CN114420912A - Ceramic phase silicon-nitrogen layer coated silicon negative material, preparation method and application thereof - Google Patents
Ceramic phase silicon-nitrogen layer coated silicon negative material, preparation method and application thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 106
- 239000010703 silicon Substances 0.000 title claims abstract description 103
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 65
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 54
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- 238000010438 heat treatment Methods 0.000 claims abstract description 34
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- 239000012298 atmosphere Substances 0.000 claims abstract description 27
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 12
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- 238000000034 method Methods 0.000 claims description 32
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- 239000002070 nanowire Substances 0.000 claims description 23
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- 238000006243 chemical reaction Methods 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
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- 239000007773 negative electrode material Substances 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
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- 239000011856 silicon-based particle Substances 0.000 abstract description 4
- 239000007784 solid electrolyte Substances 0.000 abstract description 2
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 15
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- 229910000676 Si alloy Inorganic materials 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
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- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-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
-
- 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/664—Ceramic materials
Abstract
A ceramic phase silicon-nitrogen layer coated silicon negative material, a preparation method and application thereof comprise the following steps: selecting silicon nano particles or silicon nano or porous silicon particles and the like as raw materials, soaking the raw materials in hydrofluoric acid solution to remove surface silicon oxide, and carrying out freeze drying treatment; and (3) placing the silicon sample in an atmosphere furnace, heating the silicon sample at a certain heating rate in a nitrogen-containing atmosphere, preserving the heat, performing nitridation treatment, and cooling the silicon sample to room temperature to obtain the ceramic-phase silicon-nitrogen layer-coated silicon negative electrode composite material. The silicon nitrogen layer is formed by stoichiometric ratio Si3N4And non-stoichiometric SiNxThe composite material can solve the problems of insufficient silicon conductivity and unstable solid electrolyte membrane, and simultaneously, Si3N4AsThe ceramic phase provides mechanical strength and mitigates structural chalking due to excessive expansion. In addition, SiNxIn the presence of Li+Post-formation of highly conductive and lithium ion transporting Li3And N, so that the silicon-nitrogen layer coated silicon negative electrode material shows excellent lithium storage performance and has application prospect in lithium ion batteries.
Description
Technical Field
The invention relates to a porous silicon, nano silicon particles and silicon nanowire material, in particular to a preparation method and application of a ceramic phase silicon-nitrogen layer coated silicon material, nano silicon particles and silicon nanowire material.
Background
The lithium ion battery has the advantages of light weight, large energy storage, large power, no pollution, long service life and the like, and is one of the representatives of the current green new energy industry. The graphite material has the characteristics of wide source, high tap density and stable electrochemical performance, so that the graphite material becomes the most common negative electrode material in the current commercial lithium ion battery, but is limited by low theoretical capacity and poor rate performance, and the graphite negative electrode material can not meet the requirements of energy industries such as future power automobiles and the like, so researchers are dedicated to searching the lithium ion battery negative electrode material with high energy density and long cycle life. Compared with the graphite anode material, the silicon anode material has high theoretical specific capacity (4200mAh/g) and low charge and discharge platform, so that the silicon anode material is favored by researchers. Because the material has wide sources, abundant reserves, environmental protection and wide application in the solar energy field and the semiconductor industry, and the production cost of the material is gradually reduced along with the maturity of the related technology, the silicon cathode is the first choice of the next generation of high specific energy lithium ion battery cathode material acknowledged in the industry. However, it is also limited by its own drawbacks, that high volume expansion after lithium intercalation is very likely to cause pulverization and structural damage of the electrode active material, and that electrochemical failure is caused after the silicon material is detached from the conductive agent. Silicon itself has poor conductivity, low electron conduction and ion diffusion leading to slow kinetics and poor rate performance.
The silicon can generate huge volume expansion in the electrochemical reaction process, so that natural SEI on the surface of the silicon is continuously generated and cracked, the electrochemical performance of the silicon is reduced, the electrochemical performance of the Si cathode is improved in various ways, and the construction of the surface coating layer on the surface of the Si cathode is a common way with obvious effect at present. The surface coating layer modified silicon negative electrode material is constructed, so that the interface stability of the material can be improved, and lithium ions are promotedThe transmission can avoid the direct contact of the silicon anode material and the electrolyte to a certain extent, inhibit the overgrowth of natural SEI in the battery circulation process and reduce the battery impedance, so the method can better improve the electrochemical performance of the silicon anode material. For example, in-situ polymerization reaction of monomers of a polymer on the surface of a silicon-based material is performed through the action of a deep eutectic solvent to obtain a polymer composite coating layer with uniformly distributed inorganic matters, the negative electrode material can form an organic-inorganic composite surface coating layer in situ in the processes of initial lithiation and delithiation, the structural integrity of the composite material can be ensured in a circulation process, however, a lithium-silicon alloy is required in the preparation process of the composite material, ultrasonic stirring operation is still required in the subsequent process, and although the whole step process is performed in a glove box, the high activity of the lithium-silicon alloy can cause huge potential safety hazards. In addition, the subsequent materials need to be subjected to multiple centrifugal operations, so that the yield of the composite material in the whole production process is low, once the composite material is put into large-scale production and application, the production efficiency of the whole production process is influenced, and the production cost is increased undoubtedly; in the patent, "a silicon-based composite material and its preparation method and energy storage device (CN 109728259 a)", by forming a composite surface coating layer composed of a fast ion conductor layer and a fluorocarbon-containing material layer on the surface of silicon particles, the fluorocarbon material of the outer layer of the surface coating layer has a certain ductility, which better avoids the phenomenon of structural damage easily occurring in the material expansion process, but because the surface is coated by a carbon layer and a fluorocarbon material, the bonding strength between the two layers is insufficient, so the silicon-based composite material has poor performance in structural stability, and the preparation process is complex and cannot be widely applied in a large scale. For example, in the document "aluminum Solid Electrolyte Coating to Reduce Lithium grafting in Silicon Anode for High Performance Lithium-Ion Batteries (Advanced Materials Interfaces,2019,6(21):1901187), Al is first prepared using ammonium formate and sulfuric acid as additives2O3Silicon negative electrode material as surface coating layer, and then lithium hydroxide monohydrateThe slurry is mixed and annealed in a tube furnace to prepare LiAO2The film-coated silicon negative material has simple whole preparation process and can show excellent electrochemical performance on the nano-scale silicon negative. However, the finished coating formed on the surface of the silicon particle is limited in the strength of the film material, and in the discharge process of the silicon negative material, the volume of the particle is over-expanded due to the insertion of lithium ions, and the film material and the surface of the silicon particle are in a close fit state, so that the film material cannot resist large stress generated in the expansion process of the particle, the structure is damaged, and the cycle stability and the rate capability are affected. Such as "Si @3N4The article @ Ccposite with egg-like structure as high-performance and material for lithium ion batteries, firstly, nano Si is nitridized at 1250 deg.C to prepare Si3N4And (3) coating the Si composite material, and then introducing argon and acetylene atmosphere at 850 ℃ to prepare the C shell coated multilayer ovoid structural material. Si3N4As a ceramic phase, the composite material has high strength and toughness, internal stress generated when Si expands can be effectively relieved, and the outermost C shell can improve the overall conductivity of the composite material, so that the composite material can show quite excellent electrochemical performance. However, the temperature for preparing the material in the article is high, and once the material is put into industrial production, the cost is high. For example, in the document "Scalable synthesis of ant-nest-like bulk silicon for high-performance lithium-ion batteries", the outer carbon layer can effectively improve the problem of poor conductivity of Si itself and can effectively prevent the Si from generating excessive volume expansion by coating the surface of the formicary porous silicon with a carbon layer. However, the carbon layer itself has poor mechanical strength and still cannot resist the excessive volume expansion of Si well. And in this document 850 ℃ under Ar/H2The carbonization treatment is carried out in the atmosphere, the atmosphere involved in the reaction process is dangerous, and the production has larger potential safety hazard and lower safety coefficient in industrial production. For example, in the patent "Si-conductive ceramic composite negative electrode material for lithium battery and preparation method", the conductive ceramic is used as the framework to inhibit the volume expansion of silicon negative level and improve the electricity of the materialThe mobility is high, however, the production steps are more, the sintering temperature of the material is as high as 1380-1450 ℃, and the excessively high sintering temperature increases the production cost and increases the potential safety hazard.
Disclosure of Invention
In order to solve the defects in the prior art, the invention discloses a porous silicon material coated by a ceramic phase silicon-nitrogen layer, which has the technical scheme as follows:
the ceramic phase silicon-nitrogen layer cladding silicon negative material is characterized in that: the material is a typical core-shell structure composite material formed by silicon coated by a ceramic phase silicon-nitrogen layer, porous silicon or nano silicon particles or silicon nanowires are arranged inside the material, and the ceramic phase silicon-nitrogen layer is arranged outside the material; after hydrofluoric acid surface treatment, Si-H bonds are formed, and the external silicon nitrogen layer is tightly combined with the internal silicon to form a good surface coating layer.
The invention also discloses a preparation method of the ceramic phase silicon-nitrogen layer coated silicon negative material, which is characterized by comprising the following steps: the method comprises the following steps:
step 1: selecting porous silicon or nano silicon or silicon nanowire materials, immersing the porous silicon or nano silicon or silicon nanowire materials into hydrofluoric acid solution with the mass fraction of 0.01-25%, pickling for 0.01-200min, stirring at the same time, and then carrying out suction filtration and drying treatment;
step 2: and (3) placing the sample obtained in the step (1) in a tubular furnace, heating to 600-1100 ℃ at a heating rate of 0.1-20 ℃/min in a nitrogen-containing atmosphere, preserving heat for a certain time, and cooling to room temperature to obtain the silicon material coated by the ceramic phase silicon-nitrogen layer.
The invention also discloses a method for preparing the ceramic phase silicon-nitrogen layer coated silicon negative material, and the ceramic phase silicon-nitrogen layer coated porous silicon or nano silicon particles or silicon nanowire composite material prepared by the method is applied to a lithium ion battery.
The invention also discloses application of the ceramic phase silicon-nitrogen layer coated silicon negative material in a lithium ion battery.
Has the advantages that:
the invention passes through Si3N4And SiNxThe mixed coating of (1) can effectively solve the problem of insufficient silicon conductivity, and simultaneously Si3N4As ceramic phase, SiN can provide mechanical strength and alleviate structural chalking caused by excessive expansionxIn the presence of Li+Post-formation of highly conductive and lithium ion transporting Li3N, direct contact with the Si core can minimize the problem of insufficient conductivity of silicon as a semiconductor. Besides improving the electrochemical performance of the Si cathode, the preparation method is simple, the process is short, the preparation temperature is low, the production cost is saved, and the potential safety hazard is reduced to the minimum in the preparation process.
Drawings
FIG. 1 shows Si as obtained in example 1 of the present invention3N4/SiNxSi coated as surface coating layer3N4/SiNxThe schematic drawing of a scanning electron microscope of the @ Si porous composite material is that the particle size of the negative electrode material is 3-5 microns, the negative electrode material has a three-dimensional cross-linked framework structure which is uniformly distributed, a porous space is favorable for entering of electrolyte, the transmission path of lithium ions can be shortened, and holes can provide a certain space for silicon expansion, so that pulverization of the material is reduced.
FIG. 2 shows Si as obtained in example 1 of the present invention3N4/SiNxSi coated as surface coating layer3N4/SiNxThe XRD patterns of the @ Si composite, showing the XRD patterns of p-Si and p-Si @ SiN, have almost the same peak positions, and broad diffraction peaks at 28.5 °, 47.3 °, 56.2 °, 69.2 ° and 76.5 ° are assigned to the (111), (220), (311), (400) and (331) planes of the Si cubic phase, and no peaks other than pure Si are detected. However, the p-Si @ SiN sample was weaker than p-Si, indicating that very subtle changes occurred after formation of the Si and SiN composite.
FIG. 3 shows Si as obtained in example 1 of the present invention3N4/SiNxSi coated as surface coating layer3N4/SiNxThe transmission electron microscope image of the @ Si composite material, wherein (a) is the transmission electron microscope image under 100nm, and a large number of holes and skeletons can be observed very clearly; (b) the diameter of the holes is about 20nm in a transmission electron microscope image under 20 nm; (c) is a transmission electron microscope image under the condition of 5nm, an outer ceramic phase silicon-nitrogen layer and an inner silicon coreThe core keeps close fit, the thickness of the ceramic phase silicon-nitrogen layer coated on the surface is only 3-5nm, the content of the thinner ceramic phase silicon-nitrogen layer serving as a surface coating layer is lower, the capacity of a silicon negative material cannot be reduced, meanwhile, the conductivity of the silicon negative material can be improved, and the electrochemical performance is improved.
Fig. 4 is a graph of electrochemical cycling performance of porous silicon coated with a silicon nitride ceramic phase as a surface coating layer prepared in example 1 of the present invention, and the porous silicon coated with the silicon nitride ceramic phase shows higher specific discharge capacity after 500 cycles at a current density of 2A/g and 500 cycles at a current density of 5A/g, and shows better electrochemical performance.
Detailed Description
The invention discloses a ceramic phase silicon-nitrogen layer coated silicon negative material, which is characterized in that: the material is a typical core-shell structure formed by porous silicon or nano silicon particles or a silicon nanowire composite material coated by a ceramic phase silicon-nitrogen layer, wherein silicon is arranged inside the material, and the ceramic phase silicon-nitrogen layer is arranged outside the material; after hydrofluoric acid surface treatment, Si-H bonds are formed, and the outer silicon nitrogen layer is tightly combined with the inner silicon to form a surface coating layer.
The invention also discloses a preparation method of the ceramic phase silicon-nitrogen layer coated silicon negative material, which comprises the following steps: the method comprises the following steps:
step 1: selecting porous silicon or nano silicon or silicon nanowire materials, immersing the porous silicon or nano silicon or silicon nanowire materials into hydrofluoric acid solution with the mass fraction of 0.01-25%, pickling for 0.01-200min, stirring at the same time, and then carrying out suction filtration and drying treatment;
preferably: selecting porous silicon with the particle size of 0.05-20 microns as a raw material, immersing the silicon raw material into a hydrofluoric acid solution with the mass fraction of 2%, pickling for 15min, stirring, and then carrying out suction filtration and drying treatment;
step 1 is further explained as follows: selecting porous silicon with the particle size of 0.05-20 mu m as a raw material, soaking the silicon raw material into hydrofluoric acid solution with the mass fraction of 2%, pickling for 15min, stirring, then performing suction filtration, and performing drying treatment in a freeze dryer for 24 h; the shorter drying time results in higher water content in the sample, which affects the performance of the subsequent prepared sample, and the longer drying time results in less difference in the problem of removing the water content in the sample, and increases the production cost.
Step 2: and (3) placing the sample obtained in the step (1) in a tube furnace, heating to 600-1100 ℃ at a heating rate of 0.1-20 ℃/min in a nitrogen-containing atmosphere, preserving heat for a certain time, and cooling to room temperature to obtain the silicon material coated by the ceramic phase silicon-nitrogen layer.
Preferably: and (3) placing the sample in the step (1) in a tubular furnace, heating to 600-1100 ℃ at a heating rate of 5 ℃/min in a nitrogen-containing atmosphere, preserving the heat for 10-1000 min, and cooling to room temperature to obtain the silicon material coated by the ceramic phase silicon-nitrogen layer.
This step 2 is further described as follows: and (3) placing the sample obtained in the step (1) in a tubular furnace, firstly heating to 780 ℃ at a heating rate of 5 ℃/min in a nitrogen-containing atmosphere, then carrying out heat preservation reaction for 15min, and naturally cooling the sample to room temperature to obtain the ceramic-phase silicon nitride layer-coated nano silicon composite material sample. If the content of the nitrogen-containing atmosphere in the step 2 is low, the reaction degree of the sample is not enough, and a complete ceramic phase silicon-nitrogen layer coated nano-silicon composite material sample cannot be obtained, and if the volume fraction of the nitrogen-containing atmosphere in the step 2 is too large, the reaction is too violent in a short time, so that the ceramic phase silicon-nitrogen layer on the surface is too thick, and the electrochemical performance of the composite material is reduced.
Example 1
(1) Selecting porous silicon with the particle size of 3-5 microns as a raw material, soaking the silicon raw material into a hydrofluoric acid solution with the mass fraction of 2%, pickling for 15min, stirring at the same time, then performing suction filtration, and performing drying treatment in a freeze dryer for 24 h;
(2) and (3) placing the sample in the step (1) in a tubular furnace, firstly heating to 780 ℃ at a heating rate of 5 ℃/min under the condition of a nitrogen-containing atmosphere, then carrying out heat preservation reaction for 15min, and obtaining the porous silicon sample coated by the ceramic phase silicon nitrogen layer after the sample is naturally cooled to room temperature.
Results of the experiment
As can be seen from the scanning electron micrograph of FIG. 1, Si prepared in this example3N4Si with/SiNx as surface coating layer3N4/SiNxThe @ Si composite material has a structure ofA cross-linked porous structure. The negative electrode material has the particle size of 3-5 microns, has a three-dimensional cross-linked framework structure which is uniformly distributed, a porous space is favorable for the entering of electrolyte, the transmission path of lithium ions can be shortened, and the holes can provide a certain space for silicon expansion and reduce the pulverization of the material.
The XRD patterns for p-Si and p-Si @ SiN are shown in FIG. 2, with the p-Si @ SiN having nearly identical peak positions. Broad diffraction peaks at 28.5 °, 47.3 °, 56.2 °, 69.2 °, and 76.5 ° were assigned to the (111), (220), (311), (400), and (331) planes of the Si cubic phase, and no other peaks except for pure Si were detected. However, the p-Si @ SiN sample was weaker than p-Si, indicating that very subtle changes occurred after formation of the Si and SiN composite.
As can be seen from the transmission electron microscope image in fig. 3, the porous silicon composite material coated with the ceramic-phase silicon-nitrogen layer and used as the surface coating layer has a three-dimensional cross-linked porous structure, wherein (a) is a transmission electron microscope image under 100nm, a large number of pores and frameworks can be very clearly observed, and the internal porous structure provides a certain space for internal expansion of silicon, which can alleviate excessive volume expansion in the discharge process to a certain extent. (b) The diameter of the holes is about 20nm in a transmission electron microscope image under 20 nm; (c) is a transmission electron microscope image under the condition of 5nm, the outer ceramic phase silicon nitrogen layer is tightly adhered to the inner silicon core, the thickness of the ceramic phase silicon nitrogen layer coated on the surface is only 3-5nm, and the Si without electrochemical activity3N4Can improve the mechanical property of the surface coating layer, has good promotion effect on stabilizing electrode materials, and has electrochemical activity SiNxLi capable of forming high conductivity and high lithium ion transmission after lithium intercalation3N can effectively improve the conductivity of silicon, so that the surface coating layer formed by compounding the two phases can enable the composite material to show excellent electrochemical performance.
Fig. 4 is a schematic diagram of a cycle performance test of the porous silicon coated with the ceramic-phase silicon-nitrogen layer in embodiment 1 of the present invention, and the ceramic-phase silicon-nitrogen layer still has high capacity and good cycle stability after 500 cycles at current densities of 2 and 5A/g, so that the present invention can be industrially produced and applied in a large scale.
The porous silicon material coated by the ceramic phase silicon-nitrogen layer obtained in the example 1 of the invention has a three-dimensional cross-linked porous structure, the external silicon-nitrogen layer is tightly combined with the internal silicon core, the inactive silicon nitride ceramic phase has certain mechanical strength, and although the internal silicon is lithiated, certain volume expansion can occur, the particle size of the whole material is not greatly changed under the action of the external silicon nitride layer. Electrochemically active SiNxLi capable of forming high conductivity and high lithium ion transmission after lithium intercalation3N can effectively improve the conductivity of silicon, so that the surface coating layer formed by compounding two phases can enable the composite material to show excellent electrochemical performance
Example 2
(1) Taking porous silicon with the particle size of 0.05-20 μm as a raw material, soaking the silicon raw material into hydrofluoric acid solution with the mass fraction of 5%, pickling for 15min while stirring, then performing suction filtration, and performing drying treatment in a freeze dryer for 24 h.
(2) And (3) placing the sample in the step (1) in a tube furnace, heating to 780 ℃ at a heating rate of 15 ℃/min in a nitrogen-containing atmosphere, carrying out heat preservation reaction for 180min, and naturally cooling the sample to room temperature to obtain the ceramic phase silicon nitrogen layer coated porous silicon sample.
In case 2 of the invention, as the concentration of hydrofluoric acid is increased to a certain extent in step 1, more Si-H bonds are easily formed on the silicon surface, the heat preservation time is prolonged, so that the ceramic phase silicon nitride layer outside the silicon core becomes thicker, which is about 200nm, the thicker surface coating layer can better resist the expansion of the silicon core, but the density of the coating layer is increased, so that the lithium ion transmission performance is reduced, and the lithium insertion process of silicon becomes difficult, and in addition, the higher content silicon nitrogen layer can obviously reduce the specific discharge capacity of the negative electrode material, so that the performance is poorer. Therefore, the selection of the heat preservation time is very important, and the electrochemical performance is reduced because the surface silicon-nitrogen layer is too thick due to overlong heat preservation time.
Example 3
(1) Selecting nano silicon particles with the particle size of 10-500nm as a raw material, immersing the silicon raw material into a hydrofluoric acid solution with the mass fraction of 5%, pickling for 30min, stirring at the same time, then performing suction filtration, and performing drying treatment in a freeze dryer for 24 h.
(2) And (3) placing the sample in the step (1) in a tube furnace, heating to 600 ℃ at a heating rate of 10 ℃/min in a nitrogen-containing atmosphere, carrying out heat preservation reaction for 150min, and naturally cooling the sample to room temperature to obtain the ceramic-phase silicon-nitrogen layer-coated nano silicon particles.
