CN112072172A - Polymer solid electrolyte, preparation method and application - Google Patents
Polymer solid electrolyte, preparation method and application Download PDFInfo
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- CN112072172A CN112072172A CN202010888211.9A CN202010888211A CN112072172A CN 112072172 A CN112072172 A CN 112072172A CN 202010888211 A CN202010888211 A CN 202010888211A CN 112072172 A CN112072172 A CN 112072172A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a polymer solid electrolyte, which comprises inorganic filler and polyethylene oxide loaded with the inorganic filler, wherein the polyethylene oxide loaded with the inorganic filler is uniformly dispersed in polyvinylidene fluoride-hexafluoropropylene; the inorganic filler is Li10GeP2S12、Li1.5Al0.5Ge1.5(PO4)3、Li1.3Al0.3Ti1.7(PO4)3、Li7La3Zr2O12、Li0.33La0.557TiO3One or more of the above; the invention also discloses a preparation method of the polymer solid electrolyte and a solid battery using the polymer solid electrolyte; the ionic conductivity of the invention is obviously improved, and the interface contact with the anode and the cathode is improved; the internal resistance of the solid-state battery is reduced, and the cycle performance is obviously improved.
Description
Technical Field
The invention relates to the technical field of chemical power supplies, in particular to a polyelectrolyte, a preparation method and application.
Background
All-solid-state batteries have received much attention due to their advantages of high safety and high energy density. Among them, solid-state batteries represented by sulfides, polymers, and oxides have been developed. The polymer electrolyte applied to the all-solid-state battery has the advantages of good flexibility, high safety, difficult leakage, stability to lithium metal and the like, can effectively inhibit the growth of lithium dendrites while ensuring the safety performance of the battery, and improves the cycle life of the battery. However, the low room temperature ionic conductivity and the interfacial contact problem of the electrolyte and the electrode hinder their further development.
Disclosure of Invention
A first object of the present invention is to provide a polymer solid electrolyte which is remarkably improved in ionic conductivity and improved in interface contact with a positive electrode and a negative electrode.
In order to solve the technical problem, the technical scheme of the invention is as follows: a polymer solid electrolyte comprises inorganic filler and polyethylene oxide loaded with the inorganic filler, wherein the polyethylene oxide loaded with the inorganic filler is uniformly dispersed in polyvinylidene fluoride-hexafluoropropylene;
the inorganic filler is Li10GeP2S12、Li1.5Al0.5Ge1.5(PO4)3、Li1.3Al0.3Ti1.7(PO4)3、Li7La3Zr2O12、Li0.33La0.557TiO3One or more of them.
Preferably the polyethylene oxide has a weight average molecular weight of between 500 and 900 million;
the weight average molecular weight of the polyvinylidene fluoride-hexafluoropropylene is about 40 ten thousand.
The affinity of the polyethylene oxide and the inorganic filler is relatively good, and the affinity of the polyvinylidene fluoride-hexafluoropropylene and the lithium bifluorosulfonylimide-tetraethylene glycol dimethyl ether solution is very good.
Preferably, the mass ratio of polyethylene oxide to inorganic filler is between 3:7 and 8: 2. The room temperature lithium ion conductivity of the polyethylene oxide is very low, but the polyethylene oxide has good flexibility and high tensile strength, and the inorganic filler selected by the invention has high room temperature lithium ion conductivity, but the inorganic filler can not be independently used as a battery isolating membrane. The inorganic filler with higher room temperature lithium ion conductivity is compounded with polyethylene oxide, so that the overall flexibility of the final solid electrolyte product and the higher room temperature lithium ion conductivity can be ensured.
The higher the ethylene oxide ratio is, the better the flexibility of the final polymer solid electrolyte is, but the room-temperature ionic conductivity is reduced; the higher the proportion of the inorganic filler is, the higher the conductivity of the final polymer solid electrolyte lithium ion at room temperature can be, but the flexibility is reduced, the tensile strength is reduced, and the product processing is not facilitated.
Preferably, the mass ratio of polyvinylidene fluoride-hexafluoropropylene to polyethylene oxide/inorganic filler is between 35:65 and 80: 20. The polyvinylidene fluoride-hexafluoropropylene of the invention has good affinity with lithium bifluorosulfonyl imide-tetraethylene glycol dimethyl ether ionic liquid; the larger the proportion is, the better the affinity with the ionic liquid is, the better the performance of the assembled solid-state battery is, and when the proportion reaches a certain degree, the conductivity of the lithium ion at room temperature of the solid electrolyte is reduced, thus having negative effects on the battery.
