CN112310386B - Silicon oxide/carbon lithium ion battery cathode material with hollow structure and preparation method and application thereof - Google Patents

Silicon oxide/carbon lithium ion battery cathode material with hollow structure and preparation method and application thereof Download PDF

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CN112310386B
CN112310386B CN202011206817.6A CN202011206817A CN112310386B CN 112310386 B CN112310386 B CN 112310386B CN 202011206817 A CN202011206817 A CN 202011206817A CN 112310386 B CN112310386 B CN 112310386B
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lithium ion
ion battery
hollow structure
cathode material
siox
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CN112310386A (en
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杜春雨
周晓明
刘杨
任阳
尹鸽平
丰震河
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Harbin Institute of Technology
Shanghai Institute of Space Power Sources
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Shanghai Institute of Space Power Sources
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Abstract

A silicon oxide/carbon lithium ion battery cathode material with a hollow structure and a preparation method and application thereof relate to a lithium ion battery cathode material and a preparation method and application thereof. The invention aims to solve the problems of high equipment requirement, harsh conditions, complex preparation method and poor cycle stability of the conventional method for inhibiting the volume effect of SiOx. The silicon oxide/carbon lithium ion battery cathode material with the hollow structure has the hollow structure inside, the surface of the hollow structure is of a concave spherical structure or bowl-shaped structure, and the size of the hollow structure is 200 nm-1200 nm. The method comprises the following steps: firstly, dripping a silicon source into an aldehyde solution, and then stirring for reaction; secondly, filtering, cleaning and freeze drying; and thirdly, calcining the monodisperse hollow concave spheres at high temperature under the protection of inert gas. A silicon oxide/carbon lithium ion battery cathode material with a hollow structure is used as a lithium ion battery cathode material. The invention has simple operation, low cost and high balling rate.

Description

Silicon oxide/carbon lithium ion battery cathode material with hollow structure and preparation method and application thereof
Technical Field
The invention relates to a lithium ion battery cathode material, a preparation method and application thereof.
Background
Lithium ion batteries, as a new generation of clean, environmentally friendly and renewable secondary energy, have been improved to practical approaches in the field of power vehicles due to their advantages of high energy density, high operating voltage, long cycle life, and small self-discharge. However, the lithium ion battery at present cannot meet the requirements of large-scale application of power batteries in terms of energy density, power density, safety performance, cycle life, production cost and the like, and one of the main reasons is that the lithium ion battery is limited by the electrode material of the lithium ion battery. At present, the negative electrode material adopted by commercial lithium ion batteries is mainly a graphite carbon material, but the negative electrode material has the defects of low specific capacity (372mAh/g), easy lithium precipitation due to rapid charge and discharge, easy organic solvent co-intercalation and the like, and further improvement of the battery performance is seriously limited.
The silicon oxide (SiOx, x is more than 0 and less than or equal to 2) cathode material is considered as the most potential next generation lithium ion battery cathode material due to high theoretical specific capacity (SiO: 2680mAh/g), abundant sources and low cost. However, the larger volume effect of SiOx (SiO: -200%) causes the destruction of the material structure and the instability of the Solid Electrolyte (SEI) film, which limits its further development. Meanwhile, SiOx is an amorphous material, and the disorder of atom distribution causes the low electronic conductivity (SiO: < 10:)-4S/cm) affecting the rate capability of the material. Therefore, how to construct a stable electrode structure and improve the interface stability and the electron conductivity thereof is a key to promote the practical process of the silicon oxide negative electrode material.
