CN113258043A - Silicon-based negative electrode material and preparation method and application thereof - Google Patents
Silicon-based negative electrode material and preparation method and application thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000010703 silicon Substances 0.000 title claims abstract description 54
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 53
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 11
- 239000011257 shell material Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 24
- 229910052796 boron Inorganic materials 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000010405 anode material Substances 0.000 claims description 17
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910000676 Si alloy Inorganic materials 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 36
- 239000000463 material Substances 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 239000011258 core-shell material Substances 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 description 28
- 239000007789 gas Substances 0.000 description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 239000002131 composite material Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 7
- 230000002441 reversible effect Effects 0.000 description 7
- 238000000840 electrochemical analysis Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/386—Silicon or alloys based on silicon
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Abstract
The invention provides a silicon-based negative electrode material and a preparation method and application thereof. The silicon-based negative electrode material has a core-shell structure, namely a silicon core and a shell material coating the silicon core, wherein the shell material is C3B、C2B, C-B and the like have the boron-doped amorphous carbon with the graphite-like structure, so that the surface of the silicon core forms the graphite-like amorphous carbon structure from the original defect state, and the material has a lithium storage mechanism similar to that of graphite, and can effectively improve the first coulombic effect of the materialRate, discharge capacity, and cycle performance. In addition, the silicon-based negative electrode material is easy to obtain raw materials and low in cost.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a silicon-based negative electrode material as well as a preparation method and application thereof.
Background
The cathode material, which is one of four main materials of the lithium ion battery, accounts for 5% -20% of the cost of the battery cell, and is one of important raw materials of the lithium ion battery. The negative electrode materials commercialized at present are mainly artificial graphite and natural graphite. The preparation technologies of the two are quite mature, but the theoretical specific capacity is only 372mAh/g, so that the requirement of the current market for the high-specific-energy lithium ion battery is difficult to meet. Experimental research shows that silicon is the estimated material with the largest theoretical capacity at present, and lithium forms Li in silicon4.4When Si is used, the specific capacity can reach 4200mAh/g, which is far higher than the theoretical capacity of graphite, and the silicon has the advantages of low lithium intercalation potential and low cost, and is expected to replace graphite to become a new generation of lithium ion battery cathode material.
In the related technology, the developed and applied silicon-based negative electrode material is mainly a nano silicon-carbon negative electrode material and a silicon-oxygen negative electrode material, the conductivity of the silicon-carbon negative electrode material and the silicon-oxygen negative electrode material is poor and far lower than that of a graphite negative electrode material, and the capacity and the first efficiency of the material are low. The current modification of the silicon-based negative electrode material mainly reduces defects in a carbon coating mode and improves the conductivity of the material. The main methods for carbon coating are Chemical Vapor Deposition (CVD) and organic carbon source pyrolysis. Compared with an organic carbon source pyrolysis method, the silicon-based negative electrode material prepared by the CVD method has better cycling stability and higher reversible specific capacity. However, the performance improvement of the silicon-based anode material is limited by depositing a layer of amorphous carbon on the surface of the silicon-based anode material by a CVD method, and other approaches are still needed to improve the performance of the silicon-based anode material.
Therefore, it is necessary to develop new modification methods to improve the performance of silicon-based materials.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides a silicon-based negative electrode material which has a core-shell structure, namely a silicon core and a shell material coating the silicon core, wherein the shell material is C3B、C2B and C-B and the like have the same meanings asThe boron doped amorphous carbon with the graphite structure can effectively improve the conductivity, the capacity, the first charge and discharge and the cycle performance of the material.
The invention provides a silicon-based anode material, which comprises a silicon core and a shell material for coating the silicon core; the shell material comprises boron doped amorphous carbon; in the silicon-based negative electrode material, the content of boron is 0.1 wt% -10 wt%.
The silicon-based negative electrode material disclosed by the invention at least has the following beneficial effects:
the silicon-based negative electrode material has a core-shell structure, namely a silicon core and a shell material coating the silicon core, wherein the shell material is C3B、C2The boron-doped amorphous carbon with the graphite-like structure such as B, C-B and the like enables the surface of the silicon core to form the graphite-like amorphous carbon structure from the original defect state, so that the material has a lithium storage mechanism similar to that of graphite, and the first coulombic efficiency, the discharge capacity and the cycle performance of the material can be effectively improved.
The silicon-based negative electrode material has the advantages of easily available raw materials and low cost.
