CN105185989A - Conductive polymer/SnSe<x> nanoflower anode composite material of sodium-ion cell and preparation method of conductive polymer/SnSe<x> nanoflower anode composite material - Google Patents

Conductive polymer/SnSe<x> nanoflower anode composite material of sodium-ion cell and preparation method of conductive polymer/SnSe<x> nanoflower anode composite material Download PDF

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CN105185989A
CN105185989A CN201510481626.3A CN201510481626A CN105185989A CN 105185989 A CN105185989 A CN 105185989A CN 201510481626 A CN201510481626 A CN 201510481626A CN 105185989 A CN105185989 A CN 105185989A
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snse
nano flower
nanoflower
composite material
anode material
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CN105185989B (en
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张治安
赵星星
张娟
李劼
赖延清
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

Abstract

The invention discloses a conductive polymer/SnSe<x> nanoflower anode composite material of a sodium-ion cell and a preparation method of the conductive polymer/SnSe<x> nanoflower anode composite material. The anode composite material is a three-dimensional structure material which is formed by evenly coating the surface of the SnSe<x> nanoflower with a conductive polymer; and the preparation method comprises the following steps: firstly, synthesizing the SnSe<x> nanoflower through a solvothermal method; secondly, ultrasonically dispersing the synthesized SnSe<x> nanoflower into deionized water; and finally coating the surface of the SnSe<x> nanoflower with a layer of conductive polymer through in-situ chemical polymerization reaction, so as to obtain the conductive polymer/SnSe<x> nanoflower anode composite material. The polypyrrole/SnSe<x> nanoflower composite material synthesized by the method is good in dispersity and regular and uniform in shape; through a test, the polypyrrole/SnSe<x> nanoflower composite material has high charge-discharge specific capacity, stable cycle performance and good rate capability after being prepared into a half-cell as a sodium-ion cell anode material; and the preparation method of the composite material is simple, reliable, good in process repeatability, high in operability and friendly to environment, and has a very wide application prospect.

Description

A kind of sodium-ion battery conducting polymer/SnSe xnano flower anode material and preparation method thereof
Technical field
The present invention relates to a kind of sodium-ion battery conducting polymer/SnSe xnano flower anode material and preparation method thereof, belongs to sodium-ion battery field.
Background technology
Lithium ion battery is current prevailing electrochemical energy storage system, along with popularizing rapidly of the mobile devices such as PC, video camera, mobile phone, and its application prospect good in electric motor car, hybrid vehicle, the demand of lithium battery constantly increases.But the price of lithium raises, the reserves bottleneck becoming batch production, large scale business such as limited.Sodium-ion battery is because sodium resource reserves are abundant, environmental friendliness receives extensive concern, the research and development of sodium-ion battery can relax the battery development limitation problem because lithium resource shortage causes to a certain extent, are considered to alternative lithium ion battery is equipped with power supply ideal chose as electric powered motor power supply of future generation and extensive energy-accumulating power station.Because the ionic radius (0.102nm) of sodium ion is than the ionic radius (0.76nm) large 55% of lithium ion, make sodium ion embed in battery material with deviate from more difficult than lithium ion, positive and negative electrode material is the core component of battery, its performance directly determines the chemical property of battery, thus, exploitation excellent performance, cheap anode material of lithium-ion battery will become the emphasis of research, also be significant challenge of current sodium-ion battery development.
Result of study shows, tin selenides (comprises SnSe and SnSe 2) be a kind of important IV ~ VI compound semiconductor, be widely used in fields such as resistance-variable storing device, infrared electro device, lithium ion battery negative material and solar cells.Tin selenides also has very high initial specific capacities as sodium cell negative pole material, but due to itself low electrons/ions conductivity and in removal lithium embedded process serious volumetric expansion make its cyclical stability extremely low.Therefore how to improve the cyclical stability of tin selenides, become the key that tin selenides is studied as anode material of lithium-ion battery.At present, tin selenides causes its capacity rapid decay in deintercalation sodium process method due to volumetric expansion is not also effectively slowed down.And up to the present, also do not synthesize tin selenides nano flower and the technology of composite material prepared by polypyrrole and tin selenides nano flower effective compound, more there is no related compound material as the relevant report of sode cell negative material.
Summary of the invention
For the defect that existing sodium-ion battery material exists, the object of the invention is to be to provide a kind of conducting polymer/SnSe that can be used for preparing the sodium-ion battery with high charge-discharge specific capacity, good high rate performance and long circulation life xnano flower anode material.
Another object of the present invention is that to be to provide a kind of technique simple, reproducible, workable, and environmental friendliness, what have wide application prospect prepares polypyrrole/SnSe xthe method of nano flower anode material.
In order to realize technical purpose of the present invention, the invention provides this composite material is evenly be coated on SnSe by conducting polymer xthe three-dimensional flower-shaped compound structure that nano flower surface is formed, X is 1 ~ 2, described SnSe xnano flower is by SnSe xnanometer sheet is assembled into three-dimensional flower shape.
Described SnSe xnano flower Tin tetrachloride pentahydrate, selenium oxide and Phen is joined in oleyl amine solution to be obtained by solvent structure.
Described conducting polymer is preferably polypyrrole, polyaniline or polythiophene.
Conducting polymer is evenly coated on SnSe xnano flower surface is at obtained SnSe xnano flower surface is obtained by corresponding polymer monomer home position polymerization reaction.
Polypyrrole most preferably is in described conducting polymer.Described three-dimensional flower-shaped compound structure is that pyrrole monomer is coated on SnSe by chemistry polymerizing in situ reaction xnano flower surface obtains.
Preferably comprise polypyrrole/SnSe xnano flower is at interior conducting polymer/SnSe xnano flower anode material granular size is 500 ~ 1000nm.
Polypyrrole/the SnSe preferably included xnano flower is at interior conducting polymer/SnSe xsnSe in nano flower anode material xnano flower is by SnSe xnanometer sheet assembles, and the lamellar spacing of nanometer sheet is 25 ~ 50nm.
Preferred polypyrrole/SnSe xnano flower is at interior conducting polymer/SnSe xsnSe in nano flower anode material xthe quality of nano flower accounts for 60 ~ 90% of described anode material gross mass.
Polypyrrole is coated on SnSe by chemistry polymerizing in situ reaction xnano flower surface, the thickness of polypyrrole is 5 ~ 20nm, and this thickness controls by the amount adding pyrrole monomer.
The present invention also aims to provide and a kind ofly prepare described polypyrrole/SnSe xthe method of nano flower anode material, the method comprises the following steps:
1) Tin tetrachloride pentahydrate, selenium oxide and Phen join in oleyl amine solution, the solution that (preferably 0.5 ~ 2h is advisable) obtains transparent clarification is stirred at 65 ~ 75 DEG C, then solution is transferred in autoclave, at 175 ~ 185 DEG C, carry out solvent thermal reaction, cooling is centrifugal afterwards and drying obtains SnSe xnano flower.
2) by step 1) SnSe of gained xthe deionized water for ultrasonic that joins nano flower and surfactant stirs (preferably 3 ~ 5h is advisable) and obtains even suspension-turbid liquid, then add pyrrole monomer and stir (preferably 1 ~ 2h is advisable) at 0 ~ 5 DEG C, slowly drip ammonium persulfate solution subsequently, polymerization reaction take place under Keep agitation condition, can obtain polypyrrole/SnSe finally by after centrifugal drying xnano flower anode material.
Of the present inventionly prepare polypyrrole/SnSe xthe method of nano flower anode material also comprises following preferred version:
Step 1 in preferred scheme) in Tin tetrachloride pentahydrate be 1:1 ~ 2 with the ratio of the amount of substance of selenium oxide.
Step 1 in preferred scheme) in the mass ratio of Tin tetrachloride pentahydrate and Phen be 10 ~ 5:1.
Step 2 in preferred scheme) in surfactant comprise softex kw, neopelex, polyvinylpyrrolidone etc.
Step 2 in preferred scheme) middle SnSe xthe mass ratio of nano flower and surfactant is 10 ~ 5:1.
Step 2 in preferred scheme) middle SnSe xthe solid-to-liquid ratio of nano flower and pyrrole monomer is 1g:0.2 ~ 5ml.
Step 2 in preferred scheme) in the mol ratio of pyrrole monomer and ammonium persulfate be 0.8 ~ 1.2:1.
Step 1 in preferred scheme) middle solvent thermal reaction 22 ~ 26h.
Step 2 in preferred scheme) middle polymerization reaction 3 ~ 6h.
Polypyrrole/SnSe prepared by the present invention xthe sodium-ion battery chemical property assay method of nano flower anode material:
Take the polypyrrole/SnSe of a certain amount of above-mentioned synthesis xnano flower anode material, add 10wt% conductive black as conductive agent, 10wt% sodium alginate is as binding agent, add a small amount of water and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using sodium metal as to electrode, its electrolyte is 1MNaClO 4/ EC:DEC (1:1)+5wt%FEC, test charging and discharging currents density is 500mA/g.
Beneficial effect of the present invention: first the present invention prepares SnSe by solvent thermal reaction xnano flower, then adopt chemistry polymerizing in situ method further by conducting polymer as polypyrrole is evenly coated on SnSe xnano flower surface, obtains a kind of conducting polymer/SnSe xnano flower anode material, good dispersion, regular shape is even, and it can be used for preparing the sodium-ion battery with high charge-discharge specific capacity, good high rate performance and long circulation life.Hinge structure, it has following advantage:
The present invention has successfully obtained SnSe first xnano flower three-dimensional structure, and obtain conducting polymer/SnSe by the home position polymerization reaction of the polymer such as polypyrrole more on this basis xnano flower anode material, this material structure is conducive to the contact promoting active material and electrolyte, shortens sodium ion transmission range, thus effectively improves the electrochemical utilization rate of active material.Meanwhile, nanometer flower structure can suppress the volumetric expansion of material to a certain extent, improves its structural stability in charge and discharge process, thus improves cycle performance of battery.After testing, polypyrrole/SnSe of the present invention xin nano flower anode material, the polypyrrole of chemistry polymerizing in situ is evenly coated on SnSe xnano flower surface, forms a kind of Core-shell structure material, can effectively improve anode material monolithic conductive, simultaneously to SnSe xchange in volume in charge and discharge process serves certain buffering inhibitory action.During as anode material of lithium-ion battery, there is very high charging and discharging capacity, good cycle performance and high rate performance.
Of the present invention operation is simple and reliable, selects Phen to coordinate with oleyl amine solution in preparation process especially, not only successfully obtains material required for the present invention, and obtained three-dimensional structure pattern is good, good process repeatability, workable, environmental friendliness, has boundless application prospect.
Accompanying drawing explanation
[Fig. 1] is polypyrrole/SnSe in embodiment 1 xthe X ray diffracting spectrum (XRD) of nano flower anode material;
Polypyrrole/SnSe that [Fig. 2] obtains for embodiment 1 xthe scanning electron microscope (SEM) photograph (SEM) of nano flower anode material;
Polypyrrole/SnSe that [Fig. 3] obtains for embodiment 1 xthe constant current charge-discharge performance map of the sodium-ion battery of nano flower anode material assembling;
Polypyrrole/SnSe that [Fig. 4] obtains for embodiment 1 xthe high rate performance figure of the sodium-ion battery of nano flower anode material assembling.
Embodiment
Following examples are intended to be described in further details content of the present invention, instead of the restriction to the claims in the present invention protection range.
Embodiment 1
First taking 0.175g Tin tetrachloride pentahydrate, 0.055g selenium oxide and 0.035g Phen joins in 40ml oleyl amine, at 70 DEG C, the solution that 2h obtains transparent clarification is stirred in oil bath, then solution is transferred in autoclave, at 180 DEG C, carry out solvent thermal reaction 24h, cooling is centrifugal afterwards and drying obtains SnSe xnano flower.
Take 0.2gSnSe xnano flower and 0.02g softex kw join deionized water for ultrasonic 5h, then under 0 DEG C of condition of ice bath, add 0.4ml pyrrole monomer continue to stir 2h, then slowