CN113363564A - Lithium lanthanum zirconium tantalum oxygen solid electrolyte and preparation method and application thereof - Google Patents
Lithium lanthanum zirconium tantalum oxygen solid electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a lithium lanthanum zirconium tantalum oxygen solid electrolyte and a preparation method and application thereof. The method comprises the following steps: mixing a lithium source, a zirconium source, a lanthanum source, a tantalum source, a sintering aid and a first solvent, drying, sintering, mixing the obtained sintered product with a second solvent, and washing with a ceramic membrane to obtain the lithium lanthanum zirconium tantalum oxygen solid electrolyte. The preparation method provided by the invention is used for carrying out high-purity treatment on the lithium lanthanum zirconium tantalum oxygen material prepared in batch, the PH value, the alkali content, the content of magnetic elements such as iron and the like can be effectively reduced, and chloride ions and sulfate ions are effectively removed, so that the material can be directly used in the field of solid-state batteries, and meanwhile, the conductivity of lithium ions is improved, and the improvement of the performance of the solid-state batteries is facilitated.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a lithium lanthanum zirconium tantalum oxygen solid electrolyte, and a preparation method and application thereof.
Background
The large-scale use of conventional fuel-powered automobiles is considered to be one of the causes of the gradual depletion of petroleum resources and the increasing greenhouse effect. In view of the above problems, automobile manufacturers and organizations at home and abroad have been gradually adopting electric automobiles to replace traditional fuel automobiles. Liquid lithium ion batteries are used as the main power source of battery automobiles by automobile manufacturers due to the advantages of high energy density, long cycle life and the like. With the increasing development of the electric automobile industry, the liquid lithium ion battery can not meet the requirements such as mileage requirement, safety requirement and the like. The main reason for the safety problems caused by the problems of ignition and combustion of the conventional electric vehicles equipped with lithium batteries is the use of liquid electrolyte in the lithium batteries.
Solid electrolytes have attracted attention from the electric vehicle industry due to their advantages of high safety and high energy density, as compared to liquid electrolytes. Lithium lanthanum zirconium tantalum oxide of garnet structure in these solid electrolytes has high lithium ion conductivity at room temperature and stability to lithium metal and air, and is considered as a material expected for commercial application. At present, the preparation and research of lithium lanthanum zirconium tantalum oxygen are mainly concentrated in a laboratory, which seriously restricts the progress of the lithium lanthanum zirconium tantalum oxygen in commercialization, and at present, part of enterprises begin to develop batch preparation. There are a number of problems that need to be solved and optimized from gram-scale to batch-scale preparation, including precursor compounding processes, sintering processes, material post-processing, and the like.
For the mass preparation of lithium lanthanum zirconium tantalum oxygen powder by a solid-phase high-temperature sintering method, the problems of slurry gel and low ionic conductivity are caused by the fact that residual impurities such as chloride ions, iron elements and other magnetic impurities are contained on the surface at present, and the subsequent use of the electrolyte material in the field of solid-state batteries is influenced.
CN111211272A discloses a coating diaphragm, coating slurry and a preparation method, wherein the lithium lanthanum zirconium tantalum oxygen in the scheme is prepared by the following method, 1) lithium hydroxide, lanthanum oxide, zirconium oxide and tantalum oxide are added into isopropanol and uniformly dispersed to obtain a mixture A; 2) adding the mixture A into a ball mill for ball milling; 3) drying the ball-milled mixture A, and then grinding; 4) sintering the ground mixture A for 4-6h to obtain sintered powder; 5) cleaning the sintering powder by using a cleaning agent; 6) and after the cleaning is finished, drying at the temperature of 100-120 ℃ for 4-8h to obtain the lithium lanthanum zirconium tantalum oxygen.
CN112289931A discloses a preparation method of a memristor, the memristor and a memory device. The scheme discloses that the method for preparing the LLZTO solid electrolyte comprises the following steps: reacting LiOH & H2O、La2O3、Ta2O5And ZrO2Mixing to obtain lithium lanthanum zirconium tantalum oxygen solid powder; performing ball milling treatment on the lithium lanthanum zirconium tantalum oxygen solid powder; and (3) performing high-temperature treatment on the ball-milled lithium lanthanum zirconium tantalum oxygen solid powder to obtain the LLZTO solid electrolyte.
