CN114094087B - 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 101
- 239000002210 silicon-based material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000005121 nitriding Methods 0.000 claims abstract description 22
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 22
- 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
- 239000002245 particle Substances 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 8
- 229960003638 dopamine Drugs 0.000 claims abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 92
- 229910052799 carbon Inorganic materials 0.000 claims description 89
- 229910052710 silicon Inorganic materials 0.000 claims description 35
- 239000011777 magnesium Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 34
- 239000010703 silicon Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 23
- 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
- 239000011258 core-shell material Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229920001690 polydopamine Polymers 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910019018 Mg 2 Si Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000007983 Tris buffer Substances 0.000 claims description 10
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000005253 cladding Methods 0.000 claims description 8
- 239000011856 silicon-based particle Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 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
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- -1 magnesium nitride Chemical class 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 11
- 238000005275 alloying Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract description 2
- 239000012044 organic layer Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 22
- 239000002153 silicon-carbon composite material Substances 0.000 description 12
- 238000011068 loading method Methods 0.000 description 10
- 238000001000 micrograph Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006138 lithiation reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 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
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000002969 egg yolk Anatomy 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FXWVHZGIXNUEEQ-UHFFFAOYSA-N C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1=CC=CC=C1.C=O Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1=CC=CC=C1.C=O FXWVHZGIXNUEEQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019752 Mg2Si Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- GGUPMVXPXHZNKF-UHFFFAOYSA-N benzene-1,2-diol;formaldehyde Chemical compound O=C.OC1=CC=CC=C1O GGUPMVXPXHZNKF-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
An overcladding porous silicon material, a preparation method and application thereof, comprising: (1) Silicon powder and magnesium powder with the particle size of 1-10 mu m are mixed according to the mole ratio of 1:1.8 obtaining magnesium silicide through alloying reaction; (2) Coating a dopamine organic layer on magnesium silicide as a precursor; (3) Placing the powder obtained in the steps into an atmosphere furnace, raising the temperature at a certain heating rate under a nitrogen-containing atmosphere, and preserving the temperature to perform nitriding reaction; (4) The powder obtained in the above steps is washed with an acid solution, then filtered to be neutral and dried in vacuum. The synthetic process of the patent is simple, and the sources of raw materials are wide; the externally coated porous silicon anode material has stable structure, long-acting circulation in lithium ion battery, excellent multiplying power performance and small swelling rate (less than 20%) of electrode film, and has good commercial application prospect.
Description
Technical Field
The invention relates to a material and a preparation method thereof, in particular to an externally coated porous silicon and a preparation method and application thereof.
Background
Silicon-based anode materials are considered as one of the most potential anode materials of next-generation lithium ion batteries, and have the advantages that: silicon is used as a negative electrode material of the lithium ion battery, and the theoretical lithium storage capacity can reach 4200mAh/g, which is more than 10 times of that of the traditional graphite negative electrode material battery; meanwhile, silicon is rich in reserves on the earth and wide in source.
However, the disadvantages of silicon as a negative electrode material are also very pronounced: firstly, silicon is a semiconductor, the conductivity is poor, and the irreversible degree in the lithium ion deintercalation process is high, so that the first coulomb efficiency is reduced; and secondly, the silicon anode material can generate huge volume expansion in the charge and discharge process, so that the electrode material is crushed, and the structure of the electrode material and the SEI film are seriously damaged. The development of a silicon anode material with good electrochemical performance is a hot subject of a silicon-based lithium ion battery. The carbon coating layer is favorable for improving the performance of the silicon-based negative electrode material and the conductivity of the silicon-based negative electrode material, and can be used as a protective layer for preventing the silicon material from being in direct contact with electrolyte, so that a thick solid electrolyte interface layer is avoided. There are two main ways of silicon-carbon composite materials, cladding and embedding. Most of coating type silicon-carbon composite materials are scheme routes of coating carbon along a silicon framework, the requirement on the degree of carbon coating is severe, the carbon coating is unstable and still can lead to crushing of the silicon framework in the charge-discharge process, and the excessive thickness of a carbon layer can lead to difficult intercalation or deintercalation of lithium ions and lower specific capacity; the embedded silicon-carbon composite material carbon is difficult to bear the volume change in long circulation, and the carbon is easy to be unevenly distributed, so that the silicon utilization rate is low.
