, and then carrying out light curing reaction by using an ultraviolet lamp for 30 minutes to obtain the composite solid electrolyte membrane with the thickness of 150 microns.
Example 3
The present embodiment provides a composite solid electrolyte membrane, the preparation method including the steps of:
stirring ethylene glycol (glycol) diacrylate with the weight-average molecular weight of 800 and lithium bistrifluoromethanesulfonimide according to the proportion of 3:1 for 2 hours, adding an a, a-dimethoxy-a-phenylacetophenone initiator with the mass percentage of 2% of the total mass of the monomers, and stirring and dissolving in a dark place. And (2) taking the total mass of the liquid monomer and the inorganic solid electrolyte as 100%, adding the LLTO inorganic solid electrolyte with the mass percentage of 85% into the solution after the dissolution is finished, stirring the solution for about 12 hours in a dark place to obtain uniformly dispersed white slurry, coating the slurry on lithium metal in a drying room by using a scraper, and then carrying out light curing reaction by using an ultraviolet lamp for 30 minutes to obtain the composite solid electrolyte membrane with the thickness of 150 microns.
Example 4
The present embodiment provides a composite solid electrolyte membrane, the preparation method including the steps of:
stirring methyl ethylene carbonate with the weight-average molecular weight of 1000 and lithium difluoro-oxalato-borate for 2 hours according to the proportion of 2:1, and adding azodiisobutyronitrile initiator with the mass percentage of 3% of the total mass of the monomers for stirring and dissolving. And (2) adding the LLTO inorganic solid electrolyte with the mass percentage of 80% into the solution after the dissolution is finished by taking the total mass of the liquid monomer and the inorganic solid electrolyte as 100%, stirring for about 12 hours again to obtain uniformly dispersed white slurry, coating the slurry on lithium metal in a drying room by using a scraper, heating for thermocuring reaction for 40min to obtain the composite solid electrolyte membrane with the thickness of 150 mu m.
Example 5
The present embodiment provides a composite solid electrolyte membrane, the preparation method including the steps of:
stirring vinylidene fluoride-hexafluoropropylene with the weight-average molecular weight of 2500 and lithium hexafluorophosphate for 2 hours according to the proportion of 1:1, and adding an azodiisobutyronitrile initiator with the mass percentage of 1% of the total mass of the monomers for stirring and dissolving. And (2) adding 75 mass percent of LLTO inorganic solid electrolyte into the solution after the dissolution is finished by taking the total mass of the liquid monomer and the inorganic solid electrolyte as 100%, stirring for about 12 hours again to obtain uniformly dispersed white slurry, coating the slurry on lithium metal in a drying room by using a scraper, heating for thermocuring reaction for 50min to obtain the composite solid electrolyte membrane with the thickness of 150 mu m.
Example 6
The present embodiment provides a composite solid electrolyte membrane, the preparation method including the steps of:
stirring ethylene glycol dimethacrylate with the weight-average molecular weight of 500 and lithium bistrifluoromethanesulfonimide for 2 hours according to the proportion of 1:1, adding 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide initiator with the mass percentage of 2 percent of the total mass of the monomers, and stirring and dissolving in a dark place. And (2) taking the total mass of the liquid monomer and the inorganic solid electrolyte as 100%, adding 50% by mass of the LLTO inorganic solid electrolyte into the solution after the dissolution is finished, stirring the solution in a dark place for about 12 hours to obtain uniformly dispersed white slurry, coating the slurry on lithium metal in a drying room by using a scraper, and then carrying out light curing reaction by using an ultraviolet lamp for 15 minutes to obtain the composite solid electrolyte membrane with the thickness of 200 mu m.
Example 7
The present embodiment provides a composite solid electrolyte membrane, the preparation method including the steps of:
stirring ethylene glycol dimethacrylate with the weight-average molecular weight of 5000 and lithium bistrifluoromethylsulfonyl imide for 2 hours according to the proportion of 5:1, adding an a, a-dimethoxy-a-phenyl acetophenone initiator with the mass percentage of 5 percent of the total mass of the monomers, and stirring and dissolving in a dark place. And (2) taking the total mass of the liquid monomer and the inorganic solid electrolyte as 100%, adding the LLTO inorganic solid electrolyte with the mass percentage of 99% into the solution after the dissolution is finished, stirring the solution for about 12 hours in a dark place to obtain uniformly dispersed white slurry, coating the slurry on lithium metal in a drying room by using a scraper, and then carrying out light curing reaction by using an ultraviolet lamp for 60 minutes to obtain the composite solid electrolyte membrane with the thickness of 50 microns.
