CN110518278B - Solid electrolyte with negative interface layer, preparation method and solid battery - Google Patents
Solid electrolyte with negative interface layer, preparation method and solid battery Download PDFInfo
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Abstract
The invention relates to the technical field of solid-state batteries, and particularly provides a solid-state electrolyte with a negative interface layer, a preparation method of the solid-state electrolyte and a solid-state battery. The solid electrolyte is any one of garnet-structure solid electrolyte, NASICON-structure solid electrolyte, organic polymer solid electrolyte, anti-perovskite solid electrolyte and sulfide solid electrolyte, and an indium gallium tin liquid metal alloy layer is laminated on the surface of the solid electrolyte. The surface of the solid electrolyte is provided with a liquid metal alloy layer, after the solid battery is assembled, the liquid metal alloy layer is opposite to the lithium metal cathode, the solid-solid phase compatibility problem between the lithium metal cathode and the solid electrolyte material interface can be improved by virtue of the transition effect of the liquid metal alloy layer, the interface resistance is reduced, and meanwhile, the liquid metal alloy layer can inhibit the growth of lithium dendrites on the cathode interface, so that the electrochemical performance of the solid battery is improved.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a solid-state electrolyte with a negative interface layer, a preparation method of the solid-state electrolyte and a solid-state battery.
Background
Solid-state batteries based on solid-state electrolytes have great potential application prospects due to the characteristics of high energy density, high safety and the like. The common solid electrolyte materials at present are: (1) NASICON (Nasuper-ionic Conductor) structures, e.g. NaZr2P3O12、Na1+xZr2Si2PO12、Li1+xAlxTi2-x(PO4)3(LATP)、Li1+xAlxGe2-x(PO4)3(lag); (2) perovskite-structured oxides, e.g. Li3xLa2/3-xTiO3(ii) a (3) Garnet-structured oxides, e.g. LixLa3M2O12(x is 3 to 7); (4) anti-perovskite structure Li3OX3A glassy or glass-ceramic type electrolyte of thin film solid electrolyte LiPON and sulfide; (5) a polymer electrolyte.
However, these solid electrolytes have a problem of poor compatibility with lithium metal of the negative electrode at present. To solve this problem, a second phase is introduced at the interface where the solid electrolyte and the negative lithium metal are in contact to perform surface modification, usually by means including Physical Vapor Deposition (PVD), Pulsed Laser Deposition (PLD), Atomic Layer Deposition (ALD), and the like.
For example, in the prior art, a novel thin film solid electrolyte is prepared by adding a buffer layer, and the buffer layer is added on the surface of the LiPON thin film to improve the interface performance of the LiPON thin film. The LiPON film is prepared by utilizing magnetron sputtering equipment, the working pressure is 1.5Pa, the sputtering power is set to be 180W, and the sputtering time is 1 h. However, the magnetron sputtering method has high energy consumption and complex process flow, and is not beneficial to large-scale production.
As another example, the prior art provides a high-voltage-resistant multi-stage structure composite solid electrolyte and a preparation method thereof, the method employs solid electrolytes with different components in a multi-stage structure, the electrolyte on the negative electrode side employs a polymer electrolyte with excellent compatibility with an electrode interface, the electrolyte on the positive electrode side employs a high-voltage-resistant polymer electrolyte, and the intermediate layer employs a polymer electrolyte or an inorganic electrolyte with high ionic conductivity. The preparation process of the method is not environment-friendly, the process is complex and fussy, the requirement on the precision between layers is high, and more importantly, the improvement on the interface contact is limited.
Disclosure of Invention
Aiming at the problems that the existing solid electrolyte has poor compatibility with negative lithium metal, and the existing solid electrolyte has high energy consumption, complex process and the like when being modified, the invention provides the solid electrolyte with the negative interface layer and the preparation method thereof.
Further, a solid-state battery using the solid-state electrolyte having a negative electrode interface layer of the present invention as an electrolyte is also provided.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the solid electrolyte is any one of garnet-structure solid electrolyte, NASICON-structure solid electrolyte, organic polymer solid electrolyte, anti-perovskite solid electrolyte and sulfide solid electrolyte, and a layer of indium gallium tin liquid metal alloy layer is laminated on the surface of the solid electrolyte.
