CN115799618B - Oxide solid electrolyte and preparation method and application thereof - Google Patents
Oxide solid electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an oxide solid electrolyte, a preparation method and application thereof. The method comprises the following steps: 1) Adding a solvent into the zirconium dioxide tank body, and ball-milling an oxide electrolyte by using zirconium dioxide grinding balls; the oxide electrolyte is LATP with a NASICON structure; 2) Performing sedimentation separation on the ball-milled slurry to obtain wet oxide electrolyte; 3) And drying to obtain the oxide solid electrolyte. The technical problem to be solved is how to reduce the impurity content of zirconium dioxide (zirconium content is less than or equal to 350 ppm) in the oxide solid electrolyte, and improve the purity and ion conductivity (ion conductivity is more than or equal to 7.3X10) ‑4 S/cm), the multiplying power, the circulation and other electrochemical performances of the battery are improved, and the battery is more practical.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an oxide solid electrolyte, a preparation method and application thereof.
Background
Solid-state electrolytes are core components of solid-state batteries, and are largely classified into polymer electrolytes, sulfide electrolytes, and oxide electrolytes. The oxide electrolyte has higher ionic conductivity, high chemical stability and excellent comprehensive performance, and is widely concerned.
Oxide solid electrolytes are mainly classified into LiPON thin films, LISICON type structures, naSICON type structures, perovskite (perovskie) type structures, garnet (Garnet) type structures, and the like. Of these, naSICON type is a large class of electrolyte systems which have been attracting attention in recent years, and has the advantages of higher ionic conductivity, abundant sources of raw materials and low cost, such as lithium aluminum titanium phosphate (Li) 1+x Al x Ti 2- x (PO 4 ) 3 LATP), lithium aluminum germanium phosphate (Li 1+x Al x Ge 2-x (PO 4 ) 3 I.e., LAGP), etc.
In order to prepare LATP with specific granularity, the granularity is controlled by adopting a ball milling method in various preparation methods, and three types of ball milling tanks and balls are generally used, namely stainless steel, polytetrafluoroethylene and zirconium dioxide. However, stainless steel materials are easy to introduce magnetic material iron, have serious influence on electrochemical reaction, and can replace aluminum in LATP with iron to generate impurity phases; and polytetrafluoroethylene has poor wear resistance, and organic impurities can be introduced while the grinding effect is poor. In order to ensure the grinding effect and shorten the grinding time, a tank body of zirconium dioxide and a grinding ball of zirconium dioxide are generally selected. But will typically introduce some zirconium dioxide into the material. Zirconium dioxide is generally white odorless and tasteless crystal, and has high melting point and high resistivity. The doped zirconium dioxide reduces the ionic conductivity of the overall electrolyte and affects the electrochemical performance of the battery, such as rate and cycling. Zirconium dioxide is poorly soluble in water, hydrochloric acid and dilute sulfuric acid, and is chemically inert, so zirconium dioxide is generally difficult to remove. If acid or alkali is used for removing, new impurity ions are introduced.
Disclosure of Invention
The invention mainly aims to provide an oxide solid electrolyte, a preparation method and application thereof, and aims to solve the technical problems of reducing the content of zirconium dioxide impurities (zirconium content is less than or equal to 350 ppm) in the oxide solid electrolyte and improving the purity and the ionic conductivity (ionic conductivity is more than or equal to 7.3X10) -4 S/cm), the multiplying power, the circulation and other electrochemical performances of the battery are improved, and the battery is more practical.
The aim and the technical problems of the invention are realized by adopting the following technical proposal. The preparation method of the oxide solid electrolyte provided by the invention comprises the following steps:
1) Adding a solvent into the zirconium dioxide tank body, and ball-milling an oxide electrolyte by using zirconium dioxide grinding balls; the oxide electrolyte is LATP with a NASICON structure;
2) Performing sedimentation separation on the ball-milled slurry to obtain wet oxide electrolyte;
3) And drying to obtain the oxide solid electrolyte.
