CN113809391B - Preparation method of oxide solid electrolyte film with high ionic conductivity - Google Patents

Preparation method of oxide solid electrolyte film with high ionic conductivity Download PDF

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CN113809391B
CN113809391B CN202111063606.6A CN202111063606A CN113809391B CN 113809391 B CN113809391 B CN 113809391B CN 202111063606 A CN202111063606 A CN 202111063606A CN 113809391 B CN113809391 B CN 113809391B
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electrolyte film
ionic conductivity
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彭争春
谭飞虎
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Shenzhen University
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Abstract

The invention discloses a preparation method of a high ionic conductivity oxide solid electrolyte film, which comprises the following steps: provision of Li x La y TiO 3 X is more than or equal to 0.2 and less than or equal to 0.6,0.4 and less than or equal to 0.8; li is added by means of magnetron sputtering x La y TiO 3 The first Li is made of ceramic target material x La y TiO 3 A solid electrolyte film; adding a first Li x La y TiO 3 The solid electrolyte film is subjected to rapid annealing treatment to obtain Li x La y TiO 3 A solid electrolyte membrane. The Li with the thickness of 500nm-2 mu m and high ionic conductivity prepared by the invention x La y TiO 3 The solid electrolyte film has a compact and uniform structure. The solid electrolyte film shows good structural and performance stability under the environment of 20-140 ℃, and the ionic conductivity is 10 ‑7 ～10 ‑4 S/cm, and meets the requirements of the solid electrolyte for the all-solid-state battery.

Description

Preparation method of oxide solid electrolyte film with high ionic conductivity
Technical Field
The invention relates to the technical field of all-solid-state lithium batteries, in particular to a preparation method of a high-ionic conductivity oxide solid electrolyte film.
Background
The all-solid-state lithium battery has extremely high safety, the solid electrolyte of the all-solid-state lithium battery is nonflammable, non-corrosive, non-volatile and non-leakage, meanwhile, the dendritic lithium crystal phenomenon is overcome, and the spontaneous combustion probability of an automobile carrying the all-solid-state lithium battery is greatly reduced. In addition, when the solid electrolyte is used in small-sized equipment such as mobile phones, wristwatches and even miniature devices, the solid electrolyte is adopted to replace the original liquid electrolyte, so that the requirement of packaging of the battery can be simplified, and the thinner solid electrolyte is also beneficial to improving the volume energy density and the mass energy density of the battery, and is beneficial to realizing the flexibility of an energy unit and the like. At present, the biggest disadvantage of solid electrolyte is the low ionic conductivity of the electrolyte, and the current commercial LThe ion conductivity of iPON (lithium phosphorus oxygen nitrogen) solid electrolyte is only 10 -6 -10 -8 S/cm. Therefore, the key point of all-solid battery research is to develop a solid electrolyte having high ionic conductivity.
The currently studied solid electrolytes are mainly classified into polymer, oxide, sulfide, halide, etc. systems, each having advantages. For example, polymers readily achieve higher ionic conductivities, but the temperature range of use is limited and the thickness is in the range of from 20 to 100. Mu.m at most. Sulfide has high ionic conductivity, but is sensitive to moisture or oxygen in the air, and is easy to denaturize and lose efficacy. Halide conductivity spans are large and relatively few studies are being made. Among them, the oxide solid electrolyte has relatively high ionic conductivity, and excellent structural stability and chemical stability, so that it has become a focus of attention of researchers. Specifically, oxide electrolytes can be further classified into perovskite type, anti-perovskite type, NASICON type, and Garnet type (Garnet-like type) according to their crystal structures. LiLaTiO compound 3 The system is a typical perovskite structure. Studies have shown bulk LiLaTiO 3 The ionic conductivity of the system can reach 10 -3 S/cm, which is comparable to the electrolyte. Currently, liLaTiO is used 3 The solid electrolyte of the system has been reported in part, for example, lithium Lanthanum Titanate (LLTO) prepared by the way of sol-gel by M.V. Reddy of Singapore national university reaches 1 × 10 -5 S/cm; the LLTO ionic conductivity of Haihui Wang, university of southern China, prepared by rolling was 2X 10 -5 S/cm; the conductivity of 0.96X 10 was obtained by magnetron sputtering from Mehtap Ozdemira, iszmicri institute of technology -5 An S/cm LLTO film; the ionic conductivity of the Wuhan university Xiujian ZHao is 5 multiplied by 10 and prepared by magnetron sputtering -5 S/cm LLTO film. It can be seen that the solid electrolyte film prepared by magnetron sputtering has controllable film thickness and few defects, and can be used for preparing the solid electrolyte with the thickness of 100-2000 nm, and the volume energy density of the battery is improved by reducing the thickness of the solid electrolyte. At present, the method for preparing the LLTO solid electrolyte by using magnetron sputtering does not enter the industrialization, and magnetron sputtering and rapid annealing are usedHigh ionic conductivity (> 10) for fire production -4 S/cm) has not been reported.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for preparing a high ion conductivity oxide solid electrolyte thin film, which aims to solve the problem of low ion conductivity of the oxide solid electrolyte thin film prepared by the prior art.
