CN120341351B - Sulfide solid electrolyte and preparation method thereof - Google Patents
Sulfide solid electrolyte and preparation method thereofInfo
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- CN120341351B CN120341351B CN202510798039.0A CN202510798039A CN120341351B CN 120341351 B CN120341351 B CN 120341351B CN 202510798039 A CN202510798039 A CN 202510798039A CN 120341351 B CN120341351 B CN 120341351B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
- B02C17/1805—Monitoring devices for tumbling mills
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
- B02C17/20—Disintegrating members
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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
- C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
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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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- C01—INORGANIC CHEMISTRY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- 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
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Abstract
The invention provides a sulfide solid electrolyte and a preparation method thereof, and particularly relates to the technical field of secondary batteries. The sulfide solid electrolyte is lithium phosphorus sulfur oxide, and the chemical formula of the lithium phosphorus sulfur oxide is Li 7P3S7.5+x‑5yO3.5‑x+5y, wherein x is more than or equal to 0 and less than or equal to 3.5, y is more than or equal to 0 and less than or equal to 1.5, and x-5y is more than or equal to 7.5 and less than or equal to 3.5. The lithium phosphorus oxysulfide is a sulfur-oxygen mixed coordination structure, x is the molar quantity of lithium sulfide in the raw material, y is the molar quantity of phosphorus pentoxide in the raw material, and the ratio of S/O is regulated and optimized through the joint adjustment of x and y. The sulfide solid electrolyte has ionic conductivity as high as 1mS/cm, is favorable for improving the charge and discharge efficiency and performance of the battery, has good thermal stability, and can ensure the safety and long-term stability of the battery.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a sulfide solid electrolyte and a preparation method thereof.
Background
Since the use of lithium ion batteries, the energy density of liquid lithium ion batteries has gradually approached the theoretical limit, and therefore, solid-state batteries having high safety and energy density have received much attention. Among the many solid state battery technologies, sulfide solid state electrolytes are considered to have great development potential due to their ultra-high ionic conductivity and good thermal stability comparable to liquid state electrolytes.
The existing pure sulfide solid state electrolyte is known to have high conductivity, but the extremely high air sensitivity of the electrolyte leads to the fact that the material needs to be carried out in an inert atmosphere (such as an Ar glove box) or an ultra-dry environment (with a dew point of < -50 ℃) in the whole process of synthesis, storage and battery assembly, so that the process complexity and the use difficulty are greatly increased. In addition, even brief exposure to air can trigger irreversible hydrolysis reactions (such as H 2 S and LiOH formation), severely limiting its scale-up and practical application.
In view of this, the present invention has been made.
Disclosure of Invention
It is an object of the present invention to provide a sulfide solid state electrolyte, which aims to solve at least one of the above technical problems in the prior art.
The second object of the present invention is to provide a method for producing a sulfide solid electrolyte.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the first aspect of the present invention provides a sulfide solid state electrolyte, wherein the sulfide solid state electrolyte is lithium phosphorus sulfur oxide, and the chemical formula of the lithium phosphorus sulfur oxide is Li 7P3S7.5+x-5yO3.5-x+5y;
wherein, the x is more than or equal to 0 and less than or equal to 3.5,0 y is more than or equal to 1.5, -7.5< x-5y <3.5.
The lithium phosphorus oxysulfide is a sulfur-oxygen mixed coordination structure, x is the molar quantity of lithium sulfide in the raw material, y is the molar quantity of phosphorus pentoxide in the raw material, and the ratio of S/O is regulated and optimized through the joint adjustment of x and y.
Further, in Li 7P3S7.5+x-5yO3.5-x+5y, 1≤x≤3.5 and y=0.
The preparation raw materials of the lithium phosphorus oxysulfide do not contain phosphorus pentoxide.
The second aspect of the invention provides a preparation method of the sulfide solid electrolyte, which comprises the steps of mixing lithium oxide, lithium sulfide, phosphorus pentasulfide and phosphorus pentoxide, performing ball milling, performing heat treatment after ball milling to obtain the sulfide solid electrolyte, wherein the ball milling rotating speed is 1000-2000 rpm, the radius of ball milling beads used for ball milling is 0.4-0.7 cm, and the density is 5.6-15.6 g/cm 3.
Further, the ball-milling bead ratio is 7-12:1, and the ball-milling beads comprise zirconia beads, stainless steel beads and tungsten carbide beads.
Further, the ball milling is carried out in a ball milling tank, and the height-diameter ratio of the ball milling tank is 1.2-1.4.
