CN114804055A - Solid electrolyte with high density and small size and preparation method thereof - Google Patents
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000499 gel Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000011240 wet gel Substances 0.000 claims abstract description 12
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000007605 air drying Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000002431 foraging effect Effects 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 17
- 150000001768 cations Chemical class 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims 2
- 229910052744 lithium Inorganic materials 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910003480 inorganic solid Inorganic materials 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910012465 LiTi Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
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Abstract
The invention relates to the field of solid electrolyte materials of lithium ion batteries as new energy sources, in particular to a preparation method of a solid electrolyte with high density and small size, which comprises the following steps: s0, adding butyl titanate into absolute ethyl alcohol, uniformly stirring to obtain a solution A, and dissolving citric acid into deionized water to obtain a solution B; slowly dripping the solution A into the solution B to obtain a solution C, and uniformly stirring until the solution C is clear; sequentially adding lithium nitrate, aluminum nitrate and phosphoric acid into the solution C, adjusting the pH, stirring in a water bath at 30 ℃ for 4 hours to obtain uniform white gel, and placing the uniform white gel at 30 ℃ for aging; aging for 24 hours, stirring the white gel in a water bath at 90 ℃ for 8 hours to obtain wet gel, and drying the wet gel in an air drying oven at 150 ℃ for 4 hours to obtain yellow dry gel; the yellow xerogel is put into a tube furnaceSintering is carried out to obtain Li under certain sintering temperature and atmosphere 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 A solid electrolyte powder.
Description
Technical Field
The invention relates to the field of solid electrolyte materials of new energy lithium ion batteries, in particular to a solid electrolyte with high density and small size and a preparation method thereof.
Background
In modern society, rechargeable lithium ion batteries are widely used in power fields such as portable electronic devices, electric vehicles, and large-scale energy storage power stations due to their advantages of light weight, high energy density, and low environmental pollution. With the change of energy structures and the update of large-scale electrical equipment, lithium ion batteries undoubtedly bring great changes and convenience to the lives of people, but meanwhile, the adoption of liquid electrolytes in lithium ion batteries has serious safety problems, such as leakage of the liquid electrolytes and occurrence of fire or even explosion caused by thermal runaway when the batteries are in high temperature, short circuit, poor operation and physical damage. Therefore, there is an urgent need to improve the safety performance of lithium ion batteries for longer and more widespread applications. At present, the development of an all-solid lithium ion battery assembled with a solid electrolyte instead of a liquid electrolyte is an effective approach to solve the safety problem. It is important to prepare a high-performance solid electrolyte.
The solid electrolyte is divided into an organic polymer solid electrolyte and an inorganic solid electrolyte, and the organic polymer solid electrolyte has a narrow electrochemical window and low ionic conductivity, which limits the application of the organic polymer solid electrolyte in the lithium ion battery to a great extent. The inorganic solid electrolyte has the advantages of high thermal stability, high electrochemical stability, good electronic insulation performance, high ionic conductivity, wide electrochemical window, large working temperature range and the like, and is the first choice for solving the safety problem of the lithium ion battery. Inorganic solid electrolytes are classified into sulfide solid electrolytes, halide solid electrolytes, and oxide solid electrolytes, wherein the oxide solid electrolytes include perovskite-type (perovskite-type), anti-perovskite-type (anti-perovskite-type), garnet-type (garnet-type), and sodium fast ion-type (NASICON-type), and the like. LiTi in NASICON-type solid electrolytes 2 (PO 4 ) 3 Because of simple preparation method, low material cost and good stability in water and air, especially when LiTi is used 2 (PO 4 ) 3 Part of Ti in (1) 4+ Is covered with Al 3+ After substitution, form Li 1+x Al x Ti 2-x (PO 4 ) 3 (LATP) has a high ionic conductivity (10) -4 -10 -3 S cm -1 ) And is considered as the most promising solid electrolyte by extensive researchers.
