CN103570946A - Preparation method of polyimide microsphere - Google Patents
Preparation method of polyimide microsphere Download PDFInfo
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- CN103570946A CN103570946A CN201310583099.8A CN201310583099A CN103570946A CN 103570946 A CN103570946 A CN 103570946A CN 201310583099 A CN201310583099 A CN 201310583099A CN 103570946 A CN103570946 A CN 103570946A
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Abstract
The invention provides a preparation method of a polyimide microsphere, which comprises the following steps that (1) polyamide acid is synthesized; (2) a polyamide acid microsphere is prepared; (3) the polyamide acid microsphere is subjected to imidization; a pyridine/acetic anhydride mixed solution is added to a polyamide acid microsphere solution obtained in Step (2); stirring is performed; reaction lasts for 2h; a polyimide solution is obtained; the obtained polyimide solution is centrifuged, filtered, washed and dried; the polyimide microsphere is obtained. The method is easy to realize; the prepared polyimide microsphere is small in particle size; the average particle size is 37.4-110nm.
Description
Technical field
The invention belongs to functional polymer microballoon field, be specifically related to a kind of preparation method of polyimide microsphere.
Background technology
Polyimide microsphere particle has pattern and the size of polymer microsphere uniqueness, and specific surface area is large, and adsorptivity is strong, and surface reaction ability is strong; Also have simultaneously high temperature resistant, resistance to solvent, the natural characteristics that physical strength is high, in support of the catalyst, coating, separation and sorbing material, biotechnology, the contour sophisticated technology of biological chemistry and information field has a wide range of applications.
The preparation method of polyimide microsphere mainly contains nonaqueous emulsion method and reprecipitation method etc.Wherein nonaqueous emulsion method exists polyimide microsphere particle diameter larger, and size distribution is wider, cannot obtain the polyimide microsphere of more uniform high sphericity, and in preparation process adding of emulsifying agent cause the polyimide microsphere unstable properties for preparing.Reprecipitation method is prepared polyimide microsphere and is generally used the solvability of polyimide in different solvents different, and target substance and poor solvent are mixed to get to polyimide microsphere.This method exists while dripping the precipitation agent that contains dispersion agent, and process is difficult to control, the problem of the large and wider distribution of microspherulite diameter, and also the general precipitation agent using is expensive, causes cost high.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, and a kind of preparation method of polyimide microsphere is provided, and simple process is not introduced additive, and cost is low; Prepared polyimide microsphere particle diameter is little, reaches Nano grade, and specific surface area is large, has the advantage of nanospheres and polyimide material concurrently.
The technical scheme that solution the technology of the present invention problem adopts is that the preparation method of this polyimide microsphere comprises the following steps:
(1) synthesizing polyamides acid: at 0-10 ℃, monomer diamines is dissolved in organic solvent, is stirred to completely and dissolves, obtain the solution of monomer diamines, then add tetracarboxylic dianhydride's monomer to carry out polyreaction, obtain polyamic acid solution;
(2) prepare polyamic acid microballoon: step (1) gained polyamic acid solution is added to the polyamic acid dilute solution that organic solvent diluting to solid content is 1-2wt%, in polyamic acid dilute solution, dropwise drip water again, in the process dripping, keep stirring, obtain polyamic acid microspheres solution;
(3) polyimide microsphere is prepared in the imidization of polyamic acid microballoon: will in step (2) gained polyamic acid microspheres solution, add pyridine/diacetyl oxide mixing solutions, stirring reaction 2-3 hour, obtain polyimide solution, again that the polyimide solution obtaining is centrifugal, filter, washing, dries and obtains polyimide microsphere.
The present invention utilizes polyimide intermediate polyamic acid to be difficult for reuniting, and the features such as the polyimide microsphere particle diameter forming is little, narrowly distributing add water to prepare polyamic acid microballoon in polyimide intermediate polyamic acid solution, then its imidization is obtained to polyimide microsphere.The resulting polyimide microsphere of this method is all being greatly improved aspect particle diameter and distribution thereof than existing methods.Polyimide microsphere particle diameter can reach nano level, compare with large ball diameter material, in nano structural material, there is a large amount of interfaces, dielectric confinement, and nanostructured microsphere has very high diffusivity, during for the preparation of polyimide nano-composite material, blend is more even, and the mechanical properties such as creep, superplasticity are significantly improved.In addition, polyimide material itself has high temperature resistant, corrosion-resistant, physical strength high, therefore nano level polyimide microsphere has Nano microsphere surface effects, dielectric confinement and high temperature resistant, the characteristic such as physical strength is high, has further expanded the Application Areas of polyimide material.
Preferably, the described monomer diamines of step (1) is 4,4'-diaminodiphenyl oxide, 4, a kind of in 4'-diaminodiphenylmethane, Ursol D, and described organic solvent is N,N-dimethylacetamide, the strength of solution of described monomer diamines is 5wt%.
Preferably, the described tetracarboxylic dianhydride's monomer of step (1) is pyromellitic acid anhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride or 2,3,3', a kind of in 4'-bibenzene tetracarboxylic dianhydride, tetracarboxylic dianhydride's monomer and monomer diamines mol ratio are 1.02:1, the described polymeric reaction condition of step (1) is under 500-700r/min rotating speed, at 0-10 ℃ of temperature, reacts 2-3 hour.The polyamic acid solution obtaining through step (1) is first diluted to the polyamic acid dilute solution that solid content is 1-2wt%, more further adds water and prepare polyamic acid microspheres solution.Polyamic acid solution solid content greatly easily causes soltion viscosity large, even occurs agglomeration.
Preferably, adding tetracarboxylic dianhydride's monomer described in step (1) is minute to add for 3 times, adds tetracarboxylic dianhydride's monomer of 1/3 weight part, every minor tick 30min at every turn.
Preferably, add-on and the polyamic acid dilute solution mass ratio of the described water of step (2) are 1:1, and it is 500-700r/min that described maintenance is stirred as keeping stir speed (S.S.).The too high meeting of rotating speed causes polyamic acid microballoon mutually to clash into, and causes the polyamic acid microspherulite diameter generating to distribute wide.
Preferably, the described pyridine/diacetyl oxide of step (3) mixing solutions add-on is 10% of polyamic acid microspheres solution volume, and in pyridine/diacetyl oxide mixing solutions, the volume ratio of pyridine and diacetyl oxide is 1:3.
The present invention also provides a kind of preparation method of polyimide microsphere.This preparation method comprises the following steps:
(1) synthesizing polyamides acid: at 0-10 ℃, monomer diamines is dissolved in organic solvent, is stirred to completely and dissolves, obtain the solution of monomer diamines, then add tetracarboxylic dianhydride's monomer to carry out polyreaction, obtain polyamic acid solution;
(2) prepare polyamic acid microballoon: step (1) gained polyamic acid solution is added to the polyamic acid dilute solution that organic solvent diluting to solid content is 1-2wt%, in polyamic acid dilute solution, dropwise drip water again, in the process dripping, keep stirring, obtain polyamic acid microspheres solution;
(3) polyimide microsphere is prepared in the imidization of polyamic acid microballoon: step (2) gained polyamic acid microspheres solution is coated on base material, and heats 2-3 hour at 240-270 ℃ of temperature, obtain polyimide microsphere coating.Described base material can be glass, tinsel etc.
Adopt the method for heating to the imidization of polyamic acid microballoon, be applicable to be coated on base material by polyamic acid microballoon or containing the mixture of polyamic acid microballoon, reheat and carry out forming the coating containing polyimide microsphere after imidization.
Preferably, the median size of the polyimide microsphere of being prepared by aforesaid method is 37.4-110nm, and particle diameter heterogeneity index is 0.225-0.278.
The invention has the beneficial effects as follows: adopt the method that is simple and easy to repetition to prepare at a lower temperature polyimide microsphere, in preparation process, directly take water as precipitation agent, do not need to add dispersion agent, thereby do not introduce impurity, the polyimide microsphere of preparation is purer, and with low cost.The polyimide microsphere particle diameter of preparing is little, and median size is 37.4-100nm, narrow diameter distribution, and particle diameter heterogeneity index is 0.225-0.278.
When preparing matrix material, can give matrix material better properties, and purity is higher, thereby the scope of application is wider.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of polyimide microsphere prepared in specific embodiment of the present invention;
Fig. 2 is the particle size distribution figure of polyimide microsphere prepared in embodiment mono-;
Fig. 3 is the electron-microscope scanning figure of polyimide microsphere prepared in embodiment bis-.
Embodiment
For making those skilled in the art understand better technical scheme of the present invention, below in conjunction with accompanying drawing, the present invention is described in further detail.
The embodiment of the present invention provides a kind of preparation method of polyimide microsphere, in organic solvent, monomer diamines and tetracarboxylic dianhydride's monomer reaction are obtained to polyamic acid, the water of take is again prepared polyamic acid microballoon as precipitation agent, and further the imidization of polyamic acid microballoon obtains polyimide microsphere.
Embodiment of the present invention N used, N-N,N-DIMETHYLACETAMIDE purity >=99wt%, monomer diamines 4 used, 4'-diaminodiphenyl oxide, 4,4-diamino dimethylbenzene alkane and Ursol D purity >=98wt%, tetracarboxylic dianhydride's monomer pyromellitic acid anhydride used, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride or 2,3,3', 4'-bibenzene tetracarboxylic dianhydride purity >=98wt%.
Embodiment mono-
Under frozen water mixing bath condition (0 ℃), take 5.0g4, 4'-diaminodiphenyl oxide (0.025mol) is dissolved in 90gN, in N-N,N-DIMETHYLACETAMIDE, after all dissolving, dividing adds for 3 times pyromellitic acid anhydride to carry out polyreaction, add 1.854g pyromellitic acid anhydride at every turn, add altogether 5.562g(0.0255mol), after dissolving completely each time, add again next time (4, the mol ratio of 4'-diaminodiphenyl oxide and pyromellitic acid anhydride is 1:1.02), reaction times is 3h, stir speed (S.S.) is 700r/min, obtain solid content and be 10% polyamic acid solution.Take the prepared polyamic acid solution of 20g, then add 180gN, N-N,N-DIMETHYLACETAMIDE, obtains the polyamic acid dilute solution of solid content 1wt%.Take the above-mentioned polyamic acid dilute solution of 20g, slowly drip 20g distilled water under the rotating speed of 700r/min, time for adding is 5min, prepares polyamic acid microspheres solution.
The polyamic acid microspheres solution obtaining is coated on sheet glass uniformly, and at 270 ℃, heats 2 hours in retort furnace, obtain polyimide microsphere coating.
Adopt transmission electron microscope to test the prepared polyimide microsphere of the embodiment of the present invention, be illustrated in figure 1 the transmission electron microscope picture of the prepared polyimide microsphere of the present embodiment, polyimide microsphere particle diameter is 40nm.Adopt the Britain Mastersizer3000 of Ma Erwen company particle-size analyzer to carry out testing graininess to the prepared polyimide microsphere of the present embodiment, its particle size distribution figure as shown in Figure 2.After tested, gained polyimide microsphere median size is 37.4nm, is normal distribution, and particle diameter polydispersity index is 0.225.
Embodiment bis-
At 10 ℃, take 5.0g4,4'-diaminodiphenyl oxide (0.025mol) is dissolved in 90gN, in N-N,N-DIMETHYLACETAMIDE, after all dissolving, dividing adds for 3 times pyromellitic acid anhydride to carry out polyreaction, add 1.854g pyromellitic acid anhydride at every turn, add altogether 5.562g(0.0255mol), after dissolving completely each time, add next time (mol ratio of 4,4'-diaminodiphenyl oxide and pyromellitic acid anhydride is 1:1.02), the reaction times is 2h again, stir speed (S.S.) is 500r/min, obtains solid content and be 10% polyamic acid solution.Take the prepared polyamic acid solution of 20g, then add 80gN, N-N,N-DIMETHYLACETAMIDE, obtains the polyamic acid dilute solution of solid content 2%.Take the above-mentioned polyamic acid dilute solution of 20g, slowly drip 20g distilled water under the rotating speed of 500r/min, time for adding is 5min, prepares polyamic acid microspheres solution.
