CN111392731A - Preparation method of nano silica sand mill by taking polyvinylpyrrolidone as dispersing agent - Google Patents
Preparation method of nano silica sand mill by taking polyvinylpyrrolidone as dispersing agent Download PDFInfo
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- CN111392731A CN111392731A CN202010269305.8A CN202010269305A CN111392731A CN 111392731 A CN111392731 A CN 111392731A CN 202010269305 A CN202010269305 A CN 202010269305A CN 111392731 A CN111392731 A CN 111392731A
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- Prior art keywords
- sand mill
- sanding
- silicon
- silica sand
- nano silica
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000004576 sand Substances 0.000 title claims abstract description 37
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 title claims abstract description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 title claims abstract description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 14
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000011856 silicon-based particle Substances 0.000 abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010406 cathode material Substances 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003801 milling Methods 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 abstract description 2
- 238000007709 nanocrystallization Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A nano-silica sand mill preparation method using polyvinylpyrrolidone as a dispersing agent relates to the technical field of production of lithium ion battery silicon-carbon cathode materials, and comprises the steps of dispersing coarse silica powder in a solvent and the dispersing agent, and performing sand milling in a sand mill with a grinding medium to obtain slurry containing nano-silica; the dispersant comprises at least polyvinylpyrrolidone. The nano silicon is prepared by adopting a liquid phase sanding method, silicon particles and a grinding medium are collided at a high speed through grinding to be crushed into nano particles, the dispersing agent polyvinylpyrrolidone plays an extremely important role in crushing the silicon particles, and the polyvinylpyrrolidone can remarkably reduce the aggregation of the silicon particles and the viscosity of slurry, so that the sanding efficiency, the uniformity of the particles and the dispersibility of the silicon particles in a solvent are improved. The method can carry out nanocrystallization treatment on the coarse silicon powder with the particle diameter of 0.24-60 mu m, and the coarse silicon powder can be monocrystalline silicon or polycrystalline silicon.
Description
Technical Field
The invention relates to the technical field of production of silicon-carbon cathode materials of lithium ion batteries, in particular to a preparation process of nano silicon in the silicon-carbon cathode materials.
Background
The nanometer silicon powder is a new generation photoelectric semiconductor material, has a wider gap energy semiconductor, and is also a high-power light source material. The nano silicon powder can be doped into carbon powder or graphite to be used as a lithium battery cathode material, so that the capacity of the lithium battery is greatly improved.
The lithium ion battery is widely applied to various fields due to the excellent performance, and with the development of science and technology and economy, the performance of the lithium ion battery is continuously improved, but the requirements of people on higher capacity and endurance cannot be met.
At present, most of the negative electrodes of lithium ion batteries are graphite materials, and the theoretical specific capacity of the negative electrodes is only 372mAh/g, so that the wide application of people in the fields of mobile phones, new energy automobiles and the like is limited. The silicon material has good lithium intercalation and lithium deintercalation performance, and the theoretical specific capacity can reach 4200 mAh/g. However, the silicon material is easily expanded and pulverized during charge and discharge, resulting in degradation of battery performance.
In recent years, silicon materials are made into nanometer level, so that silicon carbon cathode materials are made, and the expansion amount of silicon is remarkably reduced. One of the commonly used methods for preparing nano-silicon is a mechanical ball milling method, also called a sand milling method. At present, the problems of easy aggregation, high viscosity of slurry, low sanding efficiency, poor particle uniformity and the like exist in the nano silicon prepared by the method.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing nano silicon by using polyvinylpyrrolidone as a dispersing agent in a sand milling method.
The technical scheme of the invention is as follows: dispersing the crude silicon powder in a solvent and a dispersing agent with the molecular weight of 1000-600000, and sanding in a sand mill with a grinding medium to obtain slurry containing nano silicon; the dispersant comprises at least polyvinylpyrrolidone.