The second purpose of the invention is to provide a preparation method of the polymer solid electrolyte, and the invention has simple and convenient process and prepares the polymer solid electrolyte with a skeleton structure.
In order to solve the technical problem, the technical scheme of the invention is as follows: a preparation method of a polymer solid electrolyte comprises the following steps:
dissolving polyethylene oxide in dimethylformamide, and stirring to obtain a uniform solution;
adding inorganic filler particles into the solution, and stirring to obtain a polyethylene oxide/inorganic filler mixed solution;
step three, adding polyvinylidene fluoride-hexafluoropropylene into a polyethylene oxide/inorganic filler mixed solution, and dissolving the polyvinylidene fluoride-hexafluoropropylene to obtain a polyvinylidene fluoride-hexafluoropropylene/polyethylene oxide/inorganic filler suspension;
and step four, spreading the suspension liquid prepared in the step three on a mould with a certain depth, and drying to obtain the solid electrolyte film.
A third object of the present invention is to provide a solid-state battery in which the internal resistance of the battery is significantly reduced and the cycle performance is significantly improved.
In order to solve the technical problem, the technical scheme of the invention is as follows: a solid-state battery comprises the prepared polymer solid electrolyte film, and the solid electrolyte film is used for assembling the battery and testing after being soaked in lithium bis (fluorosulfonyl) imide-tetraethylene glycol dimethyl ether.
Preferably, the molar ratio of the lithium bis (fluorosulfonyl) imide salt to the tetraethylene glycol dimethyl ether to the polyvinylidene fluoride to the hexafluoropropylene is equal.
Preferably, the surface of the positive electrode material of the solid-state battery is coated with Li3InCl6(ii) a By coating Li on the surface of the anode material3InCl6The composite material has high ionic conductivity while inhibiting interface reaction, improves the stability of the anode material and improves the cycle performance of the battery.
Further preferably, Li3InCl6The mass accounts for 3 to 30 percent of the mass of the cathode material. The larger the coating amount of the invention is, the more sufficient the coating of the positive electrode material is, and the structure of the positive electrode material is prevented from being damaged. However, the coating capacity significantly affects the specific capacity of the active material, and the larger the coating capacity is, the lower the specific capacity of the active material is.
Preferably, the anode material is one of lithium iron phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide and a lithium-rich material.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the polymer solid electrolyte of the invention, the organic framework formed by polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and polyethylene oxide (PEO) has good mechanical propertyThe electrolyte can contact with an interface, and the ionic conductivity of the mixed electrolyte is improved by adding the inorganic filler, so that the performance of the solid-state battery is improved; the tensile strength of the polymer solid electrolyte film can reach 16.1MPa, and the ionic conductivity can reach 2.1 x 10-3S/cm；
2. The prepared polymer solid electrolyte is soaked in ionic liquid lithium bis (fluorosulfonyl) imide-tetraethylene glycol dimethyl ether (LiFSI-TEGDME) by utilizing the interaction of PVDF-HFP and the ionic liquid, so that the ionic conductivity of the polymer solid electrolyte is improved, the interface contact of the polymer solid electrolyte is increased, and the internal resistance and the cycle performance of a solid battery are obviously improved;
3. the preparation method is simple and suitable for industrial production.
Thereby achieving the above object of the present invention.
Drawings
Fig. 1 is a graph showing cycle performance of solid-state batteries manufactured in examples 1 to 5 of the present invention and a comparative example.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
The embodiment discloses a preparation method of a polymer solid electrolyte, which comprises the following steps:
firstly, dissolving PEO in Dimethylformamide (DMF), and stirring to obtain a stable solution;
step two, adding inorganic filler Li10GeP2S12Adding into the solution, stirring for 6h to obtain PEO/Li10GeP2S12Mixing the solution;
control of PEO and Li10GeP2S12The mass ratio of (A) to (B) is 4: 6;
step three, adding PVDF-HFP into the PEO/Li10GeP2S12Stirring the mixed solution for 24 hours at the temperature of 60 ℃ to obtain PVDF-HFP/PEO/Li10GeP2S12The suspension of (a);
control of PVDF-HFP and PEO/Li10GeP2S12The mass ratio of (A) to (B) is 70: 30;
step four, spreading the suspension on a mould with a certain depth, and drying at 60 ℃ to obtain PVDF-HFP/PEO/Li10GeP2S12A film.
