阅读说明：本技术 聚合物固体电解质及其制备方法 (Polymer solid electrolyte and preparation method thereof ) 是由 陈步天 余意 何凤荣 于 2020-05-16 设计创作，主要内容包括：本发明公开了一种聚合物固体电解质及其制备方法。所述聚合物固体电解质包括聚合物基体、锂盐和无机填料,其中,所述聚合物基体为PVDF或PVDF与PEO的混合物；所述锂盐包括锂盐A,所述锂盐A为三叔丁氧基氢化铝锂(LTTBA)或三乙基硼氢化锂(LTEB)或者两者的混合物。本发明还公开了上述聚合物固体电解质的制备方法。包含本发明的聚合物固体电解质的锂电池具有优异的循环性能和倍率性能以及良好的界面稳定性。(The invention discloses a polymer solid electrolyte and a preparation method thereof. The polymer solid electrolyte comprises a polymer matrix, lithium salt and an inorganic filler, wherein the polymer matrix is PVDF or a mixture of PVDF and PEO; the lithium salt comprises a lithium salt A, and the lithium salt A is lithium tri-tert-butoxyaluminum hydride (LTTBA) or Lithium Triethylborohydride (LTEB) or a mixture of the lithium salt A and the lithium salt A. The invention also discloses a preparation method of the polymer solid electrolyte. The lithium battery containing the polymer solid electrolyte has excellent cycle performance and rate performance and good interface stability.)

1. A polymer solid electrolyte, which is characterized by comprising a polymer matrix, lithium salt and inorganic filler, wherein the polymer matrix is PVDF or a mixture of PVDF and PEO; the lithium salt comprises a lithium salt A, and the lithium salt A is lithium tri-tert-butoxyaluminum hydride or lithium triethylborohydride or a mixture of the lithium tri-tert-butoxyaluminum hydride and the lithium triethylborohydride.

2. The polymer solid electrolyte according to claim 1, wherein when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of PEO to PVDF is 1: 3-25, preferably 1: 3-15.

3. The polymer solid electrolyte according to claim 1, wherein the lithium salt further comprises a lithium salt B, and the lithium salt B is lithium bistrifluoromethanesulfonate imide, lithium bistrifluorosulfonate imide, lithium bisoxalato borate, lithium tetrafluoroborate, lithium difluorobisoxalato borate, lithium perchlorate, lithium hexafluorophosphate, t-butyllithium, lithium bistrimethylsilylamide, lithium bistrifluoromethanesulfonylimide, lithium diisopropylamide, n-butyllithium, sec-butyllithium, lithium tri-sec-butylborohydride, lithium tri-t-butoxyaluminum hydride, lithium tert-butoxymethyllithium, lithium triethylborohydride, lithium diisopropylamide, lithium bistrimethylsilylamide, lithium acetoacetate, lithium pentamethylcyclopentadienyl, lithium trifluoroethyl trifluorophosphate, 4, 5-dicyano-2-trifluoromethylimidazole, lithium bis (fluoropropanoate) borate, 4, 5-dicyano-2-heptafluoropropylimidazole, lithium bis (fluoropropanoate), lithium salt B, lithium salt, 4, 5-dicyano-1, 2, 3-triazolate lithium, and lithium fluorosulfonate (n-perfluorobutylsulfonyl) imide.

4. The polymer solid electrolyte according to claim 3, wherein when the lithium salt is a mixture of lithium salt A and lithium salt B, the mass ratio of lithium salt A to lithium salt B is 20-1: 1-10, preferably 10-1: 1-10, and more preferably 5-1: 1-10.

5. The polymer solid electrolyte according to claim 1, wherein the mass ratio of the lithium salt to the polymer matrix is 1:1 to 20.

6. The polymer solid electrolyte according to claim 1, wherein the inorganic filler is at least one of alumina, zinc oxide, titanium oxide, silica, molybdenum disulfide, lithium lanthanum zirconium tantalum oxygen, lithium titanium aluminum phosphate, lithium germanium aluminum phosphate, lithium aluminate, lithium germanium sulfide, lithium lanthanum titanate, montmorillonite, copper oxide, magnesium oxide, lead titanate, and calcium silicate.

