CN116207343A

CN116207343A - Sulfide-polymer in-situ composite solid electrolyte and preparation method and application thereof

Info

Publication number: CN116207343A
Application number: CN202211696140.8A
Authority: CN
Inventors: 雷茹燕
Original assignee: Human Horizons Shandong Technology Co Ltd
Current assignee: Human Horizons Shandong Technology Co Ltd
Priority date: 2022-12-28
Filing date: 2022-12-28
Publication date: 2023-06-02

Abstract

The invention provides a sulfide-polymer in-situ composite solid electrolyte, a preparation method and application thereof. The preparation method of the electrolyte comprises the following steps: s1, preparing sulfide oligomer, and uniformly mixing sulfide solution and capping agent solution, and reacting to obtain sulfide oligomer solution; s2, preparing sulfide-polymer in-situ composite solid electrolyte, adding a polymer monomer, lithium salt, an initiator and a crosslinking agent into the sulfide oligomer solution obtained in the step S1, uniformly mixing, and performing polymerization reaction; the sulfide solution is obtained by dissolving a sulfide precursor into a solvent, wherein the solvent is EDA-EDT or EDA-ET, and EDA in the solvent accounts for 30-50 vol%. The electrolyte is prepared by a one-step in-situ synthesis method, and the polymer coats sulfide oligomer and lithium salt in situ in a crosslinking structure of a molecular chain of the electrolyte, so that an organic-inorganic phase interface is eliminated, and interface resistance is reduced.

Description

Sulfide-polymer in-situ composite solid electrolyte and preparation method and application thereof

Technical Field

The invention relates to the technical field of batteries, in particular to a sulfide-polymer in-situ composite solid electrolyte, a preparation method and application thereof.

Background

Solid-state batteries have a very promising development due to their high safety and energy density. The solid electrolyte in the solid battery has higher strength, can well inhibit the growth of lithium dendrites, and ensures that the prepared battery has good electrical performance.

Among the solid electrolytes, sulfide-polymer solid electrolytes are the most widely used solid electrolytes at present, but the preparation process of sulfide-polymer composite solid electrolyte thin films is generally that sulfide materials and polymer materials are mechanically blended and then prepared into films by adopting a dry method or a wet method, the composite form is physical contact between sulfide and polymer material substances, and a phase interface exists between inorganic materials and organic materials, so that the electrolyte film can generate larger interface impedance; the mixing effect of the mechanical blending technology of sulfide and polymer materials is poor, the aggregation of materials is easy to cause, the mechanical property of electrolyte membranes is poor, the interface compatibility with positive and negative electrodes is poor, the cycle performance of batteries is poor, and the service life is short.

The in-situ compounding of inorganic sulfide and polymer can better solve the problems, but the existing in-situ polyelectrolyte is prepared by a wet process, a solvent is required to be introduced, the production cost is increased, and the electrical performance of a battery prepared by using the electrolyte is still to be further improved.

Therefore, there is a need to develop a sulfide-polymer in-situ composite electrolyte material suitable for dry process preparation and a preparation process thereof.

Disclosure of Invention

The invention aims to provide an in-situ polymerization preparation method of sulfide-polymer in-situ composite solid electrolyte for further improving the electrical property of the solid electrolyte. The preparation process of the invention can realize the cross-linking of sulfide and organic polymer molecular level, and eliminate phase interface, thereby greatly improving the comprehensive properties of electrical property, mechanical property and the like of the battery prepared by the solid electrolyte.

It is another object of the present invention to provide a sulfide-polymer in-situ composite solid electrolyte prepared by the preparation method.

It is another object of the present invention to provide the use of the sulfide-polymer in situ composite solid state electrolyte in the preparation of a battery.