The carbon-coated silicon anode material not only achieves the utilization of silicon-carbon anode material carbon, but also achieves the purpose of relieving the volume expansion of the silicon material by utilizing a carbon-coated structure, and has great advantages and potential.
The prior art is as follows: the porous silicon anode material with a core-shell structure for a lithium ion battery and a preparation method thereof (CN 202010639804.1) disclose a porous silicon anode material with a core-shell structure for a lithium ion battery and a preparation method thereof, wherein the porous silicon anode material is of a core-shell structure, the inner core comprises nano porous silicon, graphite and amorphous carbon, and the outer shell is of amorphous carbon; the ratio of the nano porous silicon in the anode material is 30-70 wt%, the ratio of the graphite is 20-45 wt% and the ratio of the amorphous carbon is 10-40 wt%; 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 is coated with the porous silicon material, carbon can stabilize the skeleton structure of porous silicon and control the content below 10%, so that silicon contributes more to the specific capacity of the anode material and has higher specific capacity than the traditional silicon-carbon composite material.
Patent: a porous silicon-carbon composite material of a lithium ion battery and a preparation method and application thereof (CN 202010604417.4) 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: proper amount of alkyl glycosideCompletely dissolving the type activator in water to obtain a first solution; adding a proper amount of ammonia water into the first solution under the water bath condition, and stirring to obtain a second solution with the pH value of 7-9; adding tetraethoxysilane substances into the second solution, stirring, washing to neutrality, performing suction filtration, and drying the solid substances obtained by suction filtration under inert atmosphere; placing the solid matter into a reaction furnace, introducing 0.5L/min-3L/min of hydrogen at 700-1300 ℃ and sintering for 1-8 hours to prepare the silicon/silicon dioxide/porous carbon composite material; adding the silicon/silica/porous carbon composite material to an HF acid solution and continuously stirring to remove part of the SiO 2 And then drying under inert atmosphere, crushing the 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 is designed to be similar to the process of adding a carbon source into a solution to enable a product to realize carbon coating, but the process of the invention is simpler, only needs a one-step carbon coating process, does not generate unnecessary SiO2, does not need to use HF solution for pickling and etching, does not need to coat carbon again, is environment-friendly and has low energy consumption.
Patent: the invention discloses a porous silicon-carbon composite material and a preparation method and application thereof (CN 105826527A), and the invention discloses a preparation method of the porous silicon-carbon composite material, which comprises the following steps: placing magnesium silicide powder into CO 2 Carrying out heat treatment at 700-900 ℃ in Ar mixed atmosphere, and then carrying out acid washing and post-treatment to obtain the porous silicon-carbon composite material; said CO 2 In the mixed atmosphere of Ar and CO 2 The volume fraction of (2) is 10-90%. The porous silicon prepared by the method for coating carbon outside the porous silicon coated with the carbon has the advantages of simplicity, controllable carbon coating amount, no CO2 atmosphere, realization of a porous silicon structure with an advantageous carbon coating outside, more stable structure, more stable SEI film and long circulation capacity. Literature: nonfilling Carbon Coating of Porous Silicon Micrometer-Sized Particles for High-Performance Lithium Battery Anodes (DOI: 10.1021/nn505410 q) reported a non-filled porous silicon structure with a carbon coating, using commercially available SiO particles, coating the particles with a benzenediol-formaldehyde resin followed by heatingSo that SiO particles generate a disproportionation reaction, and the benzene diphenol-formaldehyde resin is pyrolyzed to form a carbon coating layer, and the SiO is removed by HF solution etching 2 Thus obtaining the unfilled carbon-coated porous silicon structure. The method needs HF solution to remove SiO 2 HF solutions are extremely corrosive and have a certain risk. According to the invention, the porous Si structure can be obtained by removing magnesium nitride only by using HCl solution, the used dopamine raw material is cheap, the required temperature in the whole process is small, the energy consumption is low, and the steps are simple.