7. The polymer solid electrolyte according to claim 1, wherein the inorganic filler is added in an amount of 5 to 40%, preferably 10 to 20% of the total mass of the polymer solid electrolyte.

8. The method for producing a polymer solid electrolyte according to any one of claims 1 to 7, comprising:

stirring and mixing a polymer matrix, lithium salt and an inorganic filler in an organic solvent to obtain slurry;

and casting the slurry in a mold, and drying in vacuum to obtain the polymer solid electrolyte.

9. The method of claim 1, wherein the organic solvent is at least one of acetonitrile, N-dimethylpyrrolidone, dimethylacetamide, and dimethylformamide.

10. A lithium battery comprising the polymer solid electrolyte according to any one of claims 1 to 7.

Technical Field

The invention relates to the technical field of lithium battery materials, in particular to a polymer solid electrolyte containing novel lithium salt and a preparation method thereof.

Background

The lithium secondary battery has the advantages of no memory effect, high volume specific capacity, high working voltage, wide temperature resistance range, low self-discharge rate, long cycle life and the like, and has good application prospect in new energy fields such as intelligent electronic products, electric automobiles, large-scale energy storage power grids and the like. However, the lithium secondary batteries widely used at present all use liquid organic small-molecule electrolytes, and have potential safety hazards of explosion under abnormal conditions such as overcharge and internal short circuit. In recent years, the safety accidents of the lithium battery frequently burst, which shows that the safety problem of the lithium secondary battery becomes a technical bottleneck restricting the wider and deeper application of the lithium secondary battery. Further development of lithium secondary batteries with higher specific energy and high safety has important significance and value for further development of new energy industries.

The polymer lithium battery using the polymer solid electrolyte to replace the organic micromolecular electrolyte is expected to thoroughly solve the safety concern of the battery while improving the energy density of the lithium battery, so the polymer lithium battery has better development prospect. One of the most common polymer matrices for polymer solid electrolytes today is a polyvinylidene fluoride (PVDF) -based polymer. However, the existing PVDF-based polymer electrolytes still have drawbacks in performance. For example, PVDF has high crystallinity and a high proportion of crystalline regions, which leads to the inability of lithium ions to rapidly transport in the PVDF matrix and poor ionic conductivity; PVDF can react with a lithium metal negative electrode, and by-products generated by the reaction cause the contact between an electrolyte and a lithium metal interface, so that the polarization of the battery is increased, and the interface stability is poor; PVDF reacts in contact with lithium metal, resulting in a lower electrochemical window; the PVDF cannot bear heat generated by thermal runaway, so that the thermal stability of the PVDF is poor and potential safety hazards exist.

Therefore, there is a need for improvement of the existing PVDF-based polymer solid electrolyte.

Disclosure of Invention

The present invention has been made to solve at least one of the above-mentioned problems occurring in the existing PVDF-based polymer solid electrolyte, and therefore, the present invention provides a polymer solid electrolyte containing a novel lithium salt and a method for preparing the same. On one hand, the ionic conductivity, electrochemical window and thermal stability of the PVDF polymer solid electrolyte are improved by adding novel lithium salt; on one hand, the crystallinity of the PVDF polymer solid electrolyte is reduced by adding the inorganic filler, and the ionic conductivity is further improved.

Specifically, the invention adopts the following technical scheme:

in one aspect, the present invention provides a polymer solid electrolyte comprising a polymer matrix, a lithium salt and an inorganic filler, wherein the polymer matrix is PVDF or a mixture of PVDF and PEO; the lithium salt comprises a lithium salt A, and the lithium salt A is lithium tri-tert-butoxyaluminum hydride (LTTBA) or Lithium Triethylborohydride (LTEB) or a mixture of the lithium salt A and the lithium salt A.

The lithium salt A has high thermal decomposition temperature, high ionic conductivity and high electrochemical oxidation voltage, and can effectively improve the thermal stability, ionic conductivity and electrochemical window of PVDF when added into the PVDF polymer solid electrolyte. Meanwhile, the filler is added into the polymer matrix, so that the mechanical property of the PVDF can be improved, and the ionic conductivity, the pressure resistance and the thermal decomposition temperature of the PVDF can be further improved.

