CN112382742A - Silicon-based negative electrode material, preparation method thereof and lithium ion battery - Google Patents

Silicon-based negative electrode material, preparation method thereof and lithium ion battery Download PDF

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CN112382742A
CN112382742A CN202011174357.3A CN202011174357A CN112382742A CN 112382742 A CN112382742 A CN 112382742A CN 202011174357 A CN202011174357 A CN 202011174357A CN 112382742 A CN112382742 A CN 112382742A
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silicon
sio
porous
coating layer
lithium metal
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邓赛君
徐德雷
赵微
程阿鸿
李海军
蔡惠群
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Yinlong New Energy Co Ltd
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Abstract

The invention provides a silicon-based negative electrode material, a preparation method thereof and a lithium ion battery. The silicon-based anode material comprises: porous Si-SiOxThe compound, wherein x is more than 0 and less than or equal to 2; lithium metal coating layer coated on porous Si-SiOxOn the complex; and an amorphous carbon coating layer covering the outer surface of the lithium metal coating layer. Through the synergistic effect of the lithium metal coating layer and the amorphous carbon coating layer, the obtained silicon-based negative electrode material can remarkably improve the conductivity of the silicon-based material, reduce the polarization of current, improve the rate capability, effectively reduce the volume expansion effect of the silicon-based material and improve the cycling stability of a battery. The silicon-based negative electrode material has wide raw material sources and lower production cost.

Description

Silicon-based negative electrode material, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon-based negative electrode material, a preparation method thereof and a lithium ion battery.
Background
Compared with the traditional common negative electrode materials such as graphite, lithium titanate and the like, silicon has absolute advantages due to the theoretical capacity of 4200mAh/g, and is particularly helpful for improving the energy density of a single cell of a lithium ion battery. However, when silicon is used as a negative electrode material, an obvious volume expansion effect occurs in the process of lithium ion lithium intercalation and deintercalation, so that the negative electrode material is crushed, the irreversible reaction between the negative electrode material and an electrolyte is aggravated, and the electrochemical performance and the service life of the lithium ion battery are seriously influenced. Most of the prior art processes for modifying silicon include: the micron-sized silicon powder is subjected to nanocrystallization, and silicon-based materials are compounded through doping and cladding, or the materials with special three-dimensional core-shell structures are prepared from the material structures. The research focus is focused on the following aspects: firstly, preparing a silicon-based negative electrode material with a special structure by a special process method to reduce the volume expansion effect so as to improve the performance of the material; the volume expansion of the silicon monoxide is smaller, and the performance of the silicon monoxide is improved and the energy density is improved through doping and coating of the silicon monoxide and the carbon material; and thirdly, introducing a metal element into the silicon-based material to improve the conductivity of the material, however, the capacity of the silicon-based negative electrode material is improved by the method in the prior art to a limited extent.
Disclosure of Invention
The invention mainly aims to provide a silicon-based negative electrode material, a preparation method thereof and a lithium ion battery, and aims to solve the problem that the capacity of the silicon-based negative electrode material in the prior art is low.
In order to achieve the above object, according to one aspect of the present invention, there is provided a silicon-based anode material comprising: porous Si-SiOxThe compound, wherein x is more than 0 and less than or equal to 2; lithium metal coating layer coated on porous Si-SiOxOn the complex; and an amorphous carbon coating layer covering the outer surface of the lithium metal coating layer.
Further, the above porous Si-SiOxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.017-0.035: 0.008-0.035, preferably 1:0.035: 0.035.
Further, the thickness of the lithium metal coating layer is 100 to 300nm, the thickness of the amorphous carbon coating layer is preferably 200 to 270nm, and the particle size of the amorphous carbon is preferably 15 to 120 nm.
Further, the above porous Si-SiOxThe aperture of the composite is 100-200 nm, and porous Si-SiO is preferredxThe particle size of the compound is 8-30 μm.
According to another aspect of the present invention, there is provided a preparation method of the foregoing silicon-based anode material, including: step S1, porous Si-SiO with lithium metalxCarrying out pre-lithiation treatment on the compound to obtain a pre-lithiation compound; and step S2, mixing the carbon source and the pre-lithiation compound, and then carrying out pyrolysis treatment to obtain the silicon-based negative electrode material.
Further, in the above step S1, porous Si-SiOxThe mass ratio of the composite to the lithium metal is 1:0.02 to 0.04, preferably 1:0.04, preferably the particle size of the lithium metal is 10-50 nm, and preferably the pre-lithiation treatment is selected from any one or more of a chemical vapor deposition method, a vacuum evaporation method, a magnetron sputtering method and a high-energy ball milling method.
