CN102306749A - Membrane electrode based on spiral carbon nanofiber bundle and preparation method thereof - Google Patents
Membrane electrode based on spiral carbon nanofiber bundle and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a membrane electrode based on a spiral carbon nanofiber bundle and a preparation method thereof, belonging to the technical field of lithium ion batteries. The membrane electrode comprises a copper coil current collector and the spiral carbon nanofiber bundle growing on the surface of the copper coil current collector, wherein the spiral carbon nanofiber bundle is formed by spirally winding a plurality of carbon nanofibers, and a graphite layer of the carbon nanofibers is vertical to the axial direction of the carbon nanofibers. The preparation method of the membrane electrode comprises the following steps: loading a nickel-based catalyst on the surface of a copper coil; and then growing the spiral carbon nanofiber bundle on the surface of the copper coil by adopting a chemical vapor deposition method. The membrane electrode and the preparation method provided by the invention have the advantages that the unique structure of the membrane electrode enables the membrane electrode to have higher reversible specific capacity, good electrochemical cycle stability and higher multiplying power performance; and the preparation technology is simple, convenient to operate, and easy to implement large-scale industrial production.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to a kind of membrane electrode based on helical form carbon nano-fiber bundle and preparation method thereof.
Background technology
It is low that graphite has a cost as lithium ion battery negative material, advantages such as the high and electrochemistry good cycling stability of cycle efficieny.But its lithium storage content is lower, and theoretical specific capacity is 372mAh/g, so the development of new negative material becomes the key that improves the lithium ion battery performance.
In recent years, people study multiple material with carbon element, and wherein carbon nanomaterial (like carbon nano-tube, Graphene, carbon nano-fiber etc.) has advantages such as specific capacity height, good stability, is considered to have the lithium ion battery negative material of new generation of development prospect.
Carbon nano-tube has higher specific capacity usually, but the complicated process of preparation of carbon nano-tube, cost are high, and carbon nanotube density is little, specific discharge capacity is on the low side, still is difficult to obtain practical application.Graphene is as a kind of novel carbon nanomaterial; Its performance as lithium ion battery negative material is unsatisfactory; Usually need and other carbon nanomaterials; Just show preferable performance like carbon nano-tube, carbon nano-fiber after compound; In addition; Also there is complicated process of preparation in Graphene, shortcomings such as cost height.
Comparatively speaking, the preparation technology of carbon nano-fiber is simple, cost is low, but its chemical property still has much room for improvement.As at document (1) Carbon; 2006; Among the 44:828-832; People such as Guifu Zou with iron powder and zinc powder as dual catalyst; With the ether is reactant, under 650 ℃ of conditions, has obtained carbon nano-fiber, and preparation technology is simple; But the specific capacity of this carbon nano-fiber is on the low side, after the circulation of 30 weeks 220mAh/g is only arranged.And for example at document (2) Chem.Mater., 2007, among the 19:4198-4204; People such as Da Deng adopt simple single step reaction method, are reactant with acetylene, in 950 ℃ of copper substrates, prepare carbon nano-fiber; But this material is under the 100mA/g current density, and specific capacity only is 260mAh/g.
This shows that research and development preparation technology carbon nanomaterial simple, that cost is low, chemical property is good is still a research work that has challenge and using value.
Summary of the invention
The objective of the invention is to be to provide a kind of lithium ion cell film electrode based on helical form carbon nano-fiber bundle and preparation method thereof.
The membrane electrode that the present invention is based on helical form carbon nano-fiber bundle by the Copper Foil collector be grown in its surperficial helical form carbon nano-fiber bundle and constitute.Wherein, the thickness of Copper Foil collector is 10～30 μ m; The amount of the helical form carbon nano-fiber bundle of Copper Foil collection liquid surface growth is 1～5mg/cm
2, every helical form carbon nano-fiber bundle is entwined by several carbon nano-fiber spirals, and the vertical carbon nano-fiber of the graphite flake layer of carbon nano-fiber is axial.
The present invention's preparation based on the method for the membrane electrode of helical form carbon nano-fiber bundle is: earlier nickel-base catalyst is loaded on copper foil surface; Adopt chemical gaseous phase depositing process at copper foil surface growth spiral shape carbon nano-fiber bundle then, concrete technology may further comprise the steps:
(1) with thickness be the Copper Foil of 10～30 μ m in ethanol ultrasonic cleaning 10～20 minutes to remove surface and oil contaminant or other dirts; Immersed concentration then and be in the nickel nitrate ethanolic solution of 20～40g/L 1～5 minute; Take out the back 50～80 ℃ of dryings 0.5～3 hour; Repeat above operation 3-6 time, at copper foil surface load nickel base catalyst granules.