InCl with the stoichiometric ratio of 1:33And LiCl in deionized water to form transparent Li3InCl6·nH2And (4) O solution. Subsequently, a positive electrode material lithium cobaltate was added to the transparent solution. Evaporating the aqueous solution at 100 deg.C, transferring the obtained dry powder to a vacuum furnace, and heating at 200 deg.C for 5 hr to remove crystal water to obtain Li3InCl6A wrapped positive electrode composite. Controlling Li in terms of mass fraction3InCl6The coating amount of (2) was 5%.
Soaking the prepared polymer solid electrolyte film in ionic liquid LiFSI-TEGDME for 4h to serve as an electrolyte of a solid lithium battery; wherein, the molar ratio of the lithium salt of the bis-fluorosulfonyl imide-the tetraethylene glycol dimethyl ether to the polyvinylidene fluoride-the hexafluoropropylene is equal;
coating Li on positive electrode3InCl6The lithium cobaltate is used as an active material, the aluminum foil is used as a current collector, the carbon black is used as a conductive agent, and the PVDF is used as a binder; the negative electrode is metallic lithium, and a solid lithium battery is assembled.
The performance of the polymer solid electrolyte prepared in this example and the performance of the solid-state battery were tested, and the specific data are shown in table 1 and fig. 1.
Example 2
The embodiment discloses a preparation method of a polymer solid electrolyte, which comprises the following steps:
step one, dissolving PEO in Dimethylformamide (DMF), and stirring to obtain a stable solution.
Step two, adding inorganic filler Li1.3Al0.3Ti1.7(PO4)3Adding into the solution, stirring for 6h to obtain PEO/Li1.3Al0.3Ti1.7(PO4)3Mixing the solution;
control of PEO and Li1.3Al0.3Ti1.7(PO4)3In a mass ratio of 5:5
Step three, adding PVDF-HFP into the PEO/Li1.3Al0.3Ti1.7(PO4)3Stirring the mixed solution for 24 hours at the temperature of 60 ℃ to obtain PVDF-HFP/PEO/Li1.3Al0.3Ti1.7(PO4)3The suspension of (a);
control of PVDF-HFP and PEO/Li1.3Al0.3Ti1.7(PO4)3The mass ratio of (A) to (B) is 80: 20;
step four, spreading the suspension on a mould with a certain depth, and drying at 60 ℃ to obtain PVDF-HFP/PEO/Li1.3Al0.3Ti1.7(PO4)3A film.
InCl with the stoichiometric ratio of 1:33And LiCl in deionized water to form transparent Li3InCl6·nH2And (4) O solution. Subsequently, a positive electrode material LiNi0.5Co0.2Mn0.3O2Added to the clear solution. Evaporating the aqueous solution at 100 deg.C, transferring the obtained dry powder to a vacuum furnace, and heating at 200 deg.C for 5 hr to remove crystal water to obtain Li3InCl6A wrapped positive electrode composite. Controlling Li in terms of mass fraction3InCl6The coating amount of (3%).
Soaking the prepared polymer solid electrolyte film in ionic liquid LiFSI-TEGDME for 4h to serve as an electrolyte of a solid lithium battery; wherein, the molar ratio of the lithium salt of the bis-fluorosulfonyl imide-the tetraethylene glycol dimethyl ether to the polyvinylidene fluoride-the hexafluoropropylene is equal;
coating Li on positive electrode3InCl6LiNi of (2)0.5Co0.2Mn0.3O2The composite material is an active material, the aluminum foil is a current collector, the carbon black is a conductive agent, and the PVDF is a binder; the negative electrode is metallic lithium, and a solid lithium battery is assembled.
The performance of the polymer solid electrolyte prepared in this example and the performance of the solid-state battery were tested, and the specific data are shown in table 1 and fig. 1.
Example 3
The embodiment discloses a preparation method of a polymer solid electrolyte, which comprises the following steps:
step one, dissolving PEO in Dimethylformamide (DMF), and stirring to obtain a stable solution.
Step two, adding inorganic filler Li1.3Al0.3Ti1.7(PO4)3Adding into the solution, stirring for 6h to obtain PEO/Li1.3Al0.3Ti1.7(PO4)3Mixing the solution; control of PEO and Li1.3Al0.3Ti1.7(PO4)3The mass ratio of (A) to (B) is 4: 6;
step three, adding PVDF-HFP into the PEO/Li1.3Al0.3Ti1.7(PO4)3Stirring the mixed solution for 24 hours at the temperature of 60 ℃ to obtain PVDF-HFP/PEO/Li1.3Al0.3Ti1.7(PO4)3The suspension of (a);
control of PVDF-HFP and PEO/Li1.3Al0.3Ti1.7(PO4)3The mass ratio of (A) to (B) is 65: 35;
step four, spreading the suspension on a mould with a certain depth, and drying at 60 ℃ to obtain PVDF-HFP/PEO/Li1.3Al0.3Ti1.7(PO4)3A film.