The technical scheme of the invention is as follows:
a method for preparing a high ionic conductivity oxide solid electrolyte film, comprising the steps of:
provision of Li x La y TiO 3 X is more than or equal to 0.2 and less than or equal to 0.6,0.4 and less than or equal to 0.8;
the Li is added by means of magnetron sputtering x La y TiO 3 The first Li is made of ceramic target material x La y TiO 3 A solid electrolyte film; wherein the magnetron sputtering process conditions are as follows: background vacuum degree<3.0×10 -4 Pa, sputtering time of 60-400min, sputtering power of 50-160W, sputtering pressure of 0.1-15Pa, and sputtering atmosphere of Ar and O 2 Mixed gas of said Ar and O 2 The volume ratio is 7-9:1;
subjecting the first Li to x La y TiO 3 The solid electrolyte film is subjected to rapid annealing treatment to obtain Li x La y TiO 3 A solid electrolyte membrane.
Alternatively, the Li x La y TiO 3 The ceramic target is prepared by the following method:
mixing the required raw materials, and carrying out ball milling treatment;
drying the ball-milled powder;
pressing and molding the dried powder to obtain a blank;
firing and molding the blank to obtain a primary ceramic target material;
processing the primary ceramic target material into a preset size, and polishing to obtain the Li x La y TiO 3 A ceramic target material.
Optionally, the step of firing and molding the blank to obtain a preliminary ceramic target specifically includes: firstly, slowly heating the blank to 300-600 ℃, and preserving heat for 1-5h; and then continuously heating to 900-1250 ℃, and preserving the heat for 1-4h to obtain the primary ceramic target material.
Alternatively, isostatic pressing is used.
Optionally, a first Li made x La y TiO 3 The thickness of the solid electrolyte film is 100nm-2 μm.
Optionally, the process conditions of the rapid annealing treatment are as follows: heating to 300-800 deg.C at a heating rate of 10-30 deg.C/s, and maintaining for 5-40min.
Optionally, the atmosphere of the rapid annealing treatment is O 2 。
Alternatively, the Li x La y TiO 3 The ceramic target material is LiLaTiO 3 A ceramic target material.
Alternatively, the Li x La y TiO 3 The solid electrolyte film is a crystalline or amorphous film.
Has the advantages that: the method successfully prepares the Li with the thickness of 500nm-2 mu m and high ionic conductivity under the optimized magnetron sputtering process parameter combination and rapid annealing process x La y TiO 3 The solid electrolyte film has a compact and uniform structure. And Li prepared by the invention x La y TiO 3 The solid electrolyte film shows good structural and performance stability under the environment of 20-140 ℃, and the ionic conductivity is 10 -7 ～10 -4 S/cm, meets the requirements of the solid electrolyte for the all-solid-state battery.
Drawings
Fig. 1 is a schematic view of the structure of the blocking electrode prepared in example 1.
FIG. 2 is an XRD pattern of LLTO thin films after rapid annealing treatment at different temperatures in example 1.