(2) Copper Foil of load nickel base catalyst granules is put into the high-temperature region of two warm area tube furnaces; With camphor is the low-temperature space that solid carbon source is put into two warm area tube furnaces; After two warm area tube furnace sealings; Feed a kind of in the inert carrier gases such as nitrogen or argon gas along low-temperature space to the high-temperature region direction; The inert carrier gas flow velocity is 40～80mL/ minute, in two warm area tube furnaces, forms inert gas shielding atmosphere.
(3) high-temperature region with two warm area tube furnaces is warming up to 600～800 ℃ of design temperatures, and the low-temperature space with two warm area tube furnaces is warming up to 200～400 ℃ of design temperatures again, utilizes inert carrier gas to bring the camphor of low-temperature space gasification into the high-temperature region deposition reaction 1～4 hour; Deposition reaction finishes continued and feeds inert carrier gas, and two warm area tube furnaces are naturally cooled to room temperature, obtains the present invention is based on the membrane electrode of helical form carbon nano-fiber bundle.
Adopt Japanese Hitachi S-4700 type field emission scanning electron microscope (FESEM) to characterize the microscopic appearance of membrane electrode, test result as shown in Figure 1.Helical form carbon nano-fiber Shu Changdu is entwined by several carbon nano-fiber spirals at 4～8 μ m.Carbon nanofibers grow is twined on the Copper Foil collector and each other, has strengthened and being connected of Copper Foil collector, and makes the carbon nano-fiber difficult drop-off, has also strengthened the conductivity between carbon nano-fiber and the Copper Foil collector simultaneously; Have the gap between the carbon nano-fiber that twines each other, the specific area that this has increased the carbon nano-fiber bundle also helps the infiltration of electrolyte.The said structure characteristics all help improving chemical properties such as the specific capacity, cycle performance, high rate performance of membrane electrode of the present invention.
Adopt Japanese JEOL JEM-2010 type high-resolution-ration transmission electric-lens (HRTEM) to characterize the fine structure of the carbon nano-fiber that constitutes the carbon nano-fiber bundle, test result as shown in Figure 2.Different with general carbon nano-fiber, carbon nano-fiber of the present invention is made up of graphite flake layer, and graphite flake layer is basically perpendicular to the carbon nano-fiber axially-aligned.This structure has reduced the distance that lithium ion embeds carbon nano-fiber, helps improving the high rate performance of material.
Adopt Britain Renishaw RM2000 type micro confocal Raman spectrum (Raman) to characterize the chemical composition of helical form carbon nano-fiber bundle, test result as shown in Figure 3.See that from the ratio at D peak and G peak helical form carbon nano-fiber bundle of the present invention has than general graphite and carbon nano-tube more defects, defective bit can store lithium ion, so helical form carbon nano-fiber bundle of the present invention will have higher specific capacity.
Using sheet-punching machine to make the electrode slice of diameter as 1cm the membrane electrode based on helical form carbon nano-fiber bundle of the present invention's preparation, is negative pole with the metal lithium sheet, and barrier film is Celgard 2400, and electrolyte solution is EC+DMC+EMC+1mol/L LiPF
6, at the German M. Braun UnLab of company argon gas glove box (O
2, H
2O content is all less than 1ppm) in be assembled into Experimental cell, adopt the blue electric CT2001A type battery test system in Wuhan to carry out electrochemical property test.When discharging and recharging the cut-ff voltage scope is 0.1～2.0V (vs.Li+/Li); Cycle performance when current density is 200mA/g as shown in Figure 4; Material discharges first and the charge ratio capacity is respectively 1005mAh/g and 604mAh/g, and capacity is stabilized in 580mAh/g after the circulation of 60 weeks, and cycle performance is excellent.The high rate performance of this material as shown in Figure 5, when electric current changes to 2000mA/g from 400mA/g, after the experience 80 week circulation; In current density is under the 2000mA/g; Specific capacity is 467mAh/g, has kept 77.4% of initial capacity, and specific capacity still is higher than the theoretical capacity of graphite.
