CN114524437B - Preparation method of silicon oxide material, product, negative electrode plate and secondary battery - Google Patents

Preparation method of silicon oxide material, product, negative electrode plate and secondary battery Download PDF

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CN114524437B
CN114524437B CN202210140626.7A CN202210140626A CN114524437B CN 114524437 B CN114524437 B CN 114524437B CN 202210140626 A CN202210140626 A CN 202210140626A CN 114524437 B CN114524437 B CN 114524437B
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molecular sieve
zsm
negative electrode
electrode sheet
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CN114524437A (en
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杨承成
吴秋丽
张凯
马斌
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Huizhou Liwinon Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention provides a preparation method of a silicon oxide material, which comprises the following steps: s1, taking a ZSM-5 molecular sieve as a raw material, and removing aluminum in the ZSM-5 molecular sieve to obtain a dealuminated ZSM-5 molecular sieve; s2, placing the dealuminated ZSM-5 molecular sieve obtained in the step S1 in a reducing atmosphere for reduction, and then washing, filtering and drying to obtain the silica material. Compared with the prior art, the invention takes ZSM-5 molecular sieve as SiO x Synthesizing a precursor, and preparing SiO with uniform particle size, regular morphology and ordered pore canal through dealumination and reduction x The negative electrode material can effectively relieve the problem of cyclic expansion of the silicon oxide material, the thickness expansion rate of the pole piece is low, the falling of the active material and repeated damage and repair of the SEI film are reduced, and the cycle performance of the battery is improved.

Description

Preparation method of silicon oxide material, product, negative electrode plate and secondary battery
Technical Field
The invention relates to the field of secondary batteries, in particular to a preparation method and product of a silicon oxygen material, a negative electrode plate and a secondary battery.
Background
With the development of digital 3C, new energy automobiles and energy storage equipment in recent years, higher requirements are put forward on the capacity density, cycle life and safety performance of lithium ion batteries. The specific capacity (372 mAh/g) of the current commercial graphite cathode is low, the energy and power density are close to the limit, and the development of a high-capacity cathode material system is an important precondition for developing a high-specific-capacity lithium ion battery. Pure silicon has higher theoretical specific capacity (4200 mAh/g) in the current anode material with lithium intercalation activity, but the huge volume expansion problem (400%) in the lithium intercalation process becomes a big obstacle for commercial application. Compared with a pure silicon anode, the silicon oxide generates lithium silicate when lithium is intercalated for the first time and the lithium oxide can buffer the volume change generated when lithium is deintercalated. Therefore, the silicon oxide has higher theoretical specific capacity (1965 mAh/g) and better cycle stability than a pure silicon anode.
But silicon oxide (SiO x ) The problems of low coulomb efficiency and cyclic decay for the first time still exist at present, because: 1) Formation of negative electrode SEI film and SiO x Irreversible formation of lithium oxide and lithium silicate upon first intercalation of lithium is two major causes of low first coulombic efficiency; 2) SiO (SiO) x The lithium/silicon alloying process of (2) is accompanied by volume change, about 200% can lead to pulverization of active material, falling off of active material and current collector, repeated damage of SEI, irreversible loss of capacity and attenuation of cycle performance; 3) SiO (SiO) x The low intrinsic conductivity of (3) also affects the performance of the material.
SiO in the industry at present x Silicon particles with the diameter of 2-10 nm are uniformly distributed on SiO by adopting a chemical vapor deposition method 2 Is contained in the matrix of (a). However, in practice, the particle and oxygen content cannot be controlled precisely, so that the prepared SiO x Recycling of material remains a major challenge.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the preparation method of the silicon-oxygen material is provided, so that the cyclic expansion problem of the silicon-oxygen material can be effectively improved, and the cyclic performance of the battery can be further improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a silicon oxide material comprises the following steps:
s1, taking a ZSM-5 molecular sieve as a raw material, and removing aluminum in the ZSM-5 molecular sieve to obtain a dealuminated ZSM-5 molecular sieve;
s2, placing the dealuminated ZSM-5 molecular sieve obtained in the step S1 in a reducing atmosphere for reduction, and then washing, filtering and drying to obtain the silica material.
