CN107353674A - A kind of preparation method of nano silicon carbon nano-tube hybridization material - Google Patents

A kind of preparation method of nano silicon carbon nano-tube hybridization material Download PDF

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CN107353674A
CN107353674A CN201710481324.5A CN201710481324A CN107353674A CN 107353674 A CN107353674 A CN 107353674A CN 201710481324 A CN201710481324 A CN 201710481324A CN 107353674 A CN107353674 A CN 107353674A
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nano
carbon nano
suspension
tube
nano silicon
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占宏君
管新兵
吴龙梅
何俊杰
李凯杰
陈文宁
韩琪
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Spectrum Detection Technology Service Co Ltd In Guangzhou
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K2201/011—Nanostructured additives

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Abstract

The present invention discloses a kind of preparation method of nano silicon carbon nano-tube hybridization material, and methods described includes：Under ul-trasonic irradiation, cationic polyelectrolyte and anionic polyelectrolyte is respectively adopted surface modification is carried out to CNT and nano silicon, finely dispersed suspension is prepared；Both suspension are uniformly mixed, nanometer silicon dioxide particle is uniformly wrapped on carbon nano tube surface, obtains nano silicon carbon nano-tube hybridization material.The nano silicon carbon nano-tube hybridization material that the present invention obtains can mutually suppress respective reunion behavior, and collaboration promotes it scattered in polymeric matrix, significantly increases polymer.This is advantageous to the potential application scope for widening CNT and nano silicon, and has important directive significance to preparing high performance polymer composite material.

