CN115763953A - Method for preparing LLZO solid electrolyte by using self-propagating combustion method - Google Patents
Method for preparing LLZO solid electrolyte by using self-propagating combustion method Download PDFInfo
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- CN115763953A CN115763953A CN202211440282.8A CN202211440282A CN115763953A CN 115763953 A CN115763953 A CN 115763953A CN 202211440282 A CN202211440282 A CN 202211440282A CN 115763953 A CN115763953 A CN 115763953A
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Abstract
The invention discloses a method for preparing a LLZO solid electrolyte by a self-propagating combustion method, which is used for preparing the LLZO solid electrolyte by the self-propagating combustion method, has short process reaction time and violent impact of combustion gas flow, is beneficial to the refinement of particles, reduces the agglomeration degree among the particles, and is easy to operate in the control process. In addition, the molten salt reaction can reduce the reaction temperature and shorten the reaction time, the growth of crystal grains in the heat treatment process can be controlled through the molten salt reaction of a lithium source, the introduction of the structural Li to generate the LLZO crystal phase is realized, and meanwhile, the high-speed mass transfer characteristic of the molten salt reaction can keep the characteristic of a precursor to realize the conversion to generate the obtained phase, so that the fluffy powder prepared through the lithium-containing molten salt reaction has the advantages of grain refinement, low agglomeration degree, small size and uniform granularity, and has feasibility.
Description
Technical Field
The invention relates to the quality field of battery materials, in particular to a method for preparing a LLZO solid electrolyte by a self-propagating combustion method.
Background
Solid electrolytes can compensate for the defects of liquid or gel electrolytes, but the development bottleneck of solid electrolytes is their low ionic conductivity, yet commercial conductivity (10) -3 S/cm) standard.
In recent years, the LLZO solid electrolyte is prepared by a common method such as a high-temperature solid phase method, a sol-gel method, a coprecipitation method, etc., wherein particles are contacted with each other during high-temperature calcination, which inevitably results in an increase in the particle size of the product, and thus, the calcined particles are generally micron-sized powder. Especially, in the high temperature solid phase method, the crystal grains of the LLZO will grow up in the high temperature heat treatment process, the sintering temperature of the prepared material is high, the uniformity of the grain diameter of the finished product is poor, if the nano-grade raw material is adopted, the sintering temperature can be reduced, the grain diameter distribution of the finished product is improved, but the price of the raw material is high. At present, cubic phase LLZO particles are mainly reduced to submicron or even nanometer by a multi-step grinding process in scientific research, and ground powder also has the problems of uneven particle size distribution, larger difference among particles, long process flow of multi-step grinding, poor cost and economy and unsuitability for mass production promotion.
Disclosure of Invention
Based on the above, in order to solve the problems of uneven particle size distribution, long process flow and easy agglomeration existing in the process of preparing the LLZO solid electrolyte in the prior art, the invention provides a method for preparing the LLZO solid electrolyte by using a self-propagating combustion method, which has the following specific technical scheme:
a method for preparing LLZO solid electrolyte using a self-propagating combustion method, comprising the steps of:
nitrate, ta 2 O 5 And C 2 H 5 NO 2 Adding the mixture into a reaction container, adding distilled water, heating to 70 ℃ under the condition of stirring, and then dropwise adding ammonia water to adjust the pH value to 4 to obtain precursor liquid;
heating the precursor liquid to generate self-propagating combustion reaction to obtain a bulky precursor powder product;
and mixing the fluffy precursor powder product with lithium-containing molten salt, and carrying out molten salt reaction to obtain the LLZO solid electrolyte.
Further, the nitrate is La (NO) 3 ) 3 ·6H 2 O、Zr(NO 3 ) 4 ·5H 2 O and Al (NO) 3 ) 3 ·9H 2 One or more of O.
Further, the lithium source in the lithium-containing molten salt is LiNO 3 、LiCl、Li 2 One or more of O.
Further, the molten salt in the lithium-containing molten salt is one or two of NaCl and potassium chloride.
Further, when Ta is used 2 O 5 In terms of mass ratio, la (NO) 3 ) 3 ·6H 2 O：Zr(NO 3 ) 4 ·5H 2 O：Ta 2 O 5 ：C 2 H 5 NO 2 ＝1-3：1-2：0.1-0.3：8.1-8.5。
Further, when Al (NO) is used 3 ) 3 ·9H 2 O, la (NO) in a mass ratio 3 ) 3 ·6H 2 O：Zr(NO 3 ) 4 ·5H 2 O：Al(NO 3 ) 3 ·9H 2 O：C 2 H 5 NO 2 ＝1-3：1-2：0.2-0.3：11.1-11.5。
Further, the ratio of the lithium-containing molten salt to the fluffy precursor powder product is 1-2.