4ml pyridine/diacetyl oxide mixing solutions (volume ratio of pyridine and diacetyl oxide is 1:3) will be added in the polyamic acid microspheres solution obtaining, stirring reaction 2 hours, obtain polyimide solution, again that the polyimide solution obtaining is centrifugal in the whizzer of 10000r/min, filter, washing, dries and obtains polyimide microsphere.
Adopt the method identical with embodiment mono-and electron-microscope scanning to carry out testing graininess to the prepared polyimide microsphere of the present embodiment.After tested, gained polyimide microsphere median size is 82.1nm, be normal distribution, particle diameter polydispersity index is 0.278, the electron-microscope scanning figure that is illustrated in figure 3 the prepared polyimide microsphere of the present embodiment, polyimide microsphere has good globosity as can be seen from Figure, and is uniformly dispersed, size homogeneous, particle diameter is about 70-110nm.
Embodiment tri-
At 0 ℃, take 5.0g4, 4 '-diaminodiphenylmethane (0.0252mol) is dissolved in 124gN, in N-N,N-DIMETHYLACETAMIDE, after all dissolving, divide and add 33 times, 3', 4, 4'-bibenzene tetracarboxylic dianhydride carries out polyreaction, add 2.520g3 at every turn, 3', 4, 4'-bibenzene tetracarboxylic dianhydride, add altogether 7.561g(0.0257mol), after dissolving completely each time, add again next time (4, 4 '-diaminodiphenylmethane and 3, 3', 4, the mol ratio of 4'-bibenzene tetracarboxylic dianhydride is 1:1.02), reaction times is 3h, stir speed (S.S.) is 600r/min, obtain the polyamic acid solution that solid content is 10wt%.Take the prepared polyamic acid solution of 20g, then add 180gN, N-N,N-DIMETHYLACETAMIDE, obtains the polyamic acid dilute solution of solid content 1wt%.Take the above-mentioned polyamic acid dilute solution of 20g, slowly drip 20g distilled water under the rotating speed of 600r/min, time for adding is 5min, prepares polyamic acid microspheres solution.
The polyamic acid microspheres solution obtaining is coated on sheet glass uniformly, and at 240 ℃ of temperature, heats 3 hours in retort furnace, obtain polyimide microsphere coating.
Adopt the method identical with embodiment mono-to carry out testing graininess to the prepared polyimide microsphere of the present embodiment.After tested, gained polyimide microsphere median size is 50.7nm, is normal distribution, and particle diameter polydispersity index is 0.258.
Embodiment tetra-
At 5 ℃, take 5.0g Ursol D (0.0463mol) and be dissolved in 171gN, in N-N,N-DIMETHYLACETAMIDE, after all dissolving, divide and add 2,3,3' 3 times, 4'-bibenzene tetracarboxylic dianhydride, add 4.625g at every turn, add altogether 13.876g(0.0472mol), after dissolving completely each time, add again next time (Ursol D and 2,3,3', the mol ratio of 4'-bibenzene tetracarboxylic dianhydride is 1:1.02), the reaction times is 3h, stir speed (S.S.) is 600r/min, obtains the polyamic acid solution that solid content is 10wt%.Take the prepared polyamic acid solution of 20g, then add 180gN, N-N,N-DIMETHYLACETAMIDE, obtains the polyamic acid dilute solution of solid content 1wt%.Take the above-mentioned polyamic acid dilute solution of 20g, slowly drip 20g distilled water under the rotating speed of 600r/min, time for adding is 5min, prepares polyamic acid microspheres solution.
4ml pyridine/diacetyl oxide mixing solutions (volume ratio of pyridine and diacetyl oxide is 1:3) will be added in the polyamic acid microspheres solution obtaining, stirring reaction 2 hours, obtain polyimide solution, again that the polyimide solution obtaining is centrifugal in the whizzer of 10000r/min, filter, washing, dries and obtains polyimide microsphere.
Adopt the method identical with embodiment bis-to carry out testing graininess to the prepared polyimide microsphere of the present embodiment.After tested, gained polyimide microsphere median size is 60.9nm, is normal distribution, and size distribution index is 0.230.
By the above detailed description to the embodiment of the present invention, can understand and the invention solves polyimide microsphere preparation method complexity in prior art, and the polyimide microsphere particle diameter obtaining is large or the wide problem that distributes, resulting polyimide microsphere median size is 37.4-110nm, and particle diameter heterogeneity index is 0.225-0.278.
