CN111063868A - Self-supporting carbon-selenium material and preparation method and application thereof - Google Patents
Self-supporting carbon-selenium material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium selenium battery anode materials, and particularly relates to a self-supporting carbon selenium material and a preparation method and application thereof. The self-supporting carbon selenium material provided by the invention comprises a selenium simple substance and porous carbon fiber cloth; the selenium carrying amount of the self-supporting carbon-selenium material is 10-17 mg/cm2. The self-supporting carbon selenium material has self-supporting performance and containsThe elemental selenium which is uniformly distributed and has high capacity is beneficial to obtaining the lithium selenium battery anode without a current collector and an adhesive in the application process, and is beneficial to improving the specific capacity of the lithium selenium battery. The embodiment result shows that when the carbon selenium material provided by the invention is used as the anode and the metallic lithium is used as the cathode, the specific capacity of the discharge area of the primary battery reaches 9mAh/cm2The specific discharge area capacity of the secondary battery is 3.4mAh/cm2The lithium selenium battery has higher specific capacity and excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of lithium selenium battery anode materials, and particularly relates to a self-supporting carbon selenium material and a preparation method and application thereof.
Background
The lithium selenium battery has the advantages of high energy density, long cycle life and low cost, and is widely concerned by researchers at home and abroad. The positive electrode of the conventional lithium-selenium battery is prepared by physically mixing and grinding selenium powder and porous carbon powder and then carrying out heat treatment at 260-300 ℃, and the method utilizes the good flowability of selenium at the heat treatment temperature to ensure that the selenium permeates into the porous carbon so as to form an integrated composite positive electrode material; however, in general, the selenium simple substance is difficult to completely melt and enters the porous carbon, XRD test is carried out on the positive electrode material obtained by the method, and the obtained XRD diffraction spectrogram shows that the composite positive electrode material has a strong selenium simple substance peak, which indicates that the composite positive electrode material has the selenium simple substance which is not fused with the porous carbon, so that the uniformity of the composite positive electrode material is reduced, and the electrochemical performance is further poor.
Disclosure of Invention
In view of the above, the present invention aims to provide a self-supporting carbon selenium material, in which selenium and carbon are uniformly mixed, the load is stable, the material has the characteristic of high selenium load, and the material exhibits high area specific capacity and stable electrical properties when applied to a lithium selenium battery positive electrode material; the invention also provides a preparation method and application of the self-supporting carbon selenium material.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a self-supporting carbon selenium material which is characterized by comprising a selenium simple substance and porous carbon fiber cloth; the selenium carrying amount of the self-supporting carbon-selenium material is 10-17 mg/cm2。
Preferably, the density of the porous carbon fiber cloth is 10-15 mg/cm2(ii) a The specific surface area of the porous carbon fiber cloth is more than or equal to 900m2Per g, pore volume is more than or equal to 0.85cm3/g。
Preferably, the preparation method of the porous carbon fiber cloth comprises the following steps: activating the basic carbon fiber cloth to obtain the porous carbon fiber cloth;
the temperature of the activation treatment is 800-950 ℃, the time is 1-3 h, and the activation atmosphere is carbon dioxide; the gas flow rate for providing the activating atmosphere is 30-50 mL/min.
The invention also provides a preparation method of the self-supporting carbon selenium material in the technical scheme, which comprises the following steps:
dipping porous carbon fiber cloth in a selenium dioxide water solution to obtain a dipping material;
and sequentially drying and selenizing the impregnation material to obtain the self-supporting carbon selenium material.
Preferably, the concentration of the selenium dioxide aqueous solution is 50-100 mg/mL.
Preferably, the porous carbon fiber cloth accounts for 30-50% of the total mass of selenium and the porous carbon fiber cloth in the selenium dioxide water solution.
Preferably, the drying treatment temperature is 40-60 ℃, and the drying treatment time is 12-24 h.
Preferably, the temperature of the selenization treatment is 260 ℃, and the time is 12-24 hours; the heating rate of heating to the selenization treatment temperature is 1-2 ℃/min
Preferably, the atmosphere of the selenization treatment is an inert atmosphere.