The invention adopts a liquid phase sanding method to prepare nano-silicon, silicon particles and a grinding medium are collided at high speed to be crushed into nano-particles through grinding, the dispersant polyvinylpyrrolidone plays an extremely important role in crushing the silicon particles, and the polyvinylpyrrolidone can remarkably reduce the aggregation of the silicon particles and the viscosity of slurry, thereby improving the sanding efficiency, the uniformity of the particles and the dispersibility of the silicon particles in the solvent.
The method can carry out nanocrystallization treatment on the coarse silicon powder with the particle diameter of 0.24-60 mu m, and the coarse silicon powder can be monocrystalline silicon or polycrystalline silicon.
In addition, the molecular weight of the dispersing agent in the process is 1000-600000, if the molecular weight of the dispersing agent is lower than 1000, a finished product is difficult to prepare, and if the molecular weight of the dispersing agent is higher than 600000, the viscosity is too high to serve as the dispersing agent.
Furthermore, the feeding mass ratio of the dispersing agent to the coarse silicon powder is 0.1-5: 100. If the amount of the dispersant is too low, the effect is not good; and if the amount is too high, the viscosity of the slurry is increased and the purity of the nano silicon is reduced.
The feeding mass ratio of the coarse silicon powder to the solvent is 8-35: 100. If the amount of the crude silicon powder is too low, the cost is obviously increased; if the amount of coarse silica powder is too high, the viscosity of the slurry becomes too high, and the sanding efficiency is lowered.
The solvent is absolute ethyl alcohol or isopropanol. The two solvents are common dispersing media at present, have low cost, low water content and high purity, have good dispersing effect on nano silicon and have small effect with high-activity nano silicon.
The grinding medium is zirconia balls with the average grain diameter of 0.1-0.8 mm. If zirconia balls with too small a particle size are used, it is expensive, and if zirconia balls with too large a particle size are used, the coarse silicon powder cannot be crushed to the desired particle size.
The sanding in the invention can be carried out by one-time sanding or grading sanding. If two-stage sanding is adopted, the first stage adopts larger zirconia ball sanding, such as average grain diameter of 0.6mm, and the second stage adopts smaller zirconia ball sanding, such as average grain diameter of 0.1 mm. During the hierarchical sanding, earlier with the silica flour of the great granule of zirconia ball sanding of great granule, the silica flour of the less granule of zirconia ball sanding of reuse, this can show and improve sanding efficiency, reduces the sanding cost.
The primary sanding time is 1-36 h, and the secondary sanding time is 1-36 h. Please supplement what the sanding times at each level have a particular impact on the final product: if the sanding time is too short, the size of the silicon particles may not meet the desired requirements, whereas if the sanding time is too long, the cost is increased and the silicon is also susceptible to oxidation.
The dispersing agent can be added in one time before sanding, or can be added into a sand mill in batches. The dispersing agent is added at one time, the operation is convenient, and the sanding is more accurate and the efficiency is higher by adding the dispersing agent in batches.
The dispersant in the present invention further includes at least one of polyacrylic acid (PAA), polyvinyl alcohol (PVA), or carboxymethyl cellulose (CMC). Polyvinylpyrrolidone may be used as a dispersant independently, or may be used in combination with PAA, PVA, or CMC. The combination of the two components can exert the respective advantages of different dispersants, so that the performance is further improved.
The sanding adopts the stick pin formula or the turbine formula sand mill that power is 2 ~ 350kw, and the grinding chamber capacity is 1 ~ 300 liters, and the sanding total time is 1 ~ 36 h. The pin type sand mill has high sanding efficiency, but also has large power consumption and higher cavity temperature. The turbine type sand mill has low power consumption and low grinding medium loss. The coarse silicon powder can be fully crushed by adopting proper power and sanding time on the premise of saving electricity. The capacity of the sand mill can be selected according to the production quantity, and the high-capacity sand mill can be selected for high yield.
