CN113013384A - Preparation and synthesis method of lithium storage silicon-based material - Google Patents
Preparation and synthesis method of lithium storage silicon-based material Download PDFInfo
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- CN113013384A CN113013384A CN202110201582.XA CN202110201582A CN113013384A CN 113013384 A CN113013384 A CN 113013384A CN 202110201582 A CN202110201582 A CN 202110201582A CN 113013384 A CN113013384 A CN 113013384A
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Abstract
The invention relates to the technical field of battery material preparation, in particular to a preparation and synthesis method of a lithium storage silicon-based material, which adopts a method combining chemical plating and magnetron sputtering and takes a three-dimensional porous support material of melamine sponge as a three-dimensional substrate to prepare a three-dimensional current collector, thereby improving the loading capacity of electrode active substances and the wettability of electrolyte, ensuring the transmission of electrons and ions, and also improving the retention of the specific capacity of a silicon electrode, thereby improving the lithiation cycle times of the silicon electrode; the method fully exerts the unique advantages of the magnetron sputtering synthesis technology, directly grows active substances on the three-dimensional connected network structure, realizes the preparation of the integrated silicon-based material, explores a new way for designing and constructing the high-performance nanostructure integrated silicon-based electrode, and provides scientific basis for the research and development of the lithium storage performance of the silicon-based material.
Description
Technical Field
The invention relates to the technical field of battery material preparation, in particular to a preparation and synthesis method of a lithium storage silicon-based material.
Background
At present, the existing commercial negative electrode material is mainly graphite, and compared with silicon materials, the silicon materials have the advantages of low lithium removal potential, rich resources, low cost, environmental friendliness and the like, so that the research on lithium storage silicon-based materials has important strategic significance on the negative electrode of a high-energy lithium ion battery, and the development of novel high-capacity negative electrode materials becomes a research hotspot.
Unfortunately, studies have shown that silicon electrodes have poor specific capacity retention, which results in higher specific capacity during the first cycle of lithiation, but that the specific capacity decays rapidly with increasing cycle times, mainly due to the large volume change of the silicon negative electrode during insertion and extraction of lithium ions.
Disclosure of Invention
Aiming at the problems, the invention aims to exert the unique advantages of the technology combining chemical plating and magnetron sputtering, realize the preparation of the integrated silicon-based lithium storage material and improve the specific capacity and the cycle performance of the electrode. In order to realize the purpose of the invention, the following technical scheme is adopted:
a preparation and synthesis method of a lithium storage silicon-based material takes a three-dimensional porous support material of melamine sponge as a three-dimensional substrate, adopts a chemical plating method to prepare a three-dimensional current collector, and then prepares the three-dimensional lithium storage silicon-based material by a radio frequency magnetron sputtering technology, and specifically comprises the following steps:
(1) pretreatment of the three-dimensional substrate: firstly, cleaning the surface of a three-dimensional substrate, sensitizing the cleaned three-dimensional substrate by adopting a sensitizing solution, then loading a layer of chemical plating reaction catalyst for activation, and then adding a sodium hypophosphite solution to remove the redundant activating solution to obtain a three-dimensional material loaded with the chemical plating reaction catalyst;
(2) chemical plating: immersing the pretreated three-dimensional material into plating solution at a certain temperature for reaction for a period of time to prepare a three-dimensional current collector;
(3) radio frequency magnetron sputtering: and controlling certain working conditions, and growing the silicon-based active material on the surface of the three-dimensional current collector in situ to obtain the three-dimensional lithium-storage silicon-based material.
Preferably, the cleaning in the pretreatment process of the three-dimensional substrate is to remove photoresist and oil on the surface of the three-dimensional substrate by acetone, absolute ethyl alcohol and distilled water.
Preferably, the sensitizing solution is hydrochloric acid solution of stannous chloride.
Preferably, the electroless plating reaction catalyst is one of nano nickel, nano copper, nano gold or nano palladium.
Preferably, the plating solution in the chemical plating process comprises 6-15% of reducing agent and 2-15% of chelating agent by weight.
Preferably, the reducing agent is sodium hypophosphite solution, and the chelating agent is one of sodium carboxymethyl cellulose, polyvinylidene fluoride or polyacrylonitrile.
Preferably, the reaction time of the electroless plating is 10-60 min.