The aim and the technical problems of the invention can be further realized by adopting the following technical measures.
Preferably, the foregoing preparation method, wherein the oxide electrolyte is prepared by the steps of: mixing the raw materials, calcining the mixture powder, and cooling to room temperature to obtain an oxide electrolyte; the raw materials comprise a lithium source, an aluminum source, a titanium source and a phosphorus source; the lithium source is selected from lithium carbonate and/or lithium oxide, the aluminum source is selected from aluminum hydroxide and/or aluminum oxide, the titanium source is titanium dioxide, and the phosphorus source is selected from ammonium phosphate and/or ammonium dihydrogen phosphate.
Preferably, the aforementioned preparation method, wherein the solvent is alcohol or glycerol.
Preferably, the aforementioned preparation method, wherein the ball milling is performed using a ball mill or a sand mill.
Preferably, the aforementioned preparation method, wherein the sedimentation separation is performed using a centrifuge or a sedimentation separator.
Preferably, the preparation method, wherein the process parameters when the centrifuge is used for sedimentation separation are as follows: the rotation speed is 6000-10000 rpm, the temperature is 5-50 ℃, the centrifugal radius is 6-10 cm, the centrifugal time is 10-30 min, the upper mixed solution after centrifugation is wet oxide electrolyte, and the lower solid is zirconium dioxide.
Preferably, the preparation method, wherein the technological parameters of the sedimentation separation by the sedimentation separator are as follows: the mass solid content of the slurry is 0.1% -2%, the flow rate of the solvent is 2-10 m/s, the collecting interval of the wet oxide electrolyte is 2.5-4.0 m, and the collecting interval of the zirconium dioxide is 0-1.5 m.
Preferably, the aforementioned preparation method, wherein the drying is spray drying or oven drying; the drying temperature is 80-400 ℃.
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. The oxide solid electrolyte prepared according to the preparation method provided by the invention has the zirconium content less than or equal to 350ppm and the ion conductivity more than or equal to 7.3X10 -4 S/cm。
The aim of the invention and the technical problems are also achieved by adopting the following technical proposal. According to the application of the oxide solid electrolyte in the technical field of all-solid batteries, the oxide solid electrolyte is provided.
By means of the technical scheme, the oxide solid electrolyte provided by the invention and the preparation method and application thereof have at least the following advantages:
the invention provides an oxide solid electrolyte and a preparation method and application thereof, wherein the oxide solid electrolyte is ball-milled to a specified granularity through a zirconium dioxide tank body and zirconium dioxide grinding balls, and zirconium dioxide impurities possibly introduced into the oxide electrolyte are removed through a sedimentation separation technology; the sedimentation separation is a physical method, which makes full use of the density difference between the oxide electrolyte and the zirconium dioxide, and can remove the zirconium dioxide in the slurry by the physical method, so that the impurity content of the zirconium dioxide in the oxide solid electrolyte is reduced to below 350ppm, and new impurity ions are not introduced into the slurry, thereby improving the purity of the oxide solid electrolyteAnd ionic conductivity, improving the multiplying power and cycle electrochemical performance of the battery, wherein the ionic conductivity is more than or equal to 7.3 multiplied by 10 -4 The multiplying power, the circulation and other electrochemical performances of the battery are greatly improved.
The foregoing description is only an overview of the present invention, and is intended to provide a more thorough understanding of the present invention, and is to be accorded the full scope of the present invention.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the preset aim of the present invention, the following describes in detail the specific implementation, structure, characteristics and effects of an oxide solid electrolyte, a preparation method thereof and application thereof according to the present invention in combination with the preferred embodiments.
The invention provides a preparation method of a high-purity oxide solid electrolyte, which comprises the following steps:
firstly, ball milling is carried out on oxide electrolyte to obtain oxide electrolyte slurry.
