CN113948677A - Silicon-alkene negative plate capable of being directly used for preparing lithium ion battery and preparation and application thereof - Google Patents

Silicon-alkene negative plate capable of being directly used for preparing lithium ion battery and preparation and application thereof Download PDF

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CN113948677A
CN113948677A CN202111208327.4A CN202111208327A CN113948677A CN 113948677 A CN113948677 A CN 113948677A CN 202111208327 A CN202111208327 A CN 202111208327A CN 113948677 A CN113948677 A CN 113948677A
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lithium ion
ion battery
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CN113948677B (en
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张校刚
王华兰
贺文杰
刘雪
李岩
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Nanjing University of Aeronautics and Astronautics
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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

Abstract

The invention discloses a silicon-alkene negative plate capable of being directly used for preparing a lithium ion battery, a preparation method thereof and application of the silicon-alkene negative plate in preparation of the lithium ion battery. The preparation method comprises the following steps: (1) mixing and dispersing a silicon precursor, conductive carbon black and a binder in a solvent, performing ultrasonic treatment and stirring to form slurry, coating the slurry on a current collector, and performing vacuum drying to remove the solvent to obtain an electrode plate; the silicon precursor is CaSi2Or MgSi2(ii) a (2) Taking a platinum wire as a cathode or an anode, inserting the platinum wire into an electrolyte containing inorganic acid and an organic solvent, and taking the electrode slice prepared in the step (1) asThe anode or the cathode is used for constructing an electrochemical reaction cell to carry out electrochemical reaction, the surface of the electrode plate is cleaned after the reaction is finished, and the silicon alkene negative electrode plate which can be directly used for preparing the lithium ion battery is obtained after vacuum drying; the conditions of the electrochemical reaction are as follows: 1mA/cm2The current density is not less than 300mA/cm2The reaction time is less than or equal to 300min and is less than or equal to 1 min.

Description

Silicon-alkene negative plate capable of being directly used for preparing lithium ion battery and preparation and application thereof
Technical Field
The invention relates to the field of preparation of two-dimensional silylene materials, in particular to a silylene negative plate capable of being directly used for preparing a lithium ion battery, and preparation and application thereof.
Background
Silicon and carbon belong to the group IVA of the periodic table of elements, and like graphene, silylene is also a layered material with a honeycomb structure, being the thinnest two-dimensional form of silicon. Unlike graphene, the six silicon atoms of the graphene on the honeycomb surface are not strictly in the same plane, but constitute a folded and bent "chair-shaped" structure. The silicon alkene layer can be used for inserting lithium ions, the lattice constant of the silicon alkene is larger than that of graphite, and the theoretical capacity of the silicon alkene serving as a lithium ion battery cathode can be about three times of that of the graphite. Van der Waals force between the silicon alkene layers ensures that the structure of the silicon alkene is not damaged in the charging and discharging process, so that the problem of huge volume expansion caused by charging and discharging of the traditional silicon electrode material is solved, and the stability and the cycle frequency of the battery taking the silicon alkene as the cathode material are greatly improved. In addition, the silylene has strong spin orbit coupling, can open a larger energy gap at a Dirac point, realizes observable quantized spin Hall effect, is also very suitable for a novel transistor, is convenient to integrate into electronic equipment, is compatible with the existing silicon semiconductor industry, and therefore has extremely wide application prospect.
