CN113201808A - Porous fiber silicon-oxygen negative electrode composite material and preparation method thereof - Google Patents

Porous fiber silicon-oxygen negative electrode composite material and preparation method thereof Download PDF

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CN113201808A
CN113201808A CN202110468544.0A CN202110468544A CN113201808A CN 113201808 A CN113201808 A CN 113201808A CN 202110468544 A CN202110468544 A CN 202110468544A CN 113201808 A CN113201808 A CN 113201808A
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composite material
preparation
sio
precursor
negative electrode
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郭华军
谭福金
颜果春
王志兴
王接喜
牛旭鹏
李新海
胡启阳
彭文杰
殷振国
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Central South University
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    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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    • D01F1/00—General methods for the manufacture of artificial filaments or the like
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    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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Abstract

The invention relates to lithium ionThe technical field of sub-batteries, in particular to a porous fiber silicon-oxygen cathode composite material and a preparation method thereof. The preparation method comprises the following steps: mixing SiOxBall milling is carried out under inert atmosphere to obtain ball-milled SiOx(ii) a Ball milling of SiOxAdding the carbon precursor, the titanium precursor and the pore-forming agent into a solvent according to a certain proportion, uniformly stirring to obtain a precursor spinning solution, and spinning to obtain a precursor fiber film; stabilizing and carbonizing the precursor fiber film to obtain porous fiber silicon-oxygen negative electrode SiOx@TiO2a/C composite material. The preparation method is simple and environment-friendly, various reaction conditions in the process are easy to control, the yield is high, and the composite material has good conductivity and interface stability, higher capacity, good cycle performance and rate capability, and can be used for a lithium ion battery cathode material.

Description

Porous fiber silicon-oxygen negative electrode composite material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a porous fiber silicon-oxygen cathode composite material and a preparation method thereof.
Background
Lithium Ion Batteries (LIBs) have the advantages of high specific energy density, long cycle life, no memory effect and the like, and are widely applied to portable electronic equipment and new energy automobiles. However, the traditional graphite negative electrode material (with low theoretical specific capacity, 372mAh g-1) is difficult to meet the requirements of the next generation of high energy density lithium ion battery. The silicon has high theoretical specific capacity (3579mAh g < -1 >), moderate reaction potential (about 0.4V) and rich resources (the second rich element in the crust), and is one of the new generation high-capacity lithium ion battery cathode materials with great application potential. However, due to a large volume change (-320%) caused by a silicon alloying reaction during charge and discharge, the silicon negative electrode has problems of particle pulverization, structural damage of the electrode, deterioration of interface stability, and the like, which severely restricts the commercial application thereof.
Thus, one turned his eyes to SiO, which has a smaller volume expansionxMaterials, but SiOxIt also suffers from poor conductivity and non-negligible volume expansion. Various methods have been proposed for modifying silica, such as ball milling, chemical vapor deposition, sol gel, and the like. Therefore, a solution to SiO was developedxTechnical materials having problems of poor conductivity and volume expansion are urgently needed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention uses the electrostatic spinning method to process SiOxCarbon coating and titanium dioxide coating are carried out, then a porous fiber structure is obtained through stabilizing treatment and high-temperature carbonization treatment, the fiber structure can avoid the problem of fracture and has good adaptability to pressure and volume deformation, better conductivity is always achieved due to the fact that better contact can exist between the active material and the conductive network and between the active material and the current collector, interface impedance between electrolyte and an electrode can be reduced, and the porous fiber structure can be used for a lithium particle battery cathode material.
In order to achieve the purpose, the invention provides a preparation method of a porous fiber silicon-oxygen negative electrode composite material, which specifically comprises the following steps:
mixing SiOxBall milling is carried out under inert atmosphere to obtain ball-milled SiOx；
Ball milling of SiOxAdding a carbon precursor, a titanium precursor and a pore-forming agent into a solvent, uniformly stirring to obtain a precursor spinning solution, and spinning to obtain a precursor fiber film;
stabilizing the precursor fiber film in an air atmosphere at the temperature of 100-300 ℃, and then carbonizing the precursor fiber film in an inert atmosphere to obtain porous fibrous SiOx@TiO2a/C composite material.