The oxide electrolyte of the invention is lithium aluminum titanium phosphate (Li) with NASICON structure 1+x Al x Ti 2- x(PO 4 ) 3 LATP; the preparation method comprises the steps of mixing and stirring the raw materials uniformly by means of manual mixing, ball milling mixing or stirring machine mixing; the raw materials comprise a lithium source, an aluminum source, a titanium source and a phosphorus source; the lithium source is selected from lithium carbonate and/or lithium oxide, the aluminum source is selected from aluminum hydroxide and/or aluminum oxide, the titanium source is titanium dioxide, and the phosphorus source is selected from ammonium phosphate and/or ammonium dihydrogen phosphate; the specific steps are that the raw materials are weighed according to the formula proportion, and the obtained mixture powder is calcined after being uniformly mixed; the calcination may be performed in any manner known in the art, and is not particularly limited in the present invention; for example, in the specific embodiment of the present invention, the mixture powder is heated from room temperature to 900 ℃ at a heating rate of 2 ℃/min, and then is kept for 6 hours; then cooling to room temperature along with furnace cooling to obtain oxide electrolyte, and then ball milling the oxide electrolyte.
When the production is large-scale batch operation, the ball milling is generally carried out by using a sand mill; when the production is a small-scale operation, the ball milling should generally be performed using a ball mill. The ball mill and the sand mill are both provided with a zirconium dioxide tank body and zirconium dioxide grinding balls. During ball milling, firstly, adding a ball milling solvent into a zirconium dioxide tank body; the solvent is alcohol or glycerol, and cannot be water; the oxide electrolyte is ball-milled by zirconium dioxide grinding balls to become oxide electrolyte slurry with specified granularity.
And secondly, carrying out sedimentation separation on the oxide electrolyte slurry to obtain wet oxide electrolyte. The sedimentation separation aims at separating out zirconium dioxide impurities possibly introduced due to ball milling in the oxide electrolyte slurry.
The mechanism of separation of zirconium dioxide impurities is as follows: the density of the zirconium dioxide is 5.85g/cm 3 While the density of lithium aluminum titanium phosphate LATP is generally close to 2.94g/cm 3 The density value is Li 1.3 Al 0.3 Ti 1.7 P 3 O 12 From the above density values, it can be seen that the density values of zirconium dioxide and lithium aluminum titanium phosphate, LATP, have a significant difference. The technical scheme of the invention fully utilizes the density value difference of the two, when the oxide electrolyte slurry is settled and separated, the descending speed of the respective particles in the oxide electrolyte slurry is different, so that under the same settling condition and settling time, the advancing distance of the two particles (zirconium dioxide particles and lithium aluminum titanium phosphate LATP particles) is also different, and the zirconium dioxide particles and the lithium aluminum titanium phosphate LATP particles can be separated.
The invention separates zirconium dioxide from oxide electrolyte slurry by a centrifuge or a sedimentation separator. In general, the separation can be performed by a centrifuge in small-scale production, and by a sedimentation separator in large-scale production.
The technological parameters are as follows when the centrifugal machine is used for sedimentation separation: the rotation speed is 6000-10000 rpm, the temperature is 5-50 ℃, the centrifugal radius is 6-10 cm, the centrifugal time is 10-30 min, the centrifuged upper mixed solution is wet oxide electrolyte and comprises solvent and lithium aluminum titanium phosphate LATP particles, and the mixed solution is collected and enters the next working procedure; the lower layer of solid is zirconium dioxide slag, and the zirconium dioxide slag is treated as waste.
When the sedimentation separator is used for sedimentation separation, the process parameters are as follows: the mass solid content of the slurry is 0.1% -2%, and the flow rate of the solvent is 2-10 m/s. Under the process conditions, the material collection interval of the wet oxide electrolyte is 2.5-4.0 m, and the material collection interval of the zirconium dioxide waste residue is 0-1.5 m. Collecting wet oxide electrolyte in a material collecting area of 2.5-4.0 m, and entering the next working procedure; and collecting zirconium dioxide slag in a material collecting area of 0-1.5 m, and disposing the zirconium dioxide slag as waste.