FIG. 3 is a graph comparing the electrochemical performance of LLTO thin films after rapid annealing treatment at different temperatures in example 1; wherein, (a) is an alternating current impedance curve of the LLTO thin film after the rapid annealing treatment at different temperatures, and (b) is the ionic conductivity of the LLTO thin film after the rapid annealing treatment at different temperatures.
FIG. 4 is a graph comparing electrochemical properties of the LLTO thin film after the rapid annealing treatment at 300 ℃ in example 1 at different testing temperatures ranging from 20 ℃ to 140 ℃; wherein, (a) is the AC impedance curve of the LLTO film at different temperatures, and (b) is the ionic conductivity of the LLTO film at different temperatures.
FIG. 5 is the ionic conductivity of the LLTO thin film prepared at a low rate for a long time in example 2.
Detailed Description
The present invention provides a method for preparing a high ion conductivity oxide solid electrolyte film, which is further described in detail below in order to make the objects, technical schemes and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of a high-ionic conductivity oxide solid electrolyte film, which comprises the following steps:
s1, providing Li x La y TiO 3 X is more than or equal to 0.2 and less than or equal to 0.6,0.4 and less than or equal to 0.8;
s2, performing magnetron sputtering on the Li x La y TiO 3 The first Li is made of ceramic target material x La y TiO 3 A solid electrolyte film; wherein the magnetron sputtering process conditions are as follows: background vacuum degree<3.0×10 -4 Pa, sputtering time of 60-400min, sputtering power of 50-160W, sputtering pressure of 0.1-15Pa, and sputtering atmosphere of Ar and O 2 Mixed gas of said Ar and O 2 The volume ratio is 7-9:1;
s3, mixing the first Li x La y TiO 3 The solid electrolyte film is subjected to rapid annealing treatment to obtain Li x La y TiO 3 A solid electrolyte membrane.
The existing magnetron sputtering process does not realize the matching of process parameters with better comprehensive performance, such as sputtering time, power, air pressure, atmosphere, flow rate and the like, and the parameters are not independent, but need to comprehensively adjust each parameter to realize an optimal parameter combination. The inventor finally determines the magnetron sputtering process parameter combination through a large number of experiments and combination exploration of various parameters, and prepares the solid electrolyte with high ionic conductivity under the process parameter combination.
Besides the parameters such as sputtering time, power, air pressure, atmosphere, flow and the like, the method also relates to the matching of the following parameters: substrate temperature (50-350 ℃), rotation speed (2-20 ℃/s), revolution amplitude (10-50 ℃) and reciprocating frequency (0.025-1 Hz). Through the combined exploration of the parameters, the optimal process parameter combination is finally determined, and the solid electrolyte with higher ion conductivity is prepared under the process parameter combination.
The existing annealing process mostly adopts a resistance furnace, the resistance furnace is heated by a silicon-molybdenum rod or a resistance wire, the heating rate is slow, and the temperature is usually 2-10 ℃ per minute. Slower ramp rates tend to result in additional crystallization during annealing, resulting in limited enhancement of ionic conductivity. In the embodiment, a rapid annealing process is adopted, for example, the heating rate is 10-30 ℃ per second, and the heating rate can reach about 100 times of the existing heating rate, so that crystallization caused by too slow heating can be avoided, defects in the electrolyte film can be reduced in a short time, and the ionic conductivity can be greatly improved.
In the embodiment, the Li with the thickness of 500nm-2 μm and high ionic conductivity is successfully prepared under the optimized magnetron sputtering process parameter combination and rapid annealing process x La y TiO 3 The solid electrolyte film has a compact and uniform structure. And Li obtained in this example x La y TiO 3 The solid electrolyte film shows good structural and performance stability under the environment of 20-140 ℃, and the ionic conductivity is 10 -7 ～10 -4 S/cm, and meets the requirements of the solid electrolyte for the all-solid-state battery.
It should be emphasized that the present embodiment has two main advantages: one is a thickness of 1 μm or more, and the other is high ionic conductivity. In magnetron sputtering, the thicker the film to be produced, the more likely the film is to be degraded in quality, and therefore, conventionally, the thickness is usually 500nm or less for the purpose of uniform and dense structure of the film. In the embodiment, the researched optimal process parameter combination can maintain the good physical structure of the film when the film with the thickness of 1000nm is prepared, so that the film has high ionic conductivity.