In addition, PEO can be added into the polymer matrix to achieve the purpose of improving the interface performance of the polymer solid electrolyte, so that the cycle performance and the rate capability of the PVDF-based polymer solid battery are improved.

According to some embodiments of the present invention, when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of PEO to PVDF is 1:3 to 25, for example: 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, and so forth.

In some embodiments, when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of the PEO to the PVDF is 1: 3-15.

In some embodiments, when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of the PEO to the PVDF is 1: 5-15.

According to some embodiments of the present invention, the mass ratio of the lithium salt to the polymer matrix is 1:1 to 20, for example: 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, and so forth.

In some embodiments, the mass ratio of the lithium salt to the polymer matrix is 1:1 to 15, in some embodiments 1:1 to 12, in some embodiments 1:1 to 5, in some embodiments 1:5 to 20, and in some embodiments 1:12 to 20.

According to some provided embodiments of the invention, the lithium salt a is lithium tri-tert-butoxyaluminum hydride or lithium triethylborohydride.

According to some embodiments of the present invention, the lithium salt a is a mixture of lithium tri-tert-butoxyaluminum hydride and lithium triethylborohydride, which may be mixed in any ratio.

The anion structure in the electrolyte lithium salt is an important factor influencing the lithium salt, and the larger the volume of the lithium salt anion is, the higher the degree of negative charge delocalization is, so that the electrostatic interaction between the lithium salt and the cation can be reduced, the lithium salt is easy to dissociate, and the polymer electrolyte has higher lithium ion conductivity. In addition, during charging and discharging, anions are gathered at an electrode/electrolyte interface to hinder the migration of cations, thereby reducing the energy efficiency and the service life of the battery. The anion with large volume is adopted, and the anion is difficult to migrate in the macromolecule due to the volume factor, so that the cation migration number is increased, and the battery performance is improved. In addition, the large-volume anion also has better electrochemical stability and thermal stability, improves the thermal stability and the electrochemical stability of the lithium salt, and plays an effective plasticizing effect, so that the technical effect of the invention is not necessarily achieved by specially selecting the electrolyte lithium salt containing the lithium salt A and replacing the lithium salt A with other lithium salts of the same type in the technical scheme provided by the invention.

According to some embodiments provided by the present invention, other common lithium salts, namely, lithium salt B in the present invention, may also be added. The addition of the lithium salt B can further improve the conductivity of the polymer solid electrolyte, and the polymer solid electrolyte with better performance can be obtained by combining the lithium salt B with the lithium salt A.

The lithium salt B is lithium bistrifluoromethanesulfonate imide (LiTFSI), lithium bistrifluoromethanesulfonate imide (LiFSI), lithium bisoxalato borate (LiBOB) and lithium tetrafluoroborate (LiBF)₄) Lithium difluorobis (oxalato) borate (LiODFB), lithium perchlorate (LiClO)₄) Lithium hexafluorophosphate (LiPF)₆) Tert-butyllithium, bistrimethylsilylaminolithium, bistrifluoromethanesulfonylimide, lithium diisopropylamide, n-butyllithium, sec-butyllithium, tri-sec-butyllithium borohydride, tri-tert-butoxylithium aluminum hydride, lithium methyllithium tert-butoxide, lithium triethylborohydride, bis (tert-butyllithium)At least one of lithium isopropylamide, lithium bistrimethylsilyl, lithium acetoacetate, lithium pentamethylcyclopentadiene, lithium trifluoroethyl trifluorophosphate, 4, 5-dicyano-2-trifluoromethylimidazole (LiTDI), lithium bis (fluoromalonic acid) borate (LiBFMB), 4, 5-dicyano-2-heptafluoropropylimidazole (LiHDI), lithium 4, 5-dicyano-1, 2, 3-triazolate (LiDCTA), lithium fluorosulfonate (n-perfluorobutylsulfonyl) imide (LiNFSI).

In addition to the above-listed lithium salts B, other lithium salts commonly used in the art to achieve comparable technical effects may also be used in the present invention.