Characteristics of the present invention and advantage are: the unique texture based on the membrane electrode of helical form carbon nano-fiber bundle of the present invention preparation makes it have higher reversible specific capacity, good electrochemistry cyclical stability and higher high rate performance; Preparation method's technology of the present invention in addition is simple, easy to operate, is easy to realize large-scale industrial production.
Description of drawings
Fig. 1 is the field emission scanning electron microscope photo based on the membrane electrode of helical form carbon nano-fiber bundle that the present invention prepares.
Fig. 2 is the high-resolution transmission electron microscope photo that constitutes the carbon nano-fiber of helical form carbon nano-fiber bundle.
Fig. 3 is the micro confocal Raman spectrogram of helical form carbon nano-fiber bundle.Wherein, abscissa-wave number, unit is 1/ centimetre (1/cm); Ordinate-intensity, unit is absolute unit (a.u.).
Fig. 4 is the charge-discharge performance curve based on the membrane electrode of helical form carbon nano-fiber bundle that the present invention prepares, and discharging and recharging the cut-ff voltage scope is 0.1～2.0V (vs.Li
+/ Li), current density is 200mA/g.Wherein, ordinate-specific discharge capacity, unit are MAH/gram (mAh/g); Abscissa-cycle-index, unit is week.
Fig. 5 is the charge-discharge magnification performance curve based on the membrane electrode of helical form carbon nano-fiber bundle that the present invention prepares, and discharging and recharging the cut-ff voltage scope is 0.1～2.0V (vs.Li
+/ Li), current density is 400～2000mA/g.Wherein, ordinate-specific discharge capacity, unit are MAH/gram (mAh/g); Abscissa-cycle-index, unit is week.
Embodiment:
Embodiment 1
With thickness is that the Copper Foil of 10 μ m is cut into 2cm * 4cm shape; Ultrasonic cleaning is 10 minutes in ethanol, immerses in the 20mL ethanolic solution contain the 0.4g nickel nitrate in 50 ℃ of baking ovens dry 3 hours then 5 minutes; Above step repeats 3 times, at copper foil surface load nickel base catalyst granules; The Copper Foil of load nickel base catalyst granules is put into the high-temperature region of two warm area tube furnaces; Camphor is put into the low-temperature space of two warm area tube furnaces as solid carbon source; After two warm area tube furnace sealings; Flow velocity along low-temperature space to the high-temperature region direction with 50mL/ minute feeds nitrogen, in two warm area tube furnaces, forms inert gas shielding atmosphere; The high-temperature region of two warm area tube furnaces is warming up to 760 ℃; Low-temperature space with two warm area tube furnaces is warming up to 200 ℃ again; Utilize nitrogen to bring the camphor of low-temperature space gasification into the high-temperature region deposition reaction 4 hours; Continuing under the feeding condition of nitrogen gas two warm area tube furnaces to be cooled to room temperature, obtain the present invention is based on the membrane electrode of helical form carbon nano-fiber bundle.
Adopt Japanese Hitachi S-4700 type field emission scanning electron microscope to characterize the microscopic appearance of membrane electrode, test result as shown in Figure 1.Helical form carbon nano-fiber Shu Changdu is entwined by several carbon nano-fiber spirals at 4～8 μ m; Have the gap between the carbon nano-fiber that twines each other, this has increased the specific area of carbon nano-fiber bundle.
Adopt Japanese JEOL JEM-2010 type high-resolution-ration transmission electric-lens to characterize the fine structure of the carbon nano-fiber that constitutes the carbon nano-fiber bundle, test result as shown in Figure 2.Different with general carbon nano-fiber, carbon nano-fiber of the present invention is made up of graphite flake layer, and graphite flake layer is basically perpendicular to the carbon nano-fiber axially-aligned.
Adopt Britain Renishaw RM2000 type micro confocal Raman spectrum to characterize the chemical composition of helical form carbon nano-fiber bundle, test result as shown in Figure 3.See that from the ratio at D peak and G peak helical form carbon nano-fiber bundle of the present invention has than general graphite and carbon nano-tube more defects.