The conventional methods for synthesizing the solid electrolyte comprise a solid-phase synthesis method and a sol-gel method, wherein the solid-phase synthesis method is more suitable for mass production, but the prepared solid electrolyte contains impurities and defects, so that the electrochemical performance of the solid electrolyte is greatly weakened. The sol-gel method can further mix the raw materials at an atomic or molecular level, and synthesize the high-crystallization LATP solid electrolyte with uniformly distributed particles at a lower sintering temperature. However, the LATP solid electrolyte synthesized at present has lower density and larger size, which has more limitation to the application of the solid electrolyte. Therefore, the preparation of the solid electrolyte with higher density and smaller size is particularly important for the development of solid batteries.
Disclosure of Invention
In order to solve the technical problems, the invention provides a solid electrolyte with high density and small size, and the electrochemical performance of the solid electrolyte is improved.
The invention also provides a preparation method of the solid electrolyte with high density and small size, which has simple process and simple and convenient operation.
The invention adopts the following technical scheme:
a preparation method of a solid electrolyte with high density and small size comprises the following steps:
s0, adding butyl titanate into absolute ethyl alcohol, uniformly stirring to obtain a solution A, and dissolving citric acid into deionized water to obtain a solution B;
s1, slowly dripping the solution A into the solution B to obtain a solution C, and uniformly stirring until the solution C is clear;
s2, sequentially adding lithium nitrate, aluminum nitrate and phosphoric acid into the solution C, adjusting the pH, stirring in a water bath at 30 ℃ for 4 hours to obtain uniform white gel, and placing the uniform white gel at 30 ℃ for aging;
s3, aging for 24 hours, stirring the white gel in a water bath at 90 ℃ for 8 hours to obtain wet gel, and drying the wet gel in a forced air drying oven at 150 ℃ for 4 hours to obtain yellow dry gel;
s4, sintering the yellow xerogel in a tubular furnace to obtain Li at a certain sintering temperature and in a certain atmosphere 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 A solid electrolyte powder.
In a further improvement of the above technical solution, in the steps S0 and S2, the concentration of the cation in the butyl titanate, the lithium nitrate, the aluminum nitrate, the phosphoric acid, the absolute ethyl alcohol and the citric acid is 0.2mol/L, and the concentration of the cation is expressed as C [ Li [ + +Ti 4+ +Al 3+ ]。
The technical proposal is further improved by that the C [ Li ] + +Ti 4+ +Al 3+ ]Is 0.2 mol/L.
The technical proposal is further improved in that the concentration ratio of the cations to the absolute ethyl alcohol plus citric acid is 1: 1, i.e. C [ Li ] + +Ti 4+ +Al 3+ ]: c [ absolute ethyl alcohol + citric acid ]]＝1:1。
The technical proposal is further improved in that the concentration ratio of the absolute ethyl alcohol to the citric acid is 1: 1.
in a further improvement of the above technical solution, in the step S2, the method for adjusting pH is to add NH 3 ·H 2 O to adjust the pH.
The technical proposal is further improved in that the pH value is 7.
In a further improvement of the above technical solution, in step S4, the sintering specifically includes: firstly heating to 500 ℃ at a heating rate of 2 ℃/min under a nitrogen atmosphere for pyrolysis for 4 hours, then heating to 750-plus-one 950 ℃ at a heating rate of 1 ℃/min for heat preservation for 2 hours, finally heating to 750-plus-one 950 ℃ at a heating rate of 2 ℃/min under an air atmosphere for heat preservation for 2 hours after cooling, and naturally cooling.
A solid electrolyte with high density and small size is prepared by the preparation method.
The further improvement of the technical proposal is that,the solid electrolyte with high density and small size is made of TiO 6 Octahedron and PO 4 The regular tetrahedrons form a three-dimensional diamond network structure by using shared oxygen atoms as vertexes.
The invention has the beneficial effects that:
lithium nitrate, aluminum nitrate, butyl titanate and phosphoric acid are used as raw materials by a sol-gel method, absolute ethyl alcohol is used as a surfactant, citric acid is used as a chelating agent, and the LATP solid electrolyte with high density and small size is obtained by sintering in the atmosphere of nitrogen and air. Wherein metal cations in the raw material are uniformly captured in a polymer network formed by esterification of citric acid and absolute ethyl alcohol, so that the local stoichiometric number can be maintained, when the xerogel is sintered in a nitrogen atmosphere, the polymer is carbonized, the polymer disperses LATP particles and inhibits the growth of the LATP particles, and the particles are prevented from being contacted with each other to aggregate, so that solid electrolyte powder with smaller size and higher density can be formed. On the other hand, the densification combination among the crystal grains is beneficial to the conduction of lithium ions at the crystal boundary, so that the aim of improving the ionic conductivity is fulfilled, and the electrochemical performance of the solid electrolyte is further improved.
Drawings
Fig. 1 is a preparation technical route diagram of the preparation method of the solid electrolyte with high density and small size according to the invention;
FIG. 2 is an XRD pattern of the material prepared by the method for preparing the solid electrolyte with high density and small size according to the invention at different sintering temperatures;
fig. 3 is XRD patterns of a sintered sample at 850 ℃ in the example of the method for preparing a solid electrolyte having high density and small size according to the present invention and a sintered sample at 850 ℃ in the comparative example.
Fig. 4 is SEM images of a sintered sample at 850 ℃ in the example of the method for producing a solid electrolyte having high density and small size according to the present invention and a sintered sample at 850 ℃ in the comparative example.
Detailed Description
The invention will now be further illustrated by reference to specific examples, which are intended to be illustrative of the invention and are not intended to be a further limitation of the invention.
As shown in fig. 1, a method for preparing a solid electrolyte with high density and small size includes the following steps:
s0, adding butyl titanate into absolute ethyl alcohol, uniformly stirring to obtain a solution A, and dissolving citric acid into deionized water to obtain a solution B;
s1, slowly dripping the solution A into the solution B to obtain a solution C, and uniformly stirring until the solution C is clear;
s2, sequentially adding lithium nitrate, aluminum nitrate and phosphoric acid into the solution C, adjusting the pH, stirring in a water bath at 30 ℃ for 4 hours to obtain uniform white gel, and placing the uniform white gel at 30 ℃ for aging;
s3, aging for 24 hours, stirring the white gel in a water bath at 90 ℃ for 8 hours to obtain wet gel, and drying the wet gel in a forced air drying oven at 150 ℃ for 4 hours to obtain yellow dry gel;
and S4, sintering the yellow xerogel in a tube furnace to obtain LATP solid electrolyte powder at a certain sintering temperature and atmosphere.
Further, in the steps S0 and S2, the concentration of the cation in the butyl titanate, the lithium nitrate, the aluminum nitrate, the phosphoric acid, the absolute ethyl alcohol and the citric acid is 0.2mol/L, and the concentration of the cation is expressed as C [ Li [ ] + +Ti 4+ +Al 3+ ]。
Further, the C [ Li ] + +Ti 4+ +Al 3+ ]Is 0.2 mol/L.
Further, the concentration ratio of the cations to the absolute ethanol plus citric acid is 1: 1, i.e. C [ Li ] + +Ti 4+ +Al 3+ ]: c [ absolute ethyl alcohol + citric acid ]]＝1:1。
Further, the concentration ratio of the absolute ethyl alcohol to the citric acid is 1: 1.
further, in the step S2, the method for adjusting pH is to add NH 3 ·H 2 O to adjust the pH.
Further, the pH value is 7.
Further, in the step S4, the sintering specifically includes: firstly heating to 500 ℃ at a heating rate of 2 ℃/min under a nitrogen atmosphere for pyrolysis for 4 hours, then heating to 750-plus-one 950 ℃ at a heating rate of 1 ℃/min for heat preservation for 2 hours, finally heating to 750-plus-one 950 ℃ at a heating rate of 2 ℃/min under an air atmosphere for heat preservation for 2 hours after cooling, and naturally cooling.
