CN106058213A - Tin diselenide/polyethyleneimine composite material and preparation method and application thereof - Google Patents

Tin diselenide/polyethyleneimine composite material and preparation method and application thereof Download PDF

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CN106058213A
CN106058213A CN201610628577.6A CN201610628577A CN106058213A CN 106058213 A CN106058213 A CN 106058213A CN 201610628577 A CN201610628577 A CN 201610628577A CN 106058213 A CN106058213 A CN 106058213A
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polymine
tin diselenide
preparation
tin
solution
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CN106058213B (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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  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a tin diselenide/polyethyleneimine composite material and a preparation method and application thereof. The preparation method comprises: dissolving selenium powder in a sodium borohydride solution with inert gas saturated to obtain a selenium-powder-containing solution, mixing the selenium-powder-containing solution with a tin sources aqueous solution according to a required ratio of selenium to tin for preparation of tin diselenide to obtain a mixed solution, adding polyethyleneimine into the mixed solution, performing full stirring, and carrying out a hydrothermal reaction; and filtering, washing and drying the obtained product to obtain the tin diselenide/polyethyleneimine composite material. In the obtained composite material, polyethyleneimine uniformly coats tin diselenide hexagonal nanosheets. The composite material can be taken as an anode material for a sodium-ion battery and has excellent electrochemical performance. The composite material is simple in preparation method and low in cost and has bright industrialized application prospects.

Description

A kind of two Tin diselenide .s/polymine composite and its preparation method and application
Technical field
The present invention relates to anode material of lithium-ion battery preparation field, be specifically related to a kind of two Tin diselenide .s/polymine Composite and its preparation method and application.
Background technology
Lithium ion battery, as a kind of electrochemical energy storing device occupying society's leading position, produces at portable electronic Product (notebook computer, intelligent mobile equipment, panel computer etc.), electric automobile and instant-plugging hybrid-power electric vehicle achieve Good application.Meanwhile, sodium-ion battery owing to sodium resource reserves are abundant, environmental friendliness also receives extensive concern, sodium from The research and development of sub-battery can relax to a certain extent because of lithium resource shortage cause battery development limitation problem it is considered to be Electric powered motor power supply of future generation and extensive energy-accumulating power station are equipped with the ideal chose of power supply.
In time decades in past, the positive electrode of sodium-ion battery has been carried out widely studied by researcher, but Research to anode material of lithium-ion battery is still at an early stage.The experimental results shows, transition metal selenides is super The fields such as conductor, infrared electro device, anode material of lithium-ion battery and solaode are widely used, and two selenizings Stannum is simple due to synthesis technique, causes the extensive concern of scientist especially.Meanwhile, two Tin diselenide .s are as sodium-ion battery Negative material also has higher initial specific capacities.
At present, two Tin diselenide .s that various methods are prepared, structure is mainly what graininess, lamellar and lamellar reunion were constituted Flower-shaped.Wherein, granular two Tin diselenide .s are easily reunited in sodium-ion battery charge and discharge process, thus reduce sodium-ion battery Cycle life；Two flower-shaped Tin diselenide .s, compared to two Tin diselenide .s of lamellar, owing to its polymerization also ratio is more serious, the most also affect 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, the industrialization seriously limiting two Tin diselenide .s produces.
Additionally, due to two Tin diselenide .s still can produce bigger volumetric expansion during deintercalation sodium ion, thus greatly Reduce its cyclical stability as electrode material.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that a kind of good dispersion, almost without reunion, shape Uniform two Tin diselenide .s/polymine composite.
Another object of the present invention is to provide that a kind of technique is simple, asepsis environment-protecting, reproducible, workable, become This method low, that be conducive to the one step hydro thermal method of industrialization large-scale production to prepare two Tin diselenide .s/polymine composite.
Another object of the present invention is to provide one to be applied in sodium-ion battery to have high charge-discharge specific capacity, good High rate performance and the negative material containing above-mentioned two Tin diselenide .s/polymine composite of stable circulation performance.
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of a kind of two Tin diselenide .s/polymine composite, comprises the following steps: selenium powder is dissolved in inertia In the sodium borohydride solution that gas is saturated, obtain containing selenium powder solution；To contain according to the selenium stannum mol ratio needed for preparing two Tin diselenide .s Selenium powder solution and stannum source aqueous solution, obtain mixed solution, adds polymine, be sufficiently stirred for laggard in mixed solution Row hydro-thermal reaction；The product that reaction obtains is through filtering, wash, obtaining two Tin diselenide .s/polymine composite after drying.