Further, in the ball milling process, the total volume of the ball milling beads and the materials is not more than 70% of the volume of the ball milling tank, and the total ball milling energy is more than or equal to 455mJ.
Further, the ball milling time is 1-30 hours.
Further, the ambient moisture content of the ball mill is <0.01ppm, and the oxygen content is <1ppm.
Further, the heat treatment process is that the temperature is raised from room temperature to 250-300 ℃ in an inert atmosphere according to the temperature rising rate of 1-5 ℃ per minute, and the heat is preserved for 1-3 hours.
Further, the molar ratio of the lithium oxide to the lithium sulfide to the phosphorus pentasulfide to the phosphorus pentoxide is (3.5-x) x (1.5-y) y, wherein x is more than or equal to 0 and less than or equal to 3.5, y is more than or equal to 0 and less than or equal to 1.5, and x-5y is more than or equal to 7.5 and less than or equal to 3.5.
Compared with the prior art, the invention has at least the following beneficial effects:
The sulfide solid electrolyte provided by the invention, in particular to lithium phosphorus sulfur oxide, has the advantages that the oxygen is used for partially replacing sulfur, the air stability and the electrochemical window are obviously improved while the high ionic conductivity is kept, and the sulfide solid electrolyte is an important breakthrough to practical sulfur-based solid electrolytes. The ionic conductivity of the lithium phosphorus sulfur oxide is as high as 1mS/cm, which is beneficial to improving the charge and discharge efficiency and performance of the battery and ensuring the safety and long-term stability of the battery.
In the preparation process provided by the invention, a high-energy ball milling mode is adopted, so that the particle refinement is realized while the raw materials are fully mixed, and the ion transmission path is facilitated to be shortened. And a heat treatment step carried out after ball milling, so that the mixed materials can fully react to finally form the required sulfide solid electrolyte. The preparation method not only improves the preparation efficiency of the solid electrolyte, but also is beneficial to obtaining electrolyte materials with uniform performance and compact structure, thereby providing reliable guarantee for the performance of the all-solid-state battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a plot of Li 7P3S8.5O2.5 ion conductivity versus ball milling energy.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments of the present invention.
The terms "comprises," "comprising," "including," or any other variation thereof, are intended to cover a specific feature, number, step, operation, element, component, or combination of the foregoing, which may be used in various embodiments of the present invention, and are not intended to first exclude the presence of or increase the likelihood of one or more other features, numbers, steps, operations, elements, components, or combinations of the foregoing.
The first aspect of the present invention provides a sulfide solid state electrolyte, wherein the sulfide solid state electrolyte is lithium phosphorus sulfur oxide, and the chemical formula of the lithium phosphorus sulfur oxide is Li 7P3S7.5+x-5yO3.5-x+5y;
wherein, the x is more than or equal to 0 and less than or equal to 3.5,0 y is more than or equal to 1.5, -7.5< x-5y <3.5.
The lithium phosphorus oxysulfide is a sulfur-oxygen mixed coordination structure, x is the molar quantity of lithium sulfide in the raw material, y is the molar quantity of phosphorus pentoxide in the raw material, and the ratio of S/O is regulated and optimized through the joint adjustment of x and y.
The sulfide solid electrolyte provided by the invention, in particular to lithium phosphorus sulfur oxide, has the advantages that the oxygen is used for partially replacing sulfur, the air stability and the electrochemical window are obviously improved while the high ionic conductivity is kept, and the sulfide solid electrolyte is an important breakthrough to practical sulfur-based solid electrolytes. The ionic conductivity of the lithium phosphorus sulfur oxide is as high as 1mS/cm, which is beneficial to improving the charge and discharge efficiency and performance of the battery and ensuring the safety and long-term stability of the battery.
In a specific implementation process, the chemical formula of the lithium phosphorus sulfur oxide can be Li7P3S1.25O9.75、Li7P3S3.5O7.5、Li7P3S3.75O7.25、Li7P3S6.25O4.75、Li7P3S7.5O3.5、Li7P3S8.5O2.5、Li7P3S9.5O1.5、Li7P3S10.5O0.5,, and the partial replacement of sulfur with oxygen can improve the stability of the lithium phosphorus sulfur oxide.
Further, in Li 7P3S7.5+x-5yO3.5-x+5y, 1≤x≤3.5 and y=0. The preparation raw materials of the lithium phosphorus oxysulfide do not contain phosphorus pentoxide.