Be understandable that, above embodiment is only used to principle of the present invention is described and the illustrative embodiments that adopts, yet the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (8)
1. a preparation method for polyimide microsphere, is characterized in that comprising the following steps:
(1) synthesizing polyamides acid: at 0-10 ℃, monomer diamines is dissolved in organic solvent, is stirred to completely and dissolves, obtain the solution of monomer diamines, then add tetracarboxylic dianhydride's monomer to carry out polyreaction, obtain polyamic acid solution;
(2) prepare polyamic acid microballoon: step (1) gained polyamic acid solution is added to the polyamic acid dilute solution that organic solvent diluting to solid content is 1-2wt%, in polyamic acid dilute solution, dropwise drip water again, in the process dripping, keep stirring, obtain polyamic acid microspheres solution;
(3) polyimide microsphere is prepared in the imidization of polyamic acid microballoon: will in step (2) gained polyamic acid microspheres solution, add pyridine/diacetyl oxide mixing solutions, stirring reaction 2-3 hour, obtain polyimide solution, again that the polyimide solution obtaining is centrifugal, filter, washing, dries and obtains polyimide microsphere.
2. the preparation method of polyimide microsphere according to claim 1, it is characterized in that the described monomer diamines of step (1) is 4,4'-diaminodiphenyl oxide, 4, a kind of in 4'-diaminodiphenylmethane, Ursol D, described organic solvent is N, N-N,N-DIMETHYLACETAMIDE, the strength of solution of described monomer diamines is 5wt%.
3. the preparation method of polyimide microsphere according to claim 2, it is characterized in that the described tetracarboxylic dianhydride's monomer of step (1) is pyromellitic acid anhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride or 2,3,3', a kind of in 4'-bibenzene tetracarboxylic dianhydride, tetracarboxylic dianhydride's monomer and monomer diamines mol ratio are 1.02:1, the described polymeric reaction condition of step (1) is under 500-700r/min rotating speed, at 0-10 ℃ of temperature, reacts 2-3 hour.
4. the preparation method of polyimide microsphere according to claim 3, it is characterized in that adding described in step (1) tetracarboxylic dianhydride's monomer is minute to add for 3 times, adds tetracarboxylic dianhydride's monomer of 1/3 weight part, every minor tick 30min at every turn.
5. the preparation method of polyimide microsphere according to claim 1, is characterized in that the add-on of the described water of step (2) and polyamic acid dilute solution mass ratio are 1:1, and it is 500-700r/min that described maintenance is stirred as keeping stir speed (S.S.).
6. the preparation method of polyimide microsphere according to claim 1, it is characterized in that the described pyridine/diacetyl oxide of step (3) mixing solutions add-on is 10% of polyamic acid microspheres solution volume, in pyridine/diacetyl oxide mixing solutions, the volume ratio of pyridine and diacetyl oxide is 1:3.
7. a preparation method for polyimide microsphere, is characterized in that comprising the following steps:
(1) synthesizing polyamides acid: at 0-10 ℃, monomer diamines is dissolved in organic solvent, is stirred to completely and dissolves, obtain the solution of monomer diamines, then add tetracarboxylic dianhydride's monomer to carry out polyreaction, obtain polyamic acid solution;
(2) prepare polyamic acid microballoon: step (1) gained polyamic acid solution is added to the polyamic acid dilute solution that organic solvent diluting to solid content is 1-2wt%, in polyamic acid dilute solution, dropwise drip water again, in the process dripping, keep stirring, obtain polyamic acid microspheres solution;
(3) polyimide microsphere is prepared in the imidization of polyamic acid microballoon: step (2) gained polyamic acid microspheres solution is coated on base material, and heats 2-3 hour at 240-270 ℃ of temperature, obtain polyimide microsphere.