And finally, drying the collected wet oxide electrolyte to obtain the high-purity oxide solid electrolyte. The drying is spray drying or oven drying; the drying temperature is 80-400 ℃.
The invention also provides an oxide solid electrolyte prepared by the preparation method, wherein the zirconium content is less than or equal to 350ppm, and the ion conductivity is more than or equal to 7.3X10 -4 S/cm, can promote the multiplying power performance and the cycle performance of battery.
The invention also provides application of the oxide solid electrolyte in the technical field of all-solid batteries.
The invention will be further described with reference to specific examples, which are not to be construed as limiting the scope of the invention, but rather as falling within the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will now occur to those skilled in the art in light of the foregoing disclosure.
Unless otherwise indicated, materials, reagents, and the like referred to below are commercially available products well known to those skilled in the art; unless otherwise indicated, the methods are all methods well known in the art. Unless otherwise defined, technical or scientific terms used should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1
This example prepares a high purity lithium aluminum titanium phosphate LATP oxide solid electrolyte according to the following steps:
1) Preparing oxide electrolyte powder by self and ball milling:
in terms of mole ratio Li 2 CO 3 ：Al 2 O 3 ：TiO 2 ：NH 4 H 2 PO 4 Ratio of=1.3:0.3:1.7:3 Li was weighed separately 2 CO 3 ，Al 2 O 3 ，TiO 2 ，NH 4 H 2 PO 4 Powder, mixing the raw materials uniformly. Then, placing the mixture powder into a high-temperature furnace, heating to 900 ℃ at a speed of 2 ℃/min, then preserving heat for 6 hours, cooling to room temperature along with furnace cooling, taking out the product, and ball-milling the product into powder in a ball mill, namely oxide electrolyte powder; the ball mill is provided with a zirconium dioxide tank body and zirconium dioxide grinding balls, and the ball milling solvent is glycerol.
2) Settling and separating oxide electrolyte slurry and drying wet oxide electrolyte:
placing oxide electrolyte slurry with mass solid content of 0.1% into a sedimentation separator, and carrying out sedimentation separation at a solvent flow rate of 4 m/s; collecting wet oxide electrolyte in a material collecting area of 2.5-4.0 m, and spray drying the wet oxide electrolyte at 200 ℃ to obtain the oxide solid electrolyte.
3) The oxide electrolyte prepared in this example was tested as follows:
the oxide solid electrolyte powder prepared in this example was pressed into an oxide solid electrolyte sheet having a diameter of 16mm and a thickness of 1mm at a pressure of 200 MPa. Placing the oxide solid electrolyte sheet into a high-temperature furnace, and heating to the calcining temperature of 950 ℃ at the heating rate of 5 ℃/min, wherein the heat preservation time is 6 hours; and cooling to room temperature, polishing and smoothing for performance test.
A. Ion conductivity test:
the ionic conductivity of the oxide solid electrolyte was obtained by assembling the blocking electrode for electrochemical impedance spectroscopy (EIS, electrochemical Impedance Spectrum abbreviation) test. The specific operation method is as follows:
the present embodiment is madeThe prepared oxide solid electrolyte sheet takes stainless steel sheets as blocking electrodes on two sides of the oxide solid electrolyte sheet to form a symmetrical battery; the electrochemical workstation is DH7001 with the frequency range of 0.01-10 6 Hz, EIS at 25 ℃ was measured for oxide solid state electrolyte flakes. The ionic conductivity of the oxide solid electrolyte is calculated as follows:
wherein delta is ion conductivity (unit S/cm), L is thickness (unit cm) of the oxide solid electrolyte sheet, R is intrinsic resistance (unit omega) of the oxide solid electrolyte, and S is effective cross-sectional area (unit cm) of the oxide solid electrolyte sheet 2 ). The higher the test result of the ion conductivity, the better the ion conductivity. The test results are shown in Table 1.
