CN109888246B - Silicon monoxide composite negative electrode material with gradient structure and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a silicon oxide composite negative electrode material with a gradient structure and a preparation method and application thereof, wherein the silicon oxide composite negative electrode material with the gradient structure comprises a core-shell structure which is formed by a silicon dioxide layer, a silicon oxide material layer (SiOx) and a carbon coating layer which are sequentially distributed from inside to outside, the silicon oxide material layer is of a laminated structure with at least two layers, and Si: the molar ratio of O gradually increases from the inside to the outside. Due to the gradient structure, the stress is more uniform when the volume of the silicon monoxide expands in the charging process, and the surface pulverization of the particles can be effectively reduced; meanwhile, as the oxygen content in the internal silicon monoxide is higher, more by-products such as lithium oxide, lithium silicate and lithium metasilicate can be generated, so that the volume expansion generated in the charging process can be further buffered. In addition, more silicon is concentrated on the outer surface during lithium intercalation, so that the polarization of the material can be reduced to a greater extent, and the performance of the material in a lithium ion battery is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon oxide composite negative electrode material with a gradient structure and a preparation method and application thereof.
Background
With the development of lithium ion battery technology, the application range of lithium ion batteries is also expanding continuously. Since Sony first realized a commercial lithium ion battery in 1991, lithium ion batteries have gradually become the mainstream power source of consumer electronics. In recent years, the application range of lithium ion batteries is expanding to high-power and high-energy applications such as electric tools, electric/hybrid vehicles, energy storage power stations and the like. As such expansion proceeds, the power density and energy density requirements of lithium ion batteries are not met in the foreseeable future by the existing graphite-based anode materials. Therefore, finding the next generation lithium ion battery anode material capable of replacing graphite becomes one of the hot spots of the related research of the current lithium ion battery.
Silicon, lithium metal, and transition metal oxides all have the potential to replace graphite. Wherein, the theoretical capacity of silicon is up to 4200mAh/g, which is more than 10 times of the graphite capacity, and the silicon has the highest capacity in alloyable lithium storage elements. The voltage plateau of silicon is slightly higher than that of graphite, lithium precipitation on the surface is difficult to cause during charging, and the safety performance is superior to that of a graphite electrode. In addition, silicon is one of the most abundant elements in the earth crust, and has wide sources and low price.
However, the silicon material will generate huge volume expansion (more than or equal to 300%) during the charging and discharging processes of the lithium ion battery, thereby causing the material to be broken and pulverized, continuously generating a new SEI film (solid electrolyte membrane), consuming electrolyte and materials, and finally causing the battery to fail.
In an attempt to solve this problem, how to reduce the volume expansion of the silicon material has become a focus of research. Scientists mainly use the Nano-sizing of materials (Stable Li-ion nanoparticles by in-situ polymerization of controlling hydrogel to form porous coating silicon nanoparticles, Nature Communications, DOI:10.1038/ncomms2941), the multi-porous (Chemical sizing of porous silicon attached by in-situ synthesized graphene sheets for lithium-ion nanoparticles, J.Pow.Source. 2015, 287,177 183'), the hollow structure (A. void-shell for stabilized and scalable Li-ion nanoparticles, NaLett., 12, 335), the Nano-wire for Nano-sizing, 3315 (High-textured 3, Nano-processing, 3313, Nano-processing, Nano-fabrication, etc.). The methods can relieve or reduce the volume expansion of the silicon material to a certain extent, but because the nanocrystallization method has the problem of agglomeration and dispersion, the porous structure can quickly consume electrolyte, the compaction density of the hollow structure is too low, the dynamic performance is poor, and the nanowire production cost is unacceptable, so that the material cannot be applied in the industrial field at a later time.
The focus of industrial research has therefore been shifted to silica materials that can reduce the volume expansion to some extent (-100%), such as patent publication No. CN 103474631 a; patent application No.: 201410268192.4.
although the volume expansion of the material can be reduced to some extent by the silica material, the material also starts to crack from outside to inside after a certain charge and discharge because of repeated volume expansion and contraction of the final material and non-uniform stress. Therefore, the development of a silicon monoxide negative electrode material capable of effectively preventing the material from being broken is a technical problem in the field of lithium ion batteries.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a silicon monoxide composite negative electrode material with a gradient structure and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the silicon oxide composite negative electrode material with the gradient structure comprises a core-shell structure which is formed by a silicon dioxide layer, a silicon oxide material layer (SiOx, wherein x is more than 0 and less than 2) and a carbon coating layer which are sequentially distributed from inside to outside, wherein the silicon oxide material layer is of a laminated structure with at least two layers, and Si: the molar ratio of O gradually increases from the inside to the outside.