However, the above methods all have the problem that impurities exist in lithium lanthanum zirconium tantalum oxygen, which affects the subsequent use as a solid electrolyte.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a lithium lanthanum zirconium tantalum oxygen solid electrolyte and a preparation method and application thereof. The method provided by the invention can be used for carrying out high purification treatment on the lithium lanthanum zirconium tantalum oxygen material prepared in batch, so that the material can be directly used in the field of solid-state batteries, and meanwhile, the lithium ion conductivity is improved, which is beneficial to the improvement of the performance of the solid-state batteries.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a lithium lanthanum zirconium tantalum oxygen solid electrolyte, comprising the following steps: mixing a lithium source, a zirconium source, a lanthanum source, a tantalum source, a sintering aid and a first solvent, drying, sintering, mixing the obtained sintered product with a second solvent, and washing with a ceramic membrane to obtain the lithium lanthanum zirconium tantalum oxygen solid electrolyte.
According to the method provided by the invention, the material is purified by ceramic membrane washing (namely, washing by a ceramic membrane washing machine), so that the lithium lanthanum zirconium tantalum oxygen material with ultra-high purity can be obtained, and impurities and powder materials are separated by adopting ceramic membrane tubes with different screening grades and different cleaning solvents, so that the purpose of purification is achieved; meanwhile, the method can be used for continuously treating the material. The method can effectively reduce the content of magnetic elements such as PH value, alkali content and iron, and effectively remove chloride ions and sulfate ions, so that the material can be directly used in the field of solid-state batteries, and meanwhile, the conductivity of lithium ions is improved, which is beneficial to the improvement of the performance of the solid-state batteries.
The lithium lanthanum zirconium tantalum oxygen solid electrolyte obtained by the preparation method provided by the invention can evaluate the washing and purifying effects by testing the conductivity, PH, alkali content, element content and residual organic impurities of lithium ion. The ionic conductivity, PH and hydroxyl and carbonate of the sample can be tested by adopting an EIS method, the magnetic elements such as iron, nickel and zinc can be tested by adopting an ICP method, and the contents of S acid radicals and Cl ions can be tested by adopting an ion chromatograph.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the lithium source includes any one or a combination of at least two of lithium hydroxide, lithium carbonate, lithium oxalate, and lithium nitrate.
Preferably, the zirconium source comprises zirconium oxide or zirconium hydroxide.
Preferably, the lanthanum source comprises lanthanum oxide or lanthanum hydroxide.
Preferably, the tantalum source comprises tantalum oxide or tantalum nitrate.
Preferably, the sintering aid comprises aluminum oxide or aluminum nitrate.
According to a preferable technical scheme of the invention, the mass ratio of the lithium source, the lanthanum source, the zirconium source, the tantalum source and the sintering aid is (18.9-20.4): 2-32): 14.1, (3.6-10.8): 1, such as 20.4:32:14.1:3.6:1, 19.6:32:14.1:7.2:1 or 18.9:2:14.1:10.8: 1.
Preferably, the first solvent comprises any one of isopropanol, n-butanol or ethanol or a combination of at least two thereof.
Preferably, the ratio of the total mass of the lithium source, the zirconium source, the lanthanum source, the tantalum source and the sintering aid to the mass of the first solvent is (0.2-0.8): 1, and preferably 0.5: 1.
Preferably, the method of mixing the lithium source, the zirconium source, the lanthanum source, the tantalum source, the sintering aid, and the first solvent comprises sand mill mixing.
Preferably, the method of drying comprises spray drying.
As a preferred embodiment of the present invention, the sintering temperature is 850-. In the invention, if the sintering temperature is too high, the lithium element can be seriously volatilized to generate a mixed phase; if the sintering temperature is too low, crystallization to a mixed crystal phase of tetragonal phase and cubic phase may occur.
Preferably, the sintering time is 7-9h, such as 7h, 7.5h, 8h, 8.5h, or 9h, etc.
In a preferred embodiment of the present invention, the second solvent includes any one or a combination of at least two of ethanol, isopropanol, N-methylpyrrolidone, N-dimethylformamide, and deionized water.
Preferably, the method of mixing the obtained sintered product with the second solvent is stirring dispersion.
Preferably, the ceramic membrane washing uses ceramic membrane tubes having a pore size of 10-200nm, such as 10nm, 50nm, 100nm, 150nm, or 200 nm. In the invention, if the aperture of the ceramic membrane tube is too large, impurities cannot be effectively removed, and meanwhile, the small particle size in the cleaned powder is cleaned, thus causing waste; if the aperture of the ceramic membrane tube is too small, the cleaning efficiency is low, the aperture is easily blocked, and the use is inconvenient.
Preferably, the mass ratio of the sintered product to the second solvent in the ceramic membrane washing is 20-200, such as 20, 50, 100, 150 or 200. In the invention, if the sintered product is too much relative to the second solvent, the viscosity of the slurry in the cleaning process is too high, and the cleaning becomes difficult; meanwhile, the temperature of the equipment is increased, and the equipment needs to be cooled for reuse; if the second solvent is too much relative to the sintered product, cleaning efficiency may be deteriorated and the second solvent may be wasted.
In the invention, the main means is to separate impurities from powder materials by adopting ceramic membrane tubes with different screening grades and different cleaning solvents such as alcohol, isopropanol, deionized water and the like, thereby achieving the purpose of purification.
Preferably, after the ceramic membrane is washed, drying the purified product obtained after washing is further included.
Preferably, the temperature of the drying is 60-120 ℃, such as 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃ and the like.
Preferably, the drying mode is any one or combination of at least two of vacuum drying, air-blast drying or spray drying.
As a preferred technical scheme of the invention, the method comprises the following steps:
mixing a lithium source, a zirconium source, a lanthanum source, a tantalum source, a sintering aid and a first solvent by sanding, sintering after spray drying, wherein the sintering temperature is 850-950 ℃, the sintering time is 7-9h, stirring and dispersing the obtained sintered product and a second solvent, washing a ceramic membrane, and drying the purified product obtained after washing at 60-120 ℃ to obtain the lithium lanthanum zirconium tantalum oxygen solid electrolyte; the aperture of the ceramic membrane tube used for washing the ceramic membrane is 10-200 nm; the mass ratio of the lithium source to the lanthanum source to the zirconium source to the tantalum source to the sintering aid is (18.9-20.4): 2-32): 14.1: (3.6-10.8): 1.
In a second aspect, the invention provides a lithium lanthanum zirconium tantalum oxygen solid electrolyte obtained by the preparation method of the first aspect.
In a third aspect, the present invention provides a positive electrode sheet with a solid electrolyte, the positive electrode sheet comprising the solid electrolyte according to the second aspect.
Preferably, the thickness of the positive electrode sheet with the solid electrolyte is 30-140 μm, such as 30 μm, 50 μm, 80 μm, 100 μm, 120 μm, 140 μm, or the like.
In a fourth aspect, the present invention provides a method for producing a positive electrode sheet with a solid electrolyte according to the third aspect, the method comprising the steps of:
and dissolving the lithium lanthanum zirconium tantalum oxygen solid electrolyte, the binder and the lithium salt in a third solvent, mixing, coating the obtained mixed slurry on a positive plate, drying, and carrying out hot pressing treatment on the dried product to obtain the positive plate with the solid electrolyte.
In the preparation method of the positive plate with the solid electrolyte, the hot-pressing treatment can be hot rolling.
Preferably, the lithium salt comprises any one of lithium fluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate or lithium dioxalate borate or a combination of at least two thereof.
Preferably, the binder comprises polyvinylidene fluoride.
Preferably, the mass fraction of the lithium salt is 15 to 50 wt%, such as 15 wt%, 20 wt%, 30 wt%, 40 wt%, or 50 wt%, etc., the mass fraction of the lithium lanthanum zirconium tantalum oxygen solid electrolyte is 10 to 60 wt%, such as 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, or 60 wt%, etc., and the mass fraction of the binder is 5 to 20 wt%, such as 5 wt%, 10 wt%, 15 wt%, or 20 wt%, etc., based on 100% of the total mass of the lithium lanthanum zirconium tantalum oxygen solid electrolyte, the binder, and the lithium salt.
Preferably, the third solvent comprises N-methylpyrrolidone.
Preferably, the mixing is stirred mixing.
Preferably, the positive plate is one of a lithium iron phosphate positive plate, a nickel-cobalt-manganese ternary material positive plate or a spinel material positive plate.
Preferably, the thickness of the positive electrode sheet is 20 to 120 μm, such as 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, or 120 μm, and the like.
Preferably, the method of coating is cast coating.
Preferably, the drying is vacuum drying, and the drying temperature is 80-120 ℃, such as 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃ and the like. The vacuum drying may be in a step temperature manner.
Preferably, the temperature of the hot pressing is 50-120 ℃, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃ and the like.
Preferably, the hot pressing pressure is from 10 to 80MPa, such as 10MPa, 20MPa, 30MPa, 40MPa, 50MPa, 60MPa, 70MPa or 80MPa, and the like.
