CN107863555B - Non-combustible solid polymer electrolyte and application thereof in solid secondary battery - Google Patents

Non-combustible solid polymer electrolyte and application thereof in solid secondary battery Download PDF

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CN107863555B
CN107863555B CN201711044195.XA CN201711044195A CN107863555B CN 107863555 B CN107863555 B CN 107863555B CN 201711044195 A CN201711044195 A CN 201711044195A CN 107863555 B CN107863555 B CN 107863555B
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刘继延
刘学清
刘志宏
曹元成
尤庆亮
周敏
邹立勇
高淑豫
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Roudian Wuhan Technology Co ltd
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Abstract

The invention discloses a non-combustible solid polymer electrolyte, which is characterized by comprising a polyphosphate polymer and a metal salt compound, wherein the metal salt compound accounts for 10-90% of the whole solid polymer electrolyte by mass percent. The solid polymer electrolyte has high phosphorus content, a methyl phosphine structure, excellent flame retardant property, complete non-combustion, excellent mechanical property, high ionic conductivity, wider electrochemical window and good electrode interface stability, is particularly suitable for high-safety high-energy-density energy storage batteries, and has very wide application prospect in the fields of military affairs, aerospace, electric automobiles, large-scale energy storage power stations and the like.

Description

Non-combustible solid polymer electrolyte and application thereof in solid secondary battery
Technical Field
The invention relates to a solid polymer electrolyte, in particular to a non-combustible solid polymer electrolyte and application thereof in a solid secondary battery.
Background
The electrolyte of the existing electrochemical energy storage battery, such as a lithium ion battery, mainly comprises a liquid organic carbonate solvent, a lithium salt and a polyolefin diaphragm. A large amount of organic electrolyte is easy to leak and volatilize, is easy to ignite and burn, even causes explosion accidents, and influences the safety performance of the battery. On the other hand, the thermal stability of the polyolefin separator is poor, and when the battery is heated or in extreme cases, the separator shrinks or melts to cause short circuit of the battery, so that fire and explosion accidents occur. The all-solid-state lithium battery using the solid electrolyte to replace the organic liquid electrolyte is expected to thoroughly solve the safety problem of the battery and meet the requirement of the development of the future high-capacity electrochemical energy storage technology. The solid electrolyte mainly comprises two main types according to the types of solid electrolyte regions: one kind is a polymer all-solid-state lithium battery composed of organic polymer electrolyte; the other type is an inorganic all-solid-state battery composed of an inorganic solid electrolyte.
The conventional polyethylene oxide (PEO)/lithium salt type electrolyte has been applied to an all solid-state lithium polymer battery, but there are still some problems to be solved from the practical viewpoint: the linear and grafted polymers have poor mechanical properties, and are not easy to prepare independently supported polymer films, while the conductivity of the network polymer is too low. Therefore, the electrolyte system is only suitable for working under the condition of high temperature or micro current, and is practically applied to the lithium battery which is difficult to work at normal temperature. The polycarbonate is a completely degradable environment-friendly polymer synthesized by taking gaseous carbon dioxide as a raw material. Because the biodegradable polyester film has photodegradation and biodegradability and excellent oxygen and water barrier performance, the biodegradable polyester film can be used as biodegradable engineering plastics, such as disposable medicine and food packaging materials, adhesives, composite materials and the like. Compared with polyethylene oxide, the polycarbonate material is low in price, has good compatibility with lithium salt, has a glass transition temperature of 10-39.5 ℃, belongs to an amorphous structure, and is easy to move in chain segments. The polycarbonate/lithium salt type electrolyte has higher ionic conductivity and high lithium ion mobility at room temperature.
However, polymer electrolytes such as polyethylene oxide and polycarbonate, which are commonly used in polymer solid electrolytes, are combustible in flames, so that it is not ensured that the solid battery manufactured by the polymer solid electrolytes is extremely unlikely to have combustion explosion accidents. Polyphosphazene solid electrolytes have been studied, but have not been widely used due to their complex synthesis and high cost.
Therefore, it is required to develop a solid polymer electrolyte having a good flame retardant effect, high conductivity and excellent mechanical properties.
