CN110817845A - Amorphous hollow carbon nanotube and preparation method thereof - Google Patents
Amorphous hollow carbon nanotube and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an amorphous hollow carbon nanotube and a preparation method thereof, wherein the inner diameter of the amorphous hollow carbon nanotube is 50-100nm, the thickness is 10-20nm, the length of the amorphous hollow carbon nanotube is 1-5 mu m, the carbon wall of the amorphous hollow carbon nanotube is of a porous amorphous structure, and a plurality of nano particles are attached to the inner wall of the amorphous hollow carbon nanotube. The amorphous hollow carbon nanotube is obtained by using zinc oxide as a template and phenolic aldehyde amine resin as a carbon source through low-temperature heat treatment and hydrochloric acid etching. The invention utilizes the lithium/sodium affinity of the metal nano-particles to realize the guiding function on lithium/sodium metal, limits the deposition and stripping processes of the lithium/sodium metal in the cavity of the carbon tube, realizes the effects of inhibiting dendritic crystal growth, limiting volume change generated in the deposition and stripping processes of the lithium/sodium metal and stabilizing a negative electrode/electrolyte interface, and has important application value for constructing a stable and efficient lithium/sodium metal battery.
Description
Technical Field
The invention relates to the technical field of lithium and sodium metal battery electrode materials, in particular to an amorphous hollow carbon nanotube and a preparation method thereof.
Background
Since metallic lithium has the highest theoretical capacity (3860 mAhg)-1And) and lowest electrochemical potential (3.04V vs. standard hydrogen electrode), lithium-based energy storage devices have long been the most attractive product in the energy storage market. However, conventional Lithium Ion Batteries (LIBs) have been increasingly challenged by energy density limitations in recent years, and safety problems caused by lithium dendrites and interfacial instability of the negative electrode material have prevented their widespread use.
Compared with lithium-based energy storage batteries, sodium metal is more abundant in resources on the earth and lower in price, and the sodium metal batteries are expected to become next-generation novel energy storage batteries to realize green large-scale energy storage and conversion. Sodium metal cathodes also face several decisive challenges in applications such as sodium dendrite growth and its associated short circuit problems, low coulombic efficiency and short cycle life, infinite volume effect during cycling, etc.
In view of the above problems, the protection of the negative electrode is becoming a necessary strategy. The patent application CN103682287A discloses a silicon-based composite anode material of a lithium ion battery, which successfully realizes the embedding of nano-silicon particles in a graphite inner layer and the uniform coating of the surface of the graphite particles by adopting a mode of combining mechanical grinding, mechanical fusion, isotropic pressure treatment and a carbon coating technology to obtain a high-performance silicon-based material; the nano silicon particles are uniformly dispersed in the graphite particles serving as the buffer matrix, the expansion of the silicon particles is fundamentally relieved by the embedded composite core structure, the conductivity of the material is greatly improved, and the direct contact between the silicon particles and electrolyte is avoided, so that the cycle performance (the cycle capacity retention rate is more than 90 percent in 300 times) and the first efficiency (more than 90 percent) of the material are greatly improved. This patent is through the embedded compound nuclear that inlays of silicon granule in graphite flake layer formation, alleviates the inflation of silicon granule through the compound nuclear structure of silicon granule-graphite as the buffering base member, has avoided silicon granule and electrolyte direct contact.
Disclosure of Invention
The invention aims to solve the problems of potential safety hazards caused by dendritic crystal growth and volume change in the charging and discharging processes and poor cycle performance of the conventional lithium ion battery, and provides an amorphous hollow carbon nanotube and a preparation method thereof.
The invention concept of the invention is as follows: in order to stabilize the metal cathode, methods such as modification of an artificial SEI protective layer, electrolyte and additives, three-dimensional cathode structure design and the like are rapidly developed, and in addition, the requirements of cathode host materials on electron conduction and ion conduction characteristics in the lithium deposition process, the carbon-based three-dimensional cathode structure design becomes one of the most effective approaches. The inventors believe that the use of carbon nanocapsules for lithium/sodium metal encapsulation has unique advantages. Each nanocapsule not only provides a completely closed space to isolate the filled lithium/sodium metal from the external electrolyte, but also stabilizes the formed SEI film by means of a strong carbon shell, thereby achieving the effects of reducing side reactions and improving cycle stability. The key to achieving this spatially controlled lithium/sodium deposition is how to direct the nucleation and growth of lithium/sodium metal within the nanocapsules. Research shows that the nucleation overpotential of lithium metal on lithium-philic elements such as Au, Ag and Mg and nanoparticles of Si, Sn and the like is almost zero, even monoatomic doping (such as doping Co, Ni, Zn and the like) can induce lithium to nucleate preferentially, the lithium and the lithium form an alloy, the lithium is induced to deposit in a carbon-based three-dimensional negative electrode current collector, and the uniform and dendrite-free deposition process of the lithium metal on a negative electrode host material is effectively controlled. Therefore, heterogeneous nanoparticles can be utilized to guide lithium/sodium metal to be preferentially deposited in the nanocapsules, thereby realizing nano-encapsulation of the lithium/sodium metal negative electrode.
Among the various nanocapsule structures, the one-dimensional hollow carbon nanomaterial has great potential in the negative electrode material of the metal battery due to the unique structure and characteristics: (1) the high specific surface area improves the contact between the electrode and the electrolyte and reduces the local current density; (2) the one-dimensional structure is easy to control, and the preparation and regulation difficulty is reduced; (3) the high conductivity and the axial structure of the carbon material enable the electron transmission to be more direct and convenient; (4) the one-dimensional carbon material also has excellent toughness and mechanical stability, and is greatly helpful for inevitable stress release in the circulating process. More notably, the one-dimensional carbon nanostructure with porous properties exhibits superior performance in battery systems, thanks to its larger contact area with the electrolyte, larger space for storing lithium/sodium and greater tolerance for volume changes during cycling. Lithium/sodium can gradually fill the pores of the porous framework and then grow further on the uniform surface it forms.
The invention provides a method for packaging lithium/sodium metal by utilizing an amorphous hollow carbon nano tube loaded with heterogeneous nano particles. The carbon tube has a porous amorphous carbon tube wall which is hydrophilic to lithium/sodium, and gold particles loaded on the inner wall of the carbon tube can induce lithium/sodium to deposit in a one-dimensional cavity of the carbon tube, so that the growth of dendritic crystals on the outer surface of the carbon wall is well avoided. Meanwhile, the amorphous carbon wall has stronger mechanical stability, can limit the deposition of lithium/sodium metal in the inner cavity of the amorphous carbon wall, effectively inhibits the volume change in the metal deposition/stripping process, and further optimizes the cycle performance of the battery. The method has simple manufacturing process and low cost, and has good prospect in the application market of carbon-based energy storage.
The invention successfully prepares the amorphous hollow carbon nano tube which has a larger inner cavity, the carbon wall is a porous amorphous structure, and a plurality of heterogeneous nano particles are attached to the inner wall. The carbon nanotube/sodium metal composite material is used as a negative current collector material of a lithium/sodium metal battery, and lithium/sodium metal can be guided into an inner cavity of a carbon tube by metal nanoparticles and deposited in the cavity until the whole cavity is filled. Secondly, after the inner cavity of the carbon tube is completely filled with the lithium/sodium metal, the lithium/sodium metal can be completely removed from the inner cavity, and the deposition/stripping process can be circulated for many times. The whole deposition process is limited by the carbon wall, and the stable structure of the carbon tube in the deposition-stripping cycle process can be ensured. Wherein, the specific mode of the heterogeneous nano-particles inducing the lithium/sodium metal to deposit in the inner cavity of the carbon tube, the loading particles take gold as an example: the gold nanoparticles and lithium/sodium metal are subjected to alloy reaction to form a lithium/sodium gold alloy, and then the lithium/sodium metal is deposited by taking the lithium/sodium metal as a nucleation point, and the cavity of the carbon tube is continuously filled.
In the preparation method of the amorphous hollow carbon nanotube, step 2) needs to carry out amino functionalization on the zinc oxide nanorod, and aims to provide an affinity site for loading gold particles. Specifically, ammonia water and an aminosilane coupling agent are used, and the aminosilane coupling agent is hydrolyzed under the alkaline catalysis of the ammonia water to obtain an amino functional group.
The nano-particle sol in the step 3) can be prepared by self or can be purchased as a commercial product. Taking the preparation of gold nanoparticle sol as an example, the method comprises the following steps: reacting sodium citrate with chloroauric acid, adding the sodium citrate into distilled water, stirring uniformly, heating to boil, quickly injecting the chloroauric acid into the distilled water, reacting for 3-6 minutes, and cooling to room temperature to obtain the zinc oxide nanorod ZnO @ Au loaded with the gold nanoparticles.
And 5) performing phenolic amine coating on the ZnO @ R obtained in the step 4), preparing for carbonization, preferably using resorcinol, formaldehyde and ethylenediamine as carbon sources, and having the advantages of gradual formation of polymerization coating, long coating process and uniform thickness of the obtained resin layer.
In the step 7), preferably, hydrochloric acid is used for etching ZnO @ R @ C, and diluted hydrochloric acid is used for etching, so that the integrity of the material structure can be well protected on the basis of completely etching the template.
The invention also provides a lithium/sodium metal battery cathode current collector which is prepared from the amorphous hollow carbon nano tube, and lithium/sodium is induced to be deposited in a cavity of the amorphous hollow carbon nano tube by utilizing nano particles in the amorphous hollow carbon nano tube. The deposition process comprises the following steps: the nano particles and lithium/sodium metal are subjected to alloy reaction to form lithium/sodium-nano particle alloy, and then the lithium/sodium metal is deposited by taking the lithium/sodium metal as a nucleation point, and the cavity of the carbon tube is continuously filled. The current collector can also be doped with a binder, a conductive agent, a solvent and the like, and the current collector doping method adopts a conventional method.
The invention also provides a lithium/sodium metal battery, which comprises a battery anode, a battery cathode and electrolyte, wherein the battery cathode is the lithium/sodium metal battery cathode current collector. The battery positive electrode, the electrolyte and the battery assembly method adopt the conventional method.
Compared with the scheme disclosed by CN103682287A, the scheme provided by the invention has the following differences:
1) the idea of improving performance is different. The patent uses a silicon particle-graphite composite core structure as a buffer matrix to relieve the expansion of silicon particles, thereby avoiding the direct contact between the silicon particles and electrolyte; the application realizes the reversible and stable encapsulation of lithium/sodium metal in the inner cavity of a closed amorphous carbon tube by the guidance of lithium-philic/sodium particles so as to inhibit the growth of dendrites.
2) The nanoparticles used are different. This patent relates to silicon nanoparticles; the present application relates to lithium/sodium philic nanoparticles such as Au nanoparticles, Ag nanoparticles, Mg nanoparticles, Si nanoparticles, Sn nanoparticles, Co nanoparticles, Ni nanoparticles or Zn nanoparticles.
3) The preparation process is different. The patent adopts a mode of combining mechanical grinding, mechanical fusion, isotropic pressure treatment and a carbon coating technology to prepare the composite material with the nano silicon particles embedded in the graphite inner layer; the amorphous hollow carbon tube loaded with nano particles is obtained by using zinc oxide as a template and phenolic aldehyde amine resin as a carbon source through low-temperature heat treatment and hydrochloric acid etching.
4) The material structure is different. The material structure related to the patent is that silicon particles are embedded in a graphite sheet layer to form an embedded composite core; the application relates to a material structure that nano particles are loaded on the inner wall of an amorphous carbon tube.
The specific scheme is as follows:
an amorphous hollow carbon nanotube, wherein the inner diameter of the amorphous hollow carbon nanotube is 50-100nm, the thickness of the amorphous hollow carbon nanotube is 10-20nm, the length of the amorphous hollow carbon nanotube is 1-5 mu m, both ends of the amorphous hollow carbon nanotube are closed, the carbon wall of the amorphous hollow carbon nanotube is of a porous amorphous structure, and a plurality of nanoparticles are attached to the inner wall of the amorphous hollow carbon nanotube. Preferably, the amorphous hollow carbon nanotube has an inner diameter of 60 to 80nm, a thickness of 12 to 16nm, and a tube length of 2 to 4 μm, for example, the amorphous hollow carbon nanotube has an inner diameter of 70nm, a thickness of 13nm, and a tube length of 3 μm; or the inner diameter of the amorphous hollow carbon nano tube is 75nm, the thickness of the amorphous hollow carbon nano tube is 15nm, and the length of the amorphous hollow carbon nano tube is 3.5 mu m;
the nano-particles are any one of Au nano-particles, Ag nano-particles, Mg nano-particles, Si nano-particles, Sn nano-particles, Co nano-particles, Ni nano-particles or Zn nano-particles with lithium/sodium affinity;
optionally, the specific surface area of the carbon wall of the amorphous hollow carbon nanotube is 900-2And g, the nanoparticles guide lithium/sodium metal ions from the holes on the carbon wall into the cavity of the amorphous hollow carbon nanotube and out of the amorphous hollow carbon nanotube through the holes on the carbon wall.
A preparation method of the amorphous hollow carbon nanotube comprises the following steps:
step 1) carrying out hydrothermal reaction on zinc salt and alkali to prepare a zinc oxide nanorod;
step 2) performing amino functionalization on the zinc oxide nanorod obtained in the step 1) by using ammonia water and an aminosilane coupling agent to obtain an aminated zinc oxide nanorod;
step 3) preparing nano-particle sol;
step 4) mixing the aminated zinc oxide nanorod obtained in the step 2) with the nanoparticle sol obtained in the step 3), and then centrifuging to obtain a nanoparticle-loaded zinc oxide nanorod ZnO @ R;
step 5) phenolic aldehyde amine coating is carried out on the ZnO @ R obtained in the step 4) to obtain a phenolic aldehyde amine coated zinc oxide nano rod ZnO @ R @ PB;
step 6) carrying out heat treatment on the ZnO @ R @ PB obtained in the step 5), and carbonizing the phenolic amine layer coated on the surface to obtain a zinc oxide nanorod ZnO @ R @ C coated by the amorphous carbon layer loaded with the nanoparticles;
and 7) etching the ZnO @ R @ C obtained in the step 6) to obtain the amorphous hollow carbon nanotube.
Further, the step 1) comprises: dissolving NaOH in ethanol to prepare solution A, dissolving zinc acetate in ethanol to prepare solution B, and mixing the solution A and the solution B, wherein the mass ratio of NaOH to zinc acetate is 10: 4-5, stirring and ultrasonically treating, introducing the obtained solution into a reaction kettle, carrying out hydrothermal reaction for 15-20 hours at the temperature of 140-160 ℃, and cleaning the product with ethanol to obtain a zinc oxide nano rod with the length of 1-2 mu m and the diameter of 50-100 nm;
the step 2) comprises the following steps: adding the zinc oxide nano rod obtained in the step 1) into ethanol, adding ammonia water and an aminosilane coupling agent, and stirring for more than 12 hours to obtain an amino functional group zinc oxide nano rod; wherein, the adding amount of the zinc oxide nano rod is as follows: adding amount of ammonia water: the addition mass ratio of the aminosilane coupling agent is 75-100 mg: 4mL of: 200-;
the preparation of the nanoparticle sol in step 3) takes gold as an example, and the method comprises the following steps: reacting sodium citrate with chloroauric acid, adding the sodium citrate into distilled water, stirring uniformly, heating to boil, quickly injecting the chloroauric acid into the distilled water, reacting for 3-6 minutes, and cooling to room temperature to obtain zinc oxide nano-rods ZnO @ Au loaded with gold nano-particles; wherein the addition amount of the sodium citrate is as follows: the addition amount of the chloroauric acid is 4-7: 10;
in the step 5), resorcinol, formaldehyde and ethylenediamine are used as carbon sources for phenolic amine coating, the zinc oxide nano rod ZnO @ Au loaded with gold nano particles is added into a mixed solution of water and ethanol, then resorcinol, formaldehyde and ethylenediamine are sequentially added, and after reaction for 20-30 hours, washing and drying are carried out to obtain ZnO @ Au @ PB; wherein the addition amount of the zinc oxide nano rod loaded with gold nano particles is as follows: addition amount of resorcinol: adding amount of formaldehyde: the addition of ethylenediamine was 125mg (100-): 15-25 mg: 25-35 μ L: 30-40 mu L;
the step 6) comprises the following steps: putting ZnO @ Au @ PB into the middle of a tubular furnace hearth, and taking H2Ar is protective gas, the temperature is raised to 550-650 ℃ at the speed of 3-5 ℃/min, the temperature is kept for 3-5h, and the temperature is cooled to room temperature after the reaction is finished, so that ZnO @ Au @ C is obtained;
the step 7) comprises the following steps: and dissolving ZnO @ Au @ C in hydrochloric acid, stirring for 5-7h, washing and drying a product to obtain the amorphous hollow carbon nanotube.
The invention also relates to the amorphous hollow carbon nano tube obtained by the preparation method of the amorphous hollow carbon nano tube.
The amorphous hollow carbon nanotube is used for packaging lithium and sodium metal, constructing negative electrode protection, and preparing a negative electrode current collector of a lithium/sodium metal battery, and has the effects of restraining dendritic crystal growth, limiting volume change generated in the deposition and stripping processes of the lithium/sodium metal and stabilizing a negative electrode/electrolyte interface.
Further, the amorphous hollow carbon nanotube encapsulation of lithium and sodium metal is a reversible process, specifically, in the deposition process, lithium/sodium metal is guided by nanoparticles to enter the inner cavity of the carbon tube of the amorphous hollow carbon nanotube, and deposition is performed in the inner cavity until the whole cavity is filled; when the inner cavity of the carbon tube is completely filled with the lithium/sodium metal, the lithium/sodium metal can be completely removed from the inner cavity, the deposition/stripping process can be circulated for multiple times, and the whole deposition process is limited by the carbon wall of the amorphous hollow carbon nanotube, so that the stability of the structure in the deposition-stripping cycle process of the lithium/sodium metal is ensured;
optionally, the deposition process comprises: the nano particles and lithium/sodium metal are subjected to alloy reaction to form lithium/sodium-nano particle alloy, and then the lithium/sodium metal is deposited by taking the lithium/sodium metal as a nucleation point, and the cavity of the carbon tube is continuously filled.
A lithium/sodium metal battery cathode active material is prepared from an amorphous hollow carbon nano tube, and lithium/sodium is induced to be deposited into a cavity of the amorphous hollow carbon nano tube by utilizing nano particles in the amorphous hollow carbon nano tube;
optionally, nanoparticles in the amorphous hollow carbon nanotube and lithium/sodium metal are subjected to alloy reaction to form a lithium/sodium-nanoparticle alloy, then the lithium/sodium metal is deposited by taking the lithium/sodium metal as a nucleation point, and the carbon tube cavity is continuously filled with the lithium/sodium metal to obtain the amorphous hollow carbon nanotube with the cavity filled with the lithium/sodium metal.
A lithium/sodium metal battery negative electrode current collector comprising the lithium/sodium metal battery negative electrode active material.
A lithium/sodium metal battery comprises a battery anode, a battery cathode and electrolyte, wherein the battery cathode is a current collector of the lithium/sodium metal battery cathode.
Has the advantages that:
the invention designs and successfully prepares the amorphous hollow carbon nano tube, can effectively inhibit dendritic crystal generation, control volume change in the lithium metal deposition/stripping process and stabilize the amorphous hollow carbon nano tube loaded with gold particles of an electrode/electrolyte interface, can be used as an ideal carbon-based negative electrode current collector material of a lithium metal negative electrode, and is used for constructing a safe lithium metal battery with high coulombic efficiency and long service life.
