CN110323439A - A kind of lithium ion battery negative material and preparation method thereof - Google Patents
A kind of lithium ion battery negative material and preparation method thereof Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
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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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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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 present invention discloses a kind of lithium ion battery negative material and preparation method thereof.The method includes the steps: it selenium source and antimony source is dissolved in solvent is placed in homogeneous reactor and carry out primary heating, react and Sb is made2Se3Nanometer rods;By Sb2Se3Nanometer rods are scattered in alcohol, are added tetraethyl orthosilicate and are carried out reheating, react and Sb is made2Se3‑SiO2;Then resorcinol-formaldehyde resin cladding process Sb is used2Se3‑SiO2It is coated, by being calcined under an inert atmosphere, so that it may in Sb2Se3‑SiO2Surface forms the carbon-coating with microcellular structure, by acid etch SiO2Obtain lithium ion battery negative material.Lithium ion battery negative material provided by the present invention not only increases the structural stability of material, controls volume expansion, and also improves the electric conductivity of material, so that the cyclical stability and high rate performance of material are improved.
Description
Technical field
The present invention relates to technical field of composite materials more particularly to a kind of lithium ion battery negative material and its preparation sides
Method.
Background technique
With the growing interest to world energy sources crisis and environmental problem, seek advanced energy storage technology as global evolution
Top priority.Currently, lithium ion battery (LIBs) has completely changed and has dominated portable electronics market, as one kind
Reliable energy storage equipment, it is becoming most environmentally friendly one of selection.However, from portable electronic device to electric car
With the transition of smart grid, it is still desirable to increase substantially the current energy and power density of LIBs.Therefore, research has Gao Li
It is of great significance by the new electrode materials of capacity.In terms of negative electrode material, many cathode materials for currently actively studying
Material, including carbon, phosphide, oxide and sulfide.Particularly, compared with traditional carbonaceous material (such as graphite and hard carbon),
The negative electrode material of alloying reaction (such as Sn and Sb) occurs during embedding and removing due to its substantially higher quality
Specific energy and much paid close attention to.In addition, chalcogenide materials (such as SnS2, SnS and Sb2S3) can change in succession and
Alloying reaction has high-energy-density.As the Common members of chalcogenide, Sb chalcogen compound has proven to have
The negative electrode material of good chemical property, for example, the flower-shaped Sb of Zhu et al. preparation2S3In 2Ag-1When show 553mAh
g-1High capacity and excellent rate capability.
Antimony selenide (Sb2Se3) it is a kind of semiconductor material for being widely used in the fields such as electronics, optics, magnetism.However, it
Electrode as battery is seldom studied.Thermodynamically, 1 mole of Sb2Se312 moles of Li can be accommodated+Or electronics, when
When conversion and alloying reaction are involved in embedding and removing process, theoretical capacity 670mAhg-1.However, chalcogenide compound
Inherent shortcoming as electrode is that volume change is violent in the lithium intercalation/deintercalation process, causes electrode structure unstable, capacity and is followed
Ring stability gradually decays.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of lithium ion battery negative material and its
Preparation method.Aim to solve the problem that existing Sb2Se3Volume change is larger in the lithium intercalation/deintercalation process, and caused battery capacity is low and follows
The problem of ring stability difference and poorly conductive.
A kind of lithium ion battery negative material, wherein the negative electrode material has yolk-shell structure, the material of the yolk
Material is Sb2Se3Nanometer rods, the material of the shell are carbon, and the yolk is arranged in the shell, and the yolk and the shell are in sky
Between upper separation.
Further, the shell has microcellular structure.
Further, the shell with a thickness of 10-20nm.
Further, the yolk and the shell are 5-10nm at a distance from spatially.
Further, the Sb2Se3The diameter of nanometer rods is 100-200nm, and length is 1-5 μm.