In order to achieve the above purpose, the invention adopts the following technical scheme:

a method for preparing sulfide-polymer in-situ composite solid electrolyte, which comprises the following steps:

s1, preparing sulfide oligomer

Uniformly mixing the sulfide solution and the capping agent solution, and reacting to obtain sulfide oligomer solution;

s2, preparing sulfide-polymer in-situ composite solid electrolyte

Adding a polymer monomer, lithium salt, an initiator and a cross-linking agent into the sulfide oligomer solution obtained in the step S1, uniformly mixing, and performing polymerization reaction to obtain the sulfide-polymer in-situ composite solid electrolyte;

the sulfide solution is obtained by dissolving a sulfide precursor into a solvent, wherein the solvent is a binary mixed solvent obtained by mixing any one of 1, 2-Ethanedithiol (EDT) or Ethanethiol (ET) with 1, 2-Ethylenediamine (EDA), and the volume percentage of 1, 2-Ethylenediamine (EDA) in the binary mixed solvent is 30-50%.

The sulfide-polymer in-situ composite solid electrolyte material is prepared by a one-step in-situ synthesis method. Firstly, dissolving sulfide precursors by using a universal solvent (EDA-EDT or EDA-ET), wherein the alkanol solvent system has strong solubility to sulfide, sulfate anions in the solvent dissociate the sulfide precursors through nucleophilic attack to form polyanion substances, and the polyanion substances have high reversible capacity and good cycle stability; secondly, the inventor of the invention also finds that if a blocking agent is added into a sulfide electrolyte solution obtained by dissolution, sulfide oligomer small molecules are further obtained by reaction under the action of hydrogen bonds, then polymer monomers are added for polymerization, sulfide oligomer small molecules and lithium salt can be uniformly locked in a crosslinking structure of polymer molecules under the synergistic action of the blocking agent and a universal solvent, and the sulfide oligomer small molecules and the polymer molecules form a composite whole, thereby avoiding the generation of organic-inorganic phase interfaces, improving the mechanical properties of materials and reducing interface resistance; and by controlling the proper proportion of the two solvents in the universal solvent, the obtained sulfide-polymer in-situ composite solid electrolyte material has higher sphericity and smaller particle size, so that the obtained battery has more excellent cycling stability after the electrolyte film is prepared by a dry process.

The one-step in-situ synthesis method provided by the invention not only can prepare the electrolyte material with excellent comprehensive performance, but also can avoid the high-temperature calcination post-treatment operation in the sulfide electrolyte preparation process, simplifies the preparation process, and is energy-saving and environment-friendly.

Preferably, the volume percentage of 1, 2-Ethylenediamine (EDA) in the binary mixed solvent is 35-40%. Through researches, the inventor of the present invention discovers that although EDA can significantly improve ionization of mercaptan in a mercaptan solvent (EDT or ET), thereby dissociating sulfide precursors into more ions, which is beneficial to improving ion conductivity of a battery; however, with the increase of the EDA duty ratio in the solvent, in the polymerization process of the polymer monomer, the amino group in the EDA in the reaction system can interact with the hydrogen bond in the sulfide oligomer, so that the sulfide oligomer is agglomerated, and the distribution in the polymer crosslinking structure is uneven, so that the density of the prepared sulfide-polymer in-situ composite solid electrolyte material is uneven, the sphericity is poor, and when the electrolyte film is prepared by adopting a dry process, the prepared electrolyte film is uneven, and the cycle performance of the obtained battery is reduced. Therefore, in the above-described range of the compounding ratio of the present invention, a battery excellent in cycle performance can be produced.

Preferably, the weight ratio of the polymer monomer to the sulfide precursor is (0.8-1.6): 1. The polymer monomer and the sulfide precursor are in a proper proportion range, so that the sulfide-polymer in-situ composite solid electrolyte material with excellent comprehensive performance can be obtained. Too much sulfide precursor is added to facilitate agglomeration in the polymer matrix; the addition amount is too small to inhibit the growth of lithium dendrites in the battery material. Therefore, in the proper addition amount range selected by the invention, the obtained electrolyte material and the battery have better electric property. The weight ratio of the polymer monomer to the sulfide precursor is further preferably (1.2 to 1.4): 1.

in the step S1, sulfide solution is also called as sulfide electrolyte precursor solution, and is prepared by a conventional liquid phase method, and is obtained by placing sulfide precursor in a universal solvent (alkanol solvent system, specifically EDA-EDT or EDA-ET) with excellent dissolution and dissociation properties, and stirring and dissolving at 10-80 ℃; then adding the end capping agent solution at the temperature of 10-80 ℃ and stirring for reaction to obtain sulfide oligomer.

