CN114773051A - Improved sol-gel method for preparing alpha-phase LiZr2(PO4)3Method for producing solid electrolyte - Google Patents
Improved sol-gel method for preparing alpha-phase LiZr2(PO4)3Method for producing solid electrolyte Download PDFInfo
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Abstract
The invention discloses an improved sol-gel method for preparing alpha-phase LiZr2(PO4)3A method of solid electrolyte relates to the field of solid electrolyte material. The method comprises the following steps: dissolving zirconium acetylacetonate in an ethanol water solution to obtain a solution A, and dissolving lithium salt and phosphate in water to obtain a solution B; adding the solution B into the solution A to obtain white gel; drying the white gel to obtain white xerogel; grinding the white xerogel, and calcining at the temperature of 700-950 ℃ to obtain the alpha-phase LiZr2(PO4)3A powder material; and tabletting and sintering the powder material to obtain the solid electrolyte ceramic chip. The invention adopts the ethanol water solution as the reaction solvent, simplifies the operation steps, reduces the consumption of resources, does not need to heat the powder material to 1200 ℃ or above, has lower requirement on heating equipment, can carry out large-scale mass production, and simultaneously has uniform particle size and good crystallinity of the obtained powder material.
Description
Technical Field
The invention relates to the field of solid electrolyte materials, in particular to an improvementSol-gel method for preparing alpha-phase LiZr2(PO4)3A method of making a solid electrolyte.
Background
The development of lithium ion batteries with high energy density, high safety and long cycle life is a research focus in the energy field in recent years. The existing lithium ion battery adopting liquid electrolyte still has the contradiction of difficult reconciliation between high energy density and high safety. The solid-state battery adopting the solid electrolyte not only can effectively solve the problem of battery safety, but also can improve the energy density and cycle life of the battery. The development of suitable solid electrolytes is therefore of great importance.
One of the most potential solid electrolytes is now NASICON material, originally referred to as fast ion conductor Na1+ xZr2SixP3-xO12(0<x<3) Later, the crystal structure is considered to have a three-dimensional framework formed by connecting tetrahedrons and transition metal octahedrons in a common vertex mode in a generalized way, and the pores of the framework are filled with Li+、Na+Or K+The materials of the plasma are all NASICON type materials. Of the lithium-based NASICON-type solid electrolyte materials, LiM has been the most studied2(PO4)3(M ═ Ti, Ge, Zr, etc.), but when M is Ti and Ge, elemental valence change or structural pulverization occurs when the corresponding material is brought into contact with a metallic lithium negative electrode, and the actual requirement has not been satisfied. In contrast, LiZr with stable element valence2(PO4)3Become a hot research point in the field of solid electrolytes. LiZr2(PO4)3Has four different crystal phases, namely alpha phase (R-3C space group), alpha 'phase (C-1 space group), beta phase (Pbna space group) and beta' phase (P2)1N space group), in which only the alpha phase of the R-3c space group has a higher ion conductivity [ Nomura, K, et al, Solid State Ionics,1993,61(4), 293-; arbi, K.et al, Journal of Materials Chemistry,2002,12(10), 2985-.]. Reported alpha phase LiZr2(PO4)3The preparation of the powder material needs high-temperature sintering at 1200 ℃ and above, and the important practical application of reducing the sintering temperature and obtaining the alpha crystal phase product with uniform grain diameter is realizedAnd (4) value.
The preparation of alpha-phase LiZr reported in the literature at present2(PO4)3The powder method mainly comprises a high-temperature solid phase method, a sol-gel method, an ion exchange technology and the like, wherein the high-temperature solid phase method is simple in process and suitable for synthesis of samples in large batches, the materials are easily mixed unevenly, and the obtained powder easily contains impurity phases and is poor in particle size uniformity, so that the performance of the material is influenced; the powder obtained by the traditional sol-gel method has uniform particle size and better performance, but the method is only suitable for synthesizing small-batch samples, and meanwhile, the operation is complex, and a large amount of organic reagents such as citric acid, glycol and the like are used as complexing agents and solvents, so that the consumption of resources is increased, and the large-scale application of the complexing agents and the solvents is limited; the ion exchange technique refers to the replacement of NaZr by molten lithium salt2(PO4)3The method is only suitable for laboratory-level preparation research with extremely small amount of Na ions. Although the above-mentioned synthesis methods have advantages, the most important disadvantage is that the obtained precursor is treated at 1200 ℃ and above to obtain LiZr with alpha crystal phase2(PO4)3Otherwise, the powder can obtain other three crystalline phase products, which has higher requirements on synthesis equipment and increases the energy consumption.
