CN112531204A - Plastic crystal-ceramic composite solid electrolyte and low-temperature hot-pressing preparation method thereof - Google Patents
Plastic crystal-ceramic composite solid electrolyte and low-temperature hot-pressing preparation method thereof Download PDFInfo
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- CN112531204A CN112531204A CN202011272201.9A CN202011272201A CN112531204A CN 112531204 A CN112531204 A CN 112531204A CN 202011272201 A CN202011272201 A CN 202011272201A CN 112531204 A CN112531204 A CN 112531204A
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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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a plastic crystal-ceramic composite solid electrolyte and a low-temperature hot-pressing preparation method thereof, wherein the method comprises the following steps: step 1, weighing oxide ceramic powder and plastic crystal solid electrolyte, and uniformly mixing to obtain mixed powder; the plastic crystal solid electrolyte comprises: plastic crystals and lithium salts; step 2, placing the mixed powder in a mould and paving; step 3, pressing and molding the mixed powder, and simultaneously, carrying out heat treatment on the mixed powder, wherein the heating temperature is lower than 600 ℃, so that the plastic crystal solid electrolyte absorbs heat and is melted; and then reducing the temperature to solidify and form the plastic crystal solid electrolyte to obtain the plastic crystal-ceramic composite solid electrolyte. The invention can realize the densification of the solid electrolyte at lower temperature, has higher ionic conductivity, and greatly reduces the processing time, energy loss and the volatilization of lithium element at high temperature.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to a plastic crystal-ceramic composite solid electrolyte and a low-temperature hot-pressing preparation method thereof.
Background
As an energy storage device, development of a high energy density battery has received much attention. Due to the flammability and the narrow electrochemical stability window, the improvement of the energy density of the battery using the organic liquid as the electrolyte is limited, and the safety risks of combustion and explosion exist. Therefore, development of a solid electrolyte that is nonflammable and has high electrochemical stability, instead of an organic electrolyte, and development of an all-solid battery have been desired. From the view point of electrochemical stability window and ionic conductivity, the oxide solid electrolyte has a development prospect in the application of all-solid batteries.
The oxide solid electrolyte is generally required to be sintered at high temperature (more than or equal to 900 ℃) to carry out densification so as to reduce the resistance of grain boundaries, which not only consumes energy, but also causes volatilization and decomposition of lithium element, thus causing the ionic conductivity of the solid electrolyte to be reduced. Although the sintering of the buried powder can inhibit the volatilization of lithium element and maintain the original chemical composition of the solid electrolyte as much as possible, a large amount of solid electrolyte powder is consumed, which is not beneficial to reducing the production cost. In addition, the high-temperature sintering treatment also causes element interdiffusion and even side reaction between the solid electrolyte cathode materials, increases the interface impedance, and is not favorable for the performance of the solid-state battery.
The cold pressing sintering method canAt low temperatures (<The ceramic powder is densified to a certain extent at 200 ℃, but the subsequent annealing treatment at higher temperature (600-650 ℃) is required, and the ionic conductivity is not high enough and is lower than 10 DEG-4S/cm, and auxiliary agents such as water or organic solvents which influence the performance of the battery are also needed in the low-temperature sintering process.
Disclosure of Invention
The invention aims to improve the preparation method of the oxide solid electrolyte and provides a low-temperature hot-pressing preparation method of the composite ceramic solid electrolyte without high-temperature annealing treatment.
In order to achieve the purpose, the invention provides a low-temperature hot-pressing preparation method of a plastic crystal-ceramic composite solid electrolyte, which comprises the following steps:
step 1, weighing oxide ceramic powder and plastic crystal solid electrolyte, and uniformly mixing to obtain mixed powder; the plastic crystal solid electrolyte comprises: plastic crystals and lithium salts;
Wherein, optionally, the heating temperature in the step 3 is 40-350 ℃; and the heat preservation is carried out in the heating process, and the heat preservation time is 0.1h-12 h.
Wherein, the heating temperature of the step 3 is preferably 100 ℃ to 160 ℃.
Wherein, the pressure of the compression molding in the step 3 is preferably 300MPa-1200 MPa.
Optionally, the oxide ceramic powder accounts for 60-94% of the mixed powder by mass, and the plastic-crystal solid electrolyte accounts for 6-40% of the mixed powder by mass.
Wherein, optionally, the oxide ceramic powder is one or more than two of garnet type, perovskite type or NASICON type solid electrolytes.
