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CN113948683B - Silicon monoxide composite negative electrode material and preparation method and application thereof - Google Patents

Silicon monoxide composite negative electrode material and preparation method and application thereof Download PDF

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CN113948683B
CN113948683B CN202010690610.4A CN202010690610A CN113948683B CN 113948683 B CN113948683 B CN 113948683B CN 202010690610 A CN202010690610 A CN 202010690610A CN 113948683 B CN113948683 B CN 113948683B
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sio
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CN113948683A (en
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薛旭金
李凌云
李倩慧
李世江
薛峰峰
李霞
张亚
李亚楠
李富斌
郭志伟
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Henan Fluorine Based New Material Technology Co ltd
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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    • H—ELECTRICITY
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Abstract

The invention provides a preparation method of a silicon monoxide composite negative electrode material, which comprises the following steps: a) Mixing silicon monoxide with carbon source organic matters, and calcining to obtain a calcined product; then, the calcined product is filtered after being washed, and the obtained filter residue is dried for the first time to obtain a GP/SiO product; b) Grinding the GP/SiO product obtained in the step a) with asphalt and polyethylene glycol for the first time to obtain slurry; and drying the slurry for the second time, then carbonizing the slurry at high temperature, and grinding the obtained high-temperature carbonized product for the second time to obtain the silicon monoxide composite negative electrode material. Compared with the prior art, the preparation method provided by the invention can directly form the network-shaped graphene in situ between SiO particles, and the prepared silicon oxide composite negative electrode material is a carbon-coated graphene-modified silicon oxide (GP/SiO @ C) negative electrode material, and has high conductivity and good cycle performance.

Description

Silicon monoxide composite negative electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon monoxide composite negative electrode material and a preparation method and application thereof.
Background
High energy and power density are important for Lithium Ion Batteries (LiBs) to meet the requirements of large-scale energy storage systems and electric vehicles. Graphite remains the dominant negative electrode material of the most advanced lithium ion batteries. However, the problems of graphite materials are more and more prominent due to the limitations of low specific capacity and poor rate capability. In order to solve this problem, many novel anode materials having a high specific volume are being widely studied.
Silicon has been a viable cathode material for over 20 years, and silicon cathodes with lithium can form Li 15 Si 4 The theoretical specific capacity of the alloy phase is up to 3572 mAh.g -1 About 10 times that of the graphite negative electrode; low levels (< 0.5V) of lithium removal; in addition, silicon is abundant (second place in crust element, 26.4%), being considered as one of the most potential candidates for the negative electrode material.
However, researches show that the volume effect of the silicon negative electrode is serious in the process of charging and discharging, the volume expansion reaches 300% in the process of lithium deintercalation, the material pulverization is caused by the breakage of silicon negative electrode particles, and the development of the silicon negative electrode in the lithium ion battery is severely limited by the huge volume effect and the lower conductivity. The silicon monoxide is used as a lithium ion battery cathode material, and the electrochemical performance of the silicon monoxide is excellent. Because the content of Si in the SiO-based cathode material is less than that of Si in the Si cathode (the theoretical capacity is still higher than 2400 mAh.g) -1 ) And the volume change of the SiO negative electrode in the circulation process is smaller than that of Si. In the electrode circulation process, siO reacts with Li to generate Li irreversibly 2 O and Li 4 SiO 4 The compounds serve as buffer phases, relieve volume change of electrode materials and improve the cycle performance of the electrode.
However, siO also has similar properties to silicon cathodes, and also has a phenomenon of low electron conductivity. In addition, li consumed in the first charge-discharge process of SiO negative electrode + Formation of irreversible by-product Li 2 O and Li 4 SiO 4 Consuming large amounts of Li + The phenomenon of (2) results in irreversible capacity, resulting in a first effect of about 70%. These problems also limit the commercial development of silica.