In a fifth aspect, the present invention provides a battery comprising a positive electrode sheet with a solid electrolyte as described in the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention is used for carrying out high-purity treatment on the lithium lanthanum zirconium tantalum oxygen material prepared in batch, the PH value, the alkali content, the content of magnetic elements such as iron and the like can be effectively reduced, and chloride ions and sulfate ions are effectively removed, so that the material can be directly used in the field of solid-state batteries, and meanwhile, the conductivity of lithium ions is improved, and the improvement of the performance of the solid-state batteries is facilitated. The lithium lanthanum zirconium tantalum oxygen solid electrolyte prepared by the method provided by the invention has the pH value as low as 10.8, the hydroxyl mass content as low as 0.22%, the carbonate mass content as low as 0.17%, the iron mass content as low as 140.9ppm, the nickel mass content as low as 52.1ppm, the zinc mass content as low as 10.1ppm, the sodium mass content as low as 10.5ppm, the chlorine ion mass content in a cleaning clear solution as low as 94.2ppm, and the sulfate radical mass content as low as 70.5 ppm.
Drawings
Fig. 1 is a graph of the ion conductivity of the pressed ceramic of the li-la-zr-ta-o solid electrolytes provided in example 1 and comparative example 1.
Fig. 2 is an infrared test curve of the lithium lanthanum zirconium tantalum oxygen solid electrolyte powder provided in example 1 and comparative example 1.
Fig. 3 is a graph showing rate performance of the lithium lanthanum zirconium tantalum oxygen solid electrolyte powders prepared into batteries according to example 1 and comparative example 1.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
This example prepares a lithium lanthanum zirconium tantalum oxygen solid electrolyte as follows:
and (2) sand-milling and mixing a lithium source (lithium hydroxide), a zirconium source (zirconium oxide), a lanthanum source (lanthanum oxide), a tantalum source (tantalum oxide), a sintering aid (aluminum oxide) and a first solvent (isopropanol) (the mass ratio of the lithium source, the lanthanum source, the zirconium source, the tantalum source and the sintering aid is 19.6:32:14.1:7.2:1, the mass ratio of the total mass of the lithium source, the zirconium source, the lanthanum source, the tantalum source and the sintering aid to the mass of the first solvent is 0.5: 1), sintering after spray drying is carried out, the sintering temperature is 900 ℃, the sintering time is 8h, stirring and dispersing the obtained sintered product and a second solvent (ethanol), washing a ceramic membrane for purification (the aperture of the ceramic membrane tube is 50nm, the mass ratio of the sintered product to the second solvent is 50), and carrying out 90 ℃ blast drying on the purified product obtained after washing to obtain the lithium-zirconium-lanthanum-tantalum-oxygen solid electrolyte.
The lithium lanthanum zirconium tantalum oxygen solid electrolyte provided by the embodiment is tested for ionic conductivity, pH, hydroxyl and carbonate by an EIS method, and magnetic elements such as iron, nickel and zinc by ICP method.
Testing the sulfate radical and Cl of the first cleaning clear liquid by an ion chromatograph-Ion content.
The test results are shown in the following table (the percentages and ppm in the table are mass content percentage):
TABLE 1
| Test items | pH | OH-(％) | CO3 2-(％) | Fe(ppm) | Ni(ppm) | Zn(ppm) | Na(ppm) |
| Test data | 10.8 | 0.22 | 0.17 | 140.9 | 52.1 | 10.1 | 10.5 |
TABLE 2
| Test items | Na+(ppm) | Cl-(ppm) | SO4 2-(ppm) | Fe2+(ppm) |
| Test data | 88.5 | 94.2 | 70.5 | 55.1 |
The embodiment also provides a preparation method of the positive plate with the solid electrolyte, which comprises the following steps:
dissolving the lithium lanthanum zirconium tantalum oxygen solid electrolyte prepared in the embodiment, a binder (PVDF) and a lithium salt (lithium fluorophosphate) in a third solvent (NMP), stirring and mixing (based on 100% of the total mass of the lithium lanthanum zirconium tantalum oxygen solid electrolyte, the binder and the lithium salt, the mass fraction of the lithium salt is 40 wt%, the mass fraction of the lithium lanthanum zirconium tantalum oxygen solid electrolyte is 50 wt%, and the mass fraction of the binder is 10 wt%), casting and coating the obtained mixed slurry on a positive plate (a lithium iron phosphate positive plate, the thickness of which is 70 μm), drying in vacuum at 100 ℃, and performing hot pressing treatment at 100 ℃ and 50MPa on the dried product to obtain the positive plate with the solid electrolyte.
