CN106058213B - A kind of two stannic selenides/polyethyleneimine composite material and its preparation method and application - Google Patents

A kind of two stannic selenides/polyethyleneimine composite material and its preparation method and application Download PDF

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CN106058213B
CN106058213B CN201610628577.6A CN201610628577A CN106058213B CN 106058213 B CN106058213 B CN 106058213B CN 201610628577 A CN201610628577 A CN 201610628577A CN 106058213 B CN106058213 B CN 106058213B
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stannic
polyethyleneimine
composite material
selenides
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CN106058213A (en
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张治安
李军明
陈晓彬
赖延清
张凯
李劼
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Central South University
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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
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/58—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a kind of two stannic selenides/polyethyleneimine composite materials and its preparation method and application, and selenium powder is dissolved in the sodium borohydride solution of inert gas saturation by the present invention, obtains solution containing selenium powder；Selenium tin molar ratio according to preparing needed for two stannic selenides will contain selenium powder solution and the mixing of tin source aqueous solution, obtain mixed solution, polyethyleneimine is added in into mixed solution, hydro-thermal reaction is carried out after being sufficiently stirred；Product obtained by the reaction obtains two stannic selenides/polyethyleneimine composite material after filtration, washing and drying.In two obtained stannic selenides/polyethyleneimine composite material, polyethyleneimine is evenly coated at two stannic selenide hexagonal nano on pieces；There is excellent chemical property as anode material of lithium-ion battery, and its preparation method is simple, it is of low cost, there is wide industrial applications prospect.

Description

A kind of two stannic selenides/polyethyleneimine composite material and its preparation method and application
Technical field
The present invention relates to anode material of lithium-ion battery preparation fields, and in particular to a kind of two stannic selenides/polyethyleneimine Composite material and its preparation method and application.
Background technology
Lithium ion battery is produced as a kind of electrochemical energy storing device for occupying social leading position in portable electronic It is achieved in product (laptop, intelligent mobile equipment, tablet computer etc.), electric vehicle and instant-plugging hybrid-power electric vehicle Good application.Meanwhile sodium-ion battery due to sodium resource reserves enrich, it is environmental-friendly also have received widespread attention, sodium from The research and development of sub- battery can be mitigated to a certain extent because the battery that lithium resource shortage triggers develops limitation problem, it is considered to be Next-generation electric powered motor power supply and extensive energy-accumulating power station match somebody with somebody the ideal chose of stand-by power source.
In past tens year, researcher the positive electrode of sodium-ion battery has been carried out it is widely studied, but It is still at an early stage to the research of anode material of lithium-ion battery.The experimental results show transition metal selenides super The fields such as conductor, infrared electro device, anode material of lithium-ion battery and solar cell are widely used, and two selenizings Tin even more causes the extensive concern of scientific worker since synthesis technology is simple.Meanwhile two stannic selenide as sodium-ion battery Negative material also has higher initial specific capacities.
At present, two stannic selenides that various methods are prepared, structure are mainly that graininess, sheet and sheet reunite what is formed It is flower-shaped.Wherein, granular two stannic selenide is easily reunited in sodium-ion battery charge and discharge process, so as to reduce sodium-ion battery Cycle life；Two flower-shaped stannic selenides, since its polymerization is also than more serious, are also influenced compared to two stannic selenides of sheet The chemical property of battery.And in existing preparation process, it is common to use the extremely toxic substances such as two selenizing selenium and hydrazine are as former Material seriously limits the industrialization production of two stannic selenides.
Further, since two stannic selenides can still generate larger volume expansion during deintercalation sodium ion, so as to greatly Reduce its cyclical stability as electrode material.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of good dispersion, almost soilless sticking, shape Uniform two stannic selenides/polyethyleneimine composite material.
Another object of the present invention is to provide a kind of simple for process, asepsis environment-protecting, it is reproducible, workable, into Originally the method that one step hydro thermal method that is low, being conducive to industrialization large-scale production prepares two stannic selenides/polyethyleneimine composite material.
Another object of the present invention is to provide a kind of be applied in sodium-ion battery with high charge-discharge specific capacity, well The negative material containing above-mentioned two stannic selenides/polyethyleneimine composite material of high rate performance and stable circulation performance.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of two stannic selenides/polyethyleneimine composite material, comprises the following steps：Selenium powder is dissolved in inertia In the sodium borohydride solution of gas saturation, solution containing selenium powder is obtained；Selenium tin molar ratio according to preparing needed for two stannic selenides will contain Selenium powder solution and the mixing of tin source aqueous solution, obtain mixed solution, polyethyleneimine are added in into mixed solution, be sufficiently stirred laggard Row hydro-thermal reaction；Product obtained by the reaction obtains two stannic selenides/polyethyleneimine composite material after filtration, washing and drying.
The preparation method of two stannic selenides/polyethyleneimine composite material of the present invention further includes following preferred embodiment：
In preferred scheme, in the tin source aqueous solution, the concentration of tin source is 0.05~0.15mol/L, described to contain selenium powder In solution, the concentration of selenium powder is 0.05~0.35mol/L；, in the sodium borohydride solution, the concentration of sodium borohydride for 0.2~ 0.6mol/L。
In the more preferable tin source aqueous solution, the concentration of tin source is 0.08~0.12mol/L.
In more preferably described solution containing selenium powder, the concentration of selenium powder is 0.1~0.3mol/L.
In the more preferable sodium borohydride solution, the concentration of sodium borohydride is 0.3~0.5mol/L.
In preferred scheme, the molecular weight of polyethyleneimine is 300~5000, more preferably 600-2000.
In preferred scheme, hydrothermal temperature is 150~210 DEG C, the hydro-thermal reaction time 18-30h.
More preferable hydrothermal temperature is 160~200 DEG C, the hydro-thermal reaction time 20-25h.
In preferred scheme, the inert gas saturation is before sodium borohydride is added in, and more than 5min is passed through into water Inert gas, inert gas are passed through flow velocity more than 10mL/min.
5~10min inert gases are more preferably passed through into water, reach saturation.
More preferable inert gas is passed through 10~20mL/min of flow velocity.
In preferred scheme, the tin source is stanniferous inorganic matter.
The stanniferous inorganic matter be more preferably butter of tin or anhydrous stannic chloride with the crystallization water in one kind or It is several.More preferable stannic chloride pentahydrate.
In preferred scheme, the ratio of selenium tin element gross mass is 1 in the quality and mixed solution of polyethyleneimine：1~9. The ratio of selenium tin element gross mass is 1 in the quality and solution of more preferable polyethyleneimine：2~7.
Hexagonal nano chip architecture, poly- second is presented in two stannic selenides in two stannic selenides/polyethyleneimine composite material of the present invention Alkene imines is evenly coated at two stannic selenide hexagonal nano on pieces；Two stannic selenides account for the 50~90% of composite material gross mass.
In preferred scheme, the thickness of the two stannic selenides hexagonal nano-flake is 5~30nm, and the length of side is 30~200nm.
Solution containing selenium powder and tin source aqueous solution are mixed according to the molar ratio of selenium and tin for 2.
The solution of the present invention, which further includes, applies two stannic selenides/polyethyleneimine composite material as sodium ion electricity Pond negative material.
Two stannic selenides produced by the present invention/polyethyleneimine composite material prepares cathode：By two stannic selenides/polyethyleneimine Composite material is with conductive black and sodium alginate binding agent according to 8:1:1 mass ratio is ground, and is added in after being sufficiently mixed Deionized water forms uniform paste, and coated in test electrode is used as on copper foil, button is made using metallic sodium as to electrode Battery, electrolyte are 1M NaClO4/EC:DMC(1:1)+5wt.%FEC, charging and discharging currents density used in test loop performance For 200mA/g.
Beneficial effects of the present invention：
The method of two stannic selenides of preparation/polyethyleneimine composite material of the present invention is simple and reliable, environmentally protective, operable Property it is strong, environmental-friendly, of low cost, have wide industrial applications prospect.Inventor is by using nontoxic or less toxic Raw material using one step hydro thermal method, prepares that shape is uniform, two stannic selenides/polyethyleneimine composite material of good dispersion.This hair It is bright during two stannic selenides are prepared, used raw material makes its preparation process more environmentally-friendly, has to be nontoxic or less toxic Important realistic meaning.And be only just prepared by one step hydro thermal method shape uniformly, two stannic selenides/polyethylene of good dispersion Imines composite material is even more that those skilled in the art are difficult to what is expected.
In addition, the reaction active site of the composite material of the present invention is high, electronic conductivity is high, can largely alleviate two The volume expansion that stannic selenide generates during deintercalation sodium ion, and polyethyleneimine can effectively reduce tin diselenide nano-plate Surface potential, reduce surface impedance, increase the diffusion velocity of surface ion.
