CN111710845A - Silica composite negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Silica composite negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention provides a silicon-oxygen composite negative electrode material, a preparation method thereof and a lithium ion battery. The silicon-oxygen composite anode material provided by the invention comprises composite particles, wherein the composite particles comprise lithium silicate and a non-metal silicon-containing material, and the lithium silicate is Li4SiO4The non-metallic silicon-containing material is dispersed in the lithium silicate, and the non-metallic silicon-containing material comprises at least one of nano silicon and silicon oxide. The preparation method provided by the invention comprises the following steps: will containRoasting a mixture of a silicon source and a lithium-containing compound in a protective gas atmosphere to obtain the silicon-oxygen composite negative electrode material, wherein the general formula of the silicon source is SiOy; the molar ratio of the silicon source to the lithium-containing compound is 1:1.2-1: 3. The silicon-oxygen composite negative electrode material provided by the invention only contains Li4SiO4The lithium silicate enables the silicon-oxygen composite anode material provided by the invention to have higher capacity.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, relates to a negative electrode material and a preparation method thereof, and a lithium ion battery, and particularly relates to a silica composite negative electrode material and a preparation method thereof, and a lithium ion battery.
Background
Lithium ion batteries have been widely used in portable electronic products and electric vehicles because of their advantages of high operating voltage, long cycle life, no memory effect, low self-discharge, and environmental friendliness. At present, a commercial lithium ion battery mainly adopts a graphite negative electrode material, but the theoretical specific capacity of the lithium ion battery is only 372mAh/g, and the requirement of the future lithium ion battery on high energy density cannot be met. Although the theoretical capacity of the existing Si is up to 4200mAh/g, the expansion of the existing Si is up to 300%, so that the cycle performance is influenced, and the market popularization and the application are restricted. The corresponding silicon-oxygen material has better cycle performance but low first-time efficiency. When the lithium ion battery is charged for the first time, 20-50% of lithium needs to be consumed for SEI film formation, so that the first coulombic efficiency is greatly reduced. Based on this, the more studied method for improving the first effect of the silicon-oxygen material is doping, wherein the effect of lithium doping is obvious.
However, the first effect is improved after lithium doping, and the capacity of the silicon oxide material is reduced. Lithium doping consumes the irreversible phase in silicon oxide and also consumes a portion of the reversible phase. The method has important significance for later use and commercialization of the silicon-oxygen material while improving the first effect of the silicon-oxygen material and reducing the capacity loss. Especially in the present circumstances, the rear end cell requires a higher energy density to meet the use and development demands. Therefore, it is important to increase the gram volume of the front end material itself.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a silicon-oxygen composite negative electrode material with relatively high capacity, a preparation method thereof and a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a silicon-oxygen composite anode material, which comprises composite particles, wherein the composite particles comprise lithium silicate and a non-metal silicon-containing material, and the lithium silicate is Li4SiO4The non-metallic silicon-containing material is dispersed in the lithium silicate, and the non-metallic silicon-containing material comprises at least one of nano silicon and silicon oxide.
In the silicon-oxygen composite anode material provided by the invention, the non-metal silicon-containing material is uniformly dispersed in the lithium silicate, in other words, the lithium silicate wraps the non-metal silicon-containing material.
The silicon-oxygen composite negative electrode material provided by the invention can be regarded as a pre-lithium silicon negative electrode, and only contains Li4SiO4The lithium silicate can realize that the silicon-oxygen cathode material still has higher capacity after being pre-lithiated.
Usually, silicon is mixedThe oxides are pre-lithiated, all with a certain capacity loss. Different types of lithium silicate are generated after the pre-lithium treatment, and the capacity loss caused by the different types of lithium silicate is different. In the case of consuming the same amount of lithium source, the amount of silicon monoxide consumed by different lithium silicates will also vary, only Li being formed4SiO4The consumption of SiO is minimized and the loss of capacity is minimized. Therefore, the silicon-oxygen composite negative electrode material provided by the invention can effectively reduce the capacity loss of the pre-lithium silicon-oxygen material.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferable technical scheme of the invention, in the silicon-oxygen composite negative electrode material, Li4SiO4The crystal grain size of (B) is 60nm or less, for example, 60nm, 50nm, 40nm, 30nm, 20nm or 10 nm.