Comparative example 1
The comparative example is different from example 1 in that toluene, lithium bistrifluoromethanesulfonylimide, polyvinylidene fluoride and LLTO oxide electrolyte are mixed in a certain proportion and ball-milled for pulping, wherein the mass ratio of the LLTO oxide electrolyte to the polyvinylidene fluoride is 85:15, and the mass ratio of the polyvinylidene fluoride to the lithium bistrifluoromethanesulfonylimide is 3: 1. After pulping, the aluminum foil is coated on an aluminum foil and dried to form a final electrolyte membrane.
Comparative example 2
This comparative example is different from example 1 in that, based on 100% by mass of the total mass of the liquid monomer and the inorganic solid electrolyte, 45% by mass of LLTO inorganic solid electrolyte was added after completion of the dissolution, and the rest was the same as example 1.
Comparative example 3
This comparative example is different from example 1 in that no LLTO inorganic solid electrolyte was added, and the rest was the same as example 1.
Comparative example 4
This comparative example is different from example 1 in that the mass ratio of the lithium salt to the liquid monomer is 1:8, and the others are the same as example 1.
Comparative example 5
This comparative example differs from example 1 in that the ratio of the lithium salt to the liquid monomer was 2:1 by mass, and the rest was the same as example 1.
Application examples 1-7 and comparative application examples 1-5
The composite solid electrolyte membranes provided in examples 1 to 7 and comparative examples 1 to 5 were prepared to obtain lithium ion batteries by the following methods:
preparing a positive plate: adding a positive electrode material lithium iron phosphate, an ionic conductor LLTO, a conductive agent and an adhesive into a solvent according to the mass ratio of 94.12:1.88:1:3, fully stirring to obtain a mixed slurry, uniformly coating the mixed slurry on a 12-micron aluminum foil, and drying, rolling and cutting into pieces to obtain a required positive plate;
preparing a negative plate: coating the composite solid electrolyte membrane on the surface of the lithium metal cathode by using a scraper, and then cutting the lithium metal cathode into pieces;
preparing a lithium ion battery: and assembling the prepared negative electrode, the composite solid electrolyte membrane and the lithium iron phosphate positive plate, and then testing the electrochemical performance.
Test conditions
The composite solid electrolyte membranes provided in examples 1 to 7 and comparative examples 1 to 5 were subjected to conductivity tests as follows:
and (3) impedance testing: using an Autolab workstation at 10-1-105The test was performed with an amplitude of 10mV at a frequency of Hz, using the formula:
wherein
For ionic conductivity, RbIs the bulk impedance, t is the thickness, A is the area value;
the lithium ion batteries provided in application examples 1 to 7 and comparative application examples 1 to 5 were subjected to electrochemical performance tests, the test methods were as follows:
the cell was charged to 3.65V with a constant current and constant voltage of 0.05C and a cutoff current of 0.01C, and then discharged to 2.5V with a constant current of 0.05C. After such charge/discharge cycles, the coulombic efficiency after the 100 th cycle was calculated.
The coulombic efficiency calculation formula after 100 cycles at 25 ℃ is as follows:
coulombic efficiency (%) - (discharge capacity/charge capacity corresponding to number of cycles) × 100%
The results of the tests are shown in tables 1 and 2:
TABLE 1
| Test sample | Ion conductivity (S/cm) |
| Example 1 | 8.6×10-4 |
| Example 2 | 1.9×10-3 |
| Example 3 | 6.1×10-4 |
| Example 4 | 2.5×10-4 |
| Example 5 | 9.3×10-5 |
| Example 6 | 7.9×10-5 |
| Example 7 | 1.2×10-3 |
| Comparative example 1 | 7.5×10-5 |
| Comparative example 2 | 5.6×10-6 |
| Comparative example 3 | 2.4×10-6 |
| Comparative example 4 | 8.2×10-5 |
| Comparative example 5 | 8.9×10-4 |
TABLE 2
As can be seen from the data in table 1, on the premise that a film can be formed, the higher the content of the added LLTO inorganic solid electrolyte in the composite solid electrolyte film, the higher the ionic conductivity of the corresponding composite solid electrolyte film is; fig. 1 is a graph showing the cycle performance of the lithium ion batteries provided in application examples 1 to 3 and comparative application example 1, and it can be seen from fig. 1 that increasing the content of the added liquid monomer is advantageous in increasing the capacity at the initial stage of the cycle, but the capacity decays relatively quickly during the later cycle.