The invention also provides the application of the self-supporting carbon selenium material in the technical scheme or the self-supporting carbon selenium material prepared by the preparation method in the technical scheme in a lithium selenium battery.
The invention provides a self-supporting carbon selenium material, which comprises a selenium simple substance and porous carbon fiber cloth; the selenium carrying amount of the self-supporting carbon-selenium material is 10-17 mg/cm2. The self-supporting carbon selenium material has self-supporting performance, selenium in the self-supporting carbon selenium material is uniformly dispersed in fibers of porous carbon fiber cloth, and the self-supporting carbon selenium material contains elemental selenium which is uniformly distributed and has high loading capacity, so that the lithium selenium battery anode without a current collector and an adhesive can be obtained in the application process, and the specific capacity of the lithium selenium battery can be improved.
The results of the examples show that when the carbon selenium material provided by the invention is used as a positive electrode and the lithium metal is used as a negative electrode, the primary battery dischargesThe specific area capacity reaches 9mAh/cm2The specific discharge area capacity of the secondary battery is 3.4mAh/cm2The lithium selenium battery has higher specific capacity and excellent electrochemical performance.
The invention also provides a preparation method of the self-supporting carbon selenium material, which comprises the steps of firstly dipping the porous carbon fiber cloth in the selenium dioxide aqueous solution to obtain a dipping material, and then sequentially drying and selenizing the dipping material to obtain the self-supporting carbon selenium material. According to the invention, the porous carbon fiber cloth is impregnated by using a stable selenium dioxide aqueous solution, so that the problems that elemental selenium and the porous carbon fiber cloth cannot be uniformly mixed and the carbon disulfide solution of selenium is toxic and volatilizes too fast are solved, the selenium dioxide generates a selenium elemental substance in the selenization process through the carbon reduction effect of the carbon fiber cloth, and the selenium elemental substance is further uniformly distributed in the porous carbon fiber cloth carrier, so that the lithium selenium material which is uniformly distributed and has high loading capacity is obtained, and the high specific area capacity of the obtained self-supporting lithium selenium material when applied to a lithium selenium battery is favorably improved.
Drawings
FIG. 1 is a scanning electron micrograph of a self-supporting carbon selenium material obtained in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of the self-supporting carbon selenium material obtained in example 1 of the present invention;
FIG. 3 is a thermogravimetric analysis curve of the self-supporting carbon selenium material obtained in example 1 of the present invention;
FIG. 4 is a curve of the charge and discharge of the lithium selenium battery obtained in test example 1 of the present invention for three previous cycles.
Detailed Description
The invention provides a self-supporting carbon selenium material, which comprises a selenium simple substance and porous carbon fiber cloth; the selenium carrying amount of the self-supporting carbon-selenium material is 10-17 mg/cm2Preferably 10 to 16mg/cm2More preferably 10 to 15mg/cm2。
In the invention, the density of the porous carbon fiber cloth is preferably 10-15 mg/cm2More preferably 11 to 15mg/cm2And more preferably 12 to 15mg/cm2(ii) a The porous carbon fiber clothThe specific surface area is preferably not less than 900m2(ii)/g, more preferably 930m or more2Per g, more preferably not less than 950m2(ii)/g; the pore volume of the carbon fiber cloth is preferably more than or equal to 0.85cm3In g, more preferably 0.87cm or more3In g, more preferably not less than 0.90cm3/g。
In the present invention, the preparation method of the porous carbon fiber cloth preferably includes: and activating the basic carbon fiber cloth to obtain the porous carbon fiber cloth. In the invention, the temperature of the activation treatment is preferably 800-950 ℃, more preferably 820-900 ℃, and further preferably 850-900 ℃; the time is preferably 1 to 3 hours, more preferably 1.5 to 3 hours, and further preferably 2 to 3 hours; the activating atmosphere is preferably carbon dioxide; the gas flow rate for providing the activating atmosphere is preferably 30 to 50mL/min, more preferably 35 to 50mL/min, and still more preferably 40 to 50 mL/min. The source of the base carbon fiber cloth is not particularly limited in the present invention, and any source known to those skilled in the art may be used, and specifically, such a source is commercially available. In a specific embodiment of the present invention, the base carbon fiber cloth is preferably a commercially available product obtained by carbonizing polyacrylonitrile, pitch, resin or cotton cloth. The equipment for the activation treatment is not particularly limited, and equipment which can keep the temperature at high temperature and control the gas flow rate, which is well known to those skilled in the art, is adopted, and in the embodiment of the invention, a quartz tube furnace is preferred. In the present invention, the base carbon fiber cloth is preferably woven in a plain weave or a twill weave. In the invention, the carbon dioxide can carry out oxidation etching to the carbon fiber cloth to a certain degree, so as to play a role in pore forming and specific surface area increasing, and the basic carbon fiber cloth has a rich pore structure through activation.