A method of preparing lithium ion battery negative material of the present invention, wherein comprising steps of
Selenium source is dissolved in hydrazine hydrate, solution A is denoted as;Antimony source is dissolved in polyethylene glycol, solution B is denoted as;It will
Solution A is added in solution B, in 180-220 DEG C of reaction 8-16h, obtains Sb2Se3Nanometer rods;
By Sb2Se3Nanometer rods are distributed in alcohol, then addition deionized water, ammonium hydroxide and tetraethyl orthosilicate, anti-at 30-50 DEG C
It answers 2-6 hours, in the Sb2Se3One layer of SiO is obtained in nanometer rods2, it is denoted as Sb2Se3-SiO2;
By the Sb2Se3-SiO2, cetyl trimethylammonium bromide, resorcinol, ammonium hydroxide, ethyl alcohol and formaldehyde mixing,
After reacting 8-12h at 25-35 DEG C, under an inert atmosphere in 400-600 DEG C of calcining 2-4h, finally silica is etched, is obtained
The negative electrode material.
Further, the selenium source is Se powder or sodium selenite, and antimony source is antimony trichloride or antimony acetate.
Further, Sb2Se3-SiO2, cetyl trimethylammonium bromide and resorcinol mass ratio be (0.2-
0.4): (0.115-0.23): (0.0175-0.035).
Further, the amount of tetraethyl orthosilicate is 0.1-0.5mL.
Further, silica is etched with HF acid.
The utility model has the advantages that the present invention provides a kind of negative electrode materials with yolk-shell structure lithium ion battery.Yolk-
Shell structure is by Sb2Se3Nanometer rods yolk and microporous carbon shell with good conductivity composition.Carbon shell and Sb2Se3Nanometer rods yolk it
Between cavity be Sb2Se3Volume expansion provide additional free space, to maintain the integrality of structure, carbon shell is not only
The electric conductivity of material is improved, but also maintains the stability of structure.Due to its superior design feature, so that Sb2Se3-
Void-C has superior chemical property.
Detailed description of the invention
Fig. 1 is Sb prepared by the embodiment of the present invention 12Se3And Sb2Se3The transmission electron microscope TEM of-Void-C schemes;
Fig. 2 is Sb prepared by the embodiment of the present invention 12Se3And Sb2Se3The XRD diagram of-Void-C;
Fig. 3 is Sb prepared by the embodiment of the present invention 12Se3And Sb2Se3The cycle performance figure of-Void-C;
Fig. 4 is Sb prepared by the embodiment of the present invention 12Se3And Sb2Se3The high rate performance figure of-Void-C.
Specific embodiment
The present invention provides a kind of lithium ion battery negative material and preparation method thereof.To make the purpose of the present invention, technical side
Case and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that specific reality described herein
It applies example to be only used to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of lithium ion battery negative material, wherein the negative electrode material has yolk-shell knot
Structure, the material of the yolk are Sb2Se3Nanometer rods, the material of the shell are carbon, and the yolk is arranged in the shell, the egg
It is yellow to be spatially separated with the shell, in other words, there is cavity between the yolk and the shell.It will be described in the present embodiment
Negative electrode material is denoted as Sb2Se3- Void-C composite material.
Present embodiments provide a kind of novel yolk-shell structure Sb2Se3- Void-C composite material is as lithium-ion electric
The negative electrode material in pond.Yolk-shell structure is by Sb2Se3Nanometer rods yolk and microporous carbon shell with good conductivity composition.Carbon shell and
Sb2Se3Cavity between nanometer rods yolk is Sb2Se3Volume expansion provide additional free space, thus keep finish
The integrality of structure;Carbon shell not only increases the electric conductivity of material, but also maintains the stability of structure.Due to its superior knot
Structure feature, so that Sb2Se3- Void-C has superior chemical property.
In one embodiment, the shell has microcellular structure.Permeable microporous carbon shell can be Li+It is mentioned with electronics
For the long-pending and short diffusion path of big electrolyte/electrode contact surface, and help to form stable SEI layer during circulation
(solid electrolyte interface) improves rate capacity and keeps structural intergrity.
In one embodiment, the shell with a thickness of 10-20nm.
In one embodiment, the yolk and the shell are 5-10nm at a distance from spatially.Purposefully design
Sb2Se3Void space between yolk and microporous carbon shell can buffer volumes expand without making carbon shell during lithiumation and de- lithium
Deformation, to generate long term stabilization.Therefore, obtained electrode has excellent lithium ion storge quality, including Fabrication of High Specific Capacitance
Amount, outstanding high rate performance and overlength cycle performance.
In one embodiment, the Sb2Se3The diameter of nanometer rods is 100-200nm, and length is 1-5 μm.
The embodiment of the present invention provides a kind of method for preparing lithium ion battery negative material, wherein comprising steps of
S10, selenium source is dissolved in hydrazine hydrate, is denoted as solution A;Antimony source is dissolved in polyethylene glycol, solution is denoted as
B;Solution A is added in solution B, in 180-220 DEG C of reaction 8-16h, obtains Sb2Se3Nanometer rods;
S20, by Sb2Se3Nanometer rods are distributed in alcohol, then addition deionized water, ammonium hydroxide and tetraethyl orthosilicate, and 30-50 DEG C
Lower reaction 2-6 hours, in the Sb2Se3One layer of SiO is obtained in nanometer rods2, it is denoted as Sb2Se3-SiO2;
S30, by the Sb2Se3-SiO2, cetyl trimethylammonium bromide, resorcinol, ammonium hydroxide, ethyl alcohol and formaldehyde it is mixed
It closes, after reacting 8-12h at 25-35 DEG C, under an inert atmosphere in 400-600 DEG C of calcining 2-4h, finally silica is etched, is obtained
To the negative electrode material.
In the present embodiment, Sb is generated first with selenium source and the reaction of antimony source2Se3Nanometer rods, then by Sb2Se3Nanometer rods dispersion
Into alcoholic solvent, hydrolyzed using tetraethyl orthosilicate in Sb2Se3One layer of SiO is generated in nanometer rods2, to obtain Sb2Se3-SiO2;
Then use resorcinol-formaldehyde resin cladding process by Sb2Se3-SiO2It is coated, by being calcined under an inert atmosphere,
It can be in Sb2Se3-SiO2Surface forms the carbon-coating with microcellular structure;Using HF acid by SiO2Etching is obtained with Sb2Se3For
Yolk-shell structure Sb of core2Se3- Void-C composite material.Yolk-shell structure is by Sb2Se3Nanometer rods yolk and conduction
Property good mesoporous carbon shell composition.Carbon shell and Sb2Se3Cavity between nanometer rods yolk is Sb2Se3Volume expansion provide
Additional free space, to maintain the integrality of structure, carbon shell not only increases the electric conductivity of material, but also maintains
The stability of structure.Due to its superior design feature, so that Sb2Se3- Void-C has superior chemical property.
In one embodiment, step S10 is specifically included: selenium source being dissolved in hydrazine hydrate, solution A is denoted as;It will
Antimony source is dissolved in polyethylene glycol, is denoted as solution B;Solution A is added drop-wise in solution B dropwise, is then transferred to polytetrafluoroethylene (PTFE)
In reaction kettle, it is subsequently placed into 180-220 DEG C of reaction 8-16h of homogeneous reactor high temperature, obtains Sb2Se3Nanometer rods.
In a kind of specific embodiment, the selenium source is Se powder or sodium selenite, and antimony source is antimony trichloride or acetic acid
Antimony.
In one embodiment, step S20 is specifically included: by Sb2Se3Nanometer rods ultrasonic disperse is into alcohol, then successively
Deionized water, ammonium hydroxide and tetraethyl orthosilicate is added, reacts 2-6h at 30-50 DEG C, obtains Sb2Se3-SiO2。
In a kind of specific embodiment, tetraethyl orthosilicate hydrolyzes to obtain silica, by controlling tetraethyl orthosilicate
Additive amount indirectly control the cavity size of final product, the amount of tetraethyl orthosilicate is 0.1-0.5mL.
In one embodiment, step S30 is specifically included: by above-mentioned gained Sb2Se3-SiO2And cetyl trimethyl
Ammonium bromide is distributed to ultrasonic disperse in deionized water, then sequentially adds resorcinol, ammonium hydroxide, ethyl alcohol and formaldehyde, and 25-35 DEG C anti-
8-12h is answered, product 400-600 DEG C of calcining 2-4h of high temperature under an inert atmosphere is collected, finally etches silica, is obtained final
Product Sb2Se3- Void-C composite material.
In a kind of specific embodiment, Sb2Se3-SiO2, cetyl trimethylammonium bromide and resorcinol matter
Amount is than being (0.2-0.4): (0.115-0.23): (0.0175-0.035).