Accordingly, a method of making a solid state electrolyte having a negative interfacial layer, comprising the steps of:
and depositing the indium-gallium-tin liquid metal alloy on the surface of the polished solid electrolyte, and leveling to form an indium-gallium-tin liquid metal alloy layer on the surface of the solid electrolyte to obtain the solid electrolyte with a negative interface layer.
Further, a solid-state battery includes a positive electrode, a negative electrode, and a solid-state electrolyte, wherein the negative electrode is a lithium metal sheet, and the solid-state electrolyte is the solid-state electrolyte having the negative electrode interface layer as described above; or the solid electrolyte is prepared by the preparation method of the solid electrolyte with the negative electrode interface layer, and the lithium metal sheet is arranged opposite to the negative electrode interface layer.
The invention has the technical effects that:
compared with the prior art, the surface of the solid electrolyte is provided with the liquid metal alloy layer, the liquid metal alloy layer modifies the negative electrode interface of the solid electrolyte in contact with the lithium metal negative electrode, and after the solid electrolyte is assembled into the solid battery, the solid-solid phase compatibility problem between the lithium metal negative electrode and the solid electrolyte material interface can be improved and the interface resistance can be reduced by virtue of the transition effect of the liquid metal alloy layer.
The preparation method of the solid electrolyte with the cathode interface layer enables the surface of the solid electrolyte to be rapidly modified by directly attaching the indium-gallium-tin liquid metal alloy layer on the surface of the polished solid electrolyte, and the whole preparation process is simple, low in energy consumption, free of pollution and suitable for large-scale production.
According to the solid-state battery provided by the invention, the lithium metal negative electrode is mutually contacted with the negative electrode interface layer of the solid electrolyte with the negative electrode interface layer, so that the solid-solid compatibility of the lithium metal and the solid electrolyte is greatly improved, the negative electrode interface resistance of the solid electrolyte contacted with the lithium metal negative electrode is reduced, and meanwhile, the dendrite crystallization of the lithium metal can be inhibited, and further, the electrochemical performance of the solid-state battery is improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a picture of the appearance of a solid electrolyte obtained by coating a liquid metal alloy of indium gallium tin on the surface of a garnet-structured solid electrolyte in example 1 of the present invention;
FIG. 2 shows the charging current of 1mA cm for a symmetrical battery assembled in accordance with example 1 of the present invention-2A time-of-flight cycle profile;
fig. 3 is a cycle curve of the solid-state battery of example 2 of the invention charged and discharged at 30 ℃ with a current of 0.5C;
fig. 4 is a capacity-voltage curve of the solid-state battery of example 2 of the present invention at different charge and discharge rates at 30 ℃;
fig. 5 is a performance curve of the solid-state battery of example 2 of the present invention at different rates at 30 ℃;
fig. 6 is an ac impedance curve of the solid-state batteries of example 2 of the present invention and comparative example 1;
fig. 7 is a rate performance curve at different currents for an assembled lithium metal symmetric battery of example 3 of the present invention;
fig. 8 is a cyclic charge-discharge curve of 0.5C at 30 ℃ for the solid-state battery of example 3 of the invention;
fig. 9 is a cyclic charge-discharge curve of 0.5C at 30 ℃ for the solid-state battery of example 4 of the invention;
FIG. 10 is a photograph showing a contact angle (taken by a contact angle tester) when a molten lithium metal is in contact with a garnet-structured solid electrolyte, which is not coated with an indium-gallium-tin liquid metal alloy on the surface thereof, according to comparative example 1 of the present invention;
FIG. 11 is a cyclic charge and discharge curve at 30 ℃ of 0.5C for the solid-state battery of comparative example 1 of the present invention;
fig. 12 is a rate performance curve at 30 ℃ for the solid-state battery of comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect of the invention, a solid state electrolyte having a negative interfacial layer is provided. The solid electrolyte is any one of garnet-structure solid electrolyte, NASICON-structure solid electrolyte, organic polymer solid electrolyte, anti-perovskite solid electrolyte and sulfide solid electrolyte, and an indium gallium tin liquid metal alloy layer is laminated on the surface of the solid electrolyte.
