CN111900460A - Solid electrolyte with self-supporting structure, preparation method and application - Google Patents
Solid electrolyte with self-supporting structure, preparation method and application Download PDFInfo
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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
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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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 solid electrolyte with a self-supporting structure, which comprises a framework material and active ceramic powder, wherein the active ceramic powder is bonded to the framework material through a binder; uniformly covering the surface of the framework material loaded with the active ceramic powder with uniformly mixed succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide; the invention also discloses a preparation method and application of the solid electrolyte; the invention not only has good mechanical property and interface contact, but also has high ionic conductivity and wide electrochemical window; the cycle performance of the all-solid-state lithium ion battery prepared by the method is obviously improved.
Description
Technical Field
The invention relates to the technical field of chemical power sources, in particular to a solid electrolyte with a self-supporting structure, a preparation method and application.
Background
All-solid-state electrolytes, including ceramic electrolytes and polymer electrolytes, have received much attention because of their high safety and suitability for high energy density lithium metal batteries.
For the polymer electrolyte, although the polymer electrolyte has good mechanical flexibility, is closely contacted with an electrode and is easy to prepare into a film, the polymer electrolyte has low ionic conductivity at normal temperature, poor electrochemical stability and poor flame retardance, and the practical application of the polymer electrolyte is severely limited.
The ceramic electrolyte has great application potential in high-safety metal lithium batteries due to the difficult combustion, high ionic conductivity, wide electrochemical window and good chemical stability of lithium ions. However, the interface contact between the ceramic solid electrolyte and the electrode is poor, and the ceramic solid electrolyte is usually thick and brittle, so that the ceramic solid electrolyte cannot meet the requirement of being molded into a thin flexible film in practical application.
Disclosure of Invention
The invention aims to provide a solid electrolyte with a self-supporting structure, which not only has good mechanical properties and interface contact, but also has high ionic conductivity and a wide electrochemical window.
In order to solve the technical problem, the technical scheme of the invention is as follows: a solid electrolyte with a self-supporting structure comprises a framework material and active ceramic powder bonded to the framework material through a binder;
the uniformly mixed succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide are uniformly covered on the surface of the framework material loaded with the active ceramic powder.
Preferably, the framework material is a nylon net, and the mesh number of the nylon net is 50-200 meshes. The nylon net has good mechanical property, a plurality of meshes and high framework strength, the composite electrolyte obtained finally has better mechanical property and is more beneficial to processing, but the active components of the conductive agent are reduced, so that the conductivity is not favorably improved; the mesh number is small, which is not beneficial to the load of the solid electrolyte and the framework, and the mechanical property is poor. The mesh number of the preferred nylon net in the invention is beneficial to effectively loading succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide, and the conductivity of the electrolyte is ensured, and meanwhile, the structural strength and the flexibility are ensured.
Preferably, the active ceramic powder is
Li7La3Zr2O12Or
Li7-xLa3Zr2-xMxO12M ═ Ta, Mo; x is more than 0.25 and less than 2; or
Li3yLa2/3-yTiO3Wherein y is more than 0 and less than 2/3.
The conductivity of the active ceramic powder in the invention directly influences the conductivity of the final solid electrolyte.
Preferably, the molar ratio of succinonitrile to lithium bis (trifluoromethylsulfonyl) imide is 90:10 to 97: 3. In the invention, the lithium bis (trifluoromethyl) sulfonyl imide is dissolved after the succinonitrile is melted, so that the use of an organic solvent is avoided, the use of the organic solvent is reduced while the conductivity of the electrolyte is ensured, and the method is beneficial to environment, production and processing. The larger the proportion of lithium bistrifluoromethylsulfonyl imide is, the higher the conductivity of the final solid electrolyte is; succinonitrile is used as the organic filler, and the larger the proportion thereof, the better the flexibility of the solid electrolyte.
Preferably, the active ceramic powder accounts for 90 to 99 parts and the binder accounts for 1 to 10 parts by weight based on 100 parts by weight. The invention effectively improves the firm bonding degree of the active ceramic powder and the framework material by controlling the proportion of the active ceramic powder and the binder.