Further, the preparation method also comprises porous Si-SiOxThe preparation process of the compound comprises the following steps: carrying out first high-energy ball milling on micron-sized silicon powder and magnesium metal to obtain a first mixture; subjecting the first mixture to oxidation treatment to obtainSi-SiOxthe/MgO compound, wherein x is more than 0 and less than or equal to 2; using strong acid to react Si-SiOxEtching the/MgO compound to obtain porous Si-SiOxA complex; the mol ratio of the micron-sized silicon powder to the magnesium metal is preferably 1: 0.05-0.3, the temperature of the oxidation treatment is preferably 600-1200 ℃, and the time of the oxidation treatment is preferably 5-12 hours.
Further, the step S2 includes: carrying out second high-energy ball milling on the carbon source and the pre-lithiation compound to obtain a second mixture; sintering the mixture at 600-1400 ℃ to obtain the silicon-based negative electrode material, preferably porous Si-SiOxThe mass ratio of the compound to the carbon source is 1: 0.01 to 0.04, preferably 1:0.04, preferably sintering in inert gas or nitrogen for 3-10 h, preferably rotating speed of the second high-energy ball milling is 150-800 r/min, preferably time of the second high-energy ball milling is 12-60 h, further preferably rotating speed of the second high-energy ball milling is 150-450 r/min, and preferably time of the second high-energy ball milling is 12-18 h.
Further, the carbon source is selected from any one or more of the group consisting of soft carbon, hard carbon, artificial graphite, natural graphite, carbon nanotubes, carbon nanotube wires, and graphene.
According to another aspect of the present invention, a lithium ion battery is provided, which includes a positive electrode and a negative electrode, wherein the negative electrode is the aforementioned silicon-based negative electrode material.
By applying the technical scheme of the invention, the lithium metal coating layer and the amorphous carbon coating layer have excellent conductivity, so that the silicon-based negative electrode material comprising the lithium metal coating layer and the amorphous carbon coating layer can obviously improve the conductivity of the silicon-based material. And when the lithium ion full battery is formed, the SEI film formed on the interface of the negative electrode consumes the lithium ions extracted from the positive electrode, so that the capacity of the battery is reduced, and the lithium metal coating layer coated on the surface of the silicon-based negative electrode material can be used as a lithium ion source consumed by the SEI film, so that the lithium ions extracted from the positive electrode are prevented from being wasted in the formation process, and the first efficiency and the capacity of the lithium ion full battery are further improved. On this basis, with loose porous amorphous carbon coating cladding on the surface of lithium metal coating, because the surface of amorphous carbon coating has abundant carboxyl, carbonyl, functional group such as hydroxyl, make it have a large amount of active sites, thereby can be more firm with the lithium ion combination on the part lithium metal coating, make lithium metal coating and the contact of amorphous carbon coating inseparabler through intermolecular force, and then obtain closely knit, porous and have certain mechanical strength's amorphous carbon coating. The amorphous carbon coating layer can effectively reduce the huge volume expansion effect of the silicon-based material in the lithium desorption and insertion process, and can also avoid the direct contact of the silicon-based material and electrolyte, thereby ensuring the structural integrity of the electrode material and further improving the cycling stability of the battery. Therefore, the silicon-based negative electrode material obtained through the synergistic effect of the lithium metal coating layer and the amorphous carbon coating layer can not only remarkably improve the conductivity of the silicon-based material, reduce the polarization of current and improve the rate capability of a battery, but also effectively reduce the volume expansion effect of the silicon-based material and improve the cycling stability of the battery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows an SEM image of a silicon-based anode material provided in accordance with example 1 of the present invention;
fig. 2 shows an SEM image of one silicon-based anode material provided according to comparative example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background art, the problem of low capacity of the silicon-based negative electrode material exists in the prior art, and in order to solve the problem, the invention provides the silicon-based negative electrode material, the preparation method thereof and the lithium ion battery.
In an exemplary embodiment of the present application, a silicon-based anode material is provided, the silicon-based anode material comprising porous Si-SiOxThe composite, the lithium metal coating layer and the amorphous carbon coating layer, wherein x is more than 0 and less than or equal to 2; the lithium metal coating layer is coated on the porous Si-SiOxOn the complex; an amorphous carbon coating layer covers an outer surface of the lithium metal coating layer.