As early as 1994, the two-dimensional layered structure of silicon was predicted (Phys Rev B1994, 50, 14916). Guzm n-Verri and Lew Yan Voon in 2007 named silicon materials in two-dimensional layered structures as silylene (Phys Rev B2007, 76, 075131). In 2009, Ciraci et al demonstrated that two-dimensional silylene can exist stably through theoretical calculations (Phys Rev Lett,2009,102,236804.). Epitaxial growth is the earliest methodAt present, a method for preparing silylene, which is used more, is presented, namely heating a silicon target under vacuum condition, evaporating silicon atoms and depositing the silicon atoms on a special substrate material such as Ag single crystal. The evaporated silicon atoms are subjected to strong silicon/silver interface interaction when the silylene is generated on the substrate, and the warping degree of the layered silylene is changed, namely, part of the silicon atoms rise and part of the silicon atoms fall, so that few layers of the silylene are formed. However, early studies of the preparation of silylene on the Ag (001) and Ag (110) planes only achieved silylene nanoribbons of limited width, and the prepared silylene unit cells became large and less symmetrical, destroying the dirac-fermi character of silylene, thus affecting the performance of silylene (Surf Sci 2007,601,262-7. Appl Phys Lett 2010,96,183102.Appl Phys Lett 2011,98,081909.Appl Phys Lett 2010,96, 261905.). Until 2012, Vogt et al successfully prepared large area monolayers of silylene on the Ag (111) face and experimentally verified the stable presence of the monolayered silylene (Phys Rev Lett 2012,108,155501.). Meanwhile, the scholars have prepared large-area single-layer silylene and multi-layer silylene on the Ag (111) surface. Then, the scholars on other substrates (ZrB)2、ZrC、Ir、Ru、MoS2) Silenes, e.g. ZrB, are also prepared2(Phys Rev Let 2012,108,245501), ZrC (J Phys Chem C2014,118,23049), Ir (Nano Lett 2013,13,685), Ru (Nano Lett.2017,17,1161) and MoS2(Adv Mater 2014,26,2096)。
In 2006, Hideyuki Nakano firstly tried to prepare silicon alkene by using chemical method and Mg-doped CaSi2(CaSi1.85Mg0.15) And hydrochloric acid as raw materials, the reaction time is as long as 10 days, but the generation rate of the silylene is only 1% (Angew. chem. int. Ed.2006,45, 6303-. 2016, Ritsuko Yaokawa et al used CaSi2And ionic liquids [ BMIM][BF4](1-butyl-3-methylimidazolium tetrafluoroborate) at 300 ℃ for 15h, BF4 -Decomposition to F-Into CaSi2Interlayer preparation of CaSi2Fx(0 ≦ x ≦ 2.3), since Si bonded to Ca was substituted with F having a stronger electronegativity, Si liberated from the original honeycomb structure was reconstituted into a double-layered structure, and thus, a double-layered silylene was prepared (nat. Commun.2016,7,10657). Yuxi Xu et al, 2018, are often used in acetonitrile solventsAt room temperature with2And CaSi2The reaction produced a few layers of silylene (adv. mater.2018,30,1800838).
Patent CN105439148A in 2015 discloses a method for preparing silylene. Processing silicon block into concave cone-shaped silicon target, mounting on sputtering target of cesium sputtering negative ion source, sputtering silicon target with cesium ions, and sputtering the generated Si2Cluster negative ion beam is led out from the extraction hole of the suction electrode, and cluster negative ion Si2After being accelerated by a suction electrode voltage, the sample is uniformly deposited on an Ag (111) substrate through a scanning electric field, the sample is placed in a vacuum chamber, Ar is added+Sputtering the surface by ions, and then annealing the sample under ultrahigh vacuum to finish the preparation of the silylene. 2016 patent CN 106554016A discloses a method for preparing a silicon alkene film by mechanical stripping. Covering a two-dimensional material (hexagonal boron nitride, molybdenum disulfide, tungsten disulfide, molybdenum diselenide and graphene) on the surface of silicon (111) with a metal (Ag, Au, Mo, Cu and Ti) film passivated, carrying out high-temperature treatment at 750-1050 ℃ for 2-4 hours, diffusing a silicon element to an interface of the metal film and the two-dimensional material, and cooling to room temperature; dispersing a sample in a solvent with a surfactant, enabling polar molecules to easily enter an interface between metal and a substrate, increasing friction between the metal and the substrate through ultrasonic stirring, and stripping the silylene and the two-dimensional material from the silicon substrate to obtain the silylene film. 2019 patent CN 110600688A discloses a method for preparing SiCl serving as a silicon source by taking ionic liquid as a medium4And a method for preparing the silylene-copper-silylene composite material by electrodepositing bivalent copper. The concentration of the divalent copper in the ionic liquid is 0.002-0.003 mol/L, and the potential of electrodeposition is-1.9 to-2.1V.
Although various methods for preparing silylene have been developed, the method for preparing high-quality silylene, which has low cost and high efficiency and can adapt to various application occasions in the future, is still very short and is also a great problem and challenge at present.
Disclosure of Invention
Aiming at the technical problems of low silicon alkene yield, high cost, difficulty in batch preparation, long reaction time for preparing silicon alkene by a chemical method, low product quality, low silicon alkene yield prepared by a mechanical stripping method, low efficiency and the like in the preparation of silicon alkene by an epitaxial growth method, the invention provides a preparation method of a silicon alkene negative plate which can be directly used for preparing a lithium ion battery, and the preparation method is a novel method for preparing a two-dimensional silicon alkene material.