Before the activation treatment, the base carbon fiber cloth is preferably heated to the temperature of the activation treatment under the inert gas atmosphere condition; the heating rate is preferably 1-3 ℃/min; the flow rate of the inert gas is preferably 30-50 mL/min, more preferably 35-50 mL/min, and still more preferably 40-50 mL/min. After the activation treatment, the porous carbon fiber cloth is preferably cooled under the inert gas atmosphere condition; the cooling is preferably furnace-cooled.
The invention also provides a preparation method of the self-supporting carbon selenium material in the technical scheme, which comprises the following steps:
dipping porous carbon fiber cloth in a selenium dioxide water solution to obtain a dipping material;
and sequentially drying and selenizing the impregnation material to obtain the self-supporting carbon selenium material.
According to the invention, porous carbon fiber cloth is soaked in selenium dioxide aqueous solution to obtain a soaking material.
In the invention, the concentration of the selenium dioxide aqueous solution is preferably 50-100 mg/mL, more preferably 55-95 mg/mL, and still more preferably 60-90 mg/mL. In the invention, the porous carbon fiber cloth preferably accounts for 30-50% of the total mass of selenium and the porous carbon fiber cloth in the selenium dioxide water solution, more preferably 30-45%, and still more preferably 30-40%. In the present invention, the impregnation is preferably performed under ultrasonic or vacuum conditions; the ultrasonic frequency and the vacuum degree of the ultrasonic are not particularly limited in the present invention, and those known to those skilled in the art can be used. According to the invention, the selenium dioxide aqueous solution is promoted to be impregnated and adsorbed in the porous carbon fiber cloth through ultrasound or vacuum, so that the uniform distribution of the selenium dioxide on the surface of the gaps of the porous carbon fiber cloth is promoted.
After the dipping material is obtained, the invention sequentially dries and selenizes the dipping material to obtain the self-supporting carbon selenium material. In the invention, the temperature of the drying treatment is preferably 40-60 ℃, more preferably 40-50 ℃, and further preferably 40-45 ℃; the time is preferably 12-24 h, more preferably 15-24 h, and still more preferably 18-24 h.
In the invention, the temperature of the selenization treatment is preferably 260 ℃, the time is preferably 12-24 h, more preferably 12-20 h, and further preferably 12-18 h; the heating rate of the temperature rise to the selenization treatment temperature is preferably 1-2 ℃/min, more preferably 1.2-2 ℃/min, and still more preferably 1.5-2 ℃/min. In the present invention, the atmosphere of the selenization treatment is preferably an inert atmosphere. The selenization apparatus is not particularly limited in the present invention, and may be an apparatus with heating and temperature maintaining functions, which is well known to those skilled in the art, and in the embodiment of the present invention, the selenization apparatus is preferably a tube furnace.
According to the invention, selenium element is uniformly dispersed on the surface of the porous carbon fiber cloth by using a selenium dioxide aqueous solution, and selenium dioxide is reduced into a selenium simple substance through a selenylation reaction, so that the selenium simple substance uniformly dispersed in the porous carbon fiber cloth is obtained.
The invention also provides the application of the self-supporting carbon selenium material in the technical scheme or the self-supporting carbon selenium material prepared by the preparation method in the technical scheme in a lithium selenium battery. In the invention, the application is preferably to prepare the lithium selenium battery by taking the self-supporting carbon selenium material as a positive electrode material of the lithium selenium battery. When the self-supporting carbon selenium material is used as the positive electrode material of the lithium selenium battery, a current collector and a bonding agent are not needed. The self-supporting carbon selenium material has self-supporting performance, is favorable for obtaining the lithium selenium battery anode without a current collector and an adhesive in the application process, and is favorable for improving the specific capacity of the lithium selenium battery.