Because the lithium metal coating layer and the amorphous carbon coating layer both have excellent conductivity, the silicon-based negative electrode material comprising the lithium metal coating layer and the amorphous carbon coating layer can obviously improve the conductivity of the silicon-based material. And when the lithium ion full battery is formed, the SEI film formed on the interface of the negative electrode consumes the lithium ions extracted from the positive electrode, so that the capacity of the battery is reduced, and the lithium metal coating layer coated on the surface of the silicon-based negative electrode material can be used as a lithium ion source consumed by the SEI film, so that the lithium ions extracted from the positive electrode are prevented from being wasted in the formation process, and the first efficiency and the capacity of the lithium ion full battery are further improved. On this basis, with loose porous amorphous carbon coating cladding on the surface of lithium metal coating, because the surface of amorphous carbon coating has abundant carboxyl, carbonyl, functional group such as hydroxyl, make it have a large amount of active sites, thereby can be more firm with the lithium ion combination on the part lithium metal coating, make lithium metal coating and the contact of amorphous carbon coating inseparabler through intermolecular force, and then obtain closely knit, porous and have certain mechanical strength's amorphous carbon coating. The amorphous carbon coating layer can effectively reduce the huge volume expansion effect of the silicon-based material in the lithium desorption and insertion process, and can also avoid the direct contact of the silicon-based material and electrolyte, thereby ensuring the structural integrity of the electrode material and further improving the cycling stability of the battery. Therefore, the silicon-based negative electrode material obtained through the synergistic effect of the lithium metal coating layer and the amorphous carbon coating layer can not only remarkably improve the conductivity of the silicon-based material, reduce the polarization of current and improve the rate capability of a battery, but also effectively reduce the volume expansion effect of the silicon-based material and improve the cycling stability of the battery.
In order to improve the synergistic effect of the lithium metal coating layer and the amorphous carbon coating layer, the above porous Si-SiO is preferablexThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.017-0.035: 0.008-0.035, preferably 1:0.035: 0.035.
In an embodiment of the present invention, the thickness of the lithium metal coating layer is 100 to 300nm, the thickness of the amorphous carbon coating layer is preferably 200 to 270nm, and the particle size of the amorphous carbon is preferably 15 to 120 nm.
The lithium metal coating layer and the amorphous carbon coating layer with the thicknesses can reduce the use of lithium metal and a carbon source as much as possible on the basis of ensuring that the silicon-based negative electrode material has excellent conductivity, higher capacity, cycling stability, mechanical strength and rate capability, thereby reducing the production cost.
In one embodiment of the present application, the above porous Si-SiOxThe aperture of the composite is 100-200 nm, and porous Si-SiO is preferredxThe particle size of the compound is 8-30 μm.
The above porous Si-SiOxThe pore diameter and the particle size of the composite are more beneficial to the adsorption effect of the composite and lithium metal, so that the content of the lithium metal coating layer is better controlled.
In another exemplary embodiment of the present application, there is provided a method for preparing the above silicon-based anode material, the method comprising step S1 of using lithium metal to couple porous Si — SiOxCarrying out pre-lithiation treatment on the compound to obtain a pre-lithiation compound; and step S2, mixing the carbon source and the pre-lithiation compound, and then carrying out pyrolysis treatment to obtain the silicon-based negative electrode material.
Porous Si-SiO with lithium metal pairxDuring the pre-lithiation treatment of the composite, the porous Si-SiOxThe composite has rich pores, which can be adsorbed on porous Si-SiOxThe composite supports a large amount of lithium metal and is simultaneously on porous Si-SiOxThe composite surface is formed with lithium metal packageThe pre-lithiation compound of the coating layer is subjected to pyrolysis treatment of the carbon source and the pre-lithiation compound, so that the silicon-based negative electrode material obtained by the method has excellent conductivity because the lithium metal coating layer and the amorphous carbon coating layer have excellent conductivity, and the conductivity of the silicon-based material can be remarkably improved by the silicon-based negative electrode material comprising the lithium metal coating layer and the amorphous carbon coating layer. And when the lithium ion full battery is formed, the SEI film formed on the interface of the negative electrode consumes the lithium ions extracted from the positive electrode, so that the capacity of the battery is reduced, and the lithium metal coating layer coated on the surface of the silicon-based negative electrode material can be used as a lithium ion source consumed by the SEI film, so that the lithium ions extracted from the positive electrode are prevented from being wasted in the formation process, and the first efficiency and the capacity of the lithium ion full battery are further improved. On this basis, with loose porous amorphous carbon coating cladding on the surface of lithium metal coating, because the surface of amorphous carbon coating has abundant carboxyl, carbonyl, functional group such as hydroxyl, make it have a large amount of active sites, thereby can be more firm with the partial lithium ion on the lithium metal coating combination, not only realized that the lithiation compound has better bonding with the carbon source material in advance, the flying piece on the carbon source material has still been eliminated, play the effect of buffering to the volume expansion of silicon-based material, and then obtain closely knit, porous and have certain mechanical strength's amorphous carbon coating. The amorphous carbon coating layer can effectively reduce the huge volume expansion effect of the silicon-based material in the lithium desorption and insertion process, and can also avoid the direct contact of the silicon-based material and electrolyte, thereby ensuring the structural integrity of the electrode material and further improving the cycling stability of the battery. Therefore, the silicon-based negative electrode material obtained through the synergistic effect of the lithium metal coating layer and the amorphous carbon coating layer can not only remarkably improve the conductivity of the silicon-based material, reduce the polarization of current and improve the rate capability of a battery, but also effectively reduce the volume expansion effect of the silicon-based material and improve the cycling stability of the battery.
