CN107681195B - Preparation method of nano garnet type solid electrolyte material - Google Patents
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- H—ELECTRICITY
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- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a nano garnet type solid electrolyte material, which comprises the following steps: (1) dissolving garnet metal ion soluble salt in deionized water or mixed solvent; (2) adding a certain amount of graphene oxide or graphene template material into the step (1); (3) adsorbing garnet metal ions on the graphene oxide or graphene sheet layer; (4) adjusting the pH value, performing hydrolysis reaction, and obtaining a garnet-type solid electrolyte precursor on the graphene oxide or graphene sheet layer; (5) adding a soluble salt solution of lithium; (6) and (4) carrying out heat treatment to obtain the nano garnet type solid electrolyte material. Compared with the prior art, the method has the advantages of low cost, easy scale production, small powder granularity and uniform distribution, can prepare the nano solid electrolyte material with specific morphology, the size of the lamella is 0.2-5 microns, each lamella is composed of 10-30 nm of superfine nano particles, and the prepared nano garnet type solid electrolyte material can be used for secondary solid lithium batteries.
Description
Technical Field
The invention relates to a preparation method of a nano garnet type solid electrolyte material, in particular to a preparation method of a garnet type solid electrolyte material with a nano lamellar structure, belonging to the technical field of battery material preparation.
Background
Lithium ion batteries have a non-replaceable function in the field of consumer electronics, and in recent years, the lithium ion batteries are developed into the fields of electric automobiles, power grid energy storage and the like. The traditional lithium ion battery adopts an organic liquid electrolyte material, and has serious safety problems of flammability, explosiveness and the like. The safety performance of the battery core of the lithium ion battery adopting the organic liquid electrolyte still cannot solve the safety problem of the battery fundamentally by adopting the technologies of selection and modification of positive and negative electrode materials, functional electrolyte, high-temperature-resistant diaphragm base material, ceramic coating of the diaphragm, reduction of internal resistance of the battery core, improvement of internal resistance after temperature rise of the battery core, heat dissipation of the battery core and the like. The solid electrolyte material, especially the oxide solid electrolyte material, has the advantages of high melting point, high mechanical strength, strong lithium dendrite resistance, stability to metal lithium, stability to environment, easy preparation, easy operation, low cost and the like, and the solid electrolyte material is used for replacing an organic liquid electrolyte, so that the safety problem of the battery is hopefully solved. On the other hand, batteries are required to have higher energy density in emerging fields such as electric vehicles, aerospace, intelligent robots and the like. In the last 20 years, the energy density of lithium batteries adopting organic liquid electrolytes is increased by about 7 percent every year, from the initial 90Wh/kg to the current 250Wh/kg, mainly by technical progress and increasing the occupied proportion of active substances in the batteries. However, the limited battery space is filled with more active energy storage materials, and the proportion of inactive materials is further reduced, which has reached a bottleneck from the technical aspect. The theoretical specific capacity of the metal lithium is 3860mAh/g which is far higher than the theoretical specific capacity 372mAh/g of graphite, and the ceramic solid electrolyte battery can adopt the metal lithium as a battery cathode, so that the energy density of the battery is greatly improved.
The garnet-type solid electrolyte material was first reported in 2007 as Weppner ≥ 10 at room temperature- 4The ionic conductivity of S/cm is very close to the practical level. More importantly, the material system has good stability to metallic lithium. However, the garnet-type solid electrolyte material is usually prepared by a solid-phase reaction method, which requires a high temperature of at least 1200 ℃ for 36 hours, and the volatilization of lithium element is difficult to control, and the uniformity of material preparation is difficult to achieve. Therefore, it is the goal of every researcher to develop a more concise and controllable method for preparing garnet-type solid electrolyte materials.
