A solid electrolyte slurry with stable sedimentation and preparation method thereof
By using a combination of nanowires/tubes and inorganic oxide solid electrolytes in solid electrolyte slurry, the settlement problem of solid electrolyte slurry is solved, and the stability of the slurry and the performance of the battery are improved.
Patent Information
- Application Number
- CN202411879163.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-19
- Publication Date
- 2025-04-01
AI Technical Summary
There are serious sedimentation problems when using solid electrolyte slurry. Traditional anti-settlement agents have problems such as incompatible with electrolyte and easy to decompose at high temperatures. It is difficult to improve battery performance while ensuring the stability of the slurry.
Using the combination of nanowires/tubes, inorganic oxide solid electrolytes and solvents, a solid electrolyte slurry with settled stable solid electrolyte slurry is prepared through the mixing and grinding steps. The nanowires/tubes form a spatial network layer to improve the slurry viscosity and improve stability.
It has achieved solid electrolyte slurry with strong settling stability, stable electrolyte compatibility, and difficult to decompose at high temperatures to prevent settling and improve battery performance.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of solid electrolyte slurry preparation, and in particular to a solid electrolyte slurry with stable sedimentation and a preparation method thereof. Background Art
[0002] Solid electrolyte slurry is generally composed of inorganic oxide solid electrolyte, dispersant, and solvent. Solid electrolyte has serious sedimentation problem when in use. The traditional way to solve the sedimentation problem of solid electrolyte is to add some anti-settling agents to increase the viscosity of the slurry, thereby preventing the slurry from not settling. However, traditional anti-settling agents are generally high molecular polymers, which are incompatible with electrolytes and easily decomposed at high temperatures. Therefore, solving the sedimentation problem of solid electrolyte slurry requires considering both improving the stability of the slurry and the application effect in the battery, so as to prevent sedimentation and stabilize the battery and even improve the battery performance.
[0003] Therefore, the present invention provides a solid electrolyte slurry with stable sedimentation and a preparation method thereof. Summary of the invention
[0004] In view of the defects of the prior art, the present invention provides a solid electrolyte slurry with strong sedimentation stability and excellent battery performance and a preparation method thereof.
[0005] The technical solution of the present invention is achieved as follows: a solid electrolyte slurry with stable sedimentation comprises nanowires / tubes, inorganic oxide solid electrolyte and solvent, and the solid content of the slurry is 30% to 85%.
[0006] Furthermore, the inorganic oxide solid electrolyte is selected from at least one of LiSICON, NASICON, perovskite, garnet, antiperovskite, phosphate lithium aluminum stone LiSICON type electrolyte, Li1-x1Ti1-x1M1x1OPO4, Li1+x2H1-x2Al(PO4)O1-yM2y, LilPO4Fx3(OH)1-x3 and Na-β / β″-Al2O3, wherein M1 is selected from at least one of Nb, Ta and Sb, M2 is selected from at least one of F, Cl, Br and I, 0≤x1≤0.7, 0≤x2<1, 0≤x3<1, 0 <y<0.1。
[0007] Furthermore, the nanowires / tubes are selected from one or more of CNT, titanium oxide nanowires, and aluminum oxide nanowires.
[0008] Furthermore, the solvent comprises at least one of water, NMP, ethanol, N,N-dimethylformamide, dimethylacetamide, 1,3-dioxolane and dimethyl carbonate.
[0009] A sedimentation-stable solid electrolyte slurry according to claim 1, wherein the laser particle size of the solid electrolyte particles is D50=100 to 500 nm.
[0010] Furthermore, the length of the nanowire is 100 to 1000 microns, and the diameter of the nanotube is 0 to 20 nm.
[0011] Furthermore, the mass ratio of the nanowires / tubes, the inorganic oxide solid electrolyte and the solvent is (0.01 to 0.05):1:(0.17 to 2.33).
[0012] A sedimentation-stable solid electrolyte slurry according to claim 1, wherein the solid content change value is ≤3%.
[0013] A method for preparing the above-mentioned sedimentation-stable solid electrolyte slurry, wherein the preparation method is:
[0014] S1. Mixing: mixing an inorganic oxide solid electrolyte with a solvent to obtain a slurry;
[0015] S2, grinding: grinding the slurry prepared in S1 to obtain an unstable solid electrolyte dispersion;
[0016] S3. Add the nanowires / tubes to the unstable solid electrolyte dispersion prepared in S2 and stir evenly.