Sulfide precursors conventional in the art, including but not limited to Li, may be used in the present invention ₂ S、P ₂ S ₅ LiX (X is halogen), na ₂ S、GeS ₂ Or SnS ₂ At least one of them.

The end capping agent solution is an ethanol solution of triethylamine, and the weight percentage of the triethylamine in the ethanol solution of the triethylamine is 5-95%.

S2, polymer reaction is obtained through ultraviolet polymerization or thermal polymerization; the ultraviolet polymerization is carried out by selecting light irradiation of 300-600 nm for 0.1-10 h; or the thermal polymerization is carried out for 0.1 to 10 hours under the condition of 10 to 80 ℃. Sulfide oligomers and lithium salts can be uniformly distributed in the crosslinked structure of the polymer by controlling appropriate reaction conditions (reaction temperature, time, etc.); if the polymerization reaction is too severe, the polymers are easy to be aggregated, and the sulfide oligomer is coated in the crosslinked molecular structure of the sulfide oligomer without a method; if the polymerization reaction is too slow, the sulfide oligomer tends to agglomerate and disperse unevenly. Under the proper polymerization conditions, the electrolyte material and the battery obtained are good in electrical property.

The polymer monomers of the present invention are common in the art and include, but are not limited to, at least one of PEO, PAN, PMMA, PVC, PVDF.

The lithium salt is a lithium salt commonly used in the art, including but not limited to at least one of lithium bistrifluoromethylsulfonimine, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalato borate, or lithium trifluoromethane sulfonate. The addition amount of the lithium salt is 0.1-50% of the total weight of the sulfide precursor and the polymer monomer.

The initiator is a peroxide initiator, an azo initiator or a photoinitiator. Corresponding initiator according to polymerization conditions: if ultraviolet polymerization is selected, a photoinitiator is needed to be selected; when thermal polymerization is selected, a conventional peroxide initiator or azo initiator is selected. Specifically, the peroxide initiator includes, but is not limited to, at least one of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide; the azo initiator comprises at least one of azodiisobutyronitrile or azodiisoheptonitrile; the photoinitiator includes, but is not limited to, at least one of 2-hydroxy-2-methyl-1-phenylpropion, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone.

The initiator is used in an amount of 0.1 to 5% by weight of the polymer monomer.

Conventional cross-linking agents may be used in the present invention including, but not limited to, polyisocyanates (e.g., JQ-1E, JQ-2E, JQ-3E, JQ-4, JQ-5, JQ-6, PAPI, emulsifiable MDI, tetraisocyanate), polyamines (e.g., propylene diamine, MOCA), polyols (e.g., polyethylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane).

The amount of the cross-linking agent is 0.1-5% of the weight of the polymer monomer.

The solid electrolyte is usually in the form of a film in the battery, so after the reaction in step s2 of the present invention is finished, the film can be further prepared: s2, after the polymerization reaction is finished, drying the obtained polymerization product at the temperature of 80-120 ℃ to obtain sulfide-polymer in-situ composite solid electrolyte powder, and preparing the sulfide-polymer in-situ composite solid electrolyte film by the sulfide-polymer in-situ composite solid electrolyte powder through a dry process.

Conventional dry processes may be used in the present invention, such as powder tabletting, vapor deposition, powder spraying, binder fibrillation, or hot extrusion of polymers.

The invention also protects the sulfide-polymer in-situ composite solid electrolyte prepared by the preparation method.

The sulfide-polymer in-situ composite solid electrolyte is a composite structure in which a polymer coats sulfide oligomer and lithium salt in situ in a crosslinking structure of a molecular chain of the polymer, and the in-situ coating structure eliminates an organic-inorganic phase interface and belongs to a molecular layer embedded composite structure; in the composite structure, polymer molecular chains are crosslinked into a network structure through crosslinking bonds, sulfide oligomers and lithium salts are uniformly embedded in the network structure of the polymer, the sulfide oligomers and the polymer molecular chains are adsorbed by Van der Waals force, and the sulfide oligomers are connected through hydrogen bonds. The in-situ composite structure can well eliminate organic-inorganic phase interfaces, and the obtained electrolyte material has high sphericity and uniform density, and can well meet the performance requirements of a dry process on raw materials. The obtained electrolyte film has excellent mechanical property and low interface resistance, and can be used for preparing a battery with excellent cycle performance.

The application of the sulfide-polymer in-situ composite solid electrolyte in preparing the battery is also within the protection scope of the invention.

Compared with the prior art, the invention has the beneficial effects that:

according to the invention, a one-step in-situ synthesis method is selected to prepare the sulfide-polymer in-situ composite solid electrolyte material, and the sulfide oligomer and the lithium salt are coated in the cross-linked structure of polymer molecules in situ in the polymerization process of polymer monomers, so that the traditional organic-inorganic phase interface can be well eliminated, the interface resistance of the electrolyte material is reduced, and meanwhile, the electrolyte material with high sphericity and uniform density is prepared by controlling the reaction conditions, the performance requirements of a dry process on raw materials can be well met, and the solid electrolyte film with excellent comprehensive mechanical and cyclic performance is prepared.

Drawings

Fig. 1 is a cycle performance chart of the battery prepared in example 1.

Detailed Description

For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples and the accompanying drawings, but the examples are not intended to limit the present invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The reagents and materials used in the present invention are commercially available unless otherwise specified.

Example 1

The embodiment provides a sulfide-polymer in-situ composite solid electrolyte, which is prepared by the following steps:

s1, preparing sulfide oligomer

S11, 1g of sulfide precursor Li ₂ S is dissolved into 10mL of universal solvent EDA-EDT (EDA accounts for 35vol% of EDA-EDT solvent), and stirred at 60 ℃ until the solvent is fully dissolved to obtain sulfide solution;

s22, dissolving 0.5g of triethylamine in 5mL of absolute ethyl alcohol to obtain a capping reagent solution;

s13, uniformly mixing the prepared end capping agent solution with sulfide, and stirring and reacting for 5 hours at 25 ℃ to obtain sulfide oligomer solution;

s2, preparing sulfide-polymer in-situ composite solid electrolyte

Adding 0.8g of polymer monomer PVDF, 0.05g of lithium hexafluorophosphate, initiator benzoyl peroxide (the dosage is 0.3% of the total weight of sulfide precursor and polymer monomer) and cross-linking agent polyethylene glycol (the dosage is 0.7% of the total weight of sulfide precursor and polymer monomer) into the sulfide oligomer solution obtained in the step S1, stirring and mixing uniformly, and then carrying out polymerization reaction for 4 hours at 60 ℃, obtaining a sulfide-polymer in-situ composite solid electrolyte crude product after the reaction is completed, filtering and washing the crude product, and drying the crude product to constant weight at 100 ℃ to obtain the sulfide-polymer in-situ composite solid electrolyte material.

Example 2

This example provides a sulfide-polymer in situ composite solid electrolyte prepared according to the preparation method of example 1, which differs from example 1 in that: in the universal solvent EDA-EDT, EDA accounts for 40vol% of the EDA-EDT solvent.

Example 3

This example provides a sulfide-polymer in situ composite solid electrolyte prepared according to the preparation method of example 1, which differs from example 1 in that: in the universal solvent EDA-EDT, EDA accounts for 50vol% of the EDA-EDT solvent.

Example 4

This example provides a sulfide-polymer in situ composite solid electrolyte prepared according to the preparation method of example 1, which differs from example 1 in that: the amount of the polymer monomer added was 1.2g.

Example 5

This example provides a sulfide-polymer in situ composite solid electrolyte prepared according to the preparation method of example 1, which differs from example 1 in that: the amount of the polymer monomer added was 1.4g.

Example 6

This example provides a sulfide-polymer in situ composite solid electrolyte prepared according to the preparation method of example 1, which differs from example 1 in that: the amount of the polymer monomer added was 1.6g.

Example 7

This example provides a sulfide-polymer in situ composite solid electrolyte prepared according to the preparation method of example 1, which differs from example 1 in that: the type of polymer monomer is replaced with PAN.