According to some embodiments of the invention, the content of boron in the silicon-based anode material is 0.5 wt% to 5 wt%.
The content of boron is preferably in the range of 0.5 wt% to 5 wt%, and should not be too high, excess boron may cause unreduced B on the surface of silicon core2O3Thereby affecting the conductivity of the material.
In the present invention, the carbon content is not directly limited. The carbon content is related to the gas flow rate, the deposition time and the deposition temperature, and the amount of the deposited carbon can be adjusted by controlling the gas flow rate and the deposition temperature time, so that the preferable gas flow rate and deposition temperature time range can be limited.
According to some embodiments of the invention, the silicon core is selected from at least one of a silicon protoxide, a nano-silicon, and a silicon alloy.
According to some embodiments of the invention, the silicon-based anode material has a particle size of 1 μm to 30 μm.
According to some embodiments of the invention, the silicon core has a particle size of 500nm to 20 μm.
According to some embodiments of the invention, the silicon core has a particle size of 2 μm to 8 μm.
The second aspect of the present invention provides a method for preparing the above silicon-based anode material, wherein the method comprises: and (3) uniformly mixing a boron source and the silicon core, and sintering in organic gas.
The method for preparing the silicon-based negative electrode material at least has the following beneficial effects:
the method for preparing the silicon-based negative electrode material has the advantages of simple process, low equipment requirement, mild conditions, no need of additional reagents because the boron source and the silicon core are mixed into a solid phase, and environmental protection.
The method for preparing the silicon-based anode material can complete the whole reaction in one step by sintering, and has simple operation and economic raw materials.
According to some embodiments of the invention, the boron source is selected from at least one of diboron trioxide and boric acid.
According to some embodiments of the invention, the boron source has a particle size of ≦ 30 μm.
According to some embodiments of the invention, the boron source has a particle size of 0.1 μm to 8 μm.
According to some embodiments of the invention, the organic gas is at least one of methane and acetylene.
According to some embodiments of the invention, the flow rate of the organic gas is 0.5L/min to 10L/min.
According to some embodiments of the invention, the flow rate of the organic gas is 3L/min to 6L/min.
According to some embodiments of the invention, the temperature of the sintering is 850 ℃ to 1100 ℃.
According to some embodiments of the invention, the temperature of the sintering is 900 ℃ to 1000 ℃.
According to some embodiments of the invention, the sintering time is 1h to 8 h.
According to some embodiments of the invention, the sintering time is between 2h and 5 h.
According to some embodiments of the invention, the sintering may be performed in a CVD furnace.
During sintering, under high temperature conditions, the boron source decomposes or melts to form B2O3Wrapping on the surface of silicon core, depositing an amorphous carbon coating layer by utilizing the reducibility of amorphous carbon, B2O3And reacting with a carbon layer to form a graphite-like structure on the surface of the silicon core to obtain the boron-doped amorphous carbon silicon-based negative electrode material with the graphite-like structure. In addition, a part B2O3Will diffuse to the carbon layer surface through the solid phase.
A third aspect of the invention provides an alkali metal battery comprising the silicon-based anode material described above.
According to some embodiments of the invention, the alkali metal battery is a sodium ion battery.
According to some embodiments of the invention, the alkali metal battery is a lithium ion battery.
Drawings
Fig. 1 is a scanning electron microscope microscopic morphology image of the silicon-based negative electrode material prepared in example 1.
Fig. 2 is a result of a performance test of half cells prepared in examples and comparative examples.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
This example prepares a 5 wt% boron doped, 4.3 wt% carbon coated silicon based anode material. The specific process is as follows:
adding 5g of diboron trioxide powder (with the median particle size D50 of 3 microns) and 100g of silicon monoxide (with the median particle size D50 of 3.03 microns) into a VC mixer, uniformly mixing, transferring into a CVD furnace, introducing acetylene gas, setting the gas flow rate to be 5L/min, heating to 950 ℃, preserving heat for 4h, naturally cooling, and then sieving with a 200-mesh sieve to obtain the 5 wt% boron-doped modified 4.3 wt% carbon-coated silicon-based negative electrode material.
The microstructure of the silicon-based negative electrode material prepared in the embodiment is shown in fig. 1, and it can be seen from fig. 1 that the surface of the silicon-based negative electrode material has an obvious coating layer structure.