Disclosure of Invention
The invention aims to solve the defects of the background technology and provide a solid polymer electrolyte with good flame retardant effect, high conductivity and excellent mechanical properties.
The technical scheme of the invention is as follows: the non-combustible solid polymer electrolyte is characterized by comprising a polyphosphonate polymer and a metal salt compound, wherein the mass percent of the metal salt compound is 10-90%, and the sum of the mass percent of the metal salt compound and the polyphosphonate polymer is 100%; the metal salt compound is a lithium salt compound or a sodium salt compound;
the polyphosphonate polymer is obtained by polymerizing methyl dichlorophosphine oxide and dihydric alcohol and/or trihydric alcohol and/or tetrahydric alcohol when the Cl/OH molar ratio in a system is 1: 1-1.2.
The polyphosphonate polymer structural units are:
Figure GDA0002180167300000021
preferably, wherein the polyphosphonate polymer is of the following I, II, III, IV or V structure:
Figure GDA0002180167300000031
wherein R is1And R2Is one of the following structures and R1≠R2：
Figure GDA0002180167300000032
Wherein m is 2-50, n is 2-50, and the molecular weight of the polyphosphonate polymer is 100-15000. In the formula III or IV, "-" represents a dendritic structure formed by trihydric alcohol and methyldichlorophosphine (all OH and Cl react), and also can be a dendritic structure formed by trihydric alcohol and/or dihydric alcohol and/or tetrahydric alcohol and methyldichlorophosphine (all OH and Cl react), and the structure cannot be expressed by a general formula, so the structure is represented by "-". In the formula V, "-" represents a dendritic structure formed by a tetrahydric alcohol and methyldichlorophosphine (all OH and Cl react), and also can be a dendritic structure formed by a trihydric alcohol and/or a dihydric alcohol and/or a tetrahydric alcohol and methyldichlorophosphine (all OH and Cl react), and the structure cannot be expressed by a general formula, so the structure is represented by "-".
Preferably, the polyphosphonate polymer is prepared by reacting methyl dichlorophosphine oxide with dihydric and/or trihydric and/or tetrahydric alcohols in N2Reacting for 5-8h at 50-80 ℃ under protection.
Preferably, the dihydric alcohol is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol, the trihydric alcohol is one or two of trimethylolpropane and glycerol, and the tetrahydric alcohol is pentaerythritol.
Preferably, the lithium salt compound is one or more of lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide and lithium bis (fluorosulfonyl) imide.
Preferably, the sodium salt compound is one or more of sodium bisoxalato, sodium difluorooxalato, sodium perchlorate, sodium hexafluorophosphate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium trifluoromethanesulfonate, sodium bistrifluoromethylsulfonyl imide and sodium bifluorosulfonimide. The sodium salt compound has a structure that sodium replaces lithium in the lithium salt compound, for example, the sodium bisoxalato borate has a structure that sodium replaces lithium in the lithium bisoxalato borate; the structure of the bis (trifluoromethyl) sulfonyl imide sodium is that sodium is used for replacing lithium in the bis (trifluoromethyl) sulfonyl imide lithium; bis (fluorosulfonyl) imide sodium salt (molecular formula NaN (FSO)2)2The structure is to replace lithium in LiFSI with sodium.
Preferably, the solid polymer electrolyte membrane has a thickness of 10 to 100 μm; the mechanical strength is 2-100MPa, and the room-temperature ionic conductivity is 1 x 10-5S/cm-5×10-3S/cm, electrochemical window greater than 3.5VLi+Per Li or 3.2VNa+/Na。
The invention also provides an application of the non-combustible solid polymer electrolyte in a solid secondary lithium battery or a solid secondary sodium battery.
Preferably, the solid-state secondary lithium battery includes a positive electrode, a negative electrode, and a non-combustible solid polymer electrolyte; the active material of the positive electrode is one of lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium manganate, lithium nickel manganese manganate, ternary manganese cobalt nickel material, sulfur compound, lithium iron sulfate, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium iron fluorophosphate and lithium manganese oxide; the active material of the negative electrode is one of metal lithium, metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene, antimony oxide, antimony-carbon composite material, tin-antimony composite material and lithium titanium oxide.