Disclosure of Invention
In order to realize the preparation of the silicon-carbon anode material which is controllable, low in cost and capable of long-acting stable circulation in a battery, the invention designs a route with multiple materials, simplicity, controllability and low cost, and realizes the preparation of the externally coated porous silicon material, and the material can achieve the purpose of stabilizing the structure of the carbon-coated porous silicon skeleton, and can reasonably control the carbon content so as to improve the specific capacity of the silicon-carbon anode material.
In order to achieve the above purpose, the invention provides the following technical scheme: a porous silicon anode material coated with carbon is characterized in that porous silicon is coated with carbon to form a typical core-shell structure. The material is internally porous silicon and externally a carbon coating layer. The outer coated carbon shell is not coated along the pore canal structure of the porous silicon, and the porous silicon particles are integrally coated in the carbon shell. A proper porous space is reserved between the carbon shell and the silicon, and the space is obtained by: carbon coated Mg 2 After the nitriding reaction, the Si particles are pickled to remove Mg 3 N 2 Leaving Si and tunnel space.
The invention provides a preparation method of externally coated porous silicon, which is characterized by comprising the following steps of: step 1, synthesizing magnesium silicide by using commercial silicon powder and magnesium powder; step 2, coating magnesium silicide particles with dopamine serving as a carbon source serving as a precursor; step 3, carrying out nitriding reaction treatment on the carbon-coated magnesium silicide 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, thereby obtaining the carbon-coated porous silicon material. The externally coated porous silicon prepared by the method is characterized in that: the carbon-coated porous silicon anode material is a core-shell structure composed of a carbon coating layer and silicon with formic nest-shaped porous structure; the size of the prepared coated porous silicon particles is 3-12 mu m; the carbon layer uniformly coating the porous silicon particles accounts for 5-20% of the whole content.
According to the invention, the carbon layer is integrally coated instead of a core-shell structure coated along porous silicon pore channels, the carbon layer can be uniformly coated, and the porous silicon can leave enough breathing space in the carbon layer to relieve the expansion of the porous silicon in the lithium intercalation and deintercalation process, and meanwhile, the externally coated carbon layer can also play a role in maintaining structural stability, so that the silicon is prevented from being directly contacted with electrolyte.
Preferably, it is: the synthesis method of the magnesium silicide comprises the following steps: using commercial silicon powder with a particle size of 1-10 μm, silicon and magnesium powder are mixed in a molar ratio of 1:1.8, uniformly mixing, placing into a reaction vessel, and then heating to 500-600 ℃ in a tubular furnace protected by argon gas for reaction for 4-6h.
Preferably, it is: the polydopamine coated Mg 2 Nitriding treatment of Si powder is as follows: polydopamine coated Mg 2 Si is placed into a tube furnace with nitrogen atmosphere, heated to 700-900 ℃ at a heating rate of 2-10 ℃ and then is kept for 3-6 hours, then the material is cooled, taken out at room temperature, acid-washed for 1-3 hours by acid solution, and then is filtered and dried to obtain the outer-cladding porous silicon material.
The invention also discloses a cathode which applies the externally coated porous silicon material to a lithium ion battery.
The invention also discloses a lithium ion battery material, which is characterized in that: the battery material is an overcladding porous silicon material prepared by the overcladding porous silicon material preparation method
Compared with the prior art, the technical scheme of the invention has the following advantages: (beneficial effects are as follows)
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 situ. The method does not involve templates, is simple and feasible and is easy to produce in large scale.
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 conductivity of the material and enhances the structural stability.
3. The core-shell structure allows the porous silicon to be freely expanded and pulverized in the carbon layer, the Si can still be kept to have higher electrochemical activity, si is prevented from being in direct contact with electrolyte, the cyclic deterioration is avoided, the swelling rate of the electrode prepared from the material is small, and the material structure has obvious advantages for controlling the expansion of the electrode film.