B. Multiplying power and cycle performance test:
a solid-state battery using lithium cobalt oxide as a positive electrode and lithium metal as a negative electrode was fabricated, and the rate performance of the oxide solid-state electrolyte was evaluated. The specific operation method is as follows:
lithium cobaltate, conductive agent Super P, binder PVDF (polyvinylidene fluoride) according to 9:0.5: mixing in a mass ratio of 0.5, adding a proper amount of solvent NMP (N-methyl pyrrolidone), stirring to prepare anode slurry, coating the anode slurry on aluminum foil, drying at 100 ℃, and cutting into wafers with the diameter of 10mm to be used as anode plates. The CR2032 button cell was assembled in the order of positive electrode sheet-oxide solid electrolyte sheet-lithium foil. Battery rate testing was performed.
The operating voltage range of the above all-solid-state lithium secondary battery was set to 3V to 4.2V at 0.1C (current density of 0.15mA/cm 2 ) Constant current charging to 4.2V, then constant voltage to 0.01C cut-off; then discharging to 3V with 0.1C, 0.2C, 0.5C and 1C current respectively, and obtaining gram capacity of the material under 0.1C, 0.2C, 0.5C and 1C multiplying power discharge respectively. The test results are shown in Table 2.
Gram capacity was measured at week 1, week 10, week 50, and week 100 of the 0.1C cycle, respectively. The test results are shown in Table 3.
C. Zirconium content test:
the oxide solid electrolyte powder prepared in this example was dissolved with hydrochloric acid and perchloric acid to obtain a test solution, and the zirconium content was tested with an ICP spectroanalyzer. The test results are shown in Table 4.
Example 2
The difference is that the ball milling solvent is alcohol as in example 1.
Performance was tested in the same manner as in example 1, and the test results are shown in tables 1, 2, 3 and 4, respectively.
Example 3
The difference from example 1 was that the mass solids content of the oxide electrolyte slurry for the precipitation separation was 1%, and the solvent flow rate for the precipitation separation was 2m/s.
Performance was tested in the same manner as in example 1, and the test results are shown in tables 1, 2, 3 and 4, respectively.
Example 4
The difference from example 1 was that the mass solids content of the oxide electrolyte slurry for the precipitation separation was 2%, and the solvent flow rate for the precipitation separation was 10m/s.
Performance was tested in the same manner as in example 1, and the test results are shown in tables 1, 2, 3 and 4, respectively.
Example 5
The difference from example 1 was that the mass solids content of the oxide electrolyte slurry for the precipitation separation was 2%, and the solvent flow rate for the precipitation separation was 7m/s.
Performance was tested in the same manner as in example 1, and the test results are shown in tables 1, 2, 3 and 4, respectively.
Example 6
The difference from example 1 is that the sedimentation separation is carried out using a centrifuge at a rotational speed of 6000 rpm at 50℃with a centrifuge radius of 6cm for a centrifugation time of 30min.
Performance was tested in the same manner as in example 1, and the test results are shown in tables 1, 2, 3 and 4, respectively.
Example 7
The difference from example 6 is that the rotation speed is 10000 rpm, the temperature is 5 ℃, the centrifugal radius is 10cm, and the centrifugal time is 10min.
Performance was tested in the same manner as in example 1, and the test results are shown in tables 1, 2, 3 and 4, respectively.
Comparative example 1
The same as in example 1 was distinguished in that the oxide electrolyte slurry obtained in step 1) was not subjected to sedimentation separation, but was directly spray-dried at 200℃to obtain an oxide solid electrolyte powder.
Performance was tested in the same manner as in example 1, and the test results are shown in tables 1, 2, 3 and 4, respectively.
Table 1 results of ionic conductivity tests for each of examples and comparative examples
As can be seen from the test results of the above Table 1, the ion conductivity test results of examples 1 to 7 are far higher than those of comparative example 1, and reach 240% -300% of the ion conductivity of comparative example 1, which indicates that the technical scheme of the invention can greatly improve the ion conductivity of the oxide solid electrolyte.
