CN113422051A - Carbon nanotube-string carbon hollow polyhedron nanosphere material and preparation and application thereof - Google Patents

Carbon nanotube-string carbon hollow polyhedron nanosphere material and preparation and application thereof Download PDF

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CN113422051A
CN113422051A CN202110660121.9A CN202110660121A CN113422051A CN 113422051 A CN113422051 A CN 113422051A CN 202110660121 A CN202110660121 A CN 202110660121A CN 113422051 A CN113422051 A CN 113422051A
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carbon
solution
carbon nanotube
nanosphere
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杨秋合
袁永锋
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Hangzhou Vocational and Technical College
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a carbon nanotube-carbon hollow polyhedral nanosphere material, a preparation method thereof and application thereof in preparation of a sodium ion battery cathode. The carbon nanotube string carbon hollow polyhedral nanosphere material is formed by connecting a plurality of carbon hollow polyhedral nanospheres through a carbon nanotube to form a sugarcoated haws string-shaped structure. The preparation method comprises the following steps: firstly growing ZIF-8 particles on the surface of a carbon nano tube to form a sugarcoated haws string-shaped structure, then treating the ZIF-8@ carbon nano tube by tannic acid to obtain a precursor, and finally carrying out carbonization treatment to obtain a final product. The invention can improve the sodium storage capacity and the structural stability of the carbon hollow nanospheres, so that the carbon hollow nanospheres have higher reversible capacity and stable cycle performance. The carbon nanotube-series hollow polyhedral nanosphere material has important application value as a sodium ion battery cathode material.

Description

Carbon nanotube-string carbon hollow polyhedron nanosphere material and preparation and application thereof
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a carbon nanotube-string carbon hollow polyhedral nanosphere material and preparation and application thereof.
Background
Although the lithium ion battery is widely applied, the lithium storage capacity is limited, and the distribution is uneven, so that the further development of the lithium ion battery is limited. Sodium has electrochemical properties similar to lithium, but reserves are abundant, raw materials are low in price and widely distributed around the world, and sodium ion batteries have a similar deintercalation mechanism to lithium ion batteries, so sodium ion batteries are one of the best candidates for replacing lithium ion batteries.
The negative electrode material is a main factor limiting the electrochemical performance of the sodium-ion battery. The carbon-based material has the characteristics of rich raw materials, low cost, simple synthesis, low working potential and the like, and is very suitable for constructing the sodium-ion battery with excellent performance.
In the carbon-based material, the hard carbon material has relatively good sodium storage performance, and the sodium storage of the hard carbon material is mainly realized through a surface adsorption-intercalation mechanism, so that in order to improve the sodium storage capacity, the specific surface area of the material needs to be increased, and a larger space is provided for surface layer adsorption; in addition, it is also necessary to further increase the conductivity thereof to improve the large current charge and discharge performance. The construction of the carbon material with a porous structure is a current main strategy, but if the particle size of the porous carbon material is small, the porous carbon material is easy to agglomerate; if the particle size is large, the electrolyte is not easy to permeate the center of the material, and the porous material with large particle size has unstable structure and poor cycle performance. Compared with the porous structure, the carbon hollow nanosphere has large specific surface area and is completely suitable for storing sodium. Tang et al have reported in 2012 that carbon Hollow nanospheres are useful in sodium ion batteries (Hollow carbon nanospheres with super rate capability for sodium-based batteries, Advanced Energy Materials 2012,201100691). At present, SiO is adopted in most of carbon hollow nanospheres2The hollow carbon nanospheres are not in tight contact with each other in the prepared electrode, and the contact resistance is relatively high, so that the application of the hollow carbon nanospheres in the field of sodium ion batteries is yet to be improvedIntensive research has been carried out.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides the carbon nanotube-serial hollow polyhedral nanosphere material which has higher reversible capacity and cycle performance as a cathode material of a sodium ion battery and has important application value in the field of sodium ion batteries.
A carbon nanotube string carbon hollow polyhedron nanosphere material is characterized in that a plurality of carbon hollow polyhedron nanospheres are connected with a carbon nanotube in a penetrating mode to form a sugarcoated haws string-shaped structure.