Example 2
This example prepares a lithium lanthanum zirconium tantalum oxygen solid electrolyte as follows:
and (2) sand-milling and mixing a lithium source (lithium hydroxide), a zirconium source (zirconium oxide), a lanthanum source (lanthanum oxide), a tantalum source (tantalum oxide), a sintering aid (aluminum oxide) and a first solvent (isopropanol) (the mass ratio of the lithium source, the lanthanum source, the zirconium source, the tantalum source and the sintering aid is 20.4:32:14.1:3.6:1, the mass ratio of the total mass of the lithium source, the zirconium source, the lanthanum source, the tantalum source and the sintering aid to the mass of the first solvent is (0.2:1), sintering after spray drying, the sintering temperature is 850 ℃, the sintering time is 9h, stirring and dispersing a ceramic membrane with a second solvent (N-methylpyrrolidone), washing and purifying (the pore diameter of the ceramic membrane tube is 10nm, the mass ratio of the sintered product to the second solvent is 20), and blowing and drying at 60 ℃ are carried out on the purified product obtained after washing to obtain the lanthanum-lithium-tantalum-zirconium-oxygen solid electrolyte.
The lithium lanthanum zirconium tantalum oxygen solid electrolyte provided by the embodiment is tested for ionic conductivity, pH, hydroxyl and carbonate by an EIS method, magnetic elements such as iron, nickel and zinc by ICP method and sulfate and Cl by an ion chromatograph-Ion content.
The test results are shown in the following table (percentages and ppm in the table are mass fractions):
TABLE 3
| Test items | pH | OH-(％) | CO3 2-(％) | Fe(ppm) | Ni(ppm) | Zn(ppm) | Na(ppm) |
| Test data | 10.7 | 0.2 | 0.18 | 140 | 49 | 9.8 | 10.2 |
TABLE 4
| Test items | Na+(ppm) | Cl-(ppm) | SO4 2-(ppm) | Fe2+(ppm) |
| Test data | 86.5 | 94.5 | 71 | 52.8 |
The embodiment also provides a preparation method of the positive plate with the solid electrolyte, which comprises the following steps:
dissolving the lithium lanthanum zirconium tantalum oxygen solid electrolyte prepared in the embodiment, a binder (PVDF) and a lithium salt (lithium fluorophosphate) in a third solvent (NMP), stirring and mixing (based on 100% of the total mass of the lithium lanthanum zirconium tantalum oxygen solid electrolyte, the binder and the lithium salt, the mass fraction of the lithium salt is 50 wt%, the mass fraction of the lithium lanthanum zirconium tantalum oxygen solid electrolyte is 45 wt%, and the mass fraction of the binder is 5 wt%), casting and coating the obtained mixed slurry on a positive plate (a lithium iron phosphate positive plate, the thickness of which is 20 μm), drying the positive plate in vacuum at 80 ℃, and performing hot pressing treatment at 50 ℃ and 80MPa on the dried product to obtain the positive plate with the solid electrolyte.
Example 3
This example prepares a lithium lanthanum zirconium tantalum oxygen solid electrolyte as follows:
mixing a lithium source (lithium hydroxide), a zirconium source (zirconium oxide), a lanthanum source (lanthanum oxide), a tantalum source (tantalum oxide), a sintering aid (aluminum oxide) and a first solvent (isopropanol) in a sand grinding mode (the mass ratio of the lithium source to the lanthanum source to the zirconium source to the tantalum source to the sintering aid is 18.9:2:14.1:10.8:1, the mass ratio of the total mass of the lithium source to the zirconium source to the lanthanum source to the tantalum source to the sintering aid to the mass of the first solvent is 0.7:1), sintering after spray drying, wherein the sintering temperature is 950 ℃, the sintering time is 7h, stirring, dispersing and washing and purifying an obtained sintering product and a second solvent (isopropanol and N, N-dimethylformamide in a mass ratio of 1: 1) (the pore diameter of a ceramic membrane tube is 200nm, and the mass ratio of the sintering product to the second solvent is 200), and (3) drying the purified product obtained after washing at 120 ℃ in vacuum to obtain the lithium lanthanum zirconium tantalum oxygen solid electrolyte.
The lithium lanthanum zirconium tantalum oxygen solid electrolyte provided by the embodiment is tested for ionic conductivity, pH, hydroxyl and carbonate by an EIS method, magnetic elements such as iron, nickel and zinc by ICP method and sulfate and Cl by an ion chromatograph-Ion content.