In step S1, in one embodiment, the Li x La y TiO 3 The ceramic target is prepared by the following method:
s11, mixing the required raw materials, and carrying out ball milling treatment;
s12, drying the powder subjected to ball milling;
s13, pressing and forming the dried powder to obtain a blank;
s14, firing and molding the blank to obtain a primary ceramic target material;
s15, processing the primary ceramic target material into a preset size, and polishing to obtain the Li x La y TiO 3 A ceramic target material.
In one embodiment, step S11 specifically includes: firstly, analytically pure powder raw materials are selected, then the materials are mixed according to a certain molar ratio, and the mixed raw materials are placed in a planetary ball mill and are ball-milled for 2 to 10 hours (such as 8 hours) under the action of a ball-milling medium. Further, the ball milling medium can be agate balls with the diameter of 3-10 mm.
In one embodiment, step S12 specifically includes: placing the ball-milled powder in an oven, and keeping the temperature at 60-300 deg.C (such as 250 deg.C) for 24h.
In one embodiment, step S13 specifically includes: and placing the dried powder into a metal die, and then pressing and molding by adopting isostatic pressing to obtain a blank body with a required shape. Further, the molding is carried out by pressing at a pressure of 20 to 100kPa (e.g., 70 kPa). Further, the blank may be cylindrical or the like.
In one embodiment, step S14 specifically includes: firstly, slowly heating the blank to 300-600 ℃ (such as 500 ℃) and preserving heat for 1-5h (such as 3 h) to release the thermal stress in the blank; and then continuously heating to 900-1250 ℃ (such as 1000 ℃) and preserving heat for 1-4h (such as 3 h) so that the blank is fully sintered into ceramic, thus obtaining the primary ceramic target material.
In one embodiment, step S15 specifically includes: grinding the preliminary ceramic target material into a preset size by machining, and then polishing to prepare regular Li x La y TiO 3 A ceramic target material. For example, the Li x La y TiO 3 The ceramic target is cylindrical, the diameter of the ceramic target is 76.2mm or 50.6mm, and the thickness of the ceramic target is 3-6cm.
In one embodiment, step S2 specifically includes: mixing Li x La y TiO 3 Respectively placing the ceramic target material and the substrate in a magnetron sputtering chamber, and depositing in a magnetron sputtering mode to obtain first Li x La y TiO 3 A solid electrolyte film;
wherein the magnetron sputtering process conditions are as follows: background vacuum degree<3.0×10 -4 Pa, sputtering time of 60-400min, sputtering power of 50-160W, sputtering pressure of 0.1-15Pa, and sputtering atmosphere of Ar and O 2 Mixed gas of said Ar and O 2 The volume ratio is 7-9:1.
In one embodiment, the substrate is a pre-treated substrate. Further, the pre-processing comprises: cleaning a substrate, such as a silicon substrate or a Polyimide (PI) substrate with a polished single surface, wherein the surface cleanliness of the substrate can influence the adhesion effect and the growth quality of a film on the substrate, then ultrasonically cleaning the substrate for 3-5min by using alcohol and acetone in sequence, and finally blowing off residual impurities or cleaning agents on the surface of the substrate by using high-purity nitrogen.
In one embodiment, the first Li is made x La y TiO 3 The thickness of the solid electrolyte film is 100nm-2 μm.
In one embodiment, step S3 specifically includes: subjecting the first Li to x La y TiO 3 The solid electrolyte film is subjected to rapid annealing treatment in a rapid annealing furnace to obtain Li x La y TiO 3 A solid electrolyte membrane. Wherein the process conditions of the rapid annealing treatment are as follows: heating to 300-800 deg.C (such as 700 deg.C) at a heating rate of 10-30 deg.C/s, and holding for 5-40min (such as 10 min). Further, the atmosphere of the rapid annealing treatment is O 2 And after the rapid annealing treatment is finished, cooling to normal temperature along with the furnace.