The preparation method of two Tin diselenide .s of the present invention/polymine composite also includes following preferred version:
Preferably in scheme, in the aqueous solution of described stannum source, the concentration of Xi Yuan is 0.05～0.15mol/L, described containing selenium powder In solution, the concentration of selenium powder is 0.05～0.35mol/L；, in described sodium borohydride solution, the concentration of sodium borohydride be 0.2～ 0.6mol/L。
In the aqueous solution of the most described stannum source, the concentration of Xi Yuan is 0.08～0.12mol/L.
More preferably described containing in selenium powder solution, the concentration of selenium powder is 0.1～0.3mol/L.
In the most described sodium borohydride solution, the concentration of sodium borohydride is 0.3～0.5mol/L.
Preferably in scheme, the molecular weight of polymine is 300～5000, more preferably 600-2000.
Preferably in scheme, hydrothermal temperature is 150～210 DEG C, and the hydro-thermal reaction time is 18-30h.
More preferably hydrothermal temperature is 160～200 DEG C, and the hydro-thermal reaction time is 20-25h.
Preferably in scheme, described noble gas is saturated is before adding sodium borohydride, is passed through more than 5min in water Noble gas, noble gas is passed through flow velocity more than 10mL/min.
In water, more preferably it is passed through 5～10min noble gases, reaches saturated.
More preferably noble gas is passed through flow velocity 10～20mL/min.
Preferably in scheme, described Xi Yuan is stanniferous inorganic matter.
One in the butter of tin of described stanniferous inorganic matter more preferably band water of crystallization or anhydrous stannic chloride or Several.More preferably stannic chloride pentahydrate.
Preferably in scheme, in the quality of polymine and mixed solution, the ratio of selenium tin element gross mass is 1:1～9. More preferably in the quality of polymine and solution, the ratio of selenium tin element gross mass is 1:2～7.
In two Tin diselenide .s of the present invention/polymine composite, two Tin diselenide .s present hexagonal nano chip architecture, poly-second Alkene imines is evenly coated on two Tin diselenide. hexagonal nano-flakes；Two Tin diselenide .s account for the 50～90% of composite gross mass.
Preferably in scheme, the thickness of described two Tin diselenide. hexagonal nano-flakes is 5～30nm, and the length of side is 30～200nm.
It is 2 mixing containing selenium powder solution and stannum source aqueous solution according to the mol ratio of selenium and stannum.
The solution of the present invention also includes two described Tin diselenide .s/polymine composite application as sodium ion electricity Pond negative material.
Negative pole prepared by two Tin diselenide .s that the present invention prepares/polymine composite: by two Tin diselenide .s/polymine Composite is ground according to the mass ratio of 8:1:1 with conductive black and sodium alginate binding agent, adds after being sufficiently mixed Deionized water forms uniform pastel, is coated on Copper Foil as test electrode, makes button using metallic sodium as to electrode Battery, its electrolyte is 1M NaClO4/ EC:DMC (1:1)+5wt.%FEC, charging and discharging currents density used by test loop performance For 200mA/g.
Beneficial effects of the present invention:
The method of preparation two Tin diselenide .s of the present invention/polymine composite is simple and reliable, environmental protection, operable Property strong, environmental friendliness, with low cost, there is wide industrial applications prospect.Inventor is nontoxic or low toxicity by using Raw material, uses one step hydro thermal method, prepares shape uniform, two Tin diselenide .s of good dispersion/polymine composite.This Bright during preparation two Tin diselenide .s, the raw material used is nontoxic or low toxicity so that it is preparation process is more environmentally-friendly, has Important realistic meaning.And only by one step hydro thermal method just prepare shape uniformly, the two Tin diselenide .s/polyethylene of good dispersion Imines composite those skilled in the art especially are difficult to expect.
Additionally, the reaction active site of the composite of the present invention is high, electronic conductivity is high, can alleviate two to a great extent The volumetric expansion that Tin diselenide. produces during deintercalation sodium ion, and polymine can effectively reduce tin diselenide nano-plate Surface potential, reduce surface impedance, increase surface ion diffusion velocity.
By the composite obtained by the inventive method on the premise of ensureing height ratio capacity, it is possible to be obviously improved electrode material The high rate performance of material and stable circulation performance, can prepare and have high specific discharge capacity, excellent high rate performance and circulation surely The sodium-ion battery of qualitative energy.
