CN103508445A - Boron and nitrogen codoped graphene and preparation method thereof - Google Patents
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Abstract
The invention provides a preparation method for boron and nitrogen codoped graphene. The preparation method comprises the following steps: uniformly mixing graphite oxide, urea and boron trioxide in a mass ratio of 1: 1-4: 1-4 and placing an obtained mixture in a reactor; introducing protective gas into the reactor; heating the interior of the reactor to a temperature of 800 to 900 DEG C at a heating speed of 15 to 20 DEG C/min and maintaining the temperature for 30 min to 2 h; and cooling the reactor to room temperature in the protective gas with flow velocity of 150 to 300 ml/min so as to prepare the boron and nitrogen codoped graphene. According to the method, urea and boron trioxide are respectively used as a nitrogen source and a boron source, maximum doping amounts of elemental boron and elemental nitrogen can both approach 10%, so the adjustable range of respective content of nitrogen and boron is wide; and the method has the advantages of simple process, convenient operation, no special requirements on equipment and easy realization of large scale industrial production. The invention further provides the boron and nitrogen codoped graphene prepared by using the preparation method.
Description
Technical field
The present invention relates to the synthetic field of material, particularly relate to nitrogen co-doped Graphene of a kind of boron and preparation method thereof.
Background technology
Graphene is a kind of Two-dimensional Carbon atomic crystal of the discoveries such as the strong K sea nurse of the peace moral of Univ Manchester UK in 2004 (Andre K.Geim), is the carbon material as thin as a wafer of single or multiple lift.Single-layer graphene has good conduction, heat conductivility and low thermal expansivity, and its theoretical specific surface area is up to 2630m
2/ g (A Peigney, Ch Laurent, et al.Carbon, 2001,39,507), can be used for effect transistor, electrode materials, matrix material, liquid crystal display material, sensor.
The method of preparing at present Graphene mainly contain graphite breakaway (et al.Science 2004,306,666 for Novoselov K S, Geim A K), chemistry redox method [D A Dikin, et al.Nature 2007,448,457; Sasha Stankovich, Dmitriy A Dikin, Richard D Piner, et al.Carbon 2007,45,1558], ultrasonic stripping method (Guohua Chen, Wengui Weng, Dajun Wu, et al.Carbon.2004,42,753), chemical Vapor deposition process (Alexander N, Obraztsov.Nature nanotechnology.2009,4,212) etc.Conventionally, the Graphene that prepared by these methods is all the Graphene of intrinsic.
Research carries out to Graphene the large focus that element doping modification is current field of nanometer material technology.Theoretical investigation shows, Graphene energy band structure after element doping has adjustment, thereby can greatly expand Graphene in the application in the fields such as optics, electricity and magnetics.At present, doped graphene preparation method's research is not very abundant, and focuses mostly in the research of nitrating Graphene and the research of boron-doping Graphene.The rare report of Graphene that boron is nitrogen co-doped, visible boron is nitrogen co-doped is at present undertaken by gas nitrogenous source (ammonia) and gaseous boron source (boron trichloride), these two kinds of materials are owing to being gaseous state, activity is lower, nitrogen or the boron that can mix are limited, every kind of element is higher than 3%, thus nitrogen and boron the variable range of content is narrower separately.
Summary of the invention
For addressing the above problem, the present invention aims to provide the preparation method of the nitrogen co-doped Graphene of a kind of boron, this preparation method is usingd urea and boron trioxide and as nitrogenous source He Peng source, is prepared the nitrogen co-doped Graphene of boron respectively, boron and nitrogen element the most highly doped amount separately all can approach 10%, thus nitrogen and boron the variable range of content is wide separately.Meanwhile, the invention provides the nitrogen co-doped Graphene of the boron making by this preparation method.
The preparation method who the invention provides the nitrogen co-doped Graphene of a kind of boron, comprises the following steps:
First, be that 1: 1～4: 1～4 ratio is got graphite oxide, urea and boron trioxide and mixed and be placed in reactor in mass ratio; Then, in reactor, pass into protective gas, the flow velocity that passes into of described protective gas is 150～300ml/min; Then, with the heat-up rate of 15～20 ℃/min, the temperature in reactor is warming up to 800～900 ℃, and keeps 30min～2h; Finally, in the protective gas that is 150～300ml/min at flow velocity, be cooled to room temperature, make the nitrogen co-doped Graphene of boron.