According to some embodiments of the present invention, when the lithium salt is a mixture of lithium salt A and lithium salt B, the mass ratio of lithium salt A to lithium salt B is 20-1: 1-10. If the lithium salt B is too much, the mechanical properties of the polymer solid electrolyte are poor and the conductivity is also low; and if the lithium salt B is too little, the conductivity-improving effect of the polymer solid electrolyte is insignificant.

In some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 2-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 2-1: 1-9.

According to some embodiments of the present invention, when the lithium salt A is lithium triethylborohydride, the mass ratio of the lithium triethylborohydride to the lithium salt B is 20-1: 1-10.

In some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 2-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 2-1: 1-9.

According to some embodiments of the present invention, when the lithium salt A is lithium tri-tert-butoxyaluminum hydride, the mass ratio of the lithium tri-tert-butoxyaluminum hydride to the lithium salt B is 20-1: 1-10.

In some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 2-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 2-1: 1-9.

According to some embodiments provided herein, the lithium salt B is lithium bistrifluoromethanesulfonate imide, lithium bistrifluoromethanesulfonate borate, lithium tetrafluoroborate, lithium difluorobis-oxalato borate, lithium perchlorate, lithium hexafluorophosphate, t-butyllithium, lithium bistrimethylsilylamide, lithium bistrifluoromethanesulfonylimide, lithium diisopropylamide, n-butyllithium, sec-butyllithium, lithium tri-sec-butylborohydride, lithium tri-t-butoxyaluminum hydride, lithium tert-butoxymethyllithium, lithium triethylborohydride, lithium diisopropylamide, lithium bistrimethylsilylamide, lithium acetoacetate, lithium pentamethylcyclopentadienyl, lithium trifluoroethyl-trifluorophosphate, 4, 5-dicyano-2-trifluoromethylimidazole, lithium bis (fluoropropanedioate) borate, 4, 5-dicyano-2-heptafluoropropylimidazole, 4, 5-dicyano-1, any one or two of 2, 3-lithium triazolate and lithium fluorosulfonate (n-perfluorobutylsulfonyl) imide.

According to some embodiments of the present invention, the inorganic filler is at least one of alumina, zinc oxide, titanium oxide, silica, molybdenum disulfide, lithium lanthanum zirconium tantalum oxygen, titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, lithium aluminate, germanium lithium sulfur phosphate, lanthanum lithium titanate, montmorillonite, copper oxide, magnesium oxide, lead titanate, and calcium silicate.

In some embodiments, the inorganic filler is any one of alumina, zinc oxide, titanium oxide, silica, molybdenum disulfide, lithium lanthanum zirconium tantalum oxygen, titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, lithium aluminate, sulfur germanium lithium phosphate, lanthanum lithium titanate, montmorillonite, copper oxide, magnesium oxide, lead titanate, and calcium silicate.

In addition to the above-listed inorganic fillers, other inorganic fillers commonly used in the art to achieve comparable technical results can also be used in the present invention.

According to some embodiments of the present invention, the inorganic filler is added in an amount of 5% to 40%, preferably 10% to 20%, of the total mass of the polymer solid electrolyte. If the addition amount of the inorganic filler is too much, the inorganic filler is not well dispersed uniformly, so that the conductivity is greatly reduced; if the amount of the inorganic filler added is too small, the effect of reducing the crystallinity of the polymer cannot be exerted, so that the effect of improving the conductivity of the polymer solid electrolyte is not significant, and the effect of improving the mechanical strength of the polymer is not ideal.

Specifically, the inorganic filler is added in a proportion of the total mass of the polymer solid electrolyte, and the proportion is as follows: 5%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, etc.

In another aspect, the present invention provides a method for preparing the polymer solid electrolyte, comprising:

stirring and mixing a polymer matrix, lithium salt and an inorganic filler in an organic solvent to obtain slurry;

and casting the slurry in a mold, and drying in vacuum to obtain the polymer solid electrolyte.

According to some embodiments provided herein, the organic solvent is at least one of acetonitrile, N-dimethylpyrrolidone (NMP), Dimethylacetamide (DMAC) and Dimethylformamide (DMF).

In some embodiments, the organic solvent is any one of acetonitrile, N-dimethylpyrrolidone (NMP), Dimethylacetamide (DMAC), and Dimethylformamide (DMF).