Another object of the present invention is to provide a method for preparing the above-mentioned silica composite anode material having a gradient structure, comprising the steps of:
(1) dispersing the silicon dioxide microspheres on a collecting device;
(2) weighing Si and SiO2Pulverizing, mixing at different molar ratios to obtain Si and SiO2Mixed material samples, as per Si: SiO22The molar ratio of Si and SiO is increased from small to large2The samples of the mixed materials are respectively marked as A1，A2…ANWherein N is more than or equal to 2;
(3) a is to be1Placing into a furnace cavity, placing the collecting device above the furnace cavity, heating the furnace cavity, A1In (1)Si and SiO2Carrying out solid-phase reaction to generate silicon monoxide, sublimating the generated silicon monoxide, and then desublimating and depositing on a collecting device;
(4)A1after the reaction is finished, A is added2Putting the mixture into a furnace cavity, and repeating the operation in the step (3) until the reaction is finished; preparing a composite material of silicon dioxide and silicon monoxide on a collecting device through continuous gradient desublimation deposition, and crushing to obtain a powder material;
(5) and (4) carrying out carbon coating on the powder material prepared in the step (4) to obtain the silicon oxide composite negative electrode material with the gradient structure.
In a further scheme, the median particle diameter D50 of the silica microspheres in the step (1) is 100nm-2000 nm.
Further, in the step (2), Si and SiO2Si in the mixed material sample: SiO22The molar ratio of (a) to (b) is 1:10 to 10: 1.
Further, in the step (2), Si and SiO2The mixing manner of (1) is kneading the powder with water.
Further, the heating of the furnace cavity in the step (3) is performed in a vacuum environment, and the heating temperature is 1300-1500 ℃.
In a further aspect, the method for coating carbon in step (5) is one of a gas phase method, a liquid phase method and a solid phase method.
In a further scheme, the carbon-coated carbon source in the step (5) is acetylene or pitch.
The third purpose of the invention is to provide the application of the silicon oxide composite negative electrode material with the gradient structure in a lithium ion battery.
The invention has the beneficial effects that:
according to the invention, silicon dioxide is used as a carrier, the silicon dioxide is firstly coated on the surface of a collecting device, in the process of desublimation and deposition of the silicon oxide, crystal nucleus silicon dioxide exists on the surface of the collecting device, the silicon oxide is preferentially desublimated on the surface of the silicon dioxide, so that the composite material of the silicon dioxide and the silicon oxide is prepared, and the Si: controlling the molar ratio of Si to O in the silicon oxide material layer by the molar ratio of SiO2 to prepare the silicon oxide material layer with a gradient structure; and finally, the target product is prepared by carbon coating, the preparation method is simple, the process is controllable, and the industrial production is easy to realize.
The silica composite negative electrode material with the gradient structure is a core-shell structure formed by a silica layer, a silica material layer and a carbon coating layer which are sequentially distributed from inside to outside, the silica material layer is of a layered structure with at least two layers, and Si: the molar ratio of O gradually increases from the inside to the outside. Due to the gradient structure, the stress is more uniform when the volume of the silicon monoxide expands in the charging process, and the surface pulverization of the particles can be effectively reduced; meanwhile, as the oxygen content in the internal silicon monoxide is higher, more by-products such as lithium oxide, lithium silicate and lithium metasilicate can be generated, so that the volume expansion generated in the charging process can be further buffered. In addition, more silicon is concentrated on the outer surface during lithium intercalation, so that the polarization of the material can be reduced to a greater extent, and the performance of the material in a lithium ion battery is improved.
Drawings
FIG. 1 is a schematic view of a manufacturing apparatus used in the present invention;
FIG. 2 is a schematic structural diagram of a silica composite anode material with a gradient structure prepared in example 1;
FIG. 3 is a comparison graph of the first charge and discharge curves of button cells made of the composite negative electrode material of silicon oxide prepared in example 1 and commercial silicon oxide material, respectively;
FIG. 4 is a graph comparing the charge and discharge cycles of the battery 1 and the battery 2 in example 1;
reference numerals: 1-vacuum chamber, 2-furnace chamber, 3-Si, SiO2Mixed material samples, 4-collection device, 5-silica, 6-vacuum system.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
FIG. 1 is a schematic structural view of a furnace cavity and a collecting device used in the invention, wherein the furnace cavity 2 is placed in a vacuum cavity 1, the collecting device 4 is placed above the furnace cavity 2, and the vacuum cavity 1 is communicated with a vacuum system 6, so that the system is in a vacuum state. Si, SiO2Mixed material sample 3 was prepared as Si: SiO22The molar ratio of the silicon monoxide to the silicon monoxide is sequentially placed in the furnace cavity 2 from small to large, and the silicon monoxide 5 is desublimated and deposited on the collecting device 2 in the experimental process.