The invention also provides a preparation method of the amorphous hollow carbon nano tube, which comprises the steps of loading nano particles, coating with phenol aldehyde amine, carbonizing, etching and the like, has simple integral process and low material cost, has market development prospect, and is expected to become a lithium/sodium metal battery cathode host material with excellent electrochemical performance and commercial value.
Furthermore, the invention takes gold nanoparticles as an example, and the prepared amorphous hollow carbon nanotube loaded with gold particles has high specific surface area (961.4744 m)2The lithium/sodium metal negative electrode has the advantages of being porous, hollow and the like, can well inhibit dendritic crystals from being generated, stabilizes an SEI film, and improves the cycle performance of the lithium/sodium metal negative electrode.
And secondly, the gold nanoparticles of the amorphous hollow carbon nanotube loaded with gold particles are about 10-20nm, so that the lithium affinity and the sodium affinity of the carbon tube can be greatly improved, a large number of nucleation sites are provided for the deposition of lithium/sodium metal, and the lithium/sodium metal is effectively induced to be preferentially deposited in the inner cavity of the carbon tube, so that the growth of lithium/sodium dendrites on the outer wall of the carbon tube is avoided, the advantages of the hollow structure of the carbon tube can be fully utilized, and the coulombic efficiency of the electrode is further improved.
Finally, the amorphous hollow carbon nanotube loaded with gold particles has an inner diameter of 50-100nm and a tube length of 1-5 μm, lithium/sodium metal can be embedded and deposited in the porous amorphous carbon wall and the inner cavity of the large-capacity carbon tube, and the amorphous carbon wall of 10-20nm can well stabilize the interface of an electrode electrolyte, so that the structural advantages of the carbon tube are exerted to the maximum.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is a diagram showing the experimental procedure for preparing carbon tubes loaded with gold particles according to example 1 of the present invention;
fig. 2(a) is a morphology of a carbon tube loaded with gold particles provided in an embodiment 1 of the present invention under a Transmission Electron Microscope (TEM);
fig. 2(b) is a morphology of a carbon tube loaded with gold particles under a Transmission Electron Microscope (TEM) according to an embodiment 1 of the present invention;
fig. 3 is a diagram illustrating an in-situ deposition and stripping process of lithium metal in a carbon tube loaded with gold particles according to an embodiment 2 of the present invention;
fig. 4 is a diagram of a first cycle of sodium metal in a carbon tube loaded with gold particles according to an embodiment 3 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1
The amorphous hollow carbon nanotube is prepared, the supported particles are exemplified by gold, the experimental process is shown in figure 1, the zinc oxide nano-rod is used as a template, and after further amino functionalization, the gold nano-particles can be supported on the zinc oxide nano-rod. On the basis, the zinc oxide nano rod with gold nano particles loaded on the outer wall is subjected to carbon coating, the coating layer can be converted into amorphous carbon by a carbonization process, and a target product can be obtained after the template is further etched: a hollow carbon tube with gold nano-particles loaded on the inner wall. The method comprises the following specific steps:
1) preparing a ZnO template: dissolving 1g of NaOH in 50mL of ethanol to prepare solution A, dissolving 0.46g of zinc acetate in 25mL of ethanol to prepare solution B, adding the solution A into the solution B, stirring and carrying out ultrasonic treatment for 30 minutes, introducing the obtained solution into a 100mL reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 18 hours, and washing with ethanol twice to obtain ZnO nanorods with the length of 1-2 mu m and the diameter of 50-100 nm.
2) Preparation of amino-functionalized ZnO: 80mg of 1) is mixed with 150mL of ethanol to prepare a solution, and 4mL of NH is added3·H2And stirring the mixture of O and 300 mu L of aminosilane coupling agent for more than 12 hours to obtain the amino-functionalized zinc oxide nano rod.
3) Preparing gold nanoparticle sol: adding a sodium citrate solution (10%) into 100mL of distilled water, diluting uniformly, heating to boil, quickly injecting chloroauric acid (0.5M) into the solution, reacting for 5 minutes, and cooling to room temperature to obtain gold nanoparticle sol (Au); wherein the addition amount of the sodium citrate is 0.55g, and the addition amount of the chloroauric acid is 1 g.
4) Preparing a zinc oxide nano rod loaded with gold particles: and (3) mixing and centrifuging the product obtained in the step (2) and the product obtained in the step (3) to obtain the zinc oxide nano rod (ZnO @ Au) loaded with gold nano particles.
5) PB coating of amino functionalized ZnO: adding the product obtained in the step 4) into a solution prepared from 28mL of distilled water and 12mL of ethanol, stirring, adding 20mg of resorcinol, adding 30 μ L of formaldehyde after 8 minutes, adding 32 μ L of ethylenediamine after 5 minutes, washing twice with distilled water after reacting for 24 hours, washing once with ethanol, and drying in a vacuum drying oven at 60 ℃ for 12 hours.
6) Carbonizing PB-coated ZnO: putting the dried sample in the step 5) into a porcelain burning boat, putting the porcelain burning boat in the middle of a hearth of a tube furnace, and taking H2and/Ar is protective gas, the temperature is raised to 600 ℃ at the speed of 5 ℃/min, the temperature is kept for 4h, and the zinc oxide nano rod coated by the oxygen-doped amorphous carbon layer is obtained after the reaction is finished and the zinc oxide nano rod is cold cut to room temperature.
7) And (3) etching the carbonized ZnO @ PB: dissolving the calcined product obtained in the step 6) in 0.1mol/L HCl solution, magnetically stirring for 6 hours, then centrifugally cleaning for three times by using distilled water/ethanol, and drying to obtain the oxygen-doped amorphous hollow carbon nanotube.
The morphology of the carbon tube loaded with gold particles was characterized by Transmission Electron Microscopy (TEM) and Transmission Electron Microscopy (TEM), respectively, and the results are shown in fig. 2(a) and fig. 2 (b).
Wherein, fig. 2(a) is a morphology of the carbon tube loaded with gold particles under a Transmission Electron Microscope (TEM), and the scale is 50 nm. The black particles in the figure are gold nanoparticles, and the gray tubular part is an amorphous carbon tube.
Fig. 2(b) is a high angle annular dark field image (HADDF) of gold particle loaded carbon tubes under Transmission Electron Microscope (TEM), with a scale of 100 nm. The white bright spots are gold nanoparticles, and other bright tubular parts are amorphous carbon tubes.