Further, publication NoChinese patent CN103474631A discloses a preparation method of a silicon oxide composite negative electrode material, the composite material comprises a carbon-coated silicon oxide substrate, a nano silicon material uniformly deposited on the silicon oxide substrate and a nano conductive material coating layer on the surface of the silicon oxide/nano silicon; although the reversible capacity can reach 1600mAh g -1 However, the introduction of Si nanoparticles with a greater volume expansion effect is clearly detrimental to the long term cycling of the composite. Chinese patent publication No. CN106410158A discloses a method for modifying a silicon oxide composite material with graphene, in which graphene is dispersed in gaps between SiO powder, so as to improve the conductivity of the material, and a layer of carbon is coated on the surfaces of SiO and graphene, so as to slow down volume expansion and improve cycle performance; however, the introduction of the graphene adopts a mechanical ball milling method, which may cause the problem of uneven dispersion of the graphene. Chinese patent publication No. CN104973589A discloses coating graphene on the surface of a ceramic powder as a substrate for chemical vapor deposition, grinding and tabletting the substrate, coating graphene for the second time by chemical vapor deposition, and finally etching the substrate to obtain three-dimensional graphene; however, the process conditions are harsh, and the vapor deposition has high requirements on equipment, so that the application of the process is limited.
Disclosure of Invention
In view of the above, the present invention provides a silicon oxide composite negative electrode material, and a preparation method and an application thereof, the preparation method provided by the present invention can directly form network graphene in situ between SiO particles, and the prepared silicon oxide composite negative electrode material has high electrical conductivity and good cycle performance.
The invention provides a preparation method of a silicon monoxide composite negative electrode material, which comprises the following steps:
a) Mixing silicon monoxide with carbon source organic matters, and calcining to obtain a calcined product; then, the calcined product is filtered after being washed, and the obtained filter residue is dried for the first time to obtain a GP/SiO product;
b) Grinding the GP/SiO product obtained in the step a) with asphalt and polyethylene glycol for the first time to obtain slurry; and drying the slurry for the second time, then carbonizing at high temperature, and grinding the obtained high-temperature carbonized product for the second time to obtain the silicon monoxide composite negative electrode material.
Preferably, the carbon source organic matter in step a) is selected from sodium gluconate and/or sodium citrate.
Preferably, the mass ratio of the silicon monoxide to the carbon source organic matter in the step a) is 1: (3-7).
Preferably, the calcination process in step a) is carried out under the protection of inert gas; the calcining temperature is 500-1100 ℃, and the heat preservation time is 1-3 h.
Preferably, the mass ratio of the GP/SiO product, the asphalt and the polyethylene glycol in step b) is 1: (0.1-0.2): (0.05-0.15).
Preferably, the first grinding treatment in step b) specifically comprises the following steps:
placing GP/SiO product, asphalt and polyethylene glycol into an agate tank, adding 10ml to 30ml of absolute ethyl alcohol, and mixing the materials according to a ball-to-material ratio of (4 to 6): 1, adding zirconia beads with the diameter of 5 mm-10 mm, and ball-milling for 3 h-8 h at the rotating speed of 250 rpm-400 rpm to obtain slurry.
Preferably, the temperature of the high-temperature carbonization in the step b) is 750-1050 ℃, and the time is 1-4 h; and inert gas is introduced for protection in the processes of temperature rise and temperature reduction in the high-temperature carbonization process.
Preferably, the second grinding treatment in step b) is dry ball milling; the ball-material ratio of the dry ball milling is (4-6): 1, the ball milling speed is 300rpm to 400rpm, and the ball milling time is 2h to 5h.
The invention also provides a silicon monoxide composite negative electrode material which is prepared by the preparation method of the technical scheme.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte;
the negative electrode comprises the silicon oxide composite negative electrode material or the silicon oxide composite negative electrode material prepared by the preparation method in the technical scheme.
The invention provides a preparation method of a silicon monoxide composite negative electrode material, which comprises the following steps: a) Mixing silicon monoxide with carbon source organic matters, and calcining to obtain a calcined product; then, the calcined product is filtered after being washed, and the obtained filter residue is dried for the first time to obtain a GP/SiO product; b) Carrying out primary grinding treatment on the GP/SiO product obtained in the step a), asphalt and polyethylene glycol to obtain slurry; and drying the slurry for the second time, then carbonizing at high temperature, and grinding the obtained high-temperature carbonized product for the second time to obtain the silicon monoxide composite negative electrode material. Compared with the prior art, the preparation method provided by the invention can directly form the network-shaped graphene among the SiO particles in situ, and the prepared silica composite negative electrode material is a carbon-coated graphene modified silica (GP/SiO @ C) negative electrode material, and has high conductivity and good cycle performance.
In addition, the preparation method provided by the invention has the advantages of simple process, easily-controlled conditions and low cost, and the prepared product has higher capacity and long cycle life, thereby providing a possibility for the commercial application of the silicon monoxide and having wide application prospects.
Drawings
FIGS. 1 and 2 are SEM images of GP/SiO @ C negative electrode material prepared by the preparation method provided by embodiment 2 of the invention;
FIG. 3 is a particle size distribution diagram of the GP/SiO @ C negative electrode material prepared by the preparation method provided in embodiment 2 of the present invention;
FIG. 4 is a first-turn charge-discharge curve of GP/SiO @ C negative electrode material prepared by the preparation method provided in embodiment 2 of the present invention;
FIG. 5 is a 50-week cycle performance diagram of the GP/SiO @ C anode material prepared by the preparation method provided in embodiment 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a silicon monoxide composite negative electrode material, which comprises the following steps:
a) Mixing silicon monoxide with carbon source organic matters, and calcining to obtain a calcined product; then, filtering the calcined product after washing, and drying the obtained filter residue for the first time to obtain a GP/SiO product;
b) Grinding the GP/SiO product obtained in the step a) with asphalt and polyethylene glycol for the first time to obtain slurry; and drying the slurry for the second time, then carbonizing the slurry at high temperature, and grinding the obtained high-temperature carbonized product for the second time to obtain the silicon monoxide composite negative electrode material.
Firstly, mixing the silicon monoxide and carbon source organic matters, and calcining to obtain a calcined product. In the present invention, the silica, i.e., siO, is not particularly limited in its source, and may be commercially available or may be self-prepared, which is well known to those skilled in the art.
In the present invention, the carbon source organic substance is preferably selected from sodium gluconate and/or sodium citrate, and more preferably is sodium gluconate or sodium citrate. The source of the organic carbon source is not particularly limited in the present invention, and commercially available products of the above sodium gluconate and sodium citrate known to those skilled in the art may be used.
In the present invention, the mass ratio of the silicon monoxide to the carbon source organic substance is preferably 1: (3 to 7), more preferably 3: (10-20).
In the present invention, the mixing process preferably includes:
and dispersing the silica and carbon source organic matters into an organic solution for ball milling. The present invention is not particularly limited in kind and source of the organic solvent, and for example, absolute ethanol for ball milling, which is well known to those skilled in the art, may be used. In the invention, the purpose of the ball milling is to uniformly disperse the silicon monoxide and carbon source organic matters in the organic solution.
In the present invention, the calcination process is preferably performed under the protection of inert gas; the inert gas is preferably nitrogen. In the invention, the calcining temperature is preferably 500-1100 ℃, and more preferably 800-1000 ℃; the holding time for the calcination is preferably 1 to 3 hours, and more preferably 2 hours.
After the calcined product is obtained, the calcined product is filtered after being washed, and the obtained filter residue is dried for the first time to obtain the GP/SiO product. In the present invention, the first drying process is preferably performed in an oven; the temperature of the first drying is preferably 70 ℃ to 90 ℃, and more preferably 80 ℃.
After the GP/SiO product is obtained, the GP/SiO product, asphalt and polyethylene glycol are ground for the first time to obtain slurry. In the present invention, the D50 of the asphalt is preferably 1 to 10 μm, more preferably 4 to 5 μm; m of the polyethylene glycol n Preferably 1000 to 10000, more preferably 2000 to 8000. The sources of the asphalt and polyethylene glycol are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the present invention, the ratio by mass of the GP/SiO product, bitumen and polyethylene glycol is preferably 1: (0.1-0.2): (0.05-0.15).
In the present invention, the first grinding process preferably includes:
placing GP/SiO product, asphalt and polyethylene glycol into an agate tank, adding 10ml to 30ml of absolute ethyl alcohol, and mixing the materials according to a ball-to-material ratio of (4 to 6): 1, adding zirconia beads with the diameter of 5-10 mm, and ball-milling for 3-8 h at the rotating speed of 250-400 rpm to obtain slurry;
more preferably:
placing GP/SiO product, asphalt and polyethylene glycol in an agate tank, adding 20ml of absolute ethyl alcohol, and mixing according to a ball-material ratio of 5:1, adding mixed zirconia beads with the diameters of 6mm and 8mm, and performing ball milling for 4 hours at the rotating speed of 350rpm to obtain slurry.
After the slurry is obtained, the slurry is dried for the second time and then carbonized at high temperature, and the obtained high-temperature carbonized product is ground for the second time to obtain the silicon oxide composite negative electrode material (GP/SiO @ C negative electrode material). In the present invention, the temperature of the second drying is preferably 70 to 90 ℃, and more preferably 80 ℃.
In the invention, the high-temperature carbonization temperature is preferably 750-1050 ℃, and more preferably 800-1000 ℃; the time for the high-temperature carbonization is preferably 1 to 4 hours, and more preferably 2 hours. In the invention, inert gas is used for protection in the processes of temperature rise and temperature reduction in the high-temperature carbonization process.
In the invention, the second grinding treatment is preferably dry ball milling; the ball-material ratio of the dry ball milling is preferably (4-6): 1, more preferably 5:1; the ball milling speed of the dry ball milling is preferably 300 rpm-400 rpm, and more preferably 350rpm; the ball milling time of the dry ball milling is preferably 2h to 5h, and more preferably 4h.
The preparation method provided by the invention has the advantages of simple process, easily-controlled conditions and low cost, and the prepared product has higher capacity and long cycle life, provides a possibility for the commercial application of the silicon monoxide, and has wide application prospect.
The invention also provides a silicon monoxide composite negative electrode material which is prepared by the preparation method of the technical scheme. The preparation method provided by the invention can directly form the network graphene among SiO particles in situ, improves the conductivity of SiO, and can effectively inhibit the volume expansion effect of SiO by coating a layer of carbon on the surfaces of the silicon monoxide and the graphene, so that the prepared silicon monoxide composite negative electrode material has high conductivity, high first efficiency and long cycle life.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte;
the negative electrode comprises the silicon oxide composite negative electrode material or the silicon oxide composite negative electrode material prepared by the preparation method in the technical scheme.
The positive electrode of the lithium ion battery is not particularly limited, and is preferably a lithium sheet; the source of the lithium sheet is not particularly limited, and a commercially available product can be adopted.
In the invention, the negative electrode includes the silicon oxide composite negative electrode material described in the above technical scheme or the silicon oxide composite negative electrode material prepared by the preparation method described in the above technical scheme, and details are not repeated herein.
The separator of the lithium ion battery according to the present invention is not particularly limited, and for example, a polypropylene microporous membrane (Celgard 2400) well known to those skilled in the art may be used.
The electrolyte of the lithium ion battery is not particularly limited in the present invention, and for example, a mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) of 1mol/L lithium hexafluorophosphate (a volume ratio of EC to DMC is 1.
The preparation method of the lithium ion battery is not particularly limited, and the method for preparing the lithium ion battery, which is well known to a person skilled in the art, can be adopted. The specific steps are preferably as follows:
the preparation method comprises the following steps of mixing the silica composite negative electrode material, the adhesive and the conductive agent according to a ratio of 90:5:5, mixing and pulping, and then uniformly coating on a copper foil current collector to obtain a pole piece; then, placing the obtained pole piece in an oven at 50-70 ℃ for drying, and then placing the pole piece in a vacuum drying oven at 110-130 ℃ for drying for 10-14 h; finally, rolling, cutting, weighing and the like the dried pole piece to prepare a negative pole piece; then using a metal lithium sheet as a counter electrode, 1mol/L LiPF 6 The mixed solvent (ethylene carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1) as an electrolyte (a small amount of VC additive may be added), and a polypropylene microporous membrane (Celgard 2400) as a separator were assembled in an argon-protected glove box to obtain a lithium ion battery.
The invention provides a preparation method of a silicon monoxide composite negative electrode material, which comprises the following steps: a) Mixing silicon monoxide with carbon source organic matters, and calcining to obtain a calcined product; then, the calcined product is filtered after being washed, and the obtained filter residue is dried for the first time to obtain a GP/SiO product; b) Grinding the GP/SiO product obtained in the step a) with asphalt and polyethylene glycol for the first time to obtain slurry; and drying the slurry for the second time, then carbonizing the slurry at high temperature, and grinding the obtained high-temperature carbonized product for the second time to obtain the silicon monoxide composite negative electrode material. Compared with the prior art, the preparation method provided by the invention can directly form the network-shaped graphene in situ between SiO particles, and the prepared silicon oxide composite negative electrode material is a carbon-coated graphene-modified silicon oxide (GP/SiO @ C) negative electrode material, and has high conductivity and good cycle performance.
In addition, the preparation method provided by the invention has the advantages of simple process, easily-controlled conditions and low cost, and the prepared product has higher capacity and long cycle life, thereby providing a possibility for the commercial application of the silicon monoxide and having wide application prospects.
To further illustrate the present invention, the following examples are provided for illustration.
