CN114094087A - Externally coated porous silicon material, preparation method and application thereof - Google Patents
Externally coated porous silicon material, preparation method and application thereof Download PDFInfo
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- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 96
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 229910021338 magnesium silicide Inorganic materials 0.000 claims abstract description 15
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 claims abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
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- 229910000861 Mg alloy Inorganic materials 0.000 claims description 15
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 claims description 15
- 229910020056 Mg3N2 Inorganic materials 0.000 claims description 14
- 239000011258 core-shell material Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
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- 229920001690 polydopamine Polymers 0.000 claims description 9
- 239000011856 silicon-based particle Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
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- 239000011148 porous material Substances 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
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- 238000006138 lithiation reaction Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
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- 229910001220 stainless steel Inorganic materials 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
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- 238000003917 TEM image Methods 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GGUPMVXPXHZNKF-UHFFFAOYSA-N benzene-1,2-diol;formaldehyde Chemical compound O=C.OC1=CC=CC=C1O GGUPMVXPXHZNKF-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
An externally coated porous silicon material, a preparation method and application thereof comprise: (1) silicon powder and magnesium powder with the particle size of 1-10 mu m are mixed according to the mol ratio of 1: 1.8 obtaining magnesium silicide through alloying reaction; (2) coating a dopamine organic layer with magnesium silicide as a precursor; (3) putting the powder obtained in the step into an atmosphere furnace, heating at a certain heating rate in a nitrogen-containing atmosphere, and carrying out heat preservation to carry out a nitriding reaction; (4) and (3) washing the powder obtained in the step with an acid solution, then performing suction filtration to neutrality, and performing vacuum drying. The synthesis process is simple, and the raw materials are wide in source; the externally coated porous silicon negative electrode material obtained by the invention has a stable structure, has long-acting circulation when being applied to a lithium ion battery, has excellent rate performance, has small swelling rate of an electrode film (less than 20 percent), and has good commercial application prospect.
Description
Technical Field
The invention relates to a material and a preparation method thereof, in particular to externally coated porous silicon and a preparation method and application thereof.
Background
Silicon-based negative electrode materials are considered as one of the most potential negative electrode materials of next-generation lithium ion batteries, and have the following advantages: the silicon is used as the lithium ion battery cathode material, the theoretical lithium storage capacity can reach 4200mAh/g, which is more than 10 times of that of the traditional graphite cathode material battery; meanwhile, silicon is abundant on the earth and has wide sources.
But the disadvantages of silicon as a negative electrode material are also very significant: firstly, silicon is a semiconductor, the conductivity is poor, and the irreversible stroke degree in the lithium ion de-intercalation process is large, so that the first coulombic efficiency is reduced; secondly, the silicon negative electrode material undergoes huge volume expansion in the process of charging and discharging, so that the electrode material is crushed, and the structure of the electrode material and an SEI film are seriously damaged. The development of silicon cathode materials with good electrochemical performance is a hot topic of silicon-based lithium ion batteries. The carbon coating layer is beneficial to improving the performance of the silicon-based negative electrode material, improves the conductivity of the silicon-based negative electrode material, and can be used as a protective layer to prevent the silicon material from directly contacting with electrolyte, so that a thick solid electrolyte interface layer is prevented from being formed. The silicon-carbon composite material has two main modes, namely a coating mode and an embedding mode. Most of the coated silicon-carbon composite materials are prepared by a scheme route that carbon is coated along a silicon framework, the requirement on the degree of carbon coating is strict, the silicon framework is crushed in the charging and discharging process due to the infirm carbon coating, and the specific capacity is reduced due to the fact that lithium ions are difficult to insert or remove due to the excessively thick carbon layer; the embedded silicon-carbon composite material carbon is difficult to bear the volume change in long circulation, and the carbon is easy to distribute unevenly, so that the utilization rate of silicon is low.
The carbon-coated silicon cathode material achieves the utilization of carbon of the silicon-carbon cathode material, also achieves the purpose of relieving the volume expansion of the silicon material by utilizing the carbon-coated structure, and has great advantages and potentials.
