CN111573714A - Tin dioxide/manganese dioxide multi-stage hollow-structure lithium ion battery cathode composite material and preparation method thereof - Google Patents
Tin dioxide/manganese dioxide multi-stage hollow-structure lithium ion battery cathode composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of composite material synthesis and electrode material preparation, and discloses a tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material and a preparation method thereof. The method comprises the following specific steps: firstly, dispersing a polysaccharide microsphere template synthesized by sucrose hydrothermal reaction in a stannic chloride aqueous solution, and carrying out adsorption and sintering reaction under nitrogen to obtain a precursor containing tin/carbon; and secondly, preparing the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material through the oxidation-reduction reaction and sintering reaction of potassium permanganate and a precursor containing tin/carbon.
Description
Technical Field
The invention belongs to the technical field of composite material synthesis and electrode material preparation, and relates to a tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material and a preparation method thereof.
Background
Lithium ion batteries have been widely used in electric vehicles and other household appliances due to their superior performance. However, in lithium ion batteries, the conventional graphite anode material has a relatively low theoretical capacity (372mAh g)-1) Limiting its further application in large-scale energy storage. In recent years, various nanostructured transition metal oxides have attracted considerable attention from researchers due to their wide availability, particularly their high theoretical capacity.
Manganese dioxide (MnO) as one of transition metal oxides2) Due to its low toxicity, abundant natural reserves and higher theoretical capacity (1233mAh g)-1) And is considered to be a lithium ion battery cathode material with application prospect. However, MnO as a negative electrode material for lithium ion batteries2There are some significant drawbacks to nanomaterials, such as drastic volume changes during the li insertion/delithiation process, which results in less than ideal cycling performance and reversible specific capacity. To overcome the above problems, two different strategies are generally employed.
The first strategy is to synthesize a transition metal oxide having a hollow nanostructure. The hollow nanostructure of the transition metal oxide can provide more active sites for the storage of lithium due to a larger surface area, and can buffer the volume change of the material during the charge-discharge cycle due to a large hollow internal space, thereby showing excellent electrochemical performance. Among them, the multi-level hollow structure assembled by nano-sized building units (such as nanoparticles and nanorods) has attracted extensive attention of researchers, particularly, because it has more excellent electrochemical properties than single microparticles and discrete nanoparticles.
Another strategy is to incorporate another transition metal oxide into the MnO2In (1). The composite nano material formed by two transition metal oxides has inconsistent charge and discharge voltage platforms, so that the volume change of the composite material in the charge and discharge process can be relieved by utilizing the difference of the charge and discharge voltage platforms of the two transition metal oxides, and the synergistic performance can be enhanced or changedHigh electrochemical performance.
However, in the first strategy, after long-term charge and discharge cycles, the hollow structure of the single-component metal oxide is subjected to volume expansion deformation to cause collapse of the hollow structure, so that the cycle performance of the lithium ion battery is deteriorated; in the second strategy, although the volume change of the composite material in the charging and discharging process can be relieved by utilizing the difference of the charging and discharging voltage platforms of two transition metal oxides in the composite material, the effect is relatively limited, so that the cycle performance of the lithium ion battery is still not ideal.
In summary, the preparation method of the negative electrode composite material of the lithium ion battery in the prior art has the problem of high raw material cost, and the cycle stability and reversible specific capacity of the negative electrode composite material synthesized in the prior art are still not ideal. An effective solution to the above problem is still lacking.
