CN114122372A - Low-expansion silicon-carbon negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Low-expansion silicon-carbon negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 36
- 239000003575 carbonaceous material Substances 0.000 claims description 27
- 239000007833 carbon precursor Substances 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims description 13
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 10
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
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- 238000000576 coating method Methods 0.000 claims description 8
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- 230000003213 activating effect Effects 0.000 claims description 7
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- 238000006243 chemical reaction Methods 0.000 claims description 6
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- 238000000034 method Methods 0.000 abstract description 8
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 3
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- 238000007599 discharging Methods 0.000 description 3
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
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- 238000002224 dissection Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011239 graphite-silicon composite material Substances 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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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Abstract
The invention discloses a low-expansion silicon-carbon negative electrode material for a lithium ion battery and a preparation method thereof. According to the invention, a three-dimensional network carbon structure is formed by using the porous carbon of the middle layer, so that the silicon expansion of the inner core in the charge and discharge process is restrained; on the other hand, the porous carbon is connected with the catalyst to improve the conductivity and tap density of the material; the boron-doped graphene on the outer layer is utilized to improve the lithium storage active points of the material and the electronic conductivity of the material, improve the liquid retention performance of the material, and improve the power and the cycle performance of the material.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery materials, and particularly relates to a low-expansion silicon-carbon negative electrode material for a lithium ion battery and a preparation method thereof.
Background
The silicon-carbon cathode material on the market at present is applied to the lithium ion battery with high specific energy density due to the advantages of high specific energy density, wide material source and the like, but the material has large expansion and causes the cycle performance deviation. The expansion is mainly caused by that the amorphous carbon does not reserve enough space for the expansion of lithium ions in the charging and discharging process, so that the expansion is large or the mechanical strength of a coating layer is insufficient in the expansion process, so that the structural collapse influences the cycle performance of the coating layer. In the prior art, expansion is mainly reduced by compounding with graphite, for example, patent (CN 104319367 a) provides a preparation method of a graphite-silicon composite negative electrode material, which mainly comprises the following steps: mixing simple substance silicon particles with graphite and then carrying out ball milling; after obtaining a sample, carrying out hydroxylation treatment on silicon; and (3) treating the product by using a silane coupling agent to obtain the silicon/graphite composite negative electrode material. But because of abundant functional groups on the surface of the material, the SEI film can be stabilized, but the expansion reduction space is limited, and meanwhile, the amorphous carbon on the outer layer has poor structural stability and poor coating uniformity, so that the expansion reduction amplitude is limited, and the cycle and the multiplying power of the SEI film are influenced.
Disclosure of Invention
Aiming at the problem of high expansion rate of the silicon-carbon material, the invention coats the double-shell structure of the porous carbon and the phosphorus-doped graphene sponge on the surface of the nano silicon by a liquid phase method, thereby reducing the expansion of the material.
The low-expansion silicon-carbon negative electrode material for the lithium ion battery is characterized by being of a core-shell structure, the inner core is made of nano silicon, the middle layer is made of a porous carbon material, and the outermost layer is made of boron-doped graphene sponge, wherein the mass ratio of the middle layer is (5-30) wt%, and the mass ratio of the outer layer is (1-10) wt%.
The preparation method of the low-expansion silicon-carbon negative electrode material for the lithium ion battery is characterized by comprising the following steps of:
1) preparation of porous carbon material:
weighing asphalt and potassium hydroxide, adding the asphalt and the potassium hydroxide into deionized water, performing ultrasonic dispersion uniformly, performing vacuum drying, performing vacuum filtration, placing the filtered mixture in a tubular furnace, activating at (150-300) DEG C for (1-6) h under the protection of nitrogen, then heating to (600-1000) DEG C for (1-6) h, washing the product to be neutral, filtering and drying to obtain the porous carbon material.