Preferably, in step S1, the ZSM-5 molecular sieve is prepared by the following steps: the ZSM-5 molecular sieve precursor is prepared by mixing an aluminum source, a silicon source, an organic template agent and a solvent, and is centrifugally separated and dried after crystallization, and then the organic template agent is removed, so that the ZSM-5 molecular sieve is obtained.
Preferably, the molar ratio of the aluminum source to the silicon source to the organic template to the solvent is 1: (83-200): (10-12): 1500.
preferably, in the preparation method of the ZSM-5 molecular sieve, crystallization conditions are as follows: crystallizing for 100-150 h at 160-180 ℃; the drying temperature is 100-120 ℃; the reaction conditions for removing the organic template agent are as follows: reacting for 4-5 h at 500-600 ℃.
Preferably, in step S1, the dealumination conditions are: placing the mixture in concentrated nitric acid for reflux for 8 to 10 hours at the temperature of between 78 and 85 ℃. Preferably, the method further comprises the step of placing the ZSM-5 molecular sieve subjected to dealumination in an inert atmosphere for activation for 4-5 hours at 530-580 ℃ before reduction after dealumination.
Preferably, in step S2, the reducing atmosphere is hydrogen, and the reducing conditions are: reacting for 3-6 h at 500-650 ℃.
The second object of the present invention is to provide a silicone material produced by the method for producing a silicone material as described in any one of the above.
Another object of the present invention is to provide a negative electrode sheet comprising the aforementioned silicon oxide material.
The fourth object of the present invention is to provide a secondary battery comprising a positive electrode sheet, a negative electrode sheet and a separator interposed between the positive electrode sheet and the negative electrode sheet, wherein the negative electrode sheet is the negative electrode sheet described above.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the silica material provided by the invention adopts ZSM-5 molecular sieve as SiO x The synthesized precursor is a three-dimensional straight-through pore structure molecular sieve with high silicon-aluminum ratio, which is formed by crossing Z-shaped round pore canal parallel to a single cell a axis and elliptic pore canal parallel to a single cell b axis, and the unit cell composition is NanAlnSi96-No192, and the molecular sieve can be flexibly controlled in particle morphology, particle diameter, pore diameter and pore canal structure, so that SiO with uniform particle diameter, regular morphology and ordered pore canal can be prepared through dealumination and reduction x SiO obtained by the method x As a negative electrode material, the cyclic expansion problem of the silicon oxide material can be effectively relieved, and the reduction ofLess active material is dropped and SEI film is repeatedly damaged and repaired, so that the cycle performance and the first coulombic efficiency of the battery are improved.
Detailed Description
The first aspect of the present invention is directed to a method for preparing a silicone material, comprising the steps of:
s1, taking a ZSM-5 molecular sieve as a raw material, and removing aluminum in the ZSM-5 molecular sieve to obtain a dealuminated ZSM-5 molecular sieve;
s2, placing the dealuminated ZSM-5 molecular sieve obtained in the step S1 in a reducing atmosphere for reduction, and then washing, filtering and drying to obtain the silica material.
The ZSM-5 molecular sieve is a molecular sieve with a three-dimensional straight-through pore structure and a high silicon-aluminum ratio, the framework is formed by intersecting a Z-shaped round pore canal parallel to a single cell a axis and an elliptic pore canal parallel to a single cell b axis, and the molecular sieve contains ten-membered rings, and the basic structural unit consists of eight five-membered rings, so that the molecular sieve has good thermal stability. Wherein the long axis of the elliptic pore canal is
Figure BDA0003506204710000031
Short axis is->
Figure BDA0003506204710000032
The aperture of the Z-shaped round pore canal is +.>
Figure BDA0003506204710000033
The zigzag channel has a folding angle of 110 degrees and belongs to the mesoporous zeolite. The crystal structure belongs to the orthorhombic system, the space group Pnma, the lattice constant +.>
Figure BDA0003506204710000034
It has special structure without cages like A type, X type and Y type zeolite, and its pore canal is the cavity.