Further, the mass ratio of the lithium source to the molten salt is 1-3.
Further, the temperature of the molten salt reaction is 700-1000 ℃, and the time of the molten salt reaction is 0.5-2 h.
Further, the temperature of the molten salt reaction is 800-900 ℃, and the time of the molten salt reaction is 1h.
In the scheme, the reaction time is short by a self-propagating method, and the violent impact of combustion gas flow is beneficial to the refinement of particles, reduces the agglomeration degree among the particles, and controls the process to be easy to operate. In addition, the reaction temperature can be reduced and the reaction time can be shortened through the molten salt reaction containing lithium, the growth of crystal grains in the heat treatment process can be controlled through the molten salt reaction containing lithium, the introduction of the structural Li is realized to generate the LLZO crystal phase, and meanwhile, the high-speed mass transfer characteristic of the molten salt reaction can keep the characteristic of a precursor to realize the conversion to generate the obtained phase, so that the fluffy powder prepared through the molten salt reaction containing lithium has feasibility in preparing fluffy powder with refined particles, low agglomeration degree, small size and uniform granularity.
Drawings
FIG. 1 is a schematic view showing a particle size distribution of LLZO solid state electrolyte prepared in example 1;
FIG. 2 is a schematic view showing a particle size distribution of LLZO solid state electrolyte prepared in example 4;
FIG. 3 is a schematic view showing a particle size distribution of LLZO powder prepared in comparative example 1;
FIG. 4 is a schematic view showing the particle size distribution of LLZO powder prepared in comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments thereof. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one embodiment of the invention, the method for preparing the LLZO solid electrolyte by the self-propagating combustion method comprises the following steps:
nitrate, ta 2 O 5 And C 2 H 5 NO 2 Adding the mixture into a reaction container, adding distilled water, heating to 70 ℃ under the condition of stirring, and then dropwise adding ammonia water to adjust the pH value to 4 to obtain precursor liquid;
heating the precursor liquid to generate self-propagating combustion reaction to obtain a bulky precursor powder product;
and mixing the fluffy precursor powder product with lithium-containing molten salt, and carrying out molten salt reaction to obtain the LLZO solid electrolyte.
In one embodiment, theThe nitrate is La (NO) 3 ) 3 ·6H 2 O、Zr(NO 3 ) 4 ·5H 2 O and Al (NO) 3 ) 3 ·9H 2 One or more of O.
In one embodiment, the lithium source in the lithium-containing molten salt is LiNO 3 、LiCl、Li 2 One or more of O.
In one embodiment, the molten salt in the lithium-containing molten salt is one or two of NaCl and potassium chloride.
In one embodiment, when Ta is used 2 O 5 In terms of mass ratio, la (NO) 3 ) 3 ·6H 2 O：Zr(NO 3 ) 4 ·5H 2 O：Ta 2 O 5 ：C 2 H 5 NO 2 ＝1-3：1-2：0.1-0.3：8.1-8.5。
In one embodiment, when Al (NO) is used 3 ) 3 ·9H 2 O, la (NO) in a mass ratio 3 ) 3 ·6H 2 O：Zr(NO 3 ) 4 ·5H 2 O：Al(NO 3 ) 3 ·9H 2 O：C 2 H 5 NO 2 ＝1-3：1-2：0.2-0.3：11.1-11.5。
In one embodiment, the ratio of the lithium-containing molten salt to the fluffy precursor powder product is 1-2.
In one embodiment, the mass ratio of the lithium source to the molten salt is 1-3.
In one embodiment, the temperature of the molten salt reaction is 700-1000 ℃, and the time of the molten salt reaction is 0.5-2 h.
In one embodiment, the temperature of the molten salt reaction is 800-900 ℃, and the time of the molten salt reaction is 1h.
In the scheme, the reaction time is short by a self-propagating method, and the violent impact of combustion gas flow is beneficial to the refinement of particles, reduces the agglomeration degree among the particles, and controls the process to be easy to operate. In addition, the molten salt reaction can reduce the reaction temperature and shorten the reaction time, the growth of crystal grains in the heat treatment process can be controlled through the lithium-containing molten salt reaction, the introduction of structural Li is realized to generate a LLZO crystal phase, and meanwhile, the high-speed mass transfer characteristic of the molten salt reaction can keep the characteristic of a precursor to realize the conversion to generate an obtained phase, so that the fluffy powder prepared through the lithium-containing molten salt reaction has feasibility in particle refinement, low agglomeration degree, small size and uniform particle size.
