CN115986076A - Silicon-based composite negative electrode material and preparation method thereof - Google Patents
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- CN115986076A CN115986076A CN202211662728.1A CN202211662728A CN115986076A CN 115986076 A CN115986076 A CN 115986076A CN 202211662728 A CN202211662728 A CN 202211662728A CN 115986076 A CN115986076 A CN 115986076A
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Abstract
The invention discloses a silicon-based composite negative electrode material which comprises a silicon-based core, an amorphous lithium fast ion conductor and a carbon coating layer, wherein the amorphous lithium fast ion conductor is coated on the outer layer of the silicon-based core, and the carbon coating layer is positioned on the outermost layer. Also discloses a preparation method of the silicon-based composite anode material, which comprises the following steps: s1, coating an amorphous fast ion conductor on the surface of a silicon-based material by adopting a liquid phase method to obtain an intermediate 1; and S2, coating carbon on the surface of the intermediate 1 by using a chemical vapor deposition method. The silicon-based composite negative electrode material can effectively inhibit the expansion of a silicon-based core, improves the chemical stability of an interface, and is beneficial to the improvement of the first efficiency and the first charging specific capacity.
Description
Technical Field
The invention belongs to the field of silicon-based anode materials, and particularly relates to a silicon-based composite anode material and a preparation method thereof.
Background
In recent years, due to the rapid development of various portable electronic devices and new energy vehicles, the market demand for high energy density lithium ion batteries is becoming more urgent. The development of high energy density lithium ion batteries and the improvement of specific capacity of positive and negative electrode materials are not divisible, and the graphite negative electrode obviously cannot meet the conditions.
The silica material is applied to the lithium ion battery with high energy density due to the advantages of high energy density, wide material source and the like, but has the defects of large full-electricity expansion, low first-time efficiency, poor quick-charge performance and the like. Meanwhile, the problems of electrode structure collapse, active material particle crushing, SEI film cracking and regeneration and the like can be caused, and the problems are also the bottleneck of urgent need for breakthrough of the current silicon-based negative electrode material in scientific research. To alleviate the silicon volume expansion problem, the current conventional approach is to coat carbon. However, the silicon @ carbon material suffers fatigue fracture of the carbon shell under stress after a certain number of cycles, resulting in still unsatisfactory electrochemical performance.
Disclosure of Invention
Based on the technical problems, the invention provides a silicon-based composite negative electrode material, which takes silicon-based as an inner core, an amorphous lithium fast ion conductor as an intermediate layer and a carbon material as a shell, can effectively inhibit the expansion of the silicon-based inner core, improves the chemical stability of an interface, and is beneficial to the improvement of the first efficiency and the first charge specific capacity.
The specific scheme of the invention is as follows:
the invention provides a silicon-based composite anode material which comprises a silicon-based core, an amorphous lithium fast ion conductor and a carbon coating layer, wherein the amorphous lithium fast ion conductor is coated on the outer layer of the silicon-based core, and the carbon coating layer is positioned on the outermost layer.
Preferably, the amorphous lithium fast ion conductor is Li 2 O-B 2 O 3 -LiX system, X is selected from one of F, cl, br and I.
Preferably, the amorphous lithium fast ion conductor is Li 2 O-B 2 O 3 -LiF。
Preferably, the silicon-based material as the inner core is selected from at least one of elemental silicon, silica, and silicon dioxide.
The invention also provides a preparation method of the silicon-based composite anode material, which comprises the following steps: s1, coating an amorphous fast ion conductor on the surface of a silicon-based material by adopting a liquid phase method to obtain an intermediate 1; and S2, coating carbon on the surface of the intermediate 1 by using a chemical vapor deposition method.
Preferably, the liquid phase method of S1 specifically includes: adding the silicon-based material into the amorphous fast ion conductor solution, and carrying out ultrasonic treatment for 0.5-2h; drying, grinding, and then treating at 500-600 ℃ for 7-10h under an inert atmosphere to obtain an intermediate 1.
Preferably, the amorphous fast ion conductor solution is obtained by dissolving lithium hydroxide monohydrate, boric acid and lithium halide serving as raw materials in water.
Preferably, the chemical vapor deposition method of S2 is obtained by using acetylene as a carbon source and depositing for 4-8h at 800-1000 ℃.
The invention has the beneficial effects that:
according to the invention, the silicon-based material is coated by taking the amorphous lithium fast ion conductor as the middle coating layer, so that the chemical stability of an interface can be remarkably improved, and the first efficiency and the first charging specific capacity of the silicon-based negative electrode material are effectively enhanced; further, the carbon coating layer is used as the outermost layer, so that the volume change of the silicon-based material in the charge-discharge process can be effectively inhibited, the conductivity of the silicon-based material is improved, the primary efficiency is improved, and the side reaction of the silicon-based material in the charge-discharge process is reduced.