In addition, the garnet-type solid electrolyte material is difficult to assemble into a battery device due to the property of the oxide thereof, and researchers find that the garnet-type solid electrolyte and the polymer electrolyte are compounded, so that the advantages of both the ceramic and the polymer material can be achieved, and the assembled solid-state battery also shows good working performance. Such composite solid electrolyte materials are reported in, for example, non-patent literature (Journal of Powersources 353(2017)287 and 297) and Chinese patent publication No. CN 106532112A. The morphology of the ceramic solid electrolyte material has an important influence on the performance of the composite solid electrolyte, for example, non-patent documents (Proceedings of the National Academy of s sciences 113(2016) (7094) 7099) report that the ion conductivity of the composite electrolyte can be greatly improved by garnet-type solid electrolyte nanofibers. This linear form is more conducive to ion conduction therein than the particulate form. However, at present, most of the methods are to obtain a garnet-type ceramic sintered body at a high temperature by a solid phase reaction method and then to obtain nano-sized particles by a ball milling technique. The particles have larger sizes and are more agglomerated, and more importantly, the particles have uneven shapes and cannot fully play the role of the particles in the composite solid electrolyte.
In China specialityIn the publication No. CN103113107A, a garnet Li is reported7-xLa3Zr2-xTaxO12The preparation method comprises the following steps: in Li7-xLa3Zr2-xTaxO12Adding sintering aid L into raw material powderi2O、LiOH、Li2CO3、LiNO3、Li2SO4Or Li3PO4And the like, thereby reducing the phase forming temperature of the garnet material. But the final result is still a bulk material.
In Chinese patent publication No. CN104332651A, a molten salt method for preparing garnet Li is reported7La3Zr2O12A material. However, the final phase formation temperature still requires high temperature of 900-.
In chinese patent publication No. CN105428706A, a method for preparing a garnet-type solid electrolyte material by a sol-gel method is reported, and similarly, the method cannot control the particle morphology of the material.
In the chinese granted patent No. CN104124467B, a method for preparing a garnet solid electrolyte material by coating lanthanum and zirconium precursors with lithium oxalate is reported, so that a petaloid powder material is obtained, and a lamellar structure of the powder material grows together, which undoubtedly causes secondary agglomeration of nano powder.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a method for preparing a nano garnet-type solid electrolyte material, wherein the garnet-type solid electrolyte material is controlled to have a specific morphology of a graphene sheet layer structure, so as to realize industrial application of the garnet-type solid electrolyte material in a secondary solid lithium battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a nano garnet-type solid electrolyte material is characterized in that graphene oxide or graphene is adopted as a nano template material, and the prepared garnet-type solid electrolyte material has a graphene lamellar structure, and the method comprises the following steps:
(1) preferably, the garnet-type solid electrolyte material has the chemical formula Li6.5La3Zr1.5Nb0.5O12Selecting the molar ratio of La, Zr and Nb, and dissolving soluble salts of La, Zr and Nb in deionized water or a mixed solvent of ethanol and deionized water.
(2) Preferably, in the step (1), the soluble salts of La, Zr and Nb are lanthanum nitrate hexahydrate, zirconyl nitrate hydrate and niobium pentachloride.
(3) And (2) adding graphene oxide or a graphene solution into the solution obtained in the step (1), and ultrasonically stirring for 0.5-2 hours to realize the adsorption of La, Zr and Nb ions on the surface of the graphene oxide or graphene sheet layer.
(4) Preferably, in the step (3), the content of the graphene oxide or graphene is 0.1-200% by weight of the garnet-type solid electrolyte.
(5) And (4) dropwise adding ammonia water into the solution obtained in the step (3), and adjusting the pH value to 7-12 to realize coprecipitation of La, Zr and Nb ions on the surface of the graphene oxide or graphene sheet layer.
(6) Preferably, in step (5), the pH is in the range of 7 to 11.
(7) And (4) centrifuging and cleaning the coprecipitate obtained in the step (5).
(8) Dissolving soluble salt of lithium, preferably lithium nitrate in deionized water, mixing with the washed precipitate obtained in step (7), heating and stirring at 70-100 ℃, and drying to obtain garnet precursor.