Preferably, described protective gas is at least one in argon gas, nitrogen and helium.
Preferably, described reactor is tube furnace.
Preferably, the mass ratio of described graphite oxide, urea and boron trioxide is 1: 3: 3.
Preferably, described graphite oxide adopts following steps to make:
In the mix acid liquor that adds the vitriol oil and concentrated nitric acid to form in graphite, form mixed solution, the temperature of mixed solution is remained on to-2～2 ℃ and stir 10～30min; In mixed solution, add at leisure potassium permanganate, continue that the temperature of mixed solution is remained on to-2～2 ℃ and stir 1h; Mixed solution is warming up to 80～90 ℃ and keep 0.5～2h; In mixed solution, add deionized water, continue at 80～90 ℃ of insulation 0.5～2h; And adding hydrogen peroxide to remove potassium permanganate in mixed solution, suction filtration, washs solids with dilute hydrochloric acid and deionized water successively, after drying solid thing, obtains graphite oxide; The solid-to-liquid ratio of described graphite and the described vitriol oil and concentrated nitric acid is 1g: 80～110ml: 15～35ml; The mass ratio of described graphite and described potassium permanganate is 1: 1～10; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g: 1～3ml.
Preferably, the purity of described graphite is 90%～99.9%.
The preparation method of the nitrogen co-doped Graphene of boron of the present invention is usingd urea and boron trioxide and as nitrogenous source He Peng source, is prepared the nitrogen co-doped Graphene of boron respectively, boron and nitrogen element the most highly doped amount separately all can approach 10%, therefore the variable range of content is wide separately for nitrogen and boron, width adjusting wide ranges between energy level, so can prepare according to the requirement of device performance the nitrogen co-doped Graphene of boron of suitable boron and nitrogen element content.In addition this preparation method's technique is simple, and convenient operation without particular requirement, is easy to realize large-scale industrial production to equipment.
The present invention also provides a kind of boron nitrogen co-doped Graphene, and the nitrogen co-doped Graphene of described boron makes by above-mentioned preparation method.
Preferably, in the nitrogen co-doped Graphene of described boron, the doping of boron and nitrogen element is 4%～10%.
In the nitrogen co-doped Graphene of this boron, mix boron and nitrogen element, mixed the specific conductivity that boron or nitrogen element can improve Graphene.In addition, the doping of boron and nitrogen element does not affect the conjugated structure of Graphene self, does not destroy the electronics transmission between large π key, has retained the excellent specific conductivity of Graphene self.Compare independent boron doping or nitrogen-doping, boron is nitrogen co-doped can not affected greatly the characteristic electron of Graphene, but can improve impurity compensation effect, this impurity compensation effect can cause the local lattice of Graphene to distort, thereby change conduction type or the specific conductivity in certain region of Graphene, therefore the nitrogen co-doped Graphene of boron making is thus applicable to some specific component structure, semiconducter device for example, has the advantages such as operating frequency of reduce power consumption and Geng Gao with respect to traditional semiconducter device.
Nitrogen co-doped Graphene of a kind of boron provided by the invention and preparation method thereof, has following beneficial effect:
This preparation method is usingd urea and boron trioxide respectively as nitrogenous source He Peng source, and nitrogen and the boron separately variable range of content are wide, and technique is simple, and convenient operation without particular requirement, is easy to realize large-scale industrial production to equipment;
The specific conductivity that the boron mixing in the nitrogen co-doped Graphene of boron making by this preparation method or nitrogen element can improve Graphene, and the doping of boron and nitrogen element does not affect the conjugated structure of Graphene self, the excellent specific conductivity that has retained Graphene self, the codoped of boron and nitrogen element can improve impurity compensation effect simultaneously, and the nitrogen co-doped Graphene of boron making is thus applicable to some specific component structure.
