CN111653737B - Silicon oxide composite material with gradient pre-lithiation structure and preparation method and application thereof - Google Patents
Silicon oxide composite material with gradient pre-lithiation structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries, and provides a silicon oxide composite material with a gradient pre-lithiation structure and a preparation method and application thereof in order to solve the problem of poor cycle stability of a traditional silicon-based negative electrode material of a lithium ion battery, wherein the silicon oxide composite material has a core-shell structure which is provided with a lithium-containing silicon oxide layer, a silicon oxide layer and a carbon coating layer from inside to outside in sequence; the number of the lithium-containing silicon oxide layers is at least one, and the lithium content of each layer is gradually reduced from inside to outside. The silicon oxide composite material has higher internal lithium content, can form more silicate lithium and silicate lithium alloy in the first charge-discharge process, supplements the loss of lithium ions, improves the first charge-discharge efficiency, maintains the stability of the structure, improves the cycle performance, ensures the coating uniformity of a lithium-containing silicon oxide layer and a silicon oxide layer by an outermost carbon coating layer, and further improves the cycle performance and the stability of the material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a silicon oxide composite material with a gradient prelithiation structure, and a preparation method and application thereof.
Background
With the rapid development of the new energy automobile industry, lithium ion batteries with high energy density, high power density and long cycle life are widely researched by people, and as one of main materials of the lithium ion batteries, the current commercialized graphite cathode material cannot meet the increasing market demand because of low theoretical capacity (372mAh/g) of a short plate thereof, so that other cathode materials capable of replacing graphite are urgently needed to be searched.
Among novel negative electrode materials, silicon materials are concerned because of the advantages of high theoretical capacity, abundant reserves, low discharge voltage and the like, but silicon itself has huge volume expansion (> 400%) and shrinkage in the charging and discharging processes, which can cause pulverization of active materials, stripping from current collectors and continuous fracture and generation of SEI films, thereby seriously affecting the cycle performance of batteries.
Although a silicon oxide material is a silicon-based material having a somewhat low theoretical capacity, a lithium-containing compound such as lithium oxide, lithium silicate, lithium metasilicate, or the like can be formed in the first charge and discharge process due to the presence of oxygen, and the silicon oxide material can be used as an inert component to suppress the volume expansion of a silicon negative electrode, and thus the silicon oxide material is considered by those skilled in the art and is the main development direction of silicon-based materials.
Although the silicon oxide negative electrode material has many advantages, the bottleneck of the silicon oxide negative electrode material still exists, on one hand, the cycle stability of the silicon oxide negative electrode material still needs to be improved, and on the other hand, the silicon oxide material needs to be coated, and the existing coating modes mainly comprise solid phase coating, liquid phase coating and gas phase coating; on the other hand, because silicon oxide forms a plurality of inert lithium silicate components in the first charge and discharge process and consumes partial lithium ions, the first efficiency of the silicon oxide is low, and the existing improvement means mainly comprise element doping, metal reduction and pre-lithiation, wherein the pre-lithiation is the most effective scheme, but a plurality of difficulties such as safety, stability and the like need to be broken through in the implementation process.
Chinese patent literature discloses a preparation method of a lithium ion battery cathode material with high initial coulombic efficiency, and application publication number is CN 103258992A.
Chinese patent literature discloses a lithium-containing silicon oxide powder and a method for producing the same, and application publication No. CN1407641A, in the invention, SiO is usedz(z is more than 0 and less than 2) powder and lithium compound are mixed and heated in vacuum or inert atmosphere to generate SiLixOyThe lithium-containing silicon oxide powder with x being more than 0 and less than 1.0 and y being more than 0 and less than 1.5 is used for preparing the lithium ion battery with high capacity, high first efficiency and good cycle performance.
Chinese patent literature discloses a "negative electrode material for nonaqueous electrolyte secondary batteries, a method for producing the same, and a lithium ion secondary battery", and application publication No. CN102214824A, in which prepared SiO is CVD-coated and then mixed with lithium hydride and/or lithium aluminum hydride at high temperature to obtain a pre-intercalated lithium product, and the CVD coating treatment is performed before lithium doping, so that the generation of SiC is effectively suppressed, and the crystallization of Si is suppressed to some extent, and the finally obtained material has high primary efficiency and good cycle durability.