A preparation method of a silicon-alkene negative plate directly used for preparing a lithium ion battery comprises the following steps:
(1) mixing and dispersing a silicon precursor, conductive carbon black and a binder in a solvent, performing ultrasonic treatment and stirring to form slurry, coating the slurry on a current collector, and performing vacuum drying to remove the solvent to obtain an electrode plate;
the silicon precursor is CaSi2Or MgSi2；
(2) Taking a platinum wire as a cathode or an anode, inserting the platinum wire into an electrolyte containing inorganic acid and an organic solvent, taking the electrode slice prepared in the step (1) as the anode or the cathode, constructing an electrochemical reaction cell, carrying out electrochemical reaction, cleaning the surface of the electrode slice after the reaction is finished, and carrying out vacuum drying to obtain the silylene negative electrode slice which can be directly used for preparing the lithium ion battery;
the conditions of the electrochemical reaction are as follows: 1mA/cm2The current density is not less than 300mA/cm2The reaction time is less than or equal to 300min and is less than or equal to 1 min.
In a preferred example, the binder is one of polyvinylidene fluoride, polysaccharide, carboxymethyl cellulose, polyacrylic acid and polyacrylonitrile.
The mass ratio of the silicon precursor to the conductive carbon black to the binder is a: b:1, wherein a is preferably not less than 7 and not more than 15, b is preferably not less than 1 and not more than 3, further preferably, a is not less than 7 and not more than 12, and b is not less than 1 and not more than 2.
In a preferred embodiment, in step (1), the solvent is nitrogen methyl pyrrolidone.
In a preferred embodiment, the current collector is one of copper foil, carbon-plated copper foil, foam copper, carbon paper and carbon cloth.
In the step (2), the following preferred technical scheme can be adopted:
the inorganic acid is one of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid and phosphoric acid;
the organic solvent is an alcohol solvent;
the volume ratio of the inorganic acid to the organic solvent is 1: 0.25-100.
In a preferred example, in the step (2), the conditions of the electrochemical reaction are as follows: 1mA/cm2The current density is not less than 100mA/cm2The reaction time is less than or equal to 120min and is less than or equal to 1 min.
The existing epitaxial growth preparation method of the silicon alkene is generally realized under the high-temperature and high-vacuum condition of hundreds of even thousands of degrees, a noble metal substrate is used, the silicon alkene needs to be post-treated to stabilize the silicon alkene, the preparation process is complex and tedious, the production period is long, and the cost is very high. The existing mechanical stripping method of the silylene has low yield and low efficiency, and is not suitable for the requirement of large-scale industrial production. The chemical preparation method has the disadvantages of long reaction time, poor quality of the prepared silylene, poor experimental reproducibility and the like. The development of a novel preparation method of the silylene with simplicity, low cost, high efficiency and high quality becomes an urgent need to promote the application of the silylene. The invention provides a method for preparing silylene by an electrochemical method, the obtained negative plate can be directly used as a negative electrode to be applied to a lithium ion battery, and high-quality silylene is successfully prepared at normal temperature by setting constant current density and reaction time on electrochemical equipment. The method avoids using a noble metal substrate and a high-temperature high-vacuum environment, greatly shortens the reaction time, effectively reduces the cost and improves the yield and the quality of the silylene. On the basis, the application of the silylene prepared by the electrochemical method as an active ingredient in the lithium ion battery cathode material is realized.
The invention also provides the silicon-alkene negative plate which is prepared by the preparation method and can be directly used for preparing the lithium ion battery.
The invention also provides application of the silicon-alkene negative plate in preparation of a lithium ion battery.
Compared with the prior art, the invention has the main advantages that:
1) the invention provides a novel electrochemical preparation method of simple, efficient, low-cost and high-quality silylene, which does not need to use a noble metal substrate, avoids high-temperature and high-vacuum reaction conditions, can be completed within minutes to several hours at normal temperature, prepares the silylene with the nanoscale thickness, greatly reduces the preparation cost and simplifies the preparation process.
2) Compared with the traditional method for preparing the silicon alkene, the silicon alkene prepared by the method provided by the invention has good quality and high yield, and provides a high-performance key material for the next generation lithium ion battery technology and the electronic field.
3) The electrochemical method for preparing the silylene has high process safety, good reproducibility and environmental protection, and is expected to be applied to industrial large-scale batch preparation.
