CN112687861A - 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 (4200mAh g)-1) The graphite type negative electrode material has the advantages of low working potential, rich natural content, low cost and the like, can improve the energy density of the lithium ion battery by replacing the graphite type negative electrode material of the commercial lithium ion battery, and therefore has attracted extensive attention. However, the significant volume expansion/contraction effect of the silicon material (up to 300% -400%) accompanied by the continuous lithiation and delithiation of the material during electrochemical cycling causes active particle pulverization, loss of electrical contact between particles, and generation of an unstable solid electrolyte interface, and the battery capacity rapidly decays. 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 material is a three-layer composite material with a core-shell structure, a graphite material is adopted as a core, porous silicon oxide is adopted as an intermediate layer, and organic pyrolytic carbon is an outermost coating layer; the preparation method comprises the steps of preparing porous SiOxThe 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) 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 for roasting, and preserving heat at leastAnd cooling for 0.5 hour to obtain the lithium ion battery cathode material. According to the technical scheme, active metal is added to reduce to obtain porous SiOxThe 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) synthesizing a silicon oxide block; (2) crushing the silicon oxide block in the step (1) to obtain micro-nano SiOxParticles; (3) subjecting the micro-nano SiO in the step (2)xMixing 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) and (5) carrying out post-treatment on the precursor III to obtain the silicon oxide/carbon composite anode material. The technical proposal mainly comprises SiOxComposition of/C material, said SiOxThe particles contain Si microcrystals and SiOxThe 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 in 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 ball milling crushing or acid washing or alkali treatment etching to expose a fresh surface, and then performing 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 under a protective atmosphere, preferably, the protective atmosphere is Ar or N2、H2One of (A) or Ar and H2And (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 1-40 h.
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 above-mentioned method, the silicon oxide SiO beingxWherein 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 cycle 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 composite material/carbon (C) aims to effectively improve the conductivity of the silicon material, buffer the volume change of the silicon-based negative electrode material in the circulating process, maintain the structural stability and integrity of the battery active material and the pole piece and improve the circulating 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 present 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 examples 3 and 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 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 oxygenx) A material.
Example 2
The oxidizing environment in this example 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 ultrapure water solution, uniformly dispersed by ultrasonic, and stirred for 15 min. 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. The heat treatment is carried out for 2h at 700 ℃, and silicon oxide (SiO) under hydrothermal condition is obtained after the temperature is cooled to room temperaturex) 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 15 min. 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 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. The heat treatment is carried out for 2h at 700 ℃, and silicon oxide (SiO) is obtained after the temperature is cooled to the room temperaturex) Carbon/carbon composite material, denoted SiOx-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 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 15 min. 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 temperaturex) Carbon/carbon composite material, denoted SiOx-2/C。
Example 5
The oxidizing ambient in this example is H2O2Solution of said controlled oxidation to H2O2Solution 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 a 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%2O2Solution and reaction for 6 h. Then, the solid product silicon oxide SiO is obtained after centrifugation and drying treatmentxA 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 2x) 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 15 min. 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 temperaturex) 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 SiOx0.036g 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, punched into a pole piece with the diameter of 10mm, and assembled with lithium metal 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 figurex) 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 seenx) Active material SiO in/carbon (C) composite materialxIs coated with carbon.
FIG. 5 shows the present inventionTG plot of example 3. From fig. 5, silicon oxide (SiO) can be seenx) The carbon/carbon (C) complex has a carbon content of about 14% (loss before 100 degrees celsius corresponds to removal of adsorbed water and subsequent loss of weight corresponds to 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)xSpecific capacity of-1)/carbon (C) is up to 1071mAh/g, and silicon oxide (SiO)xThe 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 SiOx-1/C | 14.82 | 22.69 | 62.5 |
| Example 4 SiOx-2/C | 15.28 | 35.24 | 49.48 |
As can be seen from Table 1, SiOxOxygen content of-1/C22.69%, SiOxThe 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 increasesx) 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 (10)
1. A preparation method of silicon oxide is characterized in that an original passivation layer on a silicon surface is removed through surface treatment to expose a fresh silicon surface, and the fresh surface is subjected to controllable oxidation in an oxidation environment to obtain the silicon oxide.
2. The preparation method according to claim 1, further comprising synchronously introducing carbon coating during the oxidation process, specifically mixing fresh silicon surface with carbon source and then performing controllable oxidation together.
3. The preparation method according to claim 1, further comprising introducing a carbon coating after the oxidation process is completed, specifically, compounding the generated silicon oxide with a carbon source to obtain a compound, and performing a heat treatment on the compound under a protective atmosphere, preferably, the protective atmosphere is Ar or N2、H2One of (A) or Ar and H2And (3) mixing.
4. The preparation method according to claim 2 or 3, wherein 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.
5. The method of claim 1, wherein the oxidizing environment 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.
6. The method of claim 5, wherein when the oxidizing ambient is an oxidizing gas, the controlled oxidation is a gaseous 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.
7. The preparation method according to claim 5, wherein the controllable oxidation is hydrothermal or solvothermal, the oxidation temperature is 20-400 ℃, and the oxidation time is 1-40 h.
8. The method of claim 1, wherein the surface treatment comprises one of ball milling, alkali treatment, and acid etching.
9. Silicon oxide prepared by the method according to any one of claims 1 to 8, characterized in that the silicon oxide is SiOxWherein x is in the range of 0.05 to 2.
10. Use of silicon oxide according to claim 9 as negative electrode in lithium ion batteries or as negative electrode in lithium ion batteries mixed with graphite.
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| CN116936750A (en) * | 2023-09-18 | 2023-10-24 | 季华实验室 | Lithium ion battery negative electrode plate, preparation method thereof, negative electrode plate slurry and lithium ion battery |
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