The garnet-structure solid electrolyte of the present invention may be a tantalum-doped solid electrolyte, such as Li6.5La3Zr1.5Ta0.5O12(ii) a The NASICON structure solid electrolyte may be NaZr2P3O12、Na1+xZr2Si2PO12、Li1+ xAlxTi2-x(PO4)3(LATP)、Li1+xAlxGe2-x(PO4)3(lag); the organic polymer solid electrolyte may be a polyethylene oxide (PEO) -based polymer solid electrolyte; the anti-perovskite solid electrolyte may be LiOCl3(ii) a The sulfide solid electrolyte may be Li10GeP2S12(LGPS)。
The lamination refers to that the indium gallium tin liquid metal alloy has two surfaces on the solid electrolyte, a layer is formed on one surface, the layer is tightly attached to the solid electrolyte and is firmly combined with the solid electrolyte, and a negative interface layer is arranged between a negative electrode and the solid electrolyte when the solid electrolyte is assembled into a solid battery through the indium gallium tin liquid metal alloy layer.
Preferably, the thickness of the indium gallium tin liquid metal alloy layer is (0.5-10) μm. If the thickness of the alloy layer of liquid metal indium gallium tin is too thin, for example less than 0.5 μm, the surface of the solid electrolyte cannot be completely covered, and if the thickness is too thick, the ionic conductivity of the electrolyte system is reduced, and the energy density of the solid battery is reduced due to the excessive alloy of liquid metal indium gallium tin.
Preferably, according to the mass ratio, the mass ratio of gallium to indium to tin in the indium-gallium-tin liquid metal alloy layer is indium: gallium: tin is (2 to 3), (6.5 to 8), (1 to 1.5). The alloy formed at this ratio can be kept in a liquid state at room temperature, and has good fluidity and self-healing characteristics. Such as indium: gallium: the tin can be 2:6.5:1, or 2:7:1, or 2:8:1, or 3:7:1, or 3:8:1.5, or 2.5:7:1, or 2.5:8:1, etc.
The purity of each of the above indium, gallium and tin is not less than 98%, and if the purity is too low, too high impurity content affects the contact performance between interfaces, resulting in an increase in interface contact resistance.
As a second aspect of the present invention, there is also provided a method for producing the above-described solid electrolyte having a negative electrode interface layer.
The preparation method comprises the following steps:
and depositing the indium-gallium-tin liquid metal alloy on the surface of the polished solid electrolyte, and leveling to form an indium-gallium-tin liquid metal alloy layer on the surface of the solid electrolyte to obtain the solid electrolyte with a negative interface layer.
The liquid metal alloy of indium, gallium and tin with the purity not lower than 98% is prepared by the following method, mixing indium, gallium and tin with the purity not lower than 98% according to the required mass proportion relation to obtain a mixed material of indium, gallium and tin, then heating the mixed material to 1100-1300 ℃ and preserving heat for 30-120 min to obtain the liquid metal alloy of indium, gallium and tin, and then naturally cooling to room temperature for later use. The addition temperature may be 1100 deg.C, 1150 deg.C, 1200 deg.C, 1250 deg.C, 1300 deg.C, etc.
Preferably, according to the mass ratio, the mass ratio of gallium to indium to tin in the indium-gallium-tin liquid metal alloy is indium: gallium: tin is (2 to 3), (6.5 to 8), (1 to 1.5).
The polishing treatment of the solid electrolyte can be implemented by adopting 500-2000-mesh sand paper to polish the solid electrolyte to the required thickness, and then performing polishing treatment, wherein the polishing treatment is a conventional process, and specifically, an automatic polishing machine with a cotton self-absorption grinding disc can be used for mechanically polishing the surface of the solid electrolyte. Of course, the method is not limited to sanding and then polishing, and other methods can be used, as long as the size of the solid electrolyte meets the requirement and the polishing requirement is met, and the method belongs to the polishing method of the invention.
The mode of depositing the indium-gallium-tin liquid metal alloy on the surface of the solid electrolyte can be used for dripping and scraping, so that the indium-gallium-tin liquid metal alloy is attached to the surface of the solid electrolyte to form an indium-gallium-tin liquid metal alloy layer. Or the lithium metal sheet is soaked on the indium gallium tin liquid metal alloy, and an indium gallium tin liquid metal alloy layer can also be obtained, and when the lithium metal sheet is soaked, only one surface of the lithium metal sheet needs to be soaked in the indium gallium tin liquid metal alloy.
