CN111689501A - Porous/hollow structure silicon-based anode material and preparation method thereof - Google Patents
Porous/hollow structure silicon-based anode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a porous/hollow structure silicon-based anode material, which comprises the following steps: s1: heating a raw material for supplying SiO gas in the sublimation chamber 1 to sublimate to generate SiO vapor; s2: heating soluble salt in the sublimation cavity 2 to sublimate to generate soluble salt steam; s3: introducing SiO steam and soluble salt steam into a condensation cavity for deposition to obtain a precursor; s4: and crushing, screening, washing and drying the precursor to obtain the silicon-based anode material with the porous/hollow structure. The preparation method provided by the invention is simple and feasible, has low cost, is suitable for large-scale production, and the prepared cathode material has uniform and controllable pore distribution.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a porous/hollow structure silicon-based negative electrode material and a preparation method thereof.
Background
Silicon is the lithium ion battery anode material with the highest known specific capacity (4200 mAh/g), but the silicon finally causes the electrochemical performance to be deteriorated due to the huge volume effect (> 300%), so that a great deal of modification research is carried out by researchers. At present, the multi-cavitation and hollow structure of silicon is widely considered as an effective means for solving the volume effect of silicon, and because the volume expansion reserved space possibly exists in the charge and discharge process of the silicon material with the structure, the influence of the volume effect of silicon on the pole piece is reduced. Common methods for preparing the porous structure include a template method, an etching method and a magnesiothermic reduction method, and the method for preparing the hollow structure mainly comprises the template method. However, the above methods have problems of high cost, harsh preparation conditions, and the like, and thus large-scale production cannot be achieved.
Disclosure of Invention
In view of this, the embodiment of the application provides a preparation method of a porous/hollow structure silicon-based anode material, which is low in cost, easy to operate and capable of realizing large-scale production.
In one embodiment, the present application provides a method for preparing a porous/hollow structure silicon-based anode material, the method comprising: s1: heating a raw material for supplying SiO gas in the sublimation chamber 1 to sublimate to generate SiO vapor; s2: heating soluble salt in the sublimation cavity 2 to sublimate to generate soluble salt steam; s3: introducing SiO steam and soluble salt steam into a condensation cavity for deposition to obtain a precursor; s4: and crushing, screening, washing and drying the precursor to obtain the silicon-based anode material with the porous/hollow structure.
In another embodiment, the present application provides an anode material prepared by the above preparation method.
The preparation method provided by the invention is simple and feasible, has low cost, is suitable for large-scale production, and the prepared cathode material has uniform and controllable pore distribution.
Additional aspects and advantages of embodiments of the present application will be described or shown in detail in the following description or illustrated in the accompanying drawings.
Drawings
FIG. 1 is an SEM image of a negative electrode material obtained in example 1 of the present invention.
Detailed Description
Embodiments of the present application will be described in detail below. The embodiments of the present application should not be construed as limiting the application.
In the present application, amounts, ratios, and other numerical values are presented in a range format, with the understanding that such range format is used for convenience and brevity and should be flexibly understood to include not only the numerical values explicitly specified as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly specified.
In the claims and the detailed description, a list of items linked by the term "at least one of" or other similar terms may mean any combination of the listed items. For example, if items a and B are listed, the phrase "at least one of a and B" means a only; only B; or A and B. Item a may comprise a single element or multiple elements and item B may comprise a single element or multiple elements.
The embodiment of the application provides a preparation method of a porous/hollow structure silicon-based anode material, which comprises the following steps:
s1: heating a raw material for supplying SiO gas in the sublimation chamber 1 to sublimate to generate SiO vapor;
s2: heating soluble salt in the sublimation cavity 2 to sublimate to generate soluble salt steam;
s3: introducing SiO steam and soluble salt steam into a condensation cavity for deposition to obtain a precursor;
s4: and crushing, screening, washing and drying the precursor to obtain the silicon-based anode material with the porous/hollow structure.
Specifically, step S1 is to heat a raw material for providing SiO gas under a vacuum environment and a certain temperature condition to generate SiO vapor; the certain temperature is controlled to be 900-1400 ℃; according to the heating temperature, the time of heat treatment can be controlled within 0.5-12 h; the raw material for supplying the SiO gas is not particularly limited, and preferably, a mixture of metallic silicon and silicon dioxide is selected.
