CN114524437A - Preparation method of silica material, silica material product, negative plate and secondary battery - Google Patents

Preparation method of silica material, silica material product, negative plate and secondary battery Download PDF

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CN114524437A
CN114524437A CN202210140626.7A CN202210140626A CN114524437A CN 114524437 A CN114524437 A CN 114524437A CN 202210140626 A CN202210140626 A CN 202210140626A CN 114524437 A CN114524437 A CN 114524437A
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molecular sieve
zsm
silicon
negative electrode
silica material
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CN114524437B (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

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Abstract

The invention provides a preparation method of a silicon-oxygen 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 dealuminized ZSM-5 molecular sieve; and S2, reducing the dealuminized ZSM-5 molecular sieve obtained in the step S1 in a reducing atmosphere, washing, filtering and drying to obtain the silica material. Compared with the prior art, the method takes the ZSM-5 molecular sieve as the SiOxSynthesizing a precursor, and dealuminizing and reducing to prepare SiO with uniform particle size, regular morphology and ordered pore passagesxThe negative electrode material can effectively relieve the problem of cyclic expansion of the silica material, the thickness expansion rate of the pole piece is low, and the activity is reducedThe dropping of the material and the repeated damage and repair of the SEI film, thereby improving the cycle performance of the battery.

Description

Preparation method of silica material, silica material product, negative plate and secondary battery
Technical Field
The invention relates to the field of secondary batteries, in particular to a preparation method of a silica material, a product, a negative 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. At present, the specific capacity (372mAh/g) of a commercial graphite negative electrode is low, the energy and power density are close to the limit, and the research and development of a high-capacity negative electrode material system are important prerequisites for developing a high-specific-capacity lithium ion battery. Pure silicon has higher theoretical specific capacity (4200mAh/g) in the current negative electrode material with lithium intercalation activity, but the problem of huge volume expansion (400%) in the lithium intercalation process becomes a great obstacle for the commercial application of the pure silicon. The generation of lithium silicate and lithium oxide upon the first lithium intercalation of the silicon oxide can buffer the volume change produced upon lithium deintercalation, relative to a pure silicon negative electrode. Therefore, the silicon oxide has higher theoretical specific capacity (1965mAh/g) and better cycling stability than a pure silicon negative electrode.
But silicon oxide (SiO)x) The problems of low coulombic efficiency and cyclic attenuation still exist for the first time at present, because: 1) formation of negative electrode SEI film and SiOxThe irreversible formation of lithium oxide and lithium silicate upon first intercalation of lithium is two major causes of first coulombic inefficiency; 2) SiO 2xThe lithium/silicon alloying process is accompanied by volume change, about 200 percent, which can cause active material pulverization, active material and current collector shedding, SEI repeated damage and generation, and irreversible loss of capacity and attenuation cycle performance; 3) SiO 2xThe intrinsic conductivity of the material is low, and the performance of the material is also influenced.
SiO in the industry at presentxGenerally, 2-10 nm silicon particles are uniformly distributed on SiO by adopting a chemical vapor deposition method2In the matrix of (a). However, in practice, the particle and oxygen content cannot be precisely controlled, so that the prepared SiOxRecycling of materials 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 silica material is provided, the problem of cyclic expansion of the silica material can be effectively solved, and the cyclic performance of the battery is further improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a silicon-oxygen 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 dealuminized ZSM-5 molecular sieve;
and S2, reducing the dealuminized ZSM-5 molecular sieve obtained in the step S1 in a reducing atmosphere, washing, filtering and drying to obtain the silica material.
Preferably, in step S1, the preparation method of the ZSM-5 molecular sieve is: aluminum source, silicon source, organic template agent and solvent are mixed to prepare a ZSM-5 molecular sieve precursor, the precursor is crystallized, centrifugally separated and dried, and then the organic template agent is removed to obtain the ZSM-5 molecular sieve.
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, the crystallization conditions are as follows: crystallizing at 160-180 ℃ for 100-150 h; 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: and (3) placing the mixture in concentrated nitric acid for refluxing for 8-10 h at 78-85 ℃. Preferably, the method also comprises the step of activating the dealuminized ZSM-5 molecular sieve in an inert atmosphere at 530-580 ℃ for 4-5 hours before reduction after dealuminization.
Preferably, in step S2, the reducing atmosphere is hydrogen, and the reducing conditions are: reacting for 3-6 h at 500-650 ℃.
Another object of the present invention is to provide a silicone material produced by the method for producing a silicone material according to any one of the above aspects.
The invention also provides a negative electrode sheet, which comprises the silicon-oxygen 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.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the silica material adopts a ZSM-5 molecular sieve as SiOx(x is more than 0 and less than or equal to 2), which is a molecular sieve with a three-dimensional through pore channel structure and high silicon-aluminum ratio, and is formed by crossing a Z-shaped circular pore channel parallel to a unit cell a axis and an elliptical pore channel parallel to a unit cell b axis, the unit cell is NanAlnSi96-No192, the molecular sieve can flexibly control the particle morphology, the particle size, the pore diameter and the pore channel structure, so that SiO with uniform particle size, regular morphology and ordered pore channels can be prepared by dealuminization and reductionxWith the obtained SiOxAs a negative electrode material, the problem of cyclic expansion of a silicon-oxygen material can be effectively relieved, and the falling of an active material and the repeated damage and repair of an SEI film are reduced, so that the cycle performance and the first coulombic efficiency of the battery are improved.
Detailed Description
The first aspect of the invention aims to provide a preparation method of a silicon-oxygen 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 dealuminized ZSM-5 molecular sieve;
and S2, reducing the dealuminized ZSM-5 molecular sieve obtained in the step S1 in a reducing atmosphere, washing, filtering and drying to obtain the silica material.
The ZSM-5 molecular sieve is a molecular sieve with a three-dimensional through pore channel structure and high silica-alumina ratio, a framework is formed by crossing a Z-shaped circular pore channel parallel to a unit cell axis a and an oval pore channel parallel to a unit cell axis b, the framework contains ten-membered rings, and a basic structural unit consists of eight five-membered rings, so the molecular sieve has good thermal stability. Wherein the major axis of the oval pore channel is
Figure BDA0003506204710000031
Short axis of
Figure BDA0003506204710000032
The aperture of the Z-shaped round pore canal is
Figure BDA0003506204710000033
The zigzag channels have a break angle of 110 degrees and belong to the medium pore zeolite. The crystal structure belongs to the orthorhombic system, space group Pnma and lattice constant
Figure BDA0003506204710000034
It has special structure without cage like A type, X type and Y type zeolite, and its pore channel is its cavity.
ZSM-5 is widely applied to petroleum refining, multi-carbon catalytic cracking and other directions since the development in 1972, and the synthesis method thereof is mature, and the morphology, the particle size, the pore diameter and the pore structure of the molecular sieve can be controlled by regulating and controlling Si/Al ratio, pH, concentration, a template agent, reaction temperature, pressure and the like.
The current industry-conventional method for producing silicon oxide materials is to add silicon particles to SiO2In the matrix, SiO is generated through high-temperature disproportionation reactionxHowever, the method not only has high energy consumption, but also can obtain SiOxThe product has irregular appearance. Compared with the conventional method, the preparation method is simpler, has low energy consumption, and can obtain SiO with uniform particle size, regular morphology and ordered pore canalxThe material can effectively relieve the problem of cyclic expansion of a silicon-oxygen material, reduce the falling of an active material and the repeated damage and repair of an SEI film, and further improve the cycle performance and the first coulombic efficiency of a 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, although a part of O is carried away in the subsequent dealumination process, a part of O still remains in the whole molecular sieve, the structure of the rest molecular sieve is relatively more complete, the damage degree is smaller, and the obtained SiO can be effectively ensuredxThe material has a morphological structure and ordered pores.
In some embodiments, in step S1, the ZSM-5 molecular sieve is prepared by: aluminum source, silicon source, organic template agent and solvent are mixed to prepare a ZSM-5 molecular sieve precursor, the precursor is crystallized, centrifugally separated and dried, and then the organic template agent is removed to obtain the ZSM-5 molecular sieve.
Wherein, the aluminum source can 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%, and the tetrapropylammonium hydroxide can be used for guiding the skeleton growth of molecular sieve lattices during preparation and controlling the pore size of the ZSM-5 molecular sieve; the solvent may be deionized water.