ZSM-5 has been developed since 1972 and is widely applied to petroleum refining, multi-carbon catalytic cracking and other directions, and the synthesis method thereof is mature, and the morphology, the particle size, the pore diameter and the pore channel structure of the molecular sieve can be controlled by regulating and controlling the Si/Al proportion, the pH, the concentration, the template agent, the reaction temperature, the pressure and the like.
The silicon oxide material is prepared by adding silicon particles to SiO 2 SiO is generated by high Wen Qihua reaction in matrix x However, the method has high energy consumption and the obtained SiO x The appearance of the product is irregular. Compared with the conventional method, the preparation method is simpler and has low energy consumption, and SiO with uniform particle size, regular morphology and ordered pore channels can be obtained x The material can effectively relieve the cyclic expansion problem of the silicon oxide material, reduce the falling of the active material and the repeated damage and repair of the SEI film, and further improve the cycle performance and the first coulomb efficiency of the battery. In addition, compared with molecular sieves with other structures, the ZSM-5 molecular sieve provided by the invention has the advantages that a part of O in the molecular sieve is replaced by Al, a part of O is carried away in the subsequent dealumination process, a part of O remains in the whole molecular sieve, the structure of the rest molecular sieve is relatively complete, the damage degree is smaller, and the obtained SiO can be effectively ensured x The material is provided with a morphology structure and ordered pore channels.
In some embodiments, in step S1, the ZSM-5 molecular sieve is prepared by: the ZSM-5 molecular sieve precursor is prepared by mixing an aluminum source, a silicon source, an organic template agent and a solvent, and is centrifugally separated and dried after crystallization, and then the organic template agent is removed, so that the ZSM-5 molecular sieve is obtained.
Wherein the aluminum source may be aluminum isopropoxide (AlP); the silicon source may be tetraethyl orthosilicate (TEOS); the organic template agent can be tetrapropylammonium hydroxide (TPAOH), the purity of the tetrapropylammonium hydroxide (TPAOH) is 25 percent, and the organic template agent can be used for controlling the pore size of the ZSM-5 molecular sieve by 'guiding' the growth of the framework of the molecular sieve lattice during preparation; the solvent may be deionized water.
Specifically, an aluminum source, a silicon source, an organic template agent and a solvent are mixed, a ZSM-5 molecular sieve precursor is obtained after condensation and reflux, then the mixture is transferred into a stainless steel crystallization kettle for crystallization reaction, mother liquor is removed through centrifugal separation after crystallization, deionized water is used for washing until the pH value is less than or equal to 9, unreacted substances are removed, and then the mixture is dried overnight, so that the organic template agent is removed, and the ZSM-5 molecular sieve is obtained.
In some embodiments, the molar ratio of the aluminum source, the silicon source, the organic template, and the solvent is 1: (83-200): (10-12): 1500. specifically, the molar ratio of the aluminum source to the silicon source to the organic template agent to the solvent is 1: (83-200): 10: 1500. 1: (83-200): 11: 1500. 1: (83-200): 11.5:1500 or 1: (83-200): 12:1500. preferably, the molar ratio of the aluminum source to the silicon source to the organic template to the solvent is 1: (83-200): 11.5:1500. 1, specifically, may be 1: (83-100): 11.5:1500. 1: (100-120): 11.5:1500. 1: (120-150): 11.5:1500. 1: (150-180): 11.5:1500 or 1: (180-200): 11.5:1500. the morphology, the particle size, the pore diameter and the pore channel structure of the molecular sieve can be flexibly controlled by regulating and controlling the molar ratio of the aluminum source, the silicon source, the organic template agent and the solvent.
