CN108269979A - A kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation and preparation method thereof - Google Patents
A kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation and preparation method thereof Download PDFInfo
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- CN108269979A CN108269979A CN201711459397.0A CN201711459397A CN108269979A CN 108269979 A CN108269979 A CN 108269979A CN 201711459397 A CN201711459397 A CN 201711459397A CN 108269979 A CN108269979 A CN 108269979A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation, including the sub- silicon/silicon/lithium metasilicate composite material of oxidation and inorganic matter clad.The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including：The inorganic compound mixing and ball milling of the sub- silicon of oxidation and elemental lithium is taken, is sintered in the environment of protective gas, obtains aoxidizing sub- silicon/silicon/lithium metasilicate composite material after natural cooling；Sub- silicon/silicon/lithium metasilicate the composite material of oxidation is subjected to mixing and ball milling with inorganic matter, is then sintered under the conditions of protective gas.Sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation proposed by the present invention and preparation method thereof, the preparation method is simple, safe, at low cost, easily operated and industrialized production, and obtained composite negative pole material reversible capacity is high, cycle performance is excellent, and coulombic efficiency is high for the first time.
Description
Technical field
The present invention relates to lithium ion battery material technical field more particularly to a kind of sub- silicon/silicon/lithium metasilicate of oxidation are compound
Negative material and preparation method thereof.
Background technology
Lithium ion battery is widely used in all kinds of electricity due to the features such as its higher ratio energy, longer service life cycle
In the fields such as sub- product and equipment and electric vehicle.The lithium ion battery negative material of Current commercial is mainly that graphite-like is born
Pole material, theoretical capacity only have 372mAh/g, and actual capacity can not meet high-specific energy battery between 340-360mAh/g
Design requirement.Therefore, the next-generation novel anode material of high specific capacity, cyclical stability and good rate capability is developed with reality
The key subject for having become field of batteries research is widely used on present electronic product and electric vehicle.
Nearly ten years, silica-base material is due to its high specific capacity (Si：4200mAh/g, SiO：2000mAh/g) and by
Educational circles and the extensive and lasting research of industry.But silicon materials in charge and discharge process be up to 300% volume expansion and by
Material pulverizing problem is still without good solution caused by this.Educational circles generally take nanometer silicon nitride material and with
The compound mode of material (such as graphite) of silicon volume expansion is buffered to alleviate volume expansion problem.But the system that academia takes
Standby nano-silicon procedure is exquisite complicated, not only increases cost, and trivial operations, it is difficult to be transformed into industrialized production.Phase
For Si, Si, and SiO middle meetings in process of intercalation for the first time will be less than by aoxidizing the volume expansion (200%) of sub- silicon (SiO) material
Form lithium metasilicate object phase, such as Li2SiO3, Li4SiO4There is certain ionic conductivity, and can buffer Deng, these materials
The volume expansion of system.In addition, SiO material costs are cheap compared with nano Si.Therefore, SiO is considered as high specific energy lithium ion battery
Ideal negative material, however can be formed in its process of intercalation lithium metasilicate object meet it is irreversible consumption part lithium, cause battery
Coulombic efficiency is relatively low for the first time, limits its application in lithium ion battery.
In order to improve the performance of SiO material negative materials it may first have to which solving the problems, such as it, coulombic efficiency is low for the first time.
Solution to this problem has material surface cladding, ion doping, electrolyte matching etc. at present.However, these means for
Improving SiO, coulombic efficiency is extremely limited for the first time.Currently, the way of academia is the method for using for reference the pre- lithium to Si, SiO is carried out pre-
The irreversible consumption lithium reaction of electrode cycle first time process of intercalation is advanced to the material preparation stage by lithium, pre- by electrochemistry
Lithium mode is realized, but this procedure is complicated, and efficiency is low, of high cost, it is difficult to accomplish scale production.
Currently, solve the problems, such as that low be also in of coulombic efficiency studies the starting stage to SiO materials for the first time, has no highly effective
Method.
Invention content
Technical problems based on background technology, the present invention propose a kind of sub- silicon/silicon/lithium metasilicate Compound Negative of oxidation
Pole material and preparation method thereof, the preparation method is simple, safe, at low cost, and easily operated and industrialized production, what is obtained answers
It is high to close negative material reversible capacity, cycle performance is excellent, and coulombic efficiency is high for the first time.