Example 2
This example prepares a 1 wt% boron doped, 2.1 wt% carbon coated silicon based anode material. The specific process is as follows:
adding 1g of boric acid powder (with the median particle size D50 of 6 microns) and 100g of silicon monoxide (with the median particle size D50 of 3.03 microns) into a VC mixer, uniformly mixing, transferring into a CVD furnace, introducing acetylene gas, setting the gas flow rate to be 3L/min, heating to 1000 ℃, preserving heat for 2h, naturally cooling, and carrying out 200-mesh screening treatment to obtain the 1% boron-doped modified 2.1 wt% carbon-coated silicon-based negative electrode material.
Example 3
This example prepares a silicon-based negative electrode material doped with 10 wt% boron and coated with 10.9 wt% carbon. The specific process is as follows:
adding 10g of diboron trioxide powder (with the median particle size D50 of 3 microns) and 100g of silicon monoxide (with the median particle size D50 of 3.03 microns) into a VC mixer, uniformly mixing, transferring into a CVD furnace, introducing acetylene gas, setting the gas flow rate to be 10L/min, heating to 950 ℃, preserving heat for 4h, naturally cooling, and then sieving with a 200-mesh sieve to obtain the 10% boron-doped modified 10.9 wt% carbon-coated silicon-based negative electrode material.
Example 4
This example prepares a silicon-based negative electrode material doped with 15 wt% boron and coated with 3.9 wt% carbon. The specific process is as follows: taking 15g of diboron trioxide powder (with the median particle size D50 of 3 microns) and 100g of silicon monoxide (with the median particle size D50 of 3.03 microns), adding the mixture into a VC mixer, uniformly mixing, transferring the mixture into a CVD furnace, introducing acetylene gas, setting the gas flow rate to be 5L/min, heating to 950 ℃, preserving the heat for 4 hours, naturally cooling, and screening by using a 200-mesh sieve to obtain the 15 wt% boron-doped modified 3.9 wt% carbon-coated silicon-based negative electrode material.
Comparative example 1
The silicon-based negative electrode material of the present comparative example was a raw material of silica without any treatment, and had a median particle diameter of 3.03 μm.
Comparative example 2
This comparative example prepared a 4.6 wt% carbon coated silicon-based negative electrode material.
100g of silicon monoxide (the median particle size is 3.03 mu m) is taken and transferred into a CVD furnace, acetylene gas is introduced, the gas flow rate is set to be 5L/min, the temperature is raised to 950 ℃, the temperature is kept for 4h, and after natural cooling and 200-mesh screening treatment, the 4.6 percent carbon-coated silicon-based negative electrode material is obtained.
Performance testing
Physical property tests were performed on the silicon-based anode materials of examples 1 to 3, and comparative examples 1 and 2, and the median particle diameter D50, the specific surface area and the carbon content were measured, the carbon content was measured using a carbon-sulfur analyzer, and the powder conductivity was measured using a four-probe method, and the results are shown in table 1.
Wherein, the charge and discharge test process is as follows: products prepared in examples 1 to 3 and comparative examples 1 and 2 are respectively uniformly mixed with SP, CMC and SBR according to the proportion of 90:5:2:3, then the mixture is pulped, coated and rolled, a negative pole piece is formed on copper foil, then a lithium piece is used as a counter electrode, a button cell is manufactured, and a charging and discharging test is carried out. The test results are shown in fig. 1 and table 1.
In addition, the negative electrode materials and the graphite material are mixed according to the proportion of 10:90 to be used as a negative electrode, lithium cobaltate is used as a positive electrode, and a soft package full battery test is carried out.
TABLE 1 test results
As can be seen from table 1 and fig. 1:
the lithium ion battery negative electrode material of example 1 had a medium particle diameter of 4.88 μm and a specific surface area of 2.21m2Per g, carbon content 4.3%, powder conductivity 8.6X 106μS/cm。
Electrochemical tests show that the reversible capacity of the composite material reaches 1614.8mAh/g, the first coulombic efficiency is 76.12%, the composite material has high capacity and first coulombic efficiency, the capacity retention rate of the full battery is 82.59% after 800 cycles, and the composite material has good cycle stability.
The lithium ion battery negative electrode material of example 2 had a medium particle size of 4.37 μm and a specific surface area of 2.71m2Per g, carbon content 2.1%, powder conductivity 1.8X 106μS/cm。
Electrochemical tests show that the reversible capacity of the composite material reaches 1556.4mAh/g, the first coulombic efficiency is 73.16%, the capacity and the first coulombic efficiency are high, and the capacity retention rate of a full battery is 73.25% after the full battery is cycled for 800 weeks.