Disclosure of Invention
The invention provides a tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material and a preparation method thereof, which adopts rich natural reserves, low cost, no pollution and higher theoretical capacity (MnO)2Is 1233mAh g-1，SnO21494mAh g-1) Manganese dioxide (MnO)2) And tin dioxide (SnO)2) As two components of the composite material, a multi-level hollow nanostructure is introduced into stannic oxide/manganese dioxide (SnO)2/MnO2) In the two-phase composite nano material, the synergistic effect of the two strategies is utilized to exert manganese dioxide (MnO) to the maximum extent2) With tin dioxide (SnO)2) The synergistic effect among the nano structure units can not only improve the stability of the hollow structure of the composite material, but also improve the cycling stability of the material; and the composite hollow structure can provide more lithium storage sites, so that the lithium ion battery has higher reversible specific capacity. The invention solves the problems of high raw material cost, and unsatisfactory cycle stability and reversible specific capacity of the material in the preparation method of the lithium ion battery cathode composite material in the prior art.
The technical scheme of the invention is realized as follows:
a preparation method of a tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material comprises the following steps:
s1, dissolving 40g of sucrose in 50mL of water, transferring the sucrose aqueous solution to a 100mL hydrothermal reaction kettle, preserving the temperature for 90 minutes at 220 ℃, cooling, separating, washing with water, heating and drying to obtain polysaccharide microspheres; then, dispersing a polysaccharide microsphere template synthesized by a sucrose aqueous solution through a hydrothermal reaction in a stannic chloride aqueous solution, stirring and adsorbing, centrifugally separating the obtained suspension, washing with water, drying, and sintering at 600 ℃ for 3 hours in a nitrogen atmosphere to obtain a precursor containing tin/carbon;
s2, dispersing a precursor containing tin/carbon in a potassium permanganate solution, separating, washing and drying a product obtained by oxidation-reduction reaction, and finally sintering the product at high temperature in the air to obtain the tin dioxide/manganese dioxide multi-stage hollow-structure lithium ion battery cathode composite material.
As a further technical scheme, in the process of dispersing the glycan microsphere template in the stannic chloride aqueous solution and stirring and adsorbing in the step S1, the using amount of the glycan microsphere template is 2g, and the concentration of the stannic chloride aqueous solution is 0.5-2 mol.L-1。
As a further technical solution, in step S2, the mass ratio of the tin/carbon-containing precursor to potassium permanganate is 1.0: 0.1-0.5.
As a further technical scheme, in the step S2, the redox temperature of the precursor containing tin/carbon in the potassium permanganate solution is 70-90 ℃, and the redox time is 2-8 hours.
As a further technical proposal, in the step S2, the sintering temperature in the air is 500-700 ℃, and the sintering time is 2-6 hours.
The composite material with the tin dioxide/manganese dioxide multistage hollow structure, which is obtained by the preparation method of the lithium ion battery cathode composite material with the tin dioxide/manganese dioxide multistage hollow structure, is characterized in that the lithium ion battery cathode composite material with the tin dioxide/manganese dioxide multistage hollow structure is a multistage hollow sphere constructed by nano units of tin dioxide/manganese dioxide, and the particle size is 600-1000 nm.
The working principle and the beneficial effects of the invention are as follows:
1. in the invention, the lithium ion battery cathode composite material with the stannic oxide/manganese dioxide multistage hollow structure is prepared by adopting cane sugar, stannic chloride and potassium permanganate as main materials, the raw materials are wide in source, cheap and easily available, the preparation process is simple, and the multistage hollow nano structure is introduced into stannic oxide/manganese dioxide (SnO)2/MnO2) In the two-phase composite nano material, the synergistic effect of the two strategies is utilized to exert manganese dioxide (MnO) to the maximum extent2) With tin dioxide (SnO)2) The reversible capacity and the cycling stability of the lithium ion battery of the composite material are improved by the synergistic effect of the nano structure units.