The second purpose of the invention is to provide a preparation method of a solid electrolyte with a self-supporting structure, which can prepare a solid electrolyte with good mechanical property and interface contact, high ionic conductivity and wide electrochemical window without using organic dissolution.
In order to solve the technical problem, the technical scheme of the invention is as follows: a method of making a solid state electrolyte having a self-supporting structure, comprising the steps of:
step one, preparing an active ceramic powder-binder flexible body;
mixing the active ceramic powder and the binder according to the proportion, and performing ball milling for 20-120 min to obtain an active ceramic powder-binder flexible body;
secondly, placing a framework material in the middle of the active ceramic powder-binder flexible body, and pressing the framework material into a whole to obtain an active ceramic powder-binder-nylon net self-supporting framework;
step three, preparing a mixed solution of succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide;
mixing succinonitrile with lithium bis (trifluoromethyl) sulfonyl imide under argon atmosphere, and heating to melt to obtain a mixed solution of succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide;
and step four, immersing the active ceramic powder-binder-nylon net self-supporting framework into the mixed solution of the excessive succinonitrile and the lithium bis (trifluoromethyl) sulfonyl imide, standing, and filtering the mixed solution of the excessive succinonitrile and the lithium bis (trifluoromethyl) sulfonyl imide to obtain the target solid electrolyte.
Preferably, the pressure used for pressing the active ceramic powder-binder-nylon mesh self-supporting framework in the second step is 8-15 Mpa. The support framework formed by pressing has good structural strength, and is beneficial to improving the cycle performance of the battery.
Preferably, the active ceramic powder is prepared by a solid-phase method; weighing 1.1 times of LiOH in the active ceramic powder according to the stoichiometric ratio. According to the invention, the loss of lithium in the synthesis process is compensated by adding 10% more LiOH.
Preferably, the tensile strength of the solid electrolyte is 9.3MPa to 10.5MPa, and the solid electrolyte prepared by the method has good tensile strength.
A third object of the present invention is to provide a solid electrolyte with a self-supporting structure for use in a solid-state battery, which has a high energy density and a significantly improved cycle performance.
In order to solve the technical problem, the technical scheme of the invention is as follows: the solid electrolyte with the self-supporting structure is applied to an all-solid-state battery, and the negative electrode of the all-solid-state battery is a lithium sheet.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the invention adopts the active ceramic powder-binder-nylon net self-supporting framework, the binder can ensure firm and good contact between the active ceramic powder and the nylon net, not only maintains the high ionic conductivity of the active ceramic powder, but also has the flexibility of the nylon net, and is convenient for processing and forming;
2. according to the invention, succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide are melted into liquid to be used as an organic filler of the solid electrolyte, so that the use of an organic solvent is avoided, and the ionic conductivity of the solid electrolyte is ensured;
3. the tensile strength of the solid electrolyte in the invention can reach 10.5 MPa; the transference number of the ions is as high as 0.55, and the room-temperature ionic conductivity is 5.3 multiplied by 10-4S·cm-1；
4. The preparation process method is simple, avoids the use of organic solvent, and has little harm to the environment in the preparation process;
5. the framework structure prepared by pressing in the preparation method has good controllability and good integrity, and the prepared product has uniform quality;
6. the all-solid-state battery has high energy density and obviously improved cycle performance.
Thereby achieving the above object of the present invention.
Drawings
FIG. 1 is a cycle curve of solid-state batteries manufactured in examples 1 to 3 of the present invention and 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 solid electrolyte with a self-supporting structure, a preparation method and application thereof, wherein the preparation method of the solid electrolyte comprises the following steps:
step one, preparing an active ceramic powder-binder flexible body;
according to the active ceramic powder Li7La3Zr2O12Weighing raw materials LiOH and La (OH) according to the stoichiometric ratio3、ZrO2And 10% more LiOH is added to compensate for lithium loss in the synthesis process.