Embodiments of the present invention will be described in detail below with reference to specific examples.
Example 1:
a method for preparing LLZO solid electrolyte using a self-propagating combustion method, comprising the steps of:
and (3) mixing the following components in percentage by mass: 1.75:0.125: la (NO) of 8.1 3 ) 3 ·6H 2 O：Zr(NO 3 ) 4 ·5H 2 O：Ta 2 O 5 ：C 2 H 5 NO 2 Adding the mixture into a reaction kettle, adding a proper amount of distilled water, heating and stirring the mixed solution to 70 ℃, and then dropwise adding ammonia water to adjust the pH value of the mixed solution to 4 to obtain precursor liquid;
pouring the precursor liquid into a crucible, and putting the crucible into a muffle furnace to be heated until a self-propagating combustion reaction occurs, so as to obtain a bulky precursor powder product;
lithium nitrate according to a mass ratio of 1: mixing sodium chloride to obtain lithium-containing molten salt;
mixing the solid electrolyte precursor of 1.
Example 2:
a method for preparing LLZO solid electrolyte using a self-propagating combustion method, comprising the steps of:
and (3) mixing the following components in percentage by mass: 1.75:0.125: la (NO) of 8.2 3 ) 3 ·6H 2 O：Zr(NO 3 ) 4 ·5H 2 O：Ta 2 O 5 ：C 2 H 5 NO 2 Adding into a reaction kettle, adding appropriate amount of distilled water, heating and stirring the mixed solution to 70 ℃, dropwise adding ammonia water to adjust the pH value of the mixed solution to 4,obtaining a precursor liquid;
pouring the precursor liquid into a crucible, and putting the crucible into a muffle furnace to be heated until a self-propagating combustion reaction occurs, so as to obtain a bulky precursor powder product;
lithium nitrate according to a mass ratio of 1: mixing potassium chloride to obtain lithium-containing molten salt;
mixing the solid electrolyte precursor of 1.
Example 3:
a method for preparing LLZO solid electrolyte using a self-propagating combustion method, comprising the steps of:
and (3) mixing the raw materials in mass ratio: 1.75:0.125: la (NO) of 8.3 3 ) 3 ·6H 2 O：Zr(NO 3 ) 4 ·5H 2 O：Ta 2 O 5 ：C 2 H 5 NO 2 Adding the mixture into a reaction kettle, adding a proper amount of distilled water, heating and stirring the mixed solution to 70 ℃, and then dropwise adding ammonia water to adjust the pH value of the mixed solution to 4 to obtain precursor liquid;
pouring the precursor liquid into a crucible, and putting the crucible into a muffle furnace to be heated until a self-propagating combustion reaction occurs, so as to obtain a bulky precursor powder product;
lithium nitrate according to a mass ratio of 1: mixing potassium chloride to obtain lithium-containing molten salt;
mixing the solid electrolyte precursor of 1.
Example 4:
a method for preparing LLZO solid electrolyte using a self-propagating combustion method, comprising the steps of:
and (3) mixing the raw materials in mass ratio: 1.75:0.25: la (NO) of 11.1 3 ) 3 ·6H 2 O：Zr(NO 3 ) 4 ·5H 2 O：Al(NO 3 ) 3 ·9H 2 O：C 2 H 5 NO 2 Adding into a reaction kettle, adding a proper amount of distilled water, heating and stirring the mixed solution to 70 ℃, and then dropwise adding ammonia water for regulationAdjusting the pH value of the mixed solution to be 4 to obtain precursor liquid;
pouring the precursor liquid into a crucible, and putting the crucible into a muffle furnace to be heated until a self-propagating combustion reaction occurs, so as to obtain a bulky precursor powder product;
lithium nitrate according to a mass ratio of 1: mixing potassium chloride to obtain lithium-containing molten salt;
mixing the solid electrolyte precursor of 1.
Comparative example 1:
a preparation method of LLZO powder comprises the following steps:
mixing the components in a mass ratio of 6.75:3:1.75:0.25 LiOH. H 2 O：La 2 O 3 ：ZrO 2 ：Ta 2 O 5 Adding into a ball milling tank, adding 3 times of isopropanol by mass, ball milling for 12h at the speed of 300rpm/min, quickly placing the materials in a drying box after ball milling, quickly blowing and drying at the temperature of 80 ℃, placing the uniformly mixed reaction raw materials into a sagger after drying, roasting for 6h at the temperature of 900 ℃, and cooling to room temperature along with the furnace temperature to obtain LLZO powder.
