CN113422013B - High-first-efficiency high-rate silicon-based negative electrode material and preparation method thereof - Google Patents
High-first-efficiency high-rate silicon-based negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a high-first-efficiency high-rate silicon-based negative electrode material and a preparation method thereof aiming at the problems of low first-efficiency, poor conductivity and larger expansion of a silicon-oxygen material in the prior art, wherein the silicon-based negative electrode material is a composite structure formed by distributing a high-first-efficiency SiO/C material, graphite and hard carbon in amorphous carbon; the mass ratio of each component in the silicon-based negative electrode material is high-first-effect SiO/C material: graphite: hard carbon: the amorphous carbon source is 1: 1-10: 1-5: 0.1 to 0.3. The silicon oxide material is subjected to liquid-phase pre-lithiation treatment, the high-first-effect silica material is fixed between the graphite particles and the hard carbon particles, the volume expansion of the silicon-based material is relieved through the anchoring effect of the carbon-based material, the amorphous carbon with the anchoring effect forms a carbon coating layer on the high-first-effect silica material, the graphite and the hard carbon, and the finally prepared silicon-based composite material has the characteristics of high first-effect, high multiplying power and long cycle life and is excellent in comprehensive performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-first-efficiency high-rate silicon-based negative electrode material and a preparation method thereof.
Background
With the vigorous development in the fields of consumer electronics industry, electric automobiles and the like, the requirements of people on energy storage equipment are more and more strict, lithium ion batteries are widely researched and developed due to unique advantages among numerous energy storage devices, and in order to follow up with the pace of practical application, the lithium ion batteries are continuously improved in the aspects of energy density, power density, circulation and safety; the traditional graphite lithium battery cathode material has low theoretical capacity and becomes an important factor for restricting the improvement of the energy density of the lithium battery, meanwhile, the silicon-based material has the advantages of high capacity, wide source, low lithium intercalation potential and the like and becomes the next generation cathode material which is most hopeful to replace graphite, the silicon-based material is divided into nanometer silicon and silica directions, compared with the nanometer silicon, the silica material is better seen by the industry because of smaller volume expansion and more stable circulation, and the silica material has the theoretical capacity of more than 2000mAh/g and can meet the market demand, but the silica material forms Li in the first charging process2O、Li4SiO4Etc. by-products, resulting inThe first time, the efficiency is low, and the problems of poor conductivity and large expansion of the silicon-oxygen material are still needed to be further improved.
Aiming at the problems existing in the silicon-based materials at present, researchers have already developed a great deal of research, and the means for improvement mainly focuses on prelithiation, cladding, doping and structural design; patent CN111710848A SiOxMixing the silicon source with a doping element source to obtain a doped silicon source, and then mixing and calcining the doped silicon source and a lithium source to obtain a silica anode material with good conductivity and high first effect, but the pre-lithium mode is high-temperature sintering, the uniformity is difficult to control, and the problem of processability exists in large-scale application; the patent CN110010863A dissolves metal lithium in an organic solvent, and negative electrode powder is added to complete lithium pre-preparation, so that the first effect of the material is improved, the expansion of the battery in the charging and discharging process is reduced, and the precision and consistency of the pre-lithium can be improved in the liquid phase process, but the lithium source used in the patent is single metal lithium, and the application is limited and is difficult to produce in a large scale; according to the preparation method, hard carbon particles and silicon oxide are mixed, an aqueous binder is added to adjust the viscosity of slurry, mixed particles are obtained after spray drying, small hard carbon particles are wrapped on the surface of the silicon oxide particles, and the prepared battery has the characteristic of good cycle performance.
Disclosure of Invention
The invention provides a high-first-efficiency high-rate silicon-based negative electrode material and a preparation method thereof, aiming at overcoming the problems of low first-efficiency, poor conductivity and larger expansion of a silicon-oxygen material in the prior art, the invention firstly carries out liquid-phase pre-lithiation treatment on the silicon-oxygen material, then mixes the pre-lithiated silicon-oxygen material with graphite and hard carbon, adds a carbon source for granulation, fixes the high-first-efficiency silicon-oxygen material between graphite particles and hard carbon particles, relieves the volume expansion of the silicon-oxygen material through the anchoring action of the carbon-based material, and forms a carbon coating layer on the amorphous carbon with the anchoring action on the silicon-oxygen material, the graphite and the hard carbon so as to further improve the cycle performance of the finished silicon-based material, and the existence of the hard carbon particles can improve the rate performance of the composite material, and the finally prepared silicon-based composite material has the characteristics of high-first-efficiency, high-rate and long cycle life, the comprehensive performance is excellent.
In order to achieve the purpose, the invention adopts the following technical scheme:
the high-first-efficiency high-rate silicon-based negative electrode material is a composite structure formed by distributing a high-first-efficiency SiO/C material, graphite and hard carbon in amorphous carbon.
Preferably, the mass ratio of each component in the silicon-based negative electrode material is high-first-efficiency SiO/C material: graphite: hard carbon: the amorphous carbon source is 1: 1-10: 1-5: 0.1 to 0.3.
In the prior art, pre-lithium of a silicon oxide negative electrode material is basically prepared by mixing silicon oxide and lithium source powder and then performing solid-phase sintering, so that the prepared high-efficiency silicon oxide material has large silicon particle growth, is not beneficial to long-term circulation, is difficult to control the uniformity of pre-lithium, and has the problem that the performance of the overall performance is influenced by some problems on an interface; in addition, the prior art lacks the design of a high-efficiency silica material and negative electrode composite structures such as graphite, hard carbon and the like, and does not improve the material performance through the structural control of a material end, so that the performance of the silica material in the aspects of cycle stability and multiplying power is poor.
The innovation of the invention is that: 1) the SiO/C material is subjected to pre-lithiation treatment in a liquid phase mode, compared with the traditional solid phase sintering, the pre-lithiation precision and uniformity can be improved, the pre-lithiation condition is mild, a large amount of heat cannot be generated to cause the growth of Si grains, and the adverse effect on the cycle performance of the material cannot be generated; 2) the composite structure of high-first-effect SiO/C, graphite and hard carbon is designed and synthesized, the high-first-effect silica particles are fixed between the graphite and between the graphite and the hard carbon particles, the silica material is not agglomerated in the homogenizing process, the dispersing effect is better, the carbon-based material can be used as a buffer matrix to inhibit the expansion of the silica material in the circulating process, and the circulating performance is better; 3) the addition of hard carbon particles in the compounding process improves the rate capability of the material by utilizing the characteristics of larger spacing and isotropy of hard carbon layers. Preferably, the high-first-efficiency SiO/C material is obtained by carrying out pre-lithiation treatment on a SiO/C negative electrode material by a liquid phase method, and the pre-lithiated high-efficiency SiO/C negative electrode materialThe first-effect SiO/C material mainly comprises Li2SiO3。
The preparation method of the high-efficiency high-rate silicon-based negative electrode material comprises the following preparation steps:
(1) carrying out CVD carbon coating treatment on the SiO raw material to obtain a SiO/C cathode material;
(2) dissolving a lithium source in an organic solvent, adding the SiO/C negative electrode material prepared in the step (1), ultrasonically dispersing, stirring for a period of time, and filtering and drying to obtain a high-efficiency SiO/C material;
(3) adding the high-first-efficiency SiO/C material prepared in the step (2), graphite, hard carbon and an amorphous carbon source into a mixing and granulating device to obtain a composite material precursor;
(4) and (4) placing the composite material precursor prepared in the step (3) in an inert atmosphere furnace, and carrying out high-temperature treatment for a period of time to obtain the final finished product of the cathode material.
Preferably, in the step (1), the carbon source used for the carbon coating treatment of the raw material SiO is one or more of acetylene, methane, propyne and ethylene, the coating time is 1-10 h, and the particle size D50 of the raw material SiO is 2-8 μm.