Preferably, the silicon oxygen composite anode material further includes a carbon layer formed on the surface of the composite particle.
The carbon layer may be a carbon layer formed of cracked carbon.
Preferably, the carbon layer has a thickness of 300-2000nm, such as 300nm, 500nm, 1000nm, 1500nm or 2000 nm.
Preferably, the silicon-oxygen composite negative electrode material further comprises a hydrophobic layer formed on the surface of the carbon layer.
Preferably, the thickness of the hydrophobic layer is 2-500nm, such as 2nm, 5nm, 10nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, or the like.
In the invention, the hydrophobic layer plays a role in improving the water system processing performance of the material.
Preferably, the constituent material of the hydrophobic layer includes any one of lauric acid, stearic acid, leucine, methionine or phenylalanine, or a combination of at least two thereof.
In a preferred embodiment of the present invention, when the non-metallic silicon-containing material includes nano silicon and silicon oxide, the nano silicon and the silicon oxide form a sea-island structure in which a silicon oxide is a sea and a nano silicon cluster is an island. The sea-island structure means that nano silicon is not uniformly dispersed in the silicon oxide in the form of single particles, but is distributed in the silicon oxide in the form of clusters.
Preferably, the grain size of the nano-silicon is below 10nm, such as 10nm, 9nm, 8nm, 7nm, 6nm or 5 nm.
Preferably, the silicon oxide has the formula SiOx, where 0 < x < 1.2, e.g. x is 0.2, 0.5, 0.8, 1 or 1.1, etc.
Preferably, the Li4SiO4And the non-metallic silicon-containing material is 0.05-1.1, such as 0.05, 0.1, 0.5, 1, or 1.1, etc.
In a second aspect, the present invention provides a method for preparing the silicon-oxygen composite anode material according to the first aspect, wherein the method comprises the following steps:
and roasting a mixture containing a silicon source and a lithium-containing compound in a protective gas atmosphere to obtain the silicon-oxygen composite negative electrode material, wherein the general formula of the silicon source is SiOy, and the molar ratio of the silicon source to the lithium-containing compound is 1:1.2-1: 3.
In the preparation method provided by the invention, the molar ratio of the silicon source to the lithium-containing compound and the roasting temperature are adjusted to obtain the lithium-containing compound4SiO4The silicon-oxygen composite anode material of the lithium silicate plays a key role.
In the invention, if the molar ratio of the silicon source SiOy to the lithium-containing compound is too high (namely, the silicon source is too much), the lithium-silicon alloy is generated, and the safety and stability of the material are reduced; if the molar ratio of the silicon source SiOy to the lithium-containing compound is too low (i.e., too much lithium source), Li may not be obtained4SiO4And (3) obtaining the product.
As a preferred embodiment of the present invention, 0 < y < 2, for example, y is 0.1, 0.5, 1, 1.5, or 1.9.
Preferably, the silicon source is silicon monoxide (SiO).
Preferably, the lithium-containing compound is a reduced lithium-containing compound.
Preferably, the reduced lithium-containing compound includes any one of lithium hydride, alkyl lithium, metallic lithium, lithium aluminum hydride, lithium amide, or lithium borohydride, or a combination of at least two thereof.
Preferably, the mixture is prepared by at least one of mixing, fusing or stirring by a VC mixer.
Preferably, the protective gas is a non-oxygen containing gas, preferably any one or a combination of at least two of hydrogen, nitrogen, helium, neon, argon, krypton or xenon.
Preferably, the temperature of the calcination is 300-600 ℃, such as 300 ℃, 400 ℃, 500 ℃ or 600 ℃, and the like. In the invention, if the roasting temperature is too high, silicon crystal grains grow rapidly, so that the cycle performance is reduced; if the calcination temperature is too low, the reaction of the lithium-containing compound with the silicon source is incomplete and the desired pre-lithiation effect is not achieved.