Preferably, the carbon nanotubes are crystalline materials with an outer diameter of 10-100 nm.
Preferably, the carbon hollow polyhedral nanospheres are amorphous materials, with the size of 100-1000nm and the wall thickness of 5-100 nm. In the present invention, the "size" of the carbon hollow polyhedral nanosphere refers to the diameter of the circumscribed sphere of the carbon hollow polyhedral nanosphere.
Preferably, the carbon hollow polyhedral nanospheres are formed by carbonizing tannic acid.
The invention also provides a preparation method of the carbon nanotube string carbon hollow polyhedron nanosphere material, which comprises the following steps:
(1) 1440mg of Zn (NO) was added to the mixture3)2·6H2Dissolving O in 20mL of methanol, and stirring for 10min to obtain a solution 1; 975 and 3900mg of dimethylimidazole and 40mg of acidified carbon nano tube are dissolved in 20mL of methanol, and the solution is subjected to ultrasonic treatment for 4 times, 5min each time, and is used as a solution 2; pouring the solution 1 into the solution 2, and stirring for 5min to form a mixed solution; transferring the mixed solution to a 100mL Teflon high-pressure kettle, putting the Teflon high-pressure kettle into a 90 ℃ oven, preserving heat for 6h, naturally cooling, washing with methanol for three times, centrifuging, collecting a product, putting the obtained product into a 60 ℃ oven, and drying to obtain a ZIF-8@ carbon nano tube;
(2) dispersing 500mg of ZIF-8@ carbon nano tube in 250mL of ethanol, and performing ultrasonic treatment for 15min to form a uniform mixed solution serving as a solution 3; dissolving 250-1000mg tannic acid in 250mL of deionized water, and stirring for 15min to form a uniform mixed solution as solution 4: pouring the solution 4 into the solution 3, stirring for 5min, then washing with deionized water for three times, centrifugally collecting a product, and drying in a 60 ℃ oven; and heating the obtained product to 600 ℃ at the heating rate of 1-10 ℃/min in the argon atmosphere, preserving the heat for 2h, treating the cooled product with 1M HCl, and removing residual zinc to obtain the carbon nanotube-string hollow polyhedral nanosphere material.
The preparation method comprises the steps of firstly growing ZIF-8 particles on the surface of a carbon nano tube to form a sugarcoated haw string-shaped structure, then treating the ZIF-8@ carbon nano tube by tannic acid to obtain a precursor, and finally carrying out carbonization treatment to obtain a final product.
The invention also provides application of the carbon nanotube string carbon hollow polyhedron nanosphere material in preparation of a sodium ion battery cathode.
The material of the invention is adopted to prepare the cathode of the sodium ion battery: respectively weighing a carbon nanotube string carbon hollow polyhedral nanosphere material, an acetylene black conductive agent and a polyvinylidene fluoride (PVDF) binder in a mass ratio of 80:10:10, dissolving the PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground carbon nanotube string carbon hollow polyhedral nanosphere material and acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12mm), drying in a vacuum oven at 100 ℃, and finally flattening by using a pressure intensity of 10MPa on a tablet press to obtain the electrode plate.
Assembling the prepared electrode plate, a metal sodium sheet and a diaphragm into a CR2025 button type sodium ion battery, wherein the electrolyte is 1mol L-1NaClO4The EC-DMC-FEC electrolyte adopts a Xinwei battery test system to test the charge-discharge performance and the cycle performance of the sodium ion battery.
The invention can improve the sodium storage capacity and the structural stability of the carbon hollow nanospheres, so that the carbon hollow nanospheres have higher reversible capacity and stable cycle performance.
Compared with the prior art, the invention has the main advantages that:
1) the carbon hollow polyhedral nanospheres have large specific surface area, the inner surface and the outer surface of each hollow sphere can be contacted with electrolyte, the surface utilization rate is high, sodium ion surface adsorption is facilitated, and the sodium storage capacity is improved. The carbon hollow polyhedral nanospheres are thin in wall and short in sodium ion embedding path, so that the reaction dynamic performance is good, and the carbon hollow polyhedral nanospheres are connected in series by the high-conductivity carbon nano tubes, so that the conductivity among the carbon hollow spheres is improved, the contact resistance among the carbon hollow spheres is reduced, and the improvement of the high-current charging and discharging performance is facilitated. The carbon nanotube string and the carbon tube string are twisted together in the electrode to raise the conductivity and improve the structural strength of the electrode.