Drawings
FIG. 1 is a graph showing the constant current density electrochemical reaction operation in example 4;
FIG. 2 is a field emission scanning electron micrograph of the silylene prepared in examples 1 to 6;
in fig. 3, a is a graph of the charge and discharge performance of the negative electrode sheet prepared in example 3 at the first 1-2 circles when the current density is 100mA/g, and b is a graph of the coulombic efficiency of the negative electrode sheet prepared in example 3 at the first 1-100 circles when the current density is 100 mA/g.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
The electrochemical reaction cell constructed in each of the following examples includes:
a base on which a current collector is placed;
the reaction tank is arranged on the current collector and has a hollow cylindrical structure, and the upper end and the lower end of the reaction tank are open; the hollow part of the reaction tank is used for filling electrolyte, the bottom end of the electrolyte is in contact with the current collector after the electrolyte is filled, and a platinum wire is inserted into the electrolyte.
Example 1
(1) Preparation of electrode foil: mixing CaSi2Mixing and dispersing conductive carbon black and polyvinylidene fluoride in N-methyl pyrrolidone according to the mass ratio of 7:2:1, carrying out normal temperature ultrasonic treatment for 1 hour, stirring for 3 hours to form uniform slurry, and mixingCoating the slurry on a copper foil, and performing vacuum drying to remove a solvent to prepare an electrode foil;
(2) construction of an electrochemical reaction cell: taking a platinum wire as a cathode or an anode, inserting the platinum wire into electrolyte of a reaction tank, taking an electrode foil prepared in the step (1) as the anode or the cathode, placing the electrode foil between the reaction tank and a base, and taking the electrolyte as hydrochloric acid: ethanol ═ 1: 10(v/v) of mixed solution to construct an electrochemical reaction tank; the HCl concentration in the hydrochloric acid is 37 wt%;
(3) carrying out the electrochemical reaction: setting the current density to be 10mA/cm on an electrochemical workstation2And the reaction time is 5min, after the reaction is finished, the surface of the electrode foil is cleaned by absolute ethyl alcohol, and the electrode foil is placed in a vacuum drying oven for drying, so that the silicon-alkene negative plate which can be directly used for preparing the lithium ion battery is obtained. The scanning electron micrograph of the prepared silylene is shown in FIG. 2 a.
Example 2
The difference from example 1 is only that the reaction time of step (3) is 10min, the rest steps and conditions are the same, and the scanning electron micrograph of the prepared silylene is shown in FIG. 2 b.
Example 3
The difference from the example 1 is only that the current collector in the step (1) adopts a carbon-plated copper foil, and the current density in the step (3) is 50mA/cm2And the rest steps and conditions are the same, and the scanning electron micrograph of the prepared silylene is shown in figure 2 c.
Example 4
The difference from example 1 is only that the current collector in step (1) adopts carbon paper, the constant current density electrochemical reaction working curve in step (3) is shown in figure 1, and the current density is 50mA/cm2The reaction time is 10min, the rest steps and conditions are the same, and the scanning electron micrograph of the prepared silylene is shown in FIG. 2 d.
Example 5
The difference from the example 1 is only that the current collector in the step (1) adopts carbon cloth, and the current density in the step (3) is 100mA/cm2And the rest steps and conditions are the same, and the scanning electron micrograph of the prepared silylene is shown in figure 2 e.
Example 6
The difference from the example 1 is only that the current collector in the step (1) adopts carbon cloth, and the current density in the step (3) is 100mA/cm2The reaction time is 10min, the rest steps and conditions are the same, and the scanning electron micrograph of the prepared silylene is shown in FIG. 2 f.
The electrochemical reaction parameters of the silylene negative electrode sheet and the basic performance parameters of the silylene product which can be directly used for preparing the lithium ion battery in the embodiments 1 to 6 are shown in the following table 1. The 90% silylene radial dimension parameter index represents that 90% silylene radial dimensions are concentrated in the corresponding range. The 90% silylene thickness parameter index represents that the 90% silylene thickness is concentrated in the corresponding range.