Disclosure of Invention
The invention provides an improved sol-gel method for preparing alpha-phase LiZr2(PO4)3The solid electrolyte method aims to solve the technical problems of overhigh synthesis temperature and nonuniform grain diameter in the traditional synthesis method.
In order to solve the technical problems, the invention improves the traditional sol-gel method, and compared with the traditional sol-gel method, the invention is characterized in that: zirconium acetylacetonate is used as a zirconium source; ethanol water solution is used as a reaction solvent. The invention simplifies the operation steps, reduces the consumption of resources, ensures that the temperature of the synthesized powder material does not need to be heated to 1200 ℃ or above, has lower requirements on heating equipment, and can carry out large-scale mass production. The powder material obtained by the invention has uniform particle size and good crystallinity, and the obtained solid electrolyte ceramic chip has high density and good ionic conductivity.
The invention comprises the following steps:
(1) dissolving zirconium acetylacetonate in an aqueous solution of ethanol, heating and stirring to obtain a solution A, and dissolving lithium salt and phosphate in water together to obtain a solution B;
(2) adding the solution B into the solution A under the condition of heating and stirring to obtain white gel;
(3) continuously heating and stirring the white gel, and then drying to obtain white xerogel;
(4) grinding the white xerogel into powder, and calcining for 10h-16h at 700-950 ℃ to obtain alpha-phase LiZr2(PO4)3A powder material;
(5) pressing the powder material into a blank and sintering to obtain the alpha-LiZr2(PO4)3A solid electrolyte ceramic sheet.
Preferably, in step (1), the molar ratio of water to ethanol in the ethanol aqueous solution is 1: (2-4).
Preferably, in the step (1), the lithium salt is one or more of lithium nitrate, lithium acetate, lithium oxalate and lithium hydroxide; the phosphate is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate and phosphoric acid.
Preferably, in the step (1), the mass fraction of zirconium acetylacetonate in the solution a is 20% -30%, and the total mass of solute in the solution B is 20% -50%.
Preferably, in step (1), the ratio of lithium salt to phosphate is (1-1.1) in the total stoichiometric ratio of Li to P: 3, weighing in proportion; in step (2), solution B was weighed to add to solution a in a total stoichiometric ratio of Li: Zr: P (1-1.1):2: 3.
As a preferred scheme, in the steps (1) and (2), the heating temperature is 60-90 ℃, and the stirring speed is 500-1000 r/min; in the step (3), the heating temperature is 70-120 ℃, the stirring speed is 400-900 r/min, and the heating and stirring time is 2-5 h; the drying temperature is 90-120 ℃, and the drying time is 5-12 h.
Preferably, in step (4), the white xerogel is subjected to a heat treatment at 400 ℃ for 5h before being calcined.
Preferably, in the step (5), the tabletting pressure is 400MPa for 100-.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
1. in the aspect of synthesizing raw materials, the raw materials such as citric acid, ammonia water and glycol which are commonly used in the traditional sol-gel method are removed, the mixed solution of water and ethanol is used as a reaction solvent, the operation steps are simplified, the cost is reduced, the resource consumption is reduced, the system is in a gel state after the reaction, the raw materials are mixed at a molecular or atomic level, and the mixing is more uniform; meanwhile, organic zirconium acetylacetonate is used as a zirconium source, the self hydrolysis characteristic and the lower decomposition temperature of the zirconium source are favorable for mixing and reacting raw materials, and a product with uniform particle size can be obtained while the reaction temperature is reduced.
2. The invention obtains alpha crystal phase LiZr2(PO4)3The synthesis temperature of the powder material is 700-950 ℃, the powder material does not need to be heated to 1200 ℃ or above, the requirement on heating equipment is low, large-scale preparation can be carried out, the sample yield is high, the needed synthesis equipment is simple and easy to obtain, and the obtained material has uniform particle size and good crystallinity. The solid electrolyte ceramic sheet obtained by sintering the obtained powder material has high density and good ionic conductivity. The solid electrolyte prepared based on the method is suitable for the field of solid batteries, and can be applied to energy storage equipment, electric automobiles, electric tools and the like.
Drawings
FIG. 1-photograph of white gel obtained in step (3) in the first example of the present invention;
FIG. 2-LiZr obtained in example one of the present invention2(PO4)3X-ray powder diffractogram of (a);
FIG. 3-LiZr obtained in example one of the present invention2(PO4)3Scanning electrode for powder materialTaking a mirror picture;
FIG. 4-LiZr obtained in example one of the present invention2(PO4)3Ac impedance spectrum of solid electrolyte;
FIG. 5-LiZr obtained in example two of the present invention2(PO4)3X-ray powder diffractogram of (a);
FIG. 6-LiZr obtained in example III of the invention2(PO4)3X-ray powder diffractogram of (a);
FIG. 7-LiZr obtained in example four of the present invention2(PO4)3X-ray powder diffraction pattern of (a).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Example one
Improved sol-gel method for preparing alpha-phase LiZr2(PO4)3A method of solid state electrolyte comprising the steps of:
(1) mixing water and ethanol according to a molar ratio of 1:3, adding zirconium acetylacetonate into the aqueous solution of ethanol, heating and stirring to dissolve the zirconium acetylacetonate, wherein the heating temperature is 80 ℃, and the stirring speed is 600 r/min to obtain a light yellow transparent solution A, and the mass fraction of the zirconium acetylacetonate is 25%;
(2) dissolving lithium nitrate and ammonium dihydrogen phosphate into deionized water according to the total stoichiometric ratio of Li to P of 1.1:3 to obtain a solution B, wherein the total mass fraction of solute is 50%;
(3) taking a proper amount of solution B according to the proportion of Li to Zr to P being 1.1 to 2 to 3, adding the solution B into the solution A under the condition of heating and stirring to obtain white gel, wherein the heating temperature and the stirring speed are the same as those in the step 1;
(4) continuously heating the obtained white gel and stirring for 4 hours at the heating temperature of 115 ℃ and the stirring speed of 500 r/min, and then drying the white gel in a forced air drying oven at the temperature of 120 ℃ for 5 hours to obtain white xerogel;
(5) grinding the white xerogel into powder, carrying out preheating treatment for 5 hours at 400 ℃, directly heating to 700 ℃ and calcining for 12 hours to obtain pure NASICON alpha-phase LiZr2(PO4)3A powder material;
(6) pressing the powder material under 400MPa to form a circular blank with the diameter of 10mm and the thickness of 2mm, and sintering the blank at 1200 ℃ for 6h to obtain the solid electrolyte ceramic chip. Performing AC impedance test on the ceramic wafer by using an electrochemical workstation, as shown in FIG. 4, with a test frequency range of 10Hz-1MHz, and a total conductivity of the obtained ceramic wafer of 4.9 × 10-6S/cm。
FIG. 2 shows the prepared alpha-phase LiZr2(PO4)3The X-ray powder diffraction pattern of the powder material shows that the obtained material has a rhombohedral phase crystal structure with a space group of R-3c, namely alpha-phase LiZr2(PO4)3Meanwhile, the peak shape of the diffraction peak is sharp, which shows that the crystallinity of the material is good. FIG. 3 shows the prepared alpha-phase LiZr2(PO4)3The scanning electron microscope photo of the powder material can see that the powder has uniform particle size and the particles are in a nanometer level.