Preferably, the solid-state secondary sodium battery comprises a positive electrode, a negative electrode and a non-combustible solid polymer electrolyte; the active material of the positive electrode is one of sodium vanadium phosphate, sodium ferric sulfate, sodium ion fluorophosphate, sodium vanadium fluorophosphate, sodium iron fluorophosphate, sodium manganese oxide or sodium cobalt oxide; the active material of the negative electrode is one of metallic sodium, hard carbon, molybdenum disulfide, sodium titanium oxide, nickel cobalt oxide, antimony carbon composite material, tin antimony composite material, sodium terephthalate, lithium titanium oxide or sodium lithium titanium oxide.
The invention has the beneficial effects that:
the polyphosphonate polymer has a low glass transition temperature and a phosphorus-containing flame retardant group, a solid polymer electrolyte has high phosphorus content, and has a methyl phosphine structure, excellent flame retardant performance, complete non-combustion, excellent mechanical performance, high ionic conductivity, a wider electrochemical window and good electrode interface stability, and the polyphosphonate polymer is particularly suitable for high-safety high-energy-density energy storage batteries and has a very wide application prospect in the fields of military affairs, aerospace, electric automobiles, large-scale energy storage power stations and the like.
Drawings
FIG. 1 is a chart of the infrared spectrum of polyphosphonate prepared in example 1
FIG. 2 is a DSC of polyphosphonate prepared in example 1
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
First part preparation of polyphosphonate Polymer
Example 1
Polyethylene glycol methylphosphonate: into a 100mL three-necked flask equipped with a spherical condenser, 0.1mol (10.6g) of diethylene glycol was placed, and N was added at room temperature2Under the protection condition, 0.1mol (13.3g) of dichloromethylphosphine is taken by a syringe and slowly dripped into a three-necked bottle (about 0.5h), after the dripping is finished, the temperature is raised to 50 ℃ and is preserved for 1h, the temperature is preserved for 2h at 60 ℃, the temperature is preserved for 2h at 70 ℃ and is preserved for 1h at 80 ℃, and a light yellow solid is obtained after cooling.
The specific structural formula of the obtained polymer is as follows:
Figure GDA0002180167300000061
example 2
Triethylene glycol polymethylphosphonate: into a 100mL three-necked flask equipped with a spherical condenser, 0.1mol (15.0g) of triethylene glycol was placed, and N was added at room temperature2Under the protection condition, 0.1mol (13.3g) of dichloromethylphosphine is taken by a syringe and slowly dripped into a three-necked bottle (about 0.5h), after the dripping is finished, the temperature is raised to 50 ℃ and is preserved for 1h, the temperature is preserved for 2h at 60 ℃, the temperature is preserved for 2h at 70 ℃, and after the temperature is preserved for 1h at 80 ℃, the mixture is cooled to obtain a light yellow solid.
The obtained polymer has a specific structural formula
Figure GDA0002180167300000062
Example 3
Poly (trimethylolpropane methylphosphonate): into a 100mL three-necked flask equipped with a spherical condenser, 0.12mol (16.08g) of trimethylol was placedPropane and melting at 60 ℃ and N2Under the protection condition, 0.18mol (23.94g) of dichloromethylphosphine is sucked by a syringe and slowly dripped into a three-necked bottle (about 1h), the temperature is kept for 1h at 60 ℃ and 5h at 70 ℃ after the dripping is finished, and the light yellow solid is obtained after cooling.
The specific structural formula of the obtained polymer is as follows:
Figure GDA0002180167300000071
example 4
Polymethylphosphonic acid (pentaerythritol-diethylene glycol) ester: into a 100mL three-necked flask equipped with a spherical condenser, 0.025mol (3.4g) of pentaerythritol and 0.05mol (5.3g) of diethylene glycol were placed and melted at 60 ℃ with N2Under the protection condition, 0.10mol (13.3g) of dichloromethylphosphine is sucked by a syringe and slowly dripped into a three-necked bottle (about 1h), the temperature is kept for 1h at 60 ℃ and 5h at 70 ℃ after the dripping is finished, and the light yellow solid is obtained after cooling.