In case 3 of the present invention, the heat treatment temperature in step 2 is 600 ℃, although the concentration of the hydrofluoric acid solution is increased and the heat preservation time is prolonged, the silicon-nitrogen layer on the surface of the prepared material is incompletely coated with the reduction of the reaction temperature, which indicates that the uniform ceramic phase silicon-nitrogen layer coated negative electrode material cannot be obtained at the reaction temperature. Therefore, the selection of the reaction temperature in the present invention is very important, and the temperature is too low to cause incomplete reaction.
Example 4
(1) Selecting nano silicon particles with the particle size of 10-500nm as a raw material, immersing the silicon raw material into a hydrofluoric acid solution with the mass fraction of 2%, pickling for 10min, stirring at the same time, then performing suction filtration, and performing drying treatment in a freeze dryer for 24 h.
(2) And (3) placing the sample in the step (1) in a tube furnace, heating to 1100 ℃ at a heating rate of 5 ℃/min in a nitrogen-containing atmosphere, carrying out heat preservation reaction for 1min, and naturally cooling the sample to room temperature to obtain the ceramic phase silicon nitrogen layer coated porous silicon sample.
In case 4 of the invention, although the pickling time is short and the heat preservation time is short, the heat treatment temperature in step 2 is greatly increased compared with 780 ℃, the nano silicon material coated by the ceramic phase silicon-nitrogen layer can be obtained, the thickness of the artificial coating layer on the surface is increased to about 50nm along with the increase of the reaction temperature, the content of the artificial silicon-nitrogen layer with a thicker surface plays a certain role in inhibiting the improvement of the electrochemical performance, and the performance improvement effect on the silicon negative material is not obvious. Therefore, the selection of the reaction temperature is very important in the invention, and the thickness of the silicon nitride layer on the surface is uncontrollable due to overhigh temperature, so that the electrochemical performance of the material is reduced due to overlarge thickness.
Example 5
(1) Selecting silicon nanowire with diameter of 10-500nm as raw material, soaking the silicon raw material in 25% hydrofluoric acid solution, pickling for 15min while stirring, vacuum filtering, and drying in a freeze dryer for 24 hr
(2) And (3) placing the dried silicon nanoparticles in the step (1) into a tubular furnace, firstly heating to 780 ℃ at a heating rate of 1 ℃/min in a nitrogen-containing atmosphere, carrying out heat preservation reaction for 5min, and naturally cooling the sample to room temperature to obtain the ceramic-phase silicon-nitrogen-layer-coated nano-silicon composite material sample.
In case 5 of the present invention, the hydrofluoric acid solution has a mass fraction of 25%, which causes a large amount of loss of silicon samples during the pickling process due to an excessively high concentration of hydrofluoric acid, and once put into practical production, the yield is greatly reduced in the entire production process. Therefore, the method is very important for selecting the mass fraction of the hydrofluoric acid solution, the mass fraction is too large, the etching degree of silicon is very large, and the yield of the silicon is very low.
Example 6
(1) Selecting silicon nanowire with diameter of 10-500nm as raw material, soaking the silicon raw material in 0.01 wt% hydrofluoric acid solution, pickling for 150min while stirring, vacuum filtering, and drying in freeze dryer for 24 hr
(2) And (3) placing the dried silicon nanowire in the step (1) into a tubular furnace, firstly heating to 780 ℃ at a heating rate of 10 ℃/min in a nitrogen-containing atmosphere, carrying out heat preservation reaction for 120min, and naturally cooling the sample to room temperature to obtain the ceramic-phase silicon-nitrogen-layer-coated nano-silicon composite material sample.
In case 6 of the invention, the silicon composite material is pickled in 0.01% hydrofluoric acid solution for 120min, although the reaction temperature is slightly increased, the silicon sample surface in the solution cannot be sufficiently treated due to the excessively low mass fraction of the hydrofluoric acid solution, and the ceramic phase silicon-nitrogen layer with uniform thickness cannot be generated on the sample surface in the subsequent heat treatment process, so that the prepared silicon composite material coated by the ceramic phase silicon-nitrogen layer has poor effect. Therefore, the selection of the mass fraction of the hydrofluoric acid solution is very important, and the low mass fraction of the hydrofluoric acid solution causes insufficient surface activation degree, so that the thickness distribution of the silicon nitride layer on the surface is uneven.
Example 7
(1) Selecting silicon nanowires with the diameter of 10-500nm as a raw material, immersing the silicon raw material into a hydrofluoric acid solution with the mass fraction of 2%, pickling for 15min, stirring at the same time, then performing suction filtration, and performing drying treatment in a freeze dryer for 24 h.