InCl with the stoichiometric ratio of 1:33And LiCl in deionized water to form transparent Li3InCl6·nH2And (4) O solution. Subsequently, a positive electrode material LiNi0.5Co0.2Mn0.3O2Added to the clear solution. Evaporating the aqueous solution at 100 deg.C, transferring the obtained dry powder to a vacuum furnace, and heating at 200 deg.C for 5 hr to remove crystal water to obtain Li3InCl6A wrapped positive electrode composite. Controlling Li in terms of mass fraction3InCl6The coating amount of (3%).
Soaking the prepared polymer solid electrolyte film in ionic liquid LiFSI-TEGDME for 4h to serve as an electrolyte of a solid lithium battery; wherein, the molar ratio of the lithium salt of the bis-fluorosulfonyl imide-the tetraethylene glycol dimethyl ether to the polyvinylidene fluoride-the hexafluoropropylene is equal;
coating Li on positive electrode3InCl6LiNi of (2)0.5Co0.2Mn0.3O2The composite material is an active material, the aluminum foil is a current collector, the carbon black is a conductive agent, and the PVDF is a binder; the negative electrode is metallic lithium, and a solid lithium battery is assembled.
The performance of the polymer solid electrolyte prepared in this example and the performance of the solid-state battery were tested, and the specific data are shown in table 1 and fig. 1.
The polymer solid electrolyte prepared in this example was tested for its performance and for its performance in a solid-state battery, and the detailed data are shown in table 1 and fig. 1.
Example 4
The embodiment discloses a preparation method of a polymer solid electrolyte, which comprises the following steps:
step one, dissolving PEO in Dimethylformamide (DMF), and stirring to obtain a stable solution.
Step two, adding inorganic filler Li1.3Al0.3Ti1.7(PO4)3Adding into the solution, stirring for 6h to obtain PEO/Li1.3Al0.3Ti1.7(PO4)3Mixing the solution;
control of PEO and Li1.3Al0.3Ti1.7(PO4)3The mass ratio of (A) to (B) is 4: 6.
Step three, adding PVDF-HFP into the PEO/Li1.3Al0.3Ti1.7(PO4)3Stirring the mixed solution for 24 hours at the temperature of 60 ℃ to obtain PVDF-HFP/PEO/Li1.3Al0.3Ti1.7(PO4)3The suspension of (a);
control of PVDF-HFP and PEO/Li1.3Al0.3Ti1.7(PO4)3In a mass ratio of 80: 20.
Step four, spreading the suspension on a mould with a certain depth, and drying at 60 ℃ to obtain PVDF-HFP/PEO/Li1.3Al0.3Ti1.7(PO4)3A film.
To stoichiometric ratioInCl of 1:33And LiCl in deionized water to form transparent Li3InCl6·nH2And (4) O solution. Subsequently, a positive electrode material LiNi0.5Co0.2Mn0.3O2Added to the clear solution. Evaporating the aqueous solution at 100 deg.C, transferring the obtained dry powder to a vacuum furnace, and heating at 200 deg.C for 5 hr to remove crystal water to obtain Li3InCl6A wrapped positive electrode composite. Controlling Li in terms of mass fraction3InCl6The coating amount of (3%).
The prepared polymer solid electrolyte film is used as an electrolyte of a solid lithium battery and is not soaked by an ionic liquid. Coating Li on positive electrode3InCl6LiNi of (2)0.5Co0.2Mn0.3O2The composite material is an active material, the aluminum foil is a current collector, the carbon black is a conductive agent, and the PVDF is a binder; the negative electrode is metallic lithium, and a solid lithium battery is assembled. The polymer solid electrolyte prepared in this example was tested for its performance and for its performance in a solid-state battery, and the detailed data are shown in table 1 and fig. 1.
Example 5
The embodiment discloses a preparation method of a polymer solid electrolyte, which comprises the following steps:
step one, dissolving PEO in Dimethylformamide (DMF), and stirring to obtain a stable solution.