In some embodiments, the ZSM-5 molecular sieve is prepared by a method comprising the following crystallization conditions: crystallizing at 160-180 deg.c for 100-150 hr. Specifically, the crystallization conditions include, but are not limited to, 160 ℃ crystallization 100h, 160 ℃ crystallization 120h, 160 ℃ crystallization 150h, 170 ℃ crystallization 100h, 170 ℃ crystallization 110h, 170 ℃ crystallization 120h, 170 ℃ crystallization 130h, 170 ℃ crystallization 140h, 170 ℃ crystallization 150h, 180 ℃ crystallization 100h, 180 ℃ crystallization 120h or 180 ℃ crystallization 150h. Preferably, the crystallization condition is crystallization at 170 ℃ for 110-130 h. The inventor discovers that the ZSM-5 molecular sieve with long-range order can be obtained by controlling crystallization under the conditions, and the stability of the crystal structure is higher.
In some embodiments, the ZSM-5 molecular sieve is prepared by a drying process at a temperature of 100 to 120℃for a drying time of 7 to 24 hours.
In some embodiments, the ZSM-5 molecular sieve is prepared under the following reaction conditions: reacting for 4-5 h at 500-600 ℃.
In some embodiments, in step S1, the dealumination conditions are: placing the mixture in concentrated nitric acid for reflux for 8 to 10 hours at the temperature of between 78 and 85 ℃. Preferably, the method further comprises the step of placing the ZSM-5 molecular sieve subjected to dealumination in an inert atmosphere for activation for 4-5 hours at 530-580 ℃ before reduction after dealumination. Residual moisture in the ZSM-5 molecular sieve pore channel can be removed after high-temperature activation, so that preparation is made for subsequent thermal reduction.
In some embodiments, in step S2, the reducing atmosphere is hydrogen, and the reducing conditions are: reacting for 3-6 h at 500-650 ℃. Specifically, the reduction conditions may be 3 hours at 500 ℃, 4 hours at 500 ℃, 6 hours at 500 ℃, 4 hours at 550 ℃, 5 hours at 550 ℃, 3 hours at 600 ℃, 4 hours at 600 ℃, 5 hours at 600 ℃, 4 hours at 650 ℃, or 6 hours at 650 ℃. Preferably, the reduction condition is 550-600 ℃ for 4-5 h. The reduction temperature and time difference can have different effects on the deoxidization effect, preferably SiO with uniform particle size, regular morphology and ordered pore canal can be obtained under the reduction condition x A material.
In a second aspect, the present invention is directed to a silicone material prepared by the method of preparing a silicone material as described in any one of the preceding claims. The silicon oxide material is SiO x (0＜x≤2)。
A third aspect of the present invention is directed to a negative electrode sheet comprising the aforementioned silicon oxide material. The negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer coated on at least one surface of the negative electrode current collector, wherein the negative electrode active material layer comprises the silicon oxygen material.
A fourth aspect of the present invention is directed to a secondary battery including a positive electrode sheet, a negative electrode sheet, and a separator interposed between the positive electrode sheet and the negative electrode sheet, the negative electrode sheet being the negative electrode sheet described above.
Wherein the positive electrode sheet is coated with an active material layer, the positive electrode active material may be a material having a chemical formula such as Li a Ni x Co y M z O 2-b N b (wherein 0.95.ltoreq.a.ltoreq.1.2, x)>0, y is greater than or equal to 0, z is greater than or equal to 0, and x+y+z=1, 0 is greater than or equal to b is greater than or equal to 1, M is selected from a combination of one or more of Mn, al, N is selected from a combination of one or more of F, P, S), the positive electrode active material may also be a combination of one or more of compounds including but not limited to LiCoO 2 、LiNiO 2 、LiVO 2 、LiCrO 2 、LiMn 2 O 4 、LiCoMnO 4 、Li 2 NiMn 3 O 8 、LiNi 0.5 Mn 1.5 O 4 、LiCoPO 4 、LiMnPO 4 、LiFePO 4 、LiNiPO 4 、LiCoFSO 4 、CuS 2 、FeS 2 、MoS 2 、NiS、TiS 2 And the like. The positive electrode active material may be further subjected to a modification treatment, and a method for modifying the positive electrode active material should be known to those skilled in the art, for example, the positive electrode active material may be modified by coating, doping, or the like, and the material used for the modification treatment may be one or more combinations including, but not limited to, al, B, P, zr, si, ti, ge, sn, mg, ce, W, or the like. The positive current collector used for the positive plate is usually a structure or a part for collecting current, and the positive current collector may be various materials suitable for being used as a positive current collector of a lithium ion battery in the field, for example, the positive current collector may include, but is not limited to, a metal foil, etc., and more specifically may include, but is not limited to, an aluminum foil, etc.