Specifically, mixing an aluminum source and a silicon source with an organic template and a solvent, condensing and refluxing to obtain a ZSM-5 molecular sieve precursor, then transferring the ZSM-5 molecular sieve precursor to a stainless steel crystallization kettle for crystallization reaction, centrifugally separating to remove mother liquor after crystallization, washing with deionized water until the pH value is less than or equal to 9 to remove unreacted substances, then drying overnight, and removing the organic template to obtain the ZSM-5 molecular sieve.
In some embodiments, the molar ratio of the aluminum source, the silicon source, the organic template agent 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 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, in particular 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 to the silicon source to the organic template to the solvent.
In some embodiments, in the preparation method of the ZSM-5 molecular sieve, the crystallization conditions are: crystallizing at 160-180 ℃ for 100-150 h. Specifically, the crystallization conditions include, but are not limited to, crystallization at 160 ℃ for 100 hours, crystallization at 160 ℃ for 120 hours, crystallization at 160 ℃ for 150 hours, crystallization at 170 ℃ for 100 hours, crystallization at 170 ℃ for 110 hours, crystallization at 170 ℃ for 120 hours, crystallization at 170 ℃ for 130 hours, crystallization at 170 ℃ for 140 hours, crystallization at 170 ℃ for 150 hours, crystallization at 180 ℃ for 100 hours, crystallization at 180 ℃ for 120 hours, or crystallization at 180 ℃ for 150 hours. Preferably, the crystallization condition is crystallization for 110-130 h at 170 ℃. The inventor finds that the ZSM-5 molecular sieve with long-range order can be obtained by controlling the crystallization under the conditions, and the crystal structure stability of the ZSM-5 molecular sieve is higher.
In some embodiments, in the preparation method of the ZSM-5 molecular sieve, the drying temperature is 100-120 ℃ and the drying time is 7-24 h.
In some embodiments, the method for preparing the ZSM-5 molecular sieve, the reaction conditions for removing the organic template are: reacting for 4-5 h at 500-600 ℃.
In some embodiments, in step S1, the dealumination conditions are: and (3) placing the mixture in concentrated nitric acid for refluxing for 8-10 h at 78-85 ℃. Preferably, the method also comprises the step of activating the dealuminized ZSM-5 molecular sieve in an inert atmosphere at 530-580 ℃ for 4-5 hours before reduction after dealuminization. After high-temperature activation, residual moisture in the ZSM-5 molecular sieve pore channels can be removed, and preparation is provided 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 reaction at 500 ℃ for 3 hours, at 500 ℃ for 4 hours, at 500 ℃ for 6 hours, at 550 ℃ for 4 hours, at 550 ℃ for 5 hours, at 600 ℃ for 3 hours, at 600 ℃ for 4 hours, at 600 ℃ for 5 hours, at 650 ℃ for 4 hours, or at 650 ℃ for 6 hours. Preferably, the reduction condition is 550-600 ℃ for 4-5 h. The reduction temperature and time difference can have different influences on the deoxidation effect, and SiO with uniform particle size, regular morphology and ordered pore canals can be obtained under the reduction conditionxA material.
The second aspect of the invention aims at providing a silicon-oxygen material prepared by the preparation method of any one of the silicon-oxygen materials. The silicon oxide material is SiOx(0＜x≤2)。
The third aspect of the invention aims to provide a negative electrode plate, which comprises the silicon oxygen material. The negative plate comprises a negative current collector and a negative active material layer coated on at least one surface of the negative current collector, wherein the negative active material layer comprises the silica material.
The fourth aspect of the present invention is directed to a secondary battery, which includes a positive plate, a negative plate and a diaphragm spaced between the positive plate and the negative plate, wherein the negative plate is the negative plate.
Wherein, the positive active material layer coated on the positive plate can be positive active material including but not limited to the chemical formula such as LiaNixCoyMzO2-bNb(wherein a is more than or equal to 0.95 and less than or equal to 1.2, x>0, y is more than or equal to 0, z is more than or equal to 0, and x + y + z is 1,0 is more than or equal to b and less than or equal to 1, M is selected from one or more of Mn and Al, N is selected from one or more of F, P and S), and the positive electrode active material can also be selected from one or more of LiCoO (lithium LiCoO), but not limited to2、LiNiO2、LiVO2、LiCrO2、LiMn2O4、LiCoMnO4、Li2NiMn3O8、LiNi0.5Mn1.5O4、LiCoPO4、LiMnPO4、LiFePO4、LiNiPO4、LiCoFSO4、CuS2、FeS2、MoS2、NiS、TiS2And the like. The positive electrode active material may be further modified, and the method of modifying the positive electrode active material is known to those skilled in the art, for example, the positive electrode active material may be modified by coating, doping, and the like, and the material used in the modification may be one or a combination of more of Al, B, P, Zr, Si, Ti, Ge, Sn, Mg, Ce, W, and the like. The positive electrode current collector adopted by the positive electrode plate is generally a structure or a part for collecting current, and the positive electrode current collector can be various materials suitable for serving as a positive electrode current collector of a lithium ion battery in the field, for example, the positive electrode current collector can include but is not limited to metal foil and the like, and more specifically, can include but is not limited to aluminum foil and the like.