In one embodiment of the present application, in the above step S1, porous Si-SiOxComplexes and lithium goldThe mass ratio of the metal is 1:0.02 to 0.04, preferably 1:0.04, preferably the particle size of the lithium metal is 10-50 nm, and preferably the pre-lithiation treatment is selected from any one or more of a chemical vapor deposition method, a vacuum evaporation method, a magnetron sputtering method and a high-energy ball milling method.
Lithium metal in the above particle size range is more easily adsorbed into porous Si-SiOxIn the pores of the composite without being adsorbed by carbon, and thus in the porous Si-SiOxForming a lithium metal coating layer on the surface of the composite, and preparing the porous Si-SiO with the mass ratioxThe complex with lithium metal helps to ensure the formation of lithium metal vs. porous Si-SiOxThe composite is coated, and the specific pre-lithiation treatment method is favorable for better forming a layered lithium metal coating layer.
In an embodiment of the present application, the above preparation method further comprises porous Si — SiOxThe preparation process of the compound comprises the following steps: carrying out first high-energy ball milling on micron-sized silicon powder and magnesium metal to obtain a first mixture; oxidizing the first mixture to obtain Si-SiOxthe/MgO compound, wherein x is more than 0 and less than or equal to 2; using strong acid to react Si-SiOxEtching the/MgO compound to obtain porous Si-SiOxA complex; the mol ratio of the micron-sized silicon powder to the magnesium metal is preferably 1: 0.05-0.3, the temperature of the oxidation treatment is preferably 600-1200 ℃, and the time of the oxidation treatment is preferably 5-12 hours.
The first ball milling is adopted to be beneficial to obtaining a first mixture of magnesium metal uniformly dispersed in micron-sized silicon powder, so that porous Si-SiO with pores as uniform as possible is obtained after the first mixture is subjected to oxidation treatment and etching treatmentxComposite, thereby facilitating porous Si-SiOxFormation of a lithium metal coating on the composite. Wherein the control of the mole ratio of micron-sized silicon powder to magnesium metal is beneficial to the final Si-SiOxA porous structure is formed in the composite. Control of the temperature and time of the oxidation treatment then helps to disperse the silicon in the Si-SiO as much as possiblexOxidation of Mg to MgO to obtain Si-SiOxa/MgO complex, thereby obtaining Si-SiO after etching treatment (MgO removal)xThe composite has as many pores as possible. Etching treatment for increasing strong acidPreferably, the strong acid is selected from any one or more of hydrochloric acid, sulfuric acid, and nitric acid. In order to enhance the effect of the above oxidation treatment, it is preferable that the product of the first mixture after passing through a 300-mesh sieve is put into a tube furnace and subjected to oxidation treatment in an oxygen atmosphere. In order to further improve the efficiency of the first high-energy ball milling, the rotation speed of the first high-energy ball milling is preferably 150 to 800r/min, the time of the first high-energy ball milling is preferably 12 to 60 hours, the rotation speed of the first high-energy ball milling is further preferably 150 to 450r/min, and the time of the first high-energy ball milling is preferably 12 to 18 hours.
In order to improve the interaction between the carbon source and the prelithiation compound and further coat a carbon coating layer on the prelithiation compound, preferably, step S2 includes performing a second high energy ball milling on the carbon source and the prelithiation compound to obtain a second mixture; sintering the mixture at 600-1400 ℃ to obtain the silicon-based negative electrode material, preferably porous Si-SiOxThe mass ratio of the compound to the carbon source is 1: 0.01 to 0.04, preferably 1:0.04, preferably sintering in inert gas or nitrogen for 3-10 h, preferably rotating speed of the second high-energy ball milling is 150-800 r/min, preferably time of the second high-energy ball milling is 12-60 h, further preferably rotating speed of the second high-energy ball milling is 150-450 r/min, and preferably time of the second high-energy ball milling is 12-18 h. The inert gas or nitrogen, the sintering condition of temperature and the second high-energy ball milling condition all help to ensure that the formed carbon coating layer is as uniform and compact as possible.
In one embodiment of the present application, the carbon source is selected from any one or more of the group consisting of soft carbon, hard carbon, artificial graphite, natural graphite, carbon nanotubes, carbon nanotube wires, and graphene.
The carbon source is favorable for forming a carbon coating layer and reduces the production cost.
In another exemplary embodiment of the present application, a lithium ion battery is provided, which includes a positive electrode and a negative electrode, and the negative electrode is the aforementioned silicon-based negative electrode material.