And the separator may be a variety of materials suitable for lithium ion battery separators in the art, for example, may be a combination of one or more of polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, natural fibers, and the like.
In order to make the technical solution and advantages of the present invention more apparent, the present invention and its advantageous effects will be described in further detail below with reference to the specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a silicon oxide material comprises the following steps:
s1, preparation of ZSM-5 molecular sieve: aluminum isopropoxide (AlP) is used as an aluminum source, tetraethyl orthosilicate (TEOS) is used as a silicon source, tetrapropylammonium hydroxide (TPAOH, purity 25%) is used as an organic template agent, deionized water is used as a solvent, and the molar ratio of the aluminum source, the silicon source, the organic template agent and the solvent is 1 based on the content of 2.7L of deionized water: 150:11.5:1500; taking AlP and TEOS, adding TPAOH and 30mL of deionized water, condensing and refluxing to obtain a ZSM-5 molecular sieve precursor, transferring the ZSM-5 molecular sieve precursor into a 200mL stainless steel crystallization kettle, crystallizing at 170 ℃ for 5 days, centrifugally separating the obtained product to remove mother liquor, washing with deionized water until the pH value is less than or equal to 9, drying overnight at 110 ℃, and then placing at 550 ℃ for 4 hours to remove an organic template agent to obtain the ZSM-5 molecular sieve;
s2, dealumination of ZSM-5 molecular sieve: placing the ZSM-5 molecular sieve in 13M concentrated nitric acid, and refluxing for 8-10 hours at 80 ℃ to remove aluminum in the ZSM-5 molecular sieve, thereby obtaining the dealuminated ZSM-5 molecular sieve;
s3, thermal reduction: the ZSM-5 molecular sieve after dealumination is placed in hydrogen for reduction under the following conditions: reacting for 4 hours at 600 ℃; then placing the mixture in 6M HCl solution, stirring and washing for 4 hours, filtering and drying to obtain a silica material SiO x (0＜x≤2)。
Example 2
Unlike example 1, the dealumination of the ZSM-5 molecular sieve: and (3) placing the ZSM-5 molecular sieve in 13M concentrated nitric acid, refluxing for 8-10 hours at 80 ℃ to remove aluminum in the ZSM-5 molecular sieve, filtering, washing, and activating for 4 hours at a high temperature of 550 ℃ under nitrogen to obtain the dealuminated ZSM-5 molecular sieve.
The remainder is the same as embodiment 1 and will not be described here again.
Example 3
Unlike example 2, in the preparation of ZSM-5 molecular sieve, the molar ratio of aluminium source, silicon source, organic template and solvent is 1:83:11.5:1500.
the remainder is the same as embodiment 2 and will not be described here again.
Example 4
Unlike example 2, in the preparation of ZSM-5 molecular sieve, the molar ratio of aluminium source, silicon source, organic template and solvent is 1:120:11.5:1500.
the remainder is the same as embodiment 2 and will not be described here again.
Example 5
Unlike example 2, in the preparation of ZSM-5 molecular sieve, the molar ratio of aluminium source, silicon source, organic template and solvent is 1:200:11.5:1500.
the remainder is the same as embodiment 2 and will not be described here again.
Example 6
Unlike example 2, the dealumination of the ZSM-5 molecular sieve: and (3) placing the ZSM-5 molecular sieve in 13M concentrated nitric acid, refluxing for 8-10 hours at 80 ℃ to remove aluminum in the ZSM-5 molecular sieve, filtering, washing, and activating for 4 hours at a high temperature of 450 ℃ under nitrogen to obtain the dealuminated ZSM-5 molecular sieve.
The remainder is the same as embodiment 2 and will not be described here again.