As the composite material obtained by the method for the present invention on the premise of height ratio capacity is ensured, electrode material can be obviously improved The high rate performance and stable circulation performance of material can be prepared steady with high specific discharge capacity, excellent high rate performance and Xun Huan The sodium-ion battery of qualitative energy.
Description of the drawings
【Fig. 1】For the X ray diffracting spectrum (XRD) of two stannic selenides made from embodiment 1/polyethyleneimine composite material；
【Fig. 2】For the scanning electron microscope (SEM) photograph (SEM) of two stannic selenides made from embodiment 1/polyethyleneimine composite material；
【Fig. 3】For the constant current of the sodium-ion battery of two stannic selenides made from embodiment 1/polyethyleneimine composite material assembling Charge-discharge performance figure；
【Fig. 4】For the multiplying power of the sodium-ion battery of two stannic selenides made from embodiment 1/polyethyleneimine composite material assembling Performance map.The different current density of digital representation in figure on curve, unit mA/g.
Specific embodiment
Following embodiment is intended to be described in further details present invention；And the protection domain of the claims in the present invention It is not limited by the example.
Embodiment 1
5mmol stannic chloride pentahydrates are weighed first be dissolved in 50mL deionized waters and stir 10min, be allowed to whole dissolvings.Separately 50mL water is taken, first leads to 5min nitrogen, 20mmol sodium borohydrides is then added in, is sufficiently stirred, all after dissolving, adds in 10mmol selenium Powder stirs 30min, is allowed to whole dissolvings.Then above two solution is mixed, add in 0.4g molecular weight be 1200 it is poly- Aziridine after stirring 1h, is moved in reaction kettle, hydro-thermal reaction for 24 hours, then passes through hydro-thermal reaction product under the conditions of 200 DEG C It filters, washing obtains two stannic selenides/polyethyleneimine composite material after vacuum drying.XRD is not the result shows that two selenizing tin materials have There is any impurity.
It can be seen that the thickness of two stannic selenide hexagonal nano-flakes is about 10nm, the length of side about 60nm from Fig. 2 and Fig. 3.Two selenizings Tin hexagonal nano-flake is closely distributed in polyethyleneimine frame.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, is filled from constant current Discharge performance it can be seen from the figure that, under the constant-current discharge density of 200mA/g, 100 circle specific discharge capacity of Xun Huan may remain in 560mAh/g.From high rate performance figure, it can be seen that under the power-discharging density of 2000mA/g, still there is the specific capacity of 420mAh/g.
Embodiment 2
6mmol stannic chloride pentahydrates are weighed first be dissolved in 50mL deionized waters and stir 10min, be allowed to whole dissolvings.Separately 50mL water is taken, first leads to 5min nitrogen, 25mmol sodium borohydrides is then added in, is sufficiently stirred, all after dissolving, adds in 12mmol selenium Powder stirs 30min, is allowed to whole dissolvings.Then above two solution is mixed, add in 0.4g molecular weight be 1200 it is poly- Aziridine after stirring 1h, is moved in reaction kettle, hydro-thermal reaction for 24 hours, then passes through hydro-thermal reaction product under the conditions of 200 DEG C It filters, washing obtains two stannic selenides/polyethyleneimine composite material after vacuum drying.The thickness of two stannic selenide hexagonal nano-flakes About 15nm, the length of side about 80nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/ Under the constant-current discharge density of g, 100 circle specific discharge capacity of Xun Huan may remain in 550mAh/g.
Embodiment 3
6mmol stannic chloride pentahydrates are weighed first be dissolved in 50mL deionized waters and stir 10min, be allowed to whole dissolvings.Separately 50mL water is taken, first leads to 5min nitrogen, 25mmol sodium borohydrides is then added in, is sufficiently stirred, all after dissolving, adds in 12mmol selenium Powder stirs 30min, is allowed to whole dissolvings.Then above two solution is mixed, add in 0.4g molecular weight be 2000 it is poly- Aziridine after stirring 1h, is moved in reaction kettle, hydro-thermal reaction for 24 hours, then passes through hydro-thermal reaction product under the conditions of 200 DEG C It filters, washing obtains two stannic selenides/polyethyleneimine composite material after vacuum drying.The thickness of two stannic selenide hexagonal nano-flakes About 14nm, the length of side about 80nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/ Under the constant-current discharge density of g, 100 circle specific discharge capacity of Xun Huan may remain in 540mAh/g.