Preferably, in the step (2), the lithium source is one or more of metallic lithium, lithium hydroxide, lithium peroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium hydride and lithium fluoride, and the mass ratio of the lithium source to the SiO/C negative electrode material is 1: 0.1 to 0.8; the organic solvent is one or more of ethanol, acetone, dimethyl carbonate, diethyl carbonate, benzene and tetrahydrofuran.
Preferably, in the step (3), the graphite is one of spherical graphite, natural graphite, artificial graphite and mesocarbon microbeads; the hard carbon is resin-based hard carbon or asphalt-based hard carbon, and the particle size of the hard carbon is 7-15 mu m.
Preferably, in the step (3), the amorphous carbon source is one or more of low-temperature pitch, high-temperature pitch, coal tar, phenolic resin and coumarone resin; the mixing and granulating equipment is one of a kneading machine, a VC heating coating machine, a vertical kettle and a horizontal kettle; the reaction process in the granulation equipment is to heat up to 200-500 ℃ and preserve heat for 2-8 hours.
Preferably, in the step (4), the inert atmosphere is one of nitrogen, argon and helium; the high-temperature treatment temperature is 700-900 ℃, and the high-temperature treatment time is 2-15 h.
The high-first-efficiency high-rate silicon-based negative electrode material is applied to a lithium ion battery.
Therefore, the invention has the following beneficial effects:
(1) the invention provides a high-first-efficiency high-rate silicon-based negative electrode material and a preparation method thereof, wherein the volume expansion of the silicon-based material is relieved by the anchoring effect of a carbon-based material, and amorphous carbon with the anchoring effect forms a carbon coating layer on a high-first-efficiency silica material, graphite and hard carbon, so that the finally prepared silicon-based composite material has the characteristics of high first-efficiency high-rate long cycle life and excellent comprehensive performance;
(2) the silicon-based material with the composite structure prepared by the invention has the advantages of uniform and controllable reaction steps, simple preparation process, easiness in large-scale production and excellent performance, the first effect of the silica material is improved by pre-lithium, the multiplying power of the material is improved by adding hard carbon particles, the processing performance and the cycle performance of the material are improved by designing the composite structure, and the performance of the prepared silicon-based negative electrode material in all aspects is better.
Drawings
Fig. 1 is an SEM image of a silicon-based negative electrode material prepared in example 1 of the present invention.
FIG. 2 is XRD patterns of SiO/C before pre-lithiation and high-first-effect SiO/C material after pre-lithiation prepared in example 1 of the present invention.
Detailed Description
The invention is further described with reference to specific embodiments.
General examples
The high-first-efficiency high-rate silicon-based negative electrode material is a composite structure formed by distributing a high-first-efficiency SiO/C material, graphite and hard carbon in amorphous carbon. The mass ratio of each component in the silicon-based negative electrode material is high-first-effect SiO/C material: graphite: hard carbon: the amorphous carbon source is 1: 1-10: 1-5: 0.1 to 0.3.The high-first-effect SiO/C material is obtained by carrying out pre-lithiation treatment on a SiO/C negative electrode material by a liquid phase method, and the main component of the pre-lithiated high-first-effect SiO/C material is Li2SiO3。
The preparation method of the high-efficiency high-rate silicon-based negative electrode material comprises the following preparation steps:
(1) carrying out CVD carbon coating treatment on a raw material SiO with the particle size D50 of 2-8 mu m for 1-10 h to obtain a SiO/C negative electrode material, wherein a carbon source used for the carbon coating treatment of the raw material SiO is one or more of acetylene, methane, propyne and ethylene;
(2) dissolving a lithium source (one or more of metal lithium, lithium hydroxide, lithium peroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium hydride and lithium fluoride) in an organic solvent (one or more of ethanol, acetone, dimethyl carbonate, diethyl carbonate, benzene and tetrahydrofuran), adding the SiO/C negative electrode material prepared in the step (1), ultrasonically dispersing, stirring for a period of time, filtering and drying to obtain a high-first-efficiency SiO/C material; the mass ratio of the lithium source to the SiO/C negative electrode material is 1: 0.1 to 0.8;
(3) adding the high-first-efficiency SiO/C material prepared in the step (2), graphite (one of spherical graphite, natural graphite, artificial graphite and mesocarbon microbeads), hard carbon (resin-based hard carbon or pitch-based hard carbon) with the particle size of 7-15 mu m and an amorphous carbon source (one or more of low-temperature pitch, high-temperature pitch, coal tar, phenolic resin and coumarone resin) into a mixing and granulating device (one of a kneader, a VC heating and coating machine, a vertical kettle and a horizontal kettle) to obtain a composite material precursor; the reaction process in the granulation equipment is to heat up to 200-500 ℃ and preserve heat for 2-8 h;
(4) and (3) placing the composite material precursor prepared in the step (3) in an atmosphere furnace in an inert atmosphere (one of nitrogen, argon and helium), and treating at 700-900 ℃ for 2-15 h to obtain the final finished product cathode material.