And the separator may be various materials suitable for a lithium ion battery separator in the art, for example, may be one or a combination of more of polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, natural fiber, and the like, which include but are not limited thereto.
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantageous effects will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a silicon-oxygen material comprises the following steps:
s1, preparation of a 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, the purity is 25%) is used as an organic template agent, deionized water is used as a solvent, the content of 2.7L of the deionized water is used as a reference, and the molar ratio of the aluminum source to the silicon source to the organic template agent to the solvent is 1: 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 to a 200mL stainless steel crystallization kettle, crystallizing for 5 days at 170 ℃, centrifuging the obtained product to remove mother liquor, washing with deionized water until the pH is less than or equal to 9, drying at 110 ℃ overnight, 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 h at 80 ℃ to remove aluminum in the ZSM-5 molecular sieve, so as to obtain a dealuminated ZSM-5 molecular sieve;
s3, thermal reduction: placing the dealuminized ZSM-5 molecular sieve in hydrogen for reduction under the following conditions: reacting for 4 hours at 600 ℃; then placing the mixture into 6M HCl solution, stirring and washing the mixture for 4 hours, and filtering and drying the mixture to obtain a silicon oxide material SiOx(0＜x≤2)。
Example 2
In contrast to example 1, dealumination of the ZSM-5 molecular sieve: and placing the ZSM-5 molecular sieve in 13M concentrated nitric acid, refluxing for 8-10 h at 80 ℃ to remove aluminum in the ZSM-5 molecular sieve, filtering, washing, and activating for 4h at 550 ℃ under nitrogen to obtain the dealuminized ZSM-5 molecular sieve.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
Different from the embodiment 2, in the preparation of the ZSM-5 molecular sieve, the molar ratio of the aluminum source, the silicon source, the organic template and the solvent is 1: 83: 11.5: 1500.
the rest is the same as embodiment 2, and the description is omitted here.
Example 4
Different from the embodiment 2, in the preparation of the ZSM-5 molecular sieve, the molar ratio of the aluminum source, the silicon source, the organic template and the solvent is 1: 120: 11.5: 1500.
the rest is the same as embodiment 2, and the description is omitted here.
Example 5
Different from the embodiment 2, in the preparation of the ZSM-5 molecular sieve, the mol ratio of the aluminum source, the silicon source, the organic template and the solvent is 1: 200: 11.5: 1500.
the rest is the same as embodiment 2, and the description is omitted here.
Example 6
In contrast to example 2, dealumination of the ZSM-5 molecular sieve: and placing the ZSM-5 molecular sieve in 13M concentrated nitric acid, refluxing for 8-10 h at 80 ℃ to remove aluminum in the ZSM-5 molecular sieve, filtering, washing, and activating at 450 ℃ for 4h under nitrogen to obtain the dealuminized ZSM-5 molecular sieve.
The rest is the same as embodiment 2, and the description is omitted here.
Example 7
In contrast to example 2, dealumination of the ZSM-5 molecular sieve: and placing the ZSM-5 molecular sieve in 13M concentrated nitric acid, refluxing for 8-10 h at 80 ℃ to remove aluminum in the ZSM-5 molecular sieve, filtering, washing, and activating at 600 ℃ for 4h under nitrogen to obtain the dealuminized ZSM-5 molecular sieve.
The rest is the same as embodiment 2, and the description is omitted here.
Example 8
Different from the embodiment 2, the thermal reduction is carried out, the dealuminated ZSM-5 molecular sieve is placed in nitrogen for reduction, and the reduction conditions are as follows: reacting for 4 hours at 600 ℃; then placing the mixture in 6M HCl solution to be stirredStirring and washing for 4h, filtering and drying to obtain the silica material SiOx(0＜x≤2)。
The rest is the same as embodiment 2, and the description is omitted here.