8. according to the preparation method of the arbitrary described polyimide microsphere of claim 1-7, it is characterized in that the median size of the polyimide microsphere of preparation is 37.4-110nm.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130411A (en) * | 2014-08-01 | 2014-11-05 | 黑龙江省科学院高技术研究院 | Preparation method of hollow polyimide composite microspheres |
| CN104710789A (en) * | 2015-03-16 | 2015-06-17 | 吉林大学 | Preparation method of polyimide molding powder |
| CN105713349A (en) * | 2016-03-21 | 2016-06-29 | 武汉理工大学 | Method for preparing abrasion-resistant and heat-resistant epoxy resin composite material |
| CN106111028A (en) * | 2016-06-28 | 2016-11-16 | 陈建峰 | A kind of preparation method of microcapsule battery compound polyimide dielectric material |
| CN111057237A (en) * | 2019-12-23 | 2020-04-24 | 华南理工大学 | Polyimide microsphere and preparation method thereof |
| CN111875796A (en) * | 2020-06-28 | 2020-11-03 | 东华大学 | Polyimide nano-microsphere for gas separation membrane |
| CN112266611A (en) * | 2020-10-14 | 2021-01-26 | 中国科学院合肥物质科学研究院 | Functionalized polyimide composite microsphere and preparation method thereof |
| CN113169418A (en) * | 2019-01-22 | 2021-07-23 | 东莞东阳光科研发有限公司 | Polyimide microsphere slurry, composite diaphragm and lithium ion battery |
| CN113231043A (en) * | 2021-05-06 | 2021-08-10 | 哈尔滨工程大学 | Oximato multi-layer polyimide microsphere adsorption material and preparation method thereof |
| CN117069939A (en) * | 2023-10-17 | 2023-11-17 | 宁德时代新能源科技股份有限公司 | Polyimide microsphere and preparation method thereof, negative electrode plate, battery and power utilization device |
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| CN104130411A (en) * | 2014-08-01 | 2014-11-05 | 黑龙江省科学院高技术研究院 | Preparation method of hollow polyimide composite microspheres |
| CN104710789A (en) * | 2015-03-16 | 2015-06-17 | 吉林大学 | Preparation method of polyimide molding powder |
| CN105713349A (en) * | 2016-03-21 | 2016-06-29 | 武汉理工大学 | Method for preparing abrasion-resistant and heat-resistant epoxy resin composite material |
| CN105713349B (en) * | 2016-03-21 | 2017-12-29 | 武汉理工大学 | A kind of preparation method of antiwear heat resisting epoxy resin composite material |
| CN106111028A (en) * | 2016-06-28 | 2016-11-16 | 陈建峰 | A kind of preparation method of microcapsule battery compound polyimide dielectric material |
| CN106111028B (en) * | 2016-06-28 | 2018-12-18 | 东阳市新意工业产品设计有限公司 | A kind of preparation method of microcapsules battery compound polyimide dielectric material |
| CN113169418A (en) * | 2019-01-22 | 2021-07-23 | 东莞东阳光科研发有限公司 | Polyimide microsphere slurry, composite diaphragm and lithium ion battery |
| CN111057237A (en) * | 2019-12-23 | 2020-04-24 | 华南理工大学 | Polyimide microsphere and preparation method thereof |
| CN111057237B (en) * | 2019-12-23 | 2021-10-26 | 华南理工大学 | Polyimide microsphere and preparation method thereof |
| CN111875796A (en) * | 2020-06-28 | 2020-11-03 | 东华大学 | Polyimide nano-microsphere for gas separation membrane |
| CN112266611A (en) * | 2020-10-14 | 2021-01-26 | 中国科学院合肥物质科学研究院 | Functionalized polyimide composite microsphere and preparation method thereof |
| CN112266611B (en) * | 2020-10-14 | 2023-05-05 | 中国科学院合肥物质科学研究院 | Functionalized polyimide composite microsphere and preparation method thereof |
| CN113231043A (en) * | 2021-05-06 | 2021-08-10 | 哈尔滨工程大学 | Oximato multi-layer polyimide microsphere adsorption material and preparation method thereof |
| CN117069939A (en) * | 2023-10-17 | 2023-11-17 | 宁德时代新能源科技股份有限公司 | Polyimide microsphere and preparation method thereof, negative electrode plate, battery and power utilization device |
| CN117069939B (en) * | 2023-10-17 | 2024-04-09 | 宁德时代新能源科技股份有限公司 | Polyimide microsphere and preparation method thereof, negative electrode plate, battery and power utilization device |
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