The selection of the polymer matrix, the lithium salt and the inorganic filler is the same as that of each component in the polymer electrolyte, and the details are not repeated.

According to some embodiments of the present invention, the temperature of the stirring and mixing is 25 to 80 ℃, for example: 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ and the like; the stirring time is 3-24 h, for example: 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, and so on.

In some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 6-12 hours. In some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 12-24 hours; in some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 16-24 hours.

According to some embodiments of the present invention, the temperature of the vacuum drying is 25 to 60 ℃, for example: 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ and the like; the stirring time is 3-24 h, for example: 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, and so on.

In some embodiments, the temperature of the stirring and mixing is 30 to 50 ℃, and the stirring time is 10 to 24 hours. In some embodiments, the temperature of the stirring and mixing is 30-50 ℃, and the stirring time is 12-24 hours; in some embodiments, the temperature of the stirring and mixing is 30-50 ℃, and the stirring time is 16-24 hours.

According to some embodiments of the invention, the mold is a polytetrafluoroethylene mold.

In another aspect, the present invention provides a lithium battery comprising the above-described polymer solid electrolyte material.

The invention has the following technical effects:

(1) in the polymer solid electrolyte provided by the invention, the lithium salt A has high thermal decomposition temperature, high ionic conductivity and high electrochemical oxidation voltage, and can be added into the PVDF polymer solid electrolyte to effectively improve the thermal stability, ionic conductivity and electrochemical window of PVDF. Meanwhile, the inorganic filler is added into the polymer matrix, so that the mechanical property of the PVDF can be improved, and the ionic conductivity, the pressure resistance and the thermal decomposition temperature of the PVDF can be further improved. In addition, the interface performance of the polymer solid electrolyte is improved by adding PEO into the polymer matrix, and the cycle performance and rate capability of the PVDF-based polymer solid battery are improved.

(2) The lithium battery containing the polymer solid electrolyte provided by the invention has the conductivity of 2.4x10^-4S cm^-1The electrochemical window can reach 4.9V, and the current density is preferably 0.1mA/cm²The catalyst runs for 1180h without short circuit, and has excellent stability and good cycle performance.

Drawings

FIG. 1 shows an impedance diagram of a polymer solid electrolyte prepared in example 1 of the present invention;

FIG. 2 is a graph showing the impedance of a polymer solid electrolyte prepared in example 2 of the present invention;

FIG. 3 is a graph showing the impedance of a polymer solid electrolyte prepared in example 3 of the present invention;

FIG. 4 is a graph showing the impedance of a polymer solid electrolyte prepared in example 4 of the present invention;

FIG. 5 is a graph showing the impedance of a polymer solid electrolyte prepared in example 5 of the present invention;

FIG. 6 is a graph showing the impedance of the polymer solid electrolyte prepared in comparative example 1 of the present invention;

FIG. 7 is a graph showing the impedance of the polymer solid electrolyte prepared in comparative example 2 of the present invention;

FIG. 8 is a graph showing the impedance of a polymer solid electrolyte prepared in comparative example 3 of the present invention;

fig. 9 shows a linear cyclic voltammogram of a polymer solid electrolyte assembled button cell prepared in example 4 of the present invention;

FIG. 10 is a button full cell cycle performance test chart of the polymer solid electrolyte prepared in example 4 of the present invention; and

FIG. 11 is a graph showing the test of the lithium metal interfacial stability of the polymer solid electrolyte prepared in example 4 of the present invention.

Detailed Description

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety. The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.

The method for preparing the polymer solid electrolyte will be described in detail below.

According to some embodiments provided herein, the method for preparing the polymer solid electrolyte includes:

stirring and mixing a polymer matrix, lithium salt and an inorganic filler in an organic solvent to obtain slurry;

and casting the slurry in a mold, and drying in vacuum to obtain the polymer solid electrolyte.

According to some embodiments provided herein, the polymer matrix is PVDF or a mixture of PVDF and PEO.

According to some embodiments of the present invention, when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of PEO to PVDF is 1:3 to 25, for example: 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, and so forth.

In some embodiments, when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of the PEO to the PVDF is 1: 3-15.

According to some embodiments of the present invention, the mass ratio of the lithium salt to the polymer matrix is 1:1 to 20, for example: 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, and so forth.