(9) And (3) carrying out low-temperature treatment on the garnet precursor obtained in the step (8), wherein the heat treatment temperature is preferably 500-900 ℃, the heat treatment time is 0.5-10 hours, and the atmosphere is air.
The method for preparing the garnet-type solid electrolyte material has the following advantages:
(1) the synthesized garnet-type solid electrolyte material has the morphological characteristics of a specific laminated sheet layer of graphene;
(2) the synthesized garnet-type solid electrolyte material has small particle size and no agglomeration;
(3) the preparation process is simple, the controllability is strong, the synthesis temperature is low, the time is short, and the energy consumption is low;
in conclusion, the technology of the invention is hopeful to realize the industrial application of the nano garnet type solid electrolyte material with the lamellar structure in the secondary solid lithium battery, and has practical value.
Drawings
Fig. 1 is an XRD spectrum of the garnet-type solid electrolyte material prepared in comparative example 1;
fig. 2 is an SEM picture of the garnet-type solid electrolyte material prepared in comparative example 1;
fig. 3 is an XRD spectrum of the garnet-type solid electrolyte material prepared in example 1;
fig. 4 is an SEM picture of the garnet-type solid electrolyte material prepared in example 1;
fig. 5 is an XRD pattern of the garnet-type solid electrolyte material prepared in example 2;
fig. 6 is an SEM picture of the garnet-type solid electrolyte material prepared in example 2;
fig. 7 is an XRD pattern of the garnet-type solid electrolyte material prepared in example 3;
fig. 8 is an SEM picture of the garnet-type solid electrolyte material prepared in example 3.
Detailed Description
In order to make the contents, technical solutions and advantages of the present invention more apparent, the present invention is further illustrated below by combining specific comparative examples and examples, which are only used for illustrating the present invention, and the present invention is not limited only to the following examples.
Comparative example 1
According to the formula Li6.5La3Zr1.5Nb0.5O12The mol ratio of Li, La, Zr and Nb is selected from LiNO3、La(NO3)3·6H2O、ZrO(NO3)2·xH2O、NbCl5As a raw material, LiNO, among others3Excess of 20%, adding La (NO)3)3·6H2O、ZrO(NO3)2·xH2O、NbCl5Dissolved inAdding ammonia water dropwise into deionized water to adjust pH to 9, realizing coprecipitation of La, Zr and Nb ion precursors, centrifuging, cleaning precipitate with deionized water, and adding LiNO3Dissolving in deionized water, mixing with the cleaned precipitate, heating at 70-100 deg.C under stirring until the deionized water is completely volatilized, drying at 150 deg.C for 12 hr to obtain garnet Li6.5La3Zr1.5Nb0.5O12Precursor, obtained garnet Li6.5La3Zr1.5Nb0.5O12The precursor is thermally treated at 750 ℃ for 2 hours at the heating rate of 10 ℃/min in the atmosphere of air, and naturally cooled after thermal treatment to obtain the garnet Li6.5La3Zr1.5Nb0.5O12And (3) nano powder. FIGS. 1 and 2 are respectively solid electrolyte Li6.5La3Zr1.5Nb0.5O12The XRD pattern and SEM photograph of (1) can show that: obtained Li6.5La3Zr1.5Nb0.5O12The crystal grain shape is similar to round grain, and the size distribution of secondary crystal grain is in the range of 0.5-1.5 micron.
