CN112687861B - Silicon oxide and preparation method and application thereof - Google Patents
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Abstract
The invention belongs to the field of lithium ion battery cathode materials, and particularly relates to silicon oxide and a preparation method and application thereof. The preparation method comprises the steps of removing an original passivation layer on the surface of the silicon by surface treatment to expose a fresh silicon surface, and carrying out controllable oxidation on the fresh surface in an oxidation environment to obtain the silicon oxide. The oxidation of the silicon-based material in the silicon oxide material firstly removes the original passivation layer on the surface of the silicon by ball milling crushing or acid washing or alkali etching method to expose the fresh surface, and utilizes the high reaction activity of the fresh surface to carry out controllable oxidation under the mild oxidation environment. By regulating the oxidation degree of the silicon-based material, the material has higher capacity and better cycle stability, and the problems of high preparation cost, high energy consumption and high uncontrollable property of the traditional silicon oxide are solved.
Description
Technical Field
The invention belongs to the field of lithium ion battery cathode materials, and particularly relates to silicon oxide and a preparation method and application thereof.
Background
As an important energy storage technology, lithium ion batteries have been widely used in the field of energy storage for portable electronic devices, electric vehicles, and the like. With the continuous development of the technology, people have higher and higher requirements on the energy density of energy storage materials, and the traditional graphite cathode materials cannot meet the capacity requirements of high-energy-density lithium ion batteries. The silicon material has high theoretical specific capacity (4200 mAh g) -1 ) The lithium ion battery has the advantages of low working potential, rich natural content, low cost and the like, and can improve the energy density of the lithium ion battery by replacing a graphite cathode material of a commercial lithium ion battery, thereby drawing wide attention. However, the significant volume expansion/contraction effect (up to 300-400%) of the silicon material during electrochemical cycling, accompanied by the continuous lithiation and delithiation of the material, can cause active particle pulverization, particle sizeLosing electrical contact with the particles and creating an unstable solid electrolyte interface, the cell capacity decays rapidly. In addition, pure silicon materials have poor conductivity and are not conducive to efficient use of active materials. Silicon oxide (SiO) x ) Compared with pure silicon material, the specific capacity is reduced, but still far higher than that of graphite. The volume expansion of the silicon oxide is greatly reduced in comparison with that of pure silicon in the charging and discharging processes, and better electrochemical cycle performance can be obtained.
CN103022446B discloses a silicon oxide/carbon cathode material of a lithium ion battery and a preparation method thereof, the three-layer composite material with a core-shell structure adopts a graphite material as a core, porous silicon oxide as an intermediate layer and organic pyrolytic carbon as an outermost coating layer; the preparation method comprises the steps of preparing porous SiO x The preparation and carbon coating process of (1) mixing silicon oxide, active metal and graphite to obtain a mixture; (2) Heating the mixture obtained in the step (1) to 200-1100 ℃ in a protective atmosphere, roasting, keeping the temperature for at least 0.5 hour, cooling, and removing impurities to obtain a silicon oxide/graphite negative electrode material; (3) And (3) mixing the silicon oxide/graphite cathode material obtained in the step (2) with an organic carbon source, then heating to 200-1100 ℃ in a protective atmosphere, roasting, keeping the temperature for at least 0.5 hour, and cooling to obtain the lithium ion battery cathode material. According to the technical scheme, active metal is added to reduce to obtain porous SiO x The silicon particles are subjected to self-absorption by the volume expansion effect in the charging and discharging processes, so that the volume expansion effect is greatly reduced, the first charging and discharging efficiency and the cycle stability are obviously improved, but the reaction conditions are very harsh, and the reaction controllability is poor.
CN112018334A discloses a silicon oxide/carbon composite negative electrode material, a preparation method thereof and a lithium ion battery, (1) a silicon oxide block is synthesized; (2) Crushing the silicon oxide block in the step (1) to obtain micro-nano SiO x A particle; (3) Subjecting the micro-nano SiO in the step (2) x Mixing the particles with a carbonaceous binder to obtain a precursor I; (4) Granulating the precursor I in the step (3) in a non-oxidizing atmosphere to obtain a precursor II; (5) Modifying and carbonizing the precursor II in the step (4) in a non-oxidizing atmosphere to obtain a precursor III; (6) Step by stepAnd (5) carrying out post-treatment on the precursor III to obtain the silicon oxide/carbon composite anode material. The technical proposal mainly comprises SiO x Composition of/C material, said SiO x The particles contain Si microcrystals and SiO x The particle size distribution of the particles is proper, the capacity and the first coulombic efficiency are good, but the preparation method has high energy consumption, high cost and poor controllability.