The prior art is as shown in Chinese patent: "a porous silicon negative electrode material of core-shell structure for lithium ion battery and its preparation method (CN 202010639804.1)" discloses a porous silicon negative electrode material of core-shell structure for lithium ion battery and its preparation method, wherein the porous silicon negative electrode material is of core-shell structure, the core comprises nano porous silicon, graphite and amorphous carbon, the shell is amorphous carbon; the negative electrode material contains 30-70 wt% of nano-porous silicon, 20-45 wt% of graphite and 10-40 wt% of amorphous carbon; the microporous silicon raw material contains 1-10 wt.% of oxygen, and the oxygen content in the nano-porous silicon obtained by wet grinding is 12-35 wt.%. The carbon cage designed by the invention is coated with the porous silicon material, and the carbon can stabilize the skeleton structure of the porous silicon and control the content below 10%, so that the silicon contributes more to the specific capacity of the cathode material, and the cathode material shows higher specific capacity than the traditional silicon-carbon composite material.
The patent: a porous silicon-carbon composite material of a lithium ion battery and a preparation method and application thereof (CN202010604417.4) disclose a porous silicon-carbon composite material of a lithium ion battery and a preparation method and application thereof. The preparation method comprises the following steps: completely dissolving a proper amount of an alkyl glycoside type activator in water to obtain a first solution; under the condition of water bath, adding a proper amount of ammonia water into the first solution and stirring to obtain a second solution with the pH value of 7-9; adding tetraethoxysilane substances into the second solution, stirring, washing with water to be neutral, carrying out suction filtration, and drying solid substances obtained by suction filtration in an inert atmosphere; putting the solid substance into a reaction furnace, introducing 0.5-3L/min of hydrogen at the temperature of 700-1300 ℃, and sintering for 1-8 hours to prepare the silicon/silicon dioxide/porous carbon composite material; adding the silicon/silicon dioxide/porous carbon composite material into HF acid solution and continuously stirring to remove partial SiO2And then drying in an inert atmosphere, crushing the obtained porous silicon-carbon composite material to be treated, and then carrying out carbon coating treatment to obtain the porous silicon-carbon composite material of the lithium ion battery. The invention also designs a process similar to the process of adding a carbon source into the solution to enable the product to realize carbon coating, but the process designed by the invention is simpler, only one-step carbon coating process is needed, unnecessary SiO2 is not generated, HF solution acid pickling and etching are not needed, secondary carbon coating is not needed, the environment is protected, and the energy consumption is low.
The patent: the invention discloses a porous silicon-carbon composite material and a preparation method and application thereof (CN105826527A)A preparation method of a porous silicon-carbon composite material comprises the following specific steps: subjecting magnesium silicide powder to CO2Carrying out heat treatment at 700-900 ℃ in a mixed atmosphere of/Ar, and carrying out acid washing and post-treatment to obtain the porous silicon-carbon composite material; said CO2In a mixed atmosphere of/Ar, CO2The volume fraction of (A) is 10-90%. The porous silicon prepared by the carbon-coating-outside method is simple, the carbon coating amount is controllable, the atmosphere of CO2 is not needed, and the more advantageous carbon-coating-outside porous silicon structure can be realized, so that the structure is more stable, and the SEI film and the long-circulating capacity are more stable. And the literature: nonfilling Carbon Coating of Porous Silicon micro meter-Sized Particles for High-Performance Lithium Battery Anodes (DOI: 10.1021/nn505410q) reported a non-filled Porous Silicon structure with a Carbon Coating, using commercially available SiO Particles, Coating the Particles with a benzenediol-formaldehyde resin, heating the Particles to cause thermal disproportionation of the SiO Particles and pyrolysis of the benzenediol-formaldehyde resin to form a Carbon Coating, and etching the SiO Particles with an HF solution to remove the SiO Particles2Thus obtaining the non-filled carbon coating porous silicon structure. The method needs HF solution to remove SiO2The HF solution is extremely corrosive and dangerous to some extent. According to the invention, the porous Si structure can be obtained by removing magnesium nitride only through HCl solution, the used dopamine raw material is cheap, the required temperature in the whole process is low, the energy consumption is low, and the steps are simple.
Disclosure of Invention
In order to realize the preparation of the controllable, low-cost, long-acting and stable-cycle silicon-carbon cathode material in the battery, the invention designs a route with multiple raw materials, simplicity, controllability and low cost, realizes the preparation of the externally-coated porous silicon material, and the material can not only achieve the purpose of stable structure of a carbon-coated porous silicon framework, but also reasonably control the carbon content so as to improve the specific capacity of the silicon-carbon cathode material.
In order to achieve the purpose, the invention provides the following technical scheme: a carbon-coated porous silicon negative electrode material is a carbon-coated porous silicon negative electrode material which forms a typical core-shell structure. The material is internally provided with porous silicon and externally provided with a carbon coating layer. Coated carbonThe shell is not coated along the pore structure of the porous silicon, and the porous silicon particles are integrally coated in the carbon shell. A suitable porous space is left between the carbon shell and the silicon, and the sources of the space are: carbon coated Mg2After the Si particles are subjected to nitridation reaction, acid washing is carried out to remove Mg3N2Leaving Si and pore spaces.
The invention provides a preparation method of externally coated porous silicon, which is characterized by comprising the following steps: step 1, synthesizing magnesium silicide by using commercial silicon powder and magnesium powder; step 2, coating magnesium silicide particles as a precursor by using dopamine as a carbon source; step 3, performing nitridation reaction treatment on the carbon-coated magnesium silicide obtained in the step 2; and 4, carrying out acid washing treatment on the material nitrided in the step 3 through an acid solution to remove magnesium nitride, so as to obtain the carbon-coated porous silicon material. The externally coated porous silicon prepared by the method is characterized in that: the porous silicon cathode material coated outside the carbon is a core-shell structure consisting of a carbon coating layer and silicon with an ant nest-shaped porous structure; the size of the prepared externally coated porous silicon particles is 3-12 mu m; the carbon layer uniformly coating the porous silicon particles accounts for 5 to 20 percent of the whole.
The carbon layer is integrally coated instead of a core-shell structure coated along the porous silicon pore channel, the carbon layer can be uniformly coated, sufficient 'breathing space' can be reserved in the porous silicon layer so as to relieve the expansion of the porous silicon in the lithium intercalation and lithium removal process, and meanwhile, the coated carbon layer can also play a role in maintaining the stable structure and prevent the direct contact of the silicon and electrolyte.
Preferably: the synthesis method of the magnesium silicide comprises the following steps: commercial silicon powder with a particle size of 1-10 μm is used, and silicon and magnesium powder are mixed in a molar ratio of 1: 1.8, putting the mixture into a reaction vessel after uniform mixing, and then heating the mixture to the temperature of 500-600 ℃ in a tube furnace protected by argon for reaction for 4 to 6 hours.
Preferably: the polydopamine-coated Mg2The nitriding treatment of the Si powder was as follows: polydopamine encapsulated Mg2Si is put into a tube furnace with nitrogen atmosphere to be heated to 700-900 ℃ at the heating rate of 2-10 ℃ and then is insulated for 3-6h, then the material is cooled, taken out at room temperature, acid-washed by acid solution for 1-3h, filtered and dried to obtain the silicon nitrideAnd coating the porous silicon material outside the coating.
The invention also discloses a method for applying the externally coated porous silicon material to a negative electrode of a lithium ion battery.
The invention also discloses a lithium ion battery material, which is characterized in that: the battery material is the externally coated porous silicon material prepared by the preparation method of the externally coated porous silicon material
Compared with the prior art, the technical scheme of the invention has the following advantages: (advantageous effects:)
1. The method combines a gas phase dealloying method and a carbon coating method to prepare the spongy silicon-carbon composite material with the core-shell structure in one step in situ. The method does not involve a template, is simple and feasible and is easy for large-scale production.
2. The porous silicon fully encapsulated by the carbon layer forms a core-shell structure, the space reservation is proper, and the material has higher tap density. The carbon layer both increases the material conductivity and enhances structural stability.
3. The core-shell structure allows the porous silicon to freely expand and pulverize in the carbon layer, still can keep the Si to have higher electrochemical activity, prevents the Si from directly contacting with electrolyte, avoids the cyclic deterioration, has small electrode swelling rate, and has obvious advantages for controlling the expansion of the electrode film.
Drawings
FIG. 1 is an XRD analysis chart of each reaction product in example 1 of the present invention, Mg was synthesized by alloying silicon powder and magnesium powder2Si; through the dopamine polymerization process, polydopamine-coated Mg is obtained2Si; subsequently, through a nitriding process, Mg2Nitriding of Si to obtain Mg3N2And Si, followed by acid washing to remove Mg3N2And the rest is the Si coated by the carbon;
FIG. 2 is a thermogravimetric analysis curve of the outer cladding porous silicon in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of the outer cladding porous silicon in example 1 of the present invention;
FIG. 4a is a transmission electron micrograph of porous Si over-coated in example 1 according to the present invention; FIGS. 4b and 4c are EDS spectra of the material;
FIG. 5a is a schematic view of the cycle performance test of the outer cladding porous Si in example 1 of the present invention; FIG. 5b is a schematic diagram of a rate capability test of the overclad porous Si obtained in example 1 at different current densities;
FIG. 6a is a scanning electron micrograph of a cross section of an electrode film prepared with a low loading of an overcoated porous Si in example 1 of the present invention; fig. 6b is a cross-sectional scanning electron microscope image of an electrode film prepared with low loading of overcoated porous Si after complete lithiation in example 1 of the present invention; FIG. 6c is a scanning electron micrograph of a cross-section of an electrode film prepared with high loading of overcoated porous Si in example 1 of the present invention; fig. 6d is a cross-sectional scanning electron microscope image of an electrode film prepared with high loading of overcoated porous Si in example 1 of the invention after complete lithiation.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
An externally coated porous silicon material, which is characterized in that: the material is a core-shell structure consisting of a carbon coating layer and silicon with an ant nest-shaped porous structure; the size of the selected commercial silicon powder particles is controlled to be 1-10 mu m, and the carbon layer uniformly coating the porous silicon particles accounts for 5-20 wt% of the whole. The silicon-magnesium alloy synthesized by using the silicon powder with the particle size can obtain an externally coated porous silicon material with the particle size distribution of 3-12 mu m in the last step of the embodiment, the material has low tap density due to small particle size, and the material performance and the reaction kinetics in the dealloying process are influenced due to overlarge particles.
The synthesis method of the silicon-magnesium alloy comprises the following steps: mixing silicon and magnesium powder in a molar ratio of 1: 1.8, putting the mixture into a stainless steel container after uniform mixing, and then heating the mixture to the temperature of 500-600 ℃ in a tube furnace protected by argon for reaction for 4 to 6 hours. Because the initial alloying temperature of the silicon powder and the magnesium powder is 500 ℃, Mg2Si cannot be formed when the temperature is lower than 500 ℃, and magnesium is easy to evaporate when the temperature is higher than 600 ℃, so that the loss of magnesium is caused, and partial silicon particles are not subjected to alloying reaction. The time is selected based on the lowest time for finishing the reaction and is related to the amount of the reaction materials; the less the material, the shorter the alloying time.
The method for processing the silicon-magnesium alloy by carbon coating comprises the following steps: 0.48g Tris was ultrasonically dispersed into 400ml deionized water, the pH of the deionized water was adjusted to 8.5 by adjusting the amount of Tris, followed by 600Mg Mg2Adding Si powder, adding dopamine hydrochloride under stirring, and reacting at room temperature for 1h to obtain polydopamine-coated Mg2And Si, vacuum filtering, and freeze drying. Because the silicon-magnesium alloy can react with H in water+The ions react and then decompose, and in order to ensure that the silicon-magnesium alloy can realize the carbon coating process in the deionized water, the deionized water needs to be firstly prepared to be alkaline, and then the silicon-magnesium alloy is added.
The nitriding treatment method of the carbon-coated magnesium silicide comprises the following steps: mg coated with the obtained polydopamine2The Si powder is heated to 700-900 ℃ at the heating rate of 2-10 ℃ in the nitrogen-containing atmosphere and is kept for 3-6h to carry out the nitridation reaction of the magnesium silicide. Introducing nitrogen-containing atmosphere for nitridation reaction, wherein the lowest temperature of the nitridation reaction is 700 ℃, the nitridation temperature cannot exceed 900 ℃, and otherwise, a byproduct MgSiN is generated2And (4) generating.
Tests and examples thereof prove that the adoption of the parameter ranges is more beneficial to optimizing the structure of the composite material and optimizing the catalytic activity.
Example 1
Commercial silicon metal was controlled to 3 μm in size by sanding, and silicon and magnesium powder were mixed in a molar ratio of 1: 1.8, putting the mixture into a stainless steel container after uniform mixing, and then heating the mixture to 550 ℃ in a tube furnace protected by argon to react for 6 hours to obtain the silicon-magnesium alloy. Ultrasonically dispersing 0.48g of Tris into 400ml of deionized water, adjusting the pH value of the deionized water to 8.5 by adjusting the amount of Tris, then adding 600Mg of silicon-magnesium alloy Mg2Si powder, adding dopamine hydrochloride under the condition of stirring, reacting for 1h at room temperature to obtain polydopamine-coated Mg2Si, vacuum filtering, and freeze drying; mg coated with the obtained polydopamine2Powder of Si in NH3Heating to 750 ℃ at the heating rate of 5 ℃/min and preserving heat for 6 h; acid washing the powder obtained after the nitridation reaction for 3 hours by using 1M/L HCl solution to remove Mg3N2And then, carrying out suction filtration on the solution to be neutral, and carrying out vacuum drying to obtain the carbon-coated porous silicon. Wherein the carbon layer accounts for 7.23 wt% of the total mass of the material, and the total size of the material particles is mainly concentrated in 3-5 μm.
The experimental results are as follows:
the XRD pattern of the material in each process of synthesis is obtained by utilizing the X-ray diffraction technology. From the XRD pattern of FIG. 1, it is understood that the reaction of Mg and Si after alloying completely produces Mg2Si, p-Mg2Coating Si with carbon layer, and coating Mg2Nitriding of Si produces Mg3N2And Si, followed by acid washing to remove Mg3N2I.e. leaving Si coated with carbon.
The proportion of carbon content in the material was analyzed by thermogravimetric analyzer, and the carbon content in the outer cladding porous silicon was 7.23% as seen from the thermogravimetric analysis curve of fig. 2.
The morphology of the synthesized material is observed by a scanning electron microscope, and as can be clearly seen from a TEM image of FIG. 3, the morphology of the particles of the material synthesized by the method is uniform, and the average size of the particles is 3-5 μm; the porous silicon surface is wrapped by a thin carbon layer 'cage', the spongy porous silicon is completely wrapped by the cage, and a proper space is left between the spongy porous silicon and the cage to form a typical yolk-shaped core-shell structure.
Through a transmission electron microscope and an energy spectrum technology, as can be seen from the analysis of a transmission electron microscope in fig. 4a, a porous silicon structure coated with a carbon layer can be finally obtained through the synthesis mode, sufficient gaps among the carbon layers are clearly visible, and the diameter of a continuous Si framework in a carbon cage is about 550 nm.
From the EDS spectrum analysis chart of the material in fig. 4b and 4c, the Si in the particle is composed of connected silicon skeletons, and a layer of carbon is uniformly coated outside the Si. As can be seen from the carbon distribution diagram of fig. 4b, the carbon element is uniformly distributed, which indicates that the carbon layer entirely covers the porous silicon instead of covering the surface of the porous silicon to form a non-uniform distribution. As can be seen from the Si element distribution diagram in fig. 4c, the Si element exists in the carbon layer in a form of skeleton-connected distribution, and the uneven distribution of the Si element indicates that there are significant pores inside the Si coated by the core-shell layer, which means that compared with the conventional carbon-coated porous silicon, the porous silicon of the material has more volume expansion buffer space in the carbon outer coating layer, further clearly indicating the core-shell-like yolk structure of the outer-coated porous silicon.
Fig. 5a is a schematic diagram of cycle performance test of the externally coated porous Si in example 1 of the present invention, wherein the externally coated porous Si of the present invention is tested under a long cycle at a current of 0.5C, and the first three cycles are activated by a small current of 0.05C. The results show that the outer coated porous silicon can still maintain high reversible capacity of 826.6mAh/g when circulating 1200 circles under the current density of 0.5C, and the capacity is up to 1098mAh/g when the current density is 600 circles. Fig. 5b is a schematic view of a rate performance test of the externally coated porous Si obtained in example 1 under different current densities, where the capacity retention rate of the externally coated porous Si is still about 50% when the current is increased from 0.1C to 1C and 10 times of the current is increased. Cycling at a greater 2C current still maintained a reversible capacity of 489.4 mAh/g.
FIG. 6a is a scanning electron microscope image of the cross section of the electrode film prepared by low loading amount and coated with porous Si in example 1 of the present invention, FIG. 6b is a scanning electron microscope image of the cross section of the electrode film prepared by low loading amount and coated with porous Si in example 1 of the present invention after complete lithiation, compare FIG. 6a and FIG. 6b, that is, the coated porous silicon material obtained in example 1 of the present invention has a surface loading amount of 2.8mAh/cm2The initial film thickness of the prepared electrode film is 18.4 mu m, the thickness of the electrode film is increased to 19.8 mu m after complete lithiation, and the expansion rate of the electrode film is 7.6%.