Sub- silicon/silicon/lithium metasilicate the composite negative pole material of a kind of oxidation proposed by the present invention, including as active material
Sub- silicon/silicon/lithium metasilicate the composite material of oxidation and the inorganic matter packet being coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Coating.
Preferably, sub- silicon/silicon/weight content of the lithium metasilicate composite material in composite negative pole material of the oxidation is
90-95%, weight content of the inorganic matter clad in composite negative pole material are 5-10%.
Preferably, particle size D50 is 5-10 μm.
The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including
Following steps：
S1, the inorganic compound ball milling 0.5-3h for taking the sub- silicon of oxidation and elemental lithium, are sintered 1- in the environment of protective gas
10h, wherein, sintering temperature is 400-800 DEG C, obtains aoxidizing sub- silicon/silicon/lithium metasilicate composite material after cooling；
S2, oxidation Asia silicon/silicon/lithium metasilicate composite material in S1 and inorganic matter are subjected to mixing and ball milling, then protected
It is sintered to obtain the sub- silicon/silicon/lithium metasilicate composite negative pole material of the oxidation under shield gas condition, wherein, sintering temperature is
400-800 DEG C, sintering time 1-10h.
Preferably, in S1, the sub- silicon of the oxidation, elemental lithium the molar ratio of inorganic compound be 8：0.5-8.
Preferably, in S1, Si, O atom ratio are n, 1≤n in the sub- silicon of oxidation<2；The grain size of the sub- silicon of oxidation is
3-10μm。
Preferably, in S1, the inorganic compound of the elemental lithium is one kind in lithium carbonate, lithium hydroxide, lithium acetate
Or a variety of mixture.
Preferably, in S2, the inorganic matter is carbon inorganic matter or aluminium inorganic matter；The carbon inorganic matter for heated bitumen,
The mixture of one or more of asphalt, coal tar pitch；The aluminium inorganic matter is aluminum acetate, one kind in aluminium hydroxide
Or two kinds of mixture.
Preferably, in S1 and S2, the protective gas is nitrogen, argon gas, the mixed gas of nitrogen and hydrogen, argon gas with
The mixture of one or more of the mixed gas of hydrogen.
Preferably, in the mixed gas of nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 90-98：2-10；In argon gas
With in the mixed gas of hydrogen, the volume ratio of argon gas and hydrogen is 90-98：2-10.
Preferably, in the mixed gas of nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 95：5；In argon gas and hydrogen
Mixed gas in, the volume ratio of argon gas and hydrogen is 95：5.
The beneficial effects of the invention are as follows：The present invention is prepared for using the method that solid-phase sintering reaction and high temperature cabonization are combined
Aoxidize Asia silicon/silicon/lithium metasilicate (SiO/Si/Li2SiO3) composite negative pole material, in composite negative pole material, aoxidize sub- silicon and pass through
With the solid phase reaction of the inorganic compound of lithium, the product of generation both maintains high power capacity, also improves the effect of coulomb for the first time of material
Rate.Simultaneously pure phase Li is formed during solid phase reaction2SiO3Or Li4SiO4, ionic conduction and buffering silica-base material can be improved
The volume expansion of charge and discharge process.Clad is made of inorganic matter, is on the one hand improved interface performance, on the other hand can be prevented
Contact of the silicon-based active material with electrolyte, the degradation for preventing SEI films from constantly being formed during embedding and removing.Therefore,
This oxidation Asia silicon/silicon/lithium metasilicate (SiO/Si/Li coated by inorganic matter2SiO3) composite negative pole material have it is higher
Specific capacity and for the first time coulombic efficiency and cycle performance is excellent.In addition, this preparation method is simple, safe, at low cost, it is easily operated
And industrialized production.
Description of the drawings
Fig. 1 is the structure diagram of the sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM pictures of the sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation prepared by the embodiment of the present invention 1；
Fig. 3 is the XRD diagram piece of the sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation prepared by the embodiment of the present invention 1；
Fig. 4 is the electricity that the sub- silicon/silicon/lithium metasilicate composite negative pole material of the oxidation prepared using the embodiment of the present invention 1 is assembled
The first charge-discharge curve in pond.