Using sheet-punching machine to make the electrode slice of diameter as 1cm the membrane electrode based on helical form carbon nano-fiber bundle of the present invention's preparation, is negative pole with the metal lithium sheet, and barrier film is Celgard 2400, and electrolyte solution is EC+DMC+EMC+1mol/L LiPF
6, at the German M. Braun UnLab of company argon gas glove box (O
2, H
2O is all less than 1ppm) in be assembled into Experimental cell, adopt the blue electric CT2001A type battery test system in Wuhan to carry out electrochemical property test.When discharging and recharging the cut-ff voltage scope is 0.1～2.0V (vs.Li
+/ Li), the cycle performance when current density is 200mA/g as shown in Figure 4, material discharges first and the charge ratio capacity is respectively 1005mAh/g and 604mAh/g, 60 week circulation back specific capacities are stabilized in 580mAh/g, cycle performance is excellent.The high rate performance of this material as shown in Figure 5, when electric current changes to 2000mA/g from 400mA/g, after the experience 80 week circulation; In current density is under the 2000mA/g; Specific capacity is 467mAh/g, has kept 77.4% of initial capacity, and specific capacity still is higher than the theoretical capacity of graphite.
Embodiment 2
With thickness is that the Copper Foil of 30 μ m is cut into 2cm * 4cm shape; Ultrasonic cleaning is 20 minutes in ethanol, immerses in the 20mL ethanolic solution contain the 0.5g nickel nitrate in 60 ℃ of baking ovens dry 2 hours then 4 minutes; Above step repeats 4 times, at copper foil surface load nickel base catalyst granules; The Copper Foil of load nickel base catalyst granules is put into the high-temperature region of two warm area tube furnaces; Camphor is put into the low-temperature space of two warm area tube furnaces as solid carbon source; After two warm area tube furnace sealings; Flow velocity along low-temperature space to the high-temperature region direction with 40mL/ minute feeds argon gas, in two warm area tube furnaces, forms inert gas shielding atmosphere; The high-temperature region of two warm area tube furnaces is warming up to 600 ℃; Low-temperature space with two warm area tube furnaces is warming up to 240 ℃ again; Utilize argon gas to bring the camphor of low-temperature space gasification into the high-temperature region deposition reaction 3 hours; Continuing under the feeding argon gas condition two warm area tube furnaces to be cooled to room temperature, obtain the present invention is based on the membrane electrode of helical form carbon nano-fiber bundle.
The membrane electrode based on helical form carbon nano-fiber bundle of the present invention preparation is assembled into Experimental cell carries out electrochemical property test.When discharging and recharging the cut-ff voltage scope is 0.1～2.0V (vs.Li
+/ Li), when current density was 200mA/g, material discharged first and the charge ratio capacity is respectively 945mAh/g and 589mAh/g, and specific capacity is stabilized in 570mAh/g after the circulation of 60 weeks, and cycle performance is excellent.When electric current changes to 2000mA/g from 400mA/g, after the experience 80 week circulation, be under the 2000mA/g in current density, specific capacity is 447mAh/g, has kept 70.4% of initial capacity, and specific capacity still is higher than the theoretical capacity of graphite.
Embodiment 3
With thickness is that the Copper Foil of 20 μ m is cut into 2cm * 4cm shape; Ultrasonic cleaning is 14 minutes in ethanol, immerses in the 20mL ethanolic solution contain the 0.6g nickel nitrate in 70 ℃ of baking ovens dry 1 hour then 3 minutes; Above step repeats 5 times, at copper foil surface load nickel base catalyst granules; The Copper Foil of load nickel base catalyst granules is put into the high-temperature region of two warm area tube furnaces; Camphor is put into the low-temperature space of two warm area tube furnaces as solid carbon source; After two warm area tube furnace sealings; Flow velocity along low-temperature space to the high-temperature region direction with 60mL/ minute feeds nitrogen, in two warm area tube furnaces, forms inert gas shielding atmosphere; The high-temperature region of two warm area tube furnaces is warming up to 650 ℃; Low-temperature space with two warm area tube furnaces is warming up to 260 ℃ again; Utilize nitrogen to bring the camphor of low-temperature space gasification into the high-temperature region deposition reaction 2 hours; Continuing under the feeding condition of nitrogen gas two warm area tube furnaces to be cooled to room temperature, obtain the present invention is based on the membrane electrode of helical form carbon nano-fiber bundle.