Example 7
Unlike example 2, the dealumination of the ZSM-5 molecular sieve: and (3) placing the ZSM-5 molecular sieve in 13M concentrated nitric acid, refluxing at 80 ℃ for 8-10 hours to remove aluminum in the ZSM-5 molecular sieve, filtering and washing, and activating at 600 ℃ for 4 hours under nitrogen to obtain the dealuminated ZSM-5 molecular sieve.
The remainder is the same as embodiment 2 and will not be described here again.
Example 8
Unlike example 2, the dealuminated ZSM-5 molecular sieve was reduced by thermal reduction under nitrogen under the following conditions: reacting for 4 hours at 600 ℃; then placing the mixture in 6M HCl solution, stirring and washing for 4 hours, filtering and drying to obtain a silica material SiO x (0＜x≤2)。
The remainder is the same as embodiment 2 and will not be described here again.
Example 9
Unlike example 2, the dealuminated ZSM-5 molecular sieve was reduced by thermal reduction under the following conditions: reacting for 5 hours at 500 ℃; then placing the mixture in 6M HCl solution, stirring and washing for 4 hours, filtering and drying to obtain a silica material SiO x (0＜x≤2)。
The remainder is the same as embodiment 2 and will not be described here again.
Example 10
Unlike example 2, the dealuminated ZSM-5 molecular sieve was reduced by thermal reduction under the following conditions: reacting for 4 hours at 550 ℃; then placing the mixture in 6M HCl solution, stirring and washing for 4 hours, filtering and drying to obtain a silica material SiO x (0＜x≤2)。
The remainder is the same as embodiment 2 and will not be described here again.
Example 11
Unlike example 2, the dealuminated ZSM-5 molecular sieve was reduced by thermal reduction under the following conditions: reacting for 3.5h at 650 ℃; then placing the mixture in 6M HCl solution, stirring and washing for 4 hours, filtering and drying to obtain a silica material SiO x (0＜x≤2)。
The remainder is the same as embodiment 2 and will not be described here again.
The silicon oxide materials obtained in examples 1 to 11 were used as a negative electrode active material, and were mixed with conductive carbon black Super P and sodium carboxymethyl cellulose according to a mass ratio of 8:1:1, fully and uniformly mixing the materials in deionized water to form negative electrode slurry; and coating the negative electrode slurry on a copper foil, drying and rolling to obtain the negative electrode plate.
And (3) taking the lithium sheet as a counter electrode, assembling the lithium sheet and the negative electrode sheet in a glove box under argon atmosphere, sealing, standing for 24 hours, and then performing constant-current charge and discharge test on the performance of the battery.
1) And (3) testing the thickness expansion rate of the pole piece: the battery was charged to 4.25V at a constant current of 1C, then charged to 0.05C at a constant voltage of 4.25V, left for 5min, and then discharged to 2.8V at a constant current of 1C, which was the first cycle. The battery was subjected to 20 cycles according to the above conditions. The thickness of the pole piece before and after cycling was measured with a height gauge. The thickness expansion ratio was calculated by:
thickness expansion ratio = [ (thickness after cycle-thickness before cycle)/thickness before cycle ] ×100%.
2) Cyclic capacity test: the battery is charged to 4.25V at a constant current of 1C at 25+/-2 ℃, then charged to 0.05C at a constant voltage of 4.25V, kept stand for 5min, and then discharged to 2.8V at a constant current of 1C, wherein the discharge capacity is the discharge capacity of the first cycle in a charge-discharge cycle process. The battery was subjected to 100 cycles of charge and discharge test according to the above method, and the discharge capacity per cycle was recorded.
Cycle capacity retention (%) =discharge capacity of 100 th cycle/discharge capacity of first cycle×100%
The test results are shown in Table 1 below.
