CN111118565B - Preparation method of Si-P film material - Google Patents

Preparation method of Si-P film material Download PDF

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Publication number
CN111118565B
CN111118565B CN201911354017.6A CN201911354017A CN111118565B CN 111118565 B CN111118565 B CN 111118565B CN 201911354017 A CN201911354017 A CN 201911354017A CN 111118565 B CN111118565 B CN 111118565B
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phosphorus
mol
concentration
electrodeposition
silicon
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CN111118565A (en
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周琼宇
李媛媛
王小芬
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Beijing Yunshang Power Technology Co.,Ltd.
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Foshan University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
    • C25D5/40—Nickel; Chromium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 preparation method of a Si-P film material, which comprises the following steps: mixing acetonitrile and tetraethylammonium chloride to prepare a basic electrolyte, adding a silicon source and a phosphorus source, and then carrying out electrodeposition to obtain the Si-P film material from the surface of the metal Ni substrate electrode. Compared with the prior art, the invention has the advantages that: by utilizing an electrodeposition technology which is simple to operate and easy to control, P, Si co-deposition is realized on the surface of the Ni plating layer of the electrode, P element doping is completed while the Si film layer and the Ni structure are tightly coated, and finally the Si-P film layer material with excellent electrochemical performance, which can be used as the cathode of the lithium ion power battery, is obtained by using an electrodeposition method.

Description

Preparation method of Si-P film material
Technical Field
The invention relates to the technical field of electrical elements, in particular to a preparation method of a Si-P film material.
Background
The need for renewable energy sources has been increasing since global energy shortages and environmental crisis have arisen. Lithium ion batteries, as a new generation of clean, environmentally friendly and renewable secondary energy, have attracted a great deal of attention due to their advantages of high reversible capacity, high working potential, small self-discharge, wide working temperature range, etc. Currently, research on lithium ion batteries mainly focuses on the development, application, modification and the like of positive electrode materials, and research on negative electrode materials which also determine the performance of lithium ion batteries is relatively less and slightly lagged. Therefore, research and development of high-capacity anode materials will be one of the key factors for improving the performance of lithium ion power batteries.
In recent years, a plurality of novel anode materials with development prospects, such as Sn, Sb, Si and the like, are reported, wherein the theoretical capacity of the Si material is up to 4200mAh/g, and the Si material is the material with the highest lithium storage capacity at present. Therefore, Si is considered to be one of the most ideal negative electrode materials of the lithium ion power battery. So far, Si materials have not been widely used on a large scale, and the main reasons for this are: li+In the process of embedding Si, Li is formed in a full-charge state22Si5In the alloy phase, the volume change of the Si material reaches more than 300 percent, and the huge volume effect leads the electrode to be pulverized and fall off from the current collector, thereby losing the electric contact with the current collector.In addition, Si dusting will also cause a rapid decrease in the cycle performance. Therefore, the adverse effect of the Si negative electrode material caused by the volume effect is reduced, and the improvement of the cycle performance is the first condition for the application of the Si material in the lithium ion battery. By reducing the dimension of the Si material, the constraint on Si shrinkage and expansion can be reduced (or eliminated) in a specific direction, the stress caused by volume change is released, and the adverse effect caused by the volume effect is effectively controlled (or eliminated).
Si itself is a semiconductor material, and the conductivity is low and is only 6.7 multiplied by 10-4S/cm, weak electron conductivity. In order to solve the problem of poor self-conductivity of Si as a negative electrode material, a uniform and continuous n-type Si semiconductor is formed by doping Si with a trace amount of a V-group element.
P is an n-Si dopant which is very widely used. According to the quantum chemistry theory, the doping of P instead of Si belongs to non-isocharge doping, and redundant charges are generated to participate in conduction, so that conduction electrons in a conduction band are increased. Meanwhile, due to the introduction of P doping, the electrical contact performance of the Si microcrystal active lithium embedding center is improved, and the conductivity of Si is enhanced. In the existing research, the n-Si film layer is generally prepared by adopting a vacuum evaporation or magnetron sputtering mode, and the raw material of the n-Si film layer is mostly an n-Si material obtained by P doping treatment in advance. Due to the method of obtaining the film by applying high energy to the raw material during the manufacturing process, the doping amount of P in the film is reduced, and the overall conductive capability is weakened.
Disclosure of Invention
The present invention is directed to the above-mentioned problems, and provides a method for preparing a Si — P film layer material, so as to solve one or more technical problems in the prior art, and provide at least one useful choice or creation condition.
In order to avoid the loss of P element in raw materials caused by the film preparation process such as vacuum evaporation or magnetron sputtering, the invention provides the following technical scheme:
a preparation method of a Si-P film material comprises the following steps: mixing acetonitrile and tetraethylammonium chloride to prepare a basic electrolyte, adding a silicon source and a phosphorus source, and then carrying out electrodeposition to obtain the Si-P film material from the surface of the metal Ni substrate electrode.
Preferably, the silicon source is selected from trichlorosilane, silicon tetrachloride, tribromo-hydrogen silicon or silicon tetrabromide. Further, the concentration of the trichlorosilane is 2.5-8 mol/L; the concentration of the silicon tetrachloride is 0.5-5 mol/L; the concentration of the tribromohydrogen silicon is 2-5 mol/L; the concentration of the silicon tetrabromide is 1-10 mol/L.
Preferably, the phosphorus source is selected from phosphorus trichloride, phosphorus chloride, phosphorus tribromide or phosphorus pentabromide. Further, the concentration of the phosphorus trichloride is 2.5-5 mol/L; the concentration of the phosphorus chloride is 2-10 mol/L; the concentration of the phosphorus tribromide is 1-6 mol/L; the concentration of the phosphorus pentabromide is 0.5-10 mol/L.
Preferably, the electrodeposition is pulse electrodeposition with a current density ranging from 0.05 to 35A/dm2The pulse frequency is 500-12000 Hz, and the duty ratio is 15-85%.
Compared with the prior art, the invention has the advantages that: by utilizing an electrodeposition technology which is simple to operate and easy to control, P, Si co-deposition is realized on the surface of the Ni plating layer of the electrode, P element doping is completed while the Si film layer and the Ni structure are tightly coated, and finally the Si-P film layer material with excellent electrochemical performance, which can be used as the cathode of the lithium ion power battery, is obtained by using an electrodeposition method.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples, but the present invention is not limited to these examples.
Example 1: in an acetonitrile system, tetraethylammonium chloride is taken as a supporting electrolyte, and 2mol/L SiCl is respectively added4And 3.5mol/L PCl5Current density 6A/dm2And depositing the Si-P film on the surface of the metal Ni substrate electrode by constant current direct current.
The obtained coating film is used as the cathode of the lithium ion battery, and after the lithium ion battery is assembled into a button cell, electrochemical test is carried out, and the test result is shown in table 1.
Example 2: in an acetonitrile system, tetraethylammonium chloride is taken as a supporting electrolyte, and 2mol/L SiCl is respectively added4And 3.5mol/L PCl5Current density 6A/dm2And the duty ratio is 60 percent, and the Si-P film is obtained on the surface of the metal Ni substrate electrode through constant current direct current deposition.
The obtained coating film is used as the cathode of the lithium ion battery, and after the lithium ion battery is assembled into a button cell, electrochemical test is carried out, and the test result is shown in table 1.
Example 3: in an acetonitrile system, tetraethylammonium chloride is taken as a supporting electrolyte, and 2mol/L SiCl is respectively added4And 3.5mol/L PCl5Current density 6A/dm2And the duty ratio is 60 percent, and the Si-P film is obtained on the surface of the metal Ni substrate electrode through constant current direct current deposition.
The obtained coating film is used as the cathode of the lithium ion battery, and after the lithium ion battery is assembled into a button cell, the battery is subjected to a cyclic charge-discharge test in a voltage range of 0.05-1.5Vvs. Li +/Li under the current density of 0.3A/g, and the test results are shown in table 1.
TABLE 1
Sample (I) Week 1 Week 2 Week 3 At week 50 Week 100 At week 200
Example 1 3714 2996 2571 2401 2354 2273
Example 2 3825 3013 2634 2445 2378 2290
Example 3 3920 3009 2660 2399 2303 2204
The preferred embodiments of the present invention have been described in detail, but the present invention is not limited to the details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, which fall within the protective scope of the present invention.