The membrane electrode based on helical form carbon nano-fiber bundle of the present invention preparation is assembled into Experimental cell carries out electrochemical property test.When discharging and recharging the cut-ff voltage scope is 0.1～2.0V (vs.Li
+/ Li), when current density was 200mA/g, material discharged first and the charge ratio capacity is respectively 895mAh/g and 518mAh/g, and specific capacity is stabilized in 507mAh/g after the circulation of 60 weeks, and cycle performance is excellent.When electric current changes to 2000mA/g from 400mA/g, after the experience 80 week circulation, be under the 2000mA/g in current density, specific capacity is 418mAh/g, has kept 68.2% of initial capacity, and specific capacity still is higher than the theoretical capacity of graphite.
Embodiment 4
With thickness is that the Copper Foil of 30 μ m is cut into 2cm * 4cm shape; Ultrasonic cleaning is 20 minutes in ethanol, immerses in the 20mL ethanolic solution contain the 0.8g nickel nitrate in 80 ℃ of baking ovens dry 0.5 hour then 1 minute; Above step repeats 6 times, at copper foil surface load nickel base catalyst granules; The Copper Foil of load nickel base catalyst granules is put into the high-temperature region of two warm area tube furnaces; Camphor is put into the low-temperature space of two warm area tube furnaces as solid carbon source; After two warm area tube furnace sealings; Flow velocity along low-temperature space to the high-temperature region direction with 80mL/ minute feeds nitrogen, in two warm area tube furnaces, forms inert gas shielding atmosphere; The high-temperature region of two warm area tube furnaces is warming up to 800 ℃; Low-temperature space with two warm area tube furnaces is warming up to 380 ℃ again; Utilize nitrogen to bring the camphor of low-temperature space gasification into the high-temperature region deposition reaction 1 hour; Continuing under the feeding condition of nitrogen gas two warm area tube furnaces to be cooled to room temperature, obtain the present invention is based on the membrane electrode of helical form carbon nano-fiber bundle.
The membrane electrode based on helical form carbon nano-fiber bundle of the present invention preparation is assembled into Experimental cell carries out electrochemical property test.When discharging and recharging the cut-ff voltage scope is 0.1～2.0V (vs.Li
+/ Li), when current density was 200mA/g, material discharged first and the charge ratio capacity is respectively 949mAh/g and 612mAh/g, and specific capacity is stabilized in 608mAh/g after the circulation of 60 weeks, and cycle performance is excellent.When electric current changes to 2000mA/g from 400mA/g, after the experience 80 week circulation, be under the 2000mA/g in current density, specific capacity is 438mAh/g, has kept 64.2% of initial capacity, and specific capacity still is higher than the theoretical capacity of graphite.
Claims (4)
1. membrane electrode based on helical form carbon nano-fiber bundle is characterized in that: membrane electrode by the Copper Foil collector be grown in its surperficial helical form carbon nano-fiber bundle and constitute; Wherein, the thickness of Copper Foil collector is 10～30 μ m; The amount of the helical form carbon nano-fiber bundle of Copper Foil collection liquid surface growth is 1～5mg/cm2, and every helical form carbon nano-fiber bundle is entwined by several carbon nano-fiber spirals, and the vertical carbon nano-fiber of the graphite flake layer of carbon nano-fiber is axial.
2. the preparation method of the said membrane electrode of claim 1, it is characterized in that: processing step is following:
(1) with thickness be the Copper Foil of 10～30 μ m in ethanol ultrasonic cleaning 10～20 minutes to remove surface and oil contaminant or other dirts; Immersed concentration then and be in the nickel nitrate ethanolic solution of 20～40g/L 1～5 minute; Take out the back 50～80 ℃ of dryings 0.5～3 hour; Repeat above operation 3-6 time, at copper foil surface load nickel base catalyst granules;
(2) Copper Foil of load nickel base catalyst granules is put into the high-temperature region of two warm area tube furnaces; With camphor is the low-temperature space that solid carbon source is put into two warm area tube furnaces; After two warm area tube furnace sealings; Direction feeds inert carrier gas to the high-temperature region along low-temperature space, in two warm area tube furnaces, forms inert gas shielding atmosphere;
(3) high-temperature region with two warm area tube furnaces is warming up to design temperature, and the low-temperature space with two warm area tube furnaces is warming up to design temperature again, utilizes inert carrier gas to bring the camphor of low-temperature space gasification into the high-temperature region deposition reaction 1～4 hour; Deposition reaction finishes continued and feeds inert carrier gas, and two warm area tube furnaces are naturally cooled to room temperature, obtains the present invention is based on the membrane electrode of helical form carbon nano-fiber bundle.