Embodiment
The preparation method who the invention provides the nitrogen co-doped Graphene of a kind of boron, comprises the following steps:
First, be that 1: 1～4: 1～4 ratio is got graphite oxide, urea and boron trioxide and mixed and be placed in reactor in mass ratio; Then, in reactor, pass into protective gas, the flow velocity that passes into of described protective gas is 150～300ml/min; Then, with the heat-up rate of 15～20 ℃/min, the temperature in reactor is warming up to 800～900 ℃, and keeps 30min～2h; Finally, in the protective gas that is 150～300ml/min at flow velocity, be cooled to room temperature, make the nitrogen co-doped Graphene of boron.
Described protective gas is at least one in argon gas, nitrogen and helium.
Described reactor is tube furnace.
The mass ratio of described graphite oxide, urea and boron trioxide is 1: 3: 3.
Described graphite oxide adopts following steps to make:
In the mix acid liquor that adds the vitriol oil and concentrated nitric acid to form in graphite, form mixed solution, the temperature of mixed solution is remained on to-2～2 ℃ and stir 10～30min; In mixed solution, add at leisure potassium permanganate, continue that the temperature of mixed solution is remained on to-2～2 ℃ and stir 1h; Mixed solution is warming up to 80～90 ℃ and keep 0.5～2h; In mixed solution, add deionized water, continue at 80～90 ℃ of insulation 0.5～2h; And adding hydrogen peroxide to remove potassium permanganate in mixed solution, suction filtration, washs solids with dilute hydrochloric acid and deionized water successively, after drying solid thing, obtains graphite oxide; The solid-to-liquid ratio of described graphite and the described vitriol oil and concentrated nitric acid is 1g: 80～110ml: 15～35ml; The mass ratio of described graphite and described potassium permanganate is 1: 1～10; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g: 1～3ml.
The purity of described graphite is 90%～99.9%.
The preparation method of the nitrogen co-doped Graphene of boron of the present invention is usingd urea and boron trioxide and as nitrogenous source He Peng source, is prepared the nitrogen co-doped Graphene of boron respectively, boron and nitrogen element the most highly doped amount separately all can approach 10%, therefore the variable range of content is wide separately for nitrogen and boron, width adjusting wide ranges between energy level, so can prepare according to the requirement of device performance the nitrogen co-doped Graphene of boron of suitable boron and nitrogen element content.In addition this preparation method's technique is simple, and convenient operation without particular requirement, is easy to realize large-scale industrial production to equipment.
The present invention also provides a kind of boron nitrogen co-doped Graphene, and the nitrogen co-doped Graphene of described boron makes by above-mentioned preparation method.
In the nitrogen co-doped Graphene of described boron, the doping of boron and nitrogen element is 4%～10%.
In the nitrogen co-doped Graphene of this boron, mix boron and nitrogen element, mixed the specific conductivity that boron or nitrogen element can improve Graphene.In addition, the doping of boron and nitrogen element does not affect the conjugated structure of Graphene self, does not destroy the electronics transmission between large π key, has retained the excellent specific conductivity of Graphene self.Compare independent boron doping or nitrogen-doping, boron is nitrogen co-doped can not affected greatly the characteristic electron of Graphene, but can improve impurity compensation effect, this impurity compensation effect can cause the local lattice of Graphene to distort, thereby change conduction type or the specific conductivity in certain region of Graphene, therefore the nitrogen co-doped Graphene of boron making is thus applicable to some specific component structure, semiconducter device for example, has the advantages such as operating frequency of reduce power consumption and Geng Gao with respect to traditional semiconducter device.
Nitrogen co-doped Graphene of a kind of boron provided by the invention and preparation method thereof, has following beneficial effect:
This preparation method is usingd urea and boron trioxide respectively as nitrogenous source He Peng source, and nitrogen and the boron separately variable range of content are wide, and technique is simple, and convenient operation without particular requirement, is easy to realize large-scale industrial production to equipment;
The specific conductivity that the boron mixing in the nitrogen co-doped Graphene of boron making by this preparation method or nitrogen element can improve Graphene, and the doping of boron and nitrogen element does not affect the conjugated structure of Graphene self, the codoped of boron and nitrogen element can improve impurity compensation effect simultaneously, and the nitrogen co-doped Graphene of boron making is thus applicable to some specific component structure.