Description

A kind of preparation method of nano silicon-carbon nano-tube hybridization material
Technical field
The present invention relates to a kind of preparation method of carbon nano-tube hybridization material, and in particular to a kind of nano silicon modification The preparation method of carbon nano-tube hybridization material and its application in the polymer.
Background technology
CNT causes people widely to study due to performances such as its excellent mechanics, calorifics, electricity.As one kind New Nano filling, can apply in polymer composites, significantly improve the combination property of composite.But by There is great draw ratio and specific surface area in CNT, it is difficult dispersed and and polymer in polymeric matrix to make it The interface interaction of matrix is poor, and cause brings it about serious reunion and entanglement behavior, and cause CNT excellent properties can not Embody, and form substantial amounts of stress concentration point, destroy the combination property of composite.Therefore, in order to be effectively improved CNT The scattered and its interfacial interaction with matrix in the base, it is essential to carry out surface modification to CNT.
Nano silicon is because of its nanostructured, larger specific surface area and good mechanical performance, chemical stability, Through being widely used in strengthening polymer.But because serious group easily occurs for its larger specific surface area, silica dioxide granule It is poly-, it is difficult to uniformly be scattered in polymer, therefore, nano silicon is significantly limit in polymer composites Using.
At present, using the excellent properties of CNT and the stability of nano silicon, there is researcher's preparation Nano silicon-carbon nano tube compound material.By modifying nanometer silicon dioxide particle in carbon nano tube surface, effectively Inhibit the reunion of CNT and nano silicon, collaboration promotes both in the polymer scattered.Such as Chinese patent CN106058179A and CN100515937C, it is compound that carbon nanotube/nano silica is prepared using sol-gal process Material, and propose to be applied to enhancing polymer composites.Need to introduce substantial amounts of organic solvent during but, cause ring Border is polluted, and is prepared carbon nanotube/nano silica composite surface and lacked active site, can not effectively improve it with gathering The mutual left and right in interface of compound matrix.Meanwhile Chinese patent CN105175781A, using chemical graft means, promote surface to repair The amination silica of decorations and the carboxylic carbon nano-tube of oxidation processes carry out reaction generation amido link, are further prepared Silicon dioxide modified carbon nano tube compound material, and propose to be used for that resin, rubber etc. are macromolecule modified to prepare high-performance nano Composite.But this method such as needs to be acidified CNT, aoxidized at the pretreatment, destroying carbon nanometer tube it is excellent Performance, meanwhile, preparation process is complicated, and technique is cumbersome, and severe reaction conditions, production efficiency is relatively low, and can not realize scale metaplasia Production.
Therefore, on the basis of CNT performance itself is not influenceed, need to develop a kind of simple effective method at present The uniform enveloped carbon nanometer tube of nanometer silicon dioxide particle is realized, to promote both scattered in polymeric matrix, this is to preparing High performance polymer composite material has important Research Significance, and be advantageous to widen CNT and nano silicon should Use scope.
The content of the invention
The present invention is first using polyelectrolyte as modifying agent, and by CNT and nano silicon, ultrasound is made in water respectively Standby finely dispersed suspension, is then acted on using electrostatic assembly, prepares functionalized nano silica-carbon pipe hydridization material Material.
The present invention is first under ul-trasonic irradiation, using cationic polyelectrolyte as modifying agent, to surface inactive carbon nanometer Pipe is ultrasonically treated, and water miscible cationic polyelectrolyte can be adsorbed effectively in carbon nano tube surface, be prepared scattered Uniform carbon nano tube suspension.Meanwhile using anionic polyelectrolyte as modifying agent, ultrasonic place is carried out to nano silicon Reason, water-soluble anionic polyelectrolyte can effective improved silica, finely dispersed nano silicon is prepared Suspension.Both suspension are mixed, due to electrostatic interaction, nano silicon can be uniformly wrapped on carbon nanometer Pipe surface, nano silicon-carbon nano-tube hybridization material is prepared.
This programme purpose is realized by following scheme:
A kind of preparation method of nano silicon-carbon nano-tube hybridization material, it is characterised in that including walking in detail below Suddenly:
(1) modified carbon nano-tube suspension is prepared：Take a certain amount of CNT to be dispersed in water, and add a certain amount of sun Cationic polyelectrolyte, ultrasonic disperse for a period of time after, centrifugation removes excessive polyelectrolyte, and disperses to obtain the carbon of black again Nanotube suspension.