2. In the invention, the synthesized stannic oxide/manganese dioxide composite material with the multilevel hollow structure is applied to the lithium ion battery cathode material, and the content of the composite material is 100mA g-1After the current density is cycled for 50 times, the reversible specific capacity still has 739mAh g-1Compared with the traditional commercial graphite cathode material, the specific capacity of the lithium ion battery cathode composite material is remarkably improved, and the prepared tin dioxide/manganese dioxide multistage hollow structure lithium ion battery cathode composite material has the particle size of 600-1000nm, has excellent cycling stability, and is suitable for being used as the lithium ion battery cathode material and popularized and used.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a Transmission Electron Microscope (TEM) image of a lithium ion battery negative electrode composite material with a tin dioxide/manganese dioxide multistage hollow structure prepared in example 1 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image of a lithium ion battery negative electrode composite material with a tin dioxide/manganese dioxide multistage hollow structure prepared in example 2 of the invention;
FIG. 3 is a Transmission Electron Microscope (TEM) image of a lithium ion battery negative electrode composite material with a tin dioxide/manganese dioxide multistage hollow structure prepared in example 3 of the present invention;
FIG. 4 is a Transmission Electron Microscope (TEM) image of a lithium ion battery negative electrode composite material with a tin dioxide/manganese dioxide multistage hollow structure prepared in example 4 of the invention;
FIG. 5 is a Transmission Electron Microscope (TEM) image of a lithium ion battery negative electrode composite material with a tin dioxide/manganese dioxide multistage hollow structure prepared in example 5 of the present invention;
FIG. 6 is a Transmission Electron Microscope (TEM) image of a lithium ion battery negative electrode composite material with a tin dioxide/manganese dioxide multistage hollow structure prepared in example 6 of the present invention;
FIG. 7 is a Scanning Electron Microscope (SEM) image of a lithium ion battery negative electrode composite material with a tin dioxide/manganese dioxide multistage hollow structure prepared in example 1 of the invention;
FIG. 8 is an X-ray diffraction (XRD) pattern of a lithium ion battery negative electrode composite material with a tin dioxide/manganese dioxide multilevel hollow structure prepared in example 1 of the present invention;
in the figure: the peak marked by the symbol "+" represents tin dioxide (SnO)2) The diffraction peak of (1), the peak marked with the symbol "#", represents manganese dioxide (MnO)2) A diffraction peak of (a);
FIG. 9 shows that the lithium ion battery cathode composite material with a tin dioxide/manganese dioxide multilevel hollow structure prepared in example 1 of the invention is at 100mA g-1Graph of cycle performance test data at current density.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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
A preparation method of a tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material comprises the following steps:
s1, dissolving 40g of sucrose in 50mL of water, transferring the sucrose aqueous solution to a 100mL hydrothermal reaction kettle, preserving the temperature for 90 minutes at 220 ℃, cooling, separating, washing with water, heating and drying to obtain polysaccharide microspheres; then, 2g of polysaccharide microspheres were ultrasonically dispersed in 150mL of 1 mol. L-1Stirring and adsorbing the obtained suspension in the aqueous solution of stannic chloride for 6 hours, then centrifugally separating, washing with water, drying, and sintering at 600 ℃ for 3 hours in a nitrogen atmosphere to obtain a precursor containing tin/carbon;
s2, weighing 1.0g of precursor containing tin/carbon, dispersing the precursor in 300mL of potassium permanganate solution (containing 0.28g of potassium permanganate), reacting for 4 hours at 80 ℃, and separating, washing and drying; and finally, burning the sample in the air at 600 ℃ for 3 hours to obtain the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material.
Example 2
A preparation method of a tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material comprises the following steps:
s1, dissolving 40g of sucrose in 50mL of water, transferring the sucrose aqueous solution to a 100mL hydrothermal reaction kettle, preserving the temperature for 90 minutes at 220 ℃, cooling, separating, washing with water, heating and drying to obtain polysaccharide microspheres; then, 2g of polysaccharide microspheres were ultrasonically dispersed in 150mL of 0.5 mol. L-1Stirring and adsorbing the obtained suspension in the aqueous solution of stannic chloride for 6 hours, then centrifugally separating, washing with water, drying, and sintering at 600 ℃ for 3 hours in a nitrogen atmosphere to obtain a precursor containing tin/carbon;
s2, weighing 1.0g of precursor containing tin/carbon, dispersing the precursor in 300mL of potassium permanganate solution (containing 0.1g of potassium permanganate), reacting for 8 hours at 70 ℃, and separating, washing and drying; and finally, burning the sample in the air at 700 ℃ for 2 hours to obtain the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material.