The root cause of the large SiOx volume effect is the formation of LixSi during lithiation. It is generally believed that SiOx produces elemental silicon, lithium oxide, and lithium silicate (LixSiOy) during the first lithiation process, where what really has a lithium storage function is the elemental silicon produced by the reaction. During lithiation, LixSi generated on the surface of the material and the interior of the material undergo severe nonuniform expansion, and when particles cannot bear the nonuniform expansion, the material is cracked and pulverized. Therefore, the volume effect of SiOx is closely related to the silicon content (or oxygen content, i.e. the x value). The x value is reduced, the silicon content is increased, the effective capacity is increased, but the volume effect is also increased, and the cycling stability of the material is reduced. Aiming at the problem of large volume effect of SiOx, the current solution is mainly to perform component regulation, structural design and morphology control or to compound with other metal and non-metal materials. However, the methods have high equipment requirements and strict conditions, or are complicated to prepare and lack of quantitative theoretical guidance, so that the practical application faces huge challenges. Therefore, the development of rational design of the composition and structure of the SiOx material is important for fundamentally inhibiting the volume effect of the SiOx and improving the structural stability of the SiOx.
Disclosure of Invention
The invention aims to solve the problems of high equipment requirement, harsh conditions, complex preparation method and poor cycle stability of the conventional method for inhibiting the volume effect of SiOx, and provides a silicon oxide/carbon lithium ion battery cathode material with a hollow structure, a preparation method and application thereof.
The silicon oxide/carbon lithium ion battery cathode material with the hollow structure has a hollow structure inside, a concave spherical structure or bowl-shaped structure on the surface, a size of 200 nm-1200 nm and a shell thickness of 50 nm-250 nm; in the spherical structure or the bowl-shaped structure, C is uniformly distributed in SiOx clusters in a nanometer scale, wherein the SiOx clusters are less than 5 nm.
A preparation method of a silicon oxide/carbon lithium ion battery cathode material with a hollow structure comprises the following steps:
firstly, dispersing aldehyde in deionized water to obtain an aldehyde solution; dripping a silicon source into the aldehyde solution, and stirring for reaction to obtain a flocculent solution;
filtering the flocculent solution obtained in the step one, and discarding filtrate to obtain solid substances; washing the solid substance by using distilled water and absolute ethyl alcohol alternately, and freeze-drying to obtain monodisperse hollow concave spheres;
and thirdly, placing the monodisperse hollow concave spheres in a tubular furnace, introducing inert gas into the tubular furnace, and calcining at high temperature under the protection of the inert gas to obtain the SiOx/C lithium ion battery cathode material with the hollow structure.
A silicon oxide/carbon lithium ion battery cathode material with a hollow structure is used as a lithium ion battery cathode material.
The invention has the following beneficial effects:
(1) by adopting the preparation method, different cross-linking molecules (namely different types of aldehydes) are used, and the reaction time and the reaction temperature are controlled, so that the interior of the nano-particles can be emptied in one step, and the shell layer is pressed and collapsed to form concave spheres, thereby having high yield of the hollow microspheres;
(2) in the silicon oxide/carbon lithium ion battery cathode material with the hollow structure, carbon is uniformly distributed in a Si-O-Si framework in a nanoscale, and the highly uniformly dispersed carbon network divides a SiOx matrix into a plurality of sub-nanometer domains, so that the material keeps structural integrity in the process of removing and embedding lithium, and can isolate electrolyte from contacting with the SiOx material, and the internal hollow structure can relieve the volume effect of the SiOx material;
(3) the solvent used in the polymerization process is deionized water, no other organic solvent, no template, no additive, no toxicity and no harm are generated, and the manufacturing cost is greatly reduced;
(4) the raw materials (terephthalaldehyde, glutaraldehyde, glyoxal, 3-aminopropyltriethoxysilane and deionized water) are low in price, the preparation process is simple, the reaction time is short, the cost is low, the repeatability is good, the balling rate is high, and the method is suitable for preparing electrode materials on a large scale;