Selenium source and antimony source are dissolved in solvent and are placed in homogeneous reactor by the present embodiment carries out primary heating, and reaction is made
Sb2Se3Nanometer rods;By Sb2Se3Nanometer rods are scattered in alcohol, are added tetraethyl orthosilicate and are carried out reheating, reaction is made
Sb2Se3-SiO2;Then use resorcinol-formaldehyde resin cladding process by Sb2Se3-SiO2It is coated, by inert atmosphere
Under calcined, so that it may in Sb2Se3-SiO2Surface forms the carbon-coating with microcellular structure, by acid etch SiO2It obtains
Lithium ion battery negative material.Lithium ion battery negative material provided by the present embodiment not only increases the stable structure of material
Property, volume expansion is controlled, and also improve the electric conductivity of material, so that the cyclical stability and high rate performance of material obtain
Improve.
Below by specific embodiment, the present invention is described in detail.
Embodiment 1
(1) Sb is prepared2Se3Nanometer rods: 3mmol Se powder is dissolved in 10mL hydrazine hydrate first, is denoted as solution A;It will
2mmol antimony trichloride is dissolved in 60mL polyethylene glycol, is denoted as solution B;Then solution A is added drop-wise in solution B dropwise, is shifted
Into 100mL ptfe autoclave, 200 DEG C of reaction 12h of homogeneous reactor high temperature are subsequently placed into, Sb is obtained2Se3Nanometer
Stick;
(2) Sb is prepared2Se3-SiO2: by 0.25g Sb2Se3Nanometer rods are distributed to ultrasound 30min in 97mL isopropanol, then
9mL deionized water, 5mL ammonium hydroxide and 0.1mL tetraethyl orthosilicate are sequentially added, is reacted 2 hours at 40 DEG C, obtains Sb2Se3-SiO2;
(3) Sb is prepared2Se3- Void-C: by above-mentioned gained 0.2g Sb2Se3-SiO27mL is distributed to 0.115g CTAB
Ultrasound 1h in ionized water, then sequentially adds 0.035g resorcinol, 0.05mL ammonium hydroxide, 14mL ethyl alcohol and 0.04mL formaldehyde, and 25
10h is reacted at DEG C, collects product 500 DEG C of calcining 3h of high temperature under an inert atmosphere, finally silica is etched with HF acid, is obtained
Final product Sb2Se3- Void-C composite material.
To Sb prepared by embodiment 12Se3And Sb2Se3- Void-C carries out tem study respectively, knot
Fruit is as shown in Figure 1.Fig. 1 (a, b) is Sb2Se3Transmission electron microscope figure under different amplification, therefrom it can be seen that
Sb2Se3For nano bar-shape structure, diameter is about 150nm.Fig. 1 (c, d) is Sb2Se3- Void-C is saturating under different amplification
Electron microscope picture is penetrated, therefrom can obviously observe Sb2Se3- Void-C special yolk-shell structure, wherein microporous carbon shell
Thickness be about 15nm, the width of cavity is about 5nm.
To Sb prepared by embodiment 12Se3And Sb2Se3- Void-C carries out XRD analysis respectively, and result is as shown in Figure 2.
Sb can be significantly observed in Fig. 22Se3And Sb2Se3- Void-C composite material 15.03 °, 16.87 °, 23.90 °,
Diffraction maximum at 27.39 °, 28.20 °, 31.16 °, 34.07 °, 41.30 °, 45.35 ° and 52.16 ° respectively corresponds Sb2Se3Mark
(0 2 0), (1 2 0), (1 3 0), (2 3 0), (2 1 1), (2 2 1), (2 4 0), (2 of quasi- card PDF#15-0861
5 0), (1 5 1) and (3 6 0) crystal face, without other miscellaneous peaks in XRD test result, it may be determined that resulting materials purity is high, just
It is required Sb2Se3And Sb2Se3- Void-C composite material.
To Sb prepared by embodiment 12Se3And Sb2Se3- Void-C carries out cycle performance test, result such as Fig. 3 respectively
It is shown.Sb as can see from Figure 32Se3- Void-C is in 200mAg-1Current density under circulation 50 circle after reversible specific capacity be
617.5mAh g-1, hence it is evident that it is better than Sb2Se3139.5mAh g-1, excellent performance gains are in Sb2Se3- Void-C composite material
Special yolk-shell structure.