The lithium ion battery cathode material is used as the cathode of the lithium ion battery, so that the theoretical capacity of the lithium ion battery can be obviously improved, and the rate capability and the cycle performance of the lithium ion battery are improved.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Example 1
Carrying out primary high-energy ball milling on micron-sized silicon powder and metal magnesium powder according to the mol ratio of 1:0.15, carrying out ball milling for 15h at the rotating speed of 400r/min, sieving by a 300-mesh sieve, then putting the product after ball milling and sieving into a tubular furnace, and treating for 8h at the high temperature of 1000 ℃ in the oxygen atmosphere to obtain Si-SiOxThe complex of/MgO (x is more than 0 and less than or equal to 2). Etching Si-SiO with HClxMgO, removing MgO in the composite to obtain porous composite Si/SiOxThe porous Si-SiOxThe pore diameter of the composite is 150nm, and the particle size is 20 μm.
According to porous Si-SiOxThe mass ratio of the composite to lithium metal (particle size of 30nm) was 1:0.04, and porous Si-SiOxThe mass ratio of the composite to natural graphite (with a particle size of 50nm) is 1:0.04 taking porous Si-SiOxThe composite and lithium powder are prepared by magnetron sputtering method on porous composite Si-SiOxThe method comprises the steps of depositing a layer of metal lithium on the surface of the lithium-containing silicon-based anode material, carrying out pre-lithiation treatment on the metal lithium to obtain a pre-lithiation compound, carrying out secondary high-energy ball milling on the pre-lithiation compound and natural graphite, carrying out ball milling at a rotating speed of 400r/min for 12 hours, putting the ball-milled compound and the natural graphite into a tubular furnace, and sintering at 1200 ℃ for 6 hours in a nitrogen atmosphere to obtain the silicon-based anode material with the amorphous carbon coating layer coated on the outer surface of the lithium metal coating layer, wherein an SEM image. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1:0.035:0.035, the thickness of the lithium metal coating layer is 300nm, and the thickness of the amorphous carbon coating layer is 250 nm.
Example 2
Example 2 differs from example 1 in that,
porous Si-SiOxThe mass ratio of the composite to the lithium metal is 1:0.02, and finally the silicon-based negative electrode material is obtained. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.017: 0.035 thickness of lithium Metal clad layerThe degree is 100nm, and the thickness of the amorphous carbon coating layer is 270 nm.
Example 3
Example 3 differs from example 1 in that,
porous Si-SiOxThe mass ratio of the composite to the lithium metal is 1:0.03, and finally the silicon-based negative electrode material is obtained. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.025: 0.035, the thickness of the lithium metal coating layer is 200nm, and the thickness of the amorphous carbon coating layer is 240 nm.
Example 4
Example 4 differs from example 1 in that,
porous Si-SiOxThe mass ratio of the composite to the lithium metal is 1: 0.015 percent, and finally obtaining the silicon-based negative electrode material. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.010: 0.035, the thickness of the lithium metal coating layer is 80nm, and the thickness of the amorphous carbon coating layer is 260 nm.
Example 5
Example 5 differs from example 1 in that,
the particle size of the lithium metal is 10nm, and finally the silicon-based negative electrode material is obtained. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.034: 0.035, the thickness of the lithium metal coating layer is 290nm, and the thickness of the amorphous carbon coating layer is 255 nm.
Example 6
Example 6 differs from example 1 in that,
the particle size of the lithium metal is 50nm, and finally the silicon-based negative electrode material is obtained. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.030: 0.035, the thickness of the lithium metal coating layer is 280nm, and the thickness of the amorphous carbon coating layer is 260 nm.
Example 7
Example 7 differs from example 1 in that,
lithium metalThe grain diameter of the silicon-based anode material is 8nm, and finally the silicon-based anode material is obtained. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.036: 0.035, the thickness of the lithium metal coating layer is 301nm, and the thickness of the amorphous carbon coating layer is 240 nm.
Example 8
Example 8 differs from example 1 in that,
vapor deposition method is adopted to deposit Si/SiO on porous compoundxDepositing metal lithium on the surface of (x is more than 0 and less than or equal to 2) to finally obtain a pre-lithiation compound, wherein porous Si-SiO is arranged in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.034: 0.035, the thickness of the lithium metal coating layer is 295nm, and the thickness of the amorphous carbon coating layer is 250 nm.
Example 9
Example 9 differs from example 1 in that,
the mol ratio of the micron-sized silicon powder to the magnesium metal is 1:0.05, and a porous compound Si/SiO is obtainedxPorous Si-SiOxThe pore diameter of the composite is 100nm, and the porous Si-SiO is preferredxThe particle size of the complex was 8 μm. Finally obtaining a pre-lithiation compound, wherein the silicon-based negative electrode material contains porous Si-SiOxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.038: 0.035, the thickness of the lithium metal coating layer is 300nm, and the thickness of the amorphous carbon coating layer is 250 nm.