Example 8

This example provides a sulfide-polymer in situ composite solid electrolyte prepared according to the preparation method of example 1, which differs from example 1 in that: the lithium salt species is replaced with lithium bistrifluoromethylsulfonimide.

Example 9

This example provides a sulfide-polymer in situ composite solid electrolyte prepared according to the preparation method of example 1, which differs from example 1 in that: the sulfide precursor species being replaced by P ₂ S ₅ 。

Example 10

This example provides a sulfide-polymer in situ composite solid electrolyte prepared according to the preparation method of example 1, which differs from example 1 in that: and S2, the temperature of the polymerization reaction is replaced by 45 ℃.

Comparative example 1

This comparative example provides a sulfide-polymer solid electrolyte prepared according to the preparation method of example 1, which is different from example 1 in that: the universal solvent was replaced with acetonitrile.

Comparative example 2

This comparative example provides a sulfide-polymer solid electrolyte prepared according to the preparation method of example 1, which is different from example 1 in that: in the universal solvent EDA-EDT, EDA accounts for 25vol% of the EDA-EDT solvent.

Comparative example 3

This comparative example provides a sulfide-polymer solid electrolyte prepared according to the preparation method of example 1, which is different from example 1 in that: in the universal solvent EDA-EDT, EDA accounts for 60vol% of the EDA-EDT solvent.

Comparative example 4

This comparative example provides a sulfide-polymer solid electrolyte prepared according to the preparation method of example 1, which is different from example 1 in that: and S1, preparing sulfide oligomer solution further without adding a capping reagent solution, and S2, adding a polymer monomer, lithium salt, an initiator and a crosslinking agent into the sulfide solution obtained in the S1.

Comparative example 5

This comparative example provides a sulfide-polymer solid electrolyte prepared according to the preparation method of example 1, which is different from example 1 in that: in the step S1, after removing the solvent from the obtained sulfide solution, placing the sulfide solution in Ar atmosphere, performing high-temperature calcination treatment at 550 ℃ for 5 hours to obtain sulfide electrolyte powder, and then placing the obtained sulfide electrolyte powder in an ethanol solution of triethanolamine for reaction to obtain sulfide oligomer. That is, in this comparative example, the polymerization environment (solvent) of the polymer was different from that of example 1.

Performance testing

The solid electrolyte materials obtained in the above examples and comparative examples were prepared into thin films by a dry process, wherein the dry process comprises the following specific preparation steps: the temperature is 25 ℃, a roller press is adopted to roll the raw materials into an electrolyte film, and the electrolyte film is placed in a vacuum drying oven at 60 ℃ and dried for 24 hours.

And then preparing the prepared electrolyte film into a solid battery according to the following process: and preparing the soft-package single-chip battery by adopting a ternary NCM positive electrode, a solid electrolyte membrane and a graphite negative electrode lamination.

The cycle performance of the prepared solid battery is tested, wherein the specific test conditions of the cycle performance of the battery are as follows: charging at 25 ℃ for 0.5C CCCV to 4.3V, cutting off current for 0.02C, standing for 1h, discharging for 1C CC to 2.8V, standing for 1h, and testing the capacity retention rate after 190 circles by the step of circulation.

The specific test results are shown in FIG. 1 (cycle performance chart of example 1) and Table 1.

Table 1 cycle performance of batteries prepared from electrolytes of examples and comparative examples

As can be seen from the above examples and comparative examples, the sulfide-polymer in-situ composite solid electrolyte prepared by the one-step in-situ method of the present invention has excellent initial performance and cycle stability.

Comparison of examples 1-3, comparative example 2 and comparative example 3 shows that: as the EDA duty ratio in the universal solvent is increased, the sulfide precursor is dissociated into more ions, so that the initial discharge capacity of the obtained battery shows an increasing trend; however, agglomeration easily occurs during the polymerization reaction, and thus the cycle performance of the resulting battery tends to be lowered. Therefore, EDA in the above-described range of the present invention can produce a battery having good overall properties.