Example 3
A preparation method of a tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material comprises the following steps:
s1, dissolving 40g of sucrose in 50mL of water, transferring the sucrose aqueous solution to a 100mL hydrothermal reaction kettle, preserving the temperature for 90 minutes at 220 ℃, cooling, separating, washing with water, heating and drying to obtain polysaccharide microspheres; then, 2g of polysaccharide microspheres were ultrasonically dispersed in 150mL of 2 mol. L-1Stirring and adsorbing the obtained suspension in the aqueous solution of stannic chloride for 6 hours, then centrifugally separating, washing with water, drying, and sintering at 600 ℃ for 3 hours in a nitrogen atmosphere to obtain a precursor containing tin/carbon;
s2, weighing 1.0g of precursor containing tin/carbon, dispersing the precursor in 300mL of potassium permanganate solution (containing 0.5g of potassium permanganate), reacting for 2 hours at 90 ℃, and separating, washing and drying; and finally, burning the sample in the air at 500 ℃ for 6 hours to obtain the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material.
Example 4
A preparation method of a tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material comprises the following steps:
s1, dissolving 40g of sucrose in 50mL of water, transferring the sucrose aqueous solution to a 100mL hydrothermal reaction kettle, preserving the temperature for 90 minutes at 220 ℃, cooling, separating, washing with water, heating and drying to obtain polysaccharide microspheres; then, 2g of polysaccharide microspheres were ultrasonically dispersed in 150mL of 0.5 mol. L-1Stirring and adsorbing the obtained suspension in the aqueous solution of stannic chloride for 6 hours, then centrifugally separating, washing with water, drying, and sintering at 600 ℃ for 3 hours in a nitrogen atmosphere to obtain a precursor containing tin/carbon;
s2, weighing 1.0g of precursor containing tin/carbon, dispersing the precursor in 300mL of potassium permanganate solution (containing 0.28g of potassium permanganate), reacting for 4 hours at 90 ℃, and separating, washing and drying; and finally, burning the sample in the air at 700 ℃ for 3 hours to obtain the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material.
Example 5
A preparation method of a tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material comprises the following steps:
s1, dissolving 40g of sucrose in 50mL of water, transferring the sucrose aqueous solution to a 100mL hydrothermal reaction kettle, preserving the temperature for 90 minutes at 220 ℃, cooling, separating, washing with water, heating and drying to obtain polysaccharide microspheres; then, 2g of polysaccharide microspheres were ultrasonically dispersed in 150mL of 1 mol. L-1Stirring and adsorbing the obtained suspension in the aqueous solution of stannic chloride for 6 hours, then centrifugally separating, washing with water, drying, and sintering at 600 ℃ for 3 hours in a nitrogen atmosphere to obtain a precursor containing tin/carbon;
s2, weighing 1.0g of precursor containing tin/carbon, dispersing the precursor in 300mL of potassium permanganate solution (containing 0.1g of potassium permanganate), reacting at 70 ℃ for 2 hours, separating, washing and drying; and finally, burning the sample in the air at 600 ℃ for 6 hours to obtain the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material.
Example 6
A preparation method of a tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material comprises the following steps:
s1, dissolving 40g of sucrose in 50mL of water, transferring the sucrose aqueous solution to a 100mL hydrothermal reaction kettle, preserving the temperature for 90 minutes at 220 ℃, cooling, separating, washing with water, heating and drying to obtain polysaccharide microspheres; then, 2g of polysaccharide microspheres were ultrasonically dispersed in 150mL of 2 mol. L-1Stirring and adsorbing the obtained suspension in the aqueous solution of stannic chloride for 6 hours, then centrifugally separating, washing with water, drying, and sintering at 600 ℃ for 3 hours in a nitrogen atmosphere to obtain a precursor containing tin/carbon;
s2, weighing 1.0g of precursor containing tin/carbon, dispersing the precursor in 300mL of potassium permanganate solution (containing 0.5g of potassium permanganate), reacting for 8 hours at 80 ℃, and separating, washing and drying; and finally, burning the sample in the air at 500 ℃ for 2 hours to obtain the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material.