Example 1
According to the formula Li6.5La3Zr1.5Nb0.5O12The mol ratio of Li, La, Zr and Nb is selected from LiNO3、La(NO3)·6H2O、ZrO(NO3)2·xH2O、NbCl5As a raw material, LiNO3 was added in an excess of 20%, and La (NO) was added3)3·6H2O、ZrO(NO3)2·xH2O、NbCl5Dissolving in deionized water, and adding graphene into the solution, wherein the weight of the graphene is Li6.5La3Zr1.5Nb0.5O121% of the weight of the graphene, dropwise adding ammonia water to adjust the pH value to 7, realizing the coprecipitation of La, Zr and Nb ion precursors on the surface of a graphene sheet layer, centrifuging, cleaning precipitates by using deionized water, dissolving LiNO3 in the deionized water, mixing the precipitates with the cleaned precipitates, heating and stirring at 70-100 ℃ until the deionized water is completely volatilized, drying at 150 ℃ for 12 hoursObtaining garnet Li6.5La3Zr1.5Nb0.5O12The mixture of the precursor and the graphene is subjected to heat treatment at 750 ℃ for 2 hours at a heating rate of 10 ℃/min in the atmosphere of air, and the mixture is naturally cooled after the heat treatment to obtain garnet Li6.5La3Zr1.5Nb0.5O12And (3) nano powder. FIGS. 3 and 4 are respectively solid electrolyte Li6.5La3Zr1.5Nb0.5O12The XRD pattern and SEM photograph of (1) can show that: obtained Li6.5La3Zr1.5Nb0.5O12The crystal grain shape is similar to the crystal grain without adding the graphene oxide in the comparative example, and the crystal grain is round, but the crystal grain size is smaller, the secondary crystal grain size is distributed in the range of 100-200 nanometers, and the primary crystal grain size is in the range of 30-50 nanometers.
Example 2
According to the formula Li6.5La3Zr1.5Nb0.5O12The mol ratio of Li, La, Zr and Nb is selected from LiNO3、La(NO3)·6H2O、ZrO(NO3)2·xH2O、NbCl5As a raw material, LiNO, among others3Excess of 20%, adding La (NO)3)3·6H2O、ZrO(NO3)2·xH2O、NbCl5Dissolving in deionized water, and adding graphene oxide into the solution, wherein the weight of the graphene oxide is Li6.5La3Zr1.5Nb0.5O1250% of the weight, dropwise adding ammonia water to adjust the pH value to 8.5, realizing the coprecipitation of La, Zr and Nb ion precursors on the surface of the graphene oxide sheet layer, centrifuging, cleaning precipitates with deionized water, and adding LiNO3Dissolving in deionized water, mixing with the cleaned precipitate, heating at 70-100 deg.C under stirring until the deionized water is completely volatilized, drying at 150 deg.C for 12 hr to obtain garnet Li6.5La3Zr1.5Nb0.5O12A mixture of a precursor and graphene oxide, and heat-treating the obtained mixture at 800 ℃ for 2 hours and litersThe temperature rate is 10 ℃/min, the atmosphere is nitrogen, the natural cooling is carried out after the heat treatment, the garnet Li is obtained after the powder is ground and the heat treatment is carried out for 4 hours at the temperature of 500 ℃, the temperature rise rate is 10 ℃/min, the atmosphere is air6.5La3Zr1.5Nb0.5O12And (3) nano powder. FIGS. 5 and 6 are respectively solid electrolyte Li6.5La3Zr1.5Nb0.5O12The XRD pattern and SEM photograph of (1) can show that: obtained Li6.5La3Zr1.5Nb0.5O12The crystal grain appearance is completely different from the crystal grain appearance of the comparative example without adding the graphene oxide, the crystal grain appearance is of a lamellar structure, the size of each lamellar is 1-5 microns, and each lamellar consists of 10-30 nanometers of nano particles.