Embodiment 4
4mmol stannic chloride pentahydrates are weighed first be dissolved in 50mL deionized waters and stir 10min, be allowed to whole dissolvings.Separately 50mL water is taken, first leads to 5min nitrogen, 23mmol sodium borohydrides is then added in, is sufficiently stirred, all after dissolving, adds in 8mmol selenium Powder stirs 30min, is allowed to whole dissolvings.Then above two solution is mixed, add in 0.4g molecular weight be 800 it is poly- Aziridine after stirring 1h, is moved in reaction kettle, hydro-thermal reaction for 24 hours, then passes through hydro-thermal reaction product under the conditions of 200 DEG C It filters, washing obtains two stannic selenides/polyethyleneimine composite material after vacuum drying.The thickness of two stannic selenide hexagonal nano-flakes About 8nm, the length of side about 70nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/ Under the constant-current discharge density of g, 100 circle specific discharge capacity of Xun Huan may remain in 545mAh/g.
Embodiment 5
5mmol stannic chloride pentahydrates are weighed first be dissolved in 50mL deionized waters and stir 10min, be allowed to whole dissolvings.Separately 50mL water is taken, first leads to 5min nitrogen, 20mmol sodium borohydrides is then added in, is sufficiently stirred, all after dissolving, adds in 10mmol selenium Powder stirs 30min, is allowed to whole dissolvings.Then above two solution is mixed, add in 0.4g molecular weight be 1800 it is poly- Aziridine after stirring 1h, is moved in reaction kettle, then the hydro-thermal reaction 20h under the conditions of 200 DEG C passes through hydro-thermal reaction product It filters, washing obtains two stannic selenides/polyethyleneimine composite material after vacuum drying.The composite material has a little impurity.Two selenium The thickness for changing tin hexagonal nano-flake is about 13nm, the length of side about 70nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/ Under the constant-current discharge density of g, 100 circle specific discharge capacity of Xun Huan may remain in 500mAh/g.
Embodiment 6
5mmol stannic chloride pentahydrates are weighed first be dissolved in 50mL deionized waters and stir 10min, be allowed to whole dissolvings.Separately 50mL water is taken, first leads to 5min nitrogen, 20mmol sodium borohydrides is then added in, is sufficiently stirred, all after dissolving, adds in 10mmol selenium Powder stirs 30min, is allowed to whole dissolvings.Then above two solution is mixed, add in 0.4g molecular weight be 900 it is poly- Aziridine after stirring 1h, is moved in reaction kettle, hydro-thermal reaction for 24 hours, then passes through hydro-thermal reaction product under the conditions of 160 DEG C It filters, washing obtains two stannic selenides/polyethyleneimine composite material after vacuum drying.The composite material has a little impurity.Two selenium The thickness for changing tin hexagonal nano-flake is about 10nm, the length of side about 60nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/ Under the constant-current discharge density of g, 100 circle specific discharge capacity of Xun Huan may remain in 480mAh/g.
Embodiment 7
5mmol stannic chloride pentahydrates are weighed first be dissolved in 50mL deionized waters and stir 10min, be allowed to whole dissolvings.Separately 50mL water is taken, first leads to 5min nitrogen, 25mmol sodium borohydrides is then added in, is sufficiently stirred, all after dissolving, adds in 10mmol selenium Powder stirs 30min, is allowed to whole dissolvings.Then above two solution is mixed, add in 0.5g molecular weight be 3000 it is poly- Aziridine after stirring 1h, is moved in reaction kettle, then the hydro-thermal reaction 25h under the conditions of 180 DEG C passes through hydro-thermal reaction product It filters, washing obtains two stannic selenides/polyethyleneimine composite material after vacuum drying.The thickness of two stannic selenide hexagonal nano-flakes About 11nm, the length of side about 90nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/ Under the constant-current discharge density of g, 100 circle specific discharge capacity of Xun Huan may remain in 550mAh/g.
Embodiment 8
6mmol stannic chloride pentahydrates are weighed first be dissolved in 50mL deionized waters and stir 10min, be allowed to whole dissolvings.Separately 50mL water is taken, first leads to 10min argon gas, 25mmol sodium borohydrides is then added in, is sufficiently stirred, all after dissolving, adds in 12mmol Selenium powder stirs 30min, is allowed to whole dissolvings.Then above two solution is mixed, it is 1200 to add in 0.4g molecular weight Polyethyleneimine, stir 1h after, move in reaction kettle, under the conditions of 200 DEG C hydro-thermal reaction for 24 hours, then by hydro-thermal reaction product Through filtering, washing obtains two stannic selenides/polyethyleneimine composite material after vacuum drying.The thickness of two stannic selenide hexagonal nano-flakes Degree is about 12nm, the length of side about 90nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, in 200mA/ Under the constant-current discharge density of g, 100 circle specific discharge capacity of Xun Huan may remain in 500mAh/g.