The test results are shown in the following table (percentages and ppm in the table are mass fractions):
TABLE 5
| Test items | pH | OH-(％) | CO3 2-(％) | Fe(ppm) | Ni(ppm) | Zn(ppm) | Na(ppm) |
| Test data | 10.5 | 0.18 | 0.21 | 133.8 | 46 | 10.2 | 10.1 |
TABLE 6
| Test items | Na+(ppm) | Cl-(ppm) | SO4 2-(ppm) | Fe2+(ppm) |
| Test data | 88.2 | 92.5 | 70 | 50.5 |
The embodiment also provides a preparation method of the positive plate with the solid electrolyte, which comprises the following steps:
dissolving the lithium lanthanum zirconium tantalum oxygen solid electrolyte prepared in the embodiment, a binder (PVDF) and a lithium salt (lithium fluorophosphate) in a third solvent (NMP), stirring and mixing (based on 100% of the total mass of the lithium lanthanum zirconium tantalum oxygen solid electrolyte, the binder and the lithium salt, the mass fraction of the lithium salt is 40 wt%, the mass fraction of the lithium lanthanum zirconium tantalum oxygen solid electrolyte is 40 wt%, and the mass fraction of the binder is 20 wt%), casting and coating the obtained mixed slurry on a positive plate (a lithium iron phosphate positive plate, the thickness of which is 20 μm), drying at 120 ℃ in vacuum, and performing hot pressing treatment at 120 ℃ and 10MPa on the dried product to obtain the positive plate with the solid electrolyte.
Example 4
The method for preparing lithium lanthanum zirconium tantalum oxygen solid electrolyte in the embodiment is different from the embodiment 1 in that the aperture of the ceramic membrane tube used in the ceramic membrane washing and purifying in the embodiment is 250 nm.
The lithium lanthanum zirconium tantalum oxygen solid electrolyte provided by the embodiment is tested by the same method as the embodiment 1, and the test results are shown in the following table (the percentages and ppm in the table are mass fractions):
TABLE 7
| Test items | pH | OH-(％) | CO3 2-(％) | Fe(ppm) | Ni(ppm) | Zn(ppm) | Na(ppm) |
| Test data | 11.1 | 0.25 | 0.32 | 168.5 | 51.4 | 11.5 | 10.8 |
TABLE 8
| Test items | Na+(ppm) | Cl-(ppm) | SO4 2-(ppm) | Fe2+(ppm) |
| Test data | 92.5 | 100.1 | 74 | 50.5 |
Example 5
The method for preparing lithium lanthanum zirconium tantalum oxygen solid electrolyte in the embodiment is different from the embodiment 1 in that the aperture of the ceramic membrane tube used in the ceramic membrane washing and purifying in the embodiment is 5 nm.
The lithium lanthanum zirconium tantalum oxygen solid electrolyte provided by the embodiment is tested by the same method as the embodiment 1, and the test results are shown in the following table (the percentages and ppm in the table are mass fractions):
TABLE 9
| Test items | pH | OH-(％) | CO3 2-(％) | Fe(ppm) | Ni(ppm) | Zn(ppm) | Na(ppm) |
| Test data | 11.5 | 0.31 | 0.52 | 200.2 | 55.4 | 12.2 | 11.1 |
| Test items | Na+(ppm) | Cl-(ppm) | SO4 2-(ppm) | Fe2+(ppm) |
| Test data | 95.2 | 105.6 | 75.7 | 56.8 |
Comparative example 1
The method for preparing a lithium lanthanum zirconium tantalum oxygen solid electrolyte in the comparative example is different from the method in example 1 in that the sintered product is directly used as a lithium lanthanum zirconium tantalum oxygen solid electrolyte product after sintering, and subsequent operations of mixing with a second solvent and washing and purifying with a ceramic membrane are not performed in the comparative example.
The lithium lanthanum zirconium tantalum oxygen solid electrolyte provided by the embodiment is tested by the same method as the embodiment 1, and the test results are shown in the following table (the percentages and ppm in the table are mass fractions):
TABLE 11
| Test items | pH | OH-(％) | CO3 2-(％) | Fe(ppm) | Ni(ppm) | Zn(ppm) | Na(ppm) |
| Test data | 12.2 | 0.25 | 1.17 | 340.9 | 252.1 | 60.2 | 30.5 |
Fig. 1 is a graph of the ion conductivity of the pressed ceramic of the li-la-zr-ta-o solid electrolytes provided in example 1 and comparative example 1, from which it can be seen that the conductivity of the treated solid electrolyte powder is improved.
Fig. 2 is an infrared test curve of the lithium lanthanum zirconium tantalum oxygen solid electrolyte powder provided in example 1 and comparative example 1, from which it is possible to control the transmittance of the OH root peak of comparative example 1 to 45% and the transmittance of example 1 to 39%. The OH content of the surface is reduced after the surface is cleaned.
Fig. 3 is a graph showing rate performance of batteries prepared from the lithium lanthanum zirconium tantalum oxygen solid electrolyte powders provided in example 1 and comparative example 1 (a method for preparing a positive electrode sheet with a solid electrolyte using the solid electrolyte provided in comparative example 1. referring to example 1, a battery is assembled by using the positive electrode sheet with a solid electrolyte as a positive electrode and using lithium metal as a negative electrode), and it can be seen from the graph that the rate performance of the battery is improved.