Step S2 is heating soluble salt to generate soluble salt steam under vacuum environment and certain temperature condition; the certain temperature is controlled to be 1200-1600 ℃; according to the heating temperature, the time of heat treatment can be controlled within 1-12 h.
Step S3 is that under the vacuum environment and a certain temperature, steam is cooled to separate out a precursor of SiO/soluble salt on the substrate; the certain temperature is controlled to be 300-900 ℃; according to the heating temperature, the time of heat treatment can be controlled within 0.5-24 h; the substrate is not specifically limited, researchers can select a proper substrate according to different requirements, and when the substrate is a deposition plate of a condensation chamber, the SiO/soluble salt material can be obtained; when the substrate is a certain material, the substrate can be a metal simple substance, nano silicon, a carbon nano material and the like, and a material with a SiO/soluble salt coated core-shell structure can be obtained; when the substrate is a three-dimensional porous support body, the substrate can be a copper foil mesh, a copper wire mesh, foamed copper, foamed nickel and the like, and the SiO/soluble salt material with a network structure can be obtained.
The crushing in the step S4 is to crush the precursor by at least one of ball milling, jet milling, mechanical crushing and other crushing methods so that the particle size of the material reaches micron or nanometer level; the screening is to select a material with a proper particle size to ensure excellent processing performance and electrochemical performance, and the proper particle size is generally considered to be 1-50 μm, preferably 1-10 μm; the water washing is to dissolve and remove soluble salt by at least one of filtration, suction filtration and ultrasonic vibration; the drying may be achieved by means of vacuum baking.
In some embodiments, the step S3 may be to introduce the SiO vapor and the soluble salt vapor into a condensation chamber simultaneously to co-deposit to obtain a precursor, so that the silicon negative electrode material with a porous structure is finally obtained after crushing, screening, washing and drying.
In some embodiments, in step S3, soluble salt vapor is introduced into the condensation chamber to be deposited, and then SiO vapor is introduced to be deposited to obtain a precursor, so that the silicon negative electrode material with a hollow structure can be obtained after crushing, screening, washing and drying.
In some embodiments, the soluble salts include NaCl, MgCl2、KCl、CaCl、Na2CO3、Na2SO4、K2SO4At least one of (1).
The application also provides the anode material prepared by the preparation method, and the anode material has a porous structure or a hollow structure.
Example 1
Uniformly mixing silicon powder and silicon dioxide powder in a certain proportion, then filling the mixture into a sublimation chamber 1 for heat treatment at 1400 ℃ and the vacuum degree of less than or equal to 100Pa, and heating for 1h to obtain SiO steam; putting NaCl salt into a sublimation chamber 2 for heat treatment at 1500 ℃ and a vacuum degree of less than or equal to 100Pa, and heating for 1h to obtain NaCl vapor; simultaneously introducing SiO steam and NaCl steam to a condensation cavity to carry out codeposition on a deposition plate, wherein the condensation temperature is 300 ℃, and the time is 2 hours, so as to obtain a SiO/NaCl precursor; ball-milling and crushing the precursor, and sieving to obtain a SiO/NaCl material with the particle size of 5 microns; and (3) carrying out suction filtration and washing on the SiO/NaCl material, and carrying out vacuum drying at 100 ℃ to obtain the negative electrode material with the porous structure.
The morphology of the porous silicon negative electrode material prepared in the example was analyzed by a scanning electron microscope (SEM, electronic scanning electron microscope FEI observation S50), and as shown in fig. 1, the negative electrode material was spheroidal, porous on the surface and uniformly distributed.
