CN114583131A - MXene @ porous silicon material with stable flexibility and preparation method and application thereof - Google Patents
MXene @ porous silicon material with stable flexibility and preparation method and application thereof Download PDFInfo
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- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 81
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 62
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims description 19
- 229910000676 Si alloy Inorganic materials 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 7
- 238000003828 vacuum filtration Methods 0.000 claims description 7
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical group [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 4
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 239000006258 conductive agent Substances 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000789 Aluminium-silicon alloy Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an MXene @ porous silicon material with stable flexibility, and a preparation method and application thereof. The method comprises the following steps: 1) mixing the MAX phase with a hydrochloric acid solution containing lithium fluoride, heating, centrifuging and stripping a product after reaction to obtain MXene suspension; 2) and adding porous silicon into the MXene suspension for mixing, and performing solid-liquid separation on a reaction product to obtain a flexible MXene @ porous silicon material. The MXene @ porous silicon material can improve the structural stability and the conductivity at the same time. The conductive agent and the adhesive are not required to be added, and the cycle performance is better.
Description
Technical Field
The invention belongs to the technical field of silicon-based composite materials, and particularly relates to an MXene @ porous silicon material with stable flexibility, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The silicon material as the lithium ion battery cathode has the advantage of higher theoretical specific capacity, but the silicon is a semiconductor material, and the conductivity of the silicon is poor due to the semiconductor property of the silicon; and the silicon-based negative electrode can generate huge volume change in the processes of lithium intercalation and lithium deintercalation, so that the active material is broken and lost, the cyclicity of the silicon-based negative electrode is poor, the stability of the silicon-based negative electrode in long-term use is poor, the cycle performance influences the service life of repeated charge and discharge in the actual use process, and the industrial application of the silicon-based negative electrode is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an MXene @ porous silicon material with stable flexibility, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of MXene @ porous silicon material with stable flexibility comprises the following steps:
1) mixing the MAX phase with a hydrochloric acid solution containing lithium fluoride, heating, centrifuging and stripping a product after reaction to obtain MXene suspension;
2) adding porous silicon into MXene suspension for mixing, and carrying out solid-liquid separation on a reaction product to obtain a solid product which is a flexible MXene @ porous silicon material.
The porous silicon mxene flexible self-supporting structure obtained by the preparation method can be independently used as a negative electrode of a lithium ion battery, does not need a binder and carbon black, can independently exert the negative electrode characteristics of the lithium ion battery, and has good cycle stability. The silicon-based negative electrode has flexibility and can be bent, and the lithium intercalation and de-intercalation processes of the silicon-based negative electrode can generate huge volume change, and the MXene @ porous silicon material can avoid the crushing and loss of the material in the process.
MXene suspension is prepared in the step 1), and then the suspension and porous silicon are subjected to combined reaction to obtain a flexible two-dimensional film-shaped structure with a certain thickness. MXene is a material with a two-dimensional layered structure into which porous silicon is incorporated in a suspension, eventually forming a film-like structure.
In some embodiments of the present invention, the method for preparing porous silicon is: and soaking the silicon alloy in a hydrochloric acid solution to obtain the porous silicon.
In a further embodiment of the invention, the silicon alloy is an aluminium silicon alloy, a magnesium silicon alloy or a silicon iron alloy.
In a further embodiment of the present invention, the hydrochloric acid solution has a mass concentration of 5% to 30% during the preparation of the porous silicon. In the preparation process of the porous silicon, the silicon alloy is prepared into the porous silicon through the treatment of hydrochloric acid.
In some embodiments of the invention, during the preparation of the MXene suspension, the mass percentage of the hydrochloric acid in the hydrochloric acid solution is 25-30%, and the mass concentration of the lithium fluoride is 0.05-0.1 g/mL; furthermore, the mass percent of the hydrochloric acid in the hydrochloric acid solution is 26-29%, and the mass concentration of the lithium fluoride is 0.06-0.9 g/mL. MXene was obtained by mixing the MAX phase with a hydrochloric acid solution containing lithium fluoride and heating the resulting mixture. The effect of lithium fluoride and hydrochloric acid is to etch the MAX phase to obtain MXene.