Specific embodiment
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
Sub- silicon/silicon/lithium metasilicate the composite negative pole material of a kind of oxidation proposed by the present invention, by the oxygen as active material
The carbon coating layer group changed sub- silicon/silicon/lithium metasilicate composite material and be coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Into；
Wherein, it is 90% to aoxidize sub- silicon/silicon/weight content of the lithium metasilicate composite material in composite negative pole material, carbon
Weight content of the clad in composite negative pole material is 10%, consisting of [SiO/Si/Li2SiO3]0.9/I0.1, wherein,
SiO/Si/Li2SiO3For the sub- silicon/silicon/lithium metasilicate composite material of oxidation, I is carbon coating layer.
The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including
Following steps：
S1,10.0g is aoxidized into sub- silicon, 8.4g lithium carbonates mechanical mixture 10min, ball milling 30min, is 99.99% in purity
Nitrogen in the environment of be sintered 6h, wherein, sintering temperature be 800 DEG C, obtain aoxidizing sub- silicon/silicon/lithium metasilicate after natural cooling
Composite material；
S2,5g is aoxidized into sub- silicon/silicon/lithium metasilicate composite material and 1.58g pitch mechanical mixture 10min, ball milling
Then 30min is sintered 6h in the case where purity is 99.99% nitrogen environment, sintering temperature is 800 DEG C, obtain the sub- silicon of the oxidation/
Silicon/lithium metasilicate composite negative pole material.
Fig. 1 is the structure diagram of the sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation prepared by the embodiment of the present invention 1,
As shown in Figure 1, the sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation is by oxidation Asia silicon/silicon as active material/partially
Lithium metasilicate composite material and the carbon coating layer composition being coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation.
SEM and XRD detections are carried out to the oxidation Asia silicon/silicon/lithium metasilicate composite negative pole material prepared in the present embodiment,
As a result as shown in Figures 2 and 3, as shown in Figure 2, SiO/Si/Li2SiO3It is coated outside particle by one layer of thin carbon-coating, carbon coating
Layer also connects particle, so as to help to improve intergranular electric conductivity.
From the figure 3, it may be seen that there are SiO in synthesized oxidation Asia silicon/silicon/lithium metasilicate composite negative pole material, Si and
Li2SiO3Three-phase.
Oxidation Asia silicon/silicon/lithium metasilicate composite negative pole material in the present embodiment and lithium are assembled into electrode button electricity
Pond is tested for the property, and the results are shown in Figure 4, and as shown in Figure 4, the initial charge specific capacity of battery is 805.4mAh/g
(0.8V), first charge-discharge efficiency 64.5%.
Embodiment 2
Sub- silicon/silicon/lithium metasilicate the composite negative pole material of a kind of oxidation proposed by the present invention, by the oxygen as active material
The alumina-coated changed sub- silicon/silicon/lithium metasilicate composite material and be coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Layer composition；
Wherein, it is 95% to aoxidize sub- silicon/silicon/weight content of the lithium metasilicate composite material in composite negative pole material, oxygen
It is 5% to change weight content of the aluminium clad in composite negative pole material, consisting of [SiO/Si/Li2SiO3]0.95/I0.05,
In, SiO/Si/Li2SiO3For the sub- silicon/silicon/lithium metasilicate composite material of oxidation, I is alumina-coated layer.
The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including
Following steps：
S1,10.0g is aoxidized into sub- silicon, 8.4g lithium carbonates mechanical mixture 10min, ball milling 30min, is 99.99% in purity
Nitrogen in the environment of be sintered 6h, wherein, sintering temperature be 800 DEG C, obtain aoxidizing sub- silicon/silicon/lithium metasilicate after natural cooling
Composite material；
S2,5g is aoxidized into sub- silicon/silicon/lithium metasilicate composite material and 1mmol acetic acid aluminium powder mechanical mixture 10min, ball
30min is ground, is then sintered 6h in the case where purity is 99.99% nitrogen environment, sintering temperature is 500 DEG C, and it is sub- to obtain the oxidation
Silicon/silicon/lithium metasilicate composite negative pole material.
Oxidation Asia silicon/silicon/lithium metasilicate composite negative pole material in the present embodiment and lithium are assembled into electrode button electricity
Pond is tested for the property, and the initial charge specific capacity of battery is 813.6mAh/g (0.8V), first charge-discharge efficiency 65.5%.