Example 2
Uniformly mixing silicon powder and silicon dioxide powder in a certain proportion, then filling the mixture into a sublimation chamber 1 for heat treatment at 1400 ℃ and the vacuum degree of less than or equal to 100Pa, and heating for 1h to obtain SiO steam; mixing MgCl2Charging salt into sublimation chamber 2 for heat treatment at 1450 deg.C and vacuum degree of less than or equal to 100Pa, and heating for 1 hr to obtain MgCl2Steam; mixing MgCl2Introducing the vapor into a condensation chamber for deposition on a deposition plate at a condensation temperature of 350 ℃ for 1h, and introducing the SiO vapor into the condensation chamber to form MgCl2Depositing at 350 deg.c for 1 hr to obtain SiO/MgCl2A precursor; ball-milling and crushing the precursor, and sieving to obtain SiO/MgCl with the particle size of 8 mu m2A material; SiO/MgCl2And carrying out suction filtration and washing on the material, and carrying out vacuum drying at 100 ℃ to obtain the cathode material with a hollow structure.
Example 3
Uniformly mixing silicon powder and silicon dioxide powder in a certain proportion, then filling the mixture into a sublimation chamber 1 for heat treatment at 1400 ℃ and the vacuum degree of less than or equal to 100Pa, and heating for 1h to obtain SiO steam; placing KCl salt into sublimation chamber 2 for heat treatment at 1450 deg.C and vacuum degree of less than or equal to 100Pa, and heating for 1 hr to obtain KCl vapor; placing a Carbon Nano Tube (CNT) in a condensation cavity, simultaneously introducing SiO steam and KCl steam into the condensation cavity to codeposit on the CNT, wherein the condensation temperature is 300 ℃, and the time is 2 hours, so as to obtain a SiO/KCl/CNT precursor; ball-milling and crushing the precursor, and sieving to obtain a SiO/KCl/CNT material with the particle size of 5 mu m; and (3) carrying out suction filtration and washing on the SiO/KCl/CNT material, and carrying out vacuum drying at 100 ℃ to obtain the cathode material with the core-shell structure, wherein the porous SiO material is a coating layer, and the CNT is a core body.
Example 4
Uniformly mixing silicon powder and silicon dioxide powder in a certain proportion, then filling the mixture into a sublimation chamber 1 for heat treatment at 1400 ℃ and the vacuum degree of less than or equal to 100Pa, and heating for 1h to obtain SiO steam; mixing Na2SO4Placing salt into sublimation chamber 2, heating at 1400 deg.C and vacuum degree of less than or equal to 100Pa for 1 hr to obtain Na2SO4Steam; placing foamed aluminum in a condensation chamber, and adding Na2SO4Introducing the vapor into a condensation chamber to deposit on the foam copper at the condensation temperature of 400 ℃ for 1h, and introducing the SiO vapor into the condensation chamber to deposit on Na2SO4Depositing at 400 deg.c for 1 hr to obtain SiO/Na2SO4A foam copper precursor; grinding the precursor by ball milling and sieving to obtain SiO/Na with the particle size of 15 mu m2SO4Foamed copper material; mixing SiO/Na2SO4And (2) carrying out suction filtration and washing on the copper foam material, and carrying out vacuum drying at 100 ℃ to obtain the negative electrode material with the three-dimensional hollow structure.
Comparative example 1
By magnesiothermic reductionPreparing a porous silicon material: uniformly mixing Mg powder and silica powder in a certain proportion, placing the mixture in a tubular atmosphere furnace for heat treatment, heating to 600 ℃ at a speed of 5 ℃/min under the protection of argon, and keeping the temperature for 5 hours; adding 5 wt% NH to the heat-treated product4Soaking in a Cl solution for 1h, and then gradually adding a 5% wt HCl solution until the solution is acidic; and carrying out suction filtration and drying on the mixed solution to obtain the porous silicon negative electrode material.