Drawings
FIG. 1 is an XRD analysis of the reaction products of example 1 of the present invention, in which Mg was synthesized by an alloying reaction of silicon powder and magnesium powder 2 Si; through the polymerization process of dopamine, the polydopamine coated Mg is obtained 2 Si; mg is then added by nitriding 2 Nitriding Si to obtain Mg 3 N 2 And Si, followed by removal of Mg by pickling 3 N 2 The rest is the Si coated by carbon;
FIG. 2 is a thermogravimetric analysis of the overcladded porous silicon of example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the overcladded porous silicon in example 1 of the present invention;
FIG. 4a is a transmission electron microscope image of the outer cladding porous Si in example 1 of the present invention; FIGS. 4b and 4c are EDS spectroscopy graphs of the material;
FIG. 5a is a schematic view showing the cycle performance test of the overcladding porous Si in example 1 of the present invention; FIG. 5b is a schematic view showing the rate performance test of the overcoat porous Si obtained in example 1 at different current densities;
FIG. 6a is a cross-sectional scanning electron microscope image of an electrode film prepared at a low loading of the overcoat porous Si in example 1 of the present invention; FIG. 6b is a cross-sectional scanning electron microscope image of an electrode film prepared at a low loading with porous Si overcoated in example 1 of the present invention after complete lithiation; FIG. 6c is a cross-sectional scanning electron microscope image of an electrode film prepared at high loading with porous Si overcoated in example 1 of the present invention; fig. 6d is a cross-sectional sem image of an electrode film prepared with high loading of the overcladded porous Si in example 1 of the present invention after complete lithiation.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
An overcladded porous silicon material, characterized by: the material is a core-shell structure composed of a carbon coating layer and silicon with formic nest-shaped porous structure; the grain size of the selected commercial silicon powder is controlled to be 1-10 mu m, and the carbon layer of the uniformly coated porous silicon grain accounts for 5-20wt% of the whole content. The silicon-magnesium alloy synthesized by using the silicon powder with the granularity, which is obtained in the last step of the embodiment, is coated with the porous silicon material with the granularity distribution of 3-12 mu m, the small granularity of the material can lead to lower tap density, and the oversized granularity can influence the material performance and the reaction dynamics in the dealloying process.
The synthesis method of the silicon-magnesium alloy comprises the following steps: silicon and magnesium powder are mixed according to a mole ratio of 1:1.8, uniformly mixing, placing into a stainless steel container, and heating to 500-600 ℃ in a tubular furnace protected by argon gas for reaction for 4-6h. Because the initial alloying temperature of the silicon powder and the magnesium powder is 500 ℃, mg2Si cannot be formed below 500 ℃, and when the temperature is higher than 600 ℃, magnesium is easy to evaporate, so that magnesium loss is caused, and part of silicon particles do not undergo alloying reaction. The time is selected based on the lowest time of reaction completion and is related to the quantity of reaction materials; the less material, the shorter the alloying time.
The treatment method for carbon coating of the silicon-magnesium alloy comprises the following steps: 0.48g of Tris was sonicated into 400ml of deionized water, the pH of the deionized water was adjusted to 8.5 by formulating the amount of Tris, followed by 600Mg of Mg 2 Adding Si powder, adding dopamine hydrochloride under stirring, and reacting at room temperature for 1h to obtain polydopamine coated Mg 2 Si, vacuum filtering and freeze drying. Because the silicon-magnesium alloy can be mixed 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 is firstly blended 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: coating the obtained polydopamine coated Mg 2 Under nitrogen atmosphere, the Si powder is heated to 700-900 ℃ at a temperature rising rate of 2-10 ℃ and is kept for 3-6 hours, and thenAnd nitriding the magnesium silicide. Introducing nitrogen-containing atmosphere to carry out nitriding reaction, wherein the lowest occurrence temperature of the nitriding reaction is 700 ℃, the nitriding temperature cannot exceed 900 ℃, otherwise, a byproduct MgSiN is generated 2 And (3) generating.
Experiments and examples prove that the adoption of the parameter range is more beneficial to optimizing the structure of the composite material and optimizing the catalytic activity.
Example 1
Commercial metallic silicon was sanded to a size of 3 μm and the silicon to magnesium powder was mixed in a molar ratio of 1: and 1.8, uniformly mixing, putting into a stainless steel container, and heating to 550 ℃ in a tubular furnace protected by argon to react for 6 hours to obtain the silicon-magnesium alloy. Dispersing 0.48g of Tris into 400ml of deionized water by ultrasonic, regulating the pH value of the deionized water to 8.5 by regulating the amount of the Tris, then adding 600Mg of silicon-magnesium alloy, namely Mg2Si powder, adding dopamine hydrochloride under the condition of stirring, and reacting for 1h at room temperature to obtain polydopamine coated Mg 2 Si, vacuum filtering and freeze drying; coating the obtained polydopamine coated Mg 2 Si powder at NH 3 Raising the temperature to 750 ℃ at a heating rate of 5 ℃/min and preserving the temperature for 6 hours; the powder obtained after nitriding reaction is washed by HCl solution of 1M/L for 3h to remove Mg 3 N 2 And then filtering the solution to be neutral, and drying in vacuum to obtain the carbon-coated porous silicon. Wherein the carbon layer accounts for 7.23wt% of the whole mass of the material, and the whole size of the material particles is mainly concentrated in 3-5 mu m.
Experimental results:
the XRD patterns of the material during each synthetic process are obtained by using an X-ray diffraction technique. As can be seen from the XRD patterns of FIG. 1, the reaction of Mg and Si after alloying completely produces Mg 2 Si to Mg 2 Coating Si with carbon layer to obtain Mg 2 After nitriding Si, mg is generated 3 N 2 And Si, then washing off Mg by acid 3 N 2 I.e. Si coated with carbon remains.
The carbon content of the material was analyzed by a thermogravimetric analyzer, and the carbon content of the overcoat porous silicon obtained was found to be 7.23% from the thermogravimetric analysis curve of fig. 2.
The morphology of the material synthesized by the scanning electron microscope is observed, and the TEM image of the figure 3 shows that the morphology of the material particles synthesized by the method is uniform, and the average size of the particles is 3-5 mu m; the porous silicon surface is wrapped with a thin carbon layer 'cage', the cage completely wraps the spongy porous silicon, and a proper space is reserved between the spongy porous silicon and the spongy porous silicon 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 transmission electron microscope analysis of fig. 4a, a porous silicon structure with an outer carbon coating layer can be finally obtained through the synthesis mode, and sufficient gaps between the carbon layers are clearly visible, wherein the diameter of a continuous Si skeleton in a carbon cage is about 550 nm.
As can be seen from the EDS spectrum analysis diagrams of the material shown in FIG. 4b and FIG. 4c, si in the particles consists of a connected silicon skeleton, and a layer of carbon is uniformly coated outside the Si. As can be seen from the carbon element distribution diagram of fig. 4b, the carbon elements are uniformly distributed, which indicates that the carbon layer is entirely coated with the porous silicon instead of being coated on the surface of the porous silicon to form an unevenly distributed state. As can be seen from the Si element distribution diagram of fig. 4c, the Si element exists in a skeleton-connected distribution form in the carbon layer, and the uneven distribution of the Si element indicates that there are obvious holes in the core-shell layer coated Si, which means that the porous silicon of the material has more volume expansion buffer space in the carbon outer coating layer than the conventional carbon coated porous silicon, and further clearly indicates the core-shell yolk structure of the outer coated porous silicon.
FIG. 5a is a schematic diagram showing the cycle performance test of the overcladded porous Si of example 1 of the present invention, wherein the overcladded porous Si of the present invention was subjected to a long cycle test at 0.5C current, and the first three cycles were activated with a small current of 0.05C. The result shows that the high reversible capacity of 826.6mAh/g can be maintained by the overcladding porous silicon after 1200 circles under the current density of 0.5C, and the capacity is as high as 1098mAh/g at 600 circles. Fig. 5b is a schematic diagram showing the rate performance test of the overcladding porous Si obtained in example 1 at different current densities, wherein the overcladding porous Si has a capacity retention of about 50% when the current is increased from 0.1C to 1C and 10 times the current. At a greater 2C current, the reversible capacity of 489.4mAh/g can still be maintained.
FIG. 6a is a cross-sectional scanning electron microscope image of an electrode film prepared at a low loading of the overcoated porous Si of example 1 of the present invention, FIG. 6b is a cross-sectional scanning electron microscope image of an electrode film prepared at a low loading of the overcoated porous Si of example 1 of the present invention after complete lithiation, comparing FIGS. 6a and 6b, i.e., the overcoated porous Si material obtained in example 1 of the present invention, with a surface loading of 2.8mAh/cm 2 The prepared electrode film had an initial film thickness of 18.4. Mu.m, and after complete lithiation, the electrode film had an increased thickness of 19.8. Mu.m, and the electrode film had an expansion ratio of 7.6%.
FIG. 6c is a cross-sectional scanning electron microscope image of an electrode film prepared at a high loading of the overcoated porous Si of example 1 of the present invention, FIG. 6d is a cross-sectional scanning electron microscope image of an electrode film prepared at a high loading of the overcoated porous Si of example 1 of the present invention after complete lithiation, and the overcoated porous Si material obtained in example 1 of the present invention is compared with FIGS. 6c and 6d, even with a surface loading of 5.2mAh/cm 2 The initial film thickness of the prepared electrode film was 39.8 μm, and after complete lithiation, the electrode film thickness was increased to 45.6 μm, and the electrode film expansion ratio was also only 14.6%.
The outer-cladding porous silicon material obtained in the embodiment 1 of the invention has enough space left for relieving the volume expansion of silicon, so long as a carbon cage is not damaged, although the internal Si is lithiated and expanded, the particle size of the whole material is not greatly changed, and the fact that the outer-cladding porous silicon with a yolk structure has an efficient control effect on the expansion of an electrode film is proved.
Example 2
Commercial metallic silicon was sanded to a size of 3 μm and the silicon to magnesium powder was mixed in a molar ratio of 1: and 1.8, uniformly mixing, putting into a stainless steel container, and heating to 500 ℃ in a tubular furnace protected by argon to react for 6 hours to obtain the silicon-magnesium alloy. 0.48g of Tris is ultrasonically dispersed into 400ml of deionized water, the pH value of the deionized water is adjusted to 8.5 by preparing the amount of Tris, and then 600Mg of silicon-magnesium alloy, namely Mg 2 Adding Si powder, adding dopamine hydrochloride under stirring, and reacting at room temperature for 1h to obtain polydopamine coated Mg 2 Si, vacuum suction filtrationThen freeze-drying; coating the obtained polydopamine coated Mg 2 Si powder at NH 3 Raising the temperature to 750 ℃ at a temperature raising rate of 5 ℃ and preserving the heat for 6 hours; washing the powder obtained after nitriding with 1M/L HCl solution for 3h to remove Mg 3 N 2 The solution was then filtered to neutrality with suction and dried in vacuo. Because the alloying temperature is lower, the silicon powder and the magnesium powder cannot fully react, the obtained silicon-magnesium alloy has the phenomenon of agglomeration of silicon serving as a reaction complete particle, and if the silicon-magnesium alloy cannot be synthesized, the preparation of a porous silicon structure with uniform morphology cannot be realized.
Example 3
Commercial metallic silicon was sanded to a size of 3 μm and the silicon to magnesium powder was mixed in a molar ratio of 1: and 1.8, uniformly mixing, putting into a stainless steel container, and heating to 550 ℃ in a tubular furnace protected by argon to react for 6 hours to obtain the silicon-magnesium alloy. 0.48g of Tris is ultrasonically dispersed into 400ml of deionized water, the pH value of the deionized water is adjusted to 8.5 by preparing the amount of Tris, and then 600Mg of silicon-magnesium alloy, namely Mg 2 Adding Si powder, adding dopamine hydrochloride under stirring, and reacting at room temperature for 1h to obtain polydopamine coated Mg 2 Si, vacuum filtering and freeze drying; coating the obtained polydopamine coated Mg 2 Si powder at NH 3 Raising the temperature to 700 ℃ at a temperature raising rate of 5 ℃ and preserving the heat for 6 hours under the atmosphere of (1) to carry out nitriding reaction of magnesium silicide; washing the powder obtained after nitriding with 1M/L HCl solution for 3h to remove Mg 3 N 2 The solution was then filtered to neutrality with suction and dried in vacuo. Since the nitriding reaction is started just due to the low temperature, the nitriding reaction is insufficient and Mg cannot be completely reacted 2 Conversion of Si to Mg 3 N 2 And Si, HCl is directly combined with Mg in the subsequent treatment step of hydrochloric acid etching 2 Si reacts to eliminate most of the material to form cavities, contrary to the original purpose of material synthesis.