A solid electrolyte with high density and small size is prepared by the preparation method.
Furthermore, the solid electrolyte with high density and small size is made of TiO 6 Octahedron and PO 4 The regular tetrahedrons form a three-dimensional diamond network structure by using shared oxygen atoms as vertexes.
Example (b):
59.042g of butyl titanate is added into 38.9mL of absolute ethyl alcohol and stirred evenly to obtain a solution A, and 127.4g of citric acid is dissolved into 1611mL of deionized water to obtain a solution B;
slowly dripping the solution A into the solution B to obtain a solution C, and uniformly stirring until the solution C is clear;
adding 9.054g of lithium nitrate, 11.367g of aluminum nitrate and 34.588g of phosphoric acid into the solution C in sequence, adding ammonia water to adjust the pH value to 7, stirring in a water bath at normal temperature for 4 hours to obtain uniform white gel, and placing the uniform white gel at room temperature for aging;
stirring the white gel in a water bath at 90 ℃ for 8 hours after 24 hours to obtain wet gel, and drying the wet gel in an air drying oven at 150 ℃ for 4 hours to obtain yellow dry gel;
the yellow dry gel is put into a tube furnace and is firstly heated to 500 ℃ at the heating rate of 2 ℃/min for pyrolysis for 4 hours under the nitrogen atmosphere, then heated to 750-plus-material 950 ℃ at the heating rate of 1 ℃/min for heat preservation for 2 hours, and finally heated to 750-plus-material 950 ℃ at the heating rate of 2 ℃/min for heat preservation for 2 hours under the air atmosphere after cooling, so as to respectively obtain LATP-750, LATP-800, LATP-850, LATP-900 and LATP-950 solid electrolyte powder.
As shown in fig. 2, fig. 2 is an XRD pattern of the prepared solid electrolyte powder at different temperatures.
As shown in FIG. 3, FIG. 3 is an XRD pattern of a sintered sample at 850 ℃ in the example and a sintered sample at 850 ℃ in the comparative example.
Comparative example:
59.042g of butyl titanate is added into 38.9mL of absolute ethyl alcohol and stirred evenly to obtain a solution A, and 127.4g of citric acid is dissolved into 1611mL of deionized water to obtain a solution B;
slowly dripping the solution A into the solution B to obtain a solution C, and uniformly stirring until the solution C is clear;
adding 9.054g of lithium nitrate, 11.367g of aluminum nitrate and 34.588g of phosphoric acid into the solution C in sequence, adding ammonia water to adjust the pH value to 7, stirring in a water bath at normal temperature for 4 hours to obtain uniform white gel, and placing the uniform white gel under 30 ℃ for aging;
stirring the white gel in a water bath at 90 ℃ for 8 hours after 24 hours to obtain wet gel, and drying the wet gel in an air drying oven at 150 ℃ for 4 hours to obtain yellow dry gel;
and (3) putting the yellow xerogel into ｃA tubular furnace, heating to 500 ℃ at ｃA heating rate of 2 ℃/min for pyrolysis for 4 hours under the air atmosphere, then heating to 850 ℃ at ｃA heating rate of 1 ℃/min for heat preservation for 2 hours, and respectively obtaining LATP-A-850 solid electrolyte powder.
As shown in FIG. 4, FIG. 4 is SEM images of a sintered sample at 850 ℃ in the example and a sintered sample at 850 ℃ in the comparative example.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art to which the invention pertains. Therefore, the above examples illustrate the detailed methods of the present invention, but the present invention is not limited to the specific embodiments disclosed and described above, and it is not intended that the present invention be implemented by relying on the above detailed methods, any modifications and variations of the present invention, equivalent substitutions of each raw material of the product of the present invention, addition of auxiliary components, selection of specific embodiments, etc., should also fall within the scope of the claims of the present invention.