Accompanying drawing explanation
[Fig. 1] is the X ray diffracting spectrum (XRD) of two Tin diselenide .s/polymine composite that embodiment 1 prepares；
[Fig. 2] is the scanning electron microscope (SEM) photograph (SEM) of two Tin diselenide .s/polymine composite that embodiment 1 prepares；
[Fig. 3] is the constant current of the sodium-ion battery that two Tin diselenide .s/polymine composite that embodiment 1 prepares assembles Charge-discharge performance figure；
[Fig. 4] is the multiplying power of the sodium-ion battery that two Tin diselenide .s/polymine composite that embodiment 1 prepares assembles Performance map.In figure, the numeral on curve represents different electric current densities, and unit is mA/g.
Detailed description of the invention
Following example are 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
First weigh 5mmol stannic chloride pentahydrate and be dissolved in 50mL deionized water stirring 10min, be allowed to all dissolve.Separately Take 50mL water, first lead to 5min nitrogen, be subsequently adding 20mmol sodium borohydride, be sufficiently stirred for, after all dissolving, add 10mmol selenium Powder, stirs 30min, is allowed to all dissolve.Then above two solution is mixed, add 0.4g molecular weight be 1200 poly- Aziridine, after stirring 1h, moves in reactor, 200 DEG C of Water Under thermal responses 24h, then by hydro-thermal reaction product warp Sucking filtration, washing, obtain two Tin diselenide .s/polymine composite after vacuum drying.XRD result shows that two Tin diselenide. materials do not have There is any impurity.
Can be seen that from Fig. 2 Yu Fig. 3 the thickness of two Tin diselenide. hexagonal nano-flakes is about 10nm, the length of side about 60nm.Two selenizings Stannum hexagonal nano-flake is distributed in polymine framework closely.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell with sodium sheet, fills from constant current It can be seen that under the constant-current discharge density of 200mA/g, circulation 100 circle specific discharge capacity may remain in discharge performance figure 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
First weigh 6mmol stannic chloride pentahydrate and be dissolved in 50mL deionized water stirring 10min, be allowed to all dissolve.Separately Take 50mL water, first lead to 5min nitrogen, be subsequently adding 25mmol sodium borohydride, be sufficiently stirred for, after all dissolving, add 12mmol selenium Powder, stirs 30min, is allowed to all dissolve.Then above two solution is mixed, add 0.4g molecular weight be 1200 poly- Aziridine, after stirring 1h, moves in reactor, 200 DEG C of Water Under thermal responses 24h, then by hydro-thermal reaction product warp Sucking filtration, washing, obtain two Tin diselenide .s/polymine composite after vacuum drying.The thickness of two Tin diselenide. hexagonal nano-flakes It is about 15nm, the length of side about 80nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell, at 200mA/ with sodium sheet Under the constant-current discharge density of g, circulation 100 circle specific discharge capacity may remain in 550mAh/g.
Embodiment 3
First weigh 6mmol stannic chloride pentahydrate and be dissolved in 50mL deionized water stirring 10min, be allowed to all dissolve.Separately Take 50mL water, first lead to 5min nitrogen, be subsequently adding 25mmol sodium borohydride, be sufficiently stirred for, after all dissolving, add 12mmol selenium Powder, stirs 30min, is allowed to all dissolve.Then above two solution is mixed, add 0.4g molecular weight be 2000 poly- Aziridine, after stirring 1h, moves in reactor, 200 DEG C of Water Under thermal responses 24h, then by hydro-thermal reaction product warp Sucking filtration, washing, obtain two Tin diselenide .s/polymine composite after vacuum drying.The thickness of two Tin diselenide. hexagonal nano-flakes It is about 14nm, the length of side about 80nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell, at 200mA/ with sodium sheet Under the constant-current discharge density of g, circulation 100 circle specific discharge capacity may remain in 540mAh/g.
Embodiment 4
First weigh 4mmol stannic chloride pentahydrate and be dissolved in 50mL deionized water stirring 10min, be allowed to all dissolve.Separately Take 50mL water, first lead to 5min nitrogen, be subsequently adding 23mmol sodium borohydride, be sufficiently stirred for, after all dissolving, add 8mmol selenium Powder, stirs 30min, is allowed to all dissolve.Then above two solution is mixed, add 0.4g molecular weight be 800 poly- Aziridine, after stirring 1h, moves in reactor, 200 DEG C of Water Under thermal responses 24h, then by hydro-thermal reaction product warp Sucking filtration, washing, obtain two Tin diselenide .s/polymine composite after vacuum drying.The thickness of two Tin diselenide. hexagonal nano-flakes It is about 8nm, the length of side about 70nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell, at 200mA/ with sodium sheet Under the constant-current discharge density of g, circulation 100 circle specific discharge capacity may remain in 545mAh/g.