The lithium ion battery negative electrode material of example 3 had a medium particle diameter of 8.91 μm and a specific surface area of 1.83m2Per g, carbon content 10.9%, powder conductivity 3.5X 106μS/cm。
Electrochemical tests show that the reversible capacity of the composite material reaches 1530.5mAh/g, the first coulombic efficiency is 73.81%, the composite material has higher capacity and first coulombic efficiency, and the capacity retention rate of 75.31% after the full battery is cycled for 800 weeks.
The lithium ion battery negative electrode material of example 4 was added with an excess of boron, and the test surface material had a median particle size of 7.12 μm and a specific surface area of 2.04m2Per g, carbon content 3.9%, powder conductivity 2.9X 104μS/cm。
Electrochemical tests show that the reversible capacity of the composite material reaches 1135.2mAh/g, the first coulombic efficiency is 54.25%, the composite material has higher capacity and first coulombic efficiency, and the capacity retention rate of 42.97% after the full battery is cycled for 800 weeks.
The lithium ion battery negative electrode material of comparative example 1 had a medium particle diameter of 3.07 μm and a specific surface area of 3.95m2Per g, powder conductivity 8.6X 106Mu S/cm, and an electrochemical test shows that the reversible capacity of the composite material is 536.5mAh/g, the first coulombic efficiency is 24.02%, the capacity and the first coulombic efficiency are both low, and the capacity retention rate of the full-battery cycle at 800 weeks is 23.50%.
The lithium ion battery negative electrode material of comparative example 2 had a medium particle size of 4.92 μm and a specific surface area of 2.63m2Per g, carbon content 4.6%Powder conductivity of 8.6X 106μS/cm。
Electrochemical tests show that the reversible capacity of the composite material reaches 1425.1mAh/g, the first coulombic efficiency is 73.04%, the composite material has higher capacity and first coulombic efficiency, the capacity retention rate of the full battery is 66.94% after the full battery is cycled for 800 weeks, and the capacity, the first coulombic efficiency and the cycling stability of the composite material are different from those of the composite material which is doped with boron and forms a graphite-like structure carbon coating.
As shown in fig. 2, it can be seen from comparison of performance test results of the lithium ion battery negative electrode materials prepared in examples 1 to 4 and the lithium ion battery negative electrode materials prepared in comparative examples 1 and 2 that the material prepared in example 1 is subjected to boron doping and carbon layer deposition to form a graphite-like structure, the conductivity of the material is significantly improved, the specific surface area of the lithium ion battery negative electrode material is significantly reduced, surface defects are reduced, the first coulombic efficiency and the first cycle discharge capacity are both greatly improved, and the cycle stability is also significantly improved. The invention also discloses a preparation method of the silicon-based anode material. However, the test results of example 4 show that if an excessive amount of boron source is incorporated, the unreacted boron trioxide can adversely affect the conductivity of the material, which can negatively affect the first coulombic efficiency and the first cycle discharge capacity and cycle stability.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (10)
1. The silicon-based negative electrode material is characterized by comprising a silicon core and a shell material for coating the silicon core; the shell material comprises boron doped amorphous carbon; in the silicon-based negative electrode material, the content of boron is 0.1 wt% -10 wt%.
2. The silicon-based anode material of claim 1, wherein the silicon core is selected from at least one of a silicon protoxide, a nano-silicon, and a silicon alloy.
3. The silicon-based anode material according to claim 1, wherein the silicon-based anode material has a particle size of 1 μm to 30 μm.
4. A method for preparing a silicon-based anode material according to any one of claims 1 to 3, characterized in that the method comprises: and (3) uniformly mixing a boron source and the silicon core, and sintering in organic gas.
5. The method of claim 4, wherein the boron source is selected from at least one of diboron trioxide and boric acid.
6. The method of claim 4, wherein the organic gas is at least one of methane and acetylene.
7. The method according to claim 4, wherein the flow rate of the organic gas is 0.5L/min to 10L/min.
8. The method of claim 4, wherein the sintering temperature is 850 ℃ to 1100 ℃.
9. The method of claim 4, wherein the sintering time is 1 to 8 hours.
10. Alkali metal battery, characterized in that it comprises a silicon-based negative electrode material according to any of claims 1 to 3.
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