2) Silicon-carbon precursor material:
then dissolving porous carbon in an organic solution, after uniform dispersion, adding a nano silicon material into the organic solution, performing ultrasonic dispersion uniformly, adding an oxidant hydrogen peroxide, transferring the mixture into a high-pressure reaction kettle, performing hydrothermal reaction (at the temperature of 100-200 ℃, for 1-6 hours, and under the pressure of 1-5 Mpa), filtering, and performing vacuum drying to obtain a silicon-carbon precursor material;
3) coating a silicon carbon material with the boron-doped graphene sponge:
weighing a graphene oxide solution, pouring the graphene oxide dispersion liquid into a spray gun, spraying the dispersion liquid onto a heated glass substrate by using the spray gun (the temperature is 50-100 ℃), putting the obtained graphene oxide sponge into a container containing hydrazine hydrate and boron chloride, sealing, heating to 95 ℃, and reducing and doping the graphene oxide sponge by using hydrazine steam to finally obtain the graphene sponge; and then preparing (1-5) wt% of graphene sponge solution, adding the silicon-carbon precursor into the solution, uniformly stirring, spray-drying, and carbonizing to obtain the boron-doped graphene sponge-coated silicon-carbon material.
The mass ratio of the graphene sponge to the silicon-carbon precursor is (1-5) to 100;
in the step 1), the mass ratio of asphalt, potassium hydroxide and deionized water is 100: 10-30: 500-1000;
in the step 2), the mass ratio of porous carbon, nano silicon and hydrogen peroxide is (5-15) to 100 to (0.5-2);
step 2) the mass ratio of hydrazine hydrate to boron chloride, hydrazine hydrate; 100 parts of boron chloride to 1-5 parts of boron chloride;
has the advantages that:
1) by coating the core nano-silicon material with the porous carbon material, on one hand, the porous carbon is utilized to reduce the expansion of silicon in the charging and discharging process, and the porous structure of the porous carbon is utilized to improve the liquid absorption performance of the material. 2) The surface of the outermost layer is coated with the graphene sponge doped with boron by a liquid phase method, and the electronic conductivity of the material is improved by doping of boron and the high electronic conductivity of graphene, so that the impedance of the material is reduced and the expansion of the material is reduced.
Drawings
Fig. 1 is an SEM image of the phosphorus-doped graphene-coated silicon carbon material prepared in example 1;
Detailed Description
Example 1
1) Preparation of porous carbon material:
weighing 100g of asphalt and 20g of potassium hydroxide, adding the asphalt and the potassium hydroxide into 900ml of deionized water, performing ultrasonic dispersion uniformly, performing vacuum drying at 80 ℃ for 24h, performing vacuum filtration, placing the filtered mixture in a tube furnace, activating at 200 ℃ for 3h under the protection of nitrogen, then heating to 800 ℃ for activation for 3h, washing the product to be neutral, filtering and drying to obtain the porous carbon material.
2) Silicon-carbon precursor material:
then dissolving 10g of porous carbon in 500ml of carbon tetrachloride organic solution, after uniform dispersion, adding 100g of nano silicon material into the solution, after uniform ultrasonic dispersion, adding 1g of oxidant hydrogen peroxide, then transferring the mixture into a high-pressure reaction kettle, and obtaining a silicon-carbon precursor material through hydrothermal reaction (the temperature is 150 ℃, the time is 3h, and the pressure is 3Mpa), filtering and vacuum drying;
3) coating a silicon carbon material with the boron-doped graphene sponge:
weighing 500ml of 0.5 wt% graphene oxide solution, pouring the graphene oxide dispersion liquid into a spray gun, spraying the dispersion liquid onto a heated glass substrate by using the spray gun (the temperature is 80 ℃), putting the obtained graphene oxide sponge into a container containing 100g of hydrazine hydrate and 3g of boron chloride, sealing, heating to 95 ℃, and reducing and doping the graphene oxide sponge with hydrazine vapor to finally obtain the graphene sponge; and then adding 100ml of 3 wt% graphene sponge solution and 100g of silicon-carbon precursor into the solution, uniformly stirring, spray-drying and carbonizing to obtain the boron-doped graphene sponge-coated silicon-carbon material.
Example 2
1) Preparation of porous carbon material:
weighing 100g of asphalt and 10g of potassium hydroxide, adding the asphalt and the potassium hydroxide into 500ml of deionized water, performing ultrasonic dispersion uniformly, performing vacuum drying at 80 ℃ for 24h, performing vacuum filtration, placing the filtered mixture in a tube furnace, activating at 150 ℃ for 6h under the protection of nitrogen, then heating to 600 ℃ for activating for 6h, washing the product to be neutral, and performing filtration and drying to obtain the porous carbon material.