In a specific implementation, the chemical formula of the lithium phosphorus oxysulfide may be Li7P3S8.5O2.5、Li7P3S9.5O1.5、Li7P3S10.5O0.5,, for example, and is most preferably Li 7P3S8.5O2.5.
The second aspect of the invention provides a preparation method of the sulfide solid electrolyte, which comprises the steps of mixing lithium oxide, lithium sulfide, phosphorus pentasulfide and phosphorus pentoxide, performing ball milling, performing heat treatment after ball milling to obtain the sulfide solid electrolyte, wherein the ball milling rotating speed is 1000-2000 rpm, the radius of ball milling beads used for ball milling is 0.4-0.7 cm, and the density is 5.6-15.6 g/cm 3.
The preparation process provided by the invention adopts a high-energy ball milling mode, realizes particle refinement while fully mixing raw materials, is beneficial to shortening an ion transmission path and reducing grain boundary resistance. And a heat treatment step carried out after ball milling, so that the mixed materials can fully react to finally form the required sulfide solid electrolyte. The preparation method not only improves the preparation efficiency of the solid electrolyte, but also is beneficial to obtaining electrolyte materials with uniform performance and compact structure, thereby providing reliable guarantee for the performance of the all-solid-state battery.
By adopting a high-energy ball milling technology of 1000-2000 rpm, the grinding efficiency and microscopic uniformity of material preparation can be remarkably improved, the high-speed collision of ball milling is driven by a high-strength centrifugal force in the rotating speed range, and the linear speed can reach 20m/s, so that a sample can be quickly and uniformly ground in a short time, and the research efficiency is improved. This rotational speed range of the high energy ball mill enables ultra-fine grinding of the material by a combination of friction and impact forces. In addition, in the high-energy ball milling process, the sample is subjected to uniform collision and friction, so that the uniformity and stability of the sample are improved.
Typically, but not by way of limitation, the rotational speed of the ball mill may be, for example, 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, 1600rpm, 1700rpm, 1800rpm or 2000rpm, or any value within the range of 1000rpm to 2000 rpm.
Typically, but not by way of limitation, the radius of the ball-milling beads may be, for example, 0.4cm, 0.5cm, 0.6cm or 0.7cm, or any value within the range of 0.4 to 0.7 cm.
Further, the ball-milling bead ratio is 7-12:1, and the ball-milling beads comprise zirconia beads, stainless steel beads and tungsten carbide beads. The ball milling tank is matched with ball milling ball materials, and comprises a zirconia tank, a stainless steel tank and a tungsten carbide tank. The zirconia beads have a high density and wear resistance, achieving faster milling efficiency and finer particle size during milling. Does not react with the ground material, and ensures the high quality and purity of the product. Stainless steel balls provide deformation resistance to their high strength metal matrix. The tungsten carbide beads have superhard carbide lattice structures, and the impurity release is lower.
The ball milling bead ratio can effectively improve grinding efficiency and quality, reduce energy consumption and prolong the service life of the ball mill in the preparation process of the solid electrolyte. This ratio helps to achieve uniform mixing of the material and optimizes its microstructure, thereby improving the electrochemical properties of the material, especially ionic conductivity. Typically, but not by way of limitation, the ball-milled bead ratio may be, for example, 7.0:1, 7.5:1, 8.0:1, 8.5:1, 9.0:1, 9.5:1, 10.0:1, 10.5:1, 11:1, 11.5:1, or 12:1, but may also be any value in the range of 7:1 to 12:1.
Further, the ball milling is carried out in a ball milling tank, and the height-diameter ratio of the ball milling tank is 1.2-1.4. Typically, but not by way of limitation, the aspect ratio of the milling pot may be, for example, 1.2, 1.25, 1.3, 1.35 or 1.4, or any value within the range of 1.2 to 1.4.
Further, in the ball milling process, the total volume of the ball milling beads and the materials is not more than 70% of the volume of the ball milling tank, and the total ball milling energy is more than or equal to 455mJ. The high-energy ball milling mode is adopted, so that the raw materials are fully mixed and refined, and meanwhile, overheating or structural damage of the materials possibly caused by excessive rotating speed is avoided. And a heat treatment step carried out after ball milling, so that the mixed materials can fully react to finally form the required solid electrolyte.
In the ball milling process, ball milling with different energy is realized by adjusting the particle size, the bead ratio and the rotating speed of ball milling beads, and when the total energy of ball milling is more than or equal to 455mJ, the ion conductivity of the obtained solid electrolyte is more than 0.1mS/cm.
The ball milling energy is calculated by correlating the kinetic energy E (mJ) of each ball-milling ball with the mass m (g) and the velocity V (m/s) E Single sheet =（1/2）mV2, wherein m is the mass of a single ball-milling ball, and is related to the radius R (cm) and the density ρ (g/cm 3) of the ball-milling ball, m= (4/3) pi R 3 ρ, and V is the linear velocity, and is related to the ball-milling rotational speed n (R/min) of the radius R (cm) of the ball-milling pot, V=2pi Rn/60, thus the total kinetic energy E Total (S) =aE=(1/2)a×(4/3πr3ρ)×[2π(R-r)ω/60]2 of ball milling is obtained, and a is the total number of ball-milling balls.
Further, the ball milling time is 1-30 hours.
Further, the ambient moisture content of the ball mill is <0.01ppm, and the oxygen content is <1ppm. Such restrictions prevent oxidation and hydrolysis of the material during grinding, avoid unnecessary chemical reactions, reduce agglomeration and overheating phenomena, improve grinding efficiency, and ensure that uniform and fine powders are obtained. In addition, it helps to stabilize the milling process, control the temperature, avoid thermal runaway, and thus protect the chemical stability of the material, ensuring high quality and consistency of the final product.
Further, the heat treatment process is that the temperature is raised from room temperature to 250-300 ℃ in an inert atmosphere according to the temperature rising rate of 1-5 ℃ per minute, and the heat is preserved for 1-3 hours.
Typically, but not by way of limitation, the heat treatment is performed by increasing the temperature from room temperature to 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃ or 300 ℃ in an inert atmosphere, e.g., at a rate of increase of 1 ℃,2 ℃,3 ℃, 4 ℃ or 5 ℃ or 3 hours.
Further, the molar ratio of the lithium oxide to the lithium sulfide to the phosphorus pentasulfide to the phosphorus pentoxide is (3.5-x) x (1.5-y) y, wherein x is more than or equal to 0 and less than or equal to 3.5, y is more than or equal to 0 and less than or equal to 1.5, and x-5y is more than or equal to 7.5 and less than or equal to 3.5.
The invention is further illustrated by the following specific examples and comparative examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as limiting the invention in any way. The raw materials used in the examples and comparative examples of the present invention were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The ball milling pot used in the following examples and comparative examples was a stainless steel pot, and had a volume of 65mL and an aspect ratio of 1.25.
Example 1
The embodiment provides a sulfide solid electrolyte, which is prepared by the following steps:
(1) In a glove box filled with argon (moisture content is lower than 0.01ppm, oxygen content is lower than 1 ppm), lithium oxide, lithium sulfide, phosphorus pentasulfide and phosphorus pentoxide are respectively weighed according to the molar ratio of 0.5:3:0.9:0.6, then stainless steel balls are prepared according to the bead ratio of 8:1, the particle size is 10mm, and the weighed raw materials and the ball balls are put into a ball milling tank together for sealing. Finally, ball milling is carried out for 6 hours at a rotating speed of 1800rpm per minute.
(2) Transferring the ball-milled material into a quartz crucible, uniformly heating the material from room temperature to 270 ℃ at a rate of 2 ℃ per minute, preserving heat at the temperature for 2 hours, and taking out the material after naturally cooling the material to room temperature to obtain the sulfide solid electrolyte with the chemical formula of Li 7P3S7.5O3.5.
Example 2
The difference between the sulfide solid electrolyte provided in this embodiment and that in embodiment 1 is that the molar ratio of lithium oxide, lithium sulfide, phosphorus pentasulfide and phosphorus pentoxide is 3:0.5:1.4:0.1, and the other steps are the same as those in embodiment 1, and are not described here again.
Example 3
The difference between the sulfide solid state electrolyte provided in this embodiment and embodiment 1 is that the molar ratio of lithium oxide, lithium sulfide, phosphorus pentasulfide and phosphorus pentoxide is 3.4:0.1:1.48:0.02, and the other steps are the same as those in embodiment 1, and are not repeated here.
Example 4
The difference between the sulfide solid electrolyte provided in this example and that in example 1 is that the molar ratio of lithium oxide to phosphorus pentasulfide is 3.5:1.5, and the remaining steps are the same as in example 1, and are not described here again.