Fig. 1 to 6 show Transmission Electron Microscope (TEM) images of the tin dioxide/manganese dioxide multi-stage hollow lithium ion battery negative electrode composite materials prepared in examples 1 to 6, from which it can be seen that the tin dioxide/manganese dioxide multi-stage hollow lithium ion battery negative electrode composite materials prepared in examples 1 to 6 are multi-stage hollow microspheres constructed by two nano-structure units of nano-particles and nano-rods, and the particle size is 600-1000 nm.
The invention also discloses a lithium ion battery cathode composite material with the tin dioxide/manganese dioxide multistage hollow structure prepared by the method. Fig. 7 is a Scanning Electron Microscope (SEM) image of the tin dioxide/manganese dioxide multi-stage hollow lithium ion battery negative electrode composite material prepared in example 1, and it can also be seen from the SEM image that the tin dioxide/manganese dioxide multi-stage hollow lithium ion battery negative electrode composite material prepared in example 1 is a multi-stage microsphere constructed by two nano-structure units, namely, nano-particles and nano-rods. Scanning Electron Microscope (SEM) characterization was also performed on the tin dioxide/manganese dioxide multi-stage hollow lithium ion battery negative electrode composites prepared in examples 2 to 6, and the results are the same as those in fig. 7 and thus are omitted.
The X-ray diffraction (XRD) pattern of the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery negative electrode composite material prepared in example 1 is shown in fig. 8, from which it can be seen that the diffraction peaks of tin dioxide and manganese dioxide, respectively, were also measured by X-ray diffraction (XRD) on the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery negative electrode composite materials prepared in examples 2 to 6, and the results are the same as those in fig. 8, and thus are omitted.
The cycle stability test data of the lithium ion battery cathode composite material with the tin dioxide/manganese dioxide multistage hollow structure prepared in example 1 is shown in fig. 9, and it can be seen from the figure that the lithium ion battery cathode composite material with the tin dioxide/manganese dioxide multistage hollow structure prepared in example 1 has a volume of 100mA g-1After charging and discharging under current density for 50 times, the reversible specific capacity still remains 739mAh g-1To illustrate that the lithium ion battery cathode composite material with a tin dioxide/manganese dioxide multistage hollow structure prepared in example 1 of the present invention has excellent cycle stability, the lithium ion battery cathode composite materials with a tin dioxide/manganese dioxide multistage hollow structure prepared in examples 2 to 6 were also subjected to a cycle stability test, and the test results thereofThe same as in FIG. 9, and therefore omitted.
The above-mentioned embodiments are merely exemplary, which should not be construed as limiting the present invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A preparation method of a tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material is characterized by comprising the following steps:
s1, dispersing a polysaccharide microsphere template synthesized by a sucrose aqueous solution through a hydrothermal reaction in a stannic chloride aqueous solution, stirring and adsorbing, separating, washing and drying the obtained suspension, and then sintering at a high temperature in a nitrogen atmosphere to obtain a precursor containing tin/carbon;
s2, dispersing a precursor containing tin/carbon in a potassium permanganate solution, then carrying out an oxidation reduction reaction on the obtained suspension to obtain a product, separating, washing and drying the product, and finally sintering the product at a high temperature in the air to obtain the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material.