The existing annealing process mostly adopts a resistance furnace, the resistance furnace is heated by a silicon-molybdenum rod or a resistance wire, the heating rate is slow, and the temperature is usually 2-10 ℃ per minute. Slower ramp rates tend to result in additional crystallization during annealing, resulting in limited enhancement of ionic conductivity. The rapid annealing process is adopted in the embodiment, the heating rate of the rapid annealing furnace is 10-30 ℃ per second, and the heating rate can reach about 100 times of that of a resistance furnace, so that crystallization caused by too slow heating can be avoided, defects in an electrolyte film can be reduced in a short time, and the ionic conductivity can be greatly improved.
In this example, first, the ball-milled powder was made into regular Li by isostatic pressing, sintering and machining x La y TiO 3 Ceramic target material, and then Li is prepared by magnetron sputtering x La y TiO 3 Electrolyte film and raising Li by rapid annealing treatment x La y TiO 3 The performance of (c). Li prepared by rapid annealing treatment x La y TiO 3 The solid electrolyte film may have both an amorphous state and a crystalline state, wherein the amorphous state Li x La y TiO 3 The film can be used for preparing rigid/flexible all-solid-state lithium ion batteries.
In this embodiment, magnetron sputtering may be used on Li x La y TiO 3 The upper surface and the lower surface of the solid electrolyte film are deposited with metal as electrodes to prepare a sandwich-type blocking electrode structure (metal-solid electrolyte-metal), the ionic conductivity of the blocking electrode structure is represented by adopting an alternating current impedance test, and the electrical performance of the blocking electrode structure is tested in the environment of 20-140 ℃. Wherein, li can be processed by photolithography or hard mask x La y TiO 3 Preparing regular electrode pattern on surface of solid electrolyte filmIn the method, a magnetron sputtering mode is adopted, metal (such as Au, ag and Al) is plated for 3-20 min to form an electrode, the diameter of the electrode can be 2-5mm, and a metal-solid electrolyte-metal blocking electrode structure is formed.
Tests prove that the Li with the thickness of 500nm-2 mu m and high ionic conductivity is successfully prepared in the embodiment x La y TiO 3 The solid electrolyte film has a compact and uniform structure. And Li obtained in this example x La y TiO 3 The solid electrolyte film shows good structural and performance stability under the environment of 20-140 ℃, and the ionic conductivity is 10 -7 ～10 -4 S/cm, and meets the requirements of the solid electrolyte for the all-solid-state battery.
It should be emphasized that the present embodiment has two main advantages: one is a thickness of 1 μm or more, and the other is high ionic conductivity. In magnetron sputtering, the thicker the film to be produced, the more likely the film is to be degraded in quality, and therefore, conventionally, the thickness is usually 500nm or less for the purpose of uniform and dense structure of the film. In the embodiment, the researched optimal process parameter combination can maintain the good physical structure of the film when the film with the thickness of 1000nm is prepared, so that the film has high ionic conductivity.
The invention is further illustrated by the following specific examples.
Example 1
1、Li 0.33 La 0.55 TiO 3 The preparation process of the ceramic target material comprises the following steps:
first, analytically pure La was selected 2 O 3 、Li 2 CO 3 、TiO 2 The raw materials are mixed according to the molar ratio shown in Table 1, agate balls with the diameter of 5-15mm are used as grinding media, the mixed raw materials are placed in a planetary ball mill, and ball milling is carried out for 8 hours under the action of the grinding media, so that powder is obtained.
TABLE 1
Cation(s) Li + La 3+ Ti 4+
Molar ratio of 0.33 0.55 1
Then, the obtained powder is placed into a metal mold, and is pressed and molded by adopting the pressure of 70kPa to obtain a cylindrical blank.
And then, slowly heating the cylindrical blank to 500 ℃, preserving heat for 3h to release the thermal stress in the blank, continuously heating to 1000 ℃, preserving heat for 3h to fully sinter the blank into ceramic, and forming a primary ceramic target material.