Example 2
The nano particles induce lithium metal to realize reversible stable packaging in the inner cavity of the amorphous carbon tube. The whole deposition process can be divided into three steps: (1) and (3) lithiation: under the action of an external voltage, lithium ions move along the wall of the amorphous carbon tube in one direction and are filled in the pores, defects and the like of the carbon tube; (2) and (3) guiding the nanoparticles: when lithium ions reach the site where the nanoparticle is present, the nanoparticle is lithiated; (3) lithium metal deposition: lithium ions preferentially reach the surface of the lithiated nano-particles and are stably deposited in the inner cavity of the carbon tube.
Observing the deposition and stripping process of metallic lithium by using a transmission electron microscope, the results are shown in FIG. 3. FIG. 3 shows the in-situ deposition and stripping process of metallic lithium in a carbon tube loaded with gold particles. A and C are the first and second real-time cycle process diagrams under the transmission electron microscope, respectively, (b) and (d) are corresponding model explanatory diagrams, ① and ② are the numbers of two gold particles in the carbon tube shown, respectively1-a4And c1-c4For the deposition process, a5-a8And c5-c8Is a peeling process. The white triangles in the figure represent the deposition front of lithium metal, and the different patterns in (b) and (d) correspond to three species of gold, lithium and lithium-gold alloy, respectively.
The specific process of deposition and lift-off includes, for example, FIG. 3a1As shown, the two ends of the carbon tube are in contact with copper and lithium oxide/lithium, respectively, and when a negative bias is applied to the lithium oxide/lithium end, lithium ions can be directed along the carbon tube toward the copper endThe black dashed arrows in (b) and (d) indicate the transport path of lithium ions.
As shown in figure 3a2It is shown that ① gold particles in the carbon tube are partially lithiated and swell.
As shown in figure 3a3The partially lithiated gold particles are shown to direct the deposition of lithium metal within the tube lumen, with the lithium-gold alloy surrounded by lithium metal.
As shown in figure 3a4As shown, lithium metal is deposited after entering the lumen to the front position indicated by the white arrow.
As shown in figure 3a5As shown, after a forward bias is applied to the li/li oxide end, the li ions can move along the carbon tube toward the li/li oxide end, and the li metal deposition front end starts to move downward, entering the stripping stage.
As shown in figure 3a6As shown, the lithium metal deposition tip was moved downward, and a portion of the lithium-gold alloy was deposited near the original ① -th gold particle position, and the morphology of the lithium-gold alloy was significantly changed from that of the original gold particle at that position.
As shown in figure 3a7The lithium metal deposition front is shown moving further down.
As shown in figure 3a8As shown, at the end of the stripping period of lithium metal, some lithium gold alloy particles (white boxes) were precipitated at the bottom of the carbon tubes, a8The bottom left inset is an enlarged view of the particle.
As shown in FIG. 3c1The two ends of the carbon tube are respectively contacted with copper and lithium oxide/lithium, when the negative bias is applied to the lithium oxide/lithium end, the lithium ions can move to the copper end along the carbon tube to carry out the second deposition, and the black dotted arrows in (b) and (d) are the transmission paths of the lithium ions. The white triangles in the figure refer to the positions at the front of the deposition of lithium metal that are guided into the lumen of the carbon tube by the lithium gold alloy that precipitates after the first cycle.
As shown in FIG. 3c2-3c4The front end of the lithium metal deposit in the carbon tube is shown to be constantly moving upwards.
As shown in FIG. 3c5It is shown that, when a forward bias is applied to the lithium oxide/lithium terminal, lithium ions can move along the carbon tube toward the lithium oxide/lithium terminal,the lithium metal deposition front starts moving down into the stripping phase.
As shown in FIG. 3c6The lithium metal deposition front is shown passing the position of the original ① # gold particle.
As shown in FIG. 3c7As shown, the lithium metal deposition front was further moved downward, and a portion of the lithium-gold alloy precipitated at the original position of the ① -th gold particle, and the morphology was also changed from that of the previous cycle.
As shown in FIG. 3c8At the end of the stripping of lithium metal, some of the lithium-gold alloy particles (white boxes) were similarly deposited on the bottom of the carbon tubes, c8The bottom left inset is an enlarged view of the particle.
Example 3
The nano particles induce sodium metal to realize reversible stable encapsulation in the inner cavity of the amorphous carbon tube. The whole deposition process can be divided into three steps: (1) sodium treatment: sodium ions move in one direction along the wall of the amorphous carbon tube under the action of an external voltage and are filled in the pores, defects and the like of the carbon tube; (2) and (3) guiding the nanoparticles: when sodium ions reach the site where the nanoparticles are present, the nanoparticles are sodiated; (3) sodium metal deposition: sodium ions reach the surface of the lithiated nano-particles preferentially and are stably deposited in the inner cavity of the carbon tube.
The process of sodium metal deposition and exfoliation was observed using a transmission electron microscope and the results are shown in FIG. 4.
FIG. 4 is the in-situ deposition and stripping process of metal sodium in a carbon tube loaded with gold particles, where the two ends of the carbon tube are in contact with copper and sodium oxide/sodium respectively, and when a negative bias is applied to the sodium oxide/sodium end, sodium ions can move along the carbon tube to the copper end, and (a) - (d) are the real-time deposition process diagrams under a transmission electron microscope, and when a positive bias is applied to the sodium oxide/sodium end, sodium ions can move along the carbon tube to the sodium oxide/sodium end, and (e) - (h) are the real-time stripping process diagrams under the transmission electron microscope, ① - ⑤ are the numbers of 5 gold particles in the carbon tube in the examples shown.
Example 4
The amorphous hollow carbon nanotube is prepared by the following specific steps:
1) preparing a ZnO template: dissolving 1g of NaOH in 50mL of ethanol to prepare solution A, dissolving 0.40g of zinc acetate in 25mL of ethanol to prepare solution B, adding the solution A into the solution B, stirring and carrying out ultrasonic treatment for 30 minutes, introducing the obtained solution into a 100mL reaction kettle, carrying out hydrothermal reaction for 15 hours at 160 ℃, and cleaning with ethanol twice to obtain a ZnO nanorod with the length of 1-2 mu m and the diameter of 50-100 nm.
2) Preparation of amino-functionalized ZnO: preparing 75mg of the product obtained in the step 1) with 150mL of ethanol to prepare a solution, and adding 4mL of NH3·H2O and 400 mu L of amino silane coupling agent are stirred for more than 12 hours to obtain the amino functional zinc oxide nano rod.
3) Preparing gold nanoparticle sol: preparing gold nanoparticle sol: adding a sodium citrate solution (10%) into 100mL of distilled water, diluting uniformly, heating to boil, quickly injecting chloroauric acid (0.5M) into the solution, reacting for 5 minutes, and cooling to room temperature to obtain gold nanoparticle sol (Au); wherein the addition amount of the sodium citrate is 0.4g, and the addition amount of the chloroauric acid is 1 g.