In the existing scheme of pre-embedding lithium into a silicon-based material, the SiO material is pre-embedded with lithium or the coated SiO material is pre-embedded with lithium, the process is complex and difficult to control, and the rapid growth of Si grains is easily caused by violent reaction in the lithium embedding process, so that the later cycle performance of the material is influenced; the pulverization and the fragmentation of the silicon-based material are generally carried out from outside to inside in the circulation process, so the stability of the integral framework and the outer layer of the material is very important, the design of the stable structure of the integral framework and the coating treatment of the surface are required to be combined, the stability of the material is comprehensively improved, and the problems are not well solved in the prior technical scheme.
Disclosure of Invention
The invention provides a silicon oxide composite material with a gradient pre-lithiation structure, which improves the first efficiency, maintains the structural stability and improves the cycle performance in order to overcome the problem of poor cycle stability of the traditional silicon-based negative electrode material of a lithium ion battery.
The invention also provides a preparation method of the silicon oxide composite material with the gradient prelithiation structure, which has the advantages of simplified production process, low preparation cost of the material and contribution to large-scale production.
The invention also provides application of the silicon oxide composite material with the gradient prelithiation structure as a lithium ion battery cathode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a silicon oxide composite material with a gradient pre-lithiation structure is provided, and the silicon oxide composite material with the gradient pre-lithiation structure is provided with a core-shell structure which is provided with a lithium-containing silicon oxide layer, a silicon oxide layer and a carbon coating layer from inside to outside in sequence; the number of the lithium-containing silicon oxide layers is at least one, and the lithium content of each layer is gradually reduced from inside to outside.
Before the preparation link of the silicon oxide material, the inner layer of the silicon oxide material is firstly subjected to a lithium pre-doping reaction to form a gradient pre-lithiation structure with the lithium content gradually reduced from inside to outside, the middle layer is made of a pure SiO material, and the outermost layer is a carbon coating layer. The silicon oxide composite material has higher internal lithium content, can form more silicate and silicon lithium alloy in the first charge-discharge process, supplements the loss of lithium ions, improves the first charge-discharge efficiency, maintains the stability of the structure, improves the cycle performance, ensures the coating uniformity of a lithium-containing silicon oxide layer and a silicon oxide layer by an outermost carbon coating layer, and further improves the cycle performance and the stability of the material.
Preferably, the thickness of the lithium-containing silicon oxide layer is 0.1-10 μm, and the thickness is too thin, which causes difficulty in processing, difficulty in forming a gradient structure and high preparation cost; too thick results in too large material particles and poor expansion and cycling performance at the cell level.
Preferably, each lithium-containing silicon oxide layer is represented as SiLi in terms of molar ratioxO, wherein x is more than 0 and less than 1.
Preferably, the silicon oxide layer has a single-layer structure; the thickness of the silicon oxide layer is 0.5-5 μm.
Preferably, the thickness of the carbon coating layer is 1 to 100 nm.
A method for preparing a silicon oxide composite material with a gradient prelithiation structure comprises the following steps:
(1) first lithium silicon oxide layer SiLix1Deposition of O:
mixing SiO2Uniformly mixing the powder, Si powder and a lithium-containing compound, putting the mixture into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, sublimating and desublimating to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O;
(2) Second lithium silicon oxide layer SiLix2Deposition of O:
mixing SiO2Powder, Si powder, lithium-containing compound, and first lithium silicon oxide layer SiLi obtained in step (1)x1Mixing O uniformly, placing into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, sublimating, and collecting to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O;
(3) N-th lithium silicon oxide layer SiLixnDeposition of O:
repeating the step (2) to obtain a first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO; wherein, 0 < xn < x2 < x1 < 1;
(4) deposition of a silicon oxide layer:
oxidizing the first lithium obtained in the step (3)Silicon layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO and SiO2Mixing the powder and Si powder, placing into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, sublimating, and collecting to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO @ silicon oxide layer;
(5) deposition of carbon coating layer:
the first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnPlacing the O @ silicon oxide layer powder material into a CVD rotary furnace, introducing mixed gas of nitrogen and coating gas at high temperature, performing gas phase carbon coating, and cooling to room temperature to obtain a first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO @ silicon oxide layer @ C, namely the silicon oxide composite material with the gradient prelithiation structure.
According to the invention, pre-lithium is carried out in the process of preparing the silicon oxide composite material, post-treatment is not needed, the preparation process is simplified, and the gradient pre-lithium structure is more favorable for maintaining the stability of the material and improving the cycle performance, so that the purpose of generating a novel cathode material with high capacity, high first efficiency and long cycle is achieved.
Preferably, in steps (1) to (4):
the SiO2The mol ratio of the powder to the Si powder is 1:1, and the atomic ratio of Si and O elements is ensured to be 1: 1.
The SiO2The granularity of the powder is 200 nm-10 mu m; the particle size of the Si powder is 500 nm-15 mu m.
The control of the granularity of the raw material powder in the range has the beneficial effect of best comprehensive cost performance, and the over-small granularity can cause high production and manufacturing cost; too large a particle size can result in too large a material particle that is not easily mixed uniformly.
The atmosphere deposition furnace is of a horizontal structure, one side of the atmosphere deposition furnace is a reaction area, the other side of the atmosphere deposition furnace is a collection area, the reaction atmosphere is an inert or vacuum atmosphere, the reaction temperature of high-temperature deposition is 1300-1500 ℃, the reaction time is 1-8 hours, and the temperature of the collection area is 600-800 ℃.
Preferably, in the steps (1) to (3), the lithium-containing compound is selected from LiF and Li2O、LiOH、LiNO3、Li2CO3And hydrates thereof.
Preferably, in the step (5), the volume ratio of the coating gas to the nitrogen gas is 1: (1-3); the coating gas is selected from one or more of methane, acetylene, ethane and ethylene.
Preferably, in the step (5), based on the total mass of the silicon oxide composite material with the gradient prelithiation structure, the carbon coating amount of the carbon coating layer is 1-10 wt%, and if the carbon coating amount is too low, the coating is not uniform, the cycle performance is affected by the exposure of the silicon material, and if the carbon coating amount is too high, the overall capacity of the material is too low.
Preferably, in the step (5), the reaction temperature of the gas-phase carbon coating is 850-950 ℃, and the reaction time is 3-6 h.
An application of a silicon oxide composite material with a gradient prelithiation structure as a negative electrode material of a lithium ion battery.
Therefore, the invention has the following beneficial effects:
(1) the silicon oxide composite material has higher internal lithium content, can form more silicate lithium and silicate lithium alloy in the first charge-discharge process, supplements the loss of lithium ions, improves the first charge-discharge efficiency, maintains the stability of the structure, improves the cycle performance, ensures the coating uniformity of a lithium-containing silicon oxide layer and a silicon oxide layer by an outermost carbon coating layer, and further improves the cycle performance and the stability of the material;
(2) the preparation method of the silicon oxide composite material is simple, the preparation cost of the material is low, and the large-scale production is facilitated;
(3) the silicon oxide composite material disclosed by the invention is high in first charge-discharge efficiency and stable in structure, and can be applied as a lithium ion battery cathode material.
Drawings
Fig. 1 is a schematic structural view of a silicon oxide composite material having a gradient prelithiation structure of example 4.
FIG. 2 is a graph showing the first charge and discharge curves of a button cell assembled from the silicon oxide composite material of example 1: a. first charging, b.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) First lithium silicon oxide layer SiLix1Deposition of O:
mixing SiO2Uniformly mixing powder (the granularity is 5 mu m), Si powder (the granularity is 5 mu m) and LiF powder according to the molar ratio of 10:10:3, putting 500g of the mixture into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition (the vacuum degree is more than or equal to 10)- 2Pa), heating to 1300 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, carrying out solid-phase reaction on the powder to generate products such as lithium silicate, silicon monoxide and the like, sublimating and desublimating, and obtaining a first lithium silicon oxide layer SiLi in a collecting regionx1O; the temperature of the collecting area is set to be 600 ℃;
(2) second lithium silicon oxide layer SiLix2Deposition of O:
mixing SiO2Uniformly mixing powder (the granularity is 5 mu m), Si powder (the granularity is 5 mu m) and LiF powder according to the molar ratio of 10:10:1.5, putting 500g of the mixture into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition (the vacuum degree is more than or equal to 10)-2Pa), heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving heat for 8h, sublimating and desublimating to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O; the temperature in the collecting area is set to be 800 ℃;
(3) third lithium silicon oxide layer SiLix3Deposition of O:
mixing SiO2Powder (5 μm particle size), Si powder (5 μm particle size), LiF powder in a molar ratio of 10:101, uniformly mixing, putting 500g of the mixture into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition in a vacuum atmosphere (the vacuum degree is more than or equal to 10)- 2Pa), heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving heat for 8h, sublimating and desublimating to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3O; wherein x3 is more than 0 and x2 is more than x1 is less than 1;
(4) deposition of a silicon oxide layer:
mixing SiO2Uniformly mixing powder (granularity of 5 μm) and Si powder (granularity of 5 μm) according to a molar ratio of 10:10, putting 500g of the mixture into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition (vacuum degree is more than or equal to 10)-2Pa), heating to 1400 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, sublimating and desublimating to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3O @ silicon oxide layer;
(5) deposition of carbon coating layer:
the first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3Naturally cooling the O @ silicon oxide layer powder material to room temperature, coarsely crushing and finely crushing to obtain a product with D50 of about 5 microns, putting the product into a CVD rotary furnace, introducing mixed gas of acetylene and nitrogen (the mixing ratio is 1:3) at high temperature, performing gas phase carbon coating at the reaction temperature of 900 ℃ for 3 hours, and cooling to room temperature to obtain a first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3O @ silicon oxide layer @ C, namely the silicon oxide composite material with the gradient prelithiation structure. Wherein the total thickness of the lithium-containing silicon oxide layer is 10 μm, the thickness of the silicon oxide layer is 0.5 μm, the thickness of the carbon coating layer is 50nm, and the carbon coating amount of the carbon coating layer is 8 wt%.
Example 2
(1) First lithium silicon oxide layer SiLix1Deposition of O:
mixing SiO2Powder (particle size of 3 μm), Si powder (particle size of 3 μm) and Li2CO3Uniformly mixing the powder according to the molar ratio of 10:10:2.4, putting 500g of the powder into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition (the vacuum degree is more than or equal to 10)-2Pa), heating to 1300 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, carrying out solid-phase reaction on the powder to generate products such as lithium silicate, silicon monoxide and the like, sublimating and desublimating, and obtaining a first lithium silicon oxide layer SiLi in a collecting regionx1O; the temperature in the collection area is set to 750 ℃;
(2) second lithium silicon oxide layer SiLix2Deposition of O:
mixing SiO2Powder (particle size of 3 μm), Si powder (particle size of 3 μm), Li2Mixing O powder at a molar ratio of 10:10:1.8, placing 500g into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition (vacuum degree is more than or equal to 10)-2Pa), heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving heat for 8h, sublimating and desublimating to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O; the temperature in the collecting area is set to be 800 ℃;
(3) third lithium silicon oxide layer SiLix3Deposition of O:
mixing SiO2Powder (particle size of 3 μm), Si powder (particle size of 3 μm), Li2CO3Uniformly mixing the powder according to the molar ratio of 10:10:1.2, putting 500g of the powder into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition (the vacuum degree is more than or equal to 10)-2Pa), heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving heat for 8h, sublimating and desublimating to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3O; wherein x3 is more than 0 and x2 is more than x1 is less than 1;
(4) deposition of a silicon oxide layer:
mixing SiO2Uniformly mixing powder (granularity is 3 mu m) and Si powder (granularity is 3 mu m) according to a molar ratio of 10:10, putting 500g of the mixture into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition (vacuum degree is more than or equal to 10)-2Pa), heating to 1400 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1h, sublimating and desublimatingThen, a first lithium silicon oxide layer SiLi is obtained in the collecting regionx1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3O @ silicon oxide layer;
(5) deposition of carbon coating layer:
the first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3Naturally cooling the O @ silicon oxide layer powder material to room temperature, coarsely crushing and finely crushing to obtain a product with D50 of about 5 microns, putting the product into a CVD rotary furnace, introducing mixed gas of acetylene and nitrogen (the mixing ratio is 1:3) at high temperature, performing gas phase carbon coating at the reaction temperature of 850 ℃ for 5 hours, and cooling to room temperature to obtain a first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3O @ silicon oxide layer @ C, namely the silicon oxide composite material with the gradient prelithiation structure. Wherein the total thickness of the lithium-containing silicon oxide layer is 8 μm, the thickness of the silicon oxide layer is 1 μm, the thickness of the carbon coating layer is 20nm, and the carbon coating amount of the carbon coating layer is 10 wt%.