(2) modified manometer silicon dioxide suspension is prepared：A certain amount of nano silicon is dispersed in water, and added A certain amount of anionic polyelectrolyte, ultrasonic disperse for a period of time after, centrifugation removes excessive polyelectrolyte, and disperses again To the nanometer titanium dioxide silicon suspension of white.
(3) nano silicon-carbon nano-tube hybridization material is prepared：By the certain density modified Nano of system in step (2) Silica suspension adds in certain density modified carbon nano-tube suspension, obtains uniform floccule into step (1). Then, washed repeatedly for several times using water and ethanol, 12~24h is dried in vacuo at 60~90 DEG C, obtains the nano-silica of grey SiClx-carbon nano-tube hybridization material.
The cationic polyelectrolyte is PDDA, polyethyleneimine, poly- hydroxypropyl diformazan One kind in ammonium chloride；
The anionic polyelectrolyte is Sodium Polyacrylate, kayexalate, one kind in ammonium polyacrylate；
The mass ratio of the cationic polyelectrolyte and CNT is 1:5~25；
The mass ratio of the anionic polyelectrolyte and nano silicon is 1:4~12.5；
The concentration of modified carbon nano-tube and the modified manometer silicon dioxide suspension is 25~40g/L；
Compared with prior art, advantage of the invention is that：Simple process is easy, and reaction condition is gentle, and the reaction time is short, Large-scale industrial production can be carried out.The structure-controllable of gained hybrid material, and there is good organic compatibility, it can be used in Rubber, plastics etc. are macromolecule modified to prepare high performance polymer composite material.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of pure nano-carbon tube；
Fig. 2 is the transmission electron microscope picture of pure nano silicon；
Fig. 3 is the transmission electron microscope picture of nano silicon-carbon nano-tube hybridization material prepared by embodiment 1；
Embodiment
Embodiment 1：
(1) modified carbon nano-tube suspension is prepared：Take 5g CNTs to be dispersed in water, and add 0.2g poly dimethyls two Allyl ammonium chloride, after ultrasonic disperse 0.5h, centrifugation removes excessive polyelectrolyte, and disperses to obtain the carbon modified of black again Nanotube suspension.
(2) modified manometer silicon dioxide suspension is prepared：10g nano silicon is dispersed in water, and added 0.8g kayexalates, after ultrasonic disperse 0.5h, centrifugation removes excessive polyelectrolyte, and disperses to obtain white again Modified manometer silicon dioxide suspension.
(3) nano silicon-carbon nano-tube hybridization material is prepared：By the modified Nano that concentration in step (2) is 40g/L Silica suspension is added into step (1) in the modified carbon nano-tube suspension that concentration is 40g/L, is obtained uniform cotton-shaped Thing.Then, washed repeatedly for several times using water and ethanol, 24h be dried in vacuo at 60 DEG C, obtain the nano silicon of grey- Carbon nano-tube hybridization material.
Synthesized nano silicon-carbon nano-tube hybridization material, wherein CNT account for nanometer titanium dioxide in (4) The mass percent of silico-carbo nanotube hybrid material is 36.5%.Such as Fig. 1, shown in 2, pure nano-carbon tube 40~50nm of diameter, and Easily mutually tangle, be not easy to disperse, and nanometer silicon dioxide particle particle diameter is 20nm or so, and agglomeration is presented.And by quiet Nano silicon-carbon nano-tube hybridization material prepared by electric packaging technology, carbon nano tube surface success have uniformly coated nanometer Silica dioxide granule, it is suppressed that the serious entanglement of CNT and the serious agglomeration of nano silicon, both dispersivenesses are significantly Improve.
Embodiment 2：
(1) modified carbon nano-tube suspension is prepared：Take 5g CNTs to be dispersed in water, and add 0.4g poly dimethyls two Allyl ammonium chloride, after ultrasonic disperse 1h, centrifugation removes excessive polyelectrolyte, and the carbon modified for disperseing to obtain black again is received Mitron suspension.
(2) modified manometer silicon dioxide suspension is prepared：10g nano silicon is dispersed in water, and added 1.2g kayexalates, after ultrasonic disperse 1h, centrifugation removes excessive polyelectrolyte, and disperses to obtain changing for white again Property nanometer titanium dioxide silicon suspension.
(3) nano silicon-carbon nano-tube hybridization material is prepared：By the modified Nano that concentration in step (2) is 40g/L Silica suspension is added into step (1) in the modified carbon nano-tube suspension that concentration is 40g/L, is obtained uniform cotton-shaped Thing.Then, washed repeatedly for several times using water and ethanol, 20h be dried in vacuo at 70 DEG C, obtain the nano silicon of grey- Carbon nano-tube hybridization material.
Synthesized nano silicon-carbon nano-tube hybridization material, wherein CNT account for nanometer titanium dioxide in (4) The mass percent of silico-carbo nanotube hybrid material is 30.9%.
Embodiment 3：
(1) modified carbon nano-tube suspension is prepared：Take 5g CNTs to be dispersed in water, and add 0.6g poly dimethyls two Allyl ammonium chloride, after ultrasonic disperse 2h, centrifugation removes excessive polyelectrolyte, and the carbon modified for disperseing to obtain black again is received Mitron suspension.
(2) modified manometer silicon dioxide suspension is prepared：10g nano silicon is dispersed in water, and added 1.6g kayexalates, after ultrasonic disperse 1.5h, centrifugation removes excessive polyelectrolyte, and disperses to obtain white again Modified manometer silicon dioxide suspension.