TABLE 1
Figure BDA0003307747830000071
Application example
The silicon-alkene negative electrode plate prepared in the embodiment 1-6 is directly used for manufacturing a lithium ion battery: cutting the silicon alkene negative pole piece into small round pieces, compacting the small round pieces on a tablet press under 10MPa, stacking the battery in an argon-protected glove box according to the sequence of the positive pole shell, the silicon alkene negative pole piece, the electrolyte, the diaphragm, the lithium piece, the foam nickel and the negative pole shell, and sealing the battery by using a sealing machine. Electrolyte adopts 1.0M LiPF6[ EC-EMC-DEC-FEC (EC: EMC: DEC ═ 1:1:1 (volume ratio), where EC: ethylene carbonate, EMC: methylethyl carbonate, DEC: diethyl carbonate, FEC: ethylene carbonate). The diaphragm is Celgare 2400 type porous PP film as the diaphragm, and the model of the battery shell is CR 2025. And detecting a charge-discharge curve of the battery by using the charge-discharge equipment. At a current density of 50mA/cm2Taking the negative silylene sheet prepared at the reaction time of 5min (i.e., the negative silylene sheet prepared in example 3) as an example, the charge-discharge curve is shown in fig. 3a, and the coulombic efficiency is shown in fig. 3 b. The first discharge specific capacity of the battery is 1614mAh/g, the coulombic efficiency is 9%, the second circle discharge specific capacity is 470mAhg, the coulombic efficiency is increased to 41%, the discharge specific capacity is 211mAh/g after 100 circles of charge-discharge cycles, and the coulombic efficiency value is gradually increased and finally approaches 100%.
As can be seen from examples 1 to 6, table 1, and fig. 2, the silylene prepared by the electrochemical method of the present invention has a uniform size, and the radial size and thickness of 90% silylene can be ensured to be in a concentrated range. The thickness of the obtained silicon alkene has a certain relation with electrochemical reaction parameters, and the thickness of the obtained silicon alkene sheet layer is gradually reduced along with the increase of the current density. From the application example and fig. 3, it can be seen that the silylene prepared by the electrochemical method has good electrochemical performance when being used as the negative electrode material of the lithium ion battery, and the battery has higher coulombic efficiency and good cycle performance after being activated by the first several cycles of charge and discharge.
The electrochemical preparation method of the silylene negative plate has the characteristics of mild preparation conditions, simplicity in operation, rapidness in reaction, low cost, high yield, high product quality, small volume effect in the charging and discharging process, excellent electrochemical lithium storage performance and the like.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (9)

1. A preparation method of a silicon-alkene negative plate directly used for preparing a lithium ion battery is characterized by comprising the following steps:
(1) mixing and dispersing a silicon precursor, conductive carbon black and a binder in a solvent, performing ultrasonic treatment and stirring to form slurry, coating the slurry on a current collector, and performing vacuum drying to remove the solvent to obtain an electrode plate;
the silicon precursor is CaSi2Or MgSi2；
(2) Taking a platinum wire as a cathode or an anode, inserting the platinum wire into an electrolyte containing inorganic acid and an organic solvent, taking the electrode slice prepared in the step (1) as the anode or the cathode, constructing an electrochemical reaction cell, carrying out electrochemical reaction, cleaning the surface of the electrode slice after the reaction is finished, and carrying out vacuum drying to obtain the silylene negative electrode slice which can be directly used for preparing the lithium ion battery;
the conditions of the electrochemical reaction are as follows: 1mA/cm2The current density is not less than 300mA/cm2And reaction time is less than or equal to 1minThe time is less than or equal to 300 min.
2. The method according to claim 1, wherein the binder is one of polyvinylidene fluoride, polysaccharide, carboxymethyl cellulose, polyacrylic acid, and polyacrylonitrile.
3. The preparation method of claim 1, wherein the mass ratio of the silicon precursor to the conductive carbon black and the binder is a: b:1, wherein a is greater than or equal to 7 and less than or equal to 15, and b is greater than or equal to 1 and less than or equal to 3.
4. The process according to claim 1, wherein in the step (1), the solvent is N-methylpyrrolidone.
5. The method of claim 1, wherein the current collector is one of a copper foil, a carbon-coated copper foil, a copper foam, a carbon paper, and a carbon cloth.
6. The production method according to claim 1, wherein in the step (2):
the inorganic acid is one of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid and phosphoric acid;
the organic solvent is an alcohol solvent;
the volume ratio of the inorganic acid to the organic solvent is 1: 0.25-100.
7. The method according to claim 1, wherein in the step (2), the conditions of the electrochemical reaction are as follows: 1mA/cm2The current density is not less than 100mA/cm2The reaction time is less than or equal to 120min and is less than or equal to 1 min.
8. The silicon-based negative electrode plate prepared by the preparation method according to any one of claims 1 to 7 and capable of being directly used for preparing a lithium ion battery.
9. The use of the negative silylene sheet of claim 8 in the preparation of a lithium ion battery.
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Title
QIANG GUO等: "2D Silicene Nanosheets for High-Performance Zinc-Ion Hybrid Capacitor Application", 《ACS NANO》 *
新型: "一种新的锂电池负极材料――硅烯", 《化工新型材料》 *

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