As a third aspect of the present invention, there is also provided a solid-state battery. The solid electrolyte used by the solid battery is the solid electrolyte with the negative interface layer provided by the first aspect of the invention or the solid electrolyte prepared by the preparation method of the solid electrolyte with the negative interface layer provided by the second aspect of the invention; the negative electrode is a lithium metal sheet, and the positive electrode can be lithium iron phosphate, lithium cobaltate, ternary materials and the like. In the solid-state battery, the solid electrolyte with the negative electrode interface layer is arranged opposite to the lithium metal sheet, and the negative electrode interface layer of the solid electrolyte is close to or clings to the lithium metal sheet, so that the indium gallium tin liquid metal alloy layer can form the interface layer of the lithium metal sheet and the solid electrolyte. The solid electrolyte with the cathode interface layer does not need an indium gallium tin liquid metal alloy layer on one side close to the anode.
In order to more effectively explain the technical solution of the present invention, the technical solution of the present invention is explained below by a plurality of specific examples.
Example 1
A solid electrolyte with a negative interface layer, a preparation method thereof and a solid battery are provided. The preparation method of the solid electrolyte with the negative electrode interface layer comprises the following steps:
s11. garnet oxide solid electrolyte as a substrate was ground to a thickness of 800 μm using 2000-mesh sandpaper and the surface was mechanically ground and polished using an automatic grinding and polishing machine with a self-adsorbing abrasive disk made of cotton.
S12, weighing 2g of indium with the purity not lower than 98%, 8.8g of gallium with the purity not lower than 98% and 1.0g of tin with the purity not lower than 98% according to the mass ratio of the indium to the gallium to the tin of 2:8.8:1, mixing the indium to the gallium to the tin, heating the mixture at 1200 ℃ for 60min to obtain the indium-gallium-tin liquid metal alloy, and cooling the indium-gallium-tin liquid metal alloy to room temperature to keep the liquid state.
S13, dripping 1 mu L of indium-gallium-tin liquid metal alloy on the polished surface of a garnet oxide solid electrolyte wafer with the diameter of 15mm serving as a substrate, and scraping and leveling the polished surface by using a scraper until the surface of the garnet oxide solid electrolyte wafer is completely covered with the indium-gallium-tin liquid metal alloy to obtain a solid electrolyte with a negative interface layer, wherein the thickness of the solid electrolyte is 3 mu m, and as shown in figure 1, the surface of the obtained all-solid electrolyte is metallic luster.
A lithium metal symmetric battery (model No. CR2025) was assembled by using the solid electrolyte with the negative electrode interface layer prepared in example 1 as a solid electrolyte, a lithium metal sheet as a positive electrode and a lithium metal sheet as a negative electrode, and then a constant current cyclic charge and discharge test was performed at a current density of 1mA/cm2The specific results are shown in FIG. 2.
As can be seen from FIG. 2, the solid electrolyte of the present invention is combined with a lithium metal symmetric electrode, and the magnitude of the charging/discharging current is 1mA/cm2In the process, the battery can be stably circulated, the solid electrolyte has good tolerance to high current density, and the electrolyte layer is not pierced by lithium dendrites, which shows that the solid electrolyte after the indium gallium tin liquid metal alloy layer is added can effectively inhibit the formation of the lithium dendrites.
Example 2
A solid electrolyte with a negative interface layer, a preparation method thereof and a solid battery are provided. The preparation method of the solid electrolyte with the negative electrode interface layer comprises the following steps:
s21. garnet oxide solid electrolyte as a substrate was ground to a thickness of 800 μm using 2000-mesh sandpaper and the surface was subjected to a polishing treatment.
S22, weighing 2g of indium with the purity not lower than 98%, 8.8g of gallium with the purity not lower than 98% and 1.0g of tin with the purity not lower than 98% according to the mass ratio of the indium to the gallium to the tin of 2:8.8:1, mixing the indium to the gallium to the tin, heating the mixture at 1200 ℃ for 60min to obtain the indium-gallium-tin liquid metal alloy, and cooling the indium-gallium-tin liquid metal alloy to room temperature to keep the liquid state.