(3) nano silicon-carbon nano-tube hybridization material is prepared：By the modified Nano that concentration in step (2) is 40g/L Silica suspension is added into step (1) in the modified carbon nano-tube suspension that concentration is 40g/L, is obtained uniform cotton-shaped Thing.Then, washed repeatedly for several times using water and ethanol, 16h be dried in vacuo at 80 DEG C, obtain the nano silicon of grey- Carbon nano-tube hybridization material.
Synthesized nano silicon-carbon nano-tube hybridization material, wherein CNT account for nanometer titanium dioxide in (4) The mass percent of silico-carbo nanotube hybrid material is 28.8%.
Embodiment 4：
(1) modified carbon nano-tube suspension is prepared：Take 5g CNTs to be dispersed in water, and add 0.9g poly dimethyls two Allyl ammonium chloride, after ultrasonic disperse 3h, centrifugation removes excessive polyelectrolyte, and the carbon modified for disperseing to obtain black again is received Mitron suspension.
(2) modified manometer silicon dioxide suspension is prepared：10g nano silicon is dispersed in water, and added 2.0g kayexalates, after ultrasonic disperse 2h, centrifugation removes excessive polyelectrolyte, and disperses to obtain changing for white again Property nanometer titanium dioxide silicon suspension.
(3) nano silicon-carbon nano-tube hybridization material is prepared：By the modified Nano that concentration in step (2) is 40g/L Silica suspension is added into step (1) in the modified carbon nano-tube suspension that concentration is 40g/L, is obtained uniform cotton-shaped Thing.Then, washed repeatedly for several times using water and ethanol, 12h be dried in vacuo at 90 DEG C, obtain the nano silicon of grey- Carbon nano-tube hybridization material.
Synthesized nano silicon-carbon nano-tube hybridization material, wherein CNT account for nanometer titanium dioxide in (4) The mass percent of silico-carbo nanotube hybrid material is 31.2%.
Embodiment 5：
(1) modified carbon nano-tube suspension is prepared：Take 5g CNTs to be dispersed in water, and add 1.0g poly dimethyls two Allyl ammonium chloride, after ultrasonic disperse 4h, centrifugation removes excessive polyelectrolyte, and the carbon modified for disperseing to obtain black again is received Mitron suspension.
(2) modified manometer silicon dioxide suspension is prepared：10g nano silicon is dispersed in water, and added 2.5g kayexalates, after ultrasonic disperse 2.5h, centrifugation removes excessive polyelectrolyte, and disperses to obtain white again Modified manometer silicon dioxide suspension.
(3) nano silicon-carbon nano-tube hybridization material is prepared：By the modified Nano that concentration in step (2) is 40g/L Silica suspension is added into step (1) in the modified carbon nano-tube suspension that concentration is 40g/L, is obtained uniform cotton-shaped Thing.Then, washed repeatedly for several times using water and ethanol, 12h be dried in vacuo at 90 DEG C, obtain the nano silicon of grey- Carbon nano-tube hybridization material.
Synthesized nano silicon-carbon nano-tube hybridization material, wherein CNT account for nanometer titanium dioxide in (4) The mass percent of silico-carbo nanotube hybrid material is 34.6%.
The basic recipe of styrene butadiene rubber sbr composite as shown in table 1, SBR is prepared using tradition machinery calendering process Composite.Wherein preparation technology flow is：SBR is plasticated first, then by the nano silicon prepared in embodiment- Carbon nano-tube hybridization material is added thereto, be kneaded uniformly after, sequentially add zinc oxide, stearic acid, accelerant CZ, altax, Antioxidant MB, sulphur (S), and be kneaded uniformly, obtained SBR elastomeric compounds, SBR composites are then prepared by vulcanization, Its mechanical property is as shown in table 2.Relative to blank sample (30 parts of pure nano silicons of filling), 30 parts of nanometer titanium dioxides are filled The mechanical property of composite prepared by silico-carbo nanotube is obviously improved.The drawing of composite prepared by embodiment 1~5 Stretch intensity and be respectively increased 26.6%, 45.7%, 20.2%, 47.7% and 33.8%；300% stress at definite elongation is respectively increased 30.8%th, 47.8%, 21.4%, 49.5% and 39.6%；Tearing strength has been respectively increased 72.2%, 79.6%, 63.1%, 88.5% and 60.7%.The lifting of above performance may advantageously facilitate mainly due to nano silicon-carbon nano-tube hybridization material Nano silicon and CNT are scattered in rubber matrix, improve both reunion behaviors.Meanwhile hybrid material is modified Polyelectrolyte be advantageous to improve the interfacial interaction between hydridization filler and matrix, so as to significantly increase butadiene-styrene rubber.
The basic recipe of the styrene-butadiene rubber composite material of table 1.
Embodiment Blank sample 1 2 3 4 5
SBR 100 100 100 100 100 100
Nano silicon 30 --- --- --- --- ---
Nano silicon-CNT --- 30 30 30 30 30
Zinc oxide 5 5 5 5 5 5
Stearic acid 2 2 2 2 2 2
Accelerant CZ 1.5 1.5 1.5 1.5 1.5 1.5
Altax 0.5 0.5 0.5 0.5 0.5 0.5
Antioxidant MB 1.5 1.5 1.5 1.5 1.5 1.5
Sulphur (S) 1.5 1.5 1.5 1.5 1.5 1.5
The mechanical property of table 2.SBR composites
Note：Blank sample is to add composite prepared by 30 parts of pure nano silicons；Embodiment 1~5 with the addition of respectively The composite that nano silicon-carbon nano-tube hybridization material prepared by 30 parts is prepared.