4) Preparing a zinc oxide nano rod loaded with gold particles: and (3) mixing and centrifuging the product obtained in the step (2) and the product obtained in the step (3) to obtain the zinc oxide nano rod (ZnO @ Au) loaded with gold nano particles.
5) PB coating of amino functionalized ZnO: adding the product obtained in the step 4) into a solution prepared from 28mL of distilled water and 12mL of ethanol, stirring, adding 15mg of resorcinol, adding 25 μ L of formaldehyde after 8 minutes, adding 30 μ L of ethylenediamine after 5 minutes, washing twice with distilled water after reacting for 24 hours, washing once with ethanol, and drying in a vacuum drying oven at 60 ℃ for 12 hours.
6) Carbonizing PB-coated ZnO: putting the dried sample in the step 5) into a porcelain burning boat, putting the porcelain burning boat in the middle of a hearth of a tube furnace, and taking H2and/Ar is protective gas, the temperature is raised to 600 ℃ at the speed of 5 ℃/min, the temperature is kept for 4h, and the zinc oxide nano rod coated by the oxygen-doped amorphous carbon layer is obtained after the reaction is finished and the zinc oxide nano rod is cold cut to room temperature.
7) And (3) etching the carbonized ZnO @ PB: dissolving the calcined product obtained in the step 6) in 0.1mol/L HCl solution, magnetically stirring for 6 hours, then centrifugally cleaning for three times by using distilled water/ethanol, and drying to obtain the oxygen-doped amorphous hollow carbon nanotube.
Example 5
The amorphous hollow carbon nanotube is prepared by the following specific steps:
1) preparing a ZnO template: dissolving 1g of NaOH in 50mL of ethanol to prepare solution A, dissolving 0.50g of zinc acetate in 25mL of ethanol to prepare solution B, adding the solution A into the solution B, stirring and carrying out ultrasonic treatment for 30 minutes, introducing the obtained solution into a 100mL reaction kettle, carrying out hydrothermal reaction for 20 hours at 140 ℃, and cleaning with ethanol twice to obtain a ZnO nanorod with the length of 1-2 mu m and the diameter of 50-100 nm.
2) Preparation of amino-functionalized ZnO: preparing 100mg of the product obtained in the step 1) with 150mL of ethanol to prepare a solution, and adding 4mL of NH3·H2And stirring the mixture of O and 300 mu L of aminosilane coupling agent for more than 12 hours to obtain the amino-functionalized zinc oxide nano rod.
3) Preparing gold nanoparticle sol: preparing gold nanoparticle sol: adding a sodium citrate solution (10%) into 100mL of distilled water, diluting uniformly, heating to boil, quickly injecting chloroauric acid (0.5M) into the solution, reacting for 5 minutes, and cooling to room temperature to obtain gold nanoparticle sol (Au); wherein the addition amount of the sodium citrate is 0.7g, and the addition amount of the chloroauric acid is 1 g.
4) Preparing a zinc oxide nano rod loaded with gold particles: and (3) mixing and centrifuging the product obtained in the step (2) and the product obtained in the step (3) to obtain the zinc oxide nano rod (ZnO @ Au) loaded with gold nano particles.
5) PB coating of amino functionalized ZnO: adding the product obtained in the step 4) into a solution prepared from 28mL of distilled water and 12mL of ethanol, stirring, adding 25mg of resorcinol, adding 35 μ L of formaldehyde after 8 minutes, adding 40 μ L of ethylenediamine after 5 minutes, reacting for 24 hours, washing twice with distilled water, washing once with ethanol, and drying in a vacuum drying oven at 60 ℃ for 12 hours.
6) Carbonizing PB-coated ZnO: putting the dried sample in the step 5) into a porcelain burning boat, putting the porcelain burning boat in the middle of a hearth of a tube furnace, and taking H2Heating to 650 deg.C at a speed of 5 deg.C/min under protection of Ar, maintaining for 3 hr, and cold cutting to room temperatureAnd obtaining the zinc oxide nano rod coated by the oxygen-doped amorphous carbon layer.
7) And (3) etching the carbonized ZnO @ PB: dissolving the calcined product obtained in the step 6) in 0.1mol/L HCl solution, magnetically stirring for 5 hours, then centrifugally cleaning for three times by using distilled water/ethanol, and drying to obtain the oxygen-doped amorphous hollow carbon nanotube.
Example 6
The amorphous hollow carbon nanotube is prepared by the following specific steps:
1) preparing a ZnO template: dissolving 1g of NaOH in 50mL of ethanol to prepare solution A, dissolving 0.46g of zinc acetate in 25mL of ethanol to prepare solution B, adding the solution A into the solution B, stirring and ultrasonically treating for 30 minutes, introducing the obtained solution into a 100mL reaction kettle, carrying out hydrothermal reaction at 155 ℃ for 19 hours, and cleaning with ethanol twice to obtain a ZnO nanorod with the length of 1-2 mu m and the diameter of 50-100 nm.
2) Preparation of amino-functionalized ZnO: preparing 90mg of the product obtained in the step 1) with 150mL of ethanol to prepare a solution, and adding 4mL of NH3·H2O and 200 mu L of amino silane coupling agent are stirred for more than 12 hours to obtain the amino functional zinc oxide nano rod.
3) Preparing gold nanoparticle sol: preparing gold nanoparticle sol: adding a sodium citrate solution (10%) into 100mL of distilled water, diluting uniformly, heating to boil, quickly injecting chloroauric acid (0.5M) into the solution, reacting for 5 minutes, and cooling to room temperature to obtain gold nanoparticle sol (Au); wherein the addition amount of the sodium citrate is 0.6g, and the addition amount of the chloroauric acid is 1 g.
4) Preparing a zinc oxide nano rod loaded with gold particles: and (3) mixing and centrifuging the product obtained in the step (2) and the product obtained in the step (3) to obtain the zinc oxide nano rod (ZnO @ Au) loaded with gold nano particles.
5) PB coating of amino functionalized ZnO: adding the product obtained in the step 4) into a solution prepared from 28mL of distilled water and 12mL of ethanol, stirring, adding 20mg of resorcinol, adding 30 μ L of formaldehyde after 8 minutes, adding 35 μ L of ethylenediamine after 5 minutes, reacting for 24 hours, washing twice with distilled water, washing once with ethanol, and drying in a vacuum drying oven at 60 ℃ for 12 hours.