Example 9
Different from the example 2, the thermal reduction is carried out, the dealuminized ZSM-5 molecular sieve is put into hydrogen for reduction, and the reduction conditions are as follows: reacting for 5 hours at 500 ℃; then placing the mixture into 6M HCl solution, stirring and washing the mixture for 4 hours, and filtering and drying the mixture to obtain a silica material SiOx(0＜x≤2)。
The rest is the same as embodiment 2, and the description is omitted here.
Example 10
Different from the embodiment 2, the thermal reduction is carried out, the dealuminated ZSM-5 molecular sieve is put into hydrogen for reduction, and the reduction conditions are as follows: reacting for 4 hours at 550 ℃; then placing the mixture into 6M HCl solution, stirring and washing the mixture for 4 hours, and filtering and drying the mixture to obtain a silica material SiOx(0＜x≤2)。
The rest is the same as embodiment 2, and the description is omitted here.
Example 11
Different from the example 2, the thermal reduction is carried out, the dealuminized ZSM-5 molecular sieve is put into hydrogen for reduction, and the reduction conditions are as follows: reacting for 3.5h at 650 ℃; then placing the mixture into 6M HCl solution, stirring and washing the mixture for 4 hours, and filtering and drying the mixture to obtain a silica material SiOx(0＜x≤2)。
The rest is the same as embodiment 2, and the description is omitted here.
The silicon-oxygen material obtained in the above examples 1 to 11 is used as a negative electrode active material, and is mixed with conductive carbon black Super P and sodium carboxymethyl cellulose according to a mass ratio of 8: 1: 1, fully and uniformly mixing in deionized water to form cathode slurry; and coating the negative electrode slurry on a copper foil, drying and rolling to obtain the negative electrode sheet.
And (3) taking a lithium sheet as a counter electrode, assembling the lithium sheet and the negative sheet in a glove box in an argon atmosphere, sealing, standing for 24 hours, and then carrying out constant-current charge-discharge testing on the performance of the lithium sheet.
1) Testing the thickness expansion rate of the pole piece: the cell was charged at 25 ℃ with a 1C constant current to 4.25V, then charged at 4.25V constant voltage to a current of 0.05C, left to stand for 5min, and then discharged at 1C constant current to 2.8V, which was the first cycle. The cell was cycled 20 times according to the above conditions. The thickness of the pole pieces before and after cycling was tested with a height gauge. The thickness expansion ratio was calculated by the following formula:
thickness expansion rate ═ thickness after cycle-thickness before cycle)/thickness before cycle ] × 100%.
2) And (3) testing the circulating capacity: charging the battery to 4.25V at a constant current of 1C at 25 +/-2 ℃, then charging to 0.05C at a constant voltage of 4.25V, standing for 5min, and then discharging to 2.8V at a constant current of 1C, wherein the process is a charge-discharge cycle process, and the discharge capacity at the time is the discharge capacity of the first cycle. The cell was subjected to 100 cycles of charge and discharge testing as described above, and the discharge capacity per cycle was recorded.
The cycle capacity retention (%) was 100 th cycle discharge capacity/first cycle discharge capacity × 100%
The test results are shown in table 1 below.
TABLE 1
Negative electrode sheet thickness expansion ratio (%) Capacity retention at 25 ℃ for 100 weeks
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 the comparison between the examples 1 and 2, the ZSM-5 molecular sieve is continuously activated at high temperature in nitrogen before being subjected to thermal reduction after dealumination, so that residual moisture in the pore channel of the ZSM-5 molecular sieve can be effectively removed, the subsequent thermal reduction is facilitated, the thickness expansion of a pole piece can be further relieved, and the cycle performance of the battery can be further improved. In addition, it can be seen from the 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 effect on the cycle expansion and the cycle capacity retention rate of the pole piece.
In addition, it can be seen from the comparison of examples 2 to 5 that different molar ratios of the aluminum source, the silicon source, the organic template and the solvent in the preparation of the ZSM-5 molecular sieve also affect the thickness expansion and the cycle performance of the electrode plate. Generally speaking, the higher the silicon content is, the larger the expansion rate of the pole piece will be, but the silicon-aluminum ratio will have a greater influence on the molecular sieve morphology product, even when the silicon content is relatively high, if the obtained molecular sieve has a regular morphology and ordered pore channels, the problem of the cyclic expansion of silicon can still be effectively improved, and further the cyclic performance is improved.
In conclusion, the negative electrode material prepared by the preparation method can effectively relieve the problem of cyclic expansion of the silicon-oxygen material, the thickness expansion rate of the pole piece is low, the falling of the active material and the repeated damage and repair of an SEI film are reduced, and the cycle performance of the battery is improved.
Variations and modifications to the above-described embodiments may become apparent to those skilled in the art to which the invention pertains based upon the disclosure and teachings of the above specification. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. The preparation method of the silicon-oxygen material is characterized by comprising 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 dealuminized ZSM-5 molecular sieve;
and S2, reducing the dealuminized ZSM-5 molecular sieve obtained in the step S1 in a reducing atmosphere, 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 is as follows: aluminum source, silicon source, organic template agent and solvent are mixed to prepare a ZSM-5 molecular sieve precursor, the precursor is crystallized, centrifugally separated and dried, and then the organic template agent is removed to obtain the ZSM-5 molecular sieve.
3. The method for producing a silica material according to claim 2, wherein 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.
4. the method for preparing a silica material according to claim 2 or 3, wherein in the method for preparing the ZSM-5 molecular sieve, the crystallization conditions are as follows: crystallizing at 160-180 ℃ for 100-150 h; 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 producing a silicone material according to claim 1, wherein in step S1, the dealumination conditions are: and (3) placing the mixture in concentrated nitric acid for refluxing for 8-10 h at 78-85 ℃.
6. The method for preparing a silica material according to claim 5, further comprising activating the dealuminated ZSM-5 molecular sieve in an inert atmosphere at 530-580 ℃ for 4-5 hours before reduction after dealumination.
7. The method for producing a silicon oxygen material according to claim 1 or 6, wherein in step S2, the reducing atmosphere is hydrogen, and the reducing conditions are as follows: reacting for 3-6 h at 500-650 ℃.
8. A silicone material characterized by being produced by the method for producing a silicone material according to any one of claims 1 to 7.
9. A negative electrode sheet comprising the silicone material according to claim 8.
10. 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 according to claim 9.
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CN1147420A (en) * 1995-10-06 1997-04-16 中国石油化工总公司 Phosphorus and RE containing molecular sieve with MFI structure
DE19726261C1 (en) * 1997-06-20 1998-09-10 Bad Koestritz Chemiewerk Gmbh Production of silicon-rich ZSM-5 zeolite granules
CN101857243A (en) * 2010-06-03 2010-10-13 复旦大学 Method for adjusting surface hole diameter of ZSM-5 molecular sieve by surface dealuminizing and compensating silicon
EP2372816A1 (en) * 2010-04-05 2011-10-05 Shin-Etsu Chemical Co., Ltd. Negative electrode material for secondary battery with non-aqueous electrolyte, method for manufacturing negative electrode material for secondary battery with non-aqueous elctrolyte, and lithium ion secondary battery
CN105036152A (en) * 2015-06-25 2015-11-11 太原理工大学 Hollow H-ZSM-5 molecular sieve, and preparation method and application thereof
CN105271265A (en) * 2015-10-20 2016-01-27 复榆(张家港)新材料科技有限公司 Synthetic method of pure silicalite

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1147420A (en) * 1995-10-06 1997-04-16 中国石油化工总公司 Phosphorus and RE containing molecular sieve with MFI structure
DE19726261C1 (en) * 1997-06-20 1998-09-10 Bad Koestritz Chemiewerk Gmbh Production of silicon-rich ZSM-5 zeolite granules
EP2372816A1 (en) * 2010-04-05 2011-10-05 Shin-Etsu Chemical Co., Ltd. Negative electrode material for secondary battery with non-aqueous electrolyte, method for manufacturing negative electrode material for secondary battery with non-aqueous elctrolyte, and lithium ion secondary battery
CN101857243A (en) * 2010-06-03 2010-10-13 复旦大学 Method for adjusting surface hole diameter of ZSM-5 molecular sieve by surface dealuminizing and compensating silicon
CN105036152A (en) * 2015-06-25 2015-11-11 太原理工大学 Hollow H-ZSM-5 molecular sieve, and preparation method and application thereof
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