It can be known from the above examples and comparative examples that the method for preparing a lithium lanthanum zirconium tantalum oxygen solid electrolyte provided in examples 1 to 3 can effectively reduce the PH, alkali, iron and other magnetic elements and effectively remove chloride ions and sulfate ions by performing high-purity treatment on a lithium lanthanum zirconium tantalum oxygen material prepared in batch, so that the material can be directly used in the field of solid batteries, and meanwhile, the improvement of lithium ion conductivity is beneficial to the improvement of the performance of the solid batteries.
Example 4 the cleaning effect was comparable to that of example 1 because the pore diameter of the ceramic membrane tube was too large, but resulted in the solid electrolyte powder also being partially cleaned out.
Example 5 because the pore size of the ceramic membrane tube is too small, some impurity substances with larger particle size may pass through the membrane tube with not small pore size, so that the effect of cleaning impurities cannot be more complete, and the purity cannot achieve the expected effect.
Comparative example 1 no ceramic membrane washing purification resulted in exceeding the residual alkali content of the material and the content of other elements affecting the performance in the battery.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the lithium lanthanum zirconium tantalum oxygen solid electrolyte is characterized by comprising the following steps of: mixing a lithium source, a zirconium source, a lanthanum source, a tantalum source, a sintering aid and a first solvent, drying, sintering, mixing the obtained sintered product with a second solvent, and washing with a ceramic membrane to obtain the lithium lanthanum zirconium tantalum oxygen solid electrolyte.
2. The method of claim 1, wherein the lithium source comprises any one of lithium hydroxide, lithium carbonate, lithium oxalate, or lithium nitrate, or a combination of at least two thereof;
preferably, the zirconium source comprises zirconium oxide or zirconium hydroxide;
preferably, the lanthanum source comprises lanthanum oxide or lanthanum hydroxide;
preferably, the tantalum source comprises tantalum oxide or tantalum nitrate;
preferably, the sintering aid comprises aluminum oxide or aluminum nitrate.
3. The preparation method of the lithium lanthanum zirconium tantalum oxygen solid electrolyte as claimed in claim 1 or 2, wherein the mass ratio of the lithium source, the lanthanum source, the zirconium source, the tantalum source and the sintering aid is (18.9-20.4): 2-32): 14.1: (3.6-10.8): 1;
preferably, the first solvent comprises any one of isopropanol, n-butanol or ethanol or a combination of at least two thereof;
preferably, the ratio of the total mass of the lithium source, the zirconium source, the lanthanum source, the tantalum source and the sintering aid to the mass of the first solvent is (0.2-0.8): 1
Preferably, the method of mixing the lithium source, the zirconium source, the lanthanum source, the tantalum source, the sintering aid, and the first solvent comprises sand mill mixing;
preferably, the method of drying comprises spray drying.
4. The method for preparing the lithium lanthanum zirconium tantalum oxygen solid-state electrolyte as claimed in any one of claims 1 to 3, wherein the sintering temperature is 850-950 ℃;
preferably, the sintering time is 7-9 h.
5. The method for preparing the lithium lanthanum zirconium tantalum oxygen solid-state electrolyte according to any one of claims 1 to 4, wherein the second solvent comprises any one or a combination of at least two of ethanol, isopropanol, N-methylpyrrolidone, N-dimethylformamide or deionized water;
preferably, the method for mixing the obtained sintered product with the second solvent is stirring dispersion;
preferably, the ceramic membrane washing uses a ceramic membrane tube with a pore diameter of 10-200 nm;
preferably, in the ceramic membrane washing, the mass ratio of the sintering product to the second solvent is 20-200;
preferably, after the ceramic membrane is washed, drying a purified product obtained after washing;
preferably, the drying temperature is 60-120 ℃;
preferably, the drying mode is any one or combination of at least two of vacuum drying, air-blast drying or spray drying.
6. The method for preparing according to any one of claims 1 to 5, characterized in that it comprises the steps of:
mixing a lithium source, a zirconium source, a lanthanum source, a tantalum source, a sintering aid and a first solvent by sanding, sintering after spray drying, wherein the sintering temperature is 850-950 ℃, the sintering time is 7-9h, stirring and dispersing the obtained sintered product and a second solvent, washing a ceramic membrane, and drying the purified product obtained after washing at 60-120 ℃ to obtain the lithium lanthanum zirconium tantalum oxygen solid electrolyte; the aperture of the ceramic membrane tube used for washing the ceramic membrane is 10-200 nm; the mass ratio of the lithium source to the lanthanum source to the zirconium source to the tantalum source to the sintering aid is (18.9-20.4): 2-32): 14.1: (3.6-10.8): 1.