(2) And (3) placing the dried silicon nanowire in the step (1) into a tubular furnace, firstly heating to 780 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, carrying out heat preservation reaction for 15min, and naturally cooling the sample to room temperature to obtain the ceramic-phase silicon-nitrogen layer-coated silicon nanowire composite sample.
In case 7 of the present invention, since the selected nitrogen-containing atmosphere is nitrogen, and the activity of nitrogen is low at 780 ℃, the reaction is insufficient in the heat treatment process, and a complete ceramic phase silicon-nitrogen layer-coated silicon nanowire composite material cannot be obtained after the heat treatment process. Therefore, the selection of the atmosphere is very important, and the thickness distribution of the silicon nitride layer on the surface of the composite material prepared by selecting the nitrogen-containing atmosphere with low activity is not uniform.
In the above examples, the "under nitrogen-containing atmosphere" described in step 2 is: the nitrogen-containing atmosphere is nitrogen, ammonia gas, pyridine or a mixed gas of nitrogen and argon, a mixed gas of ammonia and argon, and a mixed gas of pyridine and argon; or a mixed gas of nitrogen, ammonia and argon, a mixed gas of nitrogen, pyridine and argon, and a mixed gas of ammonia, pyridine and argon; or a mixture of nitrogen, ammonia, pyridine and argon.
The ceramic phase silicon nitride coated porous silicon or nano silicon particles or silicon nanowires prepared by the invention have the following advantages:
the silicon nitride film is formed from stoichiometric non-electrochemically active silicon nitride (Si)3N4) And non-stoichiometric electrochemically active nitrogen-deficient silicon nitride (SiN)x) And (4) forming. Si3N4Can improve the mechanical property of the surface coating layer, has good promoting effect on stabilizing electrode materials, and is SiNxLi capable of forming high conductivity and high lithium ion transmission after lithium intercalation3N, which can effectively improve the conductivity of silicon. Therefore, the silicon nitride composite coating can effectively improve the rate capability and the cycling stability of the electrode material;
according to the invention, through simple acid washing and subsequent rapid heating and short-time nitriding treatment, the ceramic phase silicon-nitrogen layer-coated silicon material is obtained at a low temperature (lower than 1200 ℃), and can be used as a lithium ion battery cathode material, so that the electrochemical performance of the material can be improved;
the invention takes nitrogen-containing atmosphere as nitrogen source, has lower cost and safe atmosphere, and can reduce the potential safety hazard problem to the minimum;
according to the invention, the ceramic-phase silicon nitride-coated porous silicon or nano silicon particles or silicon nanowires are prepared through acid washing and subsequent annealing treatment, the treatment process is simple, the raw material source is wide, and the large-scale production can be realized.
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 (8)
1. A ceramic phase silicon-nitrogen layer coated silicon negative material is characterized in that: the material is a typical core-shell structure formed by porous silicon or nano silicon particles or a silicon nanowire composite material coated by a ceramic phase silicon-nitrogen layer, wherein silicon is arranged inside the material, and the ceramic phase silicon-nitrogen layer is arranged outside the material; after hydrofluoric acid surface treatment, Si-H bonds are formed, and the external silicon nitrogen layer is tightly combined with the internal silicon to form an artificial surface layer.
2. The preparation method of the ceramic phase silicon-nitrogen layer coated silicon negative material comprises the ceramic phase silicon-nitrogen layer coated silicon negative material of claim 1, and is characterized in that: the method comprises the following steps:
step 1: selecting porous silicon or nano silicon or silicon nanowire materials, immersing the porous silicon or nano silicon or silicon nanowire materials into hydrofluoric acid solution with the mass fraction of 0.01-25%, pickling for 0.01-200min, stirring at the same time, and then carrying out suction filtration and drying treatment;
step 2: and (3) placing the sample obtained in the step (1) in a tubular furnace, heating to 600-1100 ℃ at a heating rate of 0.1-20 ℃/min in a nitrogen-containing atmosphere, preserving heat for 1-200min, and cooling to room temperature to obtain the silicon material coated by the ceramic phase silicon-nitrogen layer.
3. The method for preparing the ceramic phase silicon-nitrogen layer coated silicon negative material according to claim 2, wherein the method comprises the following steps: the step 1 further comprises the following steps: porous silicon with the grain diameter of 0.05-20 mu m or nano silicon with the grain diameter of 10-500nm or silicon nano wires with the diameter of 10-500nm are selected as raw materials, the silicon raw materials are immersed into hydrofluoric acid solution with the mass fraction of 2 percent to be pickled for 15min and stirred at the same time, and then the filtration and drying treatment are carried out.
4. The method for preparing the ceramic phase silicon-nitrogen layer coated silicon negative material according to claim 2, wherein the method comprises the following steps: the nitrogen-containing atmosphere in the step 2 is as follows: nitrogen, ammonia, pyridine or a mixed gas of nitrogen and argon, a mixed gas of ammonia and argon, and a mixed gas of pyridine and argon; or a mixed gas of nitrogen, ammonia and argon, a mixed gas of nitrogen, pyridine and argon, and a mixed gas of ammonia, pyridine and argon; or a mixture of nitrogen, ammonia, pyridine and argon.
5. The method for preparing the ceramic phase silicon-nitrogen layer coated silicon negative material according to claim 2, wherein the method comprises the following steps: the step 1 further comprises: porous silicon with the grain diameter of 3-5 mu m is selected as a raw material, the silicon raw material is immersed into hydrofluoric acid solution with the mass fraction of 2% for acid washing for 15min and stirring, and then the mixture is filtered, and is dried for 24h in a freeze dryer.
6. The method for preparing the ceramic phase silicon-nitrogen layer coated silicon negative material according to claim 2, wherein the method comprises the following steps: the step 2 further comprises: and (3) placing the sample in the step (1) in a tubular furnace, firstly heating to 780 ℃ at a heating rate of 5 ℃/min under the condition of a nitrogen-containing atmosphere, then carrying out heat preservation reaction for 15min, and obtaining the porous silicon sample coated by the ceramic phase silicon nitrogen layer after the sample is naturally cooled to room temperature.
7. The porous silicon or nano silicon particles or silicon nanowire material coated by the ceramic phase silicon-nitrogen layer prepared by the preparation method of the ceramic phase silicon-nitrogen layer coated silicon negative material according to any one of claims 2 to 6 is applied to a lithium ion battery.
8. The ceramic phase silicon-nitrogen layer-coated silicon negative material of claim 1 is applied to a lithium ion battery.
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|---|---|---|---|---|
| CN116799178A (en) * | 2023-06-19 | 2023-09-22 | 浙江锂宸新材料科技有限公司 | Silicon-carbon negative electrode material, preparation method thereof and lithium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288087A (en) * | 2013-05-28 | 2013-09-11 | 浙江大学 | Surface modification process for improving luminance and dispersity of porous silicon |
| CN106058227A (en) * | 2016-06-28 | 2016-10-26 | 南昌大学 | Surface nitriding modification method of silica powder for lithium ion battery |
| CN107342403A (en) * | 2017-06-09 | 2017-11-10 | 江永斌 | Nano material containing silicon nitride and its production and use |
| KR20170130786A (en) * | 2016-05-19 | 2017-11-29 | 숭실대학교산학협력단 | Preparing method for carbon nanofibers composites comprising silicon/ silicon nitride and silicon carbide core-shell composites |
| WO2018205665A1 (en) * | 2017-05-09 | 2018-11-15 | 武汉科技大学 | Method for preparing ant-nest like porous silicon used for lithium ion battery |
-
2022
- 2022-01-24 CN CN202210078397.0A patent/CN114420912A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288087A (en) * | 2013-05-28 | 2013-09-11 | 浙江大学 | Surface modification process for improving luminance and dispersity of porous silicon |
| KR20170130786A (en) * | 2016-05-19 | 2017-11-29 | 숭실대학교산학협력단 | Preparing method for carbon nanofibers composites comprising silicon/ silicon nitride and silicon carbide core-shell composites |
| CN106058227A (en) * | 2016-06-28 | 2016-10-26 | 南昌大学 | Surface nitriding modification method of silica powder for lithium ion battery |
| WO2018205665A1 (en) * | 2017-05-09 | 2018-11-15 | 武汉科技大学 | Method for preparing ant-nest like porous silicon used for lithium ion battery |
| CN107342403A (en) * | 2017-06-09 | 2017-11-10 | 江永斌 | Nano material containing silicon nitride and its production and use |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116799178A (en) * | 2023-06-19 | 2023-09-22 | 浙江锂宸新材料科技有限公司 | Silicon-carbon negative electrode material, preparation method thereof and lithium ion battery |
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Application publication date: 20220429 Assignee: Hubei Benxing Carbon Material Co.,Ltd. Assignor: WUHAN University OF SCIENCE AND TECHNOLOGY Contract record no.: X2022420000139 Denomination of invention: A ceramic phase silicon nitrogen coating negative grade silicon material, its preparation method and application License type: Exclusive License Record date: 20221206 |