In some embodiments of the invention, during the preparation of the MXene suspension, the heating treatment temperature is 32-40 ℃, and the heating treatment time is 18-25 h; further at 36-37 deg.C for 24 hr.
And (3) centrifuging the product after the reaction in the step 1), and then peeling by shaking by hand.
In some embodiments of the invention, in the step 2), the mass ratio of the porous silicon to the MXene is 1: 2-4. In the invention, the flexible MXene @ porous silicon material is obtained by compounding the porous silicon and MXene into a whole, and the MXene is used as a carrier and loaded on the carrier instead of other modes such as coating and the like.
In some embodiments of the invention, in the step 2), the time for the mixing reaction of the porous silicon and the MXene is 2-8 h; further 3-6 h.
In some embodiments of the present invention, the solid-liquid separation in step 2) is vacuum filtration, and the freeze drying is performed after the solid-liquid separation.
In a further embodiment of the invention, the freeze-drying temperature is between-20 ℃ and-30 ℃ and the freeze-drying time is between 36h and 48 h.
In a second aspect, the MXene @ porous silicon material obtained by the preparation method is flexible and stable.
In some embodiments of the invention, the thickness of the flexible stabilized MXene @ porous silicon material is 20-100 μm; further 30 to 60 μm.
In a third aspect, the flexible and stable MXene @ porous silicon material is applied to the field of lithium ion batteries. In particular to the application of the negative electrode of the lithium ion battery in the lithium ion battery.
One or more technical schemes of the invention have the following beneficial effects:
the invention relates to an MXene @ porous silicon material with stable flexibility, wherein MXene is used as a carrier, and porous silicon is loaded on the carrier to form a flexible and bendable lithium ion battery negative electrode material. The silicon cathode with the porous structure can better relieve stress and can keep structural stability. The compounding of MXene can improve the conductivity of the silicon negative electrode, so that the electrode has higher electron transmission speed. The MXene @ porous silicon material can improve the structural stability and the conductivity at the same time.
The MXene @ porous silicon material can be directly used as a material of a lithium ion battery cathode, does not need to be added with a conductive agent and a binder, and has good cycle performance. Thus, the MXene @ porous silicon material has commercial potential.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
Figure 1 is an XRD pattern of the MXene @ porous silicon material prepared in example 1.
FIG. 2 is a scanning electron micrograph of porous silicon prepared in example 1.
FIG. 3 is a scanning electron micrograph of MXene @ porous silicon prepared in example 1.
Fig. 4 is a photograph of MXene @ porous silicon prepared in example 1.
Fig. 5 is a charge and discharge curve of MXene @ porous silicon material prepared in example 1 as a negative electrode of a lithium ion battery.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. The invention will be further illustrated by the following examples
Example 1
The preparation method of the MXene @ porous silicon material with stable flexibility comprises the following steps:
(1) adding the aluminum-silicon alloy into a 10% hydrochloric acid solution, soaking until no bubbles are generated, taking out, performing centrifugal filtration, and drying at 50 ℃ for 12 hours under a vacuum condition to obtain porous silicon;
(2) adding 0.5g of MAX phase into a hydrochloric acid solution (7.5 ml of 36.5% hydrochloric acid and 2.5ml of deionized water) containing 0.8g of lithium fluoride, heating in a water bath at 36.5 ℃ and stirring for 24 hours, centrifuging and stripping to obtain MXene suspension;
(3) adding 12mg of the porous silicon obtained in the step (1) into a suspension containing 36mg of MXene, stirring for 6 hours, and carrying out vacuum filtration and freeze drying at-20 ℃ for 48 hours to obtain an MXene-loaded porous silicon flexible lithium ion battery cathode;
fig. 1 is an XRD pattern of the MXene-supported porous silicon flexible lithium ion battery negative electrode in example 1. The figure shows that the MXene loaded porous silicon flexible lithium ion battery cathode is successfully synthesized.