Preferably, the calcination time is 2-8h, such as 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc.
As a preferred technical solution of the present invention, the preparation method of the silicon source comprises: heating a raw material capable of generating silicon oxide gas under a vacuum condition or a protective gas atmosphere to generate the silicon oxide gas, and then cooling and shaping to obtain the silicon source.
Preferably, the raw materials capable of generating silicon oxide gas are Si and SiO2A mixture of (a).
Preferably, the shaping comprises any one or a combination of at least two of crushing, ball milling or classifying.
Preferably, the heating temperature is 900-1500 ℃, such as 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃ or 1500 ℃, etc.
Preferably, the protective gas is a non-oxygen containing gas, preferably any one or a combination of at least two of hydrogen, nitrogen, helium, neon, argon, krypton or xenon.
In a preferred embodiment of the present invention, the surface of the silicon source is coated with a carbon layer.
Preferably, the method for coating the carbon layer on the surface of the silicon source comprises the following steps: and reacting the silicon source with an organic carbon source gas in a protective gas atmosphere to obtain the silicon source coated with the carbon layer.
Preferably, the protective gas is a non-oxygen containing gas, preferably any one or a combination of at least two of hydrogen, nitrogen, helium, neon, argon, krypton or xenon.
Preferably, the organic carbon source gas is a hydrocarbon.
Preferably, the hydrocarbon comprises any one of methane, ethylene, acetylene, acetone or benzene or a combination of at least two thereof.
Preferably, the reaction temperature for carrying out the reaction is 600-1000 ℃, such as 600 ℃, 700 ℃, 800 ℃, 900 ℃ or 1000 ℃, etc.
Preferably, the reaction is carried out for a reaction time of 0.5 to 10.0h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or the like.
As a preferred technical solution of the present invention, the preparation method further comprises the steps of: and (3) dipping the silicon-oxygen composite negative electrode material in a hydrophobic solution and carrying out solid-liquid separation.
Preferably, the hydrophobic solution is a solution formed by using any one or a combination of at least two of lauric acid, stearic acid, leucine, methionine or phenylalanine as a solute and any one or a combination of at least two of water, methanol, ethanol, diethyl ether, benzene or formic acid as a solvent.
Preferably, the time of the impregnation is 2-6h, such as 2h, 3h, 4h, 5h or 6h, etc.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
for Si and SiO in vacuum or protective gas atmosphere2Heating the mixture at 900-1500 ℃ to generate silicon oxide gas, and then cooling and shaping to obtain silicon monoxide;
heating the SiO to 600-1000 ℃ in the protective gas atmosphere, introducing organic carbon source gas, keeping the temperature for 0.5-10.0h, and cooling to obtain the SiO coated with the carbon layer;
mixing the silicon monoxide coated with the carbon layer and a lithium-containing compound according to a molar ratio of 1:1.2-1:3, roasting for 2-8h at the temperature of 300-600 ℃ in a protective gas atmosphere, cooling to room temperature, and soaking the roasted product in a hydrophobic solution for 2-6h to obtain the silicon-oxygen composite negative electrode material.
In a third aspect, the present invention provides a lithium ion battery comprising the silicon-oxygen composite anode material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the silicon-oxygen composite negative electrode material provided by the invention only contains Li4SiO4The silicon-oxygen composite anode material provided by the invention has the advantages of stable processing performance, high specific capacity, high first efficiency and long cycle life. The first reversible capacity of the silicon-oxygen composite negative electrode material provided by the invention can reach 1540mAh/g, the first coulombic efficiency can reach 87.2%, and the power-on cycle capacity retention rate can reach 89.2% after 50 times.
(2) The preparation method provided by the invention ensures that the product only contains Li by controlling the molar ratio of the silicon source to the lithium-containing compound and the roasting temperature4SiO4The preparation method of the lithium silicate is simple to operate, short in flow and easy to carry out industrial large-scale production.