In order to further illustrate the present invention, the self-supporting carbon selenium material provided by the present invention, the preparation method and the application thereof are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Arranging basic carbon fibers obtained by carbonizing polyacrylonitrile in a quartz tube furnace, heating to 950 ℃ at a heating speed of 2 ℃/min under the protection condition of nitrogen (flow is 50mL/min), then immediately switching to carbon dioxide gas, keeping the flow at 50mL/min and keeping the temperature at 950 ℃ for 1h for activation treatment, and finally switching to the nitrogen protection condition to cool the activated porous carbon fiber cloth to room temperature along with the furnace to obtain the porous carbon fiber cloth;
dissolving 562mg of selenium dioxide powder in 10ml of deionized water to obtain a selenium dioxide aqueous solution, and placing the selenium dioxide aqueous solution in a glass evaporation dish; soaking 600mg of the obtained porous carbon fiber cloth in the obtained selenium dioxide aqueous solution (according to the mass ratio of selenium to carbon cloth of 6:4), fully wetting, and then drying at 40 ℃ for 12h to obtain a soaking material; and (3) placing the impregnated material in a tube furnace, heating to 260 ℃ at the speed of 2 ℃/min under the protection of inert gas, preserving heat for 12h, and cooling to room temperature along with the furnace to obtain the self-supporting carbon-selenium material.
Scanning electron microscope test is carried out on the obtained self-supporting carbon selenium material, and the test result is shown in figure 1. As can be seen from fig. 1, the surface of the self-supporting carbon selenium material obtained in this embodiment is smooth, and selenium element enters into the inside of the porous carbon fiber cloth.
The obtained self-supporting carbon selenium material is subjected to an X-ray diffraction test, and the test result is shown in figure 2. As can be seen from FIG. 2, no diffraction peak of elemental selenium was detected in the self-supporting carbon-selenium material obtained in this example, which proves that elemental selenium was well dispersed in the carbon fiber and remained in a fine amorphous state.
Thermogravimetric analysis was performed on the obtained self-supporting carbon selenium material, and the test results are shown in fig. 3. As can be seen from FIG. 3, the selenium-carrying amount of the self-supporting carbon-selenium material obtained in the embodiment reaches 56%, and the selenium-carrying amount per unit area reaches 15mg/cm2。
Test example 1
The self-supporting carbon selenium material prepared in the example 1 is used as a positive electrode material (without a current collector and an adhesive) of a flexible self-supporting lithium selenium battery, and the flexible self-supporting carbon selenium material and a metal lithium negative electrode are assembled into a button cell at 0.135mA/cm2And (3) carrying out charge and discharge tests under the current density, wherein the test chart of the charge and discharge tests in the first three circles is shown in figure 4.
As can be seen from FIG. 4, the lithium selenium battery prepared by the self-supporting carbon selenium material provided by the invention is 0.135mA/cm2The specific capacity of the first discharge area reaches 8.3mAh/cm when the charge and discharge test is carried out under the current density2Specific capacity of chargeable discharge area of 3.2mAh/cm2The lithium selenium battery obtained by using the self-supporting carbon selenium material provided by the invention is proved to have higher specific capacity of discharge area and specific capacity of charge-discharge area, and good charge-discharge performance.
Example 2
Arranging basic carbon fibers obtained by weaving twill and carbonizing asphalt in a quartz tube furnace, heating to 800 ℃ at a heating speed of 2 ℃/min under the protection condition of nitrogen (flow is 50mL/min), then immediately switching to carbon dioxide gas, keeping the flow at 50mL/min, keeping the temperature at 800 ℃ for 3h for activation treatment, and finally switching to the protection condition of nitrogen to cool the activated porous carbon fiber cloth to room temperature along with the furnace to obtain the porous carbon fiber cloth;
421.6mg of selenium dioxide powder is dissolved in 5mL of deionized water to obtain a selenium dioxide water solution, and the selenium dioxide water solution is placed in a glass evaporation dish; soaking 300mg of the obtained porous carbon fiber cloth in the obtained selenium dioxide aqueous solution (according to the mass ratio of selenium to carbon cloth of 5: 5), fully wetting, and then drying at 40 ℃ for 12h to obtain a soaking material; and (3) placing the impregnated material in a tube furnace, heating to 260 ℃ at the speed of 2 ℃/min under the protection of inert gas, preserving heat for 12h, and cooling to room temperature along with the furnace to obtain the self-supporting carbon-selenium material.