FIG. 2 is a scanning electron microscope image of the porous silicon prepared in example 1, demonstrating that the porous silicon is successfully prepared, the porous silicon is spherical, the spherical surface has a porous structure, and the diameter of the pores is 0.2-1 μm.
FIG. 3 is a scanning electron microscope image of MXene @ porous silicon prepared in example 1, which shows that MXene @ porous silicon material has a flexible film structure and a thickness of about 30-60 μm.
Fig. 4 is a photograph of a folded MXene @ porous silicon material prepared in example 1, wherein the folded MXene @ porous silicon material is held by a hand of an operator with a clamp. The MXene @ porous silicon material has flexibility and can be bent.
Charge and discharge experiments: and (3) charging and discharging the half cell assembled by the MXene @ porous silicon negative electrode material and the lithium sheet at a constant current of 200mA/g by using an electrochemical workstation.
Fig. 5 is a charge-discharge curve of the negative electrode of the MXene-supported porous silicon flexible lithium ion battery prepared in example 1. The good cycle stability of the MXene-supported porous silicon flexible lithium ion battery negative electrode is illustrated in the figure, and the negative electrode has higher first-time discharge capacity.
Example 2
A preparation method of the MXene @ porous silicon material with stable flexibility comprises the following steps:
(1) adding the magnesium-silicon alloy into a 10% hydrochloric acid solution, soaking until no bubbles are generated, taking out, performing centrifugal filtration, and drying at 50 ℃ for 12 hours under a vacuum condition to obtain porous silicon;
(2) adding 0.5g of MAX phase into a hydrochloric acid solution (7.5 ml of 36.5% hydrochloric acid and 2.5ml of deionized water) containing 0.8g of lithium fluoride, heating in a water bath at 36.5 ℃ and stirring for 24 hours, centrifuging and stripping to obtain MXene suspension;
(3) adding 12mg of the porous silicon obtained in the step (1) into a suspension containing 24mg of MXene, stirring for 6 hours, and carrying out vacuum filtration and freeze drying at-20 ℃ for 48 hours to obtain an MXene-loaded porous silicon flexible lithium ion battery cathode;
example 3
A preparation method of the MXene @ porous silicon material with stable flexibility comprises the following steps:
(1) adding the ferrosilicon into a 10% hydrochloric acid solution, soaking until no bubbles are generated, taking out, performing centrifugal filtration, and drying at 50 ℃ for 12 hours under a vacuum condition to obtain porous silicon;
(2) adding 0.5g of MAX phase into a hydrochloric acid solution (7.5 ml of 36.5% hydrochloric acid and 2.5ml of deionized water) containing 0.8g of lithium fluoride, heating in a water bath at 36.5 ℃ and stirring for 24 hours, centrifuging and stripping to obtain MXene suspension;
(3) adding 12mg of the porous silicon obtained in the step (1) into a suspension containing 36mg of MXene, stirring for 6 hours, and carrying out vacuum filtration and freeze drying at-30 ℃ for 36 hours to obtain an MXene-loaded porous silicon flexible lithium ion battery cathode;
example 4
The preparation method of the MXene @ porous silicon material with stable flexibility comprises the following steps:
(1) adding the aluminum-silicon alloy into a 20% hydrochloric acid solution, soaking until no bubbles are generated, taking out, performing centrifugal filtration, and drying at 50 ℃ for 12 hours under a vacuum condition to obtain porous silicon;
(2) adding 0.5g of MAX phase into a hydrochloric acid solution (7.5 ml of 36.5% hydrochloric acid and 2.5ml of deionized water) containing 0.8g of lithium fluoride, heating in a water bath at 36.5 ℃ and stirring for 24 hours, centrifuging and stripping to obtain MXene suspension;
(3) adding 12mg of the porous silicon obtained in the step (1) into a suspension containing 36mg of MXene, stirring for 6 hours, and carrying out vacuum filtration and freeze drying at-25 ℃ for 48 hours to obtain an MXene-loaded porous silicon flexible lithium ion battery cathode;
example 5
The preparation method of the MXene @ porous silicon material with stable flexibility comprises the following steps:
(1) adding the aluminum-silicon alloy into a 5% hydrochloric acid solution, soaking until no bubbles are generated, taking out, performing centrifugal filtration, and drying at 60 ℃ for 12 hours under a vacuum condition to obtain porous silicon;
(2) adding 0.5g of MAX phase into a hydrochloric acid solution (7.5 ml of 36.5% hydrochloric acid and 2.5ml of deionized water) containing 0.8g of lithium fluoride, heating in a water bath at 36.5 ℃ and stirring for 24 hours, centrifuging and stripping to obtain MXene suspension;
(3) adding 12mg of the porous silicon obtained in the step (1) into a suspension containing 36mg of MXene, stirring for 6h, and carrying out vacuum filtration and freeze drying at-20 ℃ for 12h to obtain an MXene-loaded porous silicon flexible lithium ion battery cathode;
the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of MXene @ porous silicon material with stable flexibility is characterized by comprising the following steps: the method comprises the following steps:
1) mixing the MAX phase with a hydrochloric acid solution containing lithium fluoride, heating, centrifuging and stripping a product after reaction to obtain MXene suspension;
2) adding porous silicon into MXene suspension for mixing, and carrying out solid-liquid separation on a reaction product to obtain a solid product which is a flexible MXene @ porous silicon material.