The specific structural formula of the obtained polymer is as follows:
Figure GDA0002180167300000072
example 5
Polymethylphosphonic acid (pentaerythritol-triethylene glycol) ester: into a 100mL three-necked flask equipped with a spherical condenser, 0.025mol (3.4g) of pentaerythritol and 0.05mol (7.5g) of triethylene glycol were placed and melted at 60 ℃ with N2Under the protection condition, 0.10mol (13.3g) of dichloromethylphosphine is sucked by a syringe and slowly dripped into a three-necked bottle (about 1h), the temperature is kept for 1h at 60 ℃ and 5h at 70 ℃ after the dripping is finished, and the light yellow solid is obtained after cooling.
The specific structural formula of the obtained polymer is as follows:
Figure GDA0002180167300000081
example 6
Polymethylphosphonic acid (trimethylolpropane-diethylene glycol)Ester: into a 100mL three-necked flask equipped with a spherical condenser, 0.04mol (5.36g) of trimethylolpropane and 0.04mol (4.24g) of diethylene glycol were placed and melted at 60 ℃ and N was added2Under the protection condition, 0.10mol (13.3g) of dichloromethylphosphine is sucked by a syringe and slowly dripped into a three-necked bottle (about 1h), the temperature is kept for 1h at 60 ℃ and 5h at 70 ℃ after the dripping is finished, and the light yellow solid is obtained after cooling.
The specific structural formula of the obtained polymer is as follows:
Figure GDA0002180167300000082
example 7
Polymethylphosphonic acid (diethylene glycol-triethylene glycol) ester: into a 100mL three-necked flask equipped with a spherical condenser were placed 0.07mol (5.3g) of diethylene glycol and 0.05mol (7.5g) of triethylene glycol, and the mixture was heated at room temperature under N2Under the protection condition, 0.1mol (13.3g) of dichloromethylphosphine is taken by a syringe and slowly dripped into a three-necked bottle (about 0.5h), after the dripping is finished, the temperature is raised to 60 ℃ and kept for 2h, the temperature is kept for 3h at 70 ℃, and a light yellow solid is obtained after cooling.
The specific structural formula of the obtained polymer is as follows:
Figure GDA0002180167300000091
example 8
Polymethylphosphonic acid pentaerythritol: in a 100mL three-necked flask equipped with a spherical condenser, 0.055mol (7.5g) of pentaerythritol was placed and melted at 60 ℃ and N was added2Under the protection condition, 0.10mol (13.3g) of dichloromethylphosphine is absorbed by a syringe and slowly dripped into a three-necked bottle (about 1h), the temperature is kept for 2h at 60 ℃ and 5h at 70 ℃ after the dripping is finished, and the light yellow solid is obtained after cooling.
The specific structural formula of the obtained polymer is as follows:
Figure GDA0002180167300000092
second part for preparing incombustible solid polymer electrolyte
Example 9
1g of trimethylolpropane polymethylphosphonate of example 3 and 20g of tetrahydrofuran were charged into a 100ml flask, followed by stirring at normal temperature for 6 hours to obtain a uniform polymer solution. And then under the protection of argon, adding 0.25g of lithium bis (fluorosulfonyl) imide into the uniform solution, and stirring at normal temperature for 6 hours to obtain a uniformly mixed solution. And uniformly pouring the solution into a film to obtain the all-solid-state electrolyte.
Example 10
1g of polymethylphosphonic acid (trimethylolpropane-diethylene glycol) ester of example 6 and 20g of tetrahydrofuran were charged in a 100ml flask, and then stirred at room temperature for 6 hours to obtain a uniform polymer solution. Then, 0.28g of lithium bis (fluorooxalato) borate (LiDFOB) was added to the above homogeneous solution under an argon shield, and stirred at room temperature for 6 hours to obtain a uniformly mixed solution. And uniformly pouring the solution into a film to obtain the all-solid-state electrolyte.
Example 11
1g of polymethylphosphonic acid (trimethylolpropane-diethylene glycol) ester of example 6 and 20g of N, N-dimethylformamide were charged into a 100ml flask, followed by stirring at room temperature for 6 hours to obtain a uniform polymer solution. Then, 0.28g of lithium difluorooxalato borate and 0.3g of lithium hexafluoroarsenate were added to the above homogeneous solution under the protection of argon gas, and stirred at room temperature for 6 hours to obtain a uniformly mixed solution. And uniformly pouring the solution into a film to obtain the all-solid-state electrolyte.
Example 12
0.1g of polymethylphosphonic acid diethylene glycol ester of example 1 and 20g of N, N-dimethylformamide were charged into a 100ml flask, followed by stirring at room temperature for 6 hours to obtain a uniform polymer solution. Then, under the protection of argon, 0.45g of sodium trifluoromethanesulfonate and 0.45g of sodium tetrafluoroborate are added into the uniform solution and stirred for 6 hours at normal temperature to obtain a uniform mixed solution. And uniformly pouring the solution into a film to obtain the all-solid-state electrolyte.
Example 13
0.9g of triethylene glycol polymethylphosphonate in example 2 and 20g of N, N-dimethylformamide were charged into a 100ml flask, and then stirred at room temperature for 6 hours to obtain a uniform polymer solution. Then, 0.1g of sodium hexafluoroarsenate was added to the above homogeneous solution under the protection of argon, and stirred at room temperature for 6 hours to obtain a homogeneous mixed solution. And uniformly pouring the solution into a film to obtain the all-solid-state electrolyte.
The all-solid-state electrolytes obtained in examples 9 to 13 were combined with a positive electrode and a negative electrode to form a non-combustible solid-state battery, and a solid-state secondary lithium battery included a positive electrode, a negative electrode, and a polyphosphonate polymer electrolyte interposed between the positive electrode and the negative electrode; the active material of the positive electrode is one of lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium manganate, lithium nickel manganese cobalt nickel ternary material, sulfur compound, lithium iron sulfate, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium iron fluorophosphate and lithium manganese oxide; the active material of the negative electrode is one of metal lithium, metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene, antimony oxide, antimony-carbon composite material, tin-antimony composite material and lithium titanium oxide.
The solid-state secondary sodium battery comprises a positive electrode, a negative electrode and a polyphosphonate polymer electrolyte arranged between the positive electrode and the negative electrode; the active material of the positive electrode is one of sodium vanadium phosphate, sodium ferric sulfate, sodium ion fluorophosphate, sodium vanadium fluorophosphate, sodium iron fluorophosphate, sodium manganese oxide or sodium cobalt oxide; the active material of the negative electrode is one of metallic sodium, hard carbon, molybdenum disulfide, sodium titanium oxide, nickel cobalt oxide, antimony carbon composite material, tin antimony composite material, sodium terephthalate, lithium titanium oxide or sodium lithium titanium oxide.
Third part of the performance test of the prepared all-solid-state electrolyte
The ir spectrum of the polyphosphonate prepared in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the hydroxyl groups substantially participate in the reaction to form the desired polyphosphonate polymer.
The DSC test chart of the polyphosphonate prepared in example 1 is shown in FIG. 2. from FIG. 2, it can be seen that the glass transition temperature is-58 deg.C, and the low glass transition temperature is advantageous for lithium ion transport.
The flame retardant properties of the polyphosphonates prepared in examples 1-8 are shown in Table 1.
And (3) characterizing electrolyte performance:
film thickness: the thickness of the all-solid electrolyte was measured using a micrometer (precision 0.01 mm), 5 points on the sample were arbitrarily sampled, and the average value was taken.
Ionic conductivity: the electrolyte was sandwiched between two pieces of stainless steel and placed in a 2032 type cell housing. The conductivity of sodium ions is measured by electrochemical ac impedance spectroscopy, using the formula: sigma-L/ARbWherein L is the thickness of the electrolyte, A is the room temperature area of the stainless steel sheet, and RbThe impedance is measured.
Electrochemical window: the electrolyte was sandwiched by a stainless steel sheet and a sodium sheet and placed in a 2032 type cell case. The electrochemical window is measured by linear voltammetry scanning with an electrochemical workstation, the initial potential is 2.5V, the maximum potential is 5.5V, and the scanning speed is 1 mV/s. (see Table 2).
The results obtained are shown in Table 2. As can be seen from the results in Table 2, the organic-inorganic composite all-solid-state electrolyte provided by the invention has higher mechanical strength than 1 MPa; the range of ionic conductivity at room temperature was 1X 10-5S/cm-5×10-3S/cm, can charge and discharge with large multiplying power; the electrochemical window is greater than 3.5V.
TABLE 1 flame retardancy test results for polyphosphonates prepared in examples 1-8
Figure GDA0002180167300000121
Table 2 examples 9-13 test results
Figure GDA0002180167300000122

Claims (8)

1. The non-combustible solid polymer electrolyte is characterized by comprising a polyphosphonate polymer and a metal salt compound, wherein the mass percent of the metal salt compound is 10-90%, and the sum of the mass percent of the metal salt compound and the polyphosphonate polymer is 100%; the metal salt compound is a lithium salt compound or a sodium salt compound;
the polyphosphonate polymer is obtained by polymerizing methyl dichlorophosphine oxide and trihydric alcohol or tetrahydric alcohol when the molar ratio of Cl to OH in a system is 1: 1-1.2; the polyphosphonate polymer is prepared by reacting methyl dichlorophosphine oxide and trihydric alcohol or tetrahydric alcohol in N2Reacting for 5-8h at 50-80 ℃ under protection to obtain the product;
wherein the polyphosphonate polymer is of the following structure III, IV or V:
Figure 661862DEST_PATH_IMAGE001
Figure 251106DEST_PATH_IMAGE002
wherein n =2-50 and polyphosphonate polymer molecular weight = 100-.
2. The noncombustible solid polymer electrolyte according to claim 1, wherein the triol is one of trimethylolpropane and glycerol, and the tetraol is pentaerythritol.
3. The non-combustible solid polymer electrolyte according to claim 1, wherein the lithium salt compound is one or more of lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium perchlorate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonyl) imide.
4. The noncombustible solid polymer electrolyte according to claim 1, wherein the sodium salt compound is one or more selected from the group consisting of sodium bisoxalato, sodium difluorooxalato, sodium perchlorate, sodium hexafluorophosphate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium trifluoromethanesulfonate, sodium bistrifluoromethylsulfonimide and sodium bifluorosulfonimide.
5. The noncombustible solid polymer electrolyte according to claim 1, wherein the solid polymer electrolyte membrane has a thickness of 10 to 100 μm; the mechanical strength is 2-100MPa, and the room-temperature ionic conductivity is 1 x 10-5S/cm-5×10-3S/cm, electrochemical window greater than 3.5VLi+Per Li or 3.2VNa+/Na。
6. Use of the incombustible solid polymer electrolyte according to claim 1 in a solid secondary lithium battery or a solid secondary sodium battery.
7. The use of the non-combustible solid polymer electrolyte according to claim 6 in a solid lithium secondary battery or a solid sodium secondary battery, wherein the solid lithium secondary battery comprises a positive electrode, a negative electrode, a non-combustible solid polymer electrolyte; the active material of the positive electrode is one of lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium manganate, lithium nickel manganese manganate, ternary manganese cobalt nickel material, sulfur compound, lithium iron sulfate, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium iron fluorophosphate and lithium manganese oxide; the active material of the negative electrode is one of metal lithium, metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene, antimony oxide, antimony-carbon composite material, tin-antimony composite material and lithium titanium oxide.
8. The use of the non-combustible solid polymer electrolyte according to claim 6 in a solid lithium secondary battery or a solid sodium secondary battery, wherein the solid sodium secondary battery comprises a positive electrode, a negative electrode, a non-combustible solid polymer electrolyte; the active material of the positive electrode is one of sodium vanadium phosphate, sodium ferric sulfate, sodium ion fluorophosphate, sodium vanadium fluorophosphate, sodium iron fluorophosphate, sodium manganese oxide or sodium cobalt oxide; the active material of the negative electrode is one of metallic sodium, hard carbon, molybdenum disulfide, sodium titanium oxide, nickel cobalt oxide, antimony carbon composite material, tin antimony composite material, sodium terephthalate, lithium titanium oxide or sodium lithium titanium oxide.
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