To Sb prepared by embodiment 12Se3And Sb2Se3- Void-C carries out high rate performance test, result such as Fig. 4 respectively
It is shown.Sb as can see from Figure 42Se3- Void-C composite material and Sb2Se3It compares, 10 circles is recycled under different current densities
There is higher capacity, and is returning 100mA g after different current densities circulation-1When, capacity retention ratio is
87.8%, present good high rate performance.
Embodiment 2
(1) Sb is prepared2Se3Nanometer rods: 3mmol Se powder is dissolved in 10mL hydrazine hydrate first, is denoted as solution A;It will
2mmol antimony trichloride is dissolved in 60mL polyethylene glycol, is denoted as solution B;Then solution A is added drop-wise in solution B dropwise, is shifted
Into 100mL ptfe autoclave, 200 DEG C of reaction 12h of homogeneous reactor high temperature are subsequently placed into, Sb is obtained2Se3Nanometer
Stick;
(2) Sb is prepared2Se3-SiO2: by 0.25g Sb2Se3Nanometer rods are distributed to ultrasound 30min in 97mL isopropanol, then
9mL deionized water, 5mL ammonium hydroxide and 0.2mL tetraethyl orthosilicate are sequentially added, is reacted 2 hours at 40 DEG C, obtains Sb2Se3-SiO2;
(3) Sb is prepared2Se3- Void-C: by above-mentioned gained 0.2g Sb2Se3-SiO27mL is distributed to 0.115g CTAB
Ultrasound 1h in ionized water, then sequentially adds 0.035g resorcinol, 0.05mL ammonium hydroxide, 14mL ethyl alcohol and 0.04mL formaldehyde, and 25
10h is reacted at DEG C, collects product 500 DEG C of calcining 3h of high temperature under an inert atmosphere, finally silica is etched with HF acid, is obtained
Final product Sb2Se3- Void-C composite material.
It is found through tem analysis, XRD analysis, cycle performance test and high rate performance test analysis, obtained by the present embodiment
Sb2Se3- Void-C composites have yolk-shell structure, have good high rate performance, electric conductivity and Fabrication of High Specific Capacitance
Amount, can alleviate the volume expansion of the material in charge and discharge process.
Embodiment 3
(1) Sb is prepared2Se3Nanometer rods: 3mmol Se powder is dissolved in 10mL hydrazine hydrate first, is denoted as solution A;It will
2mmol antimony trichloride is dissolved in 60mL polyethylene glycol, is denoted as solution B;Then solution A is added drop-wise in solution B dropwise, is shifted
Into 100mL ptfe autoclave, 200 DEG C of reaction 12h of homogeneous reactor high temperature are subsequently placed into, Sb is obtained2Se3Nanometer
Stick;
(2) Sb is prepared2Se3-SiO2: by 0.25g Sb2Se3Nanometer rods are distributed to ultrasound 30min in 97mL isopropanol, then
9mL deionized water, 5mL ammonium hydroxide and 0.3mL tetraethyl orthosilicate are sequentially added, is reacted 2 hours at 40 DEG C, obtains Sb2Se3-SiO2;
(3) Sb is prepared2Se3- Void-C: by above-mentioned gained 0.2g Sb2Se3-SiO27mL is distributed to 0.115g CTAB
Ultrasound 1h in ionized water, then sequentially adds 0.035g resorcinol, 0.05mL ammonium hydroxide, 14mL ethyl alcohol and 0.04mL formaldehyde, and 25
10h is reacted at DEG C, collects product 500 DEG C of calcining 3h of high temperature under an inert atmosphere, finally silica is etched with HF acid, is obtained
Final product Sb2Se3- Void-C composite material.
It is found through tem analysis, XRD analysis, cycle performance test and high rate performance test analysis, obtained by the present embodiment
Sb2Se3- Void-C composites have yolk-shell structure, have good high rate performance, electric conductivity and Fabrication of High Specific Capacitance
Amount, can alleviate the volume expansion of the material in charge and discharge process.