Example 1
Preparing a silicon oxide composite negative electrode material with a gradient structure:
(1) uniformly dispersing 40g of monodisperse silica microspheres with the median particle size D50-300 nm on a collecting device and pre-drying;
(2) raw materials of Si and SiO2Respectively crushing into micron size, and mixing according to Si: SiO22Are fully mixed according to the molar ratio of 1:10, 1:2, 1:1, 2:1 and 10:1, and are kneaded by adding a proper amount of deionized water to obtain five Si and SiO2Sample of the mixture, marked A1，A2，A3，A4，A5(ii) a Each weighing 900g (solid content) of A1，A2，A3，A4，A5；
(3) Firstly, A is mixed1Placing into a furnace cavity, heating the vacuum cavity 1 to 200 deg.C at a speed of 10 deg.C per minute under vacuum condition, and maintaining for 1 hr to ensure Si and SiO2Fully drying the water in the mixed material sample; placing the collecting device above the furnace cavity, heating the furnace cavity to 1350 deg.C, A1Si and SiO in2Carrying out solid-phase reaction to generate silicon monoxide, sublimating the generated silicon monoxide, and then desublimating and depositing on a collecting device;
(4)A1after the reaction is finished, A is added2Placing the sample into a furnace cavity, and repeating the operation of the step (3) until a fifth sample A5After the reaction is finished, preparing the silicon dioxide and the silicon monoxide on a collecting device through continuous gradient desublimation depositionCooling the composite material to room temperature, opening a vacuum system, taking out a product, and mechanically crushing the product to obtain a powder material with D50 being 5 um;
(5) and (4) placing the powder material prepared in the step (4) in a rotary kiln, introducing mixed gas of acetylene and nitrogen at high temperature, carrying out gas phase coating, and cooling to room temperature after the reaction is finished to obtain the silicon monoxide composite cathode material with the gradient structure.
FIG. 2 is a schematic structural diagram of a silica composite negative electrode material having a gradient structure prepared in example 1, in which black at the outermost layer is an amorphous carbon coating layer and a SiO (white) at the inner core2The intermediate body (grey) is a layer of silica (SiOx); wherein 2>X1>X2>0, i.e., silicon (Si) in the silicon oxide layer: the molar ratio of oxygen (O) gradually increases from the inside toward the outside.
Preparation and testing of button cells: the silicon oxide composite negative electrode material prepared in example 1 and a commercial silicon oxide material were mixed with conductive carbon black and sodium carboxymethylcellulose at a weight ratio of 80:10:10, respectively, to prepare a button cell, and the first cycle curve thereof was tested, and the test results are shown in fig. 3 and table 1. As can be seen from fig. 3, the button cell made of the material prepared in example 1 has significant advantages of delithiation capacity and first coulombic efficiency, compared to the button cell made of commercial silicon oxide, wherein the voltage of delithiation capacity and first coulombic efficiency is cut off to 1.0V; as can be seen from table 1, the first coulombic efficiency of the button cell made from the material prepared in example 1 was high, reaching 73.1%.
TABLE 1 test results for button cells
Preparing an electrode and testing the electrical property of the lithium ion soft package full battery: respectively mixing the silicon oxide composite negative electrode material prepared in the example 1 and a commercial silicon oxide material with graphite (the weight ratio is 25:75), mixing the mixture with conductive carbon black, polyacrylic acid and sodium carboxymethylcellulose according to the weight ratio of 93:1.5:4:1.5, and adjusting the viscosity of the slurry to the value of the viscosity of the slurry with a water solventAnd 5, fermenting at 3000-5000 mPa-. And (4) performing an electrical property test in the lithium ion soft package full cell. The battery assembly method is as follows: lithium nickel cobaltate 622(NCM622) is used as a positive electrode, Celgard2300 is used as a diaphragm, and 1M LiPF is adopted as electrolyte6Solution of EC-DEC-EMC-FEC (3:3:3:1), LiPF6Is lithium hexafluorophosphate, EC is ethylene carbonate, EMC is methyl ethyl carbonate, FEC is fluoroethylene carbonate; and assembling the soft package battery with the nominal capacity of 8 Ah. During the test, the temperature is a normal temperature test (25 +/-3 ℃), and a constant-current charge-discharge cycle test is carried out by adopting a current of 1.0C (namely 8A). The voltage control range is 3.0-4.2V.