6) Carbonizing PB-coated ZnO: putting the dried sample in the step 5) into a porcelain burning boat, putting the porcelain burning boat in the middle of a hearth of a tube furnace, and taking H2and/Ar is protective gas, the temperature is increased to 550 ℃ at the speed of 5 ℃/min, the temperature is kept for 5h, and the zinc oxide nano rod coated by the oxygen-doped amorphous carbon layer is obtained after the reaction is finished and the zinc oxide nano rod is cold cut to room temperature.
7) And (3) etching the carbonized ZnO @ PB: dissolving the calcined product obtained in the step 6) in 0.1mol/L HCl solution, magnetically stirring for 7 hours, then centrifugally cleaning for three times by using distilled water/ethanol, and drying to obtain the oxygen-doped amorphous hollow carbon nanotube.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. An amorphous hollow carbon nanotube characterized by: the amorphous hollow carbon nanotube has an inner diameter of 50-100nm, a thickness of 10-20nm, a length of 1-5 μm, and closed ends at both ends, and has a porous amorphous structure on the carbon wall and multiple nanoparticles attached to the inner wall.
2. The amorphous hollow carbon nanotube of claim 1, wherein: the nano-particles are any one of Au nano-particles, Ag nano-particles, Mg nano-particles, Si nano-particles, Sn nano-particles, Co nano-particles, Ni nano-particles or Zn nano-particles with lithium/sodium affinity;
optionally, the specific surface area of the carbon wall of the amorphous hollow carbon nanotube is 900-2And g, the nanoparticles guide lithium/sodium metal ions from the holes on the carbon wall into the cavity of the amorphous hollow carbon nanotube and out of the amorphous hollow carbon nanotube through the holes on the carbon wall.
3. A method for preparing the amorphous hollow carbon nanotube according to claim 1 or 2, wherein: the method comprises the following steps:
step 1) carrying out hydrothermal reaction on zinc salt and alkali to prepare a zinc oxide nanorod;
step 2) performing amino functionalization on the zinc oxide nanorod obtained in the step 1) by using ammonia water and an aminosilane coupling agent to obtain an aminated zinc oxide nanorod;
step 3) preparing nano-particle sol;
step 4) mixing the aminated zinc oxide nanorod obtained in the step 2) with the nanoparticle sol obtained in the step 3), and then centrifuging to obtain a nanoparticle-loaded zinc oxide nanorod ZnO @ R;
step 5) phenolic aldehyde amine coating is carried out on the ZnO @ R obtained in the step 4) to obtain a phenolic aldehyde amine coated zinc oxide nano rod ZnO @ R @ PB;
step 6) carrying out heat treatment on the ZnO @ R @ PB obtained in the step 5), and carbonizing the phenolic amine layer coated on the surface to obtain a zinc oxide nanorod ZnO @ R @ C coated by the amorphous carbon layer loaded with the nanoparticles;
and 7) etching the ZnO @ R @ C obtained in the step 6) to obtain the amorphous hollow carbon nanotube.
4. The method of preparing amorphous hollow carbon nanotubes as claimed in claim 3, wherein: the step 1) comprises the following steps: dissolving NaOH in ethanol to prepare solution A, dissolving zinc acetate in ethanol to prepare solution B, and mixing the solution A and the solution B, wherein the mass ratio of NaOH to zinc acetate is 10: 4-5, stirring and ultrasonically treating, introducing the obtained solution into a reaction kettle, carrying out hydrothermal reaction for 15-20 hours at the temperature of 140-160 ℃, and cleaning the product with ethanol to obtain a zinc oxide nano rod with the length of 1-2 mu m and the diameter of 50-100 nm;
the step 2) comprises the following steps: adding the zinc oxide nano rod obtained in the step 1) into ethanol, adding ammonia water and an aminosilane coupling agent, and stirring for more than 12 hours to obtain an amino functional group zinc oxide nano rod; wherein, the adding amount of the zinc oxide nano rod is as follows: adding amount of ammonia water: the addition mass ratio of the aminosilane coupling agent is 75-100 mg: 4mL of: 200-;
the preparation of the nanoparticle sol in step 3) takes gold as an example, and the method comprises the following steps: reacting sodium citrate with chloroauric acid, adding the sodium citrate into distilled water, stirring uniformly, heating to boil, quickly injecting the chloroauric acid into the distilled water, reacting for 3-6 minutes, and cooling to room temperature to obtain zinc oxide nano-rods ZnO @ Au loaded with gold nano-particles; wherein the mass addition of the sodium citrate is as follows: the mass addition amount of the chloroauric acid is 4-7: 10;
in the step 5), resorcinol, formaldehyde and ethylenediamine are used as carbon sources for phenolic amine coating, the zinc oxide nano rod ZnO @ Au loaded with gold nano particles is added into a mixed solution of water and ethanol, then resorcinol, formaldehyde and ethylenediamine are sequentially added, and after reaction for 20-30 hours, washing and drying are carried out to obtain ZnO @ Au @ PB; wherein the addition amount of the zinc oxide nano rod loaded with gold nano particles is as follows: addition amount of resorcinol: adding amount of formaldehyde: the addition of ethylenediamine was 125mg (100-): 15-25 mg: 25-35 μ L: 30-40 mu L;
the step 6) comprises the following steps: putting ZnO @ Au @ PB into the middle of a tubular furnace hearth, and taking H2Ar is protective gas, the temperature is raised to 550-650 ℃ at the speed of 3-5 ℃/min, the temperature is kept for 3-5h, and the temperature is cooled to room temperature after the reaction is finished, so that ZnO @ Au @ C is obtained;
the step 7) comprises the following steps: and dissolving ZnO @ Au @ C in hydrochloric acid, stirring for 5-7h, washing and drying a product to obtain the amorphous hollow carbon nanotube.
5. The amorphous hollow carbon nanotube obtained by the method of claim 3 or 4.
6. Use of the amorphous hollow carbon nanotubes of claim 5, wherein: the amorphous hollow carbon nanotube is used for packaging lithium and sodium metal, constructing negative electrode protection, and preparing a negative electrode current collector of a lithium/sodium metal battery, and has the effects of inhibiting dendritic crystal growth, limiting volume change generated in the processes of lithium/sodium metal deposition and stripping, and stabilizing a negative electrode/electrolyte interface.