The results of examples 1 and 4 to 6 show that: with the increase of the addition amount of the sulfide precursor, the cycle stability of the obtained battery is firstly increased and then decreased, which shows that the battery can have good cycle stability only in a proper addition range.

The results of example 1, examples 7-9 demonstrate that conventional polymer monomers, lithium salts, sulfide precursors can be used in the present invention.

Other types of solvents were selected for the sulfide-polymer solid electrolyte in comparative example 1, and the cycle stability of the resulting battery was significantly deteriorated. Comparative examples 4 and 5 also did not select the electrolyte prepared by the method of the present invention, and the cycle stability of the resulting battery was significantly deteriorated.

Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for preparing sulfide-polymer in-situ composite solid electrolyte, which is characterized by comprising the following steps:

s1, preparing sulfide oligomer

s2, preparing sulfide-polymer in-situ composite solid electrolyte

the sulfide solution is obtained by dissolving a sulfide precursor into a solvent, wherein the solvent is a binary mixed solvent obtained by mixing 1, 2-ethanedithiol or any one of ethanethiol and 1, 2-ethylenediamine, and the volume percentage of the 1, 2-ethylenediamine in the binary mixed solvent is 30-50%.

2. The method for preparing sulfide-polymer in-situ composite solid electrolyte according to claim 1, wherein the volume percentage of 1, 2-ethylenediamine in the binary mixed solvent is 35-40%.

3. The method for preparing a sulfide-polymer in-situ composite solid electrolyte according to claim 1, wherein the weight ratio of the polymer monomer to the sulfide precursor is (0.8-1.6): 1.

4. the method for preparing a sulfide-polymer in-situ composite solid electrolyte according to claim 1, wherein the sulfide precursor is dissolved at a temperature of 10-80 ℃ in step s 1; the reaction temperature of the sulfide oligomer is 10-80 ℃.

5. The method for preparing a sulfide-polymer in-situ composite solid electrolyte according to claim 1, wherein the polymer reaction is obtained by ultraviolet polymerization or thermal polymerization; the ultraviolet polymerization is carried out by selecting light irradiation of 300-600 nm for 0.1-10 h; or the thermal polymerization is carried out for 0.1 to 10 hours under the condition of 10 to 80 ℃.

6. The method of preparing a sulfide-polymer in-situ composite solid state electrolyte according to claim 1, comprising at least one of the following features a to f:

a. the sulfide precursor is Li ₂ S、P ₂ S ₅ 、LiX、Na ₂ S、GeS ₂ Or SnS ₂ At least one of (a) and (b);

b. the end capping agent solution is an ethanol solution of triethylamine, wherein the weight percentage of the triethylamine in the ethanol solution of the triethylamine is 5-95%;

c. the polymer monomer is at least one of PEO, PAN, PMMA, PVC or PVDF;

d. the lithium salt is at least one of lithium bistrifluoromethyl sulfoimine, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluorooxalate borate or lithium trifluoromethane sulfonate;

e. the initiator is at least one of peroxide initiator, azo initiator or photoinitiator;

f. the cross-linking agent is at least one of polyisocyanate, polyamine or polyalcohol.

7. The method of preparing a sulfide-polymer in-situ composite solid state electrolyte according to claim 6, comprising at least one of the following features a to c:

a. the addition amount of the lithium salt is 0.1-50% of the total weight of the sulfide precursor and the polymer monomer;

b. the dosage of the initiator is 0.1-5% of the weight of the polymer monomer;

c. the amount of the cross-linking agent is 0.1-5% of the weight of the polymer monomer.

8. The method for preparing a sulfide-polymer in-situ composite solid electrolyte according to claim 1, further comprising the steps of:

s2, after the polymerization reaction is finished, drying the product at 80-120 ℃ to obtain sulfide-polymer in-situ composite solid electrolyte powder, and preparing the sulfide-polymer in-situ composite solid electrolyte film by the sulfide-polymer in-situ composite solid electrolyte powder through a dry process.

9. A sulfide-polymer in-situ composite solid electrolyte, characterized in that it is prepared by the preparation method of any one of claims 1 to 8.

10. Use of the sulfide-polymer in-situ composite solid state electrolyte of claim 9 in the preparation of a battery.