FIG. 6c is a scanning electron microscope image of the cross section of the electrode film prepared with high loading amount and coated with porous Si in example 1 of the present invention, FIG. 6d is a scanning electron microscope image of the cross section of the electrode film prepared with high loading amount and coated with porous Si in example 1 of the present invention after complete lithiation, comparing FIG. 6c with FIG. 6d, the coated porous silicon material obtained in example 1 of the present invention, even though the coated porous silicon material with the area loading amount of 5.2mAh/cm2The prepared electrode film had an initial film thickness of 39.8 μm, and after complete lithiation, the thickness of the electrode film increased to 45.6 μm, and the expansion rate of the electrode film was also only 14.6%.
Enough space is left in the externally coated porous silicon material obtained in the embodiment 1 of the invention to relieve the volume expansion of silicon, as long as the carbon cage is not damaged, although the internal Si is lithiated and expanded, the particle size of the whole material is not changed greatly, and the fact that the externally coated porous silicon with the yolk structure has an efficient control effect on the expansion of an electrode film is proved.
Example 2
Commercial silicon metal was controlled to 3 μm in size by sanding, and silicon and magnesium powder were mixed in a molar ratio of 1: 1.8, putting the mixture into a stainless steel container after uniform mixing, and then heating the mixture to 500 ℃ in a tube furnace protected by argon to react for 6 hours to obtain the silicon-magnesium alloy. Ultrasonically dispersing 0.48g of Tris into 400ml of deionized water, adjusting the pH value of the deionized water to 8.5 by adjusting the amount of Tris, and then adjusting 600Mg of silicon-magnesium alloy, namely Mg2Adding Si powder, adding dopamine hydrochloride under stirring, and reacting at room temperature for 1h to obtain polydopamine-coated Mg2Si, vacuum filtering, and freeze drying; mg coated with the obtained polydopamine2Powder of Si in NH3Raising the temperature to 750 ℃ at the temperature raising rate of 5 ℃ and preserving the temperature for 6 hours; acid washing the powder obtained after the nitridation treatment for 3h by using 1M/L HCl solution to remove Mg3N2The solution was then filtered to neutrality with suction and dried in vacuo. Because the alloying temperature is lower, silicon powder and magnesium powder can not fully react, the obtained silicon-magnesium alloy has the phenomenon of complete particle agglomeration of silicon for reaction, and if the silicon-magnesium alloy can not be synthesized, a porous silicon structure with uniform appearance can not be prepared.
Example 3
Commercial silicon metal was controlled to 3 μm in size by sanding, and silicon and magnesium powder were mixed in a molar ratio of 1: 1.8, putting the mixture into a stainless steel container after uniform mixing, and then heating the mixture to 550 ℃ in a tube furnace protected by argon to react for 6 hours to obtain the silicon-magnesium alloy. Ultrasonically dispersing 0.48g of Tris into 400ml of deionized water, adjusting the pH value of the deionized water to 8.5 by adjusting the amount of Tris, and then adjusting 600Mg of silicon-magnesium alloy, namely Mg2Adding Si powder, adding dopamine hydrochloride under stirring, and reacting at room temperature for 1h to obtain polydopamine-coated Mg2Si, vacuum filtering, and freeze drying; mg coated with the obtained polydopamine2Si powderAt NH3Raising the temperature to 700 ℃ at the temperature raising rate of 5 ℃ and preserving the temperature for 6 hours to carry out the nitriding reaction of the magnesium silicide; acid washing the powder obtained after the nitridation treatment for 3h by using 1M/L HCl solution to remove Mg3N2The solution was then filtered to neutrality with suction and dried in vacuo. Because the temperature of the nitriding reaction is low, the nitriding reaction just begins, the nitriding reaction is insufficient, and Mg cannot be completely removed2Conversion of Si to Mg3N2And Si, HCl directly reacts with Mg in the subsequent treatment step of hydrochloric acid etching2Si reacts to eliminate most of the material and form voids, which is contrary to the original intention of material synthesis.