The lithium ion soft-package full cells made of the silicon oxide composite negative electrode material prepared in the embodiment 1 and the commercial silicon oxide material are respectively marked as a cell 1 and a cell 2, fig. 4 is a comparison graph of the cycle charge and discharge curves of the cell 1 and the cell 2, and it can be known from fig. 4 that the cycle charge and discharge performance of the cell 1 is greatly improved, and the corresponding cycle capacity retention rate is improved by about 4% when the current 600-cycle is performed.
Example 2
Preparing a silicon oxide composite negative electrode material with a gradient structure:
(1) uniformly dispersing 40g of monodisperse silica microspheres with the median particle size D50-100 nm on a collecting device and pre-drying;
(2) raw materials of Si and SiO2Respectively crushing into micron size, and mixing according to Si: SiO22Are fully mixed according to the molar ratio of 1:5, 3:5, 1:1, 5:3 and 5:1, and are added with proper amount of deionized water for kneading to obtain five Si and SiO2Sample of the mixture, marked A1，A2，A3，A4，A5(ii) a Each weighing 900g (solid content) of A1，A2，A3，A4，A5；
(3) Firstly, A is mixed1Placing into a furnace cavity, heating the vacuum cavity 1 to 200 deg.C at a speed of 10 deg.C per minute under vacuum condition, and maintaining for 1 hr to ensure Si and SiO2Mixed materialFully drying the moisture in the material sample; placing the collecting device above the furnace cavity, heating the furnace cavity to 1350 deg.C, A1Si and SiO in2Carrying out solid-phase reaction to generate silicon monoxide, sublimating the generated silicon monoxide, and then desublimating and depositing on a collecting device;
(4)A1after the reaction is finished, A is added2Placing the sample into a furnace cavity, and repeating the operation of the step (3) until a fifth sample A5After the reaction is finished, preparing the composite material of silicon dioxide and silicon monoxide on a collecting device through continuous echelon desublimation deposition, then cooling to room temperature, opening a vacuum system, taking out a product, and mechanically crushing the product to obtain a powder material D50 ═ 5 um;
(5) and (4) placing the powder material prepared in the step (4) in a rotary kiln, introducing mixed gas of acetylene and nitrogen at high temperature, carrying out gas phase coating, and cooling to room temperature after the reaction is finished to obtain the silicon monoxide composite cathode material with the gradient structure.
Example 3
Preparing a silicon oxide composite negative electrode material with a gradient structure:
(1) uniformly dispersing 1kg of monodisperse silica microspheres with the median particle size D50 of 1000nm on a collecting device and pre-drying;
(2) raw materials of Si and SiO2Respectively crushing into micron size, and mixing according to Si: SiO22Are fully mixed according to the molar ratio of 1:5, 3:5, 1:1, 5:3 and 5:1, and are added with proper amount of deionized water for kneading to obtain five Si and SiO2Sample of the mixture, marked A1，A2，A3，A4，A5(ii) a Each weighing 900g (solid content) of A1，A2，A3，A4，A5；
(3) Firstly, A is mixed1Placing into a furnace cavity, heating the vacuum cavity 1 to 200 deg.C at a speed of 10 deg.C per minute under vacuum condition, and maintaining for 1 hr to ensure Si and SiO2Fully drying the water in the mixed material sample; placing the collecting device above the furnace cavity, heating the furnace cavity to 1300 deg.C, A1Si and SiO in2Solid phaseThe reaction generates silicon monoxide, and the generated silicon monoxide is sublimated and then sublimated and deposited on a collecting device;
(4)A1after the reaction is finished, A is added2Placing the sample into a furnace cavity, and repeating the operation of the step (3) until a fifth sample A5After the reaction is finished, preparing the composite material of silicon dioxide and silicon monoxide on a collecting device through continuous echelon desublimation deposition, then cooling to room temperature, opening a vacuum system, taking out a product, and mechanically crushing the product to obtain a powder material D50 ═ 6 um;
(5) and (3) fully mixing the powder material prepared in the step (4) with 100g of asphalt, placing the mixture in a rotary kiln, introducing nitrogen at a high temperature, fully discharging coke at a proper temperature of 300-1000 ℃, and carbonizing at a proper temperature of 800-1000 ℃. And cooling to room temperature after the reaction is finished to obtain the silicon monoxide composite cathode material with the gradient structure.