Embodiment 3
Sub- silicon/silicon/lithium metasilicate the composite negative pole material of a kind of oxidation proposed by the present invention, by the oxygen as active material
The alumina-coated changed sub- silicon/silicon/lithium metasilicate composite material and be coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Layer composition；
Wherein, it is 90% to aoxidize sub- silicon/silicon/weight content of the lithium metasilicate composite material in composite negative pole material, oxygen
It is 10% to change weight content of the aluminium clad in composite negative pole material, consisting of [SiO/Si/Li2SiO3]0.9/I0.1,
In, SiO/Si/Li2SiO3For the sub- silicon/silicon/lithium metasilicate composite material of oxidation, I is alumina-coated layer.
The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including
Following steps：
S1,10.0g is aoxidized into sub- silicon, 4.2g lithium carbonates mechanical mixture 10min, ball milling 30min, is 99.99% in purity
Nitrogen in the environment of be sintered 6h, wherein, sintering temperature be 800 DEG C, obtain aoxidizing sub- silicon/silicon/lithium metasilicate after natural cooling
Composite material；
S2,5g is aoxidized into sub- silicon/silicon/lithium metasilicate composite material and 2mmol acetic acid aluminium powder mechanical mixture 10min, ball
30min is ground, is then sintered 6h in the case where purity is 99.99% nitrogen environment, sintering temperature is 500 DEG C, and it is sub- to obtain the oxidation
Silicon/silicon/lithium metasilicate composite negative pole material.
Oxidation Asia silicon/silicon/lithium metasilicate composite negative pole material in the present embodiment and lithium are assembled into electrode button electricity
Pond is tested for the property, and the initial charge specific capacity of battery is 810.0mAh/g (0.8V), first charge-discharge efficiency 65.9%.
Embodiment 4
Sub- silicon/silicon/lithium metasilicate the composite negative pole material of a kind of oxidation proposed by the present invention, by the oxygen as active material
The carbon coating layer group changed sub- silicon/silicon/lithium metasilicate composite material and be coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Into；
Wherein, it is 95% to aoxidize sub- silicon/silicon/weight content of the lithium metasilicate composite material in composite negative pole material, carbon
Weight content of the clad in composite negative pole material is 5%, consisting of [SiO/Si/Li2SiO3]0.95/I0.05, wherein,
SiO/Si/Li2SiO3For the sub- silicon/silicon/lithium metasilicate composite material of oxidation, I is carbon coating layer.
The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including
Following steps：
S1,10.0g is aoxidized into sub- silicon, 4.2g lithium carbonates mechanical mixture 10min, ball milling 30min, is 99.99% in purity
Nitrogen in the environment of be sintered 6h, wherein, sintering temperature be 800 DEG C, obtain aoxidizing sub- silicon/silicon/lithium metasilicate after natural cooling
Composite material；
S2,5g is aoxidized into sub- silicon/silicon/lithium metasilicate composite material and 0.79g asphalt powder mechanical mixture 10min, ball milling
Then 30min is sintered 6h in the case where purity is 99.99% nitrogen environment, sintering temperature is 800 DEG C, obtain the sub- silicon of the oxidation/
Silicon/lithium metasilicate composite negative pole material.
Oxidation Asia silicon/silicon/lithium metasilicate composite negative pole material in the present embodiment and lithium are assembled into electrode button electricity
Pond is tested for the property, and the electricity specific capacity of punching for the first time of battery is 803.3mAh/g (0.8V), first charge-discharge efficiency 65.5%.
Embodiment 5
Sub- silicon/silicon/lithium metasilicate the composite negative pole material of a kind of oxidation proposed by the present invention, by the oxygen as active material
The alumina-coated changed sub- silicon/silicon/lithium metasilicate composite material and be coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Layer composition；
Wherein, it is 95% to aoxidize sub- silicon/silicon/weight content of the lithium metasilicate composite material in composite negative pole material, oxygen
It is 5% to change weight content of the aluminium clad in composite negative pole material, consisting of [SiO/Si/Li2SiO3]0.95/I0.05,
In, SiO/Si/Li2SiO3For the sub- silicon/silicon/lithium metasilicate composite material of oxidation, I is alumina-coated layer.