Example 10
Example 10 differs from example 1 in that,
the mol ratio of the micron-sized silicon powder to the magnesium metal is 1:0.3, and a porous compound Si/SiO is obtainedxPorous Si-SiOxThe pore diameter of the composite is 200nm, and the porous Si-SiO is preferredxThe particle size of the complex was 30 μm. Finally obtaining a pre-lithiation compound, wherein the silicon-based negative electrode material contains porous Si-SiOxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.031: 0.035, the thickness of the lithium metal coating layer is 300nm, and the thickness of the amorphous carbon coating layer is 250 nm.
Example 11
Example 11 differs from example 1 in that,
the mol ratio of the micron-sized silicon powder to the magnesium metal is 1:0.03, and a porous compound Si/SiO is obtainedxPorous Si-SiOxThe pore diameter of the composite is 220nm, and the porous Si-SiO is preferredxThe particle size of the complex was 35 μm. Finally obtaining a pre-lithiation compound, wherein the silicon-based negative electrode material contains porous Si-SiOxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.025: 0.035, the thickness of the lithium metal coating layer is 250nm, and the thickness of the amorphous carbon coating layer is 270 nm.
Example 12
Example 12 differs from example 1 in that,
the temperature of the oxidation treatment is 600 ℃, the time of the oxidation treatment is 12 hours, and the porous compound Si/SiO is obtainedxPorous Si-SiOxThe pore diameter of the composite is 160nm, and the porous Si-SiO is preferredxThe particle size of the complex was 20 μm. Finally obtaining a pre-lithiation compound, wherein the silicon-based negative electrode material contains porous Si-SiOxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.028: 0.035, the thickness of the lithium metal coating layer is 250nm, and the thickness of the amorphous carbon coating layer is 270 nm.
Example 13
Example 13 differs from example 1 in that,
the temperature of the oxidation treatment is 580 ℃, the time of the oxidation treatment is 12 hours, and the porous compound Si/SiO is obtainedxPorous Si-SiOxThe pore diameter of the composite is 165nm, and the porous Si-SiO is preferredxThe particle size of the complex was 20 μm. Finally obtaining a pre-lithiation compound, wherein the silicon-based negative electrode material contains porous Si-SiOxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.025: 0.035, the thickness of the lithium metal coating layer is 245nm, and the thickness of the amorphous carbon coating layer is 270 nm.
Example 14
Example 14 differs from example 1 in that,
the temperature of the oxidation treatment is 1200 ℃, preferablyThe time of the oxidation treatment is 5 hours, and a porous compound Si/SiO is obtainedxPorous Si-SiOxThe pore diameter of the composite is 105nm, and the porous Si-SiO is preferredxThe particle size of the complex was 20 μm. Finally obtaining a pre-lithiation compound, wherein the silicon-based negative electrode material contains porous Si-SiOxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1: 0.038: 0.035, the thickness of the lithium metal coating layer is 280nm, and the thickness of the amorphous carbon coating layer is 200 nm.
Example 15
Example 15 differs from example 1 in that,
porous Si-SiOxThe mass ratio of the compound to the carbon source is 1: and 0.01, finally obtaining the silicon-based negative electrode material. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1:0.035: 0.008, the thickness of the lithium metal coating layer is 300nm, and the thickness of the amorphous carbon coating layer is 200 nm.
Example 16
Example 16 differs from example 1 in that,
porous Si-SiOxThe mass ratio of the compound to the carbon source is 1: and 0.03, finally obtaining the silicon-based negative electrode material. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1:0.035: 0.028, the thickness of the lithium metal coating layer is 300nm, and the thickness of the amorphous carbon coating layer is 260 nm.
Example 17
Example 17 differs from example 1 in that,
porous Si-SiOxThe mass ratio of the compound to the carbon source is 1:0.05, and finally obtaining the silicon-based negative electrode material. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1:0.035: 0.04, the thickness of the lithium metal coating layer is 300nm, and the thickness of the amorphous carbon coating layer is 280 nm.
Example 18
Example 18 differs from example 1 in that,
second high-energy ballThe rotation speed of the mill is 450r/min, the time of the second high-energy ball milling is 12h, and finally the silicon-based negative electrode material is obtained. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1:0.035: 0.038, the thickness of the lithium metal coating layer was 300nm, and the thickness of the amorphous carbon coating layer was 270 nm.
Example 19
Example 19 differs from example 1 in that,
the rotating speed of the second high-energy ball milling is 150r/min, and the time of the second high-energy ball milling is 18 h. And finally obtaining the silicon-based negative electrode material. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1:0.035: 0.036, the thickness of the lithium metal coating layer was 300nm, and the thickness of the amorphous carbon coating layer was 260 nm.