In summary, the existing silicon oxide/carbon composite material preparation technology is based on the existing silicon oxide and carbon for compounding, and does not involve the controllable regulation and control of the oxygen content in the silicon oxide. The prior art still lacks a preparation method of a silicon oxide-based material which is safe, reliable, high in controllability and capable of being used for a lithium ion battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a simple and controllable preparation method of silicon oxide (SiO) x ) The method of the material comprises the steps of removing or destroying an original passivation layer on the surface of the silicon by a ball milling crushing or acid washing or alkali treatment etching method to expose a fresh surface, and then carrying out controllable oxidation under a mild oxidation environment by utilizing the high reaction activity of the fresh surface under the action of an oxidant.
To achieve the above objects, according to one aspect of the present invention, an original passivation layer on a silicon surface is removed by surface treatment to expose a fresh silicon surface, and the fresh surface is controllably oxidized in an oxidizing environment to obtain silicon oxide.
Preferably, the method also comprises the step of synchronously introducing carbon coating in the oxidation process, specifically, mixing a fresh silicon surface with a carbon source and then carrying out controllable oxidation together.
Preferably, the method further comprises introducing carbon coating after the oxidation process is completed, specifically compounding the generated silicon oxide and a carbon source to obtain a compound, and performing heat treatment on the compound in a protective atmosphere, wherein the protective atmosphere is preferably Ar or N 2 、H 2 One of (A) or Ar and H 2 And (3) mixing.
Preferably, the carbon source is one or more of glucose, sucrose, phenolic resin, asphalt, petroleum coke, polydopamine, polyacrylonitrile, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl chloride and citric acid.
Preferably, the oxidizing atmosphere is an oxidizing gas or an oxidizing solution, and the oxidizing solution is one of water, an alcohol solution, and a solution in which an oxidizing agent is dissolved.
Preferably, when the oxidizing atmosphere is an oxidizing gas, the controlled oxidation is a gas heat treatment; when the oxidation environment is water, the controllable oxidation is hydrothermal treatment; when the oxidizing environment is an alcohol solution, the controllable oxidation is solvent heat treatment; the oxidation environment is a solution dissolved with an oxidant, and the controllable oxidation is a solution oxidation reaction.
Preferably, the oxidation temperature of the controllable oxidation is 20-400 ℃, and the oxidation time is 1-40h.
Preferably, the surface treatment includes one of ball milling, alkali treatment and acid etching.
According to another aspect of the present invention, there is provided a silicon oxide base prepared according to the method of preparation described above, said silicon oxide SiO being x Wherein x is in the range of 0.05 to 2.
According to another aspect of the invention, there is provided a silicon oxide based application as a negative electrode for a lithium ion battery, or as a negative electrode for a lithium ion battery in admixture with graphite.
The invention has the following beneficial effects:
(1) The oxidation of the silicon-based material in the silicon oxide material firstly removes the original passivation layer on the surface of the silicon by ball milling crushing or acid washing or alkali etching method to expose the fresh surface, and carries out controllable oxidation under the mild oxidation environment by utilizing the high reaction activity of the fresh surface under the action of an oxidant. By regulating the oxidation degree of the silicon-based material, the material has higher capacity and better cycling stability.
(2) The invention can coat a layer of carbon material on the outside of the silicon-based material synchronously or step by step to finally obtain the silicon oxide (SiO) x ) The purpose of the composite material is to effectively improve the conductivity of the silicon material and buffer the silicon-based negative electrode material in circulationThe volume change in the process keeps the structural stability and integrity of the active material and the pole piece of the battery, and improves the cycling stability of the battery.
(3) The method for controllable oxidation of silicon provided by the invention solves the problems of high preparation cost, high energy consumption and high uncontrollable property of the traditional silicon oxide.
Drawings
FIG. 1 is a graph showing the charge and discharge cycle curves of the materials obtained in examples 1, 2, 3 and 6 of the present invention and comparative example 1 as negative electrode materials for lithium ion batteries at a current density of 500mA/g in the range of 0.01 to 1V.
Figure 2 is an XRD pattern of example 3 of the invention.
FIG. 3 is an SEM photograph of example 3 of the invention.
FIG. 4 is a TEM image of embodiment 3 of the present invention, wherein (a) in FIG. 4 is an HAADF-STEM image; fig. 4 (b) is an EDS element map image of the corresponding C element; fig. 4 (c) is an EDS element map image of the corresponding O element; fig. 4 (d) is an EDS element map image of the corresponding Si element.
FIG. 5 is a TG map of example 3 of the present invention.
FIG. 6 is a graph showing the rate performance curve of example 3 of the present invention.