Example 1
(1) Weighing 6g of silicon monoxide and 20g of sodium gluconate, dispersing into an organic solution, performing ball milling, calcining at a high temperature of 800 ℃ under the protection of nitrogen, and preserving heat for 2 hours to obtain a calcined product; and then washing the obtained calcined product with water, filtering, and drying the obtained filter residue in an oven at 80 ℃ to obtain the GP/SiO product.
(2) Mixing the GP/SiO product obtained in step (1), asphalt (D50 =4 μ M), and polyethylene glycol (M) n = 2000) in a mass ratio of 1:0.1:0.05, respectively weighing 6.0g, 0.6g and 0.3g in an agate tank, adding 20ml of absolute ethyl alcohol, and mixing according to a ball-to-material ratio of 5:1, adding zirconia beads mixed with diameters of 6mm and 8mm, and ball-milling for 4 hours at the rotating speed of 350rpm to obtain slurry; drying the obtained slurry at 80 ℃, placing the dried sample in a square boat, carbonizing at high temperature in a tube furnace at 800 ℃, preserving heat for 2 hours, and introducing nitrogen for protection in the temperature rising and reducing processes of carbonization to obtain a product after high-temperature carbonization; and finally, performing ball milling on the obtained high-temperature carbonized product by using a dry method, wherein the ball-to-material ratio is 5:1, ball milling for 4 hours at the rotating speed of 350rpm to obtain GP/SiO @ C negative electrode material, namely the monox composite negative electrode material.
Example 2
(1) Weighing 6g of silica and 30g of sodium citrate, dispersing the silica and the sodium citrate into an organic solution for ball milling, calcining at the high temperature of 800 ℃ under the protection of nitrogen, and preserving heat for 2 hours to obtain a calcined product; and then washing the obtained calcined product with water, filtering, and drying the obtained filter residue in an oven at 80 ℃ to obtain the GP/SiO product.
(2) Mixing the GP/SiO product obtained in step (1), asphalt (D50 =4 μ M), and polyethylene glycol (M) n = 4000) according to a mass ratio of 1:0.1:0.1, respectively weighing 6.0g, 0.6g and 0.6g in an agate tank, adding 20ml of absolute ethyl alcohol, and mixing according to a ball-to-material ratio of 5:1, adding zirconia beads mixed with diameters of 6mm and 8mm, and performing ball milling for 4 hours at a rotating speed of 350rpm to obtain slurry; drying the obtained slurry at 80 ℃, putting the dried sample into a square boat, carbonizing at high temperature in a tube furnace at 900 ℃, preserving heat for 2 hours, and introducing nitrogen for protection in the temperature rising and reducing processes of carbonization to obtain a product after high-temperature carbonization; and finally, performing ball milling on the obtained high-temperature carbonized product by using a dry method, wherein the ball-to-material ratio is 5:1, ball milling for 4h at the rotating speed of 350rpm to obtain the GP/SiO @ C negative electrode material, namely the silicon monoxide composite negative electrode material.
The GP/SiO @ C negative electrode material prepared by the preparation method provided by the embodiment 2 of the invention is characterized, the obtained SEM images are shown in figures 1-2, and the particle size distribution diagram is shown in figure 3.
Example 3
(1) Weighing 6g of silica and 40g of sodium gluconate, dispersing the silica and the sodium gluconate into an organic solution, performing ball milling, calcining at the high temperature of 1000 ℃ under the protection of nitrogen, and preserving heat for 2 hours to obtain a calcined product; and then washing the obtained calcined product with water, filtering, and drying the obtained filter residue in an oven at 80 ℃ to obtain the GP/SiO product.
(2) Mixing the GP/SiO product obtained in the step (1), asphalt (D50 =4 μ M) and polyethylene glycol (M) n = 8000) at a mass ratio of 1:0.2:0.15, respectively weighing 6.0g, 1.2g and 0.9g in an agate tank, adding 20ml of absolute ethyl alcohol, and mixing according to a ball-to-material ratio of 5:1, adding zirconia beads mixed with diameters of 6mm and 8mm, and performing ball milling for 4 hours at a rotating speed of 350rpm to obtain slurry; drying the obtained slurry at 80 ℃, placing the dried sample in a square boat, carbonizing at high temperature in a tubular furnace at 1000 ℃, preserving heat for 2 hours, and introducing nitrogen for protection in the temperature rising and reducing processes of carbonization to obtain a product after high-temperature carbonization; finally, theAnd (3) performing ball milling on the obtained high-temperature carbonized product by using a dry method, wherein the ball-to-material ratio is 5:1, ball milling for 4h at the rotating speed of 350rpm to obtain the GP/SiO @ C negative electrode material, namely the silicon monoxide composite negative electrode material.