Drawings
Fig. 1 is a first charge-discharge curve of the silicon-oxygen composite anode material provided in example 1;
fig. 2 is an SEM photograph of the silicon oxygen composite anode material provided in example 1.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
In this example, a silicon-oxygen composite anode material was prepared as follows:
(1) taking 1kg of Si powder and 2kg of SiO2Putting the powder into a VC mixer to be mixed for 30min to obtain SiO2And Si; putting the mixture into a vacuum furnace; heating to 1300 ℃ under the negative pressure condition that the vacuum degree is 5Pa, preserving the heat for 18h, generating SiO steam in the furnace, and generating a SiOy block body after rapid condensation (the condensation temperature is 950 ℃); the SiOy block is subjected to processes such as crushing, ball milling, grading and the like to control the median particle size to be 6 mu m, so as to obtain a silicon monoxide powder material;
(2) 1kg of silicon monoxide powder material is placed in a rotary furnace, protective gas N is introduced2Heating to 1000 ℃, introducing organic carbon source gas acetone, preserving heat for 4 hours, and cooling to obtain silicon oxide particles containing a carbon layer;
(3) 2kg of silicon monoxide containing a carbon layer and 250g of lithium hydride (the molar ratio of the silicon monoxide containing the carbon layer to the lithium hydride is 1:1.2) are put into a horizontal ball milling tank and are ball milled for 2h, the revolution of the ball mill is 500rpm, the mixture is taken out and put into a graphite crucible, the mixture is put into a box furnace and is roasted for 2h at 600 ℃ under the argon atmosphere, and the mixture is cooled to room temperature to obtain the lithium-containing material only4SiO4Composites without other lithium silicates; and then, soaking the composite material in a solution formed by lauric acid and diethyl ether (the mass ratio of the composite material to the lauric acid to the diethyl ether is 1:0.005:0.005) for 5 hours, filtering and drying to obtain the silicon-oxygen composite negative electrode material.
The silicon-oxygen composite anode material provided by the embodiment comprises Li4SiO4And a non-metallic silicon-containing material dispersed in Li4SiO4The nonmetal silicon-containing material consists of nano silicon and silicon oxide (SiOx, x is 0.65), the nano silicon and the silicon oxide form a sea-island structure with silicon oxide as sea and nano silicon clusters as islands, and the grain size of the nano silicon is 8.8 nm; li4SiO4Has a grain size of 500 nm. The surface of the silicon-oxygen composite negative electrode material is coated with a carbon layer, and the surface of the carbon layer further comprises a lauric acid hydrophobic layer. The carbon layer has a thickness of 300nm, the hydrophobic layer has a thickness of 2nm, and Li is4SiO4The mass ratio of the non-metallic silicon-containing material to the non-metallic silicon-containing material is 1: 1.0.
Fig. 1 is a first charge-discharge curve of the silicon-oxygen composite negative electrode material provided in this embodiment, and it can be seen from the curve that the charge capacity of the composite material is 1700mAh/g or more and the reversible capacity is 1450mAh/g or more.
Fig. 2 is an SEM photograph of the silicon-oxygen composite negative electrode material provided in this example, and it can be seen from the SEM photograph that the composite material particles are uniformly distributed, and no residual lithium source is found, and at the same time, no substance other than the particles is found, which indicates that the hydrophobic substance in the material is uniformly coated on the particle surface.
Example 2
In this example, a silicon-oxygen composite anode material was prepared as follows:
(1) taking 1kg of Si powder and 2kg of SiO2Putting the powder into a VC mixer to be mixed for 30min to obtain SiO2And Si; feeding the mixture into a reaction furnace; heating to 1500 ℃ in nitrogen atmosphere, preserving heat for 16h, generating SiO steam in a furnace, and generating SiOy block after rapid condensation (the condensation temperature is 1300 ℃); the SiOy block is subjected to processes such as crushing, ball milling, grading and the like to control the median particle diameter to be 6 mu m, so that SiOy (y is 1.0) powder material is obtained;
(2) 1kg of SiOy powder material is placed in a rotary furnace, and protective gas N is introduced2Heating to 800 ℃, introducing organic carbon source gas methane, keeping the temperature for 0.5h, and cooling to obtain SiOy particles containing a carbon layer;
(3) taking SiOy containing a carbon layer and metallic lithium (the molar ratio of the SiOy containing the carbon layer to the metallic lithium is 1:3) to be put into a horizontal ball milling tank for ball milling for 2h, the revolution of the ball milling tank is 500rpm, taking out and putting into a graphite crucible, putting into a box furnace for roasting for 2h at 450 ℃ in an argon atmosphere, and cooling to room temperature to obtain the product containing only Li4SiO4Composites without other lithium silicates; and then, soaking the composite material in a solution formed by stearic acid and benzene (the mass ratio of the composite material to stearic acid: benzene is 1:0.05:0.03) for 10 hours, filtering and drying to obtain the silicon-oxygen composite negative electrode material.