(5) the silicon oxide/carbon lithium ion battery cathode material with the hollow structure prepared by the invention has higher first discharge capacity (1500mAh g) when being used as a lithium ion battery cathode material-1～1600mAh g-1) And better cycling stability (reversible capacity 700mAh g)-1～900mAh g-1)。
Drawings
FIG. 1 is an SEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 1;
FIG. 2 is a TEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 1;
FIG. 3 is a photograph showing the distribution of three elements, Si, O and C, in a single concave sphere of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 1;
FIG. 4 is an SEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 2;
FIG. 5 is a TEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 2;
FIG. 6 is a photograph showing the distribution of three elements, Si, O and C, in a single concave sphere of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 2;
FIG. 7 is an SEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 3;
FIG. 8 is a TEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 3;
FIG. 9 is a photograph showing the distribution of three elements, Si, O and C, in a single concave sphere of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 3;
FIG. 10 shows the cycle performance of the SiOx/C lithium ion battery negative electrode material with a hollow structure prepared in example 1;
FIG. 11 shows the cycle performance of the SiOx/C lithium ion battery negative electrode material with a hollow structure prepared in example 2;
FIG. 12 shows the cycle performance of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 3.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the silicon oxide/carbon lithium ion battery cathode material with the hollow structure has a hollow structure inside, a concave spherical structure or bowl-shaped structure on the surface, a size of 200 nm-1200 nm and a shell thickness of 50 nm-250 nm; in the spherical structure or the bowl-shaped structure, C is uniformly distributed in SiOx clusters in a nanometer scale, wherein the SiOx clusters are less than 5 nm.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the value range of x in the SiOx is more than 0 and less than or equal to 2. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the embodiment is a preparation method of a silicon oxide/carbon lithium ion battery cathode material with a hollow structure, which is completed according to the following steps:
firstly, dispersing aldehyde in deionized water to obtain an aldehyde solution; dripping a silicon source into the aldehyde solution, and stirring for reaction to obtain a flocculent solution;
filtering the flocculent solution obtained in the step one, and discarding filtrate to obtain solid substances; washing the solid substance by using distilled water and absolute ethyl alcohol alternately, and freeze-drying to obtain monodisperse hollow concave spheres;
and thirdly, placing the monodisperse hollow concave spheres in a tubular furnace, introducing inert gas into the tubular furnace, and calcining at high temperature under the protection of the inert gas to obtain the SiOx/C lithium ion battery cathode material with the hollow structure.
The fourth concrete implementation mode: the present embodiment is different from the third embodiment in that: the stirring reaction speed in the step one is 100 r/min-500 r/min, and the stirring reaction time is 20 min-40 min; the molar ratio of the silicon source to the aldehyde in the aldehyde solution in the first step is 2: 1. The other steps are the same as those in the third embodiment.
The fifth concrete implementation mode: the present embodiment differs from the third to fourth embodiments in that: the aldehyde in the step one is one or more of trimesic aldehyde, o-phthalaldehyde, terephthalaldehyde, nonane dialdehyde, hexanedial, glutaraldehyde, butanedialdehyde, malondialdehyde and glyoxal. The other steps are the same as those in the third to fourth embodiments.
The sixth specific implementation mode: the third to fifth embodiments are different from the first to fifth embodiments in that: the silicon source in the step one is 3-aminopropyl triethoxysilane. The other steps are the same as those in the third to fifth embodiments.
The seventh embodiment: the third to sixth differences from the present embodiment are as follows: the concentration of the aldehyde solution in the first step is 0.01-0.05 mol/L. The other steps are the same as those of the third to sixth embodiments.
The specific implementation mode is eight: the third to seventh differences from the present embodiment are as follows: the temperature of the freeze drying in the step two is-48 ℃ to-60 ℃, and the time of the freeze drying is 12h to 24 h. The other steps are the same as those of the third to seventh embodiments.
The specific implementation method nine: the third to eighth differences from the present embodiment are: the inert gas in the third step is nitrogen or argon; the high-temperature calcination in the third step is carried out at the temperature of 900-1200 ℃ for 5-10 h. The other steps are the same as those in the third to eighth embodiments.