Example 3
(1) First lithium silicon oxide layer SiLix1Deposition of O:
mixing SiO2Uniformly mixing powder (the granularity is 5 mu m), Si powder (the granularity is 5 mu m) and LiF powder according to the molar ratio of 10:10:2, putting 500g of the mixture into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition (the vacuum degree is more than or equal to 10)- 2Pa), heating to 1300 ℃ at the heating rate of 5 ℃/min, preserving heat for 4h, carrying out solid-phase reaction on the powder to generate products such as lithium silicate, silicon monoxide and the like, sublimating and desublimating, and obtaining a first lithium silicon oxide layer SiLi in a collecting regionx1O; the temperature in the collection area is set to 750 ℃;
(2) second lithium silicon oxide layer SiLix2Deposition of O:
mixing SiO2Powder (particle size 5 μm), Si powder (particle size 5 μm), LiNO3Uniformly mixing the powder according to the molar ratio of 10:10:1, putting 500g of the powder into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition (the vacuum degree is more than or equal to 10)- 2Pa), heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving heat for 8h, sublimating and desublimating to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O; the temperature in the collecting area is set to be 800 ℃;
(3) third lithium silicon oxide layer SiLix3Deposition of O:
mixing SiO2Powder (particle size 5 μm), Si powder (particle size 5 μm), LiOH. H2Mixing O powder at a molar ratio of 10:10:0.5, placing 500g into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition (vacuum degree is more than or equal to 10)-2Pa), heating to 1500 ℃ at the heating rate of 5 ℃/min, preserving heat for 8h, sublimating and desublimating to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3O; wherein x3 is more than 0 and x2 is more than x1 is less than 1;
(4) deposition of a silicon oxide layer:
mixing SiO2Uniformly mixing powder (granularity of 5 μm) and Si powder (granularity of 5 μm) according to a molar ratio of 10:10, putting 500g of the mixture into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, and performing vacuum deposition (vacuum degree is more than or equal to 10)-2Pa), heating to 1400 ℃ at the heating rate of 5 ℃/min, preserving heat for 1h, sublimating and desublimating to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3O @ silicon oxide layer;
(5) deposition of carbon coating layer:
the first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3Naturally cooling the O @ silicon oxide layer powder material to room temperature, coarsely crushing and finely crushing to obtain a product with D50 of about 5 microns, putting the product into a CVD rotary furnace, introducing mixed gas of acetylene and nitrogen (the mixing ratio is 1:3) at high temperature, performing gas phase carbon coating at the reaction temperature of 850 ℃ for 5 hours, and cooling to room temperature to obtain a first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ third lithium silicon oxide layer SiLix3O @ silicon layer @ C, i.e.A silicon oxide composite material having a gradient prelithiation structure. Wherein the total thickness of the lithium-containing silicon oxide layer is 9 μm, the thickness of the silicon oxide layer is 4 μm, the thickness of the carbon coating layer is 100nm, and the carbon coating amount of the carbon coating layer is 5 wt%.
Example 4
Example 4 differs from example 1 in that step (3) is not present and the remaining process is exactly the same, as shown in fig. 1, and the resulting silicon oxide composite material with a gradient prelithiation structure has the structure: first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ silicon layer @ C. The total thickness of the lithium-containing silicon oxide layer is 4 μm, the thickness of the silicon oxide layer is 6 μm, the thickness of the carbon coating layer is 1nm, and the carbon coating amount of the carbon coating layer is 2 wt%.
Example 5
Example 5 differs from example 1 in that steps (2) and (3) are not included, the remaining process is exactly the same, and the structure of the resulting silicon oxide composite material with a gradient prelithiation structure is: first lithium silicon oxide layer SiLix1O @ silicon layer @ C. The thickness of the lithium-containing silicon oxide layer was 0.1 μm, the thickness of the silicon oxide layer was 3 μm, the thickness of the carbon coating layer was 90nm, and the carbon coating amount of the carbon coating layer was 1 wt%.
Comparative example
The comparative example used a commercial silicon oxygen material with a core-shell structure in which the carbon layer directly coated the SiO.