The silicon-oxygen composite anode material provided by the embodiment comprises Li4SiO4And a non-metallic silicon-containing material dispersed in Li4SiO4The nonmetal silicon-containing material consists of nano silicon and silicon oxide (SiOx, x is 0.2), the nano silicon and the silicon oxide form a sea-island structure with silicon oxide as sea and nano silicon clusters as islands, and the grain size of the nano silicon is 5 nm; li4SiO4Has a grain size of 80 nm. The surface of the silicon-oxygen composite negative electrode material is coated with a carbon layer, and the surface of the carbon layer also comprises a stearic acid hydrophobic layer. The carbon layer has a thickness of 800nm, the hydrophobic layer has a thickness of 500nm, and Li is4SiO4The mass ratio of the non-metallic silicon-containing material to the non-metallic silicon-containing material is 1: 1.1.
Example 3
In this example, a silicon-oxygen composite anode material was prepared as follows:
(1) taking 1kg of Si powder and 2kg of SiO2Putting the powder into a VC mixer to be mixed for 30min to obtain SiO2And Si; feeding the mixture into a reaction furnace; heating to 900 ℃ in argon atmosphere, preserving heat for 20h, generating SiO steam in a furnace, and generating SiOy blocks after rapid condensation (the condensation temperature is 1300 ℃); the SiOy block is subjected to processes such as crushing, ball milling, grading and the like to control the median particle diameter to be 6 mu m, so that SiOy (y is 1.0) powder material is obtained;
(2) placing 1kg of SiOy powder material in a rotary furnace, introducing protective gas argon, heating to 600 ℃, introducing organic carbon source gas ethylene, preserving heat for 10h, and cooling to obtain SiOy particles containing a carbon layer;
(3) placing SiOy containing a carbon layer and lithium borohydride (the molar ratio of the SiOy containing the carbon layer to the lithium borohydride is 1:1.2) into a horizontal ball milling tank, carrying out ball milling for 2h, wherein the revolution of the ball milling machine is 500rpm, taking out and placing into a graphite crucible, placing into a box furnace, roasting for 8h at 300 ℃ under argon atmosphere, and cooling to room temperature to obtain the product containing only Li4SiO4Composites without other lithium silicates; and then, soaking the composite material in a solution formed by phenylalanine and ethanol (the mass ratio of the composite material to the phenylalanine to the ethanol is 1:0.02:0.05) for 2 hours, filtering and drying to obtain the silicon-oxygen composite negative electrode material.
This exampleThe silicon-oxygen composite anode material comprises Li4SiO4And a non-metallic silicon-containing material dispersed in Li4SiO4The nonmetal silicon-containing material consists of nano silicon and silicon oxide (SiOx, x is 0.98), the nano silicon and the silicon oxide form a sea-island structure with silicon oxide as sea and nano silicon clusters as islands, and the grain size of the nano silicon is 3 nm; li4SiO4Has a grain size of 20 nm. The surface of the silicon-oxygen composite negative electrode material is coated with a carbon layer, and the surface of the carbon layer also comprises a phenylalanine hydrophobic layer. The carbon layer has a thickness of 2000nm, the hydrophobic layer has a thickness of 100nm, and Li is4SiO4The mass ratio of the non-metallic silicon-containing material to the non-metallic silicon-containing material is 1: 0.6.