2) The polyhedral shape of the carbon hollow nanosphere is inherited from a regular dodecahedral structure of ZIF-8, and the carbon hollow nanosphere has higher structural strength than the traditional carbon hollow nanosphere; while amorphous carbon formed by the carbonization of tannic acid has high surface activity; the carbon hollow polyhedron nanospheres synthesized by the method have stable cycle performance and high reversible capacity.
3) The precursor of the carbon hollow polyhedral nanosphere can be synthesized in one step by treating ZIF-8 with tannic acid, the carbon hollow polyhedral nanosphere can be obtained after carbonization, no additional process is needed to be arranged to remove the template, and the synthesis method is mild, controllable, simple and efficient.
Drawings
FIG. 1 is a TEM photograph of ZIF-8@ carbon nanotubes prepared in example 1;
fig. 2 is a TEM photograph of the carbon nanotube-string hollow polyhedral nanosphere prepared in example 1;
FIG. 3 shows the current density of 1Ag for the carbon nanotube-based hollow polyhedral nanosphere material prepared in example 1-1Cycle performance map of (c).
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
(1) 720mg of Zn (NO)3)2·6H2Dissolving O in 20mL of methanol, and stirring for 10min to obtain a solution 1; 1950mg of dimethylimidazole and 40mg of acidified carbon nanotubes were dissolved in 20mL of methanol, and the solution was sonicated 4 times for 5min each to give solution 2. Quickly pouring the solution 1 into the solution 2, and stirring for 5min to form a mixed solution; and transferring the mixed solution to a 100mL Teflon high-pressure kettle, putting the Teflon high-pressure kettle into a 90 ℃ oven, preserving the heat for 6h, naturally cooling, washing with methanol for three times, centrifuging, collecting a product, and putting the obtained product into a 60 ℃ oven for drying to obtain the ZIF-8@ carbon nano tube.
(2) Dispersing 500mg of ZIF-8@ carbon nano tube in 250mL of ethanol, and performing ultrasonic treatment for 15min to form a uniform mixed solution serving as a solution 3; dissolving 500mg of tannic acid in 250mL of deionized water, and stirring for 15min to form a uniform mixed solution as solution 4: and quickly pouring the solution 4 into the solution 3, stirring for 5min, then washing for three times by using deionized water, centrifugally collecting a product, and drying in an oven at 60 ℃. And heating the obtained product to 600 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, preserving the heat for 2h, treating the cooled product with 1M HCl, and removing the residual zinc to obtain the carbon nanotube-string hollow polyhedral nanospheres.
FIG. 1 is a TEM photograph of the prepared ZIF-8@ carbon nanotubes, showing that some ZIF-8 polyhedral particles having a size of about 190nm are connected in a string, and a distinct cord, i.e., carbon nanotube, is provided at the center of each particle, and the hollow tube structure of the carbon nanotube is clearly visible. The tannin treated and carbonized product is shown in fig. 2, and some hollow polyhedral nanospheres replace solid ZIF-8 particles and are connected in series by carbon nanotubes. The outer diameter of the carbon nano tube is 30-60nm, the size of the carbon hollow polyhedron is about 200nm, and the wall thickness is 15-20 nm. Some of the carbon hollow polyhedral nanospheres are even internally connected together, while the carbon nanotubes pass through the middle of them.
The material of the invention is adopted to prepare the cathode of the sodium ion battery: respectively weighing a carbon nanotube string carbon hollow polyhedral nanosphere material, an acetylene black conductive agent and a polyvinylidene fluoride (PVDF) binder in a mass ratio of 80:10:10, dissolving the PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground carbon nanotube string carbon hollow polyhedral nanosphere material and acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12mm), drying in a vacuum oven at 100 ℃, and finally flattening by using a pressure intensity of 10MPa on a tablet press to obtain the electrode plate.