The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including
Following steps：
S1,10g is aoxidized into sub- silicon, 1.05g lithium carbonates mechanical mixture 10min, ball milling 30min, is 99.99% in purity
6h is sintered in the environment of nitrogen, wherein, sintering temperature is 800 DEG C, obtains aoxidizing sub- silicon/silicon/lithium metasilicate after natural cooling multiple
Condensation material；
S2,5g is aoxidized into sub- silicon/silicon/lithium metasilicate composite material and 1mmol acetic acid aluminium powder mechanical mixture 10min, ball
Grind 30min, be then sintered 6h under 99.99% nitrogen environment, sintering temperature is 500 DEG C, obtain the sub- silicon/silicon of the oxidation/
Lithium metasilicate composite negative pole material.
Oxidation Asia silicon/silicon/lithium metasilicate composite negative pole material in the present embodiment and lithium are assembled into electrode button electricity
Pond is tested for the property, and the initial charge specific capacity of battery is 812.5mAh/g (0.8V), first charge-discharge efficiency 65.5%.
Embodiment 6
Sub- silicon/silicon/lithium metasilicate the composite negative pole material of a kind of oxidation proposed by the present invention, including as active material
Sub- silicon/silicon/lithium metasilicate the composite material of oxidation and the inorganic matter packet being coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Coating.
The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including
Following steps：
S1, the inorganic compound ball milling 0.5h for taking the sub- silicon of oxidation and elemental lithium, are sintered 10h in the environment of protective gas,
Wherein, sintering temperature is 400 DEG C, obtains aoxidizing sub- silicon/silicon/lithium metasilicate composite material after cooling；
S2, oxidation Asia silicon/silicon/lithium metasilicate composite material in S1 and inorganic matter are subjected to mixing and ball milling, then protected
It is sintered to obtain the sub- silicon/silicon/lithium metasilicate composite negative pole material of the oxidation under shield gas condition, wherein, sintering temperature is
400 DEG C, sintering time 10h.
Embodiment 7
Sub- silicon/silicon/lithium metasilicate the composite negative pole material of a kind of oxidation proposed by the present invention, including as active material
Sub- silicon/silicon/lithium metasilicate the composite material of oxidation and the inorganic matter packet being coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Coating.
The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including
Following steps：
S1, the inorganic compound ball milling 3h for taking the sub- silicon of oxidation and elemental lithium, are sintered 1h in the environment of protective gas,
In, sintering temperature is 800 DEG C, obtains aoxidizing sub- silicon/silicon/lithium metasilicate composite material after natural cooling；
S2, oxidation Asia silicon/silicon/lithium metasilicate composite material in S1 and inorganic matter are subjected to mixing and ball milling, then protected
It is sintered to obtain the sub- silicon/silicon/lithium metasilicate composite negative pole material of the oxidation under shield gas condition, wherein, sintering temperature is
800 DEG C, sintering time 1h.
Embodiment 8
Sub- silicon/silicon/lithium metasilicate the composite negative pole material of a kind of oxidation proposed by the present invention, including as active material
Sub- silicon/silicon/lithium metasilicate the composite material of oxidation and the inorganic matter packet being coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Coating；
Wherein, sub- silicon/silicon/weight content of the lithium metasilicate composite material in composite negative pole material of the oxidation is
95%, weight content of the inorganic matter clad in composite negative pole material is 5%；
The particle size D50 of the sub- silicon/silicon/lithium metasilicate composite material of oxidation is 5 μm.
The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including
Following steps：
S1, the sub- silicon of oxidation and lithium carbonate ball milling 1h are taken, 8h is sintered in the environment of protective gas, wherein, sintering temperature is
It 500 DEG C, obtains aoxidizing sub- silicon/silicon/lithium metasilicate composite material after natural cooling；Wherein, Si, O atom in the sub- silicon of the oxidation
Than for n, n=1；The sub- silicon of the oxidation, lithium carbonate molar ratio be 8：0.5；The grain size of the sub- silicon of oxidation is 3-10 μm；
S2, oxidation Asia silicon/silicon/lithium metasilicate composite material in S1 and heated bitumen are subjected to mixing and ball milling, then protected
It is sintered to obtain the sub- silicon/silicon/lithium metasilicate composite negative pole material of the oxidation under shield gas condition, wherein, sintering temperature is
450 DEG C, sintering time 8h；
In S1 and S2, the protective gas is argon gas.