The detailed implementation mode is ten: in the present embodiment, a silicon oxide/carbon lithium ion battery negative electrode material having a hollow structure is used as a lithium ion battery negative electrode material.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1: a preparation method of a silicon oxide/carbon lithium ion battery cathode material with a hollow structure comprises the following steps:
firstly, dispersing 0.2g of terephthalaldehyde in 40mL of deionized water to obtain a terephthalaldehyde solution; dripping 1mL of 3-aminopropyltriethoxysilane into a terephthalaldehyde solution, and stirring and reacting for 30min at a stirring speed of 100r/min to obtain a flocculent solution;
filtering the flocculent solution obtained in the step one, and discarding filtrate to obtain solid substances; washing the solid substance by using distilled water and absolute ethyl alcohol alternately, and freeze-drying to obtain monodisperse hollow concave spheres;
the temperature of the freeze drying in the step two is-48 ℃, and the time of the freeze drying is 12 hours;
and thirdly, placing the monodisperse hollow concave spheres in a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 900 ℃ at the heating rate of 5 ℃/min under the protection of argon atmosphere, calcining for 5h at 900 ℃, and finally cooling to room temperature to obtain the SiOx/C lithium ion battery cathode material with the hollow structure.
Referring to the attached fig. 1, 2 and 3, they are respectively a scanning electron micrograph, a transmission electron micrograph and a single concave spherical element distribution micrograph of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 1.
FIG. 1 is an SEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 1;
FIG. 2 is a TEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 1;
FIG. 3 is a photograph showing the distribution of three elements, Si, O and C, in a single concave sphere of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 1;
as can be seen from fig. 1 to fig. 3, the hollow concave spheres of the SiOx/C lithium ion battery negative electrode material with a hollow structure prepared in example 1 have a uniform structure and a hollow structure, and the particle size is 800-900 nm; the elemental distribution photographs show that carbon is uniformly distributed in the Si-O-Si skeleton.
Example 2: a preparation method of a silicon oxide/carbon lithium ion battery cathode material with a hollow structure comprises the following steps:
firstly, dispersing 0.75mL of 60% glutaraldehyde aqueous solution by mass fraction in 40mL of deionized water to obtain an aldehyde solution; dripping 1mL of 3-aminopropyltriethoxysilane into the aldehyde solution, and stirring and reacting for 30min at a stirring speed of 100r/min to obtain a flocculent solution;
filtering the flocculent solution obtained in the step one, and discarding filtrate to obtain solid substances; washing the solid substance by using distilled water and absolute ethyl alcohol alternately, and freeze-drying to obtain monodisperse hollow concave spheres;
the temperature of the freeze drying in the step two is-48 ℃, and the time of the freeze drying is 12 hours;
and thirdly, placing the monodisperse hollow concave spheres in a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 900 ℃ at the heating rate of 5 ℃/min under the protection of argon atmosphere, calcining for 5h at 900 ℃, and finally cooling to room temperature to obtain the SiOx/C lithium ion battery cathode material with the hollow structure.
Referring to fig. 4, 5 and 6, there are respectively a scanning electron micrograph, a transmission electron micrograph and a single gravure element distribution micrograph of the SiOx/C lithium ion battery negative electrode material having a hollow structure prepared in example 2.
FIG. 4 is an SEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 2;
FIG. 5 is a TEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 2;
FIG. 6 is a photograph showing the distribution of three elements, Si, O and C, in a single concave sphere of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 2;
as can be seen from fig. 4 to 6, the hollow concave spheres of the SiOx/C lithium ion battery negative electrode material with a hollow structure prepared in example 2 have a uniform structure and a hollow structure, and the particle size is 200-300 nm. The elemental distribution photographs show that carbon is uniformly distributed in the Si-O-Si skeleton.