Comparative example 2:
a preparation method of LLZO powder comprises the following steps:
and (3) mixing the following components in percentage by mass: 1.75:0.25 of La (NO 3) 3, zr (NO 3) 3 and Al (NO 3) 3.9H 2O are dissolved in deionized water to form a reaction solution; then dissolving NaOH in deionized water to form a precipitation solution, setting the reaction temperature of a coprecipitation reaction tank to be 60 ℃, adjusting the dropping speed of the reaction solution, the precipitation solution and an ammonia water solution, and controlling the pH value of the whole reaction liquid phase to be 10; after all the reaction solution is completely dripped, continuing to react for 6 hours; after the reaction is finished, washing the precipitate with water to obtain precursor powder;
adding LiOH & H2O into the precursor powder according to the mass ratio of 1.
The LLZO solid electrolytes obtained in examples 1 to 4 and the LLZO powders obtained in comparative examples 1 to 2 were subjected to particle size distribution tests, and the results are shown in FIGS. 1 to 4. FIG. 1 is a schematic diagram of the particle size distribution of the LLZO solid electrolyte prepared in example 1, and examples 2 and 3 are the same as example 1, and thus are not repeated, and it can be seen from FIG. 1 that the particle size distribution of the LLZO solid electrolyte prepared in the present application is uniform; FIG. 2 is a schematic diagram showing the particle size distribution of the LLZO solid electrolyte prepared in example 4. Although the raw materials used in example 4 are slightly different from those used in examples 1-3, it is also within the scope of the present application, it can be seen from FIG. 2 that the method of the present application facilitates the refinement of the particles and reduces the degree of agglomeration among the particles; FIG. 3 is a schematic view showing a particle size distribution of LLZO powder prepared in comparative example 1;
FIG. 4 is a schematic view showing the particle size distribution of the LLZO powder prepared in comparative example 2, and it can be seen from the analysis in FIG. 3 and FIG. 4 that the processes in comparative example 1 and comparative example 2 do not allow obtaining a fine and uniform LLZO powder. The method can solve the problems of uneven particle size distribution, long process flow and easy agglomeration in the LLZO solid electrolyte prepared by the prior art.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for preparing LLZO solid electrolyte using a self-propagating combustion method, comprising the steps of:
nitrate is added,Ta 2 O 5 And C 2 H 5 NO 2 Adding the mixture into a reaction container, adding distilled water, heating to 70 ℃ under the condition of stirring, and then dropwise adding ammonia water to adjust the pH value to 4 to obtain precursor liquid;
heating the precursor liquid until a self-propagating combustion reaction occurs to obtain a bulky precursor powder product;
and mixing the fluffy precursor powder product with lithium-containing molten salt, and carrying out molten salt reaction to obtain the LLZO solid electrolyte.
2. The method of claim 1, wherein the nitrate is La (NO) 3 ) 3 ·6H 2 O、Zr(NO 3 ) 4 ·5H 2 O and Al (NO) 3 ) 3 ·9H 2 One or more of O.
3. The method according to claim 1, wherein the lithium source in the lithium-containing molten salt is LiNO 3 、LiCl、Li 2 One or more of O.
4. The method according to claim 3, wherein the molten salt in the lithium-containing molten salt is one or both of NaCl and potassium chloride.
5. A method according to claim 4, characterized in that Ta is used 2 O 5 In terms of mass ratio, la (NO) 3 ) 3 ·6H 2 O：Zr(NO 3 ) 4 ·5H 2 O：Ta 2 O 5 ：C 2 H 5 NO 2 ＝1-3：1-2：0.1-0.3：8.1-8.5。
6. The method of claim 4, wherein Al (NO) is used 3 ) 3 ·9H 2 O, la (NO) in a mass ratio 3 ) 3 ·6H 2 O：Zr(NO 3 ) 4 ·5H 2 O：Al(NO 3 ) 3 ·9H 2 O：C 2 H 5 NO 2 ＝1-3：1-2：0.2-0.3：11.1-11.5。
7. The method according to claim 1, wherein the ratio of the lithium-containing molten salt to the fluffy precursor powder product is 1-2.
8. The method according to claim 4, wherein the mass ratio of the lithium source to the molten salt is 1-3.
9. The method according to claim 1, characterized in that the temperature of the molten salt reaction is 700 ℃ to 1000 ℃ and the time of the molten salt reaction is 0.5h to 2h.
10. The method according to claim 9, characterized in that the temperature of the molten salt reaction is 800 ℃ to 900 ℃ and the time of the molten salt reaction is 1h.
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