The high-first-efficiency high-rate silicon-based negative electrode material is applied to a lithium ion battery.
Example 1
A high-first-efficiency high-rate silicon-based negative electrode material is high-first-efficiency SAnd the iO/C material, the graphite and the hard carbon are distributed in the amorphous carbon to form a composite structure. The mass ratio of each component in the silicon-based negative electrode material is high-first-effect SiO/C material: graphite: hard carbon: the amorphous carbon source is 1: 5: 3.5: 0.2. the high-first-effect SiO/C material is obtained by carrying out pre-lithiation treatment on a SiO/C negative electrode material by a liquid phase method, and the main component of the pre-lithiated high-first-effect SiO/C material is Li2SiO3。
The preparation method of the high-efficiency high-rate silicon-based negative electrode material comprises the following preparation steps:
(1) carrying out CVD carbon coating treatment on a raw material SiO with the granularity D50 of 5 mu m for 5h to obtain a SiO/C cathode material, wherein a carbon source used for the carbon coating treatment of the raw material SiO is acetylene;
(2) dissolving lithium source lithium hydroxide in an organic solvent ethanol, adding the SiO/C negative electrode material prepared in the step (1), ultrasonically dispersing, stirring for a period of time, filtering and drying to obtain a high-efficiency SiO/C material; the mass ratio of the lithium source to the SiO/C negative electrode material is 1: 0.5;
(3) adding the high-first-efficiency SiO/C material prepared in the step (2), spherical graphite, resin-based hard carbon with the particle size of 11 mu m and coal tar into a vertical kettle of mixing granulation equipment to obtain a composite material precursor; the reaction process in the granulation equipment is to heat up to 350 ℃ and preserve heat for 5 hours;
(4) and (4) placing the composite material precursor prepared in the step (3) in a nitrogen inert atmosphere furnace, and treating at 800 ℃ for 9h to obtain the final finished product of the negative electrode material.
The high-first-efficiency high-rate silicon-based negative electrode material is applied to a lithium ion battery.
Example 2
The high-first-efficiency high-rate silicon-based negative electrode material is a composite structure formed by distributing a high-first-efficiency SiO/C material, graphite and hard carbon in amorphous carbon. The mass ratio of each component in the silicon-based negative electrode material is high-first-effect SiO/C material: graphite: hard carbon: the amorphous carbon source is 1: 1: 1: 0.1. the high-first-effect SiO/C material is obtained by carrying out pre-lithiation treatment on a SiO/C negative electrode material by a liquid phase method, and the main component of the pre-lithiated high-first-effect SiO/C material is Li2SiO3。
The preparation method of the high-efficiency high-rate silicon-based negative electrode material comprises the following preparation steps:
(1) carrying out CVD carbon coating treatment on a raw material SiO with the particle size D50 of 2 mu m for 1h to obtain a SiO/C negative electrode material, wherein a carbon source used for the carbon coating treatment of the raw material SiO is methane;
(2) dissolving lithium source lithium peroxide in an organic solvent dimethyl carbonate, adding the SiO/C negative electrode material prepared in the step (1), ultrasonically dispersing, stirring for a period of time, and filtering and drying to obtain a high-efficiency SiO/C material; the mass ratio of the lithium source to the SiO/C negative electrode material is 1: 0.1;
(3) adding the high-first-efficiency SiO/C material prepared in the step (2), natural graphite, resin-based hard carbon with the particle size of 7 mu m and amorphous carbon source high-temperature asphalt into a mixing and granulating equipment kneader to obtain a composite material precursor; the reaction process in the granulation equipment is to heat up to 200 ℃ and preserve heat for 2 hours;
(4) and (4) placing the composite material precursor prepared in the step (3) in an inert atmosphere argon atmosphere furnace, and treating at 700 ℃ for 2h to obtain the final finished product of the cathode material.
The high-first-efficiency high-rate silicon-based negative electrode material is applied to a lithium ion battery.
Example 3
The high-first-efficiency high-rate silicon-based negative electrode material is a composite structure formed by distributing a high-first-efficiency SiO/C material, graphite and hard carbon in amorphous carbon. The mass ratio of each component in the silicon-based negative electrode material is high-first-effect SiO/C material: graphite: hard carbon: the amorphous carbon source is 1: 10: 5: 0.3. the high-first-effect SiO/C material is obtained by carrying out pre-lithiation treatment on a SiO/C negative electrode material by a liquid phase method, and the main component of the pre-lithiated high-first-effect SiO/C material is Li2SiO3。
The preparation method of the high-efficiency high-rate silicon-based negative electrode material comprises the following preparation steps:
(1) carrying out CVD carbon coating treatment on a raw material SiO with the particle size D50 of 8 mu m for 10h to obtain a SiO/C negative electrode material, wherein a carbon source used for the carbon coating treatment of the raw material SiO is propyne;
(2) dissolving lithium source metal lithium in an organic solvent diethyl carbonate, adding the SiO/C negative electrode material prepared in the step (1), ultrasonically dispersing, stirring for a period of time, and filtering and drying to obtain a high-efficiency SiO/C material; the mass ratio of the lithium source to the SiO/C negative electrode material is 1: 0.8;
(3) adding the high-first-efficiency SiO/C material prepared in the step (2), graphite mesocarbon microbeads, hard carbon asphalt-based hard carbon with the particle size of 15 microns and amorphous carbon source phenolic resin into a mixing granulation device VC heating coating machine to obtain a composite material precursor; the reaction process in the granulation equipment is to heat up to 500 ℃ and preserve heat for 8 hours;
(4) and (4) placing the composite material precursor prepared in the step (3) in a helium atmosphere furnace in an inert atmosphere, and treating at 900 ℃ for 15h to obtain the final finished product of the cathode material.
The high-first-efficiency high-rate silicon-based negative electrode material is applied to a lithium ion battery.
Comparative example 1 (different from example 1 in that the pre-lithiation treatment in the step (2) is not carried out, namely, the coated SiO/C negative electrode material is directly granulated and sintered with graphite and hard carbon to obtain a finished product material)
The silicon-based negative electrode material is a composite structure formed by distributing SiO/C negative electrode material, graphite and hard carbon in amorphous carbon. The mass ratio of each component in the silicon-based negative electrode material is SiO/C negative electrode material: graphite: hard carbon: the amorphous carbon source is 1: 5: 3.5: 0.2.
the preparation method of the high-efficiency high-rate silicon-based negative electrode material comprises the following preparation steps:
(1) carrying out CVD carbon coating treatment on a raw material SiO with the granularity D50 of 5 mu m for 5h to obtain a SiO/C cathode material, wherein a carbon source used for the carbon coating treatment of the raw material SiO is acetylene;
(2) adding the SiO/C negative electrode material prepared in the step (1), spherical graphite, resin-based hard carbon with the particle size of 11 mu m and coal tar into a vertical kettle of mixing granulation equipment to obtain a composite material precursor; the reaction process in the granulation equipment is to heat up to 350 ℃ and preserve heat for 5 hours;
(3) and (3) placing the composite material precursor prepared in the step (2) in a nitrogen inert atmosphere furnace, and treating at 800 ℃ for 9h to obtain the final finished product of the negative electrode material.