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Embodiment mono-
A preparation method for the nitrogen co-doped Graphene of boron, comprises the following steps:
It is to mix in 65% the concentrated nitric acid vitriol oil that is 98% with 90ml massfraction that the graphite that is 95% by 1g purity adds 24ml massfraction, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add potassium permanganate at leisure again, the mass ratio of potassium permanganate and graphite is 5: 1, stir 1 hour, then mixture is heated to keep 30min at 85 ℃, add afterwards deionized water to continue to keep 30min at 85 ℃, the liquid-solid ratio of deionized water and graphite is 90ml: 1g, finally adding massfraction is 30% superoxol, the liquid-solid ratio of superoxol and graphite is 10ml: 1g, stir 10min, mixture is carried out to suction filtration, with dilute hydrochloric acid and deionized water, solids is washed respectively successively again, dilute hydrochloric acid, the solid-to-liquid ratio of deionized water and graphite is 100ml: 150ml: 1g, wash altogether 3 times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ℃ of vacuum drying ovens.
Be that the ratio of 1: 4: 2 is got graphite oxide, urea and boron trioxide and mixed in mass ratio, be placed in the argon atmosphere that flow velocity is 200ml/min, heat-up rate with 20 ℃/min is warming up to 800 ℃, keep 1h, in the argon atmosphere that is 200ml/min at flow velocity subsequently, be down to room temperature, make the nitrogen co-doped Graphene of boron.
Embodiment bis-
A preparation method for the nitrogen co-doped Graphene of boron, comprises the following steps:
It is to mix in 68% the concentrated nitric acid vitriol oil that is 80% with 350ml massfraction that the graphite that is 90% by 5g purity adds 100ml massfraction, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add potassium permanganate at leisure again, the mass ratio of potassium permanganate and graphite is 4: 1, stir 1 hour, then mixture is heated to keep 30min at 85 ℃, add afterwards deionized water to continue to keep 30min at 85 ℃, the liquid-solid ratio of deionized water and graphite is 60ml: 1g, finally adding massfraction is 30% superoxol, the liquid-solid ratio of superoxol and graphite is 5ml: 1g, stir 10min, mixture is carried out to suction filtration, with dilute hydrochloric acid and deionized water, solids is washed respectively successively again, dilute hydrochloric acid, the solid-to-liquid ratio of deionized water and graphite is 90ml: 60ml: 1g, wash altogether 3 times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ℃ of vacuum drying ovens.
Be that the ratio of 1: 1: 4 is got graphite oxide, urea and boron trioxide and mixed in mass ratio, be placed in the nitrogen atmosphere that flow velocity is 200ml/min, heat-up rate with 15 ℃/min is warming up to 850 ℃, keep 1h, in the nitrogen atmosphere that is 200ml/min at flow velocity subsequently, be down to room temperature, make the nitrogen co-doped Graphene of boron.
Embodiment tri-
A preparation method for the nitrogen co-doped Graphene of boron, comprises the following steps:
It is to mix in 50% the concentrated nitric acid vitriol oil that is 98% with 180ml massfraction that the graphite that is 99.9% by 2g purity adds 48ml massfraction, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add potassium permanganate at leisure again, the mass ratio of potassium permanganate and graphite is 4: 1, stir 1 hour, then mixture is heated to keep 30min at 85 ℃, add afterwards deionized water to continue to keep 30min at 85 ℃, the liquid-solid ratio of deionized water and graphite is 90ml: 1g, finally adding massfraction is 30% superoxol, the liquid-solid ratio of superoxol and graphite is 7.5ml: 1g, stir 10min, mixture is carried out to suction filtration, with dilute hydrochloric acid and deionized water, solids is washed respectively successively again, dilute hydrochloric acid, the solid-to-liquid ratio of deionized water and graphite is 100ml: 150ml: 1g, wash altogether 3 times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ℃ of vacuum drying ovens.
Be that the ratio of 1: 3: 1 is got graphite oxide, urea and boron trioxide and mixed in mass ratio, being placed in flow velocity is the helium atmosphere of 150ml/min, heat-up rate with 20 ℃/min is warming up to 900 ℃, keep 2h, in the helium atmosphere that is 150ml/min at flow velocity subsequently, be down to room temperature, make the nitrogen co-doped Graphene of boron.