Embodiment 9
Sub- silicon/silicon/lithium metasilicate the composite negative pole material of a kind of oxidation proposed by the present invention, including as active material
Sub- silicon/silicon/lithium metasilicate the composite material of oxidation and the inorganic matter packet being coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Coating；
Wherein, sub- silicon/silicon/weight content of the lithium metasilicate composite material in composite negative pole material of the oxidation is
90%, weight content of the inorganic matter clad in composite negative pole material is 10%；
The particle size D50 of the sub- silicon/silicon/lithium metasilicate composite material of oxidation is 10 μm.
The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including
Following steps：
S1, the sub- silicon of oxidation and lithium hydroxide ball milling 2h are taken, 3h is sintered in the environment of protective gas, wherein, sintering temperature
It is 750 DEG C, obtains aoxidizing sub- silicon/silicon/lithium metasilicate composite material after natural cooling；Wherein, Si, O are former in the sub- silicon of the oxidation
Son is than being n, n=1.8；The sub- silicon of the oxidation, lithium hydroxide molar ratio be 8：8；The grain size of the sub- silicon of oxidation is 3-10 μm；
S2, oxidation Asia silicon/silicon/lithium metasilicate composite material in S1 and aluminium hydroxide are subjected to mixing and ball milling, Ran Hou
It is sintered to obtain the sub- silicon/silicon/lithium metasilicate composite negative pole material of the oxidation under the conditions of protective gas, wherein, sintering temperature
It is 720 DEG C, sintering time 4h；
In S1 and S2, mixed gas of the protective gas for nitrogen and hydrogen, and in nitrogen and the gaseous mixture of hydrogen
In body, the volume ratio of nitrogen and hydrogen is 95：5.
Embodiment 10
Sub- silicon/silicon/lithium metasilicate the composite negative pole material of a kind of oxidation proposed by the present invention, including as active material
Sub- silicon/silicon/lithium metasilicate the composite material of oxidation and the inorganic matter packet being coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Coating；
Wherein, sub- silicon/silicon/weight content of the lithium metasilicate composite material in composite negative pole material of the oxidation is
93%, weight content of the inorganic matter clad in composite negative pole material is 7%；
The particle size D50 of the sub- silicon/silicon/lithium metasilicate composite material of oxidation is 8 μm.
The preparation method of a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation that the present invention also proposes, including
Following steps：
S1, the inorganic compound ball milling 2h for taking the sub- silicon of oxidation and elemental lithium, are sintered 5h in the environment of protective gas,
In, sintering temperature is 650 DEG C, obtains aoxidizing sub- silicon/silicon/lithium metasilicate composite material after natural cooling；Wherein, the oxidation is sub-
Si, O atom ratio are n, n=1.5 in silicon；The inorganic compound of elemental lithium is lithium carbonate, the mixture of lithium hydroxide, lithium acetate,
And the weight ratio of lithium carbonate, lithium hydroxide, lithium acetate is 3：4：2；The sub- silicon of the oxidation, elemental lithium inorganic compound mole
Than being 8：7；The grain size of the sub- silicon of oxidation is 3-10 μm；
S2, oxidation Asia silicon/silicon/lithium metasilicate composite material in S1 and inorganic matter are subjected to mixing and ball milling, then protected
It is sintered to obtain the sub- silicon/silicon/lithium metasilicate composite negative pole material of the oxidation under shield gas condition, wherein, sintering temperature is
650 DEG C, sintering time 7h；Wherein, the inorganic matter is carbon inorganic matter；The carbon inorganic matter is heated bitumen, asphalt, coal
The mixture of pitch, and the weight ratio of heated bitumen, asphalt, coal tar pitch is 4：5：2；
In S1 and S2, the protective gas is argon gas.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation, which is characterized in that it includes the oxygen as active material
The inorganic matter cladding changed sub- silicon/silicon/lithium metasilicate composite material and be coated on outside the sub- silicon/silicon/lithium metasilicate composite material of oxidation
Layer.
2. sub- silicon/silicon/lithium metasilicate composite negative pole material is aoxidized according to claim 1, which is characterized in that the oxidation is sub-
Silicon/silicon/weight content of the lithium metasilicate composite material in composite negative pole material is 90-95%, and inorganic matter clad is compound
Weight content in negative material is 5-10%.
3. the sub- silicon/silicon/lithium metasilicate composite negative pole material of oxidation according to claim 1 or claim 2, which is characterized in that its particle
Dimension D 50 is 5-10 μm.