The raw materials were ball milled for 12h and then heated at 950 ℃ for 14 h.
After cooling, the ball milling is carried out for 12 h.
Obtaining active ceramic powder Li7La3Zr2O12。
Mixing the active ceramic powder and the binder PVDF according to a mass ratio of 95:5, and performing ball milling for 60min to obtain an active ceramic powder-binder flexible body;
placing the 80-mesh nylon net in the middle of the active ceramic powder-binder flexible body, and pressing the active ceramic powder-binder-nylon net into a whole by using the pressure of 12Mpa to obtain an active ceramic powder-binder-nylon net self-supporting framework;
step three, preparing a mixed solution of succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide;
mixing succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide according to a molar ratio of 94:6 in an argon atmosphere, and heating to more than 80 ℃ to melt to obtain SN-LiTFST (succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide) mixed solution;
immersing the active ceramic powder-binder-nylon net self-supporting framework into the excessive SN-LiTFST mixed solution, standing for 48 hours, and filtering the excessive SN-LiTFST to obtain a solid electrolyte;
the obtained solid electrolyte is subjected to performance test, and specific test data are shown in table 1;
the obtained solid electrolyte is used as an electrolyte, and the positive electrode is LiNi0.5Co0.2Mn0.3O2The 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. And testing the discharge specific capacity, the internal resistance and the cycle number of the assembled solid lithium battery, wherein the cycle test is finished when the capacity is attenuated to 80 percent of the initial capacity. The test cell performance is detailed in table 2 and fig. 1.
Example 2
The embodiment discloses a solid electrolyte with a self-supporting structure, a preparation method and application thereof, wherein the preparation method of the solid electrolyte comprises the following steps:
step one, preparing an active ceramic powder-binder flexible body;
according to the active ceramic powder Li6.75La3Zr1.75Ta0.25O12Weighing raw materials LiOH and La (OH) according to the stoichiometric ratio3、ZrO2、Ta2O5And 10% more LiOH is added to compensate for lithium loss in the synthesis process.
The raw materials were ball milled for 12h and then heated at 900 ℃ for 12 h.
After cooling, the ball milling is carried out for 12 h.
Obtaining active ceramic powder Li6.75La3Zr1.75Ta0.25O12。
Mixing the active ceramic powder and the adhesive PTFE according to the mass ratio of 94:6, and performing ball milling for 40min to obtain an active ceramic powder-adhesive flexible body.
And secondly, placing a 100-mesh nylon net in the middle of the active ceramic powder-binder flexible body, and pressing the active ceramic powder-binder-nylon net into a whole by using the pressure of 12Mpa to obtain the active ceramic powder-binder-nylon net self-supporting framework.
Step three, preparing a mixed solution of succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide;
mixing succinonitrile with lithium bis (trifluoromethyl) sulfonyl imide according to a molar ratio of 95:5 in an argon atmosphere, and heating to 80 ℃ or above for melting to obtain an SN-LiTFST mixed solution.
And step four, immersing the active ceramic powder-binder-nylon net self-supporting framework into the excessive SN-LiTFST mixed solution, standing for 48 hours, and filtering the excessive SN-LiTFST to obtain the solid electrolyte.
The obtained solid electrolyte is subjected to performance test, and specific test data are shown in table 1;
the obtained solid electrolyte is used as an electrolyte, and the positive electrode is LiNi0.5Mn0.3Co0.2O2The 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 assembled solid lithium battery is subjected to discharge specific capacity, internal resistance and cycle number tests, wherein the cycle tests show that the capacity is attenuated to 80 percent of the initial capacityAnd (4) bundling. The test cell performance is detailed in table 2 and fig. 1.
Example 3
The embodiment discloses a solid electrolyte with a self-supporting structure, a preparation method and application thereof, wherein the preparation method of the solid electrolyte comprises the following steps:
step one, preparing an active ceramic powder-binder flexible body;
according to the active ceramic powder Li0.35La0.55TiO3Weighing raw materials LiOH and La (OH) according to the stoichiometric ratio3、TiO2And 10% more LiOH is added to compensate for lithium loss in the synthesis process.