The carbon-coated porous silicon material is characterized in that a carbon layer is not coated along the skeleton of porous silicon, but the porous silicon particles are integrally coated in the carbon layer like a vesicle. Carbon coated Mg 2 Si is subjected to nitriding reaction to generate Mg 3 N 2 And Si, then washing with acid solution to remove Mg 3 N 2 The breathing space of the porous silicon in the coating layer is reserved, and the porous structure can relieve the volume expansion of the silicon material in the lithium removal and intercalation process. The porous silicon coated outside the carbon layer plays roles of improving the conductivity of the material, improving the coulomb efficiency and serving as a protective layer, simultaneously retains the structural advantage of the porous silicon, and can better exert the electrochemical performance.
The foregoing has shown and described the basic principles, principal 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, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The preparation method of the outer cladding porous silicon material comprises the steps of forming a typical core-shell structure by adopting carbon outer cladding porous silicon as the outer cladding porous silicon material; the inside of the material is porous silicon, and the outside is a carbon coating layer; the externally coated carbon shell is not coated along the pore canal structure of the porous silicon, and the porous silicon particles are integrally coated in the carbon shell; a proper porous space is reserved between the carbon shell and the silicon, and the space is obtained by: carbon coated Mg 2 After the nitriding reaction, the Si particles are pickled to remove Mg 3 N 2 The Si and pore space is left, and the preparation method 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 with dopamine serving as a carbon source serving as a precursor;
step 3, carrying out nitriding reaction treatment on the carbon-coated magnesium silicide 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, and obtaining the carbon-coated porous silicon material.
2. The method for preparing the overcladded porous silicon material as claimed in claim 1, wherein:
the step 1 further comprises the following steps: silicon powder with the particle size of 1-10 mu m is used, and the mole ratio of the silicon powder to the magnesium powder is 1:1.8, uniformly mixing, placing into a reaction vessel, and heating to 500-600 ℃ in a tubular furnace protected by argon to react for 4-6h to obtain the silicon-magnesium alloy.
3. The method for preparing the overcladded porous silicon material as claimed in claim 1, wherein:
the step 2 further comprises the following steps: ultrasonic dispersion of Tris into deionized water, adjustment of the pH of the deionized water to 8.5 by formulating the amount of Tris, followed by Mg 2 Adding Si powder, adding dopamine hydrochloride under stirring, and reacting at room temperature for 1h to obtain polydopamine coated Mg 2 Si, vacuum filtering and freeze drying.
4. The method for preparing an overcladded porous silicon material as recited in claim 3, wherein:
coating the obtained polydopamine coated Mg 2 The Si powder is heated to 700-900 ℃ at a temperature rising rate of 2-10 ℃ in a nitrogen-containing atmosphere and is kept at 3-6h, and magnesium silicide is nitrided to form Si and Mg 3 N 2 After the reaction, the mixture was cooled to room temperature and taken out.
5. The method for preparing the overcladded porous silicon material as claimed in claim 1, wherein:
the step 4 further comprises the following steps: washing the powder obtained in the step (3) by an acid solution to remove Mg 3 N 2 And 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.
6. The method for preparing an overcladded porous silicon material as recited in claim 3, wherein: polydopamine coated Mg 2 Si powder in nitrogen-containing gasUnder the atmosphere, the temperature is raised to 700-900 ℃ at the temperature rising rate of 2-10 ℃ and the temperature is kept at 3-6h, so as to carry out the nitriding reaction of magnesium silicide.
7. A lithium ion battery cathode material is characterized in that: the battery cathode material is an overclad porous silicon material prepared by the overclad porous silicon material preparation method according to any one of claims 1-6.
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