In some embodiments, the mass ratio of the lithium salt to the polymer matrix is 1:1 to 15, in some embodiments 1:1 to 12, in some embodiments 1:1 to 5, in some embodiments 1:5 to 20, and in some embodiments 1:12 to 20.

According to some provided embodiments of the invention, the lithium salt a is lithium tri-tert-butoxyaluminum hydride or lithium triethylborohydride.

According to some embodiments of the present invention, the lithium salt a is a mixture of lithium tri-tert-butoxyaluminum hydride and lithium triethylborohydride, which may be mixed in any ratio.

In the technical scheme provided by the invention, the lithium salt A is replaced by other lithium salts in the field, so that the technical effect of the invention cannot be achieved.

According to some embodiments provided by the present invention, other common lithium salts, namely, lithium salt B in the present invention, may also be added.

The lithium salt B is lithium bistrifluoromethanesulfonate, lithium bisoxalateborate, lithium tetrafluoroborate, lithium difluorobisoxalateborate, lithium perchlorate, lithium hexafluorophosphate, tert-butyllithium, bistrimethylsilyl lithium, bistrifluoromethanesulfonylimide, lithium diisopropylamide, n-butyllithium, sec-butyllithium, lithium tri-sec-butylborohydride, lithium tri-tert-butoxyaluminum hydride, lithium tert-butoxide methyllithium, lithium triethylborohydride, lithium diisopropylamide, bistrimethylsilyl lithium, lithium acetoacetate, lithium pentamethylcyclopentadiene, lithium trifluoroethyl trifluorophosphate, 4, 5-dicyano-2-trifluoromethylimidazole, lithium bis (fluoropropionate) borate, 4, 5-dicyano-2-heptafluoropropylimidazole, 4, 5-dicyano-1, 2, 3-triazolate, lithium tetrafluoroborate, lithium difluoroborate, at least one of lithium fluorosulfonate (n-perfluorobutylsulfonyl) imide. In addition to the above-listed lithium salts B, other lithium salts commonly used in the art to achieve comparable technical effects may also be used in the present invention.

According to some embodiments of the present invention, when the lithium salt is a mixture of lithium salt A and lithium salt B, the mass ratio of lithium salt A to lithium salt B is 20-1: 1-10.

In some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 2-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 2-1: 1-9.

Specifically, when the lithium salt is a mixture of a lithium salt a and a lithium salt B, the mass ratio of the lithium salt a to the lithium salt B may be: 20:1, 20:2, 20:3, 20:4, 20:5, 20:6, 20:7, 20:8, 20:9, 20:10, 19:1, 19:2, 19:3, 19:4, 19:5, 19:6, 19:7, 19:8, 19:9, 19:10, 18:1, 18:2, 18:3, 18:4, 18:5, 18:6, 18:7, 18:8, 18:9, 18:10, 17:1, 17:2, 17:3, 17:4, 17:5, 17:6, 17:7, 17:8, 17:9, 17:10, 16:1, 16:3, 16:5, 16:6, 16:7, 16:9, 16:10, 15:1, 15:2, 15:4, 15:6, 15:7, 15:8, 15:9, 15: 14, 14: 14, 14:7, 14: 14, 14:8, 14, 13:1, 13:2, 13:3, 13:4, 13:5, 13:6, 13:7, 13:8, 13:9, 13:10, 12:1, 12:5, 12:7, 12:9, 12:10, 11:1, 11:2, 11:3, 11:4, 11:5, 11:6, 11:7, 11:8, 11:9, 11:10, 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:9, 9:1, 9:2, 9:4, 9:5, 9:6, 9:7, 9:8, 9:10, 8:1, 8:2, 8:3, 8:4, 8:5, 8:7, 8:9, 8:10, 7:1, 7:2, 7:3, 7:4, 7:5, 7:6, 7: 5:6, 7:5, 7:5, 8:5, 7:5, 7:5, 8, 5:6, 5:7, 5:8, 5:9, 5:10, 4:1, 4:3, 4:5, 4:6, 4:7, 4:9, 3:1, 3:2, 3:4, 3:5, 3:6, 3:7, 3:8, 3:9, 3:10, 2:1, 2:3, 2:4, 2:5, 2:6, 2:7, 2:8, 2:9, 2:10, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1: 10.