Optionally, the lithium salt accounts for less than 30 mol% of the plastic-crystal solid electrolyte.
Wherein, optionally, the plastic crystal is molecular plastic crystal succinonitrile.
Wherein, optionally, the lithium salt comprises LiClO4、LiTFSI、LiBOB、LiPF6And one or more than two of LiFSI.
The invention also provides a plastic crystal-ceramic composite solid electrolyte, which is prepared by the low-temperature hot-pressing preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention avoids the decomposition reaction of the solid electrolyte at high temperature in the low-temperature hot-pressing process, and the prepared composite ceramic solid electrolyte not only has higher mechanical strength, but also has higher ionic conductivity.
(2) Compared with the traditional high-temperature sintering method, the low-temperature hot pressing method can greatly reduce the sintering temperature and the energy consumption and the sintering time, and is suitable for large-scale industrial production.
(3) The low-temperature hot pressing method of the invention utilizes the ion conduction characteristic of the plastic crystal solid electrolyte, and can reduce the grain boundary impedance between crystal grains at very low temperature, so that the method can avoid the mutual diffusion and side reaction of elements generated in the high-temperature sintering treatment process of the electrode material and the solid electrolyte.
(4) Compared with the existing low-temperature sintering method, the invention does not need high-temperature annealing treatment in the low-temperature hot pressing process, does not involve the use of any solvent, and the used plastic-crystal solid electrolyte has high oxidation voltage, good thermal stability and incombustibility, and is suitable for being used as a component of a solid-state battery.
Drawings
FIG. 1 is a scanning electron micrograph and an optical micrograph of the plastic crystal-ceramic composite solid electrolyte of the present invention.
Fig. 2 (a) is an XRD pattern of the LATP powder of the present invention and its mixed powder [ LATP + SN + LiTFSI ] with plastic crystal solid electrolyte; in the figure, LATP is oxide ceramic powder, SN is plastic crystal, LiTFSI is lithium salt, and LATP + SN + LiTFSI is mixed powder of the three;
FIG. 2 (b) is a scanning electron micrograph of a LATP powder of the present invention.
FIG. 3 is a diagram showing the room temperature AC impedance spectrum of the 5 mol% lithium salt LiTFSI doped plastic crystal solid electrolyte SN of the invention.
FIG. 4 is a normalized AC impedance spectrum of the plastic crystal-ceramic composite solid electrolyte 1, 2, 3, 4 of the present invention at 25 ℃.
Fig. 5 shows the relative densities of the plastic crystal-ceramic composite solid electrolytes 1, 2, 3 and 4 according to the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and examples.
The invention provides a low-temperature hot-pressing preparation method of a plastic crystal-ceramic composite solid electrolyte, which comprises the following steps:
step 1, weighing oxide ceramic powder and plastic crystal solid electrolyte, and uniformly mixing to obtain mixed powder; the plastic crystal solid electrolyte comprises: plastic crystals and lithium salts;
The oxide ceramic powder of the present invention accounts for 30 to 100 mass%, preferably 60 to 94 mass% of the mixed powder. The plastic crystal solid electrolyte accounts for 0-70% of the mixed powder by mass, and preferably 6-40% of the mixed powder by mass.
In some embodiments, the oxide ceramic powder may be one or two or more of garnet-type, perovskite-type, or NASICON-type solid electrolytes; more preferably, the garnet-type solid electrolyte includes Li7La3Zr2O12And derivatives thereof; the perovskite type solid electrolyte is Li3xLa2/3-xTi3O3(ii) a The NASICON type solid electrolyte comprises Li1+ yAlyTi2-y(PO4)3、Li1+zAlzGe2-z(PO4)3And LiTimZr2-m(PO4)3One or more than two of them. Wherein x is more than or equal to 0 and less than or equal to 2/3, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 2, and m is more than or equal to 0 and less than or equal to 2.
The plastic crystals of the invention are in solid form at room temperature. The plastic crystal can be molecular plastic crystal and ion plastic crystal, preferably molecular plastic crystal Succinonitrile (SN).
The lithium salt may be completely dissolved in the plastic crystal to form a plastic crystal solid electrolyte. The lithium salt comprises LiClO4、LiTFSI、LiBOB、LiPF6And LiFSI, which accounts for 0-30 mol%, preferably 1-20 mol% of the plastic crystal solid electrolyte.