Example 4
GP/SiO @ c negative electrode material and silica dioxide blank (uncoated with carbon SiO) obtained by the preparation methods provided in examples 1 to 3, respectively, were mixed with a conductive agent (SP) and a binder (SBR, CMC) in a mass ratio of 90:5:5 weighing and pulping; uniformly coating the uniformly mixed slurry on a clean copper foil by using a scraper to obtain a pole piece; then, placing the obtained pole piece in a 60 ℃ drying oven for drying, and then placing the pole piece in a vacuum drying oven for drying for 12 hours at 120 ℃; finally, the dried pole piece is rolled, cut into pieces, weighed and the like, and the dried pole piece and the lithium piece are used as a counter electrode and a reference electrode, and 1M LiPF is used as electrolyte 6 (EC: DMC =1, v.
And (3) electrochemical performance testing: at 0.1C (1C =1700mAh · g -1 ) Current density, voltage range under (0.01V-2V), carry on the charge-discharge cycle; the first-turn charge-discharge curve of the GP/SiO @ C negative electrode material prepared by the preparation method provided by the embodiment 2 of the invention is shown in figure 4, and the cycle performance of 50 weeks is shown in figure 5.
The electrochemical performance data of each negative electrode material in example 4 of the present invention is shown in table 1.
TABLE 1 comparison of capacities of respective anode materials in inventive example 4
Figure BDA0002589219110000091
As can be seen from Table 1, the GP/SiO @ C negative electrode materials prepared by the preparation methods provided in examples 1 to 3 have specific first discharge capacities of 1600mAh · g -1 The first charge-discharge efficiency can reach 80%, the cycle retention rate in 20 weeks can reach 84%, the cycle retention rate in 50 weeks can reach 58%, and the first effect of a blank product is only 73% and the cycle performance is poor.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (7)

1. A preparation method of a silicon monoxide composite negative electrode material comprises the following steps:
a) Mixing silicon monoxide with carbon source organic matters, and calcining to obtain a calcined product; then, filtering the calcined product after washing, and drying the obtained filter residue for the first time to obtain a GP/SiO product; the carbon source organic matter is selected from sodium gluconate and/or sodium citrate; the mass ratio of the silicon monoxide to the carbon source organic matter is 1: (3-7); the calcining process is carried out under the protection of inert gas; the calcining temperature is 500-1100 ℃, and the heat preservation time is 1-3 h;
b) Grinding the GP/SiO product obtained in the step a) with asphalt and polyethylene glycol for the first time to obtain slurry; and drying the slurry for the second time, then carbonizing at high temperature, and grinding the obtained high-temperature carbonized product for the second time to obtain the silicon monoxide composite negative electrode material.
2. The method according to claim 1, wherein the ratio of GP/SiO product, pitch and polyethylene glycol in step b) is 1: (0.1-0.2): (0.05-0.15).
3. The preparation method according to claim 1, wherein the first grinding treatment in step b) is carried out by:
placing GP/SiO product, asphalt and polyethylene glycol into an agate tank, adding 10ml to 30ml of absolute ethyl alcohol, and mixing the materials according to a ball-to-material ratio of (4 to 6): 1, adding zirconia beads with the diameter of 5 mm-10 mm, and ball-milling for 3 h-8 h at the rotating speed of 250 rpm-400 rpm to obtain slurry.
4. The preparation method according to claim 1, wherein the high-temperature carbonization in the step b) is performed at 750-1050 ℃ for 1-4 h; and inert gas is introduced for protection in the processes of temperature rise and temperature reduction in the high-temperature carbonization process.
5. The method according to claim 1, wherein the second grinding treatment in step b) is dry ball milling; the ball-material ratio of the dry ball milling is (4-6): 1, the ball milling speed is 300rpm to 400rpm, and the ball milling time is 2h to 5h.
6. A silica composite negative electrode material characterized by being produced by the production method according to any one of claims 1 to 5.
7. A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte;
the negative electrode comprises the silica composite negative electrode material according to claim 6.
CN202010690610.4A 2020-07-17 2020-07-17 Silicon monoxide composite negative electrode material and preparation method and application thereof Active CN113948683B (en)

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