Example 4
Preparing a silicon oxide composite negative electrode material with a gradient structure:
(1) uniformly dispersing 1kg of monodisperse silica microspheres with the median particle size D50 of 2000nm on a collecting device and pre-drying;
(2) raw materials of Si and SiO2Respectively crushing into micron size, and mixing according to Si: SiO22Are fully mixed according to the molar ratio of 1:5, 3:5, 1:1, 2:1 and 10:1, and are added with proper amount of deionized water for kneading to obtain five Si and SiO2Sample of the mixture, marked A1，A2，A3，A4，A5(ii) a 500g (solids content) of A are each weighed out1，A2，A3，A4，A5；
(3) Firstly, A is mixed1Placing into a furnace cavity, heating the vacuum cavity 1 to 200 deg.C at a speed of 10 deg.C per minute under vacuum condition, and maintaining for 1 hr to ensure Si and SiO2Fully drying the water in the mixed material sample; placing the collecting device above the furnace cavity, heating the furnace cavity to 1500 deg.C, A1Si and SiO in2Carrying out solid-phase reaction to generate silicon monoxide, sublimating the generated silicon monoxide, and then desublimating and depositing on a collecting device;
(4)A1after the reaction is finished, A is added2Placing the sample into a furnace cavity, and repeating the operation of the step (3) until a fifth sample A5After the reaction is finished, preparing the composite material of silicon dioxide and silicon monoxide on a collecting device through continuous echelon desublimation deposition, then cooling to room temperature, opening a vacuum system, taking out a product, and mechanically crushing the product to obtain a powder material D50 ═ 6 um;
(5) and (3) fully mixing the powder material prepared in the step (4) with 100g of asphalt, placing the mixture in a rotary kiln, introducing nitrogen at a high temperature, fully discharging coke at a proper temperature of 300-1000 ℃, and carbonizing at a proper temperature of 800-1000 ℃. And cooling to room temperature after the reaction is finished to obtain the silicon monoxide composite cathode material with the gradient structure.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (7)
1. A preparation method of a silicon monoxide composite negative electrode material with a gradient structure is characterized by comprising the following steps: the method comprises the following steps:
(1) dispersing the silicon dioxide microspheres on a collecting device;
(2) weighing Si and SiO2Pulverizing, mixing at different molar ratios to obtain Si and SiO2Mixed material samples, as per Si: SiO22The molar ratio of Si and SiO is increased from small to large2The samples of the mixed materials are respectively marked as A1，A2…ANWherein N is more than or equal to 2;
(3) a is to be1Placing into a furnace cavity, placing the collecting device above the furnace cavity, heating the furnace cavity, A1Si and SiO in2Solid-phase reaction to produce silicon monoxide, sublimation and desublimation of the produced silicon monoxideDepositing on a collecting device;
（4）A1after the reaction is finished, A is added2Putting the mixture into a furnace cavity, and repeating the operation in the step (3) until the reaction is finished; preparing a composite material of silicon dioxide and silicon monoxide on a collecting device through continuous gradient desublimation deposition, and crushing to obtain a powder material;
(5) carrying out carbon coating on the powder material prepared in the step (4) to obtain a silicon oxide composite negative electrode material with a gradient structure;
the silicon oxide composite negative electrode material with the gradient structure comprises a core-shell structure which is formed by a silicon dioxide layer, a silicon oxide material layer and a carbon coating layer which are sequentially distributed from inside to outside, wherein the silicon oxide material layer is of a layered structure with at least two layers, and Si: the molar ratio of O gradually increases from the inside to the outside.
2. The method of claim 1, wherein: the median particle diameter D50 of the silica microspheres in the step (1) is 100nm-2000 nm.
3. The method of claim 1, wherein: si and SiO in the step (2)2Si in the mixed material sample: SiO22The molar ratio of (a) to (b) is 1:10 to 10: 1.
4. The method of claim 1, wherein: si and SiO in the step (2)2The mixing was carried out by kneading the powder with water.
5. The method of claim 1, wherein: the heating of the furnace cavity in the step (3) is carried out in a vacuum environment, and the heating temperature is 1300-1500 ℃.
6. The method of claim 1, wherein: the method for coating carbon in the step (5) is one of a gas phase method, a liquid phase method and a solid phase method.
7. The method of claim 1, wherein: the carbon-coated carbon source in the step (5) is acetylene or asphalt.
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| CN117374235A (en) * | 2022-06-30 | 2024-01-09 | 贝特瑞新材料集团股份有限公司 | Silicon-based composite material and battery |
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| CN109167048A (en) * | 2018-09-25 | 2019-01-08 | 合肥国轩高科动力能源有限公司 | Titanium, the material of the nitrogen co-doped sub- silicon of carbon coating oxidation and its preparation method and application |
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