Preferably, the reaction temperature of the electroless plating is 30-90 ℃.
Preferably, the purity of the silicon target in the radio frequency magnetron sputtering process is 99.999%, the working pressure is 2.0Pa, the sputtering power is 200W, and the atmosphere is high-purity argon.
Preferably, the radio frequency magnetron sputtering time is 15-60 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention prepares the three-dimensional current collector by taking the three-dimensional porous support body material of the melamine sponge as the chemically plated three-dimensional substrate, and the porous structure of the three-dimensional current collector can improve the good contact among active substances, electrolyte and the current collector, improve the loading capacity of active substances of an electrode and the wettability of the electrolyte, ensure the transmission of electrons and ions, and improve the retention of the specific capacity of a silicon electrode due to the steps of sensitization, activation and loading because the fiber diameter of the melamine sponge is thinner, the pore diameter is wider, the weight is light, the mechanical strength is high, and the three-dimensional substrate is pretreated in the preparation process.
(2) The invention adopts a method of combining chemical plating and magnetron sputtering, fully exerts the unique advantages of the magnetron sputtering synthesis technology, controls the composition, the appearance and the thickness of the material by regulating and controlling experimental parameters such as a conducting layer support body, reaction temperature, reaction time and the like, directly grows active substances on a three-dimensional communication network structure, realizes the preparation of the integrated silicon-based material, explores a new way of designing and constructing the high-performance nanostructure integrated silicon-based electrode, and provides scientific basis for the research and development of the lithium storage performance of the silicon-based material.
Drawings
FIG. 1 is a flow chart of a method for preparing and synthesizing a lithium-storage silicon-based material according to the present invention;
FIG. 2 is a flow chart of the process for pre-treating a three-dimensional substrate according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Detailed description of the preferred embodiment 1
Fig. 1 is a flow chart of a method for preparing and synthesizing a lithium storage silicon-based material according to the present invention, and with reference to fig. 2, it can be seen that the method for preparing and synthesizing a lithium storage silicon-based material according to the present invention uses a three-dimensional porous support material of melamine sponge as a three-dimensional substrate, adopts a chemical plating method to prepare a three-dimensional current collector, and then prepares a three-dimensional lithium storage silicon-based material by a radio frequency magnetron sputtering technology, and specifically includes the following steps:
step S101: pretreatment of the three-dimensional substrate: the method specifically comprises the following steps:
step S201: cleaning: cleaning the surface of the three-dimensional substrate, specifically, removing the photoresist and the oil on the surface of the three-dimensional substrate by acetone, absolute ethyl alcohol and distilled water;
step S202: sensitization: sensitizing the cleaned three-dimensional substrate by using a hydrochloric acid solution of stannous chloride as a sensitizing solution;
step S203: and (3) activation: loading a layer of chemical plating reaction catalyst for activation treatment, wherein in the step, the chemical plating reaction catalyst is nano nickel;
step S204: reduction: and adding a sodium hypophosphite solution to remove the redundant activating solution to obtain the three-dimensional material loaded with the chemical plating reaction catalyst.
Step S102: chemical plating: and (3) immersing the pretreated three-dimensional material into plating solution at 30 ℃ for reaction for 60min to prepare the three-dimensional current collector. In the step, the plating solution comprises 6% of reducing agent and 2% of chelating agent in parts by weight, wherein the reducing agent is sodium hypophosphite solution, and the chelating agent is sodium carboxymethylcellulose.
Step S103: radio frequency magnetron sputtering: and controlling certain working conditions, and growing the silicon-based active material on the surface of the three-dimensional current collector in situ to obtain the three-dimensional lithium-storage silicon-based material. In the step, the purity of the silicon target in the radio frequency magnetron sputtering process is 99.999 percent, the working pressure is 2.0Pa, the sputtering power is 200W, the atmosphere is high-purity argon, and the radio frequency magnetron sputtering time is 15 min.
Specific example 2
Fig. 1 is a flow chart of a method for preparing and synthesizing a lithium storage silicon-based material according to the present invention, and with reference to fig. 2, it can be seen that the method for preparing and synthesizing a lithium storage silicon-based material according to the present invention uses a three-dimensional porous support material of melamine sponge as a three-dimensional substrate, adopts a chemical plating method to prepare a three-dimensional current collector, and then prepares a three-dimensional lithium storage silicon-based material by a radio frequency magnetron sputtering technology, and specifically includes the following steps:
step S101: pretreatment of the three-dimensional substrate: the method specifically comprises the following steps:
step S201: cleaning: cleaning the surface of the three-dimensional substrate, specifically, removing the photoresist and the oil on the surface of the three-dimensional substrate by acetone, absolute ethyl alcohol and distilled water;
step S202: sensitization: sensitizing the cleaned three-dimensional substrate by using a hydrochloric acid solution of stannous chloride as a sensitizing solution;
step S203: and (3) activation: loading a layer of chemical plating reaction catalyst for activation treatment, wherein in the step, the chemical plating reaction catalyst is nano copper;
step S204: reduction: and adding a sodium hypophosphite solution to remove the redundant activating solution to obtain the three-dimensional material loaded with the chemical plating reaction catalyst.
Step S102: chemical plating: and (3) immersing the pretreated three-dimensional material into plating solution at 90 ℃ for reaction for 10min to prepare the three-dimensional current collector. In the step, the plating solution comprises 15% of a reducing agent and 15% of a chelating agent in parts by weight, wherein the reducing agent is a sodium hypophosphite solution, and the chelating agent is polyvinylidene fluoride.
Step S103: radio frequency magnetron sputtering: and controlling certain working conditions, and growing the silicon-based active material on the surface of the three-dimensional current collector in situ to obtain the three-dimensional lithium-storage silicon-based material. In the step, the purity of the silicon target in the radio frequency magnetron sputtering process is 99.999 percent, the working pressure is 2.0Pa, the sputtering power is 200W, the atmosphere is high-purity argon, and the radio frequency magnetron sputtering time is 60 min.
Specific example 3
Fig. 1 is a flow chart of a method for preparing and synthesizing a lithium storage silicon-based material according to the present invention, and with reference to fig. 2, it can be seen that the method for preparing and synthesizing a lithium storage silicon-based material according to the present invention uses a three-dimensional porous support material of melamine sponge as a three-dimensional substrate, adopts a chemical plating method to prepare a three-dimensional current collector, and then prepares a three-dimensional lithium storage silicon-based material by a radio frequency magnetron sputtering technology, and specifically includes the following steps:
step S101: pretreatment of the three-dimensional substrate: the method specifically comprises the following steps:
step S201: cleaning: cleaning the surface of the three-dimensional substrate, specifically, removing the photoresist and the oil on the surface of the three-dimensional substrate by acetone, absolute ethyl alcohol and distilled water;
step S202: sensitization: sensitizing the cleaned three-dimensional substrate by using a hydrochloric acid solution of stannous chloride as a sensitizing solution;
step S203: and (3) activation: loading a layer of chemical plating reaction catalyst for activation treatment, wherein in the step, the chemical plating reaction catalyst is nano-gold;
step S204: reduction: and adding a sodium hypophosphite solution to remove the redundant activating solution to obtain the three-dimensional material loaded with the chemical plating reaction catalyst.
Step S102: chemical plating: and (3) immersing the pretreated three-dimensional material into plating solution at 60 ℃ for reaction for 50min to prepare the three-dimensional current collector. In the step, the plating solution comprises 10% of reducing agent and 12% of chelating agent in parts by weight, wherein the reducing agent is sodium hypophosphite solution, and the chelating agent is polyacrylonitrile.
Step S103: radio frequency magnetron sputtering: and controlling certain working conditions, and growing the silicon-based active material on the surface of the three-dimensional current collector in situ to obtain the three-dimensional lithium-storage silicon-based material. In the step, the purity of the silicon target in the radio frequency magnetron sputtering process is 99.999 percent, the working pressure is 2.0Pa, the sputtering power is 200W, the atmosphere is high-purity argon, and the radio frequency magnetron sputtering time is 40 min.
As can be seen from the above embodiments of the present invention, the three-dimensional current collector is prepared by using the three-dimensional porous support material of the melamine sponge as the chemically plated three-dimensional substrate, and the melamine sponge has the advantages of fine fiber diameter, wide pore diameter, light weight and high mechanical strength, and the three-dimensional substrate is pretreated in the preparation process, specifically including the steps of sensitization, activation and loading, so that the porous structure of the three-dimensional current collector can improve the good contact among the active material, the electrolyte and the current collector, improve the loading capacity of the active material of the electrode and the wettability of the electrolyte, ensure the transmission of electrons and ions, and improve the retention of the specific capacity of the silicon electrode, thereby improving the lithiation cycle number of the silicon electrode, and having strong practicability; the method combines chemical plating and magnetron sputtering, gives full play to the unique advantages of the magnetron sputtering synthesis technology, controls the composition, the appearance and the thickness of the material by regulating and controlling experimental parameters such as a conducting layer support body, reaction temperature, reaction time and the like, directly grows active substances on a three-dimensional communication network structure, realizes the preparation of the integrated silicon-based material, explores a new way for designing and constructing the high-performance nano-structure integrated silicon-based electrode, and provides scientific basis for the research and development of the lithium storage performance of the silicon-based material.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can understand that the changes or modifications within the technical scope of the present invention are included in the scope of the present invention, and therefore, the scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. A preparation and synthesis method of a lithium storage silicon-based material is characterized by comprising the following steps: the method comprises the following steps of taking a three-dimensional porous support material of melamine sponge as a three-dimensional substrate, preparing a three-dimensional current collector by adopting a chemical plating method, and then preparing a three-dimensional lithium-storage silicon-based material by a radio frequency magnetron sputtering technology, wherein the method specifically comprises the following steps:
(1) pretreatment of the three-dimensional substrate: firstly, cleaning the surface of a three-dimensional substrate, sensitizing the cleaned three-dimensional substrate by adopting a sensitizing solution, then loading a layer of chemical plating reaction catalyst for activation, and then adding a sodium hypophosphite solution to remove the redundant activating solution to obtain a three-dimensional material loaded with the chemical plating reaction catalyst;
(2) chemical plating: immersing the pretreated three-dimensional material into plating solution at a certain temperature for reaction for a period of time to prepare a three-dimensional current collector;
(3) radio frequency magnetron sputtering: and controlling certain working conditions, and growing the silicon-based active material on the surface of the three-dimensional current collector in situ to obtain the three-dimensional lithium-storage silicon-based material.
2. The method for preparing and synthesizing the lithium-storage silicon-based material according to claim 1, wherein the method comprises the following steps: the cleaning in the pretreatment process of the three-dimensional substrate is to remove glue and oil on the surface of the three-dimensional substrate by acetone, absolute ethyl alcohol and distilled water.
3. The method for preparing and synthesizing the lithium-storage silicon-based material according to claim 1, wherein the method comprises the following steps: the sensitizing solution is hydrochloric acid solution of stannous chloride.
4. The method for preparing and synthesizing the lithium-storage silicon-based material according to claim 1, wherein the method comprises the following steps: the chemical plating reaction catalyst is one of nano nickel, nano copper, nano gold or nano palladium.
5. The method for preparing and synthesizing the lithium-storage silicon-based material according to claim 1, wherein the method comprises the following steps: the plating solution in the chemical plating process comprises 6-15% of reducing agent and 2-15% of chelating agent by weight.
6. The method for preparing and synthesizing the lithium-storage silicon-based material according to claim 5, wherein the method comprises the following steps: the reducing agent is sodium hypophosphite solution, and the chelating agent is one of sodium carboxymethylcellulose, polyvinylidene fluoride or polyacrylonitrile.
7. The method for preparing and synthesizing the lithium-storage silicon-based material according to claim 1, wherein the method comprises the following steps: the reaction time of the chemical plating is 10-60 min.
8. The method for preparing and synthesizing the lithium-storage silicon-based material according to claim 1, wherein the method comprises the following steps: the reaction temperature of the chemical plating is 30-90 ℃.
9. The method for preparing and synthesizing the lithium-storage silicon-based material according to claim 1, wherein the method comprises the following steps: in the radio frequency magnetron sputtering process, the purity of the silicon target is 99.999 percent, the working pressure is 2.0Pa, the sputtering power is 200W, and the atmosphere is high-purity argon.
10. The method for preparing and synthesizing the lithium-storing silicon-based material according to claim 1 or 9, wherein the method comprises the following steps: the radio frequency magnetron sputtering time is 15-60 min.
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