Furthermore, the ball-material ratio in the ball milling process is 20-30:1, the rotating speed is 700-900rpm, and the ball milling time is 3-5 h.
Further, the spinning solution comprises the following raw materials in percentage by mass:
ball milling of SiOx1-10 wt% of a carbon precursor, 5-15 wt% of a titanium precursor, 1-10 wt% of a pore-forming agent and the balance of a solvent.
Further, the carbon precursor is at least one of polyvinylpyrrolidone, polyacrylonitrile, polyvinyl butyral, polyvinyl alcohol, levorotatory polylactic acid and polyacrylic acid;
the titanium precursor is at least one of isopropyl titanate, titanyl sulfate, tetrabutyl titanate, metatitanic acid and titanium tetrachloride;
the pore-forming agent is at least one of polyethylene glycol, polymethyl methacrylate and polystyrene;
the solvent is at least one of ethanol, N-dimethylformamide, N-dimethylacetamide, dichloromethane and dimethyl sulfoxide.
Further, the technological parameters of the spinning process are as follows:
the inner diameter of the needle is 0.3-2.0 mm, the spinning voltage is 8-20 kV, and the flow rate of the spinning solution is 0.03-0.15 mm min-1The receiving distance is 10-20 cm, and the spinning time is 6-15 h.
Further, the temperature rise speed of the stabilizing treatment is 2-10 ℃ min-1And the stabilizing and heat-preserving time is 0.5-3 h.
Further, the temperature rise speed of the carbonization treatment is 5-10 ℃ min-1The carbonization treatment temperature is 500-800 ℃, and the treatment time is 2-5 h.
Based on the same inventive concept, the invention also provides porous fibrous SiOx@TiO2the/C composite material is prepared by the preparation method.
Has the advantages that:
(1) the invention relates to a porous fiber silicon-oxygen cathode (SiO)x@TiO2The preparation method of the/C) composite material is simple and environment-friendly, and various reaction strips in the processEasy control, low preparation cost, short preparation time, high yield and being beneficial to large-scale production in batches.
(2) Porous fiber SiO of the inventionx@TiO2the/C composite material takes carbon fiber as a matrix and SiOxCan be attached to or embedded into the carbon fiber and simultaneously generate nano TiO2The particles may be coated on the surface of the material and the fibres contain a porous structure. The composite material effectively improves the conductivity and the interface stability of the material, has higher capacity, good cycle performance and rate capability, and the lithium ion battery taking the composite material as the negative electrode material has excellent specific capacity, rate capability and cycle performance.
Drawings
FIG. 1 is a SiO diagram of a porous fiber provided in example 1 of the present inventionx@TiO2SEM image of/C composite material.
FIG. 2 is a diagram of a ball-milled SiO solid provided in example 1 of the present inventionxAnd porous fiber SiOx@TiO2XRD pattern of the/C composite material.
FIG. 3 is a SiO diagram of a porous fiber provided in example 1 of the present inventionx@TiO2the/C composite material is used as a lithium battery negative electrode material and is 0.1Ag-1First charge-discharge curve at current density of (a).
FIG. 4 is a SiO diagram of a porous fiber provided in example 1 of the present inventionx@TiO2the/C composite material is used as a lithium battery negative electrode material and is 0.1Ag-1Activated three-turn, 0.4Ag-1Cycling stability curve for 100 cycles.