Example 4
In this example, a silicon-oxygen composite anode material was prepared as follows:
(1) taking 1kg of Si powder and 2kg of SiO2Putting the powder into a VC mixer to be mixed for 30min to obtain SiO2And Si; putting the mixture into a vacuum furnace; heating to 1300 ℃ under the negative pressure condition that the vacuum degree is 5Pa, preserving the heat for 18h, generating SiO steam in the furnace, and generating a SiOy block body after rapid condensation (the condensation temperature is 950 ℃); the SiOy block is subjected to processes such as crushing, ball milling, grading and the like to control the median particle size to be 6 mu m, so as to obtain a silicon monoxide powder material;
(2) putting 1kg of silicon monoxide powder material into a rotary furnace, introducing protective gas argon, heating to 800 ℃, introducing organic carbon source gas benzene, preserving heat for 7 hours, and cooling to obtain silicon monoxide particles containing a carbon layer;
(3) taking silicon monoxide and lithium hydride (the molar ratio of the silicon monoxide to the lithium hydride is 1:2) containing carbon layers, putting the materials into a horizontal ball milling tank, ball milling for 1.5h, the revolution of the ball milling tank is 800rpm, taking out the materials, putting the materials into a graphite crucible, putting the graphite crucible into a box furnace, roasting the materials for 2.5h at 500 ℃ under the atmosphere of argon, and cooling the materials to room temperature to obtain the material only containing Li4SiO4Composites without other lithium silicates; then, the composite material is placed in a solution formed by lauric acid and water (the mass ratio of the composite material to the lauric acid to the water is 1:0.05:0.06) to be soaked for 4 hours, filtered and driedAnd drying to obtain the silicon-oxygen composite negative electrode material.
The silicon-oxygen composite anode material provided by the embodiment comprises Li4SiO4And a non-metallic silicon-containing material dispersed in Li4SiO4The non-metal silicon-containing material consists of nano silicon and silicon oxide (SiOx, x is 0.6), the nano silicon and the silicon oxide form a sea-island structure with silicon oxide as sea and nano silicon clusters as islands, and the grain size of the nano silicon is 7 nm; li4SiO4Has a grain size of 210 nm. The surface of the silicon-oxygen composite negative electrode material is coated with a carbon layer, and the surface of the carbon layer further comprises a lauric acid hydrophobic layer. The carbon layer has a thickness of 1300nm, the hydrophobic layer has a thickness of 300nm, and Li is4SiO4The mass ratio of the non-metallic silicon-containing material to the non-metallic silicon-containing material is 1: 0.9.
Example 5
The method for preparing a silicon-oxygen composite anode material provided in this example was the same as example 1, except that the operation of step (2), i.e., the carbon coating was not performed.
The silicon-oxygen composite anode material provided by the embodiment does not contain a carbon layer compared with the product of the embodiment 1.
Example 6
The method for preparing a silicon-oxygen composite anode material provided in this example was the same as example 1 except that the impregnation operation of step (3) was not performed.
Compared with the product of example 1, the silicon-oxygen composite anode material provided by the embodiment does not contain a hydrophobic layer.
Example 7
The method for preparing a silicon-oxygen composite anode material provided in this example was the same as example 1, except that the operation of step (2) was not performed and the impregnation operation of step (3) was not performed.
The silicon-oxygen composite anode material provided by the embodiment does not contain a carbon layer and a hydrophobic layer compared with the product of the embodiment 1.
Comparative example 1
This comparative example was conducted in the same manner as example 1 except that in step (3), 120g of lithium hydride was used (molar ratio of silicon monoxide containing carbon layer to lithium hydride was 1: 0.4).
The negative electrode material prepared in this comparative example did not have Li4SiO4Wherein the lithium silicate is Li2SiO3。
The performance test results of the silicon-oxygen composite anode material prepared by the comparative example are shown in table 1.
Test method
The silicon-oxygen composite negative electrode materials prepared in the examples and the comparative examples were tested by the following methods
1. The surface appearance, particle size and the like of the sample were observed by a scanning electron microscope of Hitachi S4800.