S23, dripping 1 mu L of indium-gallium-tin liquid metal alloy on the polished surface of a garnet oxide solid electrolyte wafer with the diameter of 15mm serving as a substrate, and scraping and leveling the polished surface by using a scraper until the surface of the garnet oxide solid electrolyte wafer is completely and uniformly covered with the indium-gallium-tin liquid metal alloy to obtain the solid electrolyte with a negative interface layer, wherein the thickness of the indium-gallium-tin liquid metal alloy layer is 3 mu m, and the surface of the obtained all-solid electrolyte is metallic.
A solid-state battery was assembled by using the solid electrolyte having the negative electrode interface layer prepared in example 2 as a solid electrolyte, lithium iron phosphate as a positive electrode formed from a positive electrode active material, and a lithium metal piece as a negative electrode:
(1) preparing positive electrode slurry by adding N-methyl pyrrolidone (NMP) into lithium iron phosphate, conductive carbon black and polyvinylidene fluoride (PVDF) binder according to the mass ratio of 8:1:1, coating the positive electrode slurry on the surface of an aluminum foil, drying, tabletting and cutting into 12mm pole pieces to obtain positive pole pieces, wherein the surface density of the positive pole pieces is 1mg/cm2。
(2) Assembling the positive electrode sheet, the lithium metal negative electrode sheet and the solid electrolyte into a CR2025 type solid-state battery.
The obtained solid-state battery was subjected to electrochemical performance tests including a cycle curve at 30 ℃, a charge-discharge curve at different rates at 30 ℃, a performance curve at different rates at 30 ℃ and ac impedance, and specific results are shown in fig. 3 to 6.
As can be seen from fig. 3, the battery of example 2 has good cycling stability at 30 ℃, the specific capacity is maintained above 120mAh/g, the charge-discharge efficiency is maintained above 99% after 120 cycles, and the capacity decay is reduced.
As can be seen from fig. 4 and 5, the battery obtained in example 2 completed the charge/discharge cycle at the rate of 0.1C, 0.2C, 0.5C, 1C, 1.5C, and 2C at 30 ℃, and the 1C capacity was 100mAh/g or more, and the 2C capacity was 75mAh/g, which showed excellent rate charge/discharge performance.
As can be seen from FIG. 6, the interfacial impedance of the battery obtained in example 2 was about 160. omega. cm2。
Example 3
A solid electrolyte with a negative interface layer, a preparation method thereof and a solid battery are provided. The preparation method of the solid electrolyte with the negative electrode interface layer comprises the following steps:
s31. garnet oxide solid electrolyte as a substrate was ground to a thickness of 800 μm using 2000-mesh sandpaper and the surface was subjected to a polishing treatment.
S32, weighing 2g of indium with the purity not lower than 98%, 7.0g of gallium with the purity not lower than 98% and 1.0g of tin with the purity not lower than 98% according to the mass ratio of the indium to the gallium to the tin of 2:7:1, mixing the indium to the gallium to obtain the indium-gallium-tin liquid metal alloy, heating the mixture at 1200 ℃ for 60min, and cooling the alloy to room temperature to keep the alloy in a liquid state.
S33, dripping 1 mu L of indium-gallium-tin liquid metal alloy on the polished surface of a garnet oxide solid electrolyte wafer with the diameter of 15mm serving as a substrate, and scraping and leveling the polished surface by using a scraper until the surface of the garnet oxide solid electrolyte wafer is completely covered with the indium-gallium-tin liquid metal alloy to obtain the solid electrolyte with a negative interface layer, wherein the thickness of the indium-gallium-tin liquid metal alloy layer is 3 mu m, and the surface of the obtained all-solid electrolyte is metallic.
The solid electrolyte with the negative electrode interface layer prepared in example 3 was used as a solid electrolyte, and a positive electrode formed by using lithium iron phosphate as a positive electrode active material and a lithium metal sheet as a negative electrode were respectively assembled into a solid battery with the model number CR2025 and a lithium metal symmetrical battery with a lithium metal as a symmetrical electrode:
(1) adding NMP into the lithium iron phosphate, the conductive carbon black and the PVDF binder according to the mass ratio of 8:1:1 to prepare positive electrode slurry, then coating the positive electrode slurry on the surface of an aluminum foil, drying, tabletting and cutting the aluminum foil into pole pieces with the diameter of 12mm to obtain positive electrode pieces, wherein the surface density of the positive electrode pieces is 1mg/cm2。
(2) Assembling the positive electrode sheet, the lithium metal negative electrode sheet and the solid electrolyte into a CR2025 type solid-state battery. The obtained lithium metal symmetric battery was subjected to a symmetric battery rate charge-discharge test, and the result is shown in fig. 7.