Table 2 results of multiplying power test of each of examples and comparative examples
As can be seen from the test results of Table 2, the rate performance test results of examples 1 to 7 are all higher than that of comparative example 1, wherein the rate performance is slightly improved by 0.2C/0.1C, the rate performance is improved by 4% -5% by 0.5C/0.1C, and the rate performance is improved by 14% -15% by 1C/0.1C, which indicates that the technical scheme of the invention can greatly improve the rate performance of the oxide solid electrolyte.
Table 3 results of cyclic testing of examples and comparative examples
As can be seen from the test results of the above Table 3, the cycle performance test results of examples 1 to 7 are all higher than that of comparative example 1, wherein the cycle performance C10/C1 is improved by about 7% -8%, C50/C1 is improved by about 13% -14%, and C100/C1 is improved more significantly, and is improved by about 26% -27%, which means that the technical scheme of the invention can greatly improve the cycle performance of the oxide solid electrolyte.
Table 4 results of zirconium content test of each of examples and comparative examples
As can be seen from the test results of the above Table 4, the zirconium content test results of examples 1 to 7 are far lower than that of comparative example 1, and the zirconium content is reduced by 9-11 times compared with comparative example 1, but is only 8-11% of that of comparative example 1, which indicates that the technical scheme of the invention can greatly reduce the zirconium content of the oxide solid electrolyte, improve the purity of the oxide solid electrolyte and obtain the oxide solid electrolyte with high purity.
The technical features of the claims and/or the description of the present invention may be combined in a manner not limited to the combination of the claims by the relation of reference. The technical scheme obtained by combining the technical features in the claims and/or the specification is also the protection scope of the invention.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (7)
1. A method for preparing an oxide solid electrolyte, comprising the steps of:
1) Adding a solvent into the zirconium dioxide tank body, and ball-milling an oxide electrolyte by using zirconium dioxide grinding balls; the oxide electrolyte is LATP with a NASICON structure;
2) Performing sedimentation separation on the ball-milled slurry to obtain wet oxide electrolyte; the sedimentation separation is carried out by using a centrifuge or a sedimentation separator; the technological parameters are as follows when the centrifugal machine is used for sedimentation separation: the rotation speed is 6000-10000 rpm, the temperature is 5-50 ℃, the centrifugal radius is 6-10 cm, the centrifugal time is 10-30 min, the upper mixed solution after centrifugation is wet oxide electrolyte, and the lower solid is zirconium dioxide; when the sedimentation separator is used for sedimentation separation, the process parameters are as follows: the mass solid content of the slurry is 0.1% -2%, the flow rate of the solvent is 2-10 m/s, the collecting interval of the wet oxide electrolyte is 2.5-4.0 m, and the collecting interval of the zirconium dioxide is 0-1.5 m;
3) And drying to obtain the oxide solid electrolyte.
2. The method of manufacturing according to claim 1, wherein the oxide electrolyte is manufactured by the steps of: mixing the raw materials, calcining the mixture powder, and cooling to room temperature to obtain an oxide electrolyte; the raw materials comprise a lithium source, an aluminum source, a titanium source and a phosphorus source; the lithium source is selected from lithium carbonate and/or lithium oxide, the aluminum source is selected from aluminum hydroxide and/or aluminum oxide, the titanium source is titanium dioxide, and the phosphorus source is selected from ammonium phosphate and/or ammonium dihydrogen phosphate.
3. The method according to claim 1, wherein the solvent is alcohol or glycerol.
4. The method of claim 1, wherein the ball milling is performed using a ball mill or a sand mill.
5. The method of claim 1, wherein the drying is spray drying or oven drying; the drying temperature is 80-400 ℃.
6. An oxide solid electrolyte prepared by the method according to any one of claims 1 to 5, which has a zirconium content of 350ppm or less and an ionic conductivity of 7.3X10 or more -4 S/cm。
7. Use of the oxide solid electrolyte according to claim 6 in the field of all-solid-state battery technology.
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