Finally, the primary ceramic target was ground to a specific size (diameter 76.2mm, thickness 3 cm) by machining and subjected to surface polishing treatment to obtain Li 0.33 La 0.55 TiO 3 A ceramic target material.
2. The target material and the substrate are respectively placed in a magnetron sputtering deposition chamber, and the parameters for preparing the electrode and the solid electrolyte film are shown in the table 2:
TABLE 2
Functional layer Background vacuum degree Atmosphere(s) Flow rate Power of Time
Electrode Ag 3.0×10 -4 Pa Ar 40sccm 80 9min
LLTO film 3.0×10 -4 Pa Ar:O 2 ＝8:2 20sccm 140 180min
Electrode Ag 3.0×10 -4 Pa Ar 40sccm 80 9min
The structure of the prepared Ag/LLTO/Ag blocking electrode is shown in figure 1, the middle part is a LLTO film, the bottom part and the upper part are silver electrodes, and the diameter of the electrolyte film in the middle part is larger than that of the silver electrode at the bottom part, so that the upper electrode and the lower electrode can be completely isolated.
After the blocking electrode structure of Ag/LLTO/Ag is prepared, the multiple blocking electrode structures prepared by the same method are respectively subjected to rapid annealing treatment at different temperatures, wherein the rapid annealing treatment temperature is 25-700 ℃, the heating rate is 10 ℃/s, the heat preservation time is 10min, and the rapid annealing treatment atmosphere is O 2 And cooling to normal temperature along with the furnace.
3. The crystal structure of the LLTO thin film after the rapid annealing treatment at different temperatures was measured by XRD, the results are shown in FIG. 2, and the electrochemical properties of the LLTO thin film were measured by CHI660E electrochemical workstation, and the impedance properties are shown in FIG. 3 (a). The results showed that the LLTO thin film after the rapid annealing treatment at 300 ℃ had the highest ionic conductivity, as shown in (b) of FIG. 3.
4. In order to test the performance of the LLTO thin film under extreme conditions such as charge-discharge heating, the electrochemical performance of the LLTO thin film at an ambient temperature of 25-140 ℃ was further tested by a small temperature oven for the LLTO thin film after annealing at 300 ℃, and the results are shown in fig. 4 (a) - (b). It can be seen from the figure that the solid electrolyte can work normally under the environment from room temperature to 140 ℃, and the ionic conductivity of the solid electrolyte increases along with the increase of the ambient temperature. Therefore, even if the battery is discharged at high power or the temperature of the battery is sharply increased due to heat accumulation under extreme conditions, the battery can continue to operate normally.
Example 2
The target and the substrate were placed in a deposition chamber, respectively, and the parameters for preparing the electrode and the solid electrolyte film are shown in table 3:
TABLE 3
Functional layer Background vacuum Atmosphere(s) Flow rate Power of Time
Electrode Ag 3.0×10 -4 Pa Ar 40sccm 80 9min
Electrolyte LLTO 3.0×10 -4 Pa Ar:O 2 ＝8:2 15sccm 100 510min
Electrode Ag 3.0×10 -4 Pa Ar 40sccm 80 9min
Since the electrode silver is a simple substance, the uniformity of the metal is high, and there is no composition deviation, the main key parameters are as shown in the table. The LLTO components are complex in types, and besides 4 parameters of atmosphere, flow, power and time in the table, the LLTO components also relate to the following parameters: the working air pressure in sputtering is 0.7Pa, the substrate temperature is 120 ℃, the sample rotation speed is 10 degrees/s (namely 36 seconds rotation one circle), the sample revolution amplitude is 30 degrees, namely the sample reciprocates in the range of 30 degrees, and the revolution speed is 2 degrees/s.