Comparative example 1
6mmol stannic chloride pentahydrates are weighed first be dissolved in 50mL deionized waters and stir 10min, be allowed to whole dissolvings.Separately 50mL water is taken, is not passed through inert gas, 25mmol sodium borohydrides is then added in, is sufficiently stirred, all after dissolving, adds in 12mmol Selenium powder stirs 30min, is allowed to whole dissolvings.Then above two solution is mixed, it is 1200 to add in 0.4g molecular weight Polyethyleneimine, stir 1h after, move in reaction kettle, under the conditions of 200 DEG C hydro-thermal reaction for 24 hours, then by hydro-thermal reaction product Through filtering, wash, vacuum drying.XRD is not the result shows that product is two stannic selenides.
Comparative example 2
6mmol stannic chloride pentahydrates are weighed first be dissolved in 50mL deionized waters and stir 10min, be allowed to whole dissolvings.Separately 50mL water is taken, leads to 1min argon gas, 25mmol sodium borohydrides is then added in, is sufficiently stirred, all after dissolving, adds in 12mmol selenium Powder stirs 30min, is allowed to whole dissolvings.Then above two solution is mixed, add in 0.4g molecular weight be 1200 it is poly- Aziridine after stirring 1h, is moved in reaction kettle, hydro-thermal reaction for 24 hours, then passes through hydro-thermal reaction product under the conditions of 200 DEG C It filters, washs, vacuum drying.XRD is the result shows that product contains a large amount of impurity.
Button cell, 200mA/g are assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece Constant-current discharge density under, cycle 100 circle specific discharge capacities be maintained at 100mAh/g.

Claims (9)

1. the preparation method of a kind of two stannic selenides/polyethyleneimine composite material, which is characterized in that comprise the following steps：By selenium Powder is dissolved in the sodium borohydride solution of inert gas saturation, obtains solution containing selenium powder；According to the selenium tin prepared needed for two stannic selenides Molar ratio will contain selenium powder solution and the mixing of tin source aqueous solution, obtain mixed solution, polyethyleneimine is added in into mixed solution, fill Hydro-thermal reaction is carried out after dividing stirring；Product obtained by the reaction obtains two stannic selenides/polyethyleneimine after filtration, washing and drying Composite material.
2. preparation method according to claim 1, which is characterized in that in the tin source aqueous solution, the concentration of tin source is 0.05~0.15mol/L；In the solution containing selenium powder, the concentration of selenium powder is 0.05 ~ 0.35mol/L；The sodium borohydride solution In, the concentration of sodium borohydride is 0.2 ~ 0.6mol/L.
3. preparation method according to claim 1, which is characterized in that the hydrothermal temperature is 150 ~ 210 DEG C；It is described The hydro-thermal reaction time is 18-30 h.
4. according to claim 1-3 any one of them preparation methods, which is characterized in that the tin source is four with the crystallization water One or more of stannic chloride or anhydrous stannic chloride；The molecular weight of the polyethyleneimine is 300 ~ 5000.
5. according to claim 1-3 any one of them preparation methods, which is characterized in that the inert gas saturation is to add in Before sodium borohydride, 5 more than min inert gases are passed through into water, inert gas is passed through flow velocity more than 10mL/min.
6. according to claim 1-3 any one of them preparation methods, which is characterized in that the quality of the polyethyleneimine is with mixing The ratio for closing selenium tin element gross mass in solution is 1：1~1：9.
7. a kind of two stannic selenides/polyethyleneimine composite material, which is characterized in that hexagonal nano-flake knot is presented in two stannic selenide Structure, polyethyleneimine are evenly coated at two stannic selenide hexagonal nano on pieces；Two stannic selenides account for the 50 ~ 90% of composite material gross mass.
8. two stannic selenides according to claim 7/polyethyleneimine composite material, which is characterized in that two stannic selenides, six side The thickness of nanometer sheet is 5 ~ 30nm, and the length of side is 30 ~ 200nm.
9. the application of two stannic selenides/polyethyleneimine composite material described in claim 7 or 8, which is characterized in that by described two Stannic selenide/polyethyleneimine composite material is applied as anode material of lithium-ion battery.
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