[0017] The present invention has the following positive effects:
[0018] Firstly, the present invention obtains a solid electrolyte slurry with stable sedimentation through a mixing step by combining a proportion of nanowires / tubes, an inorganic oxide solid electrolyte and a solvent. The obtained product has strong sedimentation stability, stable electrolyte compatibility, is not easy to decompose at high temperature, and has improved slurry stability, thereby achieving the effects of preventing sedimentation, stabilizing the battery and improving battery performance.
[0019] Secondly, the present invention uses nanowires / tubes as materials. Nanowires / tubes have a special linear structure, which is interlaced and adhered in water or oil solvents. The viscosity of the slurry can be significantly improved when the solid content is very low. Adding nanowires / tubes to solid electrolyte slurry to form a spatial network layer can increase the viscosity of the slurry, thereby improving the stability of the slurry. Nanowires / tubes also have the ability to conduct electrons, and can be used as a new type of semi-solid battery blending material after being compounded with solid electrolytes. DETAILED DESCRIPTION
[0020] A solid electrolyte slurry with stable sedimentation comprises nanowires / tubes, an inorganic oxide solid electrolyte and a solvent, wherein the solid content of the solid electrolyte is 30% to 85%. The inorganic oxide solid electrolyte is selected from at least one of LiSICON, NASICON, perovskite, garnet, antiperovskite, phosphate lithium aluminum stone LiSICON type electrolyte, Li1-x1Ti1-x1M1x1OPO4, Li1+x2H1-x2Al(PO4)O1-yM2y, LilPO4Fx3(OH)1-x3 and Na-β / β″-Al2O3, wherein M1 is selected from at least one of Nb, Ta and Sb, M2 is selected from at least one of F, Cl, Br and I, 0≤x1≤0.7, 0≤x2<1, 0≤x3<1, 0 <y<0.1。
[0021] The nanowire / tube is selected from one or more of CNT, titanium oxide nanowire, and aluminum oxide nanowire. The solvent includes at least one of water, NMP, ethanol, N,N-dimethylformamide, dimethylacetamide, 1,3-dioxolane, and dimethyl carbonate.
[0022] A solid electrolyte slurry with stable sedimentation according to claim 1, wherein the laser particle size of the solid electrolyte particles is D50=100 to 500 nm. The length of the nanowire is 100 to 1000 microns, and the diameter of the nanotube is 0 to 20 nm. The mass ratio of the nanowire / tube, inorganic oxide solid electrolyte and solvent is (0.01 to 0.05):1:(0.17 to 2.33).
[0023] A sedimentation-stable solid electrolyte slurry according to claim 1, wherein the solid content change value is ≤3%.
[0024] A method for preparing a solid electrolyte slurry with stable sedimentation, characterized in that the preparation method comprises:
[0025] S1. Mixing: mixing an inorganic oxide solid electrolyte with a solvent to obtain a slurry;
[0026] S2, grinding: grinding the slurry prepared in S1 to obtain an unstable solid electrolyte dispersion;
[0027] S3. Add the nanowires / tubes to the unstable solid electrolyte dispersion prepared in S2 and stir evenly.
[0028] In specific operation, the inorganic oxide solid electrolyte is mixed with a solvent to obtain a slurry, the slurry is ground to obtain an unstable solid electrolyte dispersion, and the nanowires / tubes are added to the unstable solid electrolyte dispersion and stirred evenly.
[0029] Take the prepared solid electrolyte slurry to test the solid content, and record it as the initial solid content w0. Take 100mL of solid electrolyte slurry in a 150mL experimental bottle, seal the experimental bottle and let it stand for 30 days. After 30 days, take 1mL of solid electrolyte slurry at 5mm from the liquid surface in the experimental bottle, test the solid content, and record it as the solid content value w1 of the upper layer of the solid electrolyte slurry. Take 1mL of solid electrolyte slurry at 5mm from the bottom of the experimental bottle, test the solid content, and record it as the solid content value w2 of the lower layer of the solid electrolyte slurry.
[0030] The solid content stability S of the solid electrolyte slurry is measured by the deviation of the upper and lower solid content values w1 and w2 from the initial solid content value w0. Among them, the change value of the upper solid content is S1 = |w1-w0| / w0×100%, and the change value of the lower solid content is S2 = |w2-w0| / w0×100%; the smaller the values of S1 and S2, the more stable the slurry.