Example two
Improved sol-gel method for preparing alpha-phase LiZr2(PO4)3A method of solid state electrolyte comprising the steps of:
(1) mixing water and ethanol according to a molar ratio of 1:2, then adding zirconium acetylacetonate into the aqueous solution of ethanol, heating and stirring to dissolve the zirconium acetylacetonate, wherein the heating temperature is 90 ℃, and the stirring speed is 1000 r/min, so as to obtain a light yellow transparent solution A, and the mass fraction of the zirconium acetylacetonate is 30%;
(2) dissolving lithium acetate and lithium dihydrogen phosphate into deionized water according to the total stoichiometric ratio of Li to P of 1.05:3 to form a solution B, wherein the total mass fraction of solute is 30%;
(3) taking a proper amount of solution B according to the proportion of Li to Zr to P being 1.05 to 2 to 3, adding the solution B into the solution A under the condition of heating and stirring to obtain white gel, wherein the heating temperature and the stirring speed are the same as those in the step 1;
(4) continuously heating the obtained white gel and stirring for 5 hours at the heating temperature of 120 ℃ at the stirring speed of 900 r/min, and then drying the white gel in a forced air drying oven at the temperature of 120 ℃ for 12 hours to obtain white xerogel;
(5) grinding the white xerogel into powder, pretreating at 400 ℃ for 5 hours, directly heating to 800 ℃ and calcining for 16 hours to obtain pure NASICON alpha-phase LiZr2(PO4)3A powder material;
(6) pressing the powder material under 150MPa to form a circular blank with the diameter of 16mm and the thickness of 1mm, and sintering the blank at 1150 ℃ for 10h to obtain the solid electrolyte ceramic chip. Performing AC impedance test on the ceramic wafer by using an electrochemical workstation, wherein the test frequency range is 10Hz-1MHz, and the total conductivity of the obtained ceramic wafer is 3 multiplied by 10-6 S/cm。
FIG. 5 shows the alpha-phase LiZr prepared in example two2(PO4)3The X-ray powder diffraction pattern of the powder material shows that the obtained material is alpha-phase LiZr2(PO4)3Meanwhile, the peak shape of the diffraction peak is sharp, which shows that the crystallinity of the material is good.
EXAMPLE III
Improved sol-gel method for preparing alpha-phase LiZr2(PO4)3A method of solid state electrolyte comprising the steps of:
(1) mixing water and ethanol according to a molar ratio of 1: 4, adding zirconium acetylacetonate into the ethanol aqueous solution, heating and stirring to dissolve the zirconium acetylacetonate at the heating temperature of 60 ℃ and the stirring speed of 500 r/min to obtain a light yellow transparent solution A, wherein the mass fraction of the zirconium acetylacetonate is 20%;
(2) dissolving lithium hydroxide and phosphoric acid into deionized water together according to the total stoichiometric ratio of Li to P of 1:3 to form a solution B, wherein the total mass fraction of solute is 20%;
(3) taking a proper amount of solution B according to the proportion of Li to Zr to P being 1 to 2 to 3, adding the solution B into the solution A under the condition of heating and stirring to obtain white gel, wherein the heating temperature and the stirring speed are the same as those in the step 1;
(4) continuously heating the obtained gel and stirring for 2 hours at the heating temperature of 70 ℃ at the stirring speed of 400 r/min, and then drying the gel in a forced air drying oven at the temperature of 90 ℃ for 5 hours to obtain white xerogel;
(5) grinding the white xerogel into powder, pretreating at 400 ℃ for 5 hours, directly heating to 950 ℃ and calcining for 10 hours to obtain pure NASICON alpha-phase LiZr2(PO4)3A powder material;
(6) pressing the powder material into a circular blank with the diameter of 13mm and the thickness of 0.8mm under 100MPa, and sintering the blank at 1000 ℃ for 12h to obtain the solid electrolyte ceramic chip. Performing AC impedance test on the ceramic wafer by using an electrochemical workstation, wherein the test frequency range is 10Hz-1MHz, and the total conductivity of the obtained ceramic wafer is 1.9 multiplied by 10-6S/cm。
FIG. 6 shows the alpha-phase LiZr prepared in example III2(PO4)3X-ray powder diffraction pattern of the powder material shows that the obtained material is alpha-phase LiZr2(PO4)3Meanwhile, the peak shape of the diffraction peak is sharp, which shows that the crystallinity of the material is good.