As can be seen from fig. 7, the solid electrolyte after the surface modification of the liquid alloy of indium gallium tin can stably circulate under a current of 1mA, and is respectively charged and discharged at a constant current under different current levels, and no micro short circuit occurs, which indicates that the modified electrolyte material can effectively inhibit the formation of lithium dendrite, and the critical current that can be borne can reach 1.0 mA.
The electrochemical performance of the obtained solid-state battery was tested, including a cycle charge and discharge curve at 30 ℃, and the specific results are shown in fig. 8.
As can be seen from fig. 8, the solid-state battery of example 3 has good cycling stability at 30 ℃, the specific capacity is maintained at 100mAh/g or more, the charge/discharge efficiency is maintained at 99% or more after 180 cycles of cycling, and the solid-state battery has stable charge/discharge performance and small capacity fading during cycling. Therefore, the modification effect of the garnet-structure oxide solid electrolyte is obvious by adopting the indium gallium tin liquid metal alloy.
Example 4
A solid electrolyte with a negative interface layer, a preparation method thereof and a solid battery are provided. The preparation method of the solid electrolyte with the negative electrode interface layer comprises the following steps:
s41. garnet oxide solid electrolyte as a substrate was ground to a thickness of 800 μm using 1500-mesh sandpaper and the surface was subjected to a polishing treatment.
S42, weighing 2g of indium with the purity not lower than 98%, 7.0g of gallium with the purity not lower than 98% and 1.0g of tin with the purity not lower than 98% according to the mass ratio of the indium to the gallium to the tin of 2:7:1, mixing the indium to the gallium to obtain the indium-gallium-tin liquid metal alloy, heating the mixture at 1200 ℃ for 60min, and cooling the alloy to room temperature to keep the alloy in a liquid state.
S43, dripping 1 mu L of indium gallium tin liquid metal alloy on the polished surface of the NASICON structure solid electrolyte LAGP ceramic chip with the diameter of 15mm serving as the substrate, scraping and leveling the polished surface by using a scraper until the surface of the LAGP ceramic chip is completely covered with the indium gallium tin liquid metal alloy to obtain the solid electrolyte with a negative interface layer, wherein the thickness of the indium gallium tin liquid metal alloy layer is 3 mu m, and the surface of the obtained solid electrolyte is metallic.
A solid-state battery was assembled by using the solid electrolyte having the negative electrode interface layer prepared in example 4 as an electrolyte, lithium iron phosphate as a positive electrode formed from a positive electrode active material, and a lithium metal piece as a negative electrode:
(1) adding NMP into the lithium iron phosphate, the conductive carbon black and the PVDF binder according to the mass ratio of 8:1:1 to prepare positive electrode slurry, then coating the positive electrode slurry on the surface of an aluminum foil, drying, tabletting and cutting into 12mm pole pieces to obtain positive pole pieces, wherein the surface density of the positive pole pieces is 1mg/cm2。
(2) Assembling the positive electrode sheet, the lithium metal negative electrode sheet and the solid electrolyte into a CR2025 type solid-state battery.
The electrochemical performance of the obtained solid-state battery was measured, and the specific results are shown in fig. 9, along with the cycle charge and discharge curve at 30 ℃.
As can be seen from fig. 9, the solid-state battery of example 3 has good cycling stability at 30 ℃, the specific capacity is maintained at 125mAh/g or more, the charge-discharge efficiency is maintained at 99% or more after 110 cycles of cycling, and the capacity decay is reduced, which indicates that the performance of the solid electrolyte obtained by modifying lag p with the liquid metal alloy of indium gallium tin is changed.