Example 20
Example 20 differs from example 1 in that,
the rotating speed of the second high-energy ball milling is 800r/min, the time of the second high-energy ball milling is 12h, and finally the silicon-based negative electrode material is obtained. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1:0.035: 0.034, the thickness of the lithium metal coating layer was 300nm, and the thickness of the amorphous carbon coating layer was 250 nm.
Example 21
Example 21 differs from example 1 in that,
the rotating speed of the second high-energy ball milling is 100r/min, the time of the second high-energy ball milling is 12 hours, and finally the silicon-based negative electrode material is obtained. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1:0.035: 0.030, the thickness of the lithium metal coating layer is 300nm, and the thickness of the amorphous carbon coating layer is 240 nm.
Example 22
Example 22 differs from example 1 in that,
the sintering temperature is 600 ℃, the sintering time is 10 hours, and finally the silicon-based negative electrode material is obtained. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1:0.035: 0.037, the thickness of the lithium metal coating layer was 300nm, and the thickness of the amorphous carbon coating layer was 260 nm.
Example 23
Example 23 differs from example 1 in that,
the sintering temperature is 1400 ℃, and the sintering time is 3h, and finally the silicon-based negative electrode material is obtained. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1:0.035: 0.038, the thickness of the lithium metal coating layer was 300nm, and the thickness of the amorphous carbon coating layer was 270 nm.
Example 24
Example 24 differs from example 1 in that,
the sintering temperature is 580 ℃, the time is 10h, and finally the silicon-based negative electrode material is obtained. Porous Si-SiO in the silicon-based negative electrode materialxThe mass ratio of the compound to the lithium metal coating to the amorphous carbon coating is 1:0.035: 0.032, the thickness of the lithium metal coating layer is 300nm, and the thickness of the amorphous carbon coating layer is 200 nm.
Comparative example 1
Comparative example 1 differs from example 1 only in porous Si-SiOxAnd coating a lithium metal coating layer on the surface of the composite to obtain the silicon-based negative electrode material, wherein an SEM image of the silicon-based negative electrode material is shown in figure 2.
Comparative example 2
Comparative example 2 differs from example 1 only in porous Si-SiOxAnd coating an amorphous carbon coating layer on the surface of the compound to obtain the silicon-based negative electrode material.
The average particle diameters of the silicon-based anode materials of examples 1 to 24, comparative example 1 and comparative example 2 were respectively tested using a laser particle sizer, and the test results are listed in table 1.
Preparing a button lithium ion battery:
the silicon-based negative electrode materials prepared in the above examples 1 to 24, comparative example 1 and comparative example 2 were used as negative electrodes, the NCM811 ternary material was used as a positive electrode, a separator and an electrolyte were added to prepare button lithium ion batteries 1 to 26, the first lithium intercalation specific capacity, the first lithium deintercalation specific capacity and the capacity retention rate of 0.5C cycle for 100 weeks of the button lithium ion batteries 1 to 26 were tested, and the results thereof are listed in table 2, and the multiplying power of the button lithium ion batteries 1 to 26 at 0.5C, 1C, 2C and 3C were tested, and the results thereof are listed in table 3.
TABLE 1
Figure BDA0002748281030000101
Figure BDA0002748281030000111
TABLE 2
Figure BDA0002748281030000121
Figure BDA0002748281030000131
TABLE 3
Figure BDA0002748281030000132
Figure BDA0002748281030000141
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
because the lithium metal coating layer and the amorphous carbon coating layer both have excellent conductivity, the silicon-based negative electrode material comprising the lithium metal coating layer and the amorphous carbon coating layer can obviously improve the conductivity of the silicon-based material. And when the lithium ion full battery is formed, the SEI film formed on the interface of the negative electrode consumes the lithium ions extracted from the positive electrode, so that the capacity of the battery is reduced, and the lithium metal coating layer coated on the surface of the silicon-based negative electrode material can be used as a lithium ion source consumed by the SEI film, so that the lithium ions extracted from the positive electrode are prevented from being wasted in the formation process, and the first efficiency and the capacity of the lithium ion full battery are further improved. On this basis, with loose porous amorphous carbon coating cladding on the surface of lithium metal coating, because the surface of amorphous carbon coating has abundant carboxyl, carbonyl, functional group such as hydroxyl, make it have a large amount of active sites, thereby can be more firm with the lithium ion combination on the part lithium metal coating, make lithium metal coating and the contact of amorphous carbon coating inseparabler through intermolecular force, and then obtain closely knit, porous and have certain mechanical strength's amorphous carbon coating. The amorphous carbon coating layer can effectively reduce the huge volume expansion effect of the silicon-based material in the lithium desorption and insertion process, and can also avoid the direct contact of the silicon-based material and electrolyte, thereby ensuring the structural integrity of the electrode material and further improving the cycling stability of the battery. Therefore, the silicon-based negative electrode material obtained through the synergistic effect of the lithium metal coating layer and the amorphous carbon coating layer can not only remarkably improve the conductivity of the silicon-based material, reduce the polarization of current and improve the rate capability of a battery, but also effectively reduce the volume expansion effect of the silicon-based material and improve the cycling stability of the battery.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A silicon-based anode material, comprising:
porous Si-SiOxThe compound, wherein x is more than 0 and less than or equal to 2;
lithium metal coating layer, coatingIn the porous Si-SiOxOn the complex;
and an amorphous carbon coating layer covering an outer surface of the lithium metal coating layer.