The raw materials were ball milled for 12h and then heated at 1050 ℃ for 14 h.
After cooling, the ball milling is carried out for 12 h.
Obtaining active ceramic powder Li0.35La0.55TiO3。
And mixing the active ceramic powder and the binder PVDF according to the mass ratio of 97:3, and performing ball milling for 40min to obtain the active ceramic powder-binder flexible body.
And secondly, placing a 100-mesh nylon net in the middle of the active ceramic powder-binder flexible body, and pressing the active ceramic powder-binder-nylon net into a whole by using the pressure of 12Mpa to obtain the active ceramic powder-binder-nylon net self-supporting framework.
And step three, mixing succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide according to a molar ratio of 95:5 in an argon atmosphere, and heating to the temperature of more than 80 ℃ to melt the mixture to obtain the SN-LiTFST mixed solution.
And step four, immersing the active ceramic powder-binder-nylon net self-supporting framework into the excessive SN-LiTFST mixed solution, standing for 48 hours, and filtering the excessive SN-LiTFST to obtain the solid electrolyte.
The obtained solid electrolyte is subjected to performance test, and specific test data are shown in table 1;
the obtained solid electrolyte is used as an electrolyte, and the positive electrode is LiNi0.5Mn0.3Co0.2O2The 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 goldBelongs to lithium and assembles a solid lithium battery. And testing the discharge specific capacity, the internal resistance and the cycle number of the assembled solid lithium battery, wherein the cycle test is finished when the capacity is attenuated to 80 percent of the initial capacity. The test cell performance is detailed in table 2 and fig. 1.
Comparative example
According to the active ceramic powder Li7La3Zr2O12Weighing raw materials LiOH and La (OH) according to the stoichiometric ratio3、ZrO2And 10% more LiOH is added to compensate for lithium loss in the synthesis process. The raw materials were ball milled for 12h and then heated at 950 ℃ for 14 h. After cooling, the ball milling is carried out for 12 h. Obtaining active ceramic powder Li7La3Zr2O12. And mixing the active ceramic powder and PVDF according to the mass ratio of 97:3, and performing ball milling for 40min to obtain an active ceramic powder-binder flexible body.
The obtained solid electrolyte is subjected to performance test, and specific test data are shown in table 1;
the obtained solid electrolyte is used as an electrolyte, and the positive electrode is LiNi0.5Co0.2Mn0.3O2The 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. And testing the discharge specific capacity, the internal resistance and the cycle number of the assembled solid lithium battery, wherein the cycle test is finished when the capacity is attenuated to 80 percent of the initial capacity. The test cell performance is detailed in fig. 1 and table 2.
TABLE 1 tabulation of data of performance test of examples 1 to 3 and comparative examples to obtain solid electrolyte
| Item | Tensile strength | Electrochemical window | Transference number of ion | Ionic conductivity at room temperature |
| Example 1 | 10.5MPa | 4.8V | 0.53 | 1.7×10-4S·cm-1 |
| Example 2 | 11.2MPa | 4.9V | 0.55 | 5.3×10-4S·cm-1 |
| Example 3 | 9.3MPa | 5.0V | 0.54 | 3.2×10-4S·cm-1 |
| Comparative example | 2.5MPa | 4.8V | 0.51 | 6.3×10-5S·cm-1 |
Table 2 examples 1 to 3 and comparative examples a table of performance test data of solid state batteries was prepared
| Item | Specific discharge capacity | Internal resistance of m omega | Number of cycles |
| Example 1 | 154mAh/g | 12.5mΩ | 530 |
| Example 2 | 156mAh/g | 11.3mΩ | 760 |
| Example 3 | 155mAh/g | 14.5mΩ | 673 |
| Comparative example | 150mAh/g | 32.1mΩ | 237 |
In combination with the solid electrolytes prepared in examples 1 to 3 and comparative example and the all-solid-state battery prepared therefrom, the present invention provides a composite solid electrolyte having not only good mechanical properties and interfacial contact of polymer electrolytes, but also high ionic conductivity and wide electrochemical window of ceramic electrolytes. The tensile strength of the examples is much higher than that of the comparative examples, showing excellent mechanical properties of the composite solid electrolyte; the room-temperature ionic conductivity of the embodiment is obviously higher than that of the comparative example, which shows that the composite solid electrolyte has excellent room-temperature ionic conductivity performance; the internal resistance of the examples is significantly lower than that of the comparative examples, and the good contact effect and high ionic conductivity of the composite solid electrolyte are shown; the cycle performance of the examples is significantly better than that of the comparative examples, indicating the good combination property of the composite solid electrolyte.