Claims (3)

1. The preparation method of the Si-P film material is characterized by comprising the following steps of: mixing acetonitrile and tetraethylammonium chloride to prepare a basic electrolyte, adding a silicon source and a phosphorus source, and then carrying out electrodeposition to obtain the Si-P film material from the surface of a metal Ni substrate electrode, wherein the phosphorus source is selected from phosphorus trichloride, phosphorus chloride, phosphorus tribromide or phosphorus pentabromide; the concentration of the phosphorus trichloride is 2.5-5 mol/L; the concentration of the phosphorus chloride is 2-10 mol/L; the concentration of the phosphorus tribromide is 1-6 mol/L; the concentration of the phosphorus pentabromide is 0.5-10 mol/L; the electrodeposition is pulse electrodeposition, and the current density range of the electrodeposition is 0.05-35A/dm2The pulse frequency is 500-12000 Hz, and the duty ratio is 15-85%.
2. The preparation method of the Si-P film material as claimed in claim 1, wherein the silicon source is selected from trichlorosilane, silicon tetrachloride, trichlorosilane or silicon tetrabromide.
3. The preparation method of the Si-P film layer material according to claim 2, wherein the concentration of trichlorosilane is 2.5-8 mol/L; the concentration of the silicon tetrachloride is 0.5-5 mol/L; the concentration of the tribromohydrogen silicon is 2-5 mol/L; the concentration of the silicon tetrabromide is 1-10 mol/L.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104062249A (en) * 2014-06-30 2014-09-24 吉林师范大学 Method for detecting band gap changes of SiGe materials in electrochemical deposition process
CN107394176A (en) * 2017-07-31 2017-11-24 中国地质大学（北京） Si-C composite material, preparation method and application and lithium ion battery negative material
CN109518237A (en) * 2019-01-24 2019-03-26 合鸿新材科技有限公司 Zinc-nickel phosphorus electroplate liquid, preparation method and electro-plating method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104062249A (en) * 2014-06-30 2014-09-24 吉林师范大学 Method for detecting band gap changes of SiGe materials in electrochemical deposition process
CN107394176A (en) * 2017-07-31 2017-11-24 中国地质大学（北京） Si-C composite material, preparation method and application and lithium ion battery negative material
CN109518237A (en) * 2019-01-24 2019-03-26 合鸿新材科技有限公司 Zinc-nickel phosphorus electroplate liquid, preparation method and electro-plating method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"用电化学方法实现对硅的掺杂分析";方宝贤等;《太阳能学报》;19831031;第4卷(第4期);第429-432页 *

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Effective date of registration: 20221226

Address after: No.18-D10016, Jianshe Road, Kaixuan Street, Liangxiang, Fangshan District, Beijing 102400

Patentee after: Beijing Yunshang Power Technology Co.,Ltd.

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Patentee before: FOSHAN University