Embodiment 5
First weigh 5mmol stannic chloride pentahydrate and be dissolved in 50mL deionized water stirring 10min, be allowed to all dissolve.Separately Take 50mL water, first lead to 5min nitrogen, be subsequently adding 20mmol sodium borohydride, be sufficiently stirred for, after all dissolving, add 10mmol selenium Powder, stirs 30min, is allowed to all dissolve.Then above two solution is mixed, add 0.4g molecular weight be 1800 poly- Aziridine, after stirring 1h, moves in reactor, 200 DEG C of Water Under thermal responses 20h, then by hydro-thermal reaction product warp Sucking filtration, washing, obtain two Tin diselenide .s/polymine composite after vacuum drying.This composite has a little impurity.Two selenium The thickness changing stannum hexagonal nano-flake is about 13nm, the length of side about 70nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell, at 200mA/ with sodium sheet Under the constant-current discharge density of g, circulation 100 circle specific discharge capacity may remain in 500mAh/g.
Embodiment 6
First weigh 5mmol stannic chloride pentahydrate and be dissolved in 50mL deionized water stirring 10min, be allowed to all dissolve.Separately Take 50mL water, first lead to 5min nitrogen, be subsequently adding 20mmol sodium borohydride, be sufficiently stirred for, after all dissolving, add 10mmol selenium Powder, stirs 30min, is allowed to all dissolve.Then above two solution is mixed, add 0.4g molecular weight be 900 poly- Aziridine, after stirring 1h, moves in reactor, 160 DEG C of Water Under thermal responses 24h, then by hydro-thermal reaction product warp Sucking filtration, washing, obtain two Tin diselenide .s/polymine composite after vacuum drying.This composite has a little impurity.Two selenium The thickness changing stannum hexagonal nano-flake is about 10nm, the length of side about 60nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell, at 200mA/ with sodium sheet Under the constant-current discharge density of g, circulation 100 circle specific discharge capacity may remain in 480mAh/g.
Embodiment 7
First weigh 5mmol stannic chloride pentahydrate and be dissolved in 50mL deionized water stirring 10min, be allowed to all dissolve.Separately Take 50mL water, first lead to 5min nitrogen, be subsequently adding 25mmol sodium borohydride, be sufficiently stirred for, after all dissolving, add 10mmol selenium Powder, stirs 30min, is allowed to all dissolve.Then above two solution is mixed, add 0.5g molecular weight be 3000 poly- Aziridine, after stirring 1h, moves in reactor, 180 DEG C of Water Under thermal responses 25h, then by hydro-thermal reaction product warp Sucking filtration, washing, obtain two Tin diselenide .s/polymine composite after vacuum drying.The thickness of two Tin diselenide. hexagonal nano-flakes It is about 11nm, the length of side about 90nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell, at 200mA/ with sodium sheet Under the constant-current discharge density of g, circulation 100 circle specific discharge capacity may remain in 550mAh/g.
Embodiment 8
First weigh 6mmol stannic chloride pentahydrate and be dissolved in 50mL deionized water stirring 10min, be allowed to all dissolve.Separately Take 50mL water, first lead to 10min argon, be subsequently adding 25mmol sodium borohydride, be sufficiently stirred for, after all dissolving, add 12mmol Selenium powder, stirs 30min, is allowed to all dissolve.Then being mixed by above two solution, adding 0.4g molecular weight is 1200 Polymine, after stirring 1h, moves in reactor, 200 DEG C of Water Under thermal responses 24h, then by hydro-thermal reaction product Through sucking filtration, washing, after vacuum drying, obtain two Tin diselenide .s/polymine composite.The thickness of two Tin diselenide. hexagonal nano-flakes Degree is about 12nm, the length of side about 90nm.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell, at 200mA/ with sodium sheet Under the constant-current discharge density of g, circulation 100 circle specific discharge capacity may remain in 500mAh/g.