Step two, adding inorganic filler Li1.3Al0.3Ti1.7(PO4)3Adding into the solution, stirring for 6h to obtain PEO/Li1.3Al0.3Ti1.7(PO4)3Mixing the solution;
control of PEO and Li1.3Al0.3Ti1.7(PO4)3The mass ratio of (A) to (B) is 4: 6.
Step three, adding PVDF-HFP into the PEO/Li1.3Al0.3Ti1.7(PO4)3Stirring the mixed solution for 24 hours at the temperature of 60 ℃ to obtain PVDF-HFP/PEO/Li1.3Al0.3Ti1.7(PO4)3The suspension of (a);
control of PVDF-HFP and PEO/Li1.3Al0.3Ti1.7(PO4)3In a mass ratio of 65: 35.
Step four, spreading the suspension on a mould with a certain depth, and drying at 60 ℃ to obtain PVDF-HFP/PEO/Li1.3Al0.3Ti1.7(PO4)3A film.
Soaking the prepared polymer solid electrolyte film in ionic liquid LiFSI-TEGDME for 4h to serve as an electrolyte of a solid lithium battery; wherein, the molar ratio of the lithium salt of the bis-fluorosulfonyl imide-the tetraethylene glycol dimethyl ether to the polyvinylidene fluoride-the hexafluoropropylene is equal;
LiNi as the positive electrode0.5Co0.2Mn0.3O2Is an active material, the anode material is not coated, the aluminum foil is a current collector, the carbon black is a conductive agent, and the PVDF is a binder; the negative electrode is metallic lithium, and a solid lithium battery is assembled. The polymer solid electrolyte prepared in this example was tested for its performance and for its performance in a solid-state battery, and the detailed data are shown in table 1 and fig. 1.
Comparative example
PEO was dissolved in Dimethylformamide (DMF) and stirred to give a stable solution without the addition of inorganic fillers.
PVDF-HFP was added to the above PEO solution and stirred at 60 ℃ for 24 hours to obtain a PVDF-HFP/PEO solution. The mass ratio of PVDF-HFP to PEO is controlled to be 70: 30. And flatly spreading the suspension on a mould with a certain depth, and drying at 60 ℃ to obtain the PVDF-HFP/PEO film.
InCl with the stoichiometric ratio of 1:33And LiCl in deionized water to form transparent Li3InCl6·nH2And (4) O solution. Subsequently, a positive electrode material LiNi0.5Co0.2Mn0.3O2Added to the clear solution. Evaporating the aqueous solution at 100 deg.C, transferring the obtained dry powder to a vacuum furnace, and heating at 200 deg.C for 5 hr to remove crystal water to obtain Li3InCl6A wrapped positive electrode composite. Controlling Li in terms of mass fraction3InCl6The coating amount of (3%).
The prepared polymer solid electrolyte film is arranged onSoaking the ionic liquid LiFSI-TEGDME for 4 hours to serve as an electrolyte of the solid lithium battery; coating Li on positive electrode3InCl6LiNi of (2)0.5Co0.2Mn0.3O2The composite material is an active material, the aluminum foil is a current collector, the carbon black is a conductive agent, and the PVDF is a binder; the negative electrode is metallic lithium, and a solid lithium battery is assembled.
TABLE 1 tabulation of data of performance test of polymer solid electrolyte and solid-state battery obtained in examples 1 to 5 and comparative example
| Item | Tensile strength | Ionic conductivity | Internal resistance of battery | Number of cycles |
| Comparative example 1 | 16.8MPa | 7.3*10-4S/cm | 25.3mΩ | 542 times |
| Example 1 | 15.1MPa | 1.2*10-3S/cm | 14.3mΩ | 735 times |
| Example 2 | 15.7MPa | 1.6*10-3S/cm | 16.7mΩ | 942 times |
| Example 3 | 16.1MPa | 2.1*10-3S/cm | 11.3mΩ | 1329 times |
| Example 4 | 15.3MPa | 1.7*10-4S/cm | 48.3mΩ | 157 times (n) |
| Example 5 | 15.3MPa | 2.1*10-3S/cm | 32.3mΩ | 635 times |
As can be seen from the data of the polymer solid electrolytes and the solid batteries prepared in examples 1 to 5 and comparative example, the polymer solid electrolyte provided by the invention has significantly improved ionic conductivity, internal resistance and cycle performance after absorbing ionic liquid. The comparative example compared with example 3 shows that the addition of the inorganic filler affects the tensile strength of the polymer solid electrolyte, but the effect is small. By comparing example 3 with example 4, the interaction between the polymer electrolyte and the ionic liquid of the present invention can significantly improve the ionic conductivity, the internal resistance of the battery, and the cycle performance. By comparing example 5 with example 3, the positive electrode is coated with Li3InCl6Can improve the anode materialThe material stability, the interface reaction inhibition and the battery cycle performance improvement.