4. a kind of preparation side that sub- silicon/silicon/lithium metasilicate composite negative pole material is aoxidized as described in any one of claim 1-3
Method, which is characterized in that include the following steps：
S1, the inorganic compound ball milling 0.5-3h for taking the sub- silicon of oxidation and elemental lithium, are sintered 1-10h in the environment of protective gas,
Wherein, sintering temperature is 400-800 DEG C, obtains aoxidizing sub- silicon/silicon/lithium metasilicate composite material after cooling；
S2, oxidation Asia silicon/silicon/lithium metasilicate composite material in S1 and inorganic matter are subjected to mixing and ball milling, then in protection gas
It is sintered to obtain the sub- silicon/silicon/lithium metasilicate composite negative pole material of the oxidation under concrete conditions in the establishment of a specific crime, wherein, sintering temperature 400-
800 DEG C, sintering time 1-10h.
5. the preparation method of sub- silicon/silicon/lithium metasilicate composite negative pole material is aoxidized according to claim 4, which is characterized in that
In S1, the sub- silicon of the oxidation, elemental lithium the molar ratio of inorganic compound be 8：0.5-8.
6. the preparation method of the sub- silicon/silicon/lithium metasilicate composite negative pole material of the oxidation, feature exist according to claim 4 or 5
In in S1, Si, O atom ratio are n, 1≤n in the sub- silicon of oxidation<2；The grain size of the sub- silicon of oxidation is 3-10 μm.
7. according to the preparation method of the sub- silicon/silicon/lithium metasilicate composite negative pole material of any one of the claim 4-6 oxidations,
It is characterized in that, in S1, the inorganic compound of the elemental lithium is lithium carbonate, lithium hydroxide, one kind in lithium acetate or
A variety of mixtures.
8. according to the preparation method of the sub- silicon/silicon/lithium metasilicate composite negative pole material of any one of the claim 4-7 oxidations,
It is characterized in that, in S2, the inorganic matter is carbon inorganic matter or aluminium inorganic matter；The carbon inorganic matter is heated bitumen, oil
The mixture of one or more of pitch, coal tar pitch；The aluminium inorganic matter for aluminum acetate, one kind in aluminium hydroxide or
Two kinds of mixture.
9. according to the preparation method of the sub- silicon/silicon/lithium metasilicate composite negative pole material of any one of the claim 4-8 oxidations,
It is characterized in that, in S1 and S2, the protective gas is mixed gas, argon gas and the hydrogen of nitrogen, argon gas, nitrogen and hydrogen
One or more of mixed gas mixture.
10. aoxidizing the preparation method of sub- silicon/silicon/lithium metasilicate composite negative pole material according to claim 9, feature exists
In in the mixed gas of nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 90-98：2-10；In the mixing of argon gas and hydrogen
In gas, the volume ratio of argon gas and hydrogen is 90-98：2-10；Preferably, in the mixed gas of nitrogen and hydrogen, nitrogen with
The volume ratio of hydrogen is 95：5；In the mixed gas of argon gas and hydrogen, the volume ratio of argon gas and hydrogen is 95：5.
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| WO2023188918A1 (en) * | 2022-04-01 | 2023-10-05 | 信越化学工業株式会社 | Negative electrode active substance and method for producing negative electrode active substance |
| CN114639814A (en) * | 2022-04-06 | 2022-06-17 | 宁波杉杉新材料科技有限公司 | Doped silicon-based material and preparation method and application thereof |
| CN114914422B (en) * | 2022-05-19 | 2024-03-15 | 武汉理工大学 | Composite negative electrode suitable for sulfide all-solid-state battery, preparation method and lithium battery |
| CN114914422A (en) * | 2022-05-19 | 2022-08-16 | 武汉理工大学 | Composite negative electrode suitable for sulfide all-solid-state battery, preparation method and lithium battery |
| CN115632105B (en) * | 2022-12-19 | 2023-03-21 | 四川新能源汽车创新中心有限公司 | Porous negative pole piece, preparation method thereof and lithium ion battery |
| CN115632105A (en) * | 2022-12-19 | 2023-01-20 | 四川新能源汽车创新中心有限公司 | Porous negative pole piece, preparation method thereof and lithium ion battery |
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Application publication date: 20180710 |