Thermogravimetric analysis is carried out on the obtained self-supporting carbon-selenium material, and the selenium loading amount per unit area of the self-supporting carbon-selenium material obtained in the embodiment reaches 10mg/cm2。
Test example 2
The self-supporting carbon selenium material prepared in the embodiment 2 is used as a positive electrode material (without a current collector and an adhesive) of a flexible self-supporting lithium selenium battery, and the flexible self-supporting carbon selenium material and a metal lithium negative electrode are assembled into a button cell at 0.135mA/cm2The specific capacity of the first discharge area reaches 7.6mAh/cm when the charge and discharge test is carried out under the current density2The specific capacity of the chargeable discharge area reaches 2.7mAh/cm2The lithium selenium battery obtained by using the self-supporting carbon selenium material provided by the invention is proved to have higher specific capacity of discharge area and specific capacity of charge-discharge area, and good charge-discharge performance.
Example 3
Arranging basic carbon fibers obtained by plain weave weaving and cotton cloth carbonization in a quartz tube furnace, heating to 900 ℃ at a heating speed of 2 ℃/min under the protection condition of nitrogen (flow is 50mL/min), then immediately switching to carbon dioxide gas, keeping the flow at 50mL/min, keeping the temperature at 900 ℃ for 2h for activation treatment, and finally switching to the nitrogen protection condition to cool the activated porous carbon fiber cloth to room temperature along with the furnace to obtain the porous carbon fiber cloth;
655.8mg of selenium dioxide powder is dissolved in 10mL of deionized water to obtain a selenium dioxide water solution, and the selenium dioxide water solution is placed in a glass evaporation dish; soaking 200mg of the obtained porous carbon fiber cloth in the obtained selenium dioxide aqueous solution (according to the mass ratio of selenium to carbon cloth of 7: 3), fully wetting, and then drying at 40 ℃ for 24 hours to obtain a soaking material; and (3) placing the impregnated material in a tube furnace, heating to 260 ℃ at the speed of 2 ℃/min under the protection of inert gas, preserving heat for 12h, and cooling to room temperature along with the furnace to obtain the self-supporting carbon-selenium material. Thermogravimetric analysis is carried out on the obtained self-supporting carbon-selenium material, and the selenium loading amount per unit area of the self-supporting carbon-selenium material obtained in the embodiment reaches 17mg/cm2。
Test example 3
The self-supporting carbon selenium material prepared in the embodiment 3 is used as a positive electrode material (without a current collector and an adhesive) of a flexible self-supporting lithium selenium battery, and the flexible self-supporting carbon selenium material and a metal lithium negative electrode are assembled into a button cell at the voltage of 0.135mA/cm2The charge and discharge test is carried out under the current density, and the specific capacity of the first discharge area reaches 9mAh/cm2The specific capacity of the chargeable discharge area reaches 3.4mAh/cm2The lithium selenium battery obtained by using the self-supporting carbon selenium material provided by the invention is proved to have higher specific capacity of discharge area and specific capacity of charge-discharge area, and good charge-discharge performance.
The test results show that the selenium-carrying amount of the self-supporting carbon selenium material provided by the invention is 10-17 mg/cm2Selenium and carbon are uniformly mixed and stably loaded; the lithium selenium battery prepared by taking the self-supporting carbon selenium material provided by the invention as a positive electrode material shows good area specific capacity and cycling stability, so that the self-supporting carbon selenium material provided by the invention shows excellent application potential in the lithium selenium battery; the preparation method provided by the invention is simple in process, suitable for industrial production and has great economic value.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The self-supporting carbon selenium material is characterized by comprising a selenium simple substance and porous carbon fiber cloth; the selenium carrying amount of the self-supporting carbon-selenium material is 10-17 mg/cm2。
2. The self-supporting carbon selenium material of claim 1, wherein the density of the porous carbon fiber cloth is 10-15 mg/cm2(ii) a The specific surface area of the porous carbon fiber cloth is more than or equal to 900m2Per g, pore volume is more than or equal to 0.85cm3/g。
3. The self-supporting carbon selenium material of claim 1 or 2, wherein the preparation method of the porous carbon fiber cloth comprises the following steps: activating the basic carbon fiber cloth to obtain the porous carbon fiber cloth;
the temperature of the activation treatment is 800-950 ℃, the time is 1-3 h, and the activation atmosphere is carbon dioxide; the gas flow rate for providing the activating atmosphere is 30-50 mL/min.