Electrochemical performance test analysis is respectively carried out on button cells assembled by the silicon oxide composite materials of examples 1-5 and comparative example, and the specific scheme is as follows: the silicon oxide composite material, the conductive agent SP, the conductive agent VGCF and the adhesive LA136 are mixed according to the ratio of 75:5:10:10 to prepare a button cell with the model number of 2032, wherein a counter electrode is a lithium sheet, a diaphragm is a Celgard2400 microporous polypropylene film, the charge-discharge cutoff voltage is 0.005-1.5V, the discharge rate is 0.1C and 0.02C, and the charge rate is 0.1C. The first charge-discharge curve of the button cell assembled by the silicon oxide composite material of example 1 is shown in fig. 2, and the rest test results are shown in table 1:
TABLE 1 test results
As can be seen from table 1, the silicon oxide composite material with a gradient prelithiation structure of the present invention has a greatly improved cycling performance compared to the currently commercialized silicon oxide material. As can be seen from comparing the data of example 1 with those of examples 4 and 5, the number of layers of the lithium-containing silicon oxide layer has a large influence on the cycle performance, and the tendency is that the larger the number of layers, the more stable the cycle.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (9)
1. The silicon oxide composite material with the gradient pre-lithiation structure is characterized by having a core-shell structure which sequentially comprises a lithium-containing silicon oxide layer, a silicon oxide layer and a carbon coating layer from inside to outside; the number of the lithium-containing silicon oxide layers is at least one, and the lithium content of each layer is gradually reduced from inside to outside; in terms of molar ratio, each lithium-containing silicon oxide layer is denoted as SiLixO, wherein x is more than 0 and less than 1;
the preparation method of the silicon oxide composite material with the gradient prelithiation structure comprises the following steps:
(1) first lithium silicon oxide layer SiLix1Deposition of O:
mixing SiO2Uniformly mixing the powder, Si powder and a lithium-containing compound, putting the mixture into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, sublimating and desublimating to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O;
(2) Second lithium silicon oxide layer SiLix2Deposition of O:
mixing SiO2Powder, Si powder, lithium-containing compound, and first lithium silicon oxide layer SiLi obtained in step (1)x1Mixing O uniformly, placing into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, sublimating, and collecting to obtain first lithium silicon oxideLayer SiLix1O @ second lithium silicon oxide layer SiLix2O;
(3) N-th lithium silicon oxide layer SiLixnDeposition of O:
repeating the step (2) to obtain a first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO; wherein, 0 < xn < x2 < x1 < 1;
(4) deposition of a silicon oxide layer:
the first lithium silicon oxide layer SiLi obtained in the step (3) is treatedx1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO and SiO2Mixing the powder and Si powder, placing into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, sublimating, and collecting to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO @ silicon oxide layer;
(5) deposition of carbon coating layer:
the first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnPlacing the O @ silicon oxide layer powder material into a CVD rotary furnace, introducing mixed gas of nitrogen and coating gas at high temperature, performing gas phase carbon coating, and cooling to room temperature to obtain a first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO @ silicon oxide layer @ C, namely the silicon oxide composite material with the gradient prelithiation structure.
2. The silicon oxide composite material with the gradient prelithiation structure as claimed in claim 1, wherein the total thickness of the lithium-containing silicon oxide layer is 0.1-10 μm.
3. The silicon oxide composite material with a gradient prelithiation structure as claimed in claim 1, wherein said silicon oxide layer has a single-layer structure; the thickness of the silicon oxide layer is 0.5-5 μm.
4. The silicon oxide composite material with the gradient prelithiation structure as recited in claim 1, wherein the carbon coating layer has a thickness of 1-100 nm.