2. The method for preparing the tin dioxide/manganese dioxide multistage hollow structure lithium ion battery cathode composite material as claimed in claim 1, wherein the amount of the polysaccharide microspheres in the step S1 is 2g, and the concentration of the tin tetrachloride aqueous solution is 0.5-2mol-1。
3. The preparation method of the tin dioxide/manganese dioxide multistage hollow structure lithium ion battery cathode composite material according to claim 1, wherein the mass ratio of the tin/carbon-containing precursor to potassium permanganate in step S2 is 1.0: 0.1-0.5.
4. The preparation method of the tin dioxide/manganese dioxide multistage hollow structure lithium ion battery cathode composite material according to claim 1, wherein the redox temperature of the tin/carbon-containing precursor in the potassium permanganate solution in step S2 is 70-90 ℃, and the redox time is 2-8 hours.
5. The method for preparing the tin dioxide/manganese dioxide multistage hollow structure lithium ion battery anode composite material as claimed in claim 1, wherein the sintering temperature in air in step S2 is 500-700 ℃, and the sintering time is 2-6 hours.
6. The tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material is characterized by being obtained by the preparation method of the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material according to any one of claims 1 to 5, wherein the tin dioxide/manganese dioxide multi-stage hollow structure lithium ion battery cathode composite material is a multi-stage hollow sphere constructed by tin dioxide/manganese dioxide nano units, and the particle size is 600-1000 nm-.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111994946A (en) * | 2020-09-08 | 2020-11-27 | 广东工业大学 | Carbon composite negative electrode material of modified tin dioxide, preparation method of carbon composite negative electrode material and lithium ion battery |
| CN112331836A (en) * | 2020-11-23 | 2021-02-05 | 华中科技大学 | Tin oxide-hard carbon composite negative electrode material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104183823A (en) * | 2014-08-29 | 2014-12-03 | 华中师范大学 | SnO2, MnO or Mn3O4-based composite material based on three-dimensional carbon sphere framework structure and preparation method of material |
| CN106654185A (en) * | 2015-11-03 | 2017-05-10 | 宝山钢铁股份有限公司 | Silicon-based negative electrode active material for lithium ion battery, and preparation method thereof, negative electrode containing negative electrode active material, and secondary battery |
| CN107706353A (en) * | 2017-11-21 | 2018-02-16 | 安徽师范大学 | Preparation method, lithium-sulphur cell positive electrode and the battery of the nano composite material of tin ash/manganese dioxide load sulfur granules |
-
2020
- 2020-05-22 CN CN202010438457.6A patent/CN111573714A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104183823A (en) * | 2014-08-29 | 2014-12-03 | 华中师范大学 | SnO2, MnO or Mn3O4-based composite material based on three-dimensional carbon sphere framework structure and preparation method of material |
| CN106654185A (en) * | 2015-11-03 | 2017-05-10 | 宝山钢铁股份有限公司 | Silicon-based negative electrode active material for lithium ion battery, and preparation method thereof, negative electrode containing negative electrode active material, and secondary battery |
| CN107706353A (en) * | 2017-11-21 | 2018-02-16 | 安徽师范大学 | Preparation method, lithium-sulphur cell positive electrode and the battery of the nano composite material of tin ash/manganese dioxide load sulfur granules |
Non-Patent Citations (2)
| Title |
|---|
| HAN X. YANG ET AL.: "Multilayered Nanocrystalline SnO2 Hollow Microspheres Synthesized by Chemically Induced Self-Assembly in the Hydrothermal Environment", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| LIU, YANG ET AL.: "Enhanced Electrochemical Performance of Hybrid SnO2@MOx (M=Ni, Co, Mn) Core-shell Nanostructures Grown on Flexible Carbon Fibers as the Supercapacitor Electrode Materials", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111994946A (en) * | 2020-09-08 | 2020-11-27 | 广东工业大学 | Carbon composite negative electrode material of modified tin dioxide, preparation method of carbon composite negative electrode material and lithium ion battery |
| CN112331836A (en) * | 2020-11-23 | 2021-02-05 | 华中科技大学 | Tin oxide-hard carbon composite negative electrode material and preparation method and application thereof |
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