Drawings
Fig. 1 is a schematic structural diagram of the silicon-based composite anode material of the invention, wherein 1-silicon-based core; 2-amorphous lithium fast ion conductor; 3-a carbon coating layer;
fig. 2 is SEM images of the silicon-based composite anode material prepared in example 1 at different times;
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
The silicon-based composite negative electrode material comprises a silica core and an amorphous lithium fast ion conductor Li coated on the outer layer of the silica core 2 O-B 2 O 3 -LiF and a carbon coating layer at the outermost layer. The preparation method comprises the following steps:
s1, slowly adding 10g of SiO into an amorphous fast ion conductor solution, performing ultrasonic treatment for 30min, then drying by evaporation in a water bath at 80 ℃, performing vacuum drying and full grinding, and finally performing high-temperature treatment in a tubular heating furnace by using N 2 Treating with protective gas at 500 deg.C (temperature rise rate of 5 deg.C/min) for 8h to obtain intermediate 1 (as LBF @ SiO);
wherein the amorphous fast ion conductor solution is LiOH H 2 0、H 3 BO 3 LiF is used as a raw material, and LiOH & H are weighed according to a molar ratio of 2 2 0、H 3 BO 3 Dissolving LiF in a proper amount of deionized water, and stirring for 0.5h to obtain the solution;
s2, weighing 10g of intermediate 1 (LBF @ SiO), placing the intermediate in a porcelain boat, then placing the porcelain boat in a tubular furnace in a nitrogen protective atmosphere, heating the tubular furnace to 900 ℃ at a heating rate of 5 ℃/min, introducing acetylene gas, wherein the gas flow is 3mL/min, depositing for 6h at 900 ℃, stopping introducing the acetylene gas, and cooling to obtain the silicon-based composite material, which is marked as C @ LBF @ SiO.
The structural schematic diagram of the silicon-based composite anode material is shown in figure 1; the SEM image of the silicon-based composite material obtained in this example is shown in fig. 2, and it can be seen that the morphology of the silicon-based composite material is substantially similar to that of the SiO raw material, and is a bulk morphology, and a carbon layer coated on the surface of the material can be clearly observed in 2 (c).
Example 2
The silicon-based composite negative electrode material comprises a silica core and an amorphous lithium fast ion conductor Li coated on the outer layer of the silica core 2 O-B 2 O 3 -LiCl and a carbon coating layer at the outermost layer. The preparation method comprises the following steps:
s1, slowly adding 10g of SiO into an amorphous fast ion conductor solution, performing ultrasonic treatment for 30min, then evaporating to dryness in a water bath at 80 ℃, performing vacuum drying and full grinding, and finally performing high-temperature treatment in a tubular heating furnace by using N 2 Treating with protective gas at 500 deg.C (temperature rise rate of 5 deg.C/min) for 8 hr to obtain intermediate 1 (marked as LBCl @ SiO);
wherein the amorphous fast ion conductor solution is LiOH H 2 0、H 3 BO 3 And LiCl is used as a raw material, and LiOH & H is weighed according to a molar ratio of 2 2 0、H 3 BO 3 Dissolving LiCl in a proper amount of deionized water, and stirring for 0.5h to obtain the LiCl-containing aqueous solution;
s2, weighing 10g of intermediate 1 (LBCl @ SiO), placing the intermediate in a porcelain boat, then placing the porcelain boat in a tubular furnace in a nitrogen protective atmosphere, heating the tubular furnace to 900 ℃ at a heating rate of 5 ℃/min, introducing acetylene gas, wherein the gas flow is 3mL/min, depositing for 6h at 900 ℃, stopping introducing the acetylene gas, and cooling to obtain the silicon-based composite material, which is marked as C @ LBCl @ SiO.
Example 3
The silicon-based composite negative electrode material comprises a silica core and an amorphous lithium fast ion conductor Li coated on the outer layer of the silica core 2 O-B 2 O 3 LiBr and a carbon coating layer on the outermost layer. The preparation method comprises the following steps:
s1, slowly adding 10g of SiO into an amorphous fast ion conductor solution, performing ultrasonic treatment for 1h, then drying by evaporation in a water bath at 80 ℃, performing vacuum drying and full grinding, and finally performing high-temperature treatment in a tubular heating furnace by using N 2 As protective gas at 600 deg.C(the heating rate is 5 ℃/min) for 7h to obtain an intermediate 1 (recorded as LBBr @ SiO);
wherein the amorphous fast ion conductor solution is LiOH H 2 0、H 3 BO 3 And LiBr as a raw material, and LiOH & H are weighed according to a molar ratio of 2 2 0、H 3 BO 3 Dissolving LiBr in a proper amount of deionized water, and stirring for 0.5h to obtain the compound;
s2, weighing 10g of intermediate 1 (LBBr @ SiO), placing the intermediate in a porcelain boat, then placing the porcelain boat in a tubular furnace in a nitrogen protective atmosphere, heating the tubular furnace to 950 ℃ at a heating rate of 5 ℃/min, introducing acetylene gas, wherein the gas flow is 3mL/min, depositing for 5.5h at 950 ℃, stopping introducing the acetylene gas, and cooling to obtain the silicon-based composite material, which is marked as C @ LBBr @ SiO.
Comparative example 1
A silicon-based composite negative electrode material comprises a silica core and an outer carbon coating layer coated on the silica core. The preparation method comprises the following steps:
10g of unprocessed SiO is placed in a CVD furnace, nitrogen is introduced to discharge air in the CVD furnace, acetylene gas is introduced with the gas flow rate of 3mL/min, the CVD furnace is heated to 900 ℃ according to the heating rate of 5 ℃/min, deposition is carried out for 6h at 900 ℃, the acetylene gas is stopped to be introduced, and carbon-coated silicon monoxide is obtained after cooling and is marked as C @ SiO.
Comparative example 2
The silicon-based composite anode material comprises a silica core and a halogen fast ion conductor LiAlF coated on the outer layer of the silica core 4 And a carbon coating layer located at the outermost layer. The preparation method comprises the following steps:
s1, slowly adding 10g of SiO into a halogen fast ion conductor LiAlF 4 Performing ultrasonic treatment in the solution for 30min, evaporating to dryness in water bath at 80 deg.C, vacuum drying, grinding, and performing high temperature treatment in a tubular heating furnace with N 2 Taking the mixture as protective gas, and treating the mixture for 8 hours at 500 ℃ (the heating rate is 5 ℃/min) to obtain an intermediate 1;
wherein the halogen fast ion conductor LiAlF 4 The solution is obtained according to the method of CN 112397779A;
s2, weighing 10g of the intermediate 1, placing the intermediate in a porcelain boat, then placing the porcelain boat in a tubular furnace in a nitrogen protective atmosphere, heating the tubular furnace to 900 ℃ at a heating rate of 5 ℃/min, introducing acetylene gas, enabling the gas flow to be 3mL/min, depositing for 6h at 900 ℃, stopping introducing the acetylene gas, and cooling to obtain the silicon-based composite anode material.
The electrochemical performances of the silicon-based composite anode materials obtained in the above examples 1-3 and comparative examples 1-2 were tested, and the test methods, test conditions and results are as follows:
assembling the button cell: the silicon-carbon composite material described in the embodiments 1-3 and the comparative examples 1-2 is used as an active material to prepare a pole piece, and the specific preparation method comprises the following steps: adding 9g of active substance, 0.5g of conductive agent SP and 0.5g of binder LA133 into 200mL of deionized water, and uniformly stirring to prepare slurry; and coating the slurry on a copper foil current collector to obtain the corresponding pole piece. And then, the prepared pole piece is used as a negative pole, the lithium piece is used as a positive pole, the lithium piece and the electrolyte, and the diaphragm is assembled into the button cell in a glove box with the argon and water content lower than 0.1 ppm.
The performance of the button cell is tested by a blue light tester, and the test conditions are as follows: the charge and discharge were carried out at a rate of 0.1C, and the voltage range was (0.05-2) V, and the cycle was stopped after 3 weeks. The test results are shown in table 1 below:
electrochemical performance of button cell batteries corresponding to Table 1, examples 1-3 and comparative examples 1-2
| Specific capacity for first charge (mAh/g) | First efficiency (%) | |
| Example 1 | 1568.6 | 80.28 |
| Example 2 | 1564.8 | 80.16 |
| Example 3 | 1569.7 | 80.53 |
| Comparative example 1 | 1401.3 | 76.24 |
| Comparative example 2 | 1432.8 | 77.91 |
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The silicon-based composite negative electrode material is characterized by comprising a silicon-based core, an amorphous lithium fast ion conductor and a carbon coating layer, wherein the amorphous lithium fast ion conductor is coated on the outer layer of the silicon-based core, and the carbon coating layer is positioned on the outermost layer.
2. The silicon-based composite anode material as claimed in claim 1, wherein the amorphous lithium fast ion conductor is Li 2 O-B 2 O 3 -LiX system, X is selected from one of F, cl, br and I.
