CN113113574B - Preparation method of graphene modified silicon-carbon negative electrode material - Google Patents
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Abstract
The invention relates to a preparation method of a graphene modified silicon-carbon negative electrode material, which comprises the following steps: (1) adding a silicon-containing material into a cross-linking agent aqueous solution, and uniformly stirring to obtain a solution A; (2) adding the carbon material into another cross-linking agent aqueous solution, and uniformly stirring to obtain a solution B; (3) adding the graphene oxide aqueous solution into the solution A, and uniformly stirring to obtain a modified silicon-containing material/graphene oxide mixed solution; (4) adding the solution B into the modified silicon-containing material/graphene oxide mixed solution, and uniformly stirring to obtain a solution C; (5) and drying the solution C, and calcining at high temperature under the protection of inert gas to obtain a target product. Compared with the prior art, in the electrochemical performance of the graphene modified silicon-carbon composite material prepared by the invention, compared with the composite material without the cross-linking agent or other cross-linking agents, the capacity retention rate after the first effect and the circulation are improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and relates to a preparation method of a graphene modified silicon-carbon cathode material.
Background
The existing technologies for preparing the lithium ion battery cathode material are many, wherein the technology for modifying the silicon-carbon cathode material by the graphene is as follows:
in chinese patent CN109742363A and the like, graphene oxide is dispersed in a solvent (water or an organic solvent), SiOx particles are dispersed in an organic solvent, and then a graphene oxide solution is added to the SiOx solution for compounding, so as to obtain a graphene-coated SiOx composite material. In addition, in chinese patent CN109065878A, after graphene is modified by a surfactant, the obtained modified graphene and graphite powder are subjected to liquid phase mixing or solid phase mixing in a solution, so as to obtain a graphene/graphite composite material.
Chinese patent CN110165211A utilizes a surfactant to modify graphene, mixes the obtained modified graphene with SiOx powder in a solution to obtain a graphene/SiOx mixed solution, and then mixes the graphene/SiOx mixed solution with a graphite organic mixed solution to obtain a graphene-modified silicon-carbon negative electrode material.
In chinese patent CN108735990A, graphite powder and SiOx powder are added into (oxidized) graphene solution, and then a dispersant is added to obtain a graphene-coated silicon-carbon composite material.
In the chinese patent CN104752696A, graphene is dispersed in a solvent, silicon powder is dispersed in an organic solvent, and silane coupling agent is used to modify silicon powder, the obtained modified silicon powder is mixed with graphene solution, and graphite powder is added into the solution to perform liquid phase mixing, so as to obtain the graphene/silicon/graphite composite material.
There are other techniques, etc. The prior art has the following defects: (1) a dispersant and organic solvent system are mostly adopted, so that the cost is high and the environmental pollution is large; (2) in the silicon/graphite composite negative electrode material, graphite is not effectively modified, so that the electrochemical performance of the composite material is not ideal, and the like.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of a graphene modified silicon-carbon negative electrode material.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a graphene modified silicon-carbon negative electrode material comprises the following steps:
(1) taking a silicon-containing material (marked as SiO)x，0≤x<2) Adding the modified silicon-containing material into a cross-linking agent aqueous solution, and uniformly stirring to obtain a modified silicon-containing material aqueous solution marked as solution A;
(2) adding the carbon material into another cross-linking agent aqueous solution, and uniformly stirring to obtain a modified carbon material aqueous solution, which is marked as solution B;
(3) adding the graphene oxide aqueous solution into the solution A, and uniformly stirring to obtain a modified silicon-containing material/graphene oxide mixed solution;
(4) adding the solution B into the modified silicon-containing material/graphene oxide mixed solution, and uniformly stirring to obtain a modified silicon-containing material/graphene oxide/modified carbon material mixed solution, which is marked as solution C;
(5) and drying the solution C, and calcining at high temperature under the protection of inert gas to obtain a target product.
Further, in the step (1), the silicon-containing material is silicon powder or silicon oxide, and the particle size of the silicon-containing material is 0.01-5 μm.
Furthermore, the cross-linking agent aqueous solution is prepared by mixing hydrophilic silicone oil and water, wherein the viscosity range of the hydrophilic silicone oil is 50-2000 Pa & s.
Further, in the step (1), the addition amount of the silicon-containing material and the cross-linking agent aqueous solution satisfies the following condition: the mass ratio of the Si element to the cross-linking agent is 1: (0.1-1).
Further, in the step (2), the addition amount of the carbon material and the crosslinking agent aqueous solution satisfies: the mass ratio of the carbon material to the cross-linking agent is 1: (0.08-1).