The high-first-efficiency high-rate silicon-based negative electrode material is applied to a lithium ion battery.
Comparative example 2 (different from example 1 in that no hard carbon particles are added during the granulation in step (3)) is a high-first-efficiency high-rate silicon-based negative electrode material, which is a composite structure formed by a high-first-efficiency SiO/C material, graphite and hard carbon distributed in amorphous carbon. The mass ratio of each component in the silicon-based negative electrode material is high-first-effect SiO/C material: graphite: the amorphous carbon source is 1: 5: 3.7. the high-first-effect SiO/C material is obtained by carrying out pre-lithiation treatment on a SiO/C negative electrode material by a liquid phase method, and the main component of the pre-lithiated high-first-effect SiO/C material is Li2SiO3。
The preparation method of the high-efficiency high-rate silicon-based negative electrode material comprises the following preparation steps:
(1) carrying out CVD carbon coating treatment on a raw material SiO with the granularity D50 of 5 mu m for 5h to obtain a SiO/C cathode material, wherein a carbon source used for the carbon coating treatment of the raw material SiO is acetylene;
(2) dissolving lithium source lithium hydroxide in an organic solvent ethanol, adding the SiO/C negative electrode material prepared in the step (1), ultrasonically dispersing, stirring for a period of time, filtering and drying to obtain a high-efficiency SiO/C material; the mass ratio of the lithium source to the SiO/C negative electrode material is 1: 0.5;
(3) adding the high-first-efficiency SiO/C material prepared in the step (2), the spherical graphite and the coal tar into a vertical kettle of mixing granulation equipment to obtain a composite material precursor; the reaction process in the granulation equipment is to heat up to 350 ℃ and preserve heat for 5 hours;
(4) and (4) placing the composite material precursor prepared in the step (3) in a nitrogen inert atmosphere furnace, and treating at 800 ℃ for 9h to obtain the final finished product of the negative electrode material.
The high-first-efficiency high-rate silicon-based negative electrode material is applied to a lithium ion battery.
The finished product materials prepared in examples 1-3 and comparative examples 1 and 2 are prepared into a model 2032 button cell for evaluation, and the specific scheme is that the preparation material, a conductive agent SP, a conductive agent VGCF and a bonding agent LA136 are mixed according to the ratio of 75:5:10:10, water is used as a solvent, slurry is coated on a copper foil, a counter electrode is a lithium sheet, a diaphragm is a Celgard 2400 microporous polypropylene film, the charge-discharge cutoff voltage is 0.005-1.5V, the discharge rate is that the discharge rate is firstly discharged from 0.1C to 0.005V, then discharged from 0.02C to 0.005V, and the charge rate is charged from 0.1C to 1.5V; the second cycle is discharging to 0.005V at 1C and charging to 1.5V at 0.1C; the third cycle was 2C discharged to 0.005V and 0.1C charged to 1.5V.
Table 1 shows the results of the power-on test of examples 1 to 3 and comparative examples 1 and 2:
| material | Reversible capacity (mAh/g) | First efficiency (%) | 2C capacity retention (%) |
| Example 1 | 467.8 | 92.1 | 83.7 |
| Example 2 | 458.9 | 92.5 | 84.5 |
| Example 3 | 468.6 | 91.9 | 83.8 |
| Comparative example 1 | 470.1 | 85.5 | 80.1 |
| Comparative example 2 | 450.2 | 92.2 | 75.5 |
And (4) conclusion: according to the electricity deduction data, the prepared composite material is high in efficiency for the first time, can reach more than 90%, is excellent in rate capability, has a capacity retention rate of more than 80% at 2C, and shows obvious advantages compared with materials without SiO/C pre-lithium or hard carbon composite. The liquid phase method pre-lithiation treatment is carried out on the SiO/C, so that the precision and uniformity of pre-lithiation can be improved, the pre-lithiation condition is mild, the growth of Si grains caused by a large amount of heat cannot be generated, and the adverse effect on the cycle performance of the material cannot be generated; the addition of hard carbon particles in the compounding process improves the rate capability of the material by utilizing the characteristics of larger spacing and isotropy of hard carbon layers.