According to some embodiments of the present invention, when the lithium salt A is lithium triethylborohydride, the mass ratio of the lithium triethylborohydride to the lithium salt B is 20-1: 1-10.

In some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 2-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 2-1: 1-9.

Specifically, when the lithium salt a is lithium triethylborohydride, the mass ratio of the lithium triethylborohydride to the lithium salt B may be: 20:1, 20:2, 20:3, 20:4, 20:5, 20:6, 20:7, 20:8, 20:9, 20:10, 19:1, 19:2, 19:3, 19:4, 19:5, 19:6, 19:7, 19:8, 19:9, 19:10, 18:1, 18:2, 18:3, 18:4, 18:5, 18:6, 18:7, 18:8, 18:9, 18:10, 17:1, 17:2, 17:3, 17:4, 17:5, 17:6, 17:7, 17:8, 17:9, 17:10, 16:1, 16:3, 16:5, 16:6, 16:7, 16:9, 16:10, 15:1, 15:2, 15:4, 15:6, 15:7, 15:8, 15:9, 15: 14, 14: 14, 14:7, 14: 14, 14:8, 14, 13:1, 13:2, 13:3, 13:4, 13:5, 13:6, 13:7, 13:8, 13:9, 13:10, 12:1, 12:5, 12:7, 12:9, 12:10, 11:1, 11:2, 11:3, 11:4, 11:5, 11:6, 11:7, 11:8, 11:9, 11:10, 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:9, 9:1, 9:2, 9:4, 9:5, 9:6, 9:7, 9:8, 9:10, 8:1, 8:2, 8:3, 8:4, 8:5, 8:7, 8:9, 8:10, 7:1, 7:2, 7:3, 7:4, 7:5, 7:6, 7: 5:6, 7:5, 7:5, 8:5, 7:5, 7:5, 8, 5:6, 5:7, 5:8, 5:9, 5:10, 4:1, 4:3, 4:5, 4:6, 4:7, 4:9, 3:1, 3:2, 3:4, 3:5, 3:6, 3:7, 3:8, 3:9, 3:10, 2:1, 2:3, 2:4, 2:5, 2:6, 2:7, 2:8, 2:9, 2:10, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1: 10.

According to some embodiments of the present invention, when the lithium salt A is lithium tri-tert-butoxyaluminum hydride, the mass ratio of the lithium tri-tert-butoxyaluminum hydride to the lithium salt B is 20-1: 1-10.

In some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 3-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 3 to 1:1 to 9.

Specifically, when the lithium salt a is lithium tri-tert-butoxyaluminum hydride, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B may be exemplified by: 20:1, 20:2, 20:3, 20:4, 20:5, 20:6, 20:7, 20:8, 20:9, 20:10, 19:1, 19:2, 19:3, 19:4, 19:5, 19:6, 19:7, 19:8, 19:9, 19:10, 18:1, 18:2, 18:3, 18:4, 18:5, 18:6, 18:7, 18:8, 18:9, 18:10, 17:1, 17:2, 17:3, 17:4, 17:5, 17:6, 17:7, 17:8, 17:9, 17:10, 16:1, 16:3, 16:5, 16:6, 16:7, 16:9, 16:10, 15:1, 15:2, 15:4, 15:6, 15:7, 15:8, 15:9, 15: 14, 14: 14, 14:7, 14: 14, 14:8, 14, 13:1, 13:2, 13:3, 13:4, 13:5, 13:6, 13:7, 13:8, 13:9, 13:10, 12:1, 12:5, 12:7, 12:9, 12:10, 11:1, 11:2, 11:3, 11:4, 11:5, 11:6, 11:7, 11:8, 11:9, 11:10, 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:9, 9:1, 9:2, 9:4, 9:5, 9:6, 9:7, 9:8, 9:10, 8:1, 8:2, 8:3, 8:4, 8:5, 8:7, 8:9, 8:10, 7:1, 7:2, 7:3, 7:4, 7:5, 7:6, 7: 5:6, 7:5, 7:5, 8:5, 7:5, 7:5, 8, 5:6, 5:7, 5:8, 5:9, 5:10, 4:1, 4:3, 4:5, 4:6, 4:7, 4:9, 3:1, 3:2, 3:4, 3:5, 3:6, 3:7, 3:8, 3:9, 3:10, 2:1, 2:3, 2:4, 2:5, 2:6, 2:7, 2:8, 2:9, 2:10, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1: 10.