Claims (10)
1. A solid state electrolyte having a self-supporting structure, characterized by: comprises a framework material and active ceramic powder which is bonded to the framework material through a bonding agent;
the uniformly mixed succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide are uniformly covered on the surface of the framework material loaded with the active ceramic powder.
2. A solid state electrolyte having a self-supporting structure as claimed in claim 1, wherein: the framework material is a nylon net, and the mesh number of the nylon net is 50-200 meshes.
3. A solid state electrolyte having a self-supporting structure as claimed in claim 1, wherein: the active ceramic powder is
Li7La3Zr2O12Or
Li7-xLa3Zr2-xMxO12M ═ Ta, Mo; x is more than 0.25 and less than 2; or
Li3yLa2/3-yTiO3Wherein y is more than 0 and less than 2/3.
4. A solid state electrolyte having a self-supporting structure as claimed in claim 1, wherein: the mixing molar ratio of the succinonitrile to the lithium bis (trifluoromethyl) sulfonyl imide is 90:10 to 97: 3.
5. A solid state electrolyte having a self-supporting structure as claimed in claim 1, wherein: calculated by 100 parts by mass, 90 to 99 parts of active ceramic powder and 1 to 10 parts of binder.
6. A method for producing a solid electrolyte having a self-supporting structure according to any one of claims 1 to 5, wherein:
the method comprises the following steps:
step one, preparing an active ceramic powder-binder flexible body;
mixing the active ceramic powder and the binder according to the proportion, and performing ball milling for 20-120 min to obtain an active ceramic powder-binder flexible body;
secondly, placing a framework material in the middle of the active ceramic powder-binder flexible body, and pressing the framework material into a whole to obtain an active ceramic powder-binder-nylon net self-supporting framework;
step three, preparing a mixed solution of succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide;
mixing succinonitrile with lithium bis (trifluoromethyl) sulfonyl imide under argon atmosphere, and heating to melt to obtain a mixed solution of succinonitrile and lithium bis (trifluoromethyl) sulfonyl imide;
and step four, immersing the active ceramic powder-binder-nylon net self-supporting framework into the mixed solution of the excessive succinonitrile and the lithium bis (trifluoromethyl) sulfonyl imide, standing, and filtering the mixed solution of the excessive succinonitrile and the lithium bis (trifluoromethyl) sulfonyl imide to obtain the target solid electrolyte.
7. A method of preparing a solid electrolyte having a self-supporting structure as claimed in claim 6, wherein: and in the second step, the pressure for pressing the active ceramic powder-binder-nylon net self-supporting framework is 8-15 Mpa.
8. A method of preparing a solid electrolyte having a self-supporting structure as claimed in claim 6, wherein: the active ceramic powder is prepared by a solid phase method; weighing 1.1 times of LiOH in the active ceramic powder according to the stoichiometric ratio.
9. A method of preparing a solid electrolyte having a self-supporting structure as claimed in claim 6, wherein: the tensile strength of the solid electrolyte is 9.3MPa to 10.5 MPa.
10. Applying the solid-state electrolyte having a self-supporting structure according to any one of claims 1 to 5 to an all-solid-state battery, characterized in that: the cathode of the all-solid-state battery is a lithium sheet.
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