3. The silicon-based composite anode material as claimed in claim 1 or 2, wherein the amorphous lithium fast ion conductor is Li 2 O-B 2 O 3 -LiF。
4. The silicon-based composite anode material according to claim 1 or 2, wherein the silicon-based material as the inner core is selected from at least one of the elements silicon, silica and silicon dioxide.
5. The preparation method of the silicon-based composite anode material is characterized by comprising the following steps of: s1, coating an amorphous fast ion conductor on the surface of a silicon-based material by adopting a liquid phase method to obtain an intermediate 1; and S2, coating carbon on the surface of the intermediate 1 by using a chemical vapor deposition method.
6. The preparation method of the silicon-based composite anode material according to claim 5, wherein the liquid phase method of S1 specifically comprises: adding a silicon-based material into the amorphous fast ion conductor solution, and carrying out ultrasonic treatment for 0.5-2h; drying, grinding, and then treating for 7-10h at 500-600 ℃ under inert atmosphere to obtain the intermediate 1.
7. The method for preparing the silicon-based composite anode material according to claim 6, wherein the amorphous fast ion conductor solution is prepared by dissolving lithium hydroxide monohydrate, boric acid and lithium halide serving as raw materials in water.
8. The preparation method of the silicon-based composite anode material as claimed in claim 5 or 6, wherein the chemical vapor deposition method S2 is obtained by depositing acetylene as a carbon source at 800-1000 ℃ for 4-8 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4456177A3 (en) * | 2023-04-28 | 2025-05-21 | SK On Co., Ltd. | Anode active material for secondary battery, anode including the same, and secondary battery including the same |
| WO2025113373A1 (en) * | 2023-11-30 | 2025-06-05 | 瑞浦兰钧能源股份有限公司 | Silicon negative electrode material, preparation method therefor, and use thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025094A (en) * | 1994-11-23 | 2000-02-15 | Polyplus Battery Company, Inc. | Protective coatings for negative electrodes |
| JP2003077529A (en) * | 2001-09-03 | 2003-03-14 | Sanyo Electric Co Ltd | Lithium battery and lithium secondary battery |
| CN106299305A (en) * | 2016-09-29 | 2017-01-04 | 中国科学院新疆理化技术研究所 | A kind of fast-ionic conductor coating modification method of ternary cathode material of lithium ion battery |
| CN109728259A (en) * | 2017-10-30 | 2019-05-07 | 华为技术有限公司 | A kind of silicon-based composite negative electrode material and its preparation method and energy storage device |
| CN114005986A (en) * | 2021-10-26 | 2022-02-01 | 蜂巢能源科技有限公司 | A kind of modified ternary positive electrode material and its preparation method and application |
| WO2022062321A1 (en) * | 2020-09-27 | 2022-03-31 | 溧阳天目先导电池材料科技有限公司 | Silicon-based negative electrode composite material and lithium secondary battery |
| CN114497522A (en) * | 2022-04-01 | 2022-05-13 | 深圳索理德新材料科技有限公司 | Silica composite negative electrode material of lithium ion battery and preparation method of silica composite negative electrode material |
-
2022
- 2022-12-23 CN CN202211662728.1A patent/CN115986076A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025094A (en) * | 1994-11-23 | 2000-02-15 | Polyplus Battery Company, Inc. | Protective coatings for negative electrodes |
| JP2003077529A (en) * | 2001-09-03 | 2003-03-14 | Sanyo Electric Co Ltd | Lithium battery and lithium secondary battery |
| CN106299305A (en) * | 2016-09-29 | 2017-01-04 | 中国科学院新疆理化技术研究所 | A kind of fast-ionic conductor coating modification method of ternary cathode material of lithium ion battery |
| CN109728259A (en) * | 2017-10-30 | 2019-05-07 | 华为技术有限公司 | A kind of silicon-based composite negative electrode material and its preparation method and energy storage device |
| WO2022062321A1 (en) * | 2020-09-27 | 2022-03-31 | 溧阳天目先导电池材料科技有限公司 | Silicon-based negative electrode composite material and lithium secondary battery |
| CN114005986A (en) * | 2021-10-26 | 2022-02-01 | 蜂巢能源科技有限公司 | A kind of modified ternary positive electrode material and its preparation method and application |
| CN114497522A (en) * | 2022-04-01 | 2022-05-13 | 深圳索理德新材料科技有限公司 | Silica composite negative electrode material of lithium ion battery and preparation method of silica composite negative electrode material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4456177A3 (en) * | 2023-04-28 | 2025-05-21 | SK On Co., Ltd. | Anode active material for secondary battery, anode including the same, and secondary battery including the same |
| WO2025113373A1 (en) * | 2023-11-30 | 2025-06-05 | 瑞浦兰钧能源股份有限公司 | Silicon negative electrode material, preparation method therefor, and use thereof |
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