7. Use of the amorphous hollow carbon nanotubes of claim 6, wherein: the amorphous hollow carbon nanotube packaging lithium and sodium metal is a reversible process, specifically, in a deposition process, lithium/sodium metal ions are guided by nanoparticles to enter a carbon tube inner cavity of the amorphous hollow carbon nanotube, and deposition is carried out in the inner cavity until the whole cavity is filled; when the inner cavity of the carbon tube is completely filled with the lithium/sodium metal, the lithium/sodium metal can be completely removed from the inner cavity, the deposition/stripping process can be circulated for multiple times, and the whole deposition process is limited by the carbon wall of the amorphous hollow carbon nanotube, so that the stability of the structure in the deposition-stripping cycle process of the lithium/sodium metal is ensured;
optionally, the deposition process comprises: the nano particles and lithium/sodium metal are subjected to alloy reaction to form lithium/sodium-nano particle alloy, and then the lithium/sodium metal is deposited by taking the lithium/sodium metal as a nucleation point, and the cavity of the carbon tube is continuously filled.
8. A negative active material for lithium/sodium metal batteries, prepared from the amorphous hollow carbon nanotube of claim 5, wherein the nanoparticles in the amorphous hollow carbon nanotube are used to induce lithium/sodium deposition into the cavity of the amorphous hollow carbon nanotube;
optionally, nanoparticles in the amorphous hollow carbon nanotube and lithium/sodium metal are subjected to alloy reaction to form a lithium/sodium-nanoparticle alloy, then the lithium/sodium metal is deposited by taking the lithium/sodium metal as a nucleation point, and the carbon tube cavity is continuously filled with the lithium/sodium metal to obtain the amorphous hollow carbon nanotube with the cavity filled with the lithium/sodium metal.
9. A negative electrode current collector for a lithium/sodium metal battery comprising the negative electrode active material for a lithium/sodium metal battery according to claim 8.
10. A lithium/sodium metal battery comprising a battery positive electrode, a battery negative electrode and an electrolyte, wherein the battery negative electrode is the lithium/sodium metal battery negative electrode current collector of claim 9.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112433159A (en) * | 2020-11-11 | 2021-03-02 | 北京理工大学 | Detection method for lithium ion battery graphite negative electrode lithium separation |
| CN112615011A (en) * | 2020-12-17 | 2021-04-06 | 惠州亿纬锂能股份有限公司 | Lithium-sulfur battery negative pole piece, lithium-sulfur battery and preparation method thereof |
| CN113644267A (en) * | 2021-08-03 | 2021-11-12 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN114514642A (en) * | 2021-03-30 | 2022-05-17 | 宁德新能源科技有限公司 | Carbon current collector and electrochemical device |
| CN114538410A (en) * | 2022-02-21 | 2022-05-27 | 北京化工大学 | Lithium-philic onion carbon microsphere, preparation method and application of lithium metal secondary battery |
| CN114843524A (en) * | 2022-06-17 | 2022-08-02 | 珠海冠宇电池股份有限公司 | Modified current collector and non-negative sodium metal battery comprising same |
| CN115036502A (en) * | 2022-07-01 | 2022-09-09 | 大连理工大学 | Based on ZnCo 2 O 4 Method for preparing sodium ion battery cathode material by hollow carbon nanorings and application |
| WO2024065576A1 (en) * | 2022-09-30 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Sodium-ion battery and electric device comprising same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2045213A1 (en) * | 2007-10-04 | 2009-04-08 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Assembly of nanotube encapsulated nanofibers nanostructure materials |
| CN105314614A (en) * | 2014-06-04 | 2016-02-10 | 北京化工大学 | Nitrogen-doped porous carbon nanotube material and its preparation method and use in super capacitor electrode |
| CN106058256A (en) * | 2016-07-19 | 2016-10-26 | 复旦大学 | Preparation method of carbon nanotube composite porous silicon anode material for lithium ion battery |
| CN106935855A (en) * | 2017-03-24 | 2017-07-07 | 中南大学 | A kind of porous carbon nanotubular materials and its preparation method and application |
| CN110098066A (en) * | 2018-01-29 | 2019-08-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nanocomposite fiber electrode of core-shell structure and its preparation method and application |
-
2019
- 2019-11-19 CN CN201911131854.2A patent/CN110817845A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2045213A1 (en) * | 2007-10-04 | 2009-04-08 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Assembly of nanotube encapsulated nanofibers nanostructure materials |
| CN105314614A (en) * | 2014-06-04 | 2016-02-10 | 北京化工大学 | Nitrogen-doped porous carbon nanotube material and its preparation method and use in super capacitor electrode |
| CN106058256A (en) * | 2016-07-19 | 2016-10-26 | 复旦大学 | Preparation method of carbon nanotube composite porous silicon anode material for lithium ion battery |
| CN106935855A (en) * | 2017-03-24 | 2017-07-07 | 中南大学 | A kind of porous carbon nanotubular materials and its preparation method and application |
| CN110098066A (en) * | 2018-01-29 | 2019-08-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nanocomposite fiber electrode of core-shell structure and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| CHENG BIN ET AL: "Hydrothermal synthesis of one-dimensional ZnO nanostructures with different aspect ratios", 《CHEMICAL COMMUNICATIONS》 * |
| LAN XIANGNA ET AL: "Encapsulating lithium and sodium inside amorphous carbon nanotubes through gold-seeded growth", 《NANO ENERGY》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112433159A (en) * | 2020-11-11 | 2021-03-02 | 北京理工大学 | Detection method for lithium ion battery graphite negative electrode lithium separation |
| CN112615011A (en) * | 2020-12-17 | 2021-04-06 | 惠州亿纬锂能股份有限公司 | Lithium-sulfur battery negative pole piece, lithium-sulfur battery and preparation method thereof |
| CN114514642A (en) * | 2021-03-30 | 2022-05-17 | 宁德新能源科技有限公司 | Carbon current collector and electrochemical device |
| WO2022204908A1 (en) * | 2021-03-30 | 2022-10-06 | 宁德新能源科技有限公司 | Carbon current collector and electrochemical device |
| CN113644267A (en) * | 2021-08-03 | 2021-11-12 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN113644267B (en) * | 2021-08-03 | 2023-09-29 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN114538410A (en) * | 2022-02-21 | 2022-05-27 | 北京化工大学 | Lithium-philic onion carbon microsphere, preparation method and application of lithium metal secondary battery |
| CN114538410B (en) * | 2022-02-21 | 2023-10-20 | 北京化工大学 | Lithium-philic onion carbon microsphere, preparation method and application of lithium metal secondary battery |
| CN114843524A (en) * | 2022-06-17 | 2022-08-02 | 珠海冠宇电池股份有限公司 | Modified current collector and non-negative sodium metal battery comprising same |
| CN115036502A (en) * | 2022-07-01 | 2022-09-09 | 大连理工大学 | Based on ZnCo 2 O 4 Method for preparing sodium ion battery cathode material by hollow carbon nanorings and application |
| WO2024065576A1 (en) * | 2022-09-30 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Sodium-ion battery and electric device comprising same |
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