FIG. 5 is a SiO diagram of a porous fiber provided in example 2 of the present inventionx@TiO2SEM image of/C composite material.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to specific embodiments, but the scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
Mixing SiO with a ball-to-material ratio of 20:1xPutting the mixture into a ball milling tank, and ball milling the mixture for 4 hours at the rotating speed of 400rpm under the inert atmosphere to obtain the material ball-milled SiOx(M-SiOx)。
Preparing a spinning solution with ethanol as a solvent, wherein the ratio of various raw materials in the spinning solution is as follows: the mass fraction of the polyvinylpyrrolidone is 6.3 wt%, the mass fraction of the isopropyl titanate is 11.8 wt%, and the mass fraction of the M-SiOxThe mass fraction of (A) is 6.3 wt%, and the mass fraction of the polyethylene glycol is 3.2 wt%.
Carrying out electrostatic spinning on the spinning solution, wherein the spinning conditions are as follows: the inner diameter of the needle is 0.7mm, the spinning voltage is 12kV, and the flow rate of the spinning solution is 0.1mm min-1The receiving distance is 15cm, and the spinning time is 10h, so that the precursor fiber film is obtained.
Then stabilizing the precursor fiber film at 250 ℃ in air atmosphere, wherein the heating rate is 3 ℃ for min-1The heat preservation time is 1 h.
Finally, carbonizing the fiber film subjected to the stabilizing treatment at 650 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃ for min-1The carbonization time is 3h to obtain SiOx@TiO2a/C composite material.
When the button cell is prepared, a target material, a conductive agent Super P and a binder sodium alginate are mixed according to a mass ratio of 7:2:1 to prepare slurry, and the slurry is uniformly coated on a copper foil current collector to obtain an electrode plate. Vacuum drying oven at 80 deg.C for 12 h. The pole pieces were cut into small 12mm diameter disks. A metal lithium sheet (with the diameter of 14mm) is used as a counter electrode, glass fiber (GF/A) is used as a diaphragm, and an organic solution of LiPF6/EC + DEC (the volume ratio is 1:1)/VC + FEC (the mass fractions are 2% and 10% respectively) is used as an electrolyte. The battery assembly is carried out in a glove box filled with argon, a battery negative electrode shell, a lithium sheet, a diaphragm, a pole piece, electrolyte, a gasket, an elastic sheet and a battery positive electrode shell are sequentially placed from bottom to top, and the assembled battery is sealed by a button battery sealing machine. And a constant-current charging and discharging mode is adopted, and the voltage range is 0.01-2.0V. And performing cyclic voltammetry test on the Shanghai Chenghua electrochemical workstation at a scanning speed of 0.1mV s-1.
Example 2:
the material M-SiO was prepared by the method described in example 1x。
Preparing a spinning solution with N, N-dimethylformamide as a solvent, wherein the spinning solution comprises the following raw materials in parts by weight: the mass fraction of polyacrylonitrile is 6.1 wt%, the mass fraction of titanyl sulfate is 12.1 wt%, and M-SiOxThe mass fraction of (A) was 3.0 wt%, and the mass fraction of polymethyl methacrylate was 3.1 wt%.
And then carrying out electrostatic spinning on the spinning solution under the spinning conditions that: the inner diameter of the spinning needle is 1mm, the spinning voltage is 15kV, and the flow rate of the spinning solution is 0.08mm min-1The receiving distance is 15cm, and the spinning time is 12h, so that the precursor fiber film is obtained.
Then stabilizing the precursor fiber film at 250 ℃ in air atmosphere, wherein the heating rate is 1 ℃ for min-1The heat preservation time is 0.5 h.
Finally, carbonizing the fiber film subjected to the stabilizing treatment at 650 ℃ in an argon atmosphere, wherein the heating rate is 5 ℃ for min-1The carbonization time is 5h to obtain SiOx@TiO2a/C composite material.
The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
Example 3
The material M-SiO was prepared by the method described in example 1x。
Preparing a spinning solution with dichloromethane as a solvent, wherein the ratio of various raw materials in the spinning solution is as follows: the mass fraction of the polyvinyl butyral is 9.6 wt%, the mass fraction of the tetrabutyl titanate is 15.5 wt%, and the mass fraction of the M-SiO isxThe mass fraction of (B) is 4.8 wt%The mass fraction of polystyrene was 4.8 wt%.