The pressure of the compression molding is 30-1600MPa, the heat preservation time is 0.1-12h, and the heating temperature is 40-350 ℃. Preferably, the pressure of the press forming is 300-1200MPa, the pressing time is 0.5-2h, and the heating temperature is 50-180 ℃. More preferably, the heating temperature of the present invention may be 100-160 ℃. In the hot pressing process, the plastic crystal solid electrolyte absorbs heat and is melted, so that the densification of ceramic powder is promoted; after the hot pressing is finished and the temperature is reduced to the room temperature, the plastic crystal solid electrolyte is solidified into a solid state again, and the mechanical strength of the composite ceramic solid electrolyte is enhanced.
As shown in figure 1, the invention also provides a plastic crystal-ceramic composite solid electrolyte prepared by the low-temperature hot-pressing preparation method of the plastic crystal-ceramic composite solid electrolyte.
Example 1
Weighing CH according to stoichiometric ratio3COOLi、Al(NO3)3·9H2O、(C4H9O)4Ti and 85 wt% H3PO4(in water)，CH3COOLi in an excess of 5 mol%. Firstly, (C)4H9O)4Ti is dripped into deionized water for hydrolysis, and then white precipitate is obtained by centrifugation and dissolved in 2M oxalic acid solution at 60 ℃ to obtain colorless transparent solution. The rest raw materials are added into the colorless transparent solution, after full dissolution, the water is evaporated at 80 ℃, and the obtained white precipitate is dried in a forced air oven at 80 ℃ overnight. The white precipitate is ground in an agate mortar, absolute ethyl alcohol is used as a dispersing agent, a planetary ball mill is used for ball milling at 450r/min for 12 hours, and then the powder after ball milling and drying is presintered for 2 hours at 400 ℃. Subsequently, the calcined powder was ball-milled for 12 hours by a planetary ball mill at 400r/min, also using anhydrous ethanol as a dispersant. Finally, the powder after the second ball milling drying is calcined at 750 ℃ for 12h, and white LATP ceramic powder with good crystallization can be obtained (figure 2).
0.0159g of lithium salt LiTFSI, 0.0841g of plastic crystal solid electrolyte SN and 0.9g of LATP ceramic powder are weighed and placed in an agate mortar, after the materials are uniformly mixed for 30min, a proper amount of mixed powder is poured into a mold with a heating instrument, after the powder is spread, the mixture is pressed into a mold under 819MPa, meanwhile, the temperature is raised to 160 ℃, and the temperature is kept for 1 h. And (3) after the temperature of the mould is reduced to room temperature, demoulding to obtain the plastic crystal-ceramic composite solid electrolyte 1.
As can be seen from FIG. 2, the XRD pattern of LATP did not change significantly after one week of storage of the mixture of LATP, SN and LiTFSI, indicating that LATP is stable to SN and LiTFSI, and SN and LiTFSI do not destroy the crystal structure of LATP.
As can be seen from FIG. 3, the impedance R of the plastic crystal solid electrolyte [ SN +5 mol% LiTFSI ] is 51. omega. Further, the thickness L of [ SN +5 mol% LiTFSI ] was 0.6mm, and the area S was 0.5024cm2From the formula σ ═ L/(sxr), the room-temperature ionic conductivity thereof can be calculated to be 2.34 × 10-3S/cm. Due to the high ionic conductivity and flexibility of SN, the SN is positioned at the grain boundary and can reduce the impedance of the grain boundary, thereby playing a role of a bridge connecting the ion transmission between the grains.
The plastic crystal-ceramic composite solid electrolyte 1 is prepared in the embodiment 1 of the invention. As can be seen from FIGS. 4 and 5, the ionic conductivity of the plastic crystal-ceramic composite solid electrolyte 1 was 1.82X 10-4S/cm, relative density of93.87％。
Example 2
This example is different from example 1 only in that the temperature of press molding was changed to 140 c during the low-temperature hot-pressing, and other conditions were not changed.
The plastic crystal-ceramic composite solid electrolyte 2 is prepared in the embodiment 2 of the invention. As can be seen from FIGS. 4 and 5, the ionic conductivity of the plastic crystal-ceramic composite solid electrolyte 2 was 1.67X 10-4S/cm, its relative density was 92.44%.
Example 3
This example is different from example 1 only in that the pressure and temperature of press molding were changed to 936MPa and 120 c, respectively, during the low-temperature hot pressing, and other conditions were not changed.