TABLE 1
Expansion ratio of negative plate thickness (%) Capacity retention rate%
Example 1 8.9％ 91.4％
Example 2 6.5％ 94.3％
Example 3 15.3％ 86.4％
Example 4 10.6％ 88.6％
Example 5 18.9％ 83.6％
Example 6 8.8％ 92.1％
Example 7 6.9％ 93.8％
Example 8 13.9％ 87.3％
Example 9 10.8％ 88.9％
Example 10 8.7％ 91.8％
Example 11 15.7％ 86.1％
As can be seen from a comparison of examples 1 and 2, before the thermal reduction after dealumination of the ZSM-5 molecular sieve, the ZSM-5 molecular sieve is continuously placed in nitrogen for high-temperature activation, so that residual moisture in the pore canal of the ZSM-5 molecular sieve can be effectively removed, the subsequent thermal reduction is facilitated, and further the thickness expansion of the pole piece can be further relieved and the cycle performance of the battery can be improved. It can be seen from comparison of examples 2, 6 to 7 and 8 to 11 that the reaction conditions of high-temperature activation and thermal reduction at different temperatures also have an influence on the cyclic expansion and the cyclic capacity retention rate of the pole piece.
In addition, as can be seen from comparison of examples 2 to 5, in the preparation of the ZSM-5 molecular sieve, different molar ratios of the aluminum source, the silicon source, the organic template agent and the solvent also have an influence on the thickness expansion and the cycle performance of the pole piece. In general, the higher the silicon content is, the larger the expansion rate of the pole piece is, but the silicon-aluminum ratio has a larger influence on the morphology product of the molecular sieve, even when the silicon content is relatively high, if the morphology of the obtained molecular sieve is regular and the pore channels are ordered, the cyclic expansion problem of the silicon can be effectively improved, and the cyclic performance is further improved.
In conclusion, the negative electrode material obtained by the preparation method can effectively relieve the problem of cyclic expansion of the silicon oxide material, has low thickness expansion rate of the pole piece, reduces the falling-off of the active material and repeated damage and repair of the SEI film, and further improves the cycle performance of the battery.
Variations and modifications of the above embodiments will occur to those skilled in the art to which the invention pertains from the foregoing disclosure and teachings. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in light of the present teachings. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.

Claims (8)

1. The preparation method of the silica material is characterized by comprising the following steps of:
s1, taking a ZSM-5 molecular sieve as a raw material, placing the ZSM-5 molecular sieve in concentrated nitric acid to reflux for 8-10 hours at 78-85 ℃ and removing aluminum in the ZSM-5 molecular sieve to obtain a dealuminated ZSM-5 molecular sieve;
s2, placing the dealuminated ZSM-5 molecular sieve obtained in the step S1 in a hydrogen atmosphere, reacting for 3-6 hours at 500-650 ℃ for reduction, and then washing, filtering and drying to obtain the silica material.
2. The method for preparing a silica material according to claim 1, wherein in step S1, the method for preparing the ZSM-5 molecular sieve comprises the steps of: the ZSM-5 molecular sieve precursor is prepared by mixing an aluminum source, a silicon source, an organic template agent and a solvent, and is centrifugally separated and dried after crystallization, and then the organic template agent is removed, so that the ZSM-5 molecular sieve is obtained.
3. The method for preparing a silicon oxygen material according to claim 2, wherein the molar ratio of the aluminum source, the silicon source, the organic template agent and the solvent is 1: (83-200): (10-12): 1500.
4. a method for preparing a silica material according to claim 2 or 3, wherein in the method for preparing a ZSM-5 molecular sieve, crystallization conditions are: crystallizing for 100-150 h at 160-180 ℃; the drying temperature is 100-120 ℃; the reaction conditions for removing the organic template agent are as follows: reacting for 4-5 h at 500-600 ℃.
5. The method for preparing a silica material according to claim 1, further comprising, before the reduction after dealumination, activating the dealuminated ZSM-5 molecular sieve in an inert atmosphere at 530 to 580 ℃ for 4 to 5 hours.
6. A silicone material prepared by the method of any one of claims 1 to 5.
7. A negative electrode sheet comprising the silicon oxide material according to claim 6.
8. A secondary battery comprising a positive electrode sheet, a negative electrode sheet, and a separator interposed between the positive electrode sheet and the negative electrode sheet, wherein the negative electrode sheet is the negative electrode sheet of claim 7.
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