And then carrying out electrostatic spinning on the spinning solution under the spinning conditions that: the inner diameter of the needle is 1.5mm, the spinning voltage is 18kV, and the flow rate of the spinning solution is 0.12mm min-1The receiving distance is 20cm, and the spinning time is 8h, so that the precursor fiber film is obtained.
Then stabilizing the precursor fiber film at 250 ℃ in air atmosphere, wherein the heating rate is 2 ℃ for min-1The heat preservation time is 1.5 h.
Finally, carbonizing the fiber film subjected to the stabilizing treatment at 650 ℃ in an argon atmosphere, wherein the heating rate is 3 ℃ for min-1The carbonization time is 4h to obtain SiOx@TiO2a/C composite material.
The preparation of the material smear and button cell and the electrochemical performance testing were the same as in example 1.
SiO obtained in example 1 and example 2x@TiO2the/C composite was characterized and tested. Referring to fig. 1, it can be seen from fig. 1 that after high temperature carbonization, the material contains tiny pores, the fiber morphology is kept relatively complete, and the exposed M-SiO isxVery little, M-SiOxThe effect of compounding with carbon fiber is good. Referring to FIG. 2, as can be seen from FIG. 2, M-SiOxIs an amorphous structure, and SiOx@TiO2the/C material exhibited a sharp diffraction peak at 25 deg., which is consistent with the (101) crystal plane of anatase titania (JPCDS No.21-1272), indicating the formation of anatase titania crystals. However, no diffraction peak was observed for the crystalline carbon, indicating that the carbon formed was amorphous. Referring to FIG. 3, it can be seen from FIG. 3 that SiOx@TiO2C is 0.1Ag-1The first charge specific capacity under the current density of the lithium ion battery is 1125.1mAh g-1The first coulombic efficiency was 68.8%. Referring to FIG. 4, it can be seen from FIG. 4 that at 0.4Ag-1The charging specific capacity after circulating for 100 circles under the current density is 855.0mAh g-1The corresponding capacity retention rates were 89.5% (compared to the specific charge capacity of the fourth turn), respectively, indicating that SiOx@TiO2the/C composite material has excellent cycle stability. Referring to FIG. 5, it can be seen from FIG. 5 that SiOx@TiO2the/C composite material is a porous fiber structure, most of the composite material has the diameter of about 800nm, and the surface is rough.
The above-mentioned embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications of the technical solutions and concepts of the present invention should be covered by the scope of the present invention.

Claims (8)

1.一种多孔纤维硅氧负极复合材料的制备方法，其特征在于，具体包括以下步骤：1. a preparation method of porous fiber silicon-oxygen negative electrode composite material, is characterized in that, specifically comprises the following steps: 将SiOx在惰性气氛下进行球磨获得球磨SiOx；Ball milling SiO x in an inert atmosphere to obtain ball-milled SiO x ; 将球磨SiOx、碳前驱体、钛前驱体和造孔剂加入溶剂中搅拌均匀获得前驱体纺丝液，并进行纺丝获得前驱体纤维薄膜；adding ball-milled SiO x , carbon precursor, titanium precursor and pore-forming agent into a solvent and stirring to obtain a precursor spinning solution, and spinning to obtain a precursor fiber film; 将所述前驱体纤维薄膜在空气气氛、100-300℃条件下进行稳定化处理后，置于惰性气氛下进行碳化处理，获得多孔纤维状的SiOx@TiO2/C复合材料。The precursor fiber film is stabilized in an air atmosphere at 100-300° C., and then placed in an inert atmosphere for carbonization to obtain a porous fibrous SiO x @TiO 2 /C composite material. 2.