The porous silicon negative electrode materials prepared in the examples and comparative example 1 were assembled into lithium batteries, and electrochemical properties thereof were tested: according to the mass ratio of 80: 9: 1: 10 mixing the prepared anode material powder: SP (carbon black): CNT (carbon nanotube): PAA (polyacrylic acid) is mixed, a proper amount of deionized water is added as a solvent, and the mixture is continuously stirred for 8 hours to be pasty by a magnetic stirrer. And pouring the stirred slurry onto a copper foil with the thickness of 9 mu m, coating the copper foil by using an experimental coater, and drying the coated copper foil for 6 hours at the temperature of 85 ℃ under the vacuum (-0.1 MPa) condition to obtain the negative electrode slice. Rolling the electrode sheet to 100 μm on a manual double-roller machine, making into 12mm diameter wafer with a sheet punching machine, drying at 85 deg.C under vacuum (-0.1 MPa) for 8 hr, weighing, and calculating active substance weight. A metal lithium sheet is used as a counter electrode, a polypropylene microporous membrane is used as a diaphragm, 1mol/L LiPF6 in EC: DEC =1:1 Vol% with 5.0% FEC is used as electrolyte, and a CR2032 type button cell is assembled in a glove box. Performing charge and discharge test on the battery by using a blue electric (LAND) battery test system, standing for 6h, discharging to 0.005V at 0.05C, and then discharging to 0.005V at 0.01C; standing for 5min, and charging to 1.5V at constant current of 0.05C; standing for 5min, and repeating the steps twice; then discharging to 0.005V by adopting 0.25C; and standing for 5min, charging the battery to 1.5V at a constant current of 0.25C, circulating for 20 times, testing the cycle performance of the battery, and calculating the charge capacity of the 20 th circle/the charge capacity of the 1 st circle multiplied by 100% to obtain the capacity retention rate. Electricity is withheld after disassembling the circulation in the glove box, then measures the thickness of pole piece, and the test material expansion rate, the calculation mode is: (pole piece thickness after circulation-fresh pole piece thickness)/fresh pole piece thickness x 100%.
Table 1 test results of negative electrode materials prepared in each example and comparative example 1
| Sample (I) | Experimental aid | Expansion ratio | Capacity retention rate |
| Example 1 | NaCl | 28.2% | 90.3% |
| Example 2 | MgCl2 | 30.5% | 89.0% |
| Example 3 | KCl | 25.8% | 91.2% |
| Example 4 | Na2SO4 | 23.7% | 91.6% |
| Comparative example | Mg、NH4Cl、HCl | 31.6% | 88.7% |
Table 1 shows the test results of the negative electrode materials prepared in each example and comparative example 1, it can be seen that the experimental aids used in the preparation method of the present invention are all common salts, and have low cost, no toxicity, and environmental protection, and in addition, different deposition substrates can be selected to realize the preparation of different structural materials, and in addition, the negative electrode material prepared by the preparation method of the present invention has a smaller volume expansion rate and better cycle performance due to the uniform pore distribution.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but 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.
Claims (6)
1. A preparation method of a porous/hollow structure silicon-based anode material is characterized by comprising the following steps:
s1: heating a raw material for supplying SiO gas in the sublimation chamber 1 to sublimate to generate SiO vapor;
s2: heating soluble salt in the sublimation cavity 2 to sublimate to generate soluble salt steam;
s3: introducing SiO steam and soluble salt steam into a condensation cavity for deposition to obtain a precursor;
s4: and crushing, screening, washing and drying the precursor to obtain the silicon-based anode material with the porous/hollow structure.
2. The method for preparing the porous/hollow structure silicon-based anode material of claim 1, wherein the step S3 is to introduce SiO vapor and soluble salt vapor into a condensation chamber simultaneously for codeposition to obtain a precursor.
3. The method for preparing a porous/hollow structure silicon-based anode material as claimed in claim 1, wherein the step S3 is to introduce soluble salt vapor into a condensation chamber for deposition, and then introduce SiO vapor for re-deposition to obtain a precursor.
4. The method for preparing the porous/hollow structure silicon-based anode material of claim 1, wherein the soluble salt comprises NaCl and MgCl2、KCl、CaCl、Na2CO3、Na2SO4、K2SO4At least one of (1).
5. The method for preparing the porous/hollow structure silicon-based anode material of claim 1, wherein the heating temperature in the step S1 is 900-1400 ℃; the heating temperature in the step S2 is 1200-1600 ℃; the condensation temperature in the step S3 is 300-900 ℃.
6. A negative electrode material produced by the production method according to any one of claims 1 to 5.
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| CN115385342A (en) * | 2022-07-20 | 2022-11-25 | 长沙矿冶研究院有限责任公司 | Silicon protoxide material, preparation method, application and device thereof |
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