Example 3
According to the formula Li6.5La3Zr1.5Nb0.5O12The mol ratio of Li, La, Zr and Nb is selected from LiNO3、La(NO3)·6H2O、ZrO(NO3)2·xH2O、NbCl5As a raw material, LiNO, among others3Excess of 20%, adding La (NO)3)3·6H2O、ZrO(NO3)2·xH2O、NbCl5Dissolving in deionized water, and adding graphene oxide into the solution, wherein the weight of the graphene oxide is Li6.5La3Zr1.5Nb0.5O12100 percent of the weight of the precursor is added with ammonia water dropwise to adjust the pH value to 11, so as to realize the coprecipitation of La, Zr and Nb ion precursors on the surface of a graphene oxide sheet layer, the precipitate is centrifuged and washed by deionized water, and LiNO is added3Dissolving in deionized water, mixing with the cleaned precipitate, heating at 70-100 deg.C under stirring until the deionized water is completely volatilized, drying at 150 deg.C for 12 hr to obtain garnet Li6.5La3Zr1.5Nb0.5O12The mixture of the precursor and the graphene oxide is subjected to heat treatment at 900 ℃ for 2 hours at the heating rate of 10 ℃/min in the atmosphere of air, and then naturally cooled to obtain the garnet Li6.5La3Zr1.5Nb0.5O12And (3) nano powder. FIGS. 7 and 8 are respectively solid electrolyte Li6.5La3Zr1.5Nb0.5O12The XRD pattern and SEM photograph of (1) can show that: obtained Li6.5La3Zr1.5Nb0.5O12The crystal grain appearance is completely different from the crystal grain appearance of the comparative example without adding the graphene oxide, and is of a lamellar structure, and the size of the lamellar is 0.2-5 microns.
Finally, it must be said here that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adaptations made by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention.
Claims (4)
1. A method for preparing a nano garnet type solid electrolyte material is characterized by comprising the following steps: selecting soluble salts of La, Zr and Nb to be dissolved in deionized water or a mixed solvent of ethanol and deionized water by adopting a nano template method, adding graphene oxide or a graphene solution into the obtained mixed solution, ultrasonically stirring for 0.5-2 hours to realize the adsorption of La, Zr and Nb ions on the surface of a graphene oxide or graphene sheet layer, adjusting the pH value to 7-12, and realizing the co-precipitation of the La, Zr and Nb ions on the surface of the graphene oxide or graphene sheet layer; centrifuging and cleaning the obtained coprecipitate; dissolving soluble salt of lithium in deionized water or an organic solvent, mixing with the cleaned coprecipitate, heating and stirring at 70-100 ℃, and drying to obtain a garnet precursor; carrying out low-temperature heat treatment on the obtained garnet precursor to obtain a nano garnet type solid electrolyte material;
the garnet type solid electrolyte material is a lithium-containing fast ion conductor material with a cubic phase garnet crystal structure and the component is Li6.5La3Zr1.5Nb0.5O12(ii) a The soluble salt of lithium is nitrate, citrate, acetate or alkoxide; the nano garnet type solid electrolyteThe material is in a lamellar structure, each garnet lamellar is composed of ultrafine nanoparticles, and the size of each nanoparticle is 10-30 nanometers;
the low-temperature heat treatment means that the obtained garnet precursor is subjected to heat treatment at the temperature of 500-900 ℃ for 0.5-10 hours in the air or oxygen or nitrogen or helium atmosphere, if the air or oxygen atmosphere is used, the nano garnet-type solid electrolyte material can be obtained after the heat treatment at the temperature of 500-900 ℃ for 0.5-10 hours, and if the nitrogen or helium atmosphere is used, the nano garnet-type solid electrolyte material can be obtained after the heat treatment at the temperature of 500-900 ℃ for 0.5-10 hours in the air or oxygen atmosphere and then the nano template material is removed after the heat treatment at the temperature of 400-600 ℃ for 2-10 hours in the air or oxygen atmosphere.
2. The method of producing a nano garnet-type solid electrolyte material as set forth in claim 1, characterized in that: the organic solvent is ethanol.
3. The method of producing a nano garnet-type solid electrolyte material as set forth in claim 1, characterized in that: the pH value is adjusted by dripping alkaline solution into mixed solution of garnet metal ions and graphene oxide or graphene.
4. The method of producing a nano garnet-type solid electrolyte material as set forth in claim 3, characterized in that: the alkaline solution is ammonia water or lithium hydroxide or sodium hydroxide or potassium hydroxide or ammonium bicarbonate solution.
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