Claims (3)

1. a kind of preparation method of nano silicon-carbon nano-tube hybridization material, it is characterised in that comprise the following steps:
(1) modified carbon nano-tube suspension is prepared：It is 1 to take mass ratio:5~25 cationic polyelectrolyte and CNT is together It is dispersed in water, after 0.5~4h of ultrasonic disperse, centrifugation removes excessive polyelectrolyte, and the carbon for disperseing to obtain black again is received Mitron suspension.
(2) modified manometer silicon dioxide suspension is prepared：It is 1 by mass ratio:4~12.5 anionic polyelectrolyte and nanometer two Silica is dispersed in water together, and after 0.5~2.5h of ultrasonic disperse, centrifugation removes excessive polyelectrolyte, and disperses again To the nanometer titanium dioxide silicon suspension of white.
(3) nano silicon-carbon nano-tube hybridization material is prepared：By the modified Nano that concentration in step (2) is 25~40g/L Silica suspension is added into step (1) in the modified carbon nano-tube suspension that concentration is 25~40g/L, is obtained uniform Floccule.Then, washed repeatedly for several times using water and ethanol, 12~24h is dried in vacuo at 60~90 DEG C, obtains receiving for grey Rice silica-carbon pipe hybrid material.
2. a kind of preparation method of nano silicon-carbon nano-tube hybridization material as claimed in claim 1, its feature exist In：The cationic polyelectrolyte is PDDA, polyethyleneimine, poly- hydroxypropyl dimethyl chlorination One kind in ammonium.
3. a kind of preparation method of nano silicon-carbon nano-tube hybridization material as claimed in claim 1, its feature exist In：The anionic polyelectrolyte is Sodium Polyacrylate, kayexalate, one kind in ammonium polyacrylate.
CN201710481324.5A 2017-06-22 2017-06-22 A kind of preparation method of nano silicon carbon nano-tube hybridization material Pending CN107353674A (en)

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CN113527839A (en) * 2021-07-09 2021-10-22 航天特种材料及工艺技术研究所 High-modulus nano hybrid resin and preparation method thereof
CN114456738A (en) * 2022-01-27 2022-05-10 湖南创瑾技术研究院有限公司 Heat conduction material and preparation method and application thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112952099A (en) * 2021-03-05 2021-06-11 华中科技大学 Lithium battery composite positive electrode and preparation method thereof
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CN113527839A (en) * 2021-07-09 2021-10-22 航天特种材料及工艺技术研究所 High-modulus nano hybrid resin and preparation method thereof
CN114456738A (en) * 2022-01-27 2022-05-10 湖南创瑾技术研究院有限公司 Heat conduction material and preparation method and application thereof
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