2. And (3) testing the first charging and discharging performance of electricity buckling:
taking the silicon-oxygen composite negative electrode materials prepared in the examples and the comparative examples as active substances, taking SBR and CMC as binders, adding conductive carbon black, stirring, pulping, coating on a copper foil, and finally drying and rolling to prepare a negative electrode sheet, wherein the active substances are as follows: conductive agent: binder 85:15: 10. Using metal lithium sheet as counter electrode, PP as diaphragm, LiPF6The electrolyte solution was EC + DEC + DMC (EC, DEC and DMC in a volume ratio of 1:1:1), and the simulated cell was assembled in an argon-filled glove box. The electrochemical performance of the button cell is tested by adopting a blue 5V/10mA type cell tester, the charging voltage is 1.5V, the discharge is carried out to 0.01V, and the charging and discharging rate is 0.1C.
3. Cycle testing
Uniformly mixing the silicon-oxygen composite negative electrode materials prepared in the examples and the comparative examples with graphite according to the mass ratio of 1:9 to obtain an active material, taking a metal lithium sheet as a counter electrode, taking PP/PE as a diaphragm, and taking LiPF6The button cell is assembled in an argon-filled glove box by taking/EC + DEC + DMC (the volume ratio of EC, DEC and DMC is 1:1:1) as electrolyte, and a blue 5V/10mA type cell tester is adopted to test the electrochemical performance of the cell after 50 cycles, wherein the charging voltage is 1.5V, the discharge is 0.01V, and the charge-discharge rate is 0.1C. The test data of the silicon oxide composite anode materials of examples 1 to 7 and comparative example 1 are shown in table 1.
TABLE 1
It can be seen from the above examples and comparative examples that the silicon-oxygen composite anode materials prepared in examples 1 to 4 contained only Li4SiO4The silicon-oxygen composite anode material provided by the invention has the advantages of stable processing performance, high specific capacity, high first efficiency and long cycle life.
Example 5 does not contain a carbon layer, so that the conductivity of the material is reduced and the electron transfer resistance between particles is increased as compared with example 1.
Example 6 does not contain a hydrophobic layer, so that compared with example 1, the processing performance of the material is poorer, and gas is more easily generated in the water-based slurry.
Example 7 does not contain a carbon layer and a hydrophobic layer, so that it has poor conductivity and processability as compared to example 1.
Comparative example 1 was insufficient in Li formation due to addition of a small amount of lithium source4SiO4Resulting in the preparation of anode materials without Li4SiO4The product of this comparative example had Li as the lithium silicate2SiO3This significantly reduces the first reversible capacity of the product of comparative example 1.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The silicon-oxygen composite anode material is characterized by comprising composite particles, wherein the composite particles comprise lithium silicate and a non-metallic silicon-containing material, and the silicic acidLithium being Li4SiO4The non-metallic silicon-containing material is dispersed in the lithium silicate, and the non-metallic silicon-containing material comprises at least one of nano silicon and silicon oxide.
2. The silicon oxygen composite anode material according to claim 1, wherein the crystal grain size of the lithium silicate in the silicon oxygen composite anode material is 60nm or less;
preferably, the silicon-oxygen composite anode material further comprises a carbon layer formed on the surface of the composite particle;
preferably, the carbon layer has a thickness of 300nm to 2000 nm;
preferably, the silicon-oxygen composite negative electrode material further comprises a hydrophobic layer formed on the surface of the carbon layer;
preferably, the thickness of the hydrophobic layer is 2nm-500 nm;
preferably, the material of the hydrophobic layer comprises any one of, or a combination of at least two of, lauric acid, stearic acid, leucine, methionine or phenylalanine.
3. The silicon oxygen composite negative electrode material according to claim 1 or 2, wherein when the non-metallic silicon-containing material comprises nano silicon and silicon oxide, the nano silicon and the silicon oxide form a sea-island structure with silicon oxide as sea and nano silicon clusters as islands;
preferably, the grain size of the nano silicon is below 10 nm;
preferably, the silicon oxide has the formula SiOx, wherein 0 < x < 1.2;
preferably, the mass ratio of the lithium silicate to the non-metallic silicon-containing material is 0.05-1.1.