Embodiment 4
(1) Sb is prepared2Se3Nanometer rods: 3mmol Se powder is dissolved in 10mL hydrazine hydrate first, is denoted as solution A;It will
2mmol antimony trichloride is dissolved in 60mL polyethylene glycol, is denoted as solution B;Then solution A is added drop-wise in solution B dropwise, is shifted
Into 100mL ptfe autoclave, 200 DEG C of reaction 12h of homogeneous reactor high temperature are subsequently placed into, Sb is obtained2Se3Nanometer
Stick;
(2) Sb is prepared2Se3-SiO2: by 0.25g Sb2Se3Nanometer rods are distributed to ultrasound 30min in 97mL isopropanol, then
9mL deionized water, 5mL ammonium hydroxide and 0.5mL tetraethyl orthosilicate are sequentially added, is reacted 2 hours at 40 DEG C, obtains Sb2Se3-SiO2;
(3) Sb is prepared2Se3- Void-C: by above-mentioned gained 0.2g Sb2Se3-SiO27mL is distributed to 0.115g CTAB
Ultrasound 1h in ionized water, then sequentially adds 0.035g resorcinol, 0.05mL ammonium hydroxide, 14mL ethyl alcohol and 0.04mL formaldehyde, and 25
10h is reacted at DEG C, collects product 500 DEG C of calcining 3h of high temperature under an inert atmosphere, finally silica is etched with HF acid, is obtained
Final product Sb2Se3- Void-C composite material.
It is found through tem analysis, XRD analysis, cycle performance test and high rate performance test analysis, obtained by the present embodiment
Sb2Se3- Void-C composites have yolk-shell structure, have good high rate performance, electric conductivity and Fabrication of High Specific Capacitance
Amount, can alleviate the volume expansion of the material in charge and discharge process.
In conclusion lithium ion battery negative material provided by the present invention, with Sb2Se3Nanometer rods are yolk and electric conductivity
Good microporous carbon be hull shape at have yolk-shell structure Sb2Se3- Void-C composite material has excellent electrochemistry
Performance.Carbon shell and Sb2Se3Cavity between nanometer rods yolk is Sb2Se3Volume expansion provide additional free space, from
And the integrality of structure is maintained, carbon shell not only increases the electric conductivity of material, but also maintains the stability of structure.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of lithium ion battery negative material, which is characterized in that the negative electrode material has yolk-shell structure, the yolk
Material be Sb2Se3Nanometer rods, the material of the shell are carbon, and the yolk is arranged in the shell, the yolk and the shell
It is spatially separated.
2. lithium ion battery negative material according to claim 1, which is characterized in that the shell has microcellular structure.
3. lithium ion battery negative material according to claim 1, which is characterized in that the shell with a thickness of 10-20nm.
4. lithium ion battery negative material according to claim 1, which is characterized in that the yolk and the shell are in space
On distance be 5-10nm.
5. lithium ion battery negative material according to claim 1, which is characterized in that the Sb2Se3The diameter of nanometer rods
For 100-200nm, length is 1-5 μm.
6. a kind of method for preparing any one of claim 1-5 lithium ion battery negative material, which is characterized in that including step
It is rapid:
Selenium source is dissolved in hydrazine hydrate, solution A is denoted as;Antimony source is dissolved in polyethylene glycol, solution B is denoted as;By solution A
It is added in solution B, in 180-220 DEG C of reaction 8-16h, obtains Sb2Se3Nanometer rods;
By Sb2Se3Nanometer rods are distributed in alcohol, and deionized water, ammonium hydroxide and tetraethyl orthosilicate is then added, reacts 2- at 30-50 DEG C
6 hours, in the Sb2Se3One layer of SiO is obtained in nanometer rods2, it is denoted as Sb2Se3-SiO2;
By the Sb2Se3-SiO2, cetyl trimethylammonium bromide, resorcinol, ammonium hydroxide, ethyl alcohol and formaldehyde mixing, 25-35
After reacting 8-12h at DEG C, under an inert atmosphere in 400-600 DEG C of calcining 2-4h, finally silica is etched, is obtained described negative
Pole material.
7. according to the method described in claim 6, antimony source is trichlorine it is characterized in that, the selenium source is Se powder or sodium selenite
Change antimony or antimony acetate.
8. according to the method described in claim 6, it is characterized in that, Sb2Se3-SiO2, cetyl trimethylammonium bromide and
The mass ratio of benzenediol is (0.2-0.4): (0.115-0.23): (0.0175-0.035).
9. according to the method described in claim 6, it is characterized in that, the amount of tetraethyl orthosilicate is 0.1-0.5mL.
10. according to the method described in claim 6, it is characterized in that, silica is etched with HF acid.
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