Fig. 7 is a graph of cycle performance for example 3 and example 4.
FIG. 8 is an XPS survey of full spectrum from example 5 of the present invention.
FIG. 9 is a graph showing the cycle performance test in example 5 of the present invention.
Fig. 10 is a cycle performance curve of application example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Examples
Example 1
In this embodiment, the oxidizing atmosphere is oxygen, and the controllable oxidation is gas heat treatment.
(1) Surface treatment: placing 5g of silicon powder in a beaker, placing the beaker in a fume hood, adding 50mL of ultrapure water into the beaker, slowly adding 30mL of HF solution with the mass fraction of 15% into the beaker, and placing the beaker on a stirring table to stir and react for 12 hours; after the reaction, the silicon particles were washed with ultrapure water and 97.5% by mass ethanol, centrifuged three times, and then dried in a vacuum oven at 80 ℃ to obtain silicon particle powder (pristine Si) with the surface passivation layer removed.
(2) Controllable oxidation: placing the silicon material with fresh silicon surface in an oxygen atmosphere tube furnace for heat treatment, keeping the temperature for 2h at 1000 ℃, and cooling to room temperature to obtain silicon oxide (SiO) subjected to heat treatment in oxygen x ) A material.
Example 2
The oxidizing environment in this embodiment is water and the controlled oxidation is hydrothermal treatment.
(1) Surface treatment: placing 5g of silicon powder in a beaker, placing the beaker in a fume hood, adding 50mL of ultrapure water into the beaker, slowly adding 30mL of HF solution with the mass fraction of 15% into the beaker, and placing the beaker on a stirring table to stir and react for 12 hours; after the reaction is finished, respectively washing and centrifuging the silicon particles by using ultrapure water and 97.5 mass percent ethanol for three times, and then placing the silicon particles in an air-blast drying oven at the temperature of 80 ℃ for drying to obtain silicon particle powder with the surface passivation layer removed.
(2) Controllable oxidation: 1g of silicon material with fresh silicon surface is dispersed into 20mL of ultra-pure water solution, dispersed evenly by ultrasonic, and stirred for 15min. Then, the solution was transferred to a hydrothermal reaction vessel having a capacity of 100mL, sealed and placed in an oven at 200 ℃ for reaction for 24 hours.
(3) Cleaning and drying: after the reaction was completed, the reaction mixture was washed 3 times with an ultrapure water solution and 97.5% by mass ethanol, and the obtained material was dried in an air-blast drying oven at 80 ℃. The dried product was ground with a mortar and heat-treated in an Ar atmosphere tube furnace. Heat treatment is carried out at 700 deg.C2h, cooling to room temperature to obtain silicon oxide (SiO) under hydrothermal conditions x ) A material.
Example 3
The difference between this example and example 2 is that glucose is also added as a carbon source to perform carbon coating during the controlled oxidation process, as described in detail below.
(1) Surface treatment: placing 5g of silicon powder in a beaker, placing the beaker in a fume hood, adding 50mL of ultrapure water into the beaker, slowly adding 30mL of HF solution with the mass fraction of 15% into the beaker, and placing the beaker on a stirring table to stir and react for 12 hours; after the reaction is finished, respectively washing and centrifuging the silicon particles by using ultrapure water and 97.5 mass percent ethanol for three times, and then placing the silicon particles in an air-blast drying oven at the temperature of 80 ℃ for drying to obtain silicon particle powder with the surface passivation layer removed.
(2) Controllable oxidation: dispersing 1g of silicon material with fresh silicon surface into 20mL of ultrapure water solution, performing ultrasonic dispersion to obtain silicon suspension, dissolving glucose particles into 20mL of ultrapure water solution to obtain glucose solution, pouring the silicon suspension into the glucose solution, and then continuing stirring for 15min. Then, the mixed solution was transferred to a hydrothermal reaction vessel having a capacity of 100mL, sealed and placed in an oven at 200 ℃ for reaction for 24 hours.
(3) Cleaning and drying: after the reaction is finished, the material is washed for 3 times by using ultrapure water solution and ethanol with the mass fraction of 97.5 percent, and the obtained material is placed in a forced air drying box at the temperature of 80 ℃ for drying. The dried product was ground with a mortar and heat-treated in an Ar atmosphere tube furnace. The heat treatment is carried out for 2h at 700 ℃, and silicon oxide (SiO) is obtained after the temperature is cooled to the room temperature x ) Carbon/carbon composite material, denoted SiO x -1/C。
Example 4
This example differs from example 3 in that the oxidation time of the controlled oxidation was varied and was placed in an oven at 200 ℃ for 30h of reaction, as described below.
(1) Surface treatment: placing 5g of silicon powder in a beaker, placing the beaker in a fume hood, adding 50mL of ultrapure water into the beaker, slowly adding 30mL of HF solution with the mass fraction of 15% into the beaker, and placing the beaker on a stirring table to stir and react for 12 hours; after the reaction is finished, respectively washing and centrifuging the silicon particles by using ultrapure water and 97.5 mass percent ethanol for three times, and then placing the silicon particles in an air-blast drying box at the temperature of 80 ℃ for drying to obtain silicon particle powder with the surface passivation layer removed.
(2) Controllable oxidation: dispersing 1g of silicon material with fresh silicon surface into 20mL of ultra-pure aqueous solution, performing ultrasonic dispersion to obtain silicon suspension, dissolving glucose particles into 20mL of ultra-pure aqueous solution to obtain glucose solution, pouring the silicon suspension into the glucose solution, and then continuing stirring for 15min. Then, the mixed solution was transferred to a hydrothermal reaction vessel having a capacity of 100mL, sealed and placed in an oven at 200 ℃ for reaction for 30 hours.
(3) And (3) cleaning and drying, after the reaction is finished, cleaning for 3 times by using ultrapure water solution and 97.5 mass percent ethanol, and drying the obtained material in a forced air drying oven at 80 ℃. The dried product was ground with a mortar and heat-treated in an Ar atmosphere tube furnace. The heat treatment is carried out for 2h at 700 ℃, and silicon oxide (SiO) is obtained after the temperature is cooled to the room temperature x ) Carbon/carbon composite material, denoted SiO x -2/C。
Example 5
The oxidizing ambient in this example is H 2 O 2 Solution of said controlled oxidation to H 2 O 2 Solution oxidation reaction
(1) 5g of silicon powder was placed in a beaker and placed in a fume hood, 50mL of ultrapure water was added thereto, 50mL of 1Mol/L NaOH solution was slowly added to the beaker, and the beaker was placed on a stirring table and stirred to react for 12 hours. After the reaction is finished, respectively washing and centrifuging the silicon particles by using ultrapure water and 97.5 mass percent ethanol for three times, and then placing the silicon particles in an air-blast drying oven at the temperature of 80 ℃ for drying to obtain silicon particle powder with the surface passivation layer removed.
(2) Weighing 1g of silicon material with fresh silicon surface after alkali etching, and dispersing the silicon material in 40mL of H with the mass fraction of 30% 2 O 2 Solution and reaction for 6h. Then, the solid product silicon oxide SiO is obtained after centrifugation and drying treatment x A material.
Example 6
The difference between the embodiment and the embodiment 2 is that carbon coating is introduced after the oxidation process is completed, and the carbon source is phenolic resin.
1g of the product silicon oxide (SiO) obtained in example 2 x ) Dispersing the material into 20mL of ultrapure water solution, performing ultrasonic dispersion to obtain a silicon suspension, dissolving phenolic resin particles into 20mL of ultrapure water solution to obtain a phenolic resin solution, pouring the silicon suspension into the phenolic resin solution, and then continuing stirring for 15min. Then, the mixed solution was transferred to a hydrothermal reaction vessel having a capacity of 100mL, sealed and placed in an oven at 200 ℃ for reaction for 4 hours. The dried product was ground with a mortar and heat-treated in an Ar atmosphere tube furnace. The heat treatment is carried out for 2h at 700 ℃, and silicon oxide (SiO) is obtained after the temperature is cooled to the room temperature x ) A carbon (C) composite material.
Application example 1
The silicon oxide obtained in example 3 of the present invention was used as a negative electrode for a lithium ion battery by mixing with graphite, as described below.
The composite material prepared in example 3 was weighed to obtain SiO x 0.036g of-1/C, and uniformly mixing the graphite material and the graphite material in a mortar to obtain a composite.
Comparative example 1
The present example was carried out only for surface treatment, as described below.
(1) Surface treatment: placing 5g of silicon powder in a beaker, placing the beaker in a fume hood, adding 50mL of ultrapure water into the beaker, slowly adding 30mL of HF solution with the mass fraction of 15% into the beaker, and placing the beaker on a stirring table to stir and react for 12 hours; after the reaction is finished, respectively washing and centrifuging the silicon particles by using ultrapure water and 97.5 mass percent ethanol for three times, and then placing the silicon particles in a vacuum oven at 80 ℃ for drying to obtain silicon particle powder with the surface passivation layer removed, wherein the silicon particle powder is marked as pristine Si.
And (4) performing electrochemical test. 0.24g of the products prepared in examples 1 to 5, application example 1 and comparative example 1, 0.03g of a conductive agent (Super-P) and 0.6g of a CMC solution with the mass fraction of 5% were weighed, uniformly mixed, homogenized, coated on a copper current collector, dried at 80 ℃, and then dried in a vacuum oven at 60 ℃ for two hours, die-cut into pole pieces with the diameter of 10mm, and assembled with metal lithium into a half cell for testing.
FIG. 1 is a charge-discharge cycle curve of the materials obtained in examples 1, 2, 3 and 5 of the present invention and comparative example 1 as a negative electrode material of a lithium ion battery at a current density of 500mA/g at 0.01-1V;
figure 2 is an XRD pattern of example 3 of the invention. As can be seen from fig. 2, the peaks measured by XRD correspond to the (111), (220), (311), (400), (331), and (422) crystal planes of crystalline silicon, respectively.
FIG. 3 is an SEM photograph of example 3 of the present invention. As can be seen from fig. 3, a silicon oxide (SiO) can be seen from the figure x ) The/carbon (C) composite material is irregular in shape.
FIG. 4 is a TEM image of example 3 of the present invention. FIG. 4 (a) is a HAADF-STEM diagram; fig. 4 (b) is an EDS element map image of the corresponding C element; fig. 4 (c) is an EDS element map image of the corresponding O element; fig. 4 (d) is an EDS element map image of the corresponding Si element.
From fig. 4, silicon oxide (SiO) can be seen x ) Active material SiO in/carbon (C) composite material x Is coated with carbon.
FIG. 5 is a TG map of example 3 of the present invention. From fig. 5, silicon oxide (SiO) can be seen x ) The carbon/carbon (C) composite has a carbon content of about 14% (the loss before 100 degrees celsius corresponds to the removal of adsorbed water, the subsequent loss of weight corresponds to the removal of carbon oxidation).
FIG. 6 is a graph showing the rate performance curve of example 3 of the present invention. As can be seen from FIG. 6, the capacity at 500mA/g is as high as 1591mAh/g, and the capacity at 2500mA/g can still maintain 970mAh/g, which shows that the material has very excellent rate capability.
Fig. 7 is a graph of cycle performance for examples 3 and 4. As can be seen from FIG. 7, after a current density of 500mA/g was cycled for 100 cycles, silicon oxide (SiO) x Specific capacity of-1)/carbon (C) is up to 1071mAh/g, and silicon oxide (SiO) x The specific capacity of-2)/carbon (C) is 606mAh/g, which indicates that the surfaces of the two materials are oxidized to different degrees.
FIG. 8 is an XPS survey of full spectrum from example 5 of the present invention. As can be seen from the figure, the signal for oxygen is very significant, indicating that a controlled oxidation process is actually occurring.
FIG. 9 is a graph showing the cycle performance test in example 5 of the present invention. As can be seen from the figure, by controlling the oxidation process of the fresh silicon material surface, the cycling stability of the material can be significantly improved.
Fig. 10 is a cycle performance curve of application example 1 of the present invention. The initial charging specific capacity is 496mAh/g, the charging specific capacity is 447mAh/g after 100 cycles, and the capacity retention rate is 90.1%, which shows that the silicon-carbon nano material and the graphite material still have good cycling stability after being compounded, and show good commercial application prospects.
Table 1 shows the results of the analysis of the EPMA test data of example 3 and example 4.
TABLE 1EPMA test data analysis results Table
| Examples | C K | O K | Si K |
| Example 3 SiO x -1/C | 14.82 | 22.69 | 62.5 |
| Example 4 SiO x -2/C | 15.28 | 35.24 | 49.48 |
As can be seen from Table 1, siO x Oxygen content of-1/C22.69%, siO x The oxygen content of-2/C was 35.24%. The controllability of the oxidation reaction was demonstrated corresponding to the cycle performance of both fig. 7, while showing that silicon oxide (SiO) increases as the degree of oxidation increases x ) The capacity of the/carbon (C) material is reduced and the cycle stability is improved.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (1)
1. A preparation method of silicon oxide is characterized in that an original passivation layer on the surface of a silicon is removed through surface treatment to expose a fresh silicon surface, and then the obtained silicon material on the fresh surface and a glucose aqueous solution are subjected to hydrothermal reaction together, so that carbon coating is introduced while controllable oxidation is realized, and silicon oxide coated by carbon is obtained; wherein the surface treatment comprises alkali treatment or acid washing etching; the silicon oxide SiO x Wherein x is in the range of 0.05 to 2; the temperature of the hydrothermal reaction is 200-400 ℃, and the reaction time is 1-40h.
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