After the Ag/LLTO/Ag blocking electrode structure is prepared, the temperature is kept at 280 ℃ for 10min, the heating rate is 20 ℃/s, and the atmosphere of rapid annealing treatment is Ar 2 +O 2 And cooling to room temperature along with the furnace. The ionic conductivity is shown in fig. 5. As can be seen from FIG. 5, when a thin film is prepared at a lower deposition rate, for example, by simultaneously using a mode of lower power, low flow rate and proper substrate temperature, the target atoms have sufficient energy and time to undergo spontaneous diffusion migration on the substrate surface, so that the low-speed preparation mode improves the compactness and uniformity of the thin film, and thus a sample with a thickness of more than 1 μm is successfully prepared, wherein the thickness of the sample in FIG. 5 is 1142nm, and the ionic conductivity of the sample is 3.64X 10 -4 S/cm, far beyond the same kind of LLTO thin film prepared by magnetron sputtering. Table 4 below is a comparison of the properties of the LLTO films prepared by magnetron sputtering of the same type:
TABLE 4
Ionic conductivity S/cm Thickness of Atmosphere(s)
This example 3.64×10 -4 S/cm 1142nm Ar:O 2 ＝8:2
University of electronic science and technology teaching to courageTeaching 1.81×10 -5 S/cm 180～306nm Ar:O 2 ＝7:3
Professor Li Geqin of combined fertilizer industry university 5.00×10 -6 S/cm 200-400nm Ar:O 2 ＝6.3:3.7
Professor Deng Hong, university of electronic technology 6.35×10 -5 S/cm 150-350nm Ar:O 2 ＝7:3
Professor Zhao Xiujian, university of Wuhan's science and engineering 5.25×10 -5 S/cm 190nm Ar:O 2 ＝7:3
Professor Wu Feng, beijing university of Physician 9.40×10 -7 S/cm 2630nm N 2
The thickness of the film of Beijing's theory of technology university reaches 2.63 μm, and the thickness is very high, but the quality of the film is poor just because of the high thickness, so that the ion conductivity is lower than that of the embodiment by 2 orders of magnitude. It can be seen that two key links of this embodiment: the relative optimized magnetron parameter set + rapid annealing process = the high ionic conductivity LLTO thin film obtained in this example.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (1)

1. A method for preparing a high ionic conductivity oxide solid electrolyte film is characterized by comprising the following steps:
provision of Li x La y TiO 3 A ceramic target, wherein x =0.33, y =0.55;
the Li is added by means of magnetron sputtering x La y TiO 3 The first Li is made of ceramic target material x La y TiO 3 A solid electrolyte film; wherein the magnetron sputtering process conditions are as follows: background vacuum degree of 3.0-10 -4 Pa, sputtering time of 510min, sputtering power of 100W, flow rate of 15sccm, sputtering pressure of 0.7Pa, and sputtering atmosphere of Ar and O 2 Mixed gas of said Ar and O 2 The volume ratio is 8:2, the substrate temperature is 120 ℃, and Li x La y TiO 3 The autorotation speed of the ceramic target material is 10 DEG/s, li x La y TiO 3 The revolution amplitude of the ceramic target is 30 degrees and Li x La y TiO 3 The revolution speed of the ceramic target material is 2 degrees/s;
subjecting the first Li to x La y TiO 3 The solid electrolyte film is subjected to rapid annealing treatment to obtain Li x La y TiO 3 A solid electrolyte film;
the process conditions of the rapid annealing treatment are as follows: heating to 280 ℃ at the heating rate of 20 ℃/s, preserving the heat for 10min, and then cooling to room temperature;
the Li x La y TiO 3 The thickness of the solid electrolyte film is 1142nm;
Li 0.33 La 0.55 TiO 3 the ceramic target is prepared by the following method:
selection of analytically pure La 2 O 3 Analytically pure Li 2 CO 3 Analytically pure TiO 2 As a raw material, according to Li + 、La 3+ 、Ti 4+ The method comprises the following steps of (1) preparing materials according to a molar ratio of 0.33;
putting the obtained powder into a metal die, and pressing and forming by adopting the pressure of 70kPa to obtain a cylindrical blank;
heating the cylindrical blank to 500 ℃, preserving heat for 3h, then continuing to heat to 1000 ℃, preserving heat for 3h, sintering the cylindrical blank into ceramic, and forming a primary ceramic target material;
grinding the primary ceramic target material into the size with the diameter of 76.2mm and the thickness of 3cm by machining, and performing surface polishing treatment to obtain the Li 0.33 La 0.55 TiO 3 A ceramic target material.
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