5. A method of preparing a silicon oxide composite material with a gradient prelithiation structure as claimed in any one of claims 1 to 4, comprising the steps of:
(1) first lithium silicon oxide layer SiLix1Deposition of O:
mixing SiO2Uniformly mixing the powder, Si powder and a lithium-containing compound, putting the mixture into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, sublimating and desublimating to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O;
(2) Second lithium silicon oxide layer SiLix2Deposition of O:
mixing SiO2Powder, Si powder, lithium-containing compound, and first lithium silicon oxide layer SiLi obtained in step (1)x1Mixing O uniformly, placing into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, sublimating, and collecting to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O;
(3) N-th lithium silicon oxide layer SiLixnDeposition of O:
repeating the step (2) to obtain a first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO; wherein, 0 < xn < x2 < x1 < 1;
(4) deposition of a silicon oxide layer:
the first lithium silicon oxide layer SiLi obtained in the step (3) is treatedx1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO and SiO2Mixing the powder and Si powder, placing into a reaction cavity of an atmosphere deposition furnace, performing high-temperature deposition, sublimating, and collecting to obtain a first lithium silicon oxide layer SiLi in a collecting regionx1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO @ silicon oxide layer;
(5) deposition of carbon coating layer:
the first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnPlacing the O @ silicon oxide layer powder material into a CVD rotary furnace, introducing mixed gas of nitrogen and coating gas at high temperature, performing gas phase carbon coating, and cooling to room temperature to obtain a first lithium silicon oxide layer SiLix1O @ second lithium silicon oxide layer SiLix2O @ nth lithium silicon oxide layer SiLixnO @ silicon oxide layer @ C, namely the silicon oxide composite material with the gradient prelithiation structure.
6. The method for preparing a silicon oxide composite material having a gradient prelithiation structure according to claim 5, wherein in steps (1) to (4):
the SiO2The molar ratio of the powder to the Si powder is 1: 1;
the SiO2The particle size of the powder is 200 nm-10 m; the granularity of the Si powder is 500 nm-15 mu m;
the atmosphere deposition furnace is of a horizontal structure, one side of the atmosphere deposition furnace is a reaction area, the other side of the atmosphere deposition furnace is a collection area, the reaction atmosphere is an inert or vacuum atmosphere, the reaction temperature of high-temperature deposition is 1300-1500 ℃, the reaction time is 1-8 hours, and the temperature of the collection area is 600-800 ℃.
7. The method of claim 5, wherein the lithium-containing compound is selected from LiF and Li in steps (1) - (3)2O、LiOH、LiNO3、Li2CO3And hydrates thereof.
8. The method for preparing a silicon oxide composite material with a gradient prelithiation structure according to claim 5, wherein in step (5), the volume ratio of the cladding gas to nitrogen gas is 1: (1-3); the coating gas is selected from one or more of methane, acetylene, ethane and ethylene; the total mass of the silicon oxide composite material with the gradient pre-lithiation structure is taken as a reference, and the carbon coating amount of the carbon coating layer is 1-10 wt%; the reaction temperature of the gas phase carbon coating is 850-950 ℃, and the reaction time is 3-6 h.
9. Use of a silicon oxide composite material with a graded prelithiation structure according to any one of claims 1 to 4 as a negative electrode material for a lithium ion battery.
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Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102473902A (en) * | 2010-04-23 | 2012-05-23 | 松下电器产业株式会社 | Negative electrode for lithium-ion battery, production method therefor, and lithium-ion battery |
KR20150098487A (en) * | 2014-02-20 | 2015-08-28 | 지에스에너지 주식회사 | Capacity retention enhanced oxide-based anode active material and lithium secondary battery comprising the same |
CN108232145A (en) * | 2017-10-23 | 2018-06-29 | 中航锂电(洛阳)有限公司 | A kind of space buffer, the silicon oxide composite material and preparation method thereof of elements doped lithium, lithium ion battery |
CN108269979A (en) * | 2017-12-28 | 2018-07-10 | 合肥国轩高科动力能源有限公司 | Silicon monoxide/silicon/lithium metasilicate composite anode material and preparation method thereof |