Example 3: a preparation method of a silicon oxide/carbon lithium ion battery cathode material with a hollow structure comprises the following steps:
firstly, dispersing 0.6mL of 40% aqueous glyoxal solution in mass fraction into 40mL of deionized water to obtain an aldehyde solution; dripping 1mL of 3-aminopropyltriethoxysilane into the aldehyde solution, and stirring and reacting for 30min at a stirring speed of 100r/min to obtain a flocculent solution;
filtering the flocculent solution obtained in the step one, and discarding filtrate to obtain solid substances; washing the solid substance by using distilled water and absolute ethyl alcohol alternately, and freeze-drying to obtain monodisperse hollow concave spheres;
the temperature of the freeze drying in the step two is-48 ℃, and the time of the freeze drying is 12 hours;
and thirdly, placing the monodisperse hollow concave spheres in a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 900 ℃ at the heating rate of 5 ℃/min under the protection of argon atmosphere, calcining for 5h at 900 ℃, and finally cooling to room temperature to obtain the SiOx/C lithium ion battery cathode material with the hollow structure.
Referring to fig. 7, 8 and 9, there are respectively a scanning electron micrograph, a transmission electron micrograph and a single gravure element distribution micrograph of the SiOx/C lithium ion battery negative electrode material having a hollow structure prepared in example 3.
FIG. 7 is an SEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 3;
FIG. 8 is a TEM image of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 3;
FIG. 9 is a photograph showing the distribution of three elements, Si, O and C, in a single concave sphere of the SiOx/C lithium ion battery anode material with a hollow structure prepared in example 3;
from fig. 7 to 9, it can be seen that the hollow concave spheres of the SiOx/C lithium ion battery negative electrode material with the hollow structure prepared in example 3 have a uniform structure and a hollow structure, and the particle size is 400-500 nm. The elemental distribution photographs show that carbon is uniformly distributed in the Si-O-Si skeleton.
The SiOx/C lithium ion battery negative electrode material with the hollow structure prepared in the embodiment 1-3 is used as the lithium ion battery negative electrode material, and the preparation method comprises the following steps:
the SiOx/C lithium ion battery negative electrode material with the hollow structure prepared in the embodiment 1, acetylene black and CMC/SBR are uniformly mixed according to the mass ratio of 7:2:1, and then coated on a copper foil current collector, dried and cut into a 14 cm-diameter wafer to assemble a half battery for testing, wherein the testing conditions are as follows: the voltage range is 0.01-3V; the current density was 0.1A/g, see FIG. 10;
the SiOx/C lithium ion battery negative electrode material with the hollow structure prepared in the embodiment 2, acetylene black and CMC/SBR are uniformly mixed according to the mass ratio of 7:2:1, and then coated on a copper foil current collector, dried and cut into a 14 cm-diameter wafer to assemble a half battery for testing, wherein the testing conditions are as follows: the voltage range is 0.01-3V; the current density was 0.1A/g, see FIG. 11;
the SiOx/C lithium ion battery negative electrode material with the hollow structure prepared in the embodiment 3, acetylene black and CMC/SBR are uniformly mixed according to the mass ratio of 7:2:1, and then coated on a copper foil current collector, dried and cut into a 14 cm-diameter wafer to assemble a half battery for testing, wherein the testing conditions are as follows: the voltage range is 0.01-3V; the current density was 0.1A/g, see FIG. 12;
FIG. 10 shows the cycle performance of the SiOx/C lithium ion battery negative electrode material with a hollow structure prepared in example 1;
FIG. 11 shows the cycle performance of the SiOx/C lithium ion battery negative electrode material with a hollow structure prepared in example 2;
FIG. 12 shows the cycle performance of the SiOx/C lithium ion battery negative electrode material with a hollow structure prepared in example 3;
the SiOx/C lithium ion battery anode materials with hollow structures prepared in examples 1, 2 and 3 all show higher first-time discharge capacity (1500mAh g)-1-1600mAh g-1) Better circulation stability (reversible capacity 700mAh g)-1-900mAh g-1)。

Claims (6)

1. A preparation method of a silicon oxide/carbon lithium ion battery cathode material with a hollow structure is characterized in that the preparation method of the silicon oxide/carbon lithium ion battery cathode material with the hollow structure is completed according to the following steps:
firstly, dispersing aldehyde in deionized water to obtain an aldehyde solution; dripping a silicon source into the aldehyde solution, and stirring for reaction to obtain a flocculent solution;
the silicon source in the step one is 3-aminopropyl triethoxysilane;
filtering the flocculent solution obtained in the step one, and discarding filtrate to obtain solid substances; washing the solid substance by using distilled water and absolute ethyl alcohol alternately, and freeze-drying to obtain monodisperse hollow concave spheres;
placing the monodisperse hollow concave spheres in a tubular furnace, introducing inert gas into the tubular furnace, and calcining at high temperature under the protection of the inert gas to obtain the SiOx/C lithium ion battery cathode material with a hollow structure;
the SiOx/C lithium ion battery cathode material with the hollow structure in the third step has a hollow structure inside, a concave spherical structure or bowl-shaped structure on the surface, the size of 200 nm-1200 nm, and the thickness of a shell layer of 50 nm-250 nm; in the spherical structure or the bowl-shaped structure, C is uniformly distributed in SiOx clusters in a nano scale, wherein the SiOx clusters are smaller than 5nm, and the value range of x in the SiOx is more than 0 and less than or equal to 2.