Example four
Improved sol-gel method for preparing alpha-phase LiZr2(PO4)3A method of solid state electrolyte comprising the steps of:
(1) mixing water and ethanol according to a molar ratio of 1:3, adding zirconium acetylacetonate into the aqueous solution of ethanol, heating and stirring to dissolve the zirconium acetylacetonate, wherein the heating temperature is 85 ℃, and the stirring speed is 400 r/min, so as to obtain a light yellow transparent solution A, wherein the mass fraction of the zirconium acetylacetonate is 20%;
(2) dissolving lithium oxalate and diammonium phosphate in deionized water according to the total stoichiometric ratio of Li to P of 1:3 to form a solution B, wherein the total mass fraction of solute is 20%;
(3) taking a proper amount of solution B according to the proportion of Li to Zr to P being 1 to 2 to 3, adding the solution B into the solution A under the condition of heating and stirring to obtain white gel, wherein the heating temperature and the stirring speed are the same as those in the step 1;
(4) continuously heating the obtained gel and stirring for 2 hours at the heating temperature of 100 ℃ and the stirring speed of 400 r/min, and then drying the gel in a forced air drying oven at the temperature of 115 ℃ for 5 hours to obtain white xerogel;
(5) grinding the white xerogel into powder, pretreating at 400 ℃ for 5 hours, directly heating to 850 ℃ and calcining for 10 hours to obtain pure NASICON alpha-phase LiZr2(PO4)3A powder material;
(6) pressing the powder material into a circular blank with the diameter of 13mm and the thickness of 1.5mm under 100MPa, and sintering the blank at 1200 ℃ for 8h to obtain the solid electrolyte ceramic chip. Performing AC impedance test on the ceramic wafer by using an electrochemical workstation, wherein the test frequency range is 10Hz-1MHz, and the total conductivity of the obtained ceramic wafer is 3.9 multiplied by 10-6S/cm。
FIG. 7 shows the alpha-phase LiZr prepared in example four2(PO4)3X-ray powder diffraction pattern of the powder material shows that the obtained material is alpha-phase LiZr2(PO4)3Meanwhile, the peak shape of the diffraction peak is sharp, which shows that the crystallinity of the material is good.
The above-mentioned embodiments are provided to further explain the objects, technical solutions and advantages of the present invention in detail, and it should be understood that the above-mentioned embodiments are only examples of the present invention and are not intended to limit the scope of the present invention. It should be understood that any modifications, equivalents, improvements and the like, which come within the spirit and principle of the invention, may occur to those skilled in the art and are intended to be included within the scope of the invention.
Claims (10)
1. Improved sol-gel method for preparing alpha-phase LiZr2(PO4)3A method of producing a solid electrolyte, comprising the steps of:
(1) dissolving zirconium acetylacetonate in an aqueous solution of ethanol, heating and stirring to obtain a solution A, and dissolving lithium salt and phosphate in water together to obtain a solution B;
(2) adding the solution B into the solution A under the condition of heating and stirring to obtain white gel;
(3) continuously heating and stirring the white gel, and then drying to obtain white xerogel;
(4) grinding the white xerogel into powder, and calcining for 10-16 h at 700-950 ℃ to obtain alpha-phase LiZr2(PO4)3A powder material;
(5) pressing the powder material into a blank and sintering to obtain the alpha-LiZr2(PO4)3A solid electrolyte ceramic sheet.
2. The method according to claim 1, wherein in the step (1), the molar ratio of water to ethanol in the aqueous ethanol solution is 1: (2-4).
3. The method according to claim 1, wherein in the step (1), the lithium salt is one or more of lithium nitrate, lithium acetate, lithium oxalate and lithium hydroxide; the phosphate is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate and phosphoric acid.
4. The method according to claim 1, wherein in the step (1), the mass fraction of zirconium acetylacetonate in the solution a is 20% to 30%, and the total mass of solutes in the solution B is 20% to 50%.
5. The production method according to claim 1, wherein in the step (1), the ratio of the lithium salt to the phosphate is (1-1.1): 3, weighing in proportion; in step (2), solution B was weighed to add to solution a in a total stoichiometric ratio of Li: Zr: P (1-1.1):2: 3.
6. The preparation method according to claim 1, wherein in steps (1) and (2), the heating temperature is 60 ℃ to 90 ℃, and the stirring rotation speed is 500 rpm to 1000 rpm; in the step (3), the heating temperature is 70-120 ℃, the stirring speed is 400-900 r/min, and the heating and stirring time is 2-5 h; the drying temperature is 90-120 ℃, and the drying time is 5-12 h.
7. The method according to claim 1, wherein in the step (4), the white xerogel is subjected to a heat treatment at 400 ℃ for 5 hours before being calcined.
8. The preparation method as claimed in claim 1, wherein in step (5), the tabletting pressure is 400MPa for 100-.
9. An alpha-phase LiZr prepared by the modified sol-gel method as claimed in any one of claims 1 to 82(PO4)3A solid electrolyte.
10. The alpha-phase LiZr as claimed in claim 92(PO4)3The application of solid electrolyte in the field of solid batteries.
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