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法，其特征在于，所述球磨过程中球料比为20-30:1，转速为700-900rpm，球磨时间为3-5h。2. The preparation method of porous fiber silicon-oxygen negative electrode composite material according to claim 1, characterized in that, in the ball milling process, the ball-to-material ratio is 20-30:1, the rotating speed is 700-900rpm, and the ball-milling time is 3- 5h. 3.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法，其特征在于，所述纺丝液中各原料及其质量百分含量为：3. the preparation method of porous fiber silicon-oxygen negative electrode composite material according to claim 1, is characterized in that, each raw material and its mass percentage in the described spinning solution are: 球磨SiOx 1～10wt％，碳前驱体5～15wt％，钛前驱体5～25wt％，造孔剂1～10wt％，其余量为溶剂。Ball milling SiO x 1-10wt%, carbon precursor 5-15wt%, titanium precursor 5-25wt%, pore-forming agent 1-10wt%, and the rest is solvent. 4.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法，其特征在于，所述碳前驱体为聚乙烯基吡咯烷酮、聚丙烯腈、聚乙烯醇缩丁醛、聚乙烯醇、左旋聚乳酸、聚丙烯酸中的至少一种；4. The preparation method of porous fiber silicon-oxygen negative electrode composite material according to claim 1, wherein the carbon precursor is polyvinyl pyrrolidone, polyacrylonitrile, polyvinyl butyral, polyvinyl alcohol, At least one of L-polylactic acid and polyacrylic acid; 所述钛前驱体为钛酸异丙酯、硫酸氧钛、钛酸四丁酯、偏钛酸、四氯化钛中的至少一种；The titanium precursor is at least one of isopropyl titanate, titanyl sulfate, tetrabutyl titanate, metatitanic acid, and titanium tetrachloride; 所述造孔剂为聚乙二醇、聚甲基丙烯酸甲酯和聚苯乙烯中的至少一种；The pore-forming agent is at least one of polyethylene glycol, polymethyl methacrylate and polystyrene; 所述溶剂为乙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二氯甲烷、二甲基亚砜的至少一种。The solvent is at least one of ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, dichloromethane and dimethylsulfoxide. 5.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法，其特征在于，所述纺丝过程的工艺参数为：5. the preparation method of porous fiber silicon-oxygen negative electrode composite material according to claim 1, is characterized in that, the technological parameter of described spinning process is: 针头内径为0.3～2.0mm，纺丝电压为8～20kV，纺丝液的流速为0.03～0.15mm min-1，接收距离为10～20cm，以及纺丝时间为6～15h。The inner diameter of the needle is 0.3-2.0 mm, the spinning voltage is 8-20 kV, the flow rate of the spinning solution is 0.03-0.15 mm min -1 , the receiving distance is 10-20 cm, and the spinning time is 6-15 h. 6.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法，其特征在于，所述稳定化处理的升温速度为2～10℃ min-1，稳定化保温时间为0.5～3h。6 . The preparation method of the porous fiber silicon-oxygen negative electrode composite material according to claim 1 , wherein the heating rate of the stabilization treatment is 2-10° C. min −1 , and the stabilization holding time is 0.5-3 h. 7 . 7.根据权利要求1所述的多孔纤维硅氧负极复合材料的制备方法，其特征在于，所述碳化处理的升温速度为5～10℃ min-1，碳化处理温度为500-800℃，处理时间为2-5h。7 . The preparation method of the porous fiber silicon-oxygen negative electrode composite material according to claim 1 , wherein the heating rate of the carbonization treatment is 5-10° C. min −1 , and the carbonization treatment temperature is 500-800° C. The time is 2-5h. 8.一种多孔纤维硅氧负极复合材料，其特征在于，所述复合材料由权利要求1-7任意所述的制备方法制备获得。8 . A porous fiber silicon-oxygen negative electrode composite material, characterized in that, the composite material is prepared by the preparation method described in any of claims 1-7.
CN202110468544.0A 2021-04-28 2021-04-28 Porous fiber silicon-oxygen negative electrode composite material and preparation method thereof Pending CN113201808A (en)

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