Further, in the step (2), the carbon material is natural graphite, artificial graphite or mesocarbon microbeads, and the particle size of the carbon material is 0.1-20 μm.
Further, in the step (3), the concentration of the graphene oxide aqueous solution is 0.1-10mg/mL, and the addition amount of the graphene oxide aqueous solution and the solution A satisfies the following condition: the mass ratio of the silicon-containing material to the graphene oxide is 1: (0.03-0.8).
Further, in the step (4), the addition amounts of the solution B and the modified silicon-containing material/graphene oxide mixed solution satisfy: the mass ratio of the carbon material to the graphene oxide is 1: (0.01-0.5).
Further, in the step (5), the process conditions of the high-temperature calcination are as follows: calcining at 500-1500 ℃ for 2-6 h.
Further, in the step (5), the inert gas is nitrogen or argon.
Hydrophilic silicone oil is adopted as SiOxModifying the carbon material with a modifier and a cross-linking agent step by step and then mixing the modified carbon material with a liquid phase to obtain SiOxAnd better bonding between the carbon material particles and graphene oxide. First, modified SiOxThe particles are more easily coated or adsorbed on the surface by oxidized graphene;secondly, the modified carbon material particles are further oxidized with graphene and SiOxThe particles are coated. Due to the existence of the hydrophilic silicone oil, the acting force between particles and between the graphene oxide and the particles is increased.
Therefore, compared with the prior art, the invention has the following advantages:
(1) hydrophilic silicone oil is adopted as a powder cross-linking agent and a modifier, and liquid phase mixing is carried out after step modification, so that SiOxAnd better bonding between the carbon material particles and the graphene oxide;
(2) graphene oxide modified SiOxThe silicon material and the graphene oxide are further coated by the modified carbon material, so that the problem of particle expansion of the silicon material in the charging and discharging processes can be more effectively inhibited, and the reduced graphene has higher conductivity and can improve the conductivity and electrochemical stability of the composite material;
(3) the process is simple, water is used as a solvent, and the method is green and pollution-free.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 shows 1M LiPF as an electrode sheet prepared from the silicon-carbon anode materials obtained in example 4 and comparative example 16(DMC: EC 1: 1 vol%) as an electrolyte and a polypropylene film as a separator, and the charging and discharging curve of the button lithium ion battery is formed at a current density of 0.5C.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following embodiments, the hydrophilic silicone oil used is an ultrafine particle non/weak cationic amino silicone softener, the chemical components of which are compounded by modified amino silicone oil and a small amount of penetrant, and the viscosity range is as follows: 50-2000 Pa s, which is a conventional commercial product.
The rest of the raw material products (such as mesophase carbon microspheres and the like) or processing techniques which are not specifically described indicate that the raw material products are conventional commercial products or conventional techniques in the field.
Example 1:
a graphene modified silicon-carbon negative electrode composite material is prepared by the following steps as shown in figure 1:
(1) dispersing graphene oxide in deionized water, and uniformly dispersing the graphene oxide in a high-pressure homogenizer to obtain 0.5mg/mL graphene oxide slurry;
(2) adding 10mL of hydrophilic silicone oil with the viscosity of 200 Pa.s into 200mL of water to prepare an aqueous solution containing the hydrophilic silicone oil, and averagely dividing the aqueous solution into two parts, namely A and B; adding 50nm Si powder into the part A, and uniformly dispersing to obtain a hydrophilic silicone oil modified Si aqueous solution, and recording the hydrophilic silicone oil modified Si aqueous solution as an A solution; adding 2 mu m of natural graphite into the part B, and uniformly dispersing to obtain a hydrophilic silicone oil modified natural graphite aqueous solution, which is recorded as a solution B;
(3) adding the graphene oxide aqueous solution in the step (1) into the solution A in the step (2), and uniformly dispersing to obtain a modified Si/graphene oxide mixed solution;
(4) adding the solution B in the step (2) into the solution B in the step (3), and uniformly dispersing to obtain a modified Si/graphene oxide/modified graphite mixed solution;
(5) and (4) carrying out suction filtration on the solution obtained in the step (4), drying, and calcining at 900 ℃ for 3h under the protection of nitrogen to finally obtain the graphene modified silicon-carbon composite material.
And (3) detecting data: in the negative electrode tab, Si: graphene: the mass ratio of the natural graphite is 36: 9: 55. under the condition that the current density is 0.5C (1C is 1500mA/g), the first specific capacity is 1440mAh/g, the first efficiency reaches 92%, and after 100 cycles, the capacity can be kept at 92%, so that the high-efficiency lithium ion battery has better cycling stability.
Example 2:
a graphene modified silicon-carbon negative electrode composite material is prepared by the following steps as shown in figure 1:
(1) dispersing graphene oxide in deionized water, and uniformly dispersing the graphene oxide in the deionized water by using a sand mill to obtain 1.5mg/mL graphene oxide slurry;
(2) adding 10mL of hydrophilic silicone oil with the viscosity of 500 Pa.s into 200mL of water to prepare an aqueous solution containing the hydrophilic silicone oil, and averagely dividing the aqueous solution into two parts, namely A and B; then adding SiO of 200nm into the A part, and uniformly dispersing to obtain a hydrophilic silicone oil modified SiO aqueous solution, and recording the solution as the A solution; adding 2 mu m of natural graphite into the part B, and uniformly dispersing to obtain a hydrophilic silicone oil modified natural graphite aqueous solution, which is recorded as a solution B;
(3) adding the graphene oxide aqueous solution in the step (1) into the solution A in the step (2), and uniformly dispersing to obtain a modified SiO/graphene oxide mixed solution;
(4) adding the solution B in the step (2) into the solution B in the step (3), and uniformly dispersing to obtain a modified SiO/graphene oxide/modified graphite mixed solution;
(5) and (4) carrying out suction filtration on the solution obtained in the step (4), drying, and calcining at 900 ℃ for 3h under the protection of nitrogen to finally obtain the graphene modified silicon-carbon composite material.
And (3) detection data: in the negative electrode tab, SiO: graphene: the mass ratio of the graphite is 25:5: 70. Under the condition that the current density is 0.5C (1C is 1000mA/g), the first specific capacity is 1120mAh/g, the first efficiency reaches 90%, and after 100 cycles, 94% of capacity can be maintained, so that the high-efficiency lithium ion battery has better cycling stability.
Example 3:
a graphene modified silicon-carbon negative electrode composite material is prepared by the following steps:
(1) dispersing graphene oxide in deionized water, and uniformly dispersing the graphene oxide in the deionized water by using a sand mill to obtain 10mg/mL graphene oxide slurry;
(2) adding 10mL of hydrophilic silicone oil with the viscosity of 500 Pa.s into 200mL of water to prepare an aqueous solution containing the hydrophilic silicone oil, and averagely dividing the aqueous solution into two parts, namely A and B; then adding 200nm Si powder into the part A, and uniformly dispersing to obtain a hydrophilic silicone oil modified Si aqueous solution, and recording the hydrophilic silicone oil modified Si aqueous solution as an A solution; adding 20 mu m of mesocarbon microbeads into the part B, and uniformly dispersing to obtain a hydrophilic silicone oil modified mesocarbon microbead aqueous solution which is recorded as a solution B;
(3) adding the graphene oxide aqueous solution in the step (1) into the solution A in the step (2), and uniformly dispersing to obtain a modified Si/graphene oxide mixed solution;
(4) adding the solution B in the step (2) into the solution B in the step (3), and uniformly dispersing to obtain a modified Si/graphene oxide/modified mesophase carbon microsphere mixed solution;
(5) and (4) drying the solution after suction filtration, and calcining for 2 hours at 1000 ℃ under the protection of nitrogen to finally obtain the graphene modified silicon-carbon composite material.
And (3) detecting data: in the negative electrode tab, Si: graphene: the mass ratio of the mesocarbon microbeads is 50:20: 30. Under the condition that the current density is 0.1C (1C is 2000mA/g), the first specific capacity is 1500mAh/g, the first efficiency reaches 89%, and after 100 cycles, 91% of capacity can be maintained, so that the high-efficiency lithium ion battery has better cycling stability.
Example 4:
a graphene modified silicon-carbon negative electrode composite material is prepared by the following steps:
(1) dispersing graphene oxide in deionized water, and uniformly dispersing the graphene oxide in the deionized water by using a sand mill to obtain 5.0mg/mL graphene oxide slurry;
(2) adding 10mL of hydrophilic silicone oil with the viscosity of 1000 Pa.s into 300mL of water to prepare an aqueous solution containing the hydrophilic silicone oil, and averagely dividing the aqueous solution into two parts, namely A and B; then adding 100nm Si powder into the part A, and uniformly dispersing to obtain a hydrophilic silicone oil modified Si aqueous solution, and recording the hydrophilic silicone oil modified Si aqueous solution as an A solution; adding 10 mu m of natural graphite into the part B, and uniformly dispersing to obtain a hydrophilic silicone oil modified natural graphite aqueous solution, which is recorded as a solution B;
(3) adding the graphene oxide aqueous solution obtained in the step (1) into the solution A obtained in the step (2), and uniformly dispersing to obtain a modified Si/graphene oxide mixed solution;
(4) adding the solution B in the step (2) into the solution B in the step (3), and uniformly dispersing to obtain a modified Si/graphene oxide/modified graphite mixed solution;
(5) and (5) filtering the solution obtained in the step (4), drying, and calcining at 900 ℃ for 2 hours under the protection of nitrogen to obtain the graphene modified silicon-carbon composite material.
And (3) detecting data: in the negative electrode tab, Si: graphene: the mass ratio of the graphite is 19:5: 76. Under the condition that the current density is 0.1C (1C is 1000mA/g), the first specific capacity is 1019mAh/g, the first efficiency reaches 93%, and after 100 cycles, the capacity can be kept at 95%, so that the high-efficiency lithium ion battery has good cycle stability.
Comparative example 1:
a graphene modified silicon-carbon negative electrode composite material is prepared by the following steps:
(1) dispersing graphene oxide in deionized water, and uniformly dispersing the graphene oxide in the deionized water by using a sand mill to obtain 5.0mg/mL graphene oxide slurry;
(2) adding 5mL of hydrophilic silicone oil with the viscosity of 1000 Pa.s into 150mL of water to prepare an aqueous solution containing the hydrophilic silicone oil, then adding 100nm of Si powder, and uniformly dispersing to obtain a hydrophilic silicone oil modified Si aqueous solution
(3) Adding the graphene oxide aqueous solution obtained in the step (1) into the modified Si aqueous solution, and uniformly dispersing to obtain a modified Si/graphene oxide mixed solution;
(4) adding 10 mu m of natural graphite into the step (3), and uniformly dispersing to obtain a modified Si/graphene oxide/graphite mixed solution;
(5) and (4) carrying out suction filtration on the solution obtained in the step (4), drying, and calcining at 900 ℃ for 2h under the protection of nitrogen to finally obtain the graphene modified silicon-carbon composite material.
And (3) detecting data: in the negative electrode tab, Si: graphene: the mass ratio of the graphite is 19:5: 76. Under the condition that the current density is 0.1C (1C is 1000mA/g), the first specific capacity is 736mAh/g, the first efficiency reaches 85%, and 75% of capacity can be maintained after 100 cycles.
Comparative example 2:
a graphene modified silicon-carbon negative electrode composite material is prepared by the following steps:
(1) dispersing graphene oxide in deionized water, and uniformly dispersing the graphene oxide in the deionized water by using a sand mill to obtain 5.0mg/mL graphene oxide slurry;
(2) adding 100nm Si powder into the graphene oxide aqueous solution obtained in the step (1), and uniformly dispersing to obtain a Si/graphene oxide mixed solution;
(3) adding 5mL of hydrophilic silicone oil with the viscosity of 1000 Pa.s into 150mL of water to prepare an aqueous solution containing the hydrophilic silicone oil, adding 10 mu m of natural graphite, and uniformly dispersing to obtain a hydrophilic silicone oil modified graphite aqueous solution;
(4) adding the solution obtained in the step (2) into the solution obtained in the step (3), and uniformly dispersing to obtain a Si/graphene oxide/modified graphite mixed solution;
(5) and (4) carrying out suction filtration on the solution obtained in the step (4), drying, and calcining at 900 ℃ for 2h under the protection of nitrogen to finally obtain the graphene modified silicon-carbon composite material.
And (3) detecting data: in the negative electrode tab, Si: graphene: the mass ratio of the graphite is 19:5: 76. Under the condition that the current density is 0.1C (1C is 1000mA/g), the first specific capacity is 786mAh/g, the first efficiency reaches 86%, and after 100 cycles, the capacity can be maintained at 70%.
Comparative example 3:
a graphene modified silicon-carbon negative electrode composite material is prepared by the following steps:
(1) dispersing graphene oxide in deionized water, and uniformly dispersing the graphene oxide in the deionized water by using a sand mill to obtain 5.0mg/mL graphene oxide slurry;
(2) adding 10g of citric acid into 300mL of water to prepare a citric acid aqueous solution, and averagely dividing the solution into two parts, namely A and B; then adding 100nm Si powder into the part A, and uniformly dispersing to obtain a citric acid modified Si aqueous solution, and recording the solution as solution A; adding 10 mu m of natural graphite into the part B, and uniformly dispersing to obtain a citric acid modified natural graphite water solution, which is recorded as a solution B;
(3) adding the graphene oxide aqueous solution in the step (1) into the solution A in the step (2), and uniformly dispersing to obtain a modified Si/graphene oxide mixed solution;
(4) adding the solution B in the step (2) into the solution B in the step (3), and uniformly dispersing to obtain a modified Si/graphene oxide/modified graphite mixed solution;
(5) and (4) carrying out suction filtration on the solution obtained in the step (4), drying, and calcining at 900 ℃ for 2h under the protection of nitrogen to finally obtain the graphene modified silicon-carbon composite material.
And (3) detecting data: in the negative electrode tab, Si: graphene: the mass ratio of the graphite is 19:5: 76. Under the condition that the current density is 0.1C (1C is 1000mA/g), the first specific capacity is 850mAh/g, the first efficiency reaches 89%, and after 100 cycles, 90% of capacity can be maintained, so that the high-efficiency lithium ion battery has better cycling stability.
The performance data of the negative electrode tabs obtained in the above examples 1 to 4 and comparative examples 1 to 3 are shown in table 1 below.
TABLE 1
Comparing the electrode plates prepared from the silicon-carbon negative electrode materials obtained in the embodiment 4 and the comparative example 1, the silicon-carbon material modified by hydrophilic silicone oil through crosslinking has the first specific capacity of 1019mAh/g, the first efficiency of 93%, and the capacity retention rate after 100 weeks of circulation of 95%, which are all higher than those of the unmodified silicon-carbon material.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. A preparation method of a graphene modified silicon-carbon anode material is characterized by comprising the following steps:
(1) adding a silicon-containing material into a cross-linking agent aqueous solution, and uniformly stirring to obtain a modified silicon-containing material aqueous solution, which is marked as solution A;
(2) adding the carbon material into another cross-linking agent aqueous solution, and uniformly stirring to obtain a modified carbon material aqueous solution, which is marked as solution B;
(3) adding the graphene oxide aqueous solution into the solution A, and uniformly stirring to obtain a modified silicon-containing material/graphene oxide mixed solution;
(4) adding the solution B into the modified silicon-containing material/graphene oxide mixed solution, and uniformly stirring to obtain a modified silicon-containing material/graphene oxide/modified carbon material mixed solution, which is marked as solution C;
(5) carrying out solid-liquid separation on the solution C, drying, and calcining at high temperature under the protection of inert gas to obtain a target product;
in the step (1), the silicon-containing material is silicon powder or silicon oxide which is marked as SiOx，0≤x<2, the particle size is 0.01-5 μm;
the cross-linking agent aqueous solution is prepared by mixing hydrophilic silicone oil and water, wherein the viscosity range of the hydrophilic silicone oil is 50-2000 Pa.s.
2. The preparation method of the graphene modified silicon-carbon negative electrode material according to claim 1, wherein in the step (1), the addition amount of the silicon-containing material and the cross-linking agent aqueous solution satisfies the following condition: the mass ratio of the Si element to the cross-linking agent is 1: (0.1-1).
3. The preparation method of the graphene modified silicon carbon negative electrode material as claimed in claim 1, wherein in the step (2), the addition amount of the carbon material and the cross-linking agent aqueous solution satisfies the following requirement: the mass ratio of the carbon material to the cross-linking agent is 1: (0.08-1).
4. The preparation method of the graphene modified silicon-carbon anode material according to claim 1, wherein in the step (2), the carbon material is one of natural graphite, artificial graphite or mesocarbon microbeads, and the particle size of the carbon material is 0.1-20 μm.
5. The preparation method of the graphene modified silicon-carbon negative electrode material according to claim 1, wherein in the step (3), the concentration of the graphene oxide aqueous solution is 0.1-10mg/mL, and the addition amount of the graphene oxide aqueous solution and the solution A satisfies the following requirements: the mass ratio of the silicon-containing material to the graphene oxide is 1: (0.03-0.8).
6. The preparation method of the graphene modified silicon-carbon negative electrode material according to claim 1, wherein in the step (4), the addition amounts of the solution B and the modified silicon-containing material/graphene oxide mixed solution satisfy: the mass ratio of the carbon material to the graphene oxide is 1: (0.01-0.5).
7. The preparation method of the graphene modified silicon carbon anode material according to claim 1, wherein in the step (5), the high-temperature calcination process conditions are as follows: calcining at 500-1500 ℃ for 2-6 h.
8. The method for preparing the graphene modified silicon carbon anode material according to claim 1, wherein in the step (5), the inert gas is nitrogen or argon.
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