[0031] In specific operation, the inorganic oxide solid electrolyte is mixed with a solvent to obtain a slurry, the slurry is ground to obtain an unstable solid electrolyte dispersion, and the nanowires / tubes are added to the unstable solid electrolyte dispersion and stirred evenly.
[0032] The prepared solid electrolyte slurry was coated on aluminum foil with a coating thickness of 50 microns, and after drying, a surface resistance test a was performed using a resistivity meter. The surface resistance b of the blank dispersion without nanowires was tested, and the relative value of the conductivity improvement η=a / b*100% was calculated.
[0033] Table 1 Raw material parameters and processing technology description table.
[0034]
[0035] Table 2 Slurry product parameter description table.
[0036]
[0037] The present invention obtains a solid electrolyte slurry with stable sedimentation through a mixing step by combining a proportion of nanowires / tubes, an inorganic oxide solid electrolyte and a solvent. The obtained product has strong sedimentation stability, stable electrolyte compatibility, is not easy to decompose at high temperature, and has improved slurry stability, which has the effects of preventing sedimentation, stabilizing the battery and improving battery performance. The present invention uses nanowires / tubes as a material. The nanowires / tubes have a special linear structure, which are staggered and adhered in water or oil solvents, and the slurry viscosity can be significantly improved when the solid content is very low. Adding nanowires / tubes to the solid electrolyte slurry to form a spatial network layer can increase the slurry viscosity, thereby improving the slurry stability. The nanowires / tubes also have the ability to conduct electrons, and can be used as a new semi-solid battery blending material after being compounded with a solid electrolyte.
[0038] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
Claims
1. A solid electrolyte slurry with stable sedimentation, characterized in that: The invention comprises nanowires / tubes, inorganic oxide solid electrolyte and solvent, and the solid content thereof is 30% to 85%.
2. The sedimentation-stable solid electrolyte slurry according to claim 1, characterized in that: The inorganic oxide solid electrolyte is selected from at least one of LiSICON, NASICON, perovskite, garnet, antiperovskite, phosphate lithium aluminum stone LiSICON type electrolyte, Li1-x1Ti1-x1M1x1OPO4, Li1+x2H1-x2Al(PO4)O1-yM2y, LilPO4Fx3(OH)1-x3 and Na-β / β″-Al2O3, wherein M1 is selected from at least one of Nb, Ta and Sb, M2 is selected from at least one of F, Cl, Br and I, 0≤x1≤0.7, 0≤x2<1, 0≤x3<1, 0 <y<0.1。 3. The sedimentation-stable solid electrolyte slurry according to claim 1, characterized in that: The nanowires / tubes are selected from one or more of CNT, titanium oxide nanowires and aluminum oxide nanowires.
4. The sedimentation-stable solid electrolyte slurry according to claim 1, characterized in that: The solvent comprises at least one of water, NMP, ethanol, N,N-dimethylformamide, dimethylacetamide, 1,3-dioxolane and dimethyl carbonate.
5. A sedimentation-stable solid electrolyte slurry according to claim 1, characterized in that: The laser particle size of the solid electrolyte particles is D50=100 to 500 nm.
6. The sedimentation-stable solid electrolyte slurry according to claim 1 or 3, characterized in that: The length of the nanowire is 100 to 1000 microns, and the diameter of the nanotube is 0 to 20 nm.
7. The sedimentation-stable solid electrolyte slurry according to claim 1, characterized in that: The mass ratio of the nanowire / tube, inorganic oxide solid electrolyte and solvent is (0.01 to 0.05):1:(0.17 to 2.33).
8. A sedimentation-stable solid electrolyte slurry according to claim 1, characterized in that: The solid content change is ≤3%.
9. A method for preparing a sedimentation-stable solid electrolyte slurry according to any one of claims 1 to 8, characterized in that: Its preparation method is: S1. Mixing: mixing an inorganic oxide solid electrolyte with a solvent to obtain a slurry; S2, grinding: grinding the slurry prepared in S1 to obtain an unstable solid electrolyte dispersion; S3. Add the nanowires / tubes to the unstable solid electrolyte dispersion prepared in S2 and stir evenly.