Assembling the prepared electrode plate, a metal sodium sheet and a diaphragm into a CR2025 button type sodium ion battery, wherein the electrolyte is 1mol L-1NaClO4The EC-DMC-FEC electrolyte adopts a Xinwei battery test system to test the charge-discharge performance and the cycle performance of the sodium ion battery.
FIG. 3 is the prepared carbon nanotube string carbon hollow polyhedron nanosphere material with current density of 1A g-1The cycle performance of (c). The charge-discharge voltage range is 0.01-3.0V. The specific discharge capacity of the 2 nd cycle is 216mAh g-1After that, the discharge capacity slowly decreased to 175mAh g at the 153 th cycle-1And the stability is maintained to 2000 th cycle, and good cycle stability is shown. The specific capacity and the cycle performance of the carbon nano tube string carbon hollow polyhedral nanospheres exceed that of the carbon hollow nanospheres of K.Tang et al at the current density of 1Ag-1Hour 120mAh g-1The discharge capacity (Hollow carbon nanoparticles with super rate capability for sodium-based batteries, Advanced Energy Materials 2012,201100691.) is also superior to that of the graphene-coated carbon Hollow sphere of Lei Song et al at a current density of 1Ag-1145mAh g after 1000 cycles-1Discharge capacity (Graphene-drawn graphic carbon halogen spheres: bioelectrical synthesized and applied in batteries and supercapacitors, ChemNanoMat 2016,20600079).
Example 2
(1) 720mg of Zn (NO)3)·6H2Dissolving O in 20mL of methanol, and stirring for 10min to obtain a solution 1; 1950mg of dimethylimidazole and 40mg of acidified carbon nanotubes were dissolved in 20mL of methanol, and the solution was sonicated 4 times for 5min each to give solution 2. Quickly pouring the solution 1 into the solution 2, and stirring for 5min to form a mixed solution; transferring the mixed solution to a 100mL Teflon autoclave, putting the Teflon autoclave into a 90 ℃ oven, and preserving heat for 6h until the mixed solution is self-containedAnd then cooling, washing for three times by using methanol, centrifuging to collect a product, and putting the obtained product into a 60 ℃ oven for drying to obtain the ZIF-8@ carbon nano tube.
(2) Dispersing 500mg of ZIF-8@ carbon nano tube in 250mL of ethanol, and performing ultrasonic treatment for 15min to form a uniform mixed solution serving as a solution 3; dissolving 750mg tannic acid in 250mL of deionized water, stirring for 15min to form a uniform mixed solution as solution 4: and quickly pouring the solution 4 into the solution 3, stirring for 5min, then washing for three times by using deionized water, centrifugally collecting a product, and drying in an oven at 60 ℃. And heating the obtained product to 600 ℃ at the heating rate of 5 ℃/min in the argon atmosphere, preserving the heat for 2h, treating the cooled product with 1M HCl, and removing the residual zinc to obtain the carbon nanotube-string hollow polyhedral nanospheres.
The structure of the carbon nanotube-series hollow polyhedral nanosphere material is similar to that of example 1, and the main difference is that the wall thickness of the carbon hollow polyhedral nanosphere is increased to 21-26 nm.
The same process as in example 1 was used to fabricate a negative electrode of a sodium ion battery, which was assembled into a sodium ion battery at a current density of 1A g-1And carrying out cyclic charge and discharge test in the voltage range of 0.01-3.0V. The cycle performance trend was similar to that of example 1, and the specific discharge capacity at the 2 nd cycle was 193mAh g-1Then the discharge capacity slowly dropped to 150 th cycle, the discharge capacity dropped to 155mAh g-1After which the discharge capacity remained stable to the 2000 th cycle.
Example 3
(1) 936mg of Zn (NO)3)·6H2Dissolving O in 20mL of methanol, and stirring for 10min to obtain a solution 1; 2535mg of dimethylimidazole and 40mg of acidified carbon nanotubes were dissolved in 20mL of methanol, and the solution was sonicated 4 times for 5min each time to give solution 2. Quickly pouring the solution 1 into the solution 2, and stirring for 5min to form a mixed solution; and transferring the mixed solution to a 100mL Teflon high-pressure kettle, putting the Teflon high-pressure kettle into a 90 ℃ oven, preserving the heat for 6h, naturally cooling, washing with methanol for three times, centrifuging, collecting a product, and putting the obtained product into a 60 ℃ oven for drying to obtain the ZIF-8@ carbon nano tube.