2. The silicon-based anode material of claim 1, wherein the porous Si-SiOxThe mass ratio of the compound to the lithium metal coating layer to the amorphous carbon coating layer is 1: 0.017-0.035: 0.008-0.035, preferably 1:0.035: 0.035.
3. The silicon-based negative electrode material as claimed in claim 1, wherein the thickness of the lithium metal coating layer is 100-300 nm, preferably the thickness of the amorphous carbon coating layer is 200-270 nm, and preferably the particle size of the amorphous carbon is 15-120 nm.
4. The silicon-based anode material of claim 1, wherein the porous Si-SiOxThe aperture of the composite is 100-200 nm, and the porous Si-SiO is preferably selectedxThe particle size of the compound is 8-30 μm.
5. The method for preparing a silicon-based anode material according to any one of claims 1 to 4, wherein the method comprises:
step S1, coating the porous Si-SiO with lithium metalxCarrying out pre-lithiation treatment on the compound to obtain a pre-lithiation compound;
and step S2, mixing a carbon source with the pre-lithiation compound, and then carrying out pyrolysis treatment to obtain the silicon-based negative electrode material.
6. The production method according to claim 5, wherein in the step S1, the porous Si-SiOxThe mass ratio of the complex to the lithium metal is 1:0.02 to 0.04, preferably 1:0.04, preferably the particle size of the lithium metal is 10-50 nm, and preferably the pre-lithiation treatment is any one or more selected from a chemical vapor deposition method, a vacuum evaporation method, a magnetron sputtering method and a high-energy ball milling method。
7. The method according to claim 5, further comprising the step of preparing the porous Si-SiOxThe preparation process of the compound comprises the following steps:
carrying out first high-energy ball milling on micron-sized silicon powder and magnesium metal to obtain a first mixture;
oxidizing the first mixture to obtain Si-SiOxthe/MgO compound, wherein x is more than 0 and less than or equal to 2;
using strong acid to react the Si-SiOxEtching the/MgO compound to obtain the porous Si-SiOxA complex;
preferably, the molar ratio of the micron-sized silicon powder to the magnesium metal is 1: 0.05-0.3, the temperature of the oxidation treatment is 600-1200 ℃, and the time of the oxidation treatment is 5-12 hours.
8. The method for preparing a composite material according to claim 5, wherein the step S2 includes:
carrying out second high-energy ball milling on the carbon source and the pre-lithiation compound to obtain a second mixture;
sintering the mixture at the temperature of 600-1400 ℃ to obtain the silicon-based negative electrode material,
preferably, the porous Si-SiOxThe mass ratio of the compound to the carbon source is 1: 0.01 to 0.04, preferably 1:0.04, preferably sintering in inert gas or nitrogen for 3-10 h, preferably rotating speed of the second high-energy ball milling is 150-800 r/min, preferably time of the second high-energy ball milling is 12-60 h, further preferably rotating speed of the second high-energy ball milling is 150-450 r/min, and preferably time of the second high-energy ball milling is 12-18 h.
9. The method according to claim 5, wherein the carbon source is selected from one or more of soft carbon, hard carbon, artificial graphite, natural graphite, carbon nanotube wire, and graphene.
10. A lithium ion battery, comprising a positive electrode and a negative electrode, wherein the negative electrode is the silicon-based negative electrode material of any one of claims 1 to 4.
CN202011174357.3A 2020-10-28 2020-10-28 Silicon-based negative electrode material, preparation method thereof and lithium ion battery Pending CN112382742A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115196641A (en) * 2022-09-11 2022-10-18 隆能科技(南通)有限公司 Preparation process of porous SiOx negative electrode material with high lithium storage performance
WO2024050756A1 (en) * 2022-09-08 2024-03-14 宁德时代新能源科技股份有限公司 Silicon-carbon negative electrode material and preparation method therefor, secondary battery and electric device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024050756A1 (en) * 2022-09-08 2024-03-14 宁德时代新能源科技股份有限公司 Silicon-carbon negative electrode material and preparation method therefor, secondary battery and electric device
CN115196641A (en) * 2022-09-11 2022-10-18 隆能科技(南通)有限公司 Preparation process of porous SiOx negative electrode material with high lithium storage performance

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