Comparative example 1
First weigh 6mmol stannic chloride pentahydrate and be dissolved in 50mL deionized water stirring 10min, be allowed to all dissolve.Separately Take 50mL water, be not passed through noble gas, be subsequently adding 25mmol sodium borohydride, be sufficiently stirred for, after all dissolving, add 12mmol Selenium powder, stirs 30min, is allowed to all dissolve.Then being mixed by above two solution, adding 0.4g molecular weight is 1200 Polymine, after stirring 1h, moves in reactor, 200 DEG C of Water Under thermal responses 24h, then by hydro-thermal reaction product Through sucking filtration, washing, vacuum drying.XRD result shows that product is not two Tin diselenide .s.
Comparative example 2
First weigh 6mmol stannic chloride pentahydrate and be dissolved in 50mL deionized water stirring 10min, be allowed to all dissolve.Separately Take 50mL water, logical 1min argon, it is subsequently adding 25mmol sodium borohydride, is sufficiently stirred for, after all dissolving, add 12mmol selenium Powder, stirs 30min, is allowed to all dissolve.Then above two solution is mixed, add 0.4g molecular weight be 1200 poly- Aziridine, after stirring 1h, moves in reactor, 200 DEG C of Water Under thermal responses 24h, then by hydro-thermal reaction product warp Sucking filtration, washing, vacuum drying.XRD result shows that product contains a large amount of impurity.
The sodium-ion battery anode material using the present embodiment to prepare is assembled into button cell, 200mA/g with sodium sheet Constant-current discharge density under, circulation 100 circle specific discharge capacities be maintained at 100mAh/g.

Claims (10)

1. the preparation method of two Tin diselenide .s/polymine composite, it is characterised in that comprise the following steps: by selenium Powder is dissolved in the sodium borohydride solution that noble gas is saturated, obtains containing selenium powder solution；According to the selenium stannum prepared needed for two Tin diselenide .s Mol ratio will contain selenium powder solution and stannum source aqueous solution, obtain mixed solution, add polymine, fill in mixed solution Hydro-thermal reaction is carried out after dividing stirring；The product that reaction obtains is through filtering, wash, obtaining two Tin diselenide .s/polymine after drying Composite.
Preparation method the most according to claim 1, it is characterised in that in the aqueous solution of described stannum source, the concentration of Xi Yuan is 0.05～0.15mol/L；Described containing in selenium powder solution, the concentration of selenium powder is 0.05～0.35mol/L；Described sodium borohydride solution In, the concentration of sodium borohydride is 0.2～0.6mol/L.
Preparation method the most according to claim 1, it is characterised in that described hydrothermal temperature is 150～210 DEG C；Institute Stating the hydro-thermal reaction time is 18-30h.
4. according to the preparation method described in any one of claim 1-3, it is characterised in that described Xi Yuan is the four of band water of crystallization One or more in stannic chloride or anhydrous stannic chloride；The molecular weight of described polymine is 300～5000.
5. according to the preparation method described in any one of claim 1-3, it is characterised in that described noble gas is saturated is to add Before sodium borohydride, being passed through more than 5min noble gas in water, noble gas is passed through flow velocity more than 10mL/min.
Preparation method the most according to claim 5, it is characterised in that described noble gas is saturated is to add sodium borohydride Before, being passed through 5～10min noble gases in water, noble gas is passed through flow velocity 10～20mL/min.
7. according to the preparation method described in any one of claim 1-3, it is characterised in that the quality of described polymine is with mixed Closing the ratio of selenium tin element gross mass in solution is 1:1～1:9.
8. two Tin diselenide .s/polymine composite, it is characterised in that described two Tin diselenide .s present hexagonal nano-flake knot Structure, polymine is evenly coated on two Tin diselenide. hexagonal nano-flakes；Two Tin diselenide .s account for composite gross mass 50～ 90%.
Two Tin diselenide .s the most according to claim 8/polymine composite, it is characterised in that two Tin diselenide. six sides The thickness of nanometer sheet is 5～30nm, and the length of side is 30～200nm.
10. the application of two Tin diselenide .s described in claim 8 or 9/polymine composite, it is characterised in that by described Two Tin diselenide .s/polymine composite is applied as anode material of lithium-ion battery.
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CN107352515A (en) * 2017-07-06 2017-11-17 陕西科技大学 A kind of brilliant method of hydro-thermal method synthesis stannic selenide micron
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CN114796485A (en) * 2022-02-25 2022-07-29 中南大学湘雅医院 Preparation of Sn nanosheet and composite material thereof and application of Sn nanosheet in acoustodynamic antibiosis

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