The subsequent steps were the same as in example 1.
The structure of the carbon nanotube-string hollow polyhedral nanosphere material of the product was similar to that of example 1, except that the size of the carbon hollow polyhedral nanospheres was increased to about 250 nm.
The same process as in example 1 was used to fabricate a negative electrode of a sodium ion battery, which was assembled into a sodium ion battery at a current density of 1A g-1And carrying out cyclic charge and discharge test in the voltage range of 0.01-3.0V. The cycle performance trend was similar to that of example 1, and the specific discharge capacity at the 2 nd cycle was 246mAh g-1After that, the discharge capacity slowly dropped to 209mAh g at the 158 th cycle-1After which the discharge capacity remained stable to the 2000 th cycle.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (6)

1. The carbon nanotube string hollow polyhedral nanosphere material is characterized in that a plurality of carbon hollow polyhedral nanospheres are connected with a carbon nanotube in a penetrating manner to form a sugarcoated haws string-shaped structure.
2. The carbon nanotube bulk hollow polyhedron nanosphere material of claim 1, wherein the carbon nanotubes are crystalline and have an outer diameter of 10-100 nm.
3. The carbon nanotube string hollow polyhedral nanosphere material of claim 1 or 2, wherein the hollow polyhedral nanosphere is an amorphous material with a size of 100-1000nm and a wall thickness of 5-100 nm.
4. The carbon nanotube string-carbon hollow polyhedral nanosphere material of claim 1, wherein said carbon hollow polyhedral nanosphere is formed by carbonizing tannic acid.
5. The method for preparing the carbon nanotube string hollow polyhedron nanosphere material as claimed in any one of claims 1 to 4, comprising the steps of:
(1) 1440mg of Zn (NO) was added to the mixture3)2·6H2Dissolving O in 20mL of methanol, and stirring for 10min to obtain a solution 1; 975 and 3900mg of dimethylimidazole and 40mg of acidified carbon nano tube are dissolved in 20mL of methanol, and the solution is subjected to ultrasonic treatment for 4 times, 5min each time, and is used as a solution 2; pouring the solution 1 into the solution 2, and stirring for 5min to form a mixed solution; transferring the mixed solution to a 100mL Teflon high-pressure kettle, putting the Teflon high-pressure kettle into a 90 ℃ oven, preserving heat for 6h, naturally cooling, washing with methanol for three times, centrifuging, collecting a product, putting the obtained product into a 60 ℃ oven, and drying to obtain a ZIF-8@ carbon nano tube;
(2) dispersing 500mg of ZIF-8@ carbon nano tube in 250mL of ethanol, and performing ultrasonic treatment for 15min to form a uniform mixed solution serving as a solution 3; dissolving 250-1000mg tannic acid in 250mL of deionized water, and stirring for 15min to form a uniform mixed solution as solution 4: pouring the solution 4 into the solution 3, stirring for 5min, then washing with deionized water for three times, centrifugally collecting a product, and drying in a 60 ℃ oven; and heating the obtained product to 600 ℃ at the heating rate of 1-10 ℃/min in the argon atmosphere, preserving the heat for 2h, treating the cooled product with 1M HCl, and removing residual zinc to obtain the carbon nanotube-string hollow polyhedral nanosphere material.
6. The use of the carbon nanotube-in-series carbon hollow polyhedron nanosphere material as claimed in any one of claims 1 to 4 in the preparation of a negative electrode of a sodium ion battery.
CN202110660121.9A 2021-06-15 2021-06-15 Carbon nanotube-string carbon hollow polyhedron nanosphere material and preparation and application thereof Withdrawn CN113422051A (en)

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Publication number Priority date Publication date Assignee Title
CN114420883A (en) * 2022-01-20 2022-04-29 成都大学 Sodium ion battery negative electrode material PTA macroporous layered carbon rod and preparation method thereof
CN114420883B (en) * 2022-01-20 2023-10-03 成都大学 Sodium ion battery anode material PTA large Kong Cengzhuang carbon rod and preparation method thereof

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