Example 5
The embodiment provides a sulfide solid electrolyte, which is prepared by the following steps:
(1) In a glove box filled with argon (moisture content is lower than 0.01ppm, oxygen content is lower than 1 ppm), lithium oxide, phosphorus pentasulfide and phosphorus pentoxide are respectively weighed according to a molar ratio of 3.5:1.25:0.25, then stainless steel balls are prepared according to a bead ratio of 8:1, the particle size is 10mm, and the weighed raw materials and the ball-milling balls are placed into a ball-milling tank together for sealing. Finally, ball milling is carried out for 6 hours at a rotating speed of 1800rpm per minute.
(2) Transferring the ball-milled material into a quartz crucible, heating to 270 ℃ from room temperature at a constant speed of 2 ℃ per min, preserving heat for 2 hours at the temperature, and taking out after naturally cooling to room temperature to obtain the sulfide solid electrolyte with the chemical formula of Li 7P3S6.25O4.75.
Example 6
The difference between the sulfide solid electrolyte provided in this example and that in example 5 is that the molar ratio of lithium oxide, phosphorus pentasulfide and phosphorus pentoxide is 3.5:0.75:0.75, and the remaining steps are the same as those in example 5, and are not described in detail herein, to obtain the sulfide solid electrolyte having the chemical formula of Li 7P3S3.75O7.25.
Example 7
The difference between the sulfide solid electrolyte provided in this example and that in example 5 is that the molar ratio of lithium oxide, phosphorus pentasulfide and phosphorus pentoxide is 3.5:0.25:1.25, and the remaining steps are the same as those in example 5, and are not described in detail herein, to obtain the sulfide solid electrolyte having the chemical formula of Li 7P3S1.25O9.75.
Example 8
The difference between the sulfide solid electrolyte provided in this example and that in example 5 is that the molar ratio of lithium sulfide to phosphorus pentoxide is 3.5:1.5, and the remaining steps are the same as those in example 5, and are not described in detail herein, to obtain a sulfide solid electrolyte having a chemical formula of Li 7P3S3.5O7.5.
Example 9
The difference between the sulfide solid electrolyte provided in this embodiment and embodiment 5 is that the molar ratio of lithium oxide, lithium sulfide and phosphorus pentasulfide is 2.5:1:1.5, and the rest steps are the same as those in embodiment 5, and are not described in detail herein, so as to obtain the sulfide solid electrolyte with a chemical formula of Li 7P3S8.5O2.5.
Example 10
The difference between the sulfide solid electrolyte provided in this embodiment and embodiment 5 is that the molar ratio of lithium oxide, lithium sulfide and phosphorus pentasulfide is 1.5:2:1.5, and the rest steps are the same as those in embodiment 5, and are not described in detail herein, so as to obtain the sulfide solid electrolyte with a chemical formula of Li 7P3S9.5O1.5.
Example 11
The difference between the sulfide solid electrolyte provided in this embodiment and embodiment 5 is that the molar ratio of lithium oxide, lithium sulfide and phosphorus pentasulfide is 0.5:3:1.5, and the rest steps are the same as those in embodiment 5, and are not described in detail herein, so as to obtain the sulfide solid electrolyte with a chemical formula of Li 7P3S10.5O0.5.
Example 12
The difference between the sulfide solid electrolyte provided in this embodiment and that in embodiment 9 is that the bead ratio is 10:1, and the other steps are the same as those in embodiment 9, and are not described here again, so as to obtain the sulfide solid electrolyte with the chemical formula of Li 7P3S8.5O2.5.
Example 13
The difference between the sulfide solid electrolyte provided in this embodiment and that in embodiment 9 is that the bead ratio is 12:1, and the other steps are the same as those in embodiment 9, and are not described here again, so as to obtain the sulfide solid electrolyte with the chemical formula of Li 7P3S8.5O2.5.
Example 14
The embodiment provides a sulfide solid electrolyte, which is prepared by the following steps:
(1) This procedure is the same as in example 9.
(2) Transferring the ball-milled material into a quartz crucible, heating to 250 ℃ from room temperature at a constant speed of 2 ℃ per min, preserving heat at the temperature for 2 hours, and taking out after naturally cooling to room temperature to obtain the solid electrolyte with the chemical formula of Li 7P3S8.5O2.5.
Example 15
The embodiment provides a sulfide solid electrolyte, which is prepared by the following steps:
(1) This procedure is the same as in example 9.
(2) Transferring the ball-milled material into a quartz crucible, heating to 290 ℃ from room temperature at a constant speed of 2 ℃ per min, preserving heat at the temperature for 2 hours, and taking out after naturally cooling to room temperature to obtain the sulfide solid electrolyte with the chemical formula of Li 7P3S8.5O2.5.