CN108281664A (en) * | 2018-01-22 | 2018-07-13 | 欣旺达电子股份有限公司 | Negative current collector, lithium ion battery and lithium-ion battery system mend lithium method |
CN108461723A (en) * | 2018-02-11 | 2018-08-28 | 安普瑞斯(南京)有限公司 | A kind of silicon based composite material and preparation method thereof for lithium ion battery |
CN109417167A (en) * | 2016-03-31 | 2019-03-01 | 通用汽车环球科技运作有限责任公司 | Cladding lithium titanate for lithium ion battery |
CN109599551A (en) * | 2018-12-28 | 2019-04-09 | 安普瑞斯(南京)有限公司 | A kind of doping type multi-layer core-shell silicon based composite material and preparation method thereof for lithium ion battery |
CN109755500A (en) * | 2018-12-05 | 2019-05-14 | 华为技术有限公司 | A kind of silicon oxygen composite negative pole material and preparation method thereof |
CN109888246A (en) * | 2019-03-25 | 2019-06-14 | 合肥国轩高科动力能源有限公司 | Silicon monoxide composite negative electrode material with gradient structure and preparation method and application thereof |
CN110165160A (en) * | 2019-04-24 | 2019-08-23 | 深圳市斯诺实业发展有限公司 | The preparation method of lithium doping silicon oxygen carbon graphite composite negative pole material |
CN110556529A (en) * | 2019-10-15 | 2019-12-10 | 溧阳天目先导电池材料科技有限公司 | Cathode composite material with multilayer core-shell structure and preparation method and application thereof |
CN110620223A (en) * | 2019-09-25 | 2019-12-27 | 福建翔丰华新能源材料有限公司 | Lithium ion battery pre-lithiation silicon-carbon multilayer composite negative electrode material and preparation method thereof |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101610995B1 (en) * | 2012-11-30 | 2016-04-08 | 주식회사 엘지화학 | Silicon based composite and manufacturing method thereof |
WO2016141032A1 (en) * | 2015-03-02 | 2016-09-09 | Eocell Ltd. | Silicon-silicon oxide-lithium composite material having nano silicon particles embedded in a silicon:silicon lithium silicate composite matrix, and a process for manufacture thereof |
-
2020
- 2020-04-20 CN CN202010312309.XA patent/CN111653737B/en active Active
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102473902A (en) * | 2010-04-23 | 2012-05-23 | 松下电器产业株式会社 | Negative electrode for lithium-ion battery, production method therefor, and lithium-ion battery |
KR20150098487A (en) * | 2014-02-20 | 2015-08-28 | 지에스에너지 주식회사 | Capacity retention enhanced oxide-based anode active material and lithium secondary battery comprising the same |
CN109417167A (en) * | 2016-03-31 | 2019-03-01 | 通用汽车环球科技运作有限责任公司 | Cladding lithium titanate for lithium ion battery |
CN108232145A (en) * | 2017-10-23 | 2018-06-29 | 中航锂电(洛阳)有限公司 | A kind of space buffer, the silicon oxide composite material and preparation method thereof of elements doped lithium, lithium ion battery |
CN108269979A (en) * | 2017-12-28 | 2018-07-10 | 合肥国轩高科动力能源有限公司 | Silicon monoxide/silicon/lithium metasilicate composite anode material and preparation method thereof |
CN108281664A (en) * | 2018-01-22 | 2018-07-13 | 欣旺达电子股份有限公司 | Negative current collector, lithium ion battery and lithium-ion battery system mend lithium method |
CN108461723A (en) * | 2018-02-11 | 2018-08-28 | 安普瑞斯(南京)有限公司 | A kind of silicon based composite material and preparation method thereof for lithium ion battery |
CN109755500A (en) * | 2018-12-05 | 2019-05-14 | 华为技术有限公司 | A kind of silicon oxygen composite negative pole material and preparation method thereof |
CN109599551A (en) * | 2018-12-28 | 2019-04-09 | 安普瑞斯(南京)有限公司 | A kind of doping type multi-layer core-shell silicon based composite material and preparation method thereof for lithium ion battery |
CN109888246A (en) * | 2019-03-25 | 2019-06-14 | 合肥国轩高科动力能源有限公司 | Silicon monoxide composite negative electrode material with gradient structure and preparation method and application thereof |
CN110165160A (en) * | 2019-04-24 | 2019-08-23 | 深圳市斯诺实业发展有限公司 | The preparation method of lithium doping silicon oxygen carbon graphite composite negative pole material |
CN110620223A (en) * | 2019-09-25 | 2019-12-27 | 福建翔丰华新能源材料有限公司 | Lithium ion battery pre-lithiation silicon-carbon multilayer composite negative electrode material and preparation method thereof |
CN110556529A (en) * | 2019-10-15 | 2019-12-10 | 溧阳天目先导电池材料科技有限公司 | Cathode composite material with multilayer core-shell structure and preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
Controlled Prelithiation of Silicon Monoxide for High Performance Lithium-Ion Rechargeable Full Cells;Hye Jin Kim,et al.;《Nano Letters》;20130930;第13卷(第9期);全文 * |
锂离子电池硅基负极材料预锂化技术的研究进展;宋广生 等;《安徽工业大学学报(自然科学版)》;20190930;第36卷(第3期);全文 * |
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