Comparative examples 1 and 3 illustrate inorganic solid electrolytes or polymer solid electrolytes alone, which have ion conductivities far inferior to those of the composite solid electrolyte membranes provided in examples 1 to 7; comparative example 2 illustrates that when the mass ratio of the liquid monomer to the inorganic solid electrolyte is out of the range selected in the present invention, the conductivity of the resulting composite solid electrolyte membrane is also not ideal; comparative examples 4 and 5, when the mass ratio of lithium salt to liquid monomer is adjusted to be out of the range selected in the present invention, show that the conductivity of the resulting composite solid electrolyte membrane is lower than that of example 1 by decreasing the ratio of lithium salt, whereas if the ratio of lithium salt is increased, although the ionic conductivity can be improved, the cost is increased accordingly; further shows that the ionic conductivity of the prepared composite solid electrolyte membrane is comprehensively improved by optimizing the proportion of each component.
As can be seen from the data in table 2, the coulombic efficiency of the lithium ion batteries in application examples 1 to 7 provided by the present invention is not lower than 99.36% after 100 cycles at a current density of 0.05C. Application examples 6 and 7 can be compared to each other, and although the increase of the LLTO inorganic solid electrolyte can improve the ionic conductivity of the composite solid electrolyte membrane, the composite solid electrolyte membrane is easy to crack and fall off after the cycle due to the low polymer content.
The comparative application example 1 and the comparative application example 3 illustrate that only an inorganic solid electrolyte or a polymer solid electrolyte cannot comprehensively ensure high coulombic efficiency and low cost; comparative application example 2 shows that when the mass ratio of the liquid monomer to the inorganic solid electrolyte is out of the range selected by the present invention, the coulombic efficiency of the obtained composite solid electrolyte membrane is lower than that of example 1, and it can be known from the above that the lithium salt has a large influence on the conductivity, and the factor influencing the coulombic efficiency of the battery is mainly the inorganic solid electrolyte, and the coating quality of the electrolyte membrane itself also has an influence.
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A method for producing a composite solid electrolyte membrane, characterized by comprising the steps of:
and mixing the liquid monomer, the inorganic solid electrolyte, the lithium salt and the initiator, and then carrying out a curing reaction to obtain the composite solid electrolyte membrane.
2. The method according to claim 1, wherein the liquid monomer comprises any one of or a combination of at least two of methyl ethylene carbonate, vinylene carbonate, vinylidene fluoride-hexafluoropropylene, acrylonitrile, ethylene glycol (diol) diacrylate, ethylene glycol dimethacrylate, ethylene glycol methyl ether acrylate, methyl methacrylate, or ethylene glycol.
3. The method according to claim 1 or 2, wherein the liquid monomer has a weight average molecular weight of 500 to 5000;
preferably, the mass percentage of the liquid monomer is 1-50% based on 100% of the total mass of the liquid monomer and the inorganic solid electrolyte.
4. The production method according to any one of claims 1 to 3, characterized in that the inorganic solid electrolyte is an oxide solid electrolyte;
preferably, the oxide solid electrolyte includes any one of perovskite type, NASICON type, LISICON type, garnet type, or LiPON type, or a combination of at least two of them.
5. The production method according to any one of claims 1 to 4, wherein the inorganic solid electrolyte is contained in an amount of 50 to 99% by mass based on 100% by mass of the total mass of the liquid monomer and the inorganic solid electrolyte.
6. The production method according to any one of claims 1 to 5, wherein the lithium salt comprises any one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium bis (difluorosulfonimide) or lithium bis (trifluoromethylsulfonimide) or a combination of at least two thereof;
preferably, the mass ratio of the lithium salt to the liquid monomer is 1 (1-5).
7. The production method according to any one of claims 1 to 6, characterized in that the initiator comprises any one of a, a-dimethoxy-a-phenylacetophenone, benzophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, or azobisisobutyronitrile or a combination of at least two thereof;
preferably, the mass percentage of the initiator is 1-5% based on the total mass of the liquid monomer as 100%.
8. The production method according to any one of claims 1 to 7, wherein the curing reaction is any one or a combination of two of a thermal curing reaction and a photo curing reaction;
preferably, the curing reaction time is 10min to 60 min.
9. A composite solid electrolyte membrane produced by the production method according to any one of claims 1 to 8;
preferably, the thickness of the composite solid electrolyte membrane is 50 μm to 200 μm.
10. An electrochemical energy storage device comprising a positive electrode, a negative electrode, and an electrolyte, wherein the electrolyte is the composite solid electrolyte membrane of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111405032.6A CN114142099A (en) | 2021-11-24 | 2021-11-24 | Preparation method of composite solid electrolyte membrane and electrochemical energy storage device |
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