4. A method of preparing a self-supporting carbon selenium material as claimed in any one of claims 1 to 3, comprising the steps of:
dipping porous carbon fiber cloth in a selenium dioxide water solution to obtain a dipping material;
and sequentially drying and selenizing the impregnation material to obtain the self-supporting carbon selenium material.
5. The preparation method according to claim 4, wherein the concentration of the selenium dioxide aqueous solution is 50-100 mg/mL.
6. The preparation method according to claim 4, wherein the porous carbon fiber cloth accounts for 30-50% of the total mass of the selenium and the porous carbon fiber cloth in the selenium dioxide aqueous solution.
7. The preparation method according to claim 4, wherein the drying treatment is carried out at a temperature of 40 to 60 ℃ for 12 to 24 hours.
8. The preparation method according to claim 4, wherein the temperature of the selenization treatment is 260 ℃ and the time is 12-24 hours; the heating rate of heating to the selenization treatment temperature is 1-2 ℃/min.
9. The method according to claim 4, wherein the atmosphere of the selenization treatment is an inert atmosphere.
10. Use of the self-supporting carbon selenium material of any one of claims 1 to 3 or the self-supporting carbon selenium material obtained by the preparation method of any one of claims 4 to 9 in a lithium selenium battery.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104201389A (en) * | 2014-08-20 | 2014-12-10 | 中南大学 | Preparation method of lithium-selenium battery positive electrode |
| CN104716345A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Fuel cell cathode electrocatalyst and preparation and application thereof |
| CN106571460A (en) * | 2015-10-09 | 2017-04-19 | 中国科学院上海硅酸盐研究所 | Binder-free selenium cathode material with self-supporting structure and preparation method thereof |
| CN108091497A (en) * | 2017-12-06 | 2018-05-29 | 中国科学院上海技术物理研究所 | A kind of preparation method of multidimensional structure carbon fiber flexible electrode |
| CN108140818A (en) * | 2015-10-06 | 2018-06-08 | 法拉典有限公司 | A kind of method for being used to prepare hard carbon composite material |
| CN109560270A (en) * | 2018-11-19 | 2019-04-02 | 肇庆市华师大光电产业研究院 | A kind of Se@CNT/CP self-supporting flexible electrode material, preparation method and application |
-
2019
- 2019-07-30 CN CN201910693045.4A patent/CN111063868B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104716345A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Fuel cell cathode electrocatalyst and preparation and application thereof |
| CN104201389A (en) * | 2014-08-20 | 2014-12-10 | 中南大学 | Preparation method of lithium-selenium battery positive electrode |
| CN108140818A (en) * | 2015-10-06 | 2018-06-08 | 法拉典有限公司 | A kind of method for being used to prepare hard carbon composite material |
| CN106571460A (en) * | 2015-10-09 | 2017-04-19 | 中国科学院上海硅酸盐研究所 | Binder-free selenium cathode material with self-supporting structure and preparation method thereof |
| CN108091497A (en) * | 2017-12-06 | 2018-05-29 | 中国科学院上海技术物理研究所 | A kind of preparation method of multidimensional structure carbon fiber flexible electrode |
| CN109560270A (en) * | 2018-11-19 | 2019-04-02 | 肇庆市华师大光电产业研究院 | A kind of Se@CNT/CP self-supporting flexible electrode material, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| BEIBEI YUAN ET AL.: ""A Freestanding and Long-Life Sodium-Selenium Cathode by Encapsulation of Selenium into Microporous Multichannel Carbon Nanofibers"", 《SMALL》 * |
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