2) Silicon-carbon precursor material:
then dissolving 5g of porous carbon in 500ml of N-methyl pyrrolidone organic solution, after uniform dispersion, adding 100g of nano silicon material into the solution, after uniform ultrasonic dispersion, adding 0.5g of oxidant hydrogen peroxide, then transferring the mixture into a high-pressure reaction kettle, and obtaining a silicon-carbon precursor material through hydrothermal reaction (the temperature is 100 ℃, the time is 6 hours, and the pressure is 1Mpa), filtering and vacuum drying;
3) coating a silicon carbon material with the boron-doped graphene sponge:
weighing 500ml of 1 wt% graphene oxide solution, pouring the graphene oxide dispersion liquid into a spray gun, spraying the dispersion liquid onto a heated glass substrate by using the spray gun (the temperature is 50 ℃), putting the obtained graphene oxide sponge into a container containing 100g of hydrazine hydrate and 1g of boron chloride, sealing, heating to 95 ℃, and reducing and doping the graphene oxide sponge with hydrazine vapor to finally obtain the graphene sponge; and then preparing 100ml of 1 wt% graphene sponge solution, adding 100g of silicon-carbon precursor into the solution, uniformly stirring, spray-drying, and carbonizing to obtain the boron-doped graphene sponge-coated silicon-carbon material.
Example 3
1) Preparation of porous carbon material:
weighing 100g of asphalt and 30g of potassium hydroxide, adding the asphalt and the potassium hydroxide into 1000ml of deionized water, performing ultrasonic dispersion uniformly, performing vacuum drying at 80 ℃ for 24h, performing vacuum filtration, placing the filtered mixture in a tube furnace, activating at 300 ℃ for 1h under the protection of nitrogen, then heating to 1000 ℃ for activation for 1h, washing the product to be neutral, and performing filtration and drying to obtain the porous carbon material.
2) Silicon-carbon precursor material:
then dissolving 15g of porous carbon in 500ml of tetrahydrofuran organic solution, after uniform dispersion, adding 100g of nano silicon material into the solution, after uniform ultrasonic dispersion, adding 2g of oxidant hydrogen peroxide, then transferring the mixture into a high-pressure reaction kettle, and obtaining a silicon-carbon precursor material through hydrothermal reaction (at 200 ℃, for 1h and under the pressure of 5Mpa), filtering and vacuum drying;
3) coating a silicon carbon material with the boron-doped graphene sponge:
weighing 500ml of 0.1 wt% graphene oxide solution, pouring the graphene oxide dispersion liquid into a spray gun, spraying the dispersion liquid onto a heated glass substrate by using the spray gun (the temperature is 100 ℃), putting the obtained graphene oxide sponge into a container containing 100g of hydrazine hydrate and 5g of boron chloride, sealing, heating to 95 ℃, and reducing and doping the graphene oxide sponge with hydrazine vapor to finally obtain the graphene sponge; and then preparing 100ml of 5 wt% graphene sponge solution, adding 100g of silicon-carbon precursor into the solution, uniformly stirring, spray-drying, and carbonizing to obtain the boron-doped graphene sponge-coated silicon-carbon material.
Comparative example
Dissolving 5g of phenolic resin in 500ml of N-methyl pyrrolidone organic solution, after uniform dispersion, adding 100g of nano silicon material into the solution, performing ultrasonic dispersion, adding 0.5g of oxidant hydrogen peroxide, transferring the mixture into a high-pressure reaction kettle, performing hydrothermal reaction (the temperature is 100 ℃, the time is 6 hours, and the pressure is 1Mpa), filtering, and performing vacuum drying to obtain a silicon-carbon precursor material; weighing 500ml of 1 wt% graphene oxide solution, pouring the graphene oxide dispersion liquid into a spray gun, spraying the dispersion liquid onto a heated glass substrate by using the spray gun (the temperature is 50 ℃), and obtaining graphene oxide sponge; and then preparing 100ml of 1 wt% graphene sponge solution, adding 100g of silicon-carbon precursor into the solution, uniformly stirring, and performing spray drying to obtain the graphene sponge-coated silicon-carbon material.
Test example 1
SEM tests were performed on the silicon carbon composite of example 1. The test results are shown in fig. 1. As can be seen from FIG. 1, the particle size of the silicon-carbon composite material is 5-15 μm, and a small amount of graphene material is incorporated on the surface.
Test example 2
The physicochemical properties (powder conductivity, tap density, etc.) of the silicon-carbon composite materials of examples 1-3 and the silicon-carbon composite material of the comparative example were tested according to the method of the national standard GBT-2433and 2009 graphite-type cathode material for lithium ion batteries, and the test results are shown in table 1.
TABLE 1 comparison of the physico-chemical properties of the examples and of the comparative examples
| Sample (I) | Tap density (g/cm3) | Powder conductivity (S/cm) | Specific surface area (m2/g) |
| Example 1 | 1.11 | 14.5 | 12.1 |
| Example 2 | 1.04 | 13.3 | 11.8 |
| Example 3 | 1.02 | 11.4 | 11.5 |
| Comparative example | 0.91 | 5.4 | 7.2 |
As can be seen from Table 1: compared with the comparative example, the powder conductivity of the silicon-carbon composite material is obviously improved because the sponge graphene is doped in the example material, the electronic conductivity of the material is improved, and meanwhile, the porous carbon material has high specific surface area and improves the specific surface area of the whole material.
Test example 3
The silicon-carbon composite materials of the embodiments 1-3 and the silicon-carbon composite materials in the comparative examples are respectively used as active materials to prepare the 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 220mL of deionized water, and uniformly stirring to obtain slurry; and coating the slurry on a copper foil current collector to obtain the copper foil current collector.
The pole piece using the silicon-carbon composite material of example 1 as an active material is labeled a, the pole piece using the silicon-carbon composite material of example 2 as an active material is labeled B, the pole piece using the silicon-carbon composite material of example 3 as an active material is labeled C, and the pole piece using the silicon-carbon composite material of comparative example as an active material is labeled D.
And then, the prepared pole piece is used as a positive electrode, and the pole piece, a lithium piece, electrolyte and a diaphragm are assembled into a button cell in a glove box with the oxygen and water contents lower than 0.1 ppm. Wherein the membrane is celegard 2400; the electrolyte is a solution of LiPF6, LiPF6Is 1.2mol/L, and the solvent is a mixed solution of Ethylene Carbonate (EC) and diethyl carbonate (DMC) (weight ratio is 1: 1). The button cells are labeled A-1, B-1, C-1, and D-1, respectively. And then testing the performance of the button cell by adopting a blue light tester under the following test conditions: and (3) carrying out charge and discharge at a multiplying power of 0.1C, wherein the voltage range is 0.05-2V, the cycle is stopped after 3 weeks, and then the full-electricity expansion of the negative pole piece is tested, and the test results are shown in table 2.
TABLE 2 electrochemical Performance test results
| Button cell | First discharge capacity (mAh/g) | First time efficiency | Full electric expansion |
| A-1 | 1880 | 87.9％ | 65.5％ |
| B-1 | 1740 | 87.3％ | 67.4％ |
| C-1 | 1720 | 87.1％ | 70.9％ |
| D-1 | 1520 | 83.5％ | 110.4％ |
As can be seen from Table 2, compared with the comparative example, the first efficiency of the silicon-carbon composite material is obviously improved, the specific capacity of the silicon-carbon composite material and the boron-doped material is improved, and the full-electricity expansion of the material is reduced because the inner core contains a porous carbon structure.
Test example 4
The silicon-carbon composite materials of examples 1-3 and comparative example, which were doped with 90% artificial graphite, were used as negative electrode materials, and a 5Ah pouch cell was assembled with a positive electrode ternary material (LiNi1/3Co1/3Mn1/3O2), an electrolyte, and a separator. Wherein the diaphragm is celegard 2400, and the electrolyte is LiPF6Solution (solvent is mixed solution of EC and DEC with volume ratio of 1:1, LiPF6The concentration of (1.3 mol/L). And marking the prepared soft package batteries as A-2, B-2, C-2 and D-2 respectively.
The following performance tests were performed on the pouch cells:
(1) the thickness D1 of the negative pole piece of the soft package battery A-2-D-2 after constant volume is dissected and tested, then the soft package battery is fully charged after each soft package battery is circulated for 100 times (1C/1C @25 +/-3 ℃ @2.5-4.2V), then the thickness D2 of the negative pole piece after the cycle of dissection and testing is carried out again, then the expansion rate (the expansion rate is) is calculated, and the test result is shown in table 3.