3. like the preparation method of membrane electrode as described in the claim 2, it is characterized in that inert carrier gas described in step (2) and the step (3) is a kind of in nitrogen or the argon gas, the inert carrier gas flow velocity is 40～80mL/ minute.
4. like the preparation method of membrane electrode as described in the claim 2, it is characterized in that the high-temperature region design temperature of two warm area tube furnaces is 600～800 ℃ described in the step (3), the low-temperature space design temperature is 200～400 ℃.
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| CN102646821A (en) * | 2012-05-08 | 2012-08-22 | 电子科技大学 | Preparing method of negative materials for lithium ion batteries |
| CN103000906A (en) * | 2012-12-13 | 2013-03-27 | 天津大学 | Preparation method of foamy copper/carbon nanophase composite negative electrode material for lithium ion battery |
| CN106952738A (en) * | 2017-03-09 | 2017-07-14 | 安徽大学 | Electrode with flexible self-supporting structure and preparation method and application thereof |
| CN108666581A (en) * | 2018-06-29 | 2018-10-16 | 华南理工大学 | A kind of checkerboard composite current collector and preparation method thereof for lithium ion battery |
| CN108774381A (en) * | 2018-06-14 | 2018-11-09 | 哈尔滨工业大学 | A kind of preparation method of bi-directional drive carbon nanotube spiral fiber composite structure |
| CN110114915A (en) * | 2016-12-22 | 2019-08-09 | I&T新材料株式会社 | The electrode and its manufacturing method of electrical storage device |
| CN112064339A (en) * | 2020-08-28 | 2020-12-11 | 山东非金属材料研究所 | Iron oxyhydroxide-copper-clad carbon nanotube coaxial core-shell material and preparation method and application thereof |
| CN114835111A (en) * | 2022-05-30 | 2022-08-02 | 中北大学 | Nano spiral graphite fiber material and preparation method and application thereof |
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| CN102646821A (en) * | 2012-05-08 | 2012-08-22 | 电子科技大学 | Preparing method of negative materials for lithium ion batteries |
| CN102646821B (en) * | 2012-05-08 | 2014-05-21 | 电子科技大学 | Preparing method of negative materials for lithium ion batteries |
| CN103000906A (en) * | 2012-12-13 | 2013-03-27 | 天津大学 | Preparation method of foamy copper/carbon nanophase composite negative electrode material for lithium ion battery |
| CN103000906B (en) * | 2012-12-13 | 2014-10-15 | 天津大学 | Preparation method of foamy copper/carbon nanophase composite negative electrode material for lithium ion battery |
| CN110114915A (en) * | 2016-12-22 | 2019-08-09 | I&T新材料株式会社 | The electrode and its manufacturing method of electrical storage device |
| CN106952738A (en) * | 2017-03-09 | 2017-07-14 | 安徽大学 | Electrode with flexible self-supporting structure and preparation method and application thereof |
| CN108774381A (en) * | 2018-06-14 | 2018-11-09 | 哈尔滨工业大学 | A kind of preparation method of bi-directional drive carbon nanotube spiral fiber composite structure |
| CN108774381B (en) * | 2018-06-14 | 2021-04-06 | 哈尔滨工业大学 | Preparation method of bidirectional-driving carbon nanotube spiral fiber composite material structure |
| CN108666581A (en) * | 2018-06-29 | 2018-10-16 | 华南理工大学 | A kind of checkerboard composite current collector and preparation method thereof for lithium ion battery |
| CN112064339A (en) * | 2020-08-28 | 2020-12-11 | 山东非金属材料研究所 | Iron oxyhydroxide-copper-clad carbon nanotube coaxial core-shell material and preparation method and application thereof |
| CN112064339B (en) * | 2020-08-28 | 2022-10-28 | 山东非金属材料研究所 | Iron oxyhydroxide-copper-coated carbon nanotube coaxial core-shell material and preparation method and application thereof |
| CN114835111A (en) * | 2022-05-30 | 2022-08-02 | 中北大学 | Nano spiral graphite fiber material and preparation method and application thereof |
| CN114835111B (en) * | 2022-05-30 | 2024-04-30 | 中北大学 | Nano spiral graphite fiber material and preparation method and application thereof |
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