Detailed Description
Example 1:
the cavity capacity of the pin-and-rod type sand mill was 1 liter, and 1.5kg of zirconia balls having an average particle diameter of 0.6mm were put into the storage tank.
500g of crude silicon with an average particle size of 60 μm was dispersed in 3000g of absolute ethanol, and 4g of polyvinylpyrrolidone with a molecular weight of 3500 was added and uniformly dispersed to obtain a slurry.
And (3) moving the slurry into a storage tank of a sand mill and sanding, wherein the rotating speed of the sand mill is 2200rpm, the temperature of a cavity is 35 +/-5 ℃, and sanding is finished after 4 hours. Sampling tests showed that the average particle size of the silicon particles in the slurry was 0.240. mu.m.
Transferring the slurry into a material storage tank of another rod pin type sand mill with the capacity of 1 liter, adding 1.8kg of zirconia balls with the average particle size of 0.1mm into the material storage tank, continuously grinding for 10 hours, wherein the rotation speed of the sand mill is 2400rpm, the cavity temperature is 32 +/-5 ℃, and finishing the grinding after 15 hours. Sampling tests showed that the average particle size of the silicon particles in the slurry was 0.0450 μm.
Example 2:
the rod pin type sand mill had a cavity capacity of 10 liters, and 30kg of zirconia balls having an average particle diameter of 0.3mm were put into a storage tank.
5kg of crude silicon having an average particle diameter of 1 μm was dispersed in 35kg of isopropyl alcohol, and 120g of polyvinylpyrrolidone having a molecular weight of 152000 was added thereto and uniformly dispersed to obtain a slurry.
And (3) moving the slurry into a storage tank of a sand mill and sanding the slurry, wherein the rotating speed of the sand mill is 1200rpm, the temperature of a cavity is 30 +/-5 ℃, and sanding is finished after 10 hours. Sampling tests showed that the average particle size of the silicon particles in the slurry was 0.106. mu.m.
Example 3:
the capacity of the cavity of the turbine-type sand mill was 90 liters, and 200kg of zirconia balls having an average particle diameter of 0.1mm were put into the storage tank.
45kg of crude silicon having an average particle size of 0.350 μm was dispersed in 330kg of isopropyl alcohol, and 90g of polyvinylpyrrolidone having a molecular weight of 12000 was added thereto and uniformly dispersed to obtain a slurry.
And (3) moving the slurry into a storage tank of a sand mill, sanding at the rotating speed of 430rpm and the temperature of the cavity of 20 +/-5 ℃, adding 360g of polyvinyl alcohol (PVA) into the storage tank after 7 hours, and finishing sanding after 15 hours. Sampling tests show that the average particle size of the silicon particles in the slurry is 0.0527 μm.
Claims (10)
1. The preparation method of the nano silica sand mill with polyvinylpyrrolidone as a dispersant is characterized by comprising the following steps: dispersing the crude silicon powder in a solvent and a dispersing agent with the molecular weight of 1000-600000, and sanding in a sand mill with a grinding medium to obtain slurry containing nano silicon; the dispersant comprises at least polyvinylpyrrolidone.
2. The method for preparing nano silica sand mill according to claim 1, characterized in that: the feeding mass ratio of the polyvinylpyrrolidone to the coarse silicon powder is 0.1-5: 100.
3. The method for preparing nano silica sand mill according to claim 1, characterized in that: the feeding mass ratio of the coarse silicon powder to the solvent is 8-35: 100.
4. The method for preparing nano silica sand mill according to claim 1 or 3, characterized in that: the solvent is absolute ethyl alcohol or isopropanol.
5. The method for preparing nano silica sand mill according to claim 1, characterized in that: the grinding medium is zirconia balls with the average grain diameter of 0.1-0.8 mm.
6. The method for preparing nano silica sand mill according to claim 5, characterized in that: adopt the two-stage sanding, the great zirconia ball sanding of particle diameter is adopted in the first order sanding, and the less zirconia ball of particle diameter is adopted in the second level sanding.
7. The method for preparing nano silica sand mill according to claim 6, characterized in that: the primary sanding time is 1-36 h, and the secondary sanding time is 1-36 h.
8. The method for preparing nano silica sand mill according to claim 1, characterized in that: the dispersing agent is added into the sand mill in batches.
9. The method for preparing nano silica sand mill according to claim 1, characterized in that: the dispersing agent also comprises at least one of polyacrylic acid, polyvinyl alcohol or carboxymethyl cellulose.
10. The method for preparing nano silica sand mill according to claim 1, characterized in that: the sanding adopts the stick pin formula or the turbine formula sand mill that power is 2 ~ 350kw, and the grinding chamber capacity is 1 ~ 300 liters, and the sanding total time is 1 ~ 36 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010269305.8A CN111392731A (en) | 2020-04-08 | 2020-04-08 | Preparation method of nano silica sand mill by taking polyvinylpyrrolidone as dispersing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010269305.8A CN111392731A (en) | 2020-04-08 | 2020-04-08 | Preparation method of nano silica sand mill by taking polyvinylpyrrolidone as dispersing agent |
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| Publication Number | Publication Date |
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| CN111392731A true CN111392731A (en) | 2020-07-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010269305.8A Pending CN111392731A (en) | 2020-04-08 | 2020-04-08 | Preparation method of nano silica sand mill by taking polyvinylpyrrolidone as dispersing agent |
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| CN (1) | CN111392731A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113675532A (en) * | 2021-08-13 | 2021-11-19 | 东莞维科电池有限公司 | Diaphragm and preparation method and application thereof |
| CN115777701A (en) * | 2022-12-20 | 2023-03-14 | 惠州市银农科技股份有限公司 | Thiacloprid-containing nano suspending agent and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702796A (en) * | 2012-05-28 | 2012-10-03 | 深圳市贝特瑞新能源材料股份有限公司 | Method for improving dispersion property of nanosilicon grinding fluid |
| CN105655570A (en) * | 2016-04-01 | 2016-06-08 | 四川创能新能源材料有限公司 | Refining preparation method of nanoscale silicon powder material |
| CN109860548A (en) * | 2019-01-17 | 2019-06-07 | 长沙矿冶研究院有限责任公司 | A kind of preparation method and applications of nano silicon material |
| CN110890537A (en) * | 2018-09-11 | 2020-03-17 | 江苏中能硅业科技发展有限公司 | Production method of high-purity nanocrystalline silicon |
-
2020
- 2020-04-08 CN CN202010269305.8A patent/CN111392731A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702796A (en) * | 2012-05-28 | 2012-10-03 | 深圳市贝特瑞新能源材料股份有限公司 | Method for improving dispersion property of nanosilicon grinding fluid |
| CN105655570A (en) * | 2016-04-01 | 2016-06-08 | 四川创能新能源材料有限公司 | Refining preparation method of nanoscale silicon powder material |
| CN110890537A (en) * | 2018-09-11 | 2020-03-17 | 江苏中能硅业科技发展有限公司 | Production method of high-purity nanocrystalline silicon |
| CN109860548A (en) * | 2019-01-17 | 2019-06-07 | 长沙矿冶研究院有限责任公司 | A kind of preparation method and applications of nano silicon material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113675532A (en) * | 2021-08-13 | 2021-11-19 | 东莞维科电池有限公司 | Diaphragm and preparation method and application thereof |
| CN115777701A (en) * | 2022-12-20 | 2023-03-14 | 惠州市银农科技股份有限公司 | Thiacloprid-containing nano suspending agent and preparation method thereof |
| CN115777701B (en) * | 2022-12-20 | 2023-08-11 | 惠州市银农科技股份有限公司 | Thiacloprid-containing nanosuspension and preparation method thereof |
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