Comparative example 1
This comparative example provides a solid electrolyte, which is different from example 9 in that the high-energy ball milling speed is 500rpm, the ball milling time is 20 hours, and the rest of the raw materials and the preparation method are the same as in example 9, and are not repeated here.
The comparative example failed to produce a solid electrolyte having the chemical formula Li 7P3S8.5O2.5.
Comparative example 2
This comparative example provides a solid electrolyte, which is different from example 9 in that stainless steel balls are 5mm in length and ball milling time is 6 hours, and the other raw materials and preparation methods are the same as example 1.
The comparative example failed to produce a solid electrolyte having the chemical formula Li 7P3S8.5O2.5.
Comparative example 3
This comparative example provides a solid electrolyte, except that the stainless steel balls of 10mm are replaced with agate balls of 10mm, the ball milling time is 6 hours, and the remaining raw materials and the preparation method are the same as in example 1.
The comparative example failed to produce a solid electrolyte having the chemical formula Li 7P3S8.5O2.5.
Test example 1
The solid electrolyte obtained in the example was subjected to ion conductivity and electron conductivity tests.
Ion conductivity 0.13g of the solid electrolyte is weighed and put into a stainless steel grinding tool for tabletting, a piece of carbon-coated aluminum foil is respectively placed at two ends to serve as a blocking electrode, a small wafer with the diameter of 10mm is pressed under 10MPa, and the thickness of the sulfide electrolyte wafer is measured to be L (unit mm) by using a micrometer. The above samples were tested by ac impedance method using an electrochemical workstation at 25 ℃ with a frequency range of 1Hz to 7MHz to calculate the ionic conductivity σ, σ=l/re×s, where Re represents the impedance (ohm) of the sample to be tested, obtained from the intersection of semicircular arcs and oblique lines in the electrochemical impedance spectrogram, and S represents the area (cm 2) of the electrode.
Electronic conductivity 0.13g of the sulfide electrolyte is weighed and put into a stainless steel grinding tool for tabletting, a piece of carbon-coated aluminum foil is respectively placed at two ends to serve as a blocking electrode, a small wafer with the diameter of 10mm is pressed under 10MPa, and the thickness of the sulfide electrolyte wafer is measured to be d (unit mm) by using a micrometer. The above samples were tested using an electrochemical workstation at 25 ℃ using direct current polarization to calculate the electron conductivity G, g=d/r×s, r=u/I, where R represents the impedance (ohm) of the sample being tested, U is the voltage applied by the test, I is the current measured, and S represents the electrode area (cm 2).
The data obtained are shown in table 1 below.
TABLE 1
From Table 1, it can be concluded that solid electrolytes of the same chemical formula can be obtained using different molar ratios of the starting materials, i.e., different values of x and y. The greater the amount of phosphorus pentoxide (P 2S5) and the smaller the amount of lithium oxide (Li 2 O), i.e., the smaller the value of y, the greater the value of x, the higher the ionic conductivity of the resulting solid electrolyte.
TABLE 2
As can be seen from Table 2 above, solid electrolytes of different chemical formulas can also be obtained using different molar ratios of the starting materials, i.e., different values of x and y. Doping is performed on the basis of Li 7P3S7.5O3.5, the ion conductivity is higher when the y value is smaller when phosphorus pentoxide (P 2O5) is doped, and the ion conductivity is highest when x is about 1 when lithium sulfide (Li 2 S) is doped.
TABLE 3 Table 3
As can be seen from table 3 above, in examples 9, 12 and 13, the bead ratio during the ball milling, i.e., the energy of the ball milling was increased appropriately, which was advantageous for synthesizing products with higher ion conductivity. It can be seen from examples 9, 14 and 15 that the optimum annealing temperature for Li 7P3S8.5O2.5 is about 270 ℃.
Fig. 1 is a graph showing the relationship between the ball milling energy and the ion conductivity of Li 7P3S8.5O2.5 in comparative examples 1 to 3 and examples 9, 12, and 13. As can be seen from fig. 1, as the ball milling energy increases, the ionic conductivity of the product decreases. In order to balance the ball milling efficiency and the preparation cost, the ball milling energy is recommended to be more than or equal to 455 mJ.
It should be noted that the foregoing embodiments are merely illustrative embodiments of the present invention, and not restrictive, and the scope of the invention is not limited to the embodiments, and although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that any modification, variation or substitution of some of the technical features of the embodiments described in the foregoing embodiments may be easily contemplated within the scope of the present invention, and the spirit and scope of the technical solutions of the embodiments do not depart from the spirit and scope of the embodiments of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
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