Fig. 1 is an SEM image of the silicon-based negative electrode material prepared in example 1 of the present invention, and it can be seen that the overall particles are a granulation structure of the silicon-based material and graphite, the components are uniformly distributed, the uniformity of the particle size of each additive component is good, the obtained silicon-based negative electrode material is stable, and the material cycle performance is good;
FIG. 2 is XRD patterns of SiO/C before pre-lithiation and high first-effect SiO/C material after pre-lithiation prepared in example 1 of the present invention; it can be seen from the figure that the silicate component formed after the prelithiation treatment is mainly Li2SiO3。
The elements and equipment used in the invention are common elements and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modifications, alterations and equivalent changes made to the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (7)
1. A high-first-efficiency high-rate silicon-based negative electrode material is characterized in that the silicon-based negative electrode material is a composite structure formed by a high-first-efficiency SiO/C material, graphite and hard carbon distributed in amorphous carbon; the mass ratio of each component in the silicon-based negative electrode material is high-first-effect SiO/C material: graphite: hard carbon: the amorphous carbon source is 1: 1-10: 1-5: 0.1 to 0.3;
the preparation method comprises the following preparation steps:
(1) carrying out CVD carbon coating treatment on the SiO raw material to obtain a SiO/C cathode material;
(2) dissolving a lithium source in an organic solvent, adding the SiO/C negative electrode material prepared in the step (1), ultrasonically dispersing, stirring for a period of time, and filtering and drying to obtain a high-efficiency SiO/C material; the high-first-effect SiO/C material is obtained by carrying out pre-lithiation treatment on a SiO/C negative electrode material by a liquid phase method, and the main component of the pre-lithiated high-first-effect SiO/C material is Li2SiO3；
(3) Adding the high-first-efficiency SiO/C material prepared in the step (2), graphite, hard carbon and an amorphous carbon source into a mixing and granulating device to obtain a composite material precursor;
(4) and (4) placing the composite material precursor prepared in the step (3) in an inert atmosphere furnace, and carrying out high-temperature treatment for a period of time to obtain the final finished product of the cathode material.
2. The high-first-efficiency high-rate silicon-based anode material as claimed in claim 1, wherein in the step (1), the carbon source used for carbon coating treatment of the raw material SiO is one or more of acetylene, methane, propyne, and ethylene, the coating time is 1-10 h, and the particle size D50 of the raw material SiO is 2-8 μm.
3. The high-first-efficiency high-rate silicon-based negative electrode material according to claim 1, wherein in the step (2), the lithium source is one or more of metallic lithium, lithium hydroxide, lithium peroxide, lithium carbonate, lithium acetate, lithium oxalate, lithium hydride and lithium fluoride, and the mass ratio of the lithium source to the SiO/C negative electrode material is 1: 0.1 to 0.8; the organic solvent is one or more of ethanol, acetone, dimethyl carbonate, diethyl carbonate, benzene and tetrahydrofuran.
4. The high-efficiency high-rate silicon-based anode material of claim 1, wherein in the step (3), the graphite is one of spherical graphite, natural graphite, artificial graphite and mesocarbon microbeads; the hard carbon is resin-based hard carbon or asphalt-based hard carbon, and the particle size of the hard carbon is 7-15 mu m.
5. The high-first-efficiency high-rate silicon-based negative electrode material as claimed in claim 1, wherein in the step (3), the amorphous carbon source is one or more of low-temperature pitch, high-temperature pitch, coal tar, phenolic resin and coumarone resin; the mixing and granulating equipment is one of a kneading machine, a VC heating coating machine, a vertical kettle and a horizontal kettle; the reaction process in the granulation equipment is to heat up to 200-500 ℃ and preserve heat for 2-8 hours.
6. The high-first-efficiency high-rate silicon-based anode material of claim 1, wherein in the step (4), the inert atmosphere is one of nitrogen, argon and helium; the high-temperature treatment temperature is 700-900 ℃, and the high-temperature treatment time is 2-15 h.
7. The application of the high-first-efficiency high-rate silicon-based negative electrode material as claimed in claim 1 in a lithium ion battery.
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| CN114023948B (en) * | 2021-10-29 | 2023-03-03 | 合肥国轩高科动力能源有限公司 | Silicon-carbon negative electrode material, preparation method thereof and lithium ion battery |
| CN114335456A (en) * | 2021-12-06 | 2022-04-12 | 桂林电子科技大学 | Fast-charging composite negative electrode material and preparation method and application thereof |
| CN114275785A (en) * | 2021-12-24 | 2022-04-05 | 安徽科达新材料有限公司 | High-first-efficiency silicon monoxide negative electrode and preparation method thereof |
| CN114464785B (en) * | 2021-12-31 | 2024-03-22 | 长沙矿冶研究院有限责任公司 | Carbon-coated silicon oxide negative electrode material, preparation method thereof and lithium ion battery |
| CN114497480A (en) * | 2021-12-31 | 2022-05-13 | 深圳市翔丰华科技股份有限公司 | Preparation method of silicon-carbon negative electrode material for lithium ion battery |
| CN114864888B (en) * | 2022-04-07 | 2023-08-01 | 湖南金硅科技有限公司 | Lithium difluoro oxalate borate doped coated SiO/C composite material and preparation method and application thereof |
| CN115818648B (en) * | 2022-12-30 | 2024-04-05 | 赣州立探新能源科技有限公司 | Silicon-carbon composite material and preparation method and application thereof |
| CN117174857A (en) * | 2023-08-29 | 2023-12-05 | 广东凯金新能源科技股份有限公司 | Silicon-based composite material and preparation method thereof |
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| JP6397262B2 (en) * | 2014-02-07 | 2018-09-26 | 信越化学工業株式会社 | Nonaqueous electrolyte secondary battery |
| US9774033B2 (en) * | 2015-03-27 | 2017-09-26 | Nanotek Instruments, Inc. | Process for producing silicon nanowires directly from silicon particles |
| US10879531B2 (en) * | 2015-10-26 | 2020-12-29 | Lg Chem, Ltd. | Negative electrode active particle and method for manufacturing the same |
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| CN110649236B (en) * | 2019-09-24 | 2021-06-08 | 中国科学院化学研究所 | Porous silicon-carbon composite material and preparation method thereof |
| CN111261838A (en) * | 2020-03-25 | 2020-06-09 | 上海电气集团股份有限公司 | Method for pre-lithiation of silicon monoxide negative pole piece |
| CN112670462B (en) * | 2020-03-31 | 2022-11-08 | 宁波杉杉新材料科技有限公司 | Pre-lithiated silica-graphite composite negative electrode material and preparation method and application thereof |
| CN111653739B (en) * | 2020-04-28 | 2021-05-18 | 万向一二三股份公司 | Method for preparing high-cycle-performance SiO negative electrode material of lithium battery |
| CN112201779B (en) * | 2020-10-14 | 2022-02-08 | 江西壹金新能源科技有限公司 | Preparation method and application of silicon-based composite material slurry |
| CN112820869B (en) * | 2020-12-31 | 2022-11-01 | 宁德新能源科技有限公司 | Negative electrode active material, electrochemical device, and electronic device |
| CN112886000A (en) * | 2021-01-05 | 2021-06-01 | 昆山宝创新能源科技有限公司 | Pre-lithiated silica negative electrode material and preparation method and application thereof |
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