Claims (10)
1. A preparation method of a solid electrolyte with high density and small size is characterized by comprising the following steps:
s0, adding butyl titanate into absolute ethyl alcohol, uniformly stirring to obtain a solution A, and dissolving citric acid into deionized water to obtain a solution B;
s1, slowly dripping the solution A into the solution B to obtain a solution C, and uniformly stirring until the solution C is clear;
s2, sequentially adding lithium nitrate, aluminum nitrate and phosphoric acid into the solution C, adjusting the pH, stirring in a water bath at 30 ℃ for 4 hours to obtain uniform white gel, and placing the uniform white gel at 30 ℃ for aging;
s3, aging for 24 hours, stirring the white gel in a water bath at 90 ℃ for 8 hours to obtain wet gel, and drying the wet gel in a forced air drying oven at 150 ℃ for 4 hours to obtain yellow dry gel;
s4, sintering the yellow xerogel in a tubular furnace to obtain Li at a certain sintering temperature and in a certain atmosphere 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 A solid electrolyte powder.
2. The method according to claim 1, wherein the concentration of the cations in the butyl titanate, the lithium nitrate, the aluminum nitrate, the phosphoric acid, the anhydrous ethanol and the citric acid is 0.2mol/L, and the concentration of the cations is expressed as C [ Li, or C ] in the steps S0 and S2 + +Ti 4+ +Al 3+ ]。
3. The method according to claim 2, wherein the C [ Li ] is used to prepare the solid electrolyte with high density and small size + +Ti 4+ +Al 3+ ]Is 0.2 mol/L.
4. The method for preparing a solid electrolyte with high density and small size according to claim 2, wherein the concentration ratio of the cations to the absolute ethyl alcohol plus citric acid is 1: 1, i.e. C [ Li ] + +Ti 4+ +Al 3+ ]: c [ absolute ethyl alcohol + citric acid ]]＝1:1。
5. The method for preparing a solid electrolyte with high density and small size according to claim 4, wherein the concentration ratio of the absolute ethyl alcohol to the citric acid is 1: 1.
6. the method for preparing a solid electrolyte with high density and small size according to claim 1, wherein in the step S2, the method for adjusting pH is to add NH 3 ·H 2 O to adjust the pH.
7. The method for producing a solid electrolyte having high density and small size according to claim 6, wherein the pH is 7.
8. The method for preparing a solid electrolyte with high density and small size according to claim 1, wherein in the step S4, the sintering comprises the following specific steps: firstly heating to 500 ℃ at a heating rate of 2 ℃/min under a nitrogen atmosphere for pyrolysis for 4 hours, then heating to 750-plus-one 950 ℃ at a heating rate of 1 ℃/min for heat preservation for 2 hours, finally heating to 750-plus-one 950 ℃ at a heating rate of 2 ℃/min under an air atmosphere for heat preservation for 2 hours after cooling, and naturally cooling.
9. A solid electrolyte having high density and small size, which is produced by the production method according to any one of claims 1 to 8.
10. The high density small size solid state electrolyte of claim 9, wherein the high density small size solid state electrolyte is made of TiO 6 Octahedron and PO 4 The regular tetrahedrons form a three-dimensional diamond network structure by using shared oxygen atoms as vertexes.
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| CN115312848A (en) * | 2022-10-10 | 2022-11-08 | 山东永浩新材料科技有限公司 | Preparation method of LATP inorganic solid electrolyte material |
| CN115403022A (en) * | 2022-10-17 | 2022-11-29 | 合肥国轩高科动力能源有限公司 | Nanoscale lithium titanium aluminum phosphate material, and preparation method and application thereof |
| CN115966692A (en) * | 2023-01-19 | 2023-04-14 | 重庆长安新能源汽车科技有限公司 | High-load lithium battery negative electrode material, preparation method and application |
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