The plastic crystal-ceramic composite solid electrolyte 3 is prepared in embodiment 3 of the invention. As can be seen from FIGS. 4 and 5, the ionic conductivity of the plastic crystal-ceramic composite solid electrolyte 3 was 1.93X 10-4S/cm, the relative density of which is 94.22 percent.
Example 4
This example is different from example 1 only in that the pressure and temperature of press molding were changed to 1170MPa and 100 ℃ respectively during the low-temperature hot pressing, and other conditions were not changed.
The plastic crystal-ceramic composite solid electrolyte 4 is prepared in embodiment 4 of the invention. As can be seen from FIGS. 4 and 5, the ionic conductivity of the plastic crystal-ceramic composite solid electrolyte 4 was 2.00X 10-4S/cm, the relative density of which is 94.03 percent.
In conclusion, the present invention can realize the densification of the solid electrolyte at a very low temperature, has a high ionic conductivity, and greatly reduces the processing time, the energy loss and the volatilization of lithium element at a high temperature. In addition, the low-temperature hot pressing method can also avoid side reactions and mutual diffusion of elements of the cathode material and the solid electrolyte under high-temperature treatment.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. A low-temperature hot-pressing preparation method of plastic crystal-ceramic composite solid electrolyte is characterized by comprising the following steps:
step 1, weighing oxide ceramic powder and plastic crystal solid electrolyte, and uniformly mixing to obtain mixed powder; the plastic crystal solid electrolyte comprises: plastic crystals and lithium salts;
step 2, placing the mixed powder in a mould and paving;
step 3, pressing and molding the mixed powder, and simultaneously, carrying out heat treatment on the mixed powder, wherein the heating temperature is lower than 600 ℃, so that the plastic crystal solid electrolyte absorbs heat and is melted; and then reducing the temperature to solidify and mold the plastic crystal solid electrolyte to obtain the plastic crystal-ceramic composite solid electrolyte.
2. The low-temperature hot-pressing preparation method of plastic crystal-ceramic composite solid electrolyte as claimed in claim 1, wherein the heating temperature of step 3 is 40-350 ℃; and the heat preservation is carried out in the heating process, and the heat preservation time is 0.1h-12 h.
3. The method for preparing plastic crystal-ceramic composite solid electrolyte according to claim 2, wherein the heating temperature in step 3 is 100-160 ℃.
4. The method for preparing plastic crystal-ceramic composite solid electrolyte according to claim 1, wherein the pressure of the compression molding in step 3 is 300MPa-1200 MPa.
5. The low-temperature hot-pressing preparation method of the plastic crystal-ceramic composite solid electrolyte as claimed in claim 1, wherein the oxide ceramic powder accounts for 60-94% by mass of the mixed powder, and the plastic crystal solid electrolyte accounts for 6-40% by mass of the mixed powder.
6. The method for producing a plastic crystal-ceramic composite solid electrolyte according to claim 1, wherein the oxide ceramic powder is one or more of garnet-type, perovskite-type, and NASICON-type solid electrolytes.
7. The method for preparing the plastic crystal-ceramic composite solid electrolyte according to claim 1, wherein the molar fraction of the lithium salt in the plastic crystal solid electrolyte is less than 30 mol%.
8. The method for preparing the plastic crystal-ceramic composite solid electrolyte according to claim 1, wherein the plastic crystal is molecular plastic crystal succinonitrile.
9. The method of claim 1, wherein the lithium salt comprises LiClO4、LiTFSI、LiBOB、LiPF6And one or more than two of LiFSI.
10. The plastic crystal-ceramic composite solid electrolyte is characterized by being prepared by the low-temperature hot-pressing preparation method of the plastic crystal-ceramic composite solid electrolyte according to any one of claims 1 to 9.
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Cited By (3)
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| CN113571764A (en) * | 2021-07-14 | 2021-10-29 | 北京理工大学 | Composite solid electrolyte membrane and preparation method thereof |
| CN114171784A (en) * | 2021-11-19 | 2022-03-11 | 吉林省东驰新能源科技有限公司 | Integrated solid electrolyte-positive electrode assembly and preparation method and application thereof |
| CN114759269A (en) * | 2022-05-18 | 2022-07-15 | 电子科技大学 | Integrated all-solid-state battery based on ceramic-based electrolyte sheet and preparation method |
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| CN114759269A (en) * | 2022-05-18 | 2022-07-15 | 电子科技大学 | Integrated all-solid-state battery based on ceramic-based electrolyte sheet and preparation method |
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