2. The method of claim 1, wherein the method comprises the steps of: the preparation method of the porous silicon comprises the following steps: and soaking the silicon alloy in a hydrochloric acid solution to obtain the porous silicon.
3. The method of claim 2 wherein the step of forming a flexible stable MXene @ porous silica material comprises: the silicon alloy is aluminum-silicon alloy, magnesium-silicon alloy or silicon-iron alloy;
or, in the preparation process of the porous silicon, the mass concentration of the hydrochloric acid solution is 5-30%.
4. The method of claim 1, wherein the method comprises the steps of: in the preparation process of the MXene suspension, the mass percent of hydrochloric acid in the hydrochloric acid solution is 25-30%, and the mass concentration of lithium fluoride is 0.05-0.1 g/mL.
5. The method of claim 1, wherein the method comprises the steps of: in the preparation process of MXene suspension, the heating treatment temperature is 32-40 ℃, and the heating treatment time is 18-25 h.
6. The method of claim 1, wherein the method comprises the steps of: in the step 2), the mass ratio of the porous silicon to the MXene is 1: 2-4.
7. The method of claim 1, wherein the method comprises the steps of: in the step 2), the time for the mixed reaction of the porous silicon and MXene is 2-8 h; further 3-6 h.
8. The method of claim 1, wherein the method comprises the steps of: the solid-liquid separation method in the step 2) is to carry out vacuum filtration, and freeze drying is carried out after solid-liquid separation.
9. An MXene @ porous silicon material with stable flexibility obtained by the preparation method according to any one of claims 1 to 8;
preferably, the thickness of the flexible stable MXene @ porous silicon material is 20-100 μm; further 30 to 60 μm.
10. The use of the flexible stabilized MXene @ porous silicon material of claim 9 in the field of lithium ion batteries.
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| CN112875706A (en) * | 2021-01-05 | 2021-06-01 | 昆山宝创新能源科技有限公司 | Self-supporting MXene/Si composite anode material and preparation method and application thereof |
| KR20210079442A (en) * | 2019-12-19 | 2021-06-30 | 우석대학교 산학협력단 | Anode material with graphene-mxene-silicon of secondary battery and the method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103247792A (en) * | 2013-03-22 | 2013-08-14 | 济南大学 | Nano porous silicon alloy material and preparation method thereof |
| CN106920954A (en) * | 2017-05-05 | 2017-07-04 | 北京科技大学 | A kind of preparation of porous silicon composite cathode material of graphene coated and application process |
| KR20210079442A (en) * | 2019-12-19 | 2021-06-30 | 우석대학교 산학협력단 | Anode material with graphene-mxene-silicon of secondary battery and the method thereof |
| CN112875706A (en) * | 2021-01-05 | 2021-06-01 | 昆山宝创新能源科技有限公司 | Self-supporting MXene/Si composite anode material and preparation method and application thereof |
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