2. The method for preparing a silicon oxide/carbon lithium ion battery cathode material with a hollow structure according to claim 1, wherein the stirring reaction speed in the step one is 100r/min to 500r/min, and the stirring reaction time is 20min to 40 min; the molar ratio of the silicon source to the aldehyde in the aldehyde solution in the first step is 2: 1.
3. The method for preparing a silicon oxide/carbon lithium ion battery anode material with a hollow structure according to claim 1, wherein the aldehyde in the step one is one or more of trimesic aldehyde, o-phthalaldehyde, terephthalaldehyde, azelaic aldehyde, adipic dialdehyde, glutaraldehyde, succinic aldehyde, malonic dialdehyde, and glyoxal.
4. The method for preparing a silicon oxide/carbon lithium ion battery anode material with a hollow structure according to claim 1, wherein the concentration of the aldehyde solution in the step one is 0.01mol/L to 0.05 mol/L.
5. The method for preparing silicon oxide/carbon lithium ion battery anode material with hollow structure according to claim 3, characterized in that the freeze drying temperature in the second step is-48 ℃ to-60 ℃, and the freeze drying time is 12h to 24 h.
6. The method for preparing a silicon oxide/carbon lithium ion battery cathode material with a hollow structure according to claim 1, wherein the inert gas in the third step is argon; the high-temperature calcination in the third step is carried out at the temperature of 900-1200 ℃ for 5-10 h.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103872327A (en) * 2014-04-04 2014-06-18 西华师范大学 Preparation method of negative composite material for lithium battery, negative electrode and lithium ion battery
CN105655564A (en) * 2016-03-30 2016-06-08 深圳市国创新能源研究院 SiO<x>/C composite cathode material, method for preparing same and application of SiO<x>/C composite cathode material
CN106629747A (en) * 2017-01-20 2017-05-10 中国科学院宁波材料技术与工程研究所 Hollow bowl-shaped silicon dioxide nanoparticles, preparation method and application thereof
CN110048101A (en) * 2019-04-03 2019-07-23 江苏科技大学 A kind of silicon oxygen carbosphere composite negative pole material and the preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103872327A (en) * 2014-04-04 2014-06-18 西华师范大学 Preparation method of negative composite material for lithium battery, negative electrode and lithium ion battery
CN105655564A (en) * 2016-03-30 2016-06-08 深圳市国创新能源研究院 SiO<x>/C composite cathode material, method for preparing same and application of SiO<x>/C composite cathode material
CN106629747A (en) * 2017-01-20 2017-05-10 中国科学院宁波材料技术与工程研究所 Hollow bowl-shaped silicon dioxide nanoparticles, preparation method and application thereof
CN110048101A (en) * 2019-04-03 2019-07-23 江苏科技大学 A kind of silicon oxygen carbosphere composite negative pole material and the preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Interpenetrated tunnel routes in silicon/carbon hollow sphere anodes to boost their lithium storage;Song Chen 等;《Mater. Chem. Front.》;20200715;第4卷;摘要、2783-2784页 *

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