Claims (10)
1. A polymer solid electrolyte characterized by:
comprises inorganic filler and polyethylene oxide loaded with the inorganic filler, wherein the polyethylene oxide loaded with the inorganic filler is uniformly dispersed in polyvinylidene fluoride-hexafluoropropylene;
the inorganic filler is Li10GeP2S12、Li1.5Al0.5Ge1.5(PO4)3、Li1.3Al0.3Ti1.7(PO4)3、Li7La3Zr2O12、Li0.33La0.557TiO3One or more of them.
2. A polymer solid electrolyte as defined in claim 1 wherein:
the polyethylene oxide has a weight average molecular weight of between 500 and 900 ten thousand;
the weight average molecular weight of the polyvinylidene fluoride-hexafluoropropylene is about 40 ten thousand.
3. A polymer solid electrolyte as defined in claim 1 wherein: the mass ratio of polyethylene oxide to inorganic filler is between 3:7 and 8: 2.
4. A polymer solid electrolyte as defined in claim 1 wherein: the mass ratio of polyvinylidene fluoride-hexafluoropropylene to polyethylene oxide/inorganic filler is between 35:65 and 80: 20.
5. A method for producing a polymer solid electrolyte as defined in any one of claims 1 to 4, wherein:
the method comprises the following steps:
dissolving polyethylene oxide in dimethylformamide, and stirring to obtain a uniform solution;
adding inorganic filler particles into the solution, and stirring to obtain a polyethylene oxide/inorganic filler mixed solution;
step three, adding polyvinylidene fluoride-hexafluoropropylene into a polyethylene oxide/inorganic filler mixed solution, and dissolving the polyvinylidene fluoride-hexafluoropropylene to obtain a polyvinylidene fluoride-hexafluoropropylene/polyethylene oxide/inorganic filler suspension;
and step four, spreading the suspension liquid prepared in the step three on a mould with a certain depth, and drying to obtain the solid electrolyte film.
6. A solid-state battery characterized by: comprising the polymer solid electrolyte film prepared according to claim 5, which is used for assembling a battery and testing after being soaked in lithium bis (fluorosulfonyl) imide-tetraglyme.
7. The solid-state battery according to claim 6, wherein: the molar ratio of the lithium salt of the bis-fluorosulfonyl imide to the tetraethylene glycol dimethyl ether to the polyvinylidene fluoride to the hexafluoropropylene is equal.
8. The solid-state battery according to claim 6, wherein: the surface of the anode material of the solid-state battery is coated with Li3InCl6。
9. The solid-state battery according to claim 6, wherein: li3InCl6The mass accounts for 3 to 30 percent of the mass of the cathode material.
10. The solid-state battery according to claim 6, wherein: the anode material is one of lithium iron phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium manganese oxide and a lithium-rich material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112563567A (en) * | 2020-12-17 | 2021-03-26 | 上海电气集团股份有限公司 | Composite solid electrolyte material, method for producing same, method for producing composite solid electrolyte membrane, and solid battery |
| CN113036214A (en) * | 2021-03-29 | 2021-06-25 | 欣旺达电动汽车电池有限公司 | Inorganic filler powder, solid electrolyte, preparation method of solid electrolyte and battery |
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| CN112563567A (en) * | 2020-12-17 | 2021-03-26 | 上海电气集团股份有限公司 | Composite solid electrolyte material, method for producing same, method for producing composite solid electrolyte membrane, and solid battery |
| CN112563567B (en) * | 2020-12-17 | 2022-05-13 | 上海电气集团股份有限公司 | Composite solid electrolyte material, method for producing same, method for producing composite solid electrolyte membrane, and solid battery |
| CN113036214A (en) * | 2021-03-29 | 2021-06-25 | 欣旺达电动汽车电池有限公司 | Inorganic filler powder, solid electrolyte, preparation method of solid electrolyte and battery |
| CN113036214B (en) * | 2021-03-29 | 2023-10-31 | 欣旺达电动汽车电池有限公司 | Inorganic filler powder, solid electrolyte, preparation method of solid electrolyte and battery |
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Application publication date: 20201211 |