Comparative example 1
A solid-state battery. The preparation method of the solid-state battery comprises the following steps:
D11. grinding garnet oxide solid electrolyte as a substrate to a thickness of 800 μm using 2000 mesh sandpaper and polishing the surface to obtain a solid electrolyte;
D12. and D11, assembling the solid electrolyte, the lithium iron phosphate as a positive electrode active material, and the lithium metal sheet as a negative electrode to form the solid battery with the model CR 2025.
The solid electrolyte obtained in comparative example 1 was subjected to a lithium metal contact angle test, and the test results are shown in fig. 10; carrying out electrochemical performance tests including an alternating current impedance test on the solid-state battery obtained in comparative example 1, wherein specific results are shown in fig. 6; the specific results of the cycle curve test at 30 ℃ are shown in FIG. 11; the specific results of the rate performance test at 30 ℃ are shown in fig. 12.
As can be seen from fig. 10, when molten metallic lithium is dropped on the surface of the unmodified garnet-structured solid electrolyte for contact angle test, the contact angle reaches 157.50 °, and the metallic lithium is not infiltrated with the unmodified garnet-structured solid electrolyte and has poor infiltration performance.
As can be seen from the comparison between example 1 and comparative example 1 in fig. 6, the impedance of example 1 after the surface of the solid electrolyte is modified is reduced from 350 Ω to 160 Ω, the interface impedance is reduced, and the transmission efficiency of lithium ions at the interface is effectively improved.
As can be seen from fig. 11, the solid-state battery of comparative example 1 has a low capacity exertion, about 75mAh/g at 0.5C, and the battery failed after 100 cycles, although having a certain cycle stability at 30 ℃.
As can be seen from fig. 12, at 30 ℃, since the lithium iron phosphate// lithium metal battery was assembled using the unmodified garnet-structured oxide solid state electrolyte in comparative example 1, charge and discharge cycles were completed at 0.1C, 0.2C, 0.5C, and 1C rates, in which the 1C capacity was maintained at 50mAh/g, and the battery failed at 2C, 5C, no capacity was exhibited, and the rate charge and discharge performance was poor.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. A method for preparing a solid electrolyte with a negative interface layer, comprising the steps of:
depositing the indium-gallium-tin liquid metal alloy on the surface of the polished solid electrolyte, and leveling to form an indium-gallium-tin liquid metal alloy layer on the surface of the solid electrolyte to obtain the solid electrolyte with a negative interface layer; according to the mass ratio, in the indium gallium tin liquid metal alloy layer, gallium: indium (b): tin (6.5 to 8), (2 to 3) and (1 to 1.5).
2. The method for preparing a solid electrolyte with a negative interface layer according to claim 1, wherein the thickness of the indium gallium tin liquid metal alloy layer is (0.5-10) μm.
3. The method of claim 1, wherein the deposition is either knife coating or dipping.
4. A solid-state battery, comprising a positive electrode, a negative electrode and a solid-state electrolyte, wherein the negative electrode is a lithium metal sheet, and the solid-state electrolyte is prepared by the method for preparing the solid-state electrolyte with the negative electrode interface layer according to any one of claims 1 to 3, and the lithium metal sheet is arranged opposite to the negative electrode interface layer.
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| CN111193062A (en) * | 2020-02-20 | 2020-05-22 | 青岛科技大学 | Solid-state lithium ion battery and preparation method thereof |
| CN111799466A (en) * | 2020-06-28 | 2020-10-20 | 浙江工业大学 | Flexible solid-state battery containing electron conduction interface layer and preparation method thereof |
| CN113880571B (en) * | 2020-07-01 | 2022-12-13 | 中国科学院上海硅酸盐研究所 | Gallium compound modified garnet type oxide solid electrolyte and preparation method and application thereof |
| CN112768695A (en) * | 2021-01-13 | 2021-05-07 | 山东大学 | High-safety dendrite-free lithium metal battery and preparation method and application thereof |
| CN115513538B (en) * | 2021-06-07 | 2024-04-30 | 山东大学 | Flexible buffer layer for solid lithium metal battery and preparation method and application thereof |
| CN114094042A (en) * | 2021-11-10 | 2022-02-25 | 惠州亿纬锂能股份有限公司 | Liquid metal negative pole piece and preparation method and application thereof |
| CN114388803B (en) * | 2021-12-28 | 2023-03-24 | 广东马车动力科技有限公司 | Passivation layer sulfide solid electrolyte and preparation method and application thereof |
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