According to some embodiments provided herein, the lithium salt B is lithium bistrifluoromethanesulfonate imide, lithium bistrifluoromethanesulfonate borate, lithium tetrafluoroborate, lithium difluorobis-oxalato borate, lithium perchlorate, lithium hexafluorophosphate, t-butyllithium, lithium bistrimethylsilylamide, lithium bistrifluoromethanesulfonylimide, lithium diisopropylamide, n-butyllithium, sec-butyllithium, lithium tri-sec-butylborohydride, lithium tri-t-butoxyaluminum hydride, lithium tert-butoxymethyllithium, lithium triethylborohydride, lithium diisopropylamide, lithium bistrimethylsilylamide, lithium acetoacetate, lithium pentamethylcyclopentadienyl, lithium trifluoroethyl-trifluorophosphate, 4, 5-dicyano-2-trifluoromethylimidazole, lithium bis (fluoropropanedioate) borate, 4, 5-dicyano-2-heptafluoropropylimidazole, 4, 5-dicyano-1, any one or two of 2, 3-lithium triazolate and lithium fluorosulfonate (n-perfluorobutylsulfonyl) imide.

According to some embodiments of the present invention, the inorganic filler is at least one of alumina, zinc oxide, titanium oxide, silica, molybdenum disulfide, lithium lanthanum zirconium tantalum oxygen, titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, lithium aluminate, germanium lithium sulfur phosphate, lanthanum lithium titanate, montmorillonite, copper oxide, magnesium oxide, lead titanate, and calcium silicate.

In some embodiments, the inorganic filler is any one of alumina, zinc oxide, titanium oxide, silica, molybdenum disulfide, lithium lanthanum zirconium tantalum oxygen, titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, lithium aluminate, sulfur germanium lithium phosphate, lanthanum lithium titanate, montmorillonite, copper oxide, magnesium oxide, lead titanate, and calcium silicate.

In addition to the above-listed inorganic fillers, other inorganic fillers commonly used in the art to achieve comparable technical results can also be used in the present invention.

According to some embodiments of the present invention, the inorganic filler is added in an amount of 5% to 40%, preferably 5% to 30%, more preferably 8% to 30%, and particularly preferably 10% to 20% of the total mass of the polymer solid electrolyte.

Specifically, the inorganic filler is added in a proportion of the total mass of the polymer solid electrolyte, and the proportion is as follows: 5%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, etc.

According to some embodiments provided herein, the organic solvent is at least one of acetonitrile, N-dimethylpyrrolidone (NMP), Dimethylacetamide (DMAC) and Dimethylformamide (DMF).

In some embodiments, the organic solvent is any one of acetonitrile, N-dimethylpyrrolidone (NMP), Dimethylacetamide (DMAC), and Dimethylformamide (DMF).

According to some embodiments of the present invention, the temperature of the stirring and mixing is 25 to 80 ℃, for example: 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ and the like; the stirring time is 3-24 h, for example: 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, and so on.

In some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 6-12 hours. In some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 12-24 hours; in some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 16-24 hours.

According to some embodiments of the present invention, the temperature of the vacuum drying is 25 to 60 ℃, for example: 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ and the like; the stirring time is 3-24 h, for example: 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, and so on.

In some embodiments, the temperature of the stirring and mixing is 30 to 50 ℃, and the stirring time is 10 to 24 hours. In some embodiments, the temperature of the stirring and mixing is 30-50 ℃, and the stirring time is 12-24 hours; in some embodiments, the temperature of the stirring and mixing is 30-50 ℃, and the stirring time is 16-24 hours.

According to some embodiments of the invention, the mold is a polytetrafluoroethylene mold.

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples were carried out under the conditions described in the specification, under the conventional conditions or under the conditions recommended by the manufacturer, unless otherwise specified. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.