TABLE 3 negative pole piece expansion ratio test results
As can be seen from table 3, the expansion rate of the negative electrode plate of the soft-package lithium ion battery using the silicon-carbon composite material of the present invention is significantly lower than that of the comparative example. The reason is that the silicon-carbon composite material contains porous carbon, so that the expansion of a pole piece caused by lithium intercalation is reduced in the charging and discharging processes.
(2) And (3) carrying out cycle performance test and rate test on the soft package batteries A-2-D-2 under the following test conditions: the charge-discharge voltage range is 2.5-4.2V, the temperature is 25 +/-3.0 ℃, and the charge-discharge multiplying power is 0.5C/1.0C. And (3) rate testing: the test results are shown in Table 4.
TABLE 4 results of the cycle performance test
As can be seen from table 4, the cycle performance of the soft-package lithium ion battery prepared by using the silicon-carbon composite material of the present invention is superior to that of the comparative example in each stage of the cycle, because the porous carbon in the silicon-carbon composite material of the present invention is coated on the surface of the nano-silicon to reduce the expansion, and the amorphous carbon of the outer shell has the characteristic of stable structure to improve the cycle performance of the material.
Claims (5)
1. The low-expansion silicon-carbon negative electrode material for the lithium ion battery is characterized by being of a core-shell structure, the inner core is made of nano silicon, the middle layer is made of a porous carbon material, and the outermost layer is made of boron-doped graphene sponge, wherein the mass ratio of the middle layer is (5-30) wt%, and the mass ratio of the outer layer is (1-10) wt%.
2. The preparation method of the low-expansion silicon-carbon negative electrode material for the lithium ion battery according to claim 1, characterized by comprising the following steps:
1) preparation of porous carbon material:
weighing asphalt and potassium hydroxide, adding the asphalt and the potassium hydroxide into deionized water, performing ultrasonic dispersion uniformly, performing vacuum drying, performing vacuum filtration, putting a filtered mixture into a tubular furnace, activating for 1-6 h at (150-300) DEG C under the protection of nitrogen, then heating to (600-1000) DEG C for activating for 1-6 h, washing a product to be neutral, filtering and drying to obtain a porous carbon material;
2) silicon-carbon precursor material:
then dissolving porous carbon in an organic solution, after uniform dispersion, adding a nano silicon material into the organic solution, performing ultrasonic dispersion uniformly, adding an oxidant hydrogen peroxide, transferring the mixture into a high-pressure reaction kettle, performing hydrothermal reaction (at the temperature of 100-200 ℃, for 1-6 hours, and under the pressure of 1-5 Mpa), filtering, and performing vacuum drying to obtain a silicon-carbon precursor material;
3) coating a silicon carbon material with the boron-doped graphene sponge:
weighing a graphene oxide solution, pouring the graphene oxide dispersion liquid into a spray gun, spraying the dispersion liquid onto a heated glass substrate by using the spray gun (the temperature is 50-100 ℃), putting the obtained graphene oxide sponge into a container containing hydrazine hydrate and boron chloride, sealing, heating to 95 ℃, and reducing and doping the graphene oxide sponge by using hydrazine steam to finally obtain the graphene sponge; preparing (1-5) wt% of graphene sponge solution, adding a silicon-carbon precursor into the solution, uniformly stirring, spray-drying, and carbonizing to obtain a boron-doped graphene sponge-coated silicon-carbon material;
the mass ratio of the graphene sponge to the silicon-carbon precursor is (1-5): 100.
3. the preparation method of the low-expansion silicon-carbon negative electrode material for the lithium ion battery according to claim 2, wherein the mass ratio of asphalt, potassium hydroxide: 100 parts of deionized water: (10-30): (500-1000).
4. The preparation method of the low-expansion silicon-carbon negative electrode material for the lithium ion battery according to claim 2, wherein in the step 2), the mass ratio of porous carbon: nano silicon: hydrogen peroxide (5-15): 100: (0.5-2).
5. The preparation method of the low-expansion silicon-carbon negative electrode material for the lithium ion battery according to claim 2, wherein in the step 2), the mass ratio of hydrazine hydrate to boron chloride is hydrazine hydrate; boron chloride 100: (1-5).
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