4. A method for preparing a silicon-oxygen composite anode material according to any one of claims 1 to 3, characterized in that the method comprises the following steps:
and roasting a mixture containing a silicon source and a lithium-containing compound in a protective gas atmosphere to obtain the silicon-oxygen composite negative electrode material, wherein the general formula of the silicon source is SiOy, and the molar ratio of the silicon source to the lithium-containing compound is 1:1.2-1: 3.
5. The method for preparing a silicon-oxygen composite anode material according to claim 4, wherein 0 < y < 2;
preferably, the silicon source is silicon monoxide;
preferably, the lithium-containing compound is a reducing lithium-containing compound;
preferably, the lithium-containing reducing compound comprises any one of lithium hydride, alkyl lithium, metallic lithium, lithium aluminum hydride, lithium amide or lithium borohydride or a combination of at least two thereof;
preferably, the mixture is prepared by at least one of mixing, fusing, or stirring by a VC mixer;
preferably, the protective gas is a gas not containing oxygen, preferably any one or a combination of at least two of hydrogen, nitrogen, helium, neon, argon, krypton or xenon;
preferably, the roasting temperature is 300-600 ℃;
preferably, the roasting time is 2-8 h.
6. The method according to claim 4 or 5, wherein the method comprises: heating a raw material capable of generating silicon oxide gas under a vacuum condition or a protective gas atmosphere, cooling and shaping the raw material after the silicon oxide gas is generated to obtain a silicon source;
preferably, the raw materials capable of generating silicon oxide gas are Si and SiO2A mixture of (a);
preferably, the shaping comprises any one or a combination of at least two of crushing, ball milling or classifying;
preferably, the heating temperature is 900-1500 ℃;
preferably, the protective gas is a non-oxygen containing gas, preferably any one or a combination of at least two of hydrogen, nitrogen, helium, neon, argon, krypton or xenon.
7. The method according to any one of claims 4 to 6, wherein the surface of the silicon source is coated with a carbon layer;
preferably, the method for coating the carbon layer on the surface of the silicon source comprises the following steps: reacting the silicon source with an organic carbon source gas under a protective gas atmosphere to obtain a silicon source coated with a carbon layer;
preferably, the protective gas is a gas not containing oxygen, preferably any one or a combination of at least two of hydrogen, nitrogen, helium, neon, argon, krypton or xenon;
preferably, the organic carbon source gas is a hydrocarbon;
preferably, the hydrocarbon comprises any one of methane, ethylene, acetylene, acetone or benzene or a combination of at least two thereof;
preferably, the reaction temperature for the reaction is 600-1000 ℃;
preferably, the reaction is carried out for a reaction time of 0.5 to 10.0 h.
8. The method of any one of claims 4-7, further comprising the steps of: dipping the silicon-oxygen composite negative electrode material in a hydrophobic solution;
preferably, the hydrophobic solution is a solution formed by taking any one or a combination of at least two of lauric acid, stearic acid, leucine, methionine or phenylalanine as a solute and taking any one or a combination of at least two of water, methanol, ethanol, diethyl ether, benzene or formic acid as a solvent;
preferably, the time of the impregnation is 2 to 6 h.
9. The method for preparing according to any one of claims 4 to 8, characterized in that it comprises the steps of:
for Si and SiO in vacuum or protective gas atmosphere2Heating the mixture at 900-1500 ℃ to generate silicon oxide gas, cooling and shaping to obtain oxygenSilicon is oxidized;
heating the SiO to 600-1000 ℃ in the protective gas atmosphere, introducing organic carbon source gas, keeping the temperature for 0.5-10.0h, and cooling to obtain the SiO coated with the carbon layer;
mixing the silicon monoxide coated with the carbon layer and a lithium-containing compound according to a molar ratio of 1:1.2-1:3, roasting for 2-8h at the temperature of 300-600 ℃ in a protective gas atmosphere, cooling to room temperature, and soaking the roasted product in a hydrophobic solution for 2-6h to obtain the silicon-oxygen composite negative electrode material.
10. A lithium ion battery comprising the silicon-oxygen composite anode material according to any one of claims 1 to 3.
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