7. The lithium lanthanum zirconium tantalum oxygen solid electrolyte obtained by the preparation method of any one of claims 1 to 6.
8. A positive electrode sheet with a solid electrolyte, characterized in that the positive electrode sheet contains the solid electrolyte according to claim 7;
preferably, the thickness of the positive electrode sheet with the solid electrolyte is 30-140 μm.
9. The method for producing a positive electrode sheet with a solid electrolyte according to claim 8, comprising the steps of:
dissolving the lithium lanthanum zirconium tantalum oxygen solid electrolyte, the binder and the lithium salt in a third solvent, mixing, coating the obtained mixed slurry on a positive plate, drying, and performing hot-pressing treatment on the dried product to obtain the positive plate with the solid electrolyte;
preferably, the lithium salt comprises any one of lithium fluorophosphate, lithium bistrifluoromethanesulfonylimide, lithium tetrafluoroborate or lithium dioxalate borate or a combination of at least two of the above;
preferably, the binder comprises polyvinylidene fluoride;
preferably, the mass fraction of the lithium salt is 15-50 wt%, the mass fraction of the lithium lanthanum zirconium tantalum oxygen solid electrolyte is 10-60 wt%, and the mass fraction of the binder is 5-20 wt%, based on 100% of the total mass of the lithium lanthanum zirconium tantalum oxygen solid electrolyte, the binder and the lithium salt;
preferably, the third solvent comprises N-methylpyrrolidone;
preferably, the mixing is stirring mixing;
preferably, the positive plate is one of a lithium iron phosphate positive plate, a nickel-cobalt-manganese ternary material positive plate or a spinel material positive plate;
preferably, the thickness of the positive plate is 20-120 μm;
preferably, the method of coating is cast coating;
preferably, the drying is vacuum drying, and the drying temperature is 80-120 ℃;
preferably, the temperature of the hot pressing treatment is 50-120 ℃;
preferably, the hot pressing pressure is 10-80 MPa.
10. A battery comprising the positive electrode sheet with a solid electrolyte according to claim 8.
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| CN114300733A (en) * | 2021-12-31 | 2022-04-08 | 南方科技大学 | All-solid-state thin film lithium battery and preparation method thereof |
| CN115584397A (en) * | 2022-11-24 | 2023-01-10 | 中自环保科技股份有限公司 | Method for recovering lithium, lanthanum, zirconium, titanium and oxygen in lithium ion semi-solid battery |
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| CN102280659A (en) * | 2011-06-30 | 2011-12-14 | 清华大学 | Lithium-lanthanum-zirconium (Li-La-Zr) oxide solid electrolyte material as well as manufacturing method and application thereof |
| CN105244536A (en) * | 2015-10-21 | 2016-01-13 | 上海动力储能电池系统工程技术有限公司 | Tantalum-doped cubic garnet structure Li7La3Zr2-xTaxO12 material and preparation method thereof |
| CN108511793A (en) * | 2018-02-06 | 2018-09-07 | 东华大学 | Solid-state lithium lanthanum zirconium oxygen ceramic nanofibers electrolytic thin-membrane and its preparation |
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| CN102280659A (en) * | 2011-06-30 | 2011-12-14 | 清华大学 | Lithium-lanthanum-zirconium (Li-La-Zr) oxide solid electrolyte material as well as manufacturing method and application thereof |
| CN105244536A (en) * | 2015-10-21 | 2016-01-13 | 上海动力储能电池系统工程技术有限公司 | Tantalum-doped cubic garnet structure Li7La3Zr2-xTaxO12 material and preparation method thereof |
| CN108511793A (en) * | 2018-02-06 | 2018-09-07 | 东华大学 | Solid-state lithium lanthanum zirconium oxygen ceramic nanofibers electrolytic thin-membrane and its preparation |
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| CN114300733A (en) * | 2021-12-31 | 2022-04-08 | 南方科技大学 | All-solid-state thin film lithium battery and preparation method thereof |
| CN115584397A (en) * | 2022-11-24 | 2023-01-10 | 中自环保科技股份有限公司 | Method for recovering lithium, lanthanum, zirconium, titanium and oxygen in lithium ion semi-solid battery |
| CN115584397B (en) * | 2022-11-24 | 2023-03-24 | 中自环保科技股份有限公司 | Method for recovering lithium, lanthanum, zirconium, titanium and oxygen in lithium ion semi-solid battery |
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