Embodiment tetra-
A preparation method for the nitrogen co-doped Graphene of boron, comprises the following steps:
It is to mix in 65% the concentrated nitric acid vitriol oil that is 90% with 95ml massfraction that the graphite that is 95% by 1g purity adds 25ml massfraction, mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add potassium permanganate at leisure again, the mass ratio of potassium permanganate and graphite is 3: 1, stir 1 hour, then mixture is heated to keep 30min at 85 ℃, add afterwards deionized water to continue to keep 30min at 85 ℃, the liquid-solid ratio of deionized water and graphite is 100ml: 1g, finally adding massfraction is 30% superoxol, the liquid-solid ratio of superoxol and graphite is 8ml: 1g, stir 10min, mixture is carried out to suction filtration, with dilute hydrochloric acid and deionized water, solids is washed respectively successively again, dilute hydrochloric acid, the solid-to-liquid ratio of deionized water and graphite is 100ml: 150ml: 1g, wash altogether 3 times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ℃ of vacuum drying ovens.
Be that the ratio of 1: 3: 3 is got graphite oxide, urea and boron trioxide and mixed in mass ratio, be placed in the argon atmosphere that flow velocity is 300ml/min, heat-up rate with 20 ℃/min is warming up to 800 ℃, keep 30min, in the argon atmosphere that is 300ml/min at flow velocity subsequently, be down to room temperature, make the nitrogen co-doped Graphene of boron.
Effect embodiment
The nitrogen co-doped Graphene of the prepared boron of embodiment mono-～tetra-is passed through to the wherein content of each principal element of XPS measurements determination, and test result is as following table 1.
Each principal element content of the nitrogen co-doped Graphene of boron in table 1 embodiment mono-～embodiment tetra-
| Carbon (%) | Boron (%) | Nitrogen element (%) | Oxygen element (%) | |
| Embodiment mono- | 80.9 | 7.1 | 6.8 | 5.2 |
| Embodiment bis- | 77.8 | 4.6 | 9.5 | 6.1 |
| Embodiment tri- | 80 | 6.9 | 4.8 | 6.3 |
| Embodiment tetra- | 80.3 | 6.8 | 7.5 | 5.4 |
As can be seen from Table 1, boron, nitrogen content in the nitrogen co-doped Graphene of boron that the embodiment of the present invention makes are all higher, and the amplitude regulating is wider.
The nitrogen co-doped Graphene specific conductivity of boron performance test in table 2 embodiment mono-～embodiment tetra-
| Specific conductivity (S/m) | |
| Embodiment mono- | 1624 |
| Embodiment bis- | 1578 |
| Embodiment tri- | 1724 |
| Embodiment tetra- | 1596 |
As can be seen from Table 2, through the test of four point probe resistance meter, the specific conductivity of the nitrogen co-doped Graphene of boron that the embodiment of the present invention makes is higher, is up to 1724S/m.
Claims (8)
1. a preparation method for the nitrogen co-doped Graphene of boron, is characterized in that, comprises the following steps: first, be that 1: 1～4: 1～4 ratio is got graphite oxide, urea and boron trioxide and mixed and be placed in reactor in mass ratio; Then, in reactor, pass into protective gas, the flow velocity that passes into of described protective gas is 150～300ml/min; Then, with the heat-up rate of 15～20 ℃/min, the temperature in reactor is warming up to 800～900 ℃, and keeps 30min～2h; Finally, in the protective gas that is 150～300ml/min at flow velocity, be cooled to room temperature, make the nitrogen co-doped Graphene of boron.
2. the preparation method of the nitrogen co-doped Graphene of a kind of boron as claimed in claim 1, is characterized in that, described protective gas is at least one in argon gas, nitrogen and helium.
3. the preparation method of the nitrogen co-doped Graphene of a kind of boron as claimed in claim 1, is characterized in that, described reactor is tube furnace.
4. the preparation method of the nitrogen co-doped Graphene of a kind of boron as claimed in claim 1, is characterized in that, the mass ratio of described graphite oxide, urea and boron trioxide is 1: 3: 3.
5. the preparation method of the nitrogen co-doped Graphene of a kind of boron as claimed in claim 1, is characterized in that, described graphite oxide adopts following steps to make:
In the mix acid liquor that adds the vitriol oil and concentrated nitric acid to form in graphite, form mixed solution, the temperature of mixed solution is remained on to-2～2 ℃ and stir 10～30min; In mixed solution, add at leisure potassium permanganate, continue that the temperature of mixed solution is remained on to-2～2 ℃ and stir 1h; Mixed solution is warming up to 80～90 ℃ and keep 0.5～2h; In mixed solution, add deionized water, continue at 80～90 ℃ of insulation 0.5～2h; And adding hydrogen peroxide to remove potassium permanganate in mixed solution, suction filtration, washs solids with dilute hydrochloric acid and deionized water successively, after drying solid thing, obtains graphite oxide; The solid-to-liquid ratio of described graphite and the described vitriol oil and concentrated nitric acid is 1g: 80～110ml: 15～35ml; The mass ratio of described graphite and described potassium permanganate is 1: 1～10; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g: 1～3ml.
6. the preparation method of the nitrogen co-doped Graphene of a kind of boron as claimed in claim 5, is characterized in that, the purity of described graphite is 90%～99.9%.
7. the nitrogen co-doped Graphene of boron, is characterized in that, the nitrogen co-doped Graphene of described boron is made by the preparation method described in arbitrary claim in claim 1～6.
8. the nitrogen co-doped Graphene of a kind of boron as claimed in claim 7, is characterized in that, in the nitrogen co-doped Graphene of described boron, the doping of boron and nitrogen element is 4%～10%.
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| CN104108712A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Boron-doped graphene and preparation method thereof |
| CN104150475A (en) * | 2014-08-04 | 2014-11-19 | 深圳新宙邦科技股份有限公司 | Binary doped graphene and preparation method thereof |
| CN106477561A (en) * | 2016-09-22 | 2017-03-08 | 广西大学 | A kind of preparation method of boron nitrogen double base auto-dope three-dimensional drape Graphene electrodes material |
| CN107029694A (en) * | 2017-05-23 | 2017-08-11 | 中国石油大学(北京) | One kind doping carbon material and preparation method thereof |
| CN107697902A (en) * | 2017-09-29 | 2018-02-16 | 中国石油大学(北京) | A kind of double-doped class graphene nano carbon material of boron nitrogen and preparation method and application |
| CN109110748A (en) * | 2018-11-07 | 2019-01-01 | 河南师范大学 | A kind of preparation method of nitrogen, the three-dimensional porous graphene of boron codope |
| CN110790268B (en) * | 2019-10-29 | 2021-05-25 | 中国科学院宁波材料技术与工程研究所 | Boron and nitrogen co-doped graphene wave-absorbing material and preparation method and application thereof |
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| CN104108712B (en) * | 2014-07-25 | 2016-01-20 | 深圳新宙邦科技股份有限公司 | A kind of boron doped graphene and preparation method thereof |
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| CN107029694B (en) * | 2017-05-23 | 2020-03-27 | 中国石油大学(北京) | Doped carbon material and preparation method thereof |
| CN107697902A (en) * | 2017-09-29 | 2018-02-16 | 中国石油大学(北京) | A kind of double-doped class graphene nano carbon material of boron nitrogen and preparation method and application |
| CN109110748A (en) * | 2018-11-07 | 2019-01-01 | 河南师范大学 | A kind of preparation method of nitrogen, the three-dimensional porous graphene of boron codope |
| CN110790268B (en) * | 2019-10-29 | 2021-05-25 | 中国科学院宁波材料技术与工程研究所 | Boron and nitrogen co-doped graphene wave-absorbing material and preparation method and application thereof |
| CN115403853A (en) * | 2022-09-30 | 2022-11-29 | 万华化学（宁波）有限公司 | Composite material for shielding direct/alternating current high-voltage cable and preparation method thereof |
| CN115403853B (en) * | 2022-09-30 | 2024-04-09 | 万华化学（宁波）有限公司 | Composite material for shielding direct-current/alternating-current high-voltage cable and preparation method thereof |
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