In the carbon-coated porous silicon material designed by the invention, the carbon layer is not coated along the skeleton of the porous silicon, but the porous silicon particles are integrally coated in the carbon layer just like 'vesicles'. Carbon coated Mg2Nitriding Si to generate Mg3N2And Si, and then washed by an acid solution to remove Mg3N2The 'breathing space' of the porous silicon in the cladding layer is reserved, and the volume expansion of the silicon material in the lithium removal and insertion process can be relieved by the porous structure. The carbon layer is coated with porous silicon, so that the carbon layer not only has the functions of improving the conductivity of the material, improving the coulombic efficiency and serving as a protective layer, but also retains the structural advantages of the porous silicon and can better exert the electrochemical performance.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. An overclad porous silica material characterized by: the material is a typical core-shell structure formed by coating porous silicon outside carbon; the material is internally provided with porous silicon and externally provided with a carbon coating layer; outer coatingThe carbon shell is not coated along the pore structure of the porous silicon, and the porous silicon particles are integrally coated in the carbon shell; a suitable porous space is left between the carbon shell and the silicon, and the sources of the space are: carbon coated Mg2After the Si particles are subjected to nitridation reaction, acid washing is carried out to remove Mg3N2Leaving Si and pore spaces.
2. A method for producing an overclad porous silicon material comprising the overclad porous silicon material of claim 1, characterized in that: the method comprises the following steps:
step 1, synthesizing magnesium silicide by using commercial silicon powder and magnesium powder;
step 2, coating magnesium silicide particles as a precursor by using dopamine as a carbon source;
step 3, performing nitridation reaction treatment on the carbon-coated magnesium silicide obtained in the step 2;
and 4, carrying out acid washing treatment on the material nitrided in the step 3 through an acid solution to remove magnesium nitride, so as to obtain the carbon-coated porous silicon material.
3. The method of preparing an overclad porous silica material as claimed in claim 2, wherein:
the step 1 further comprises the following steps: silicon powder with the particle size of 1-10 mu m is used, and the molar ratio of silicon to magnesium powder is 1: 1.8, putting the mixture into a reaction vessel after uniform mixing, and then heating the mixture to the temperature of 500-600 ℃ in a tube furnace protected by argon for reaction for 4 to 6 hours to obtain the silicon-magnesium alloy.
4. The method of preparing an overclad porous silica material as claimed in claim 2, wherein:
the step 2 further comprises the following steps: ultrasonically dispersing Tris into deionized water, adjusting the pH value of the deionized water to 8.5 by adjusting the amount of Tris, and then Mg2Adding Si powder, adding dopamine hydrochloride under stirring, and reacting at room temperature for 1h to obtain polydopamine-coated Mg2And Si, vacuum filtering, and freeze drying.
5. The method of preparing an overclad porous silica material as claimed in claim 2, wherein:
the step 3 further comprises the following steps: mg coated with the obtained polydopamine2The Si powder is heated to 700-900 ℃ at the temperature rising rate of 2-10 ℃ in the atmosphere containing nitrogen and is kept for 3-6h, and magnesium silicide is nitrided to form Si and Mg3N2After the reaction, the reaction mixture was cooled to room temperature and taken out.
6. The method of preparing an overclad porous silica material as claimed in claim 2, wherein:
the step 4 further comprises the following steps: washing the powder obtained in the step (3) with an acid solution to remove Mg3N2And then, carrying out suction filtration on the solution to be neutral, and carrying out vacuum drying to obtain the core-shell structure carbon-coated porous silicon.
7. The method of preparing an overclad porous silica material as claimed in claim 3, wherein: the grain size of the used silicon powder is controlled to be 1-10 mu m, the temperature of the alloying reaction is 500-600 ℃, and the reaction time is 4-6 h.
8. The method of preparing an overclad porous silica material as claimed in claim 4, wherein: polydopamine coated Mg in step 22The Si powder is heated to 700-900 ℃ at the heating rate of 2-10 ℃ in the nitrogen-containing atmosphere and is kept for 3-6h to carry out the nitridation reaction of the magnesium silicide.
9. The application of the externally coated porous silicon material of claim 1 to the negative electrode of a lithium ion battery.
10. A lithium ion battery material characterized by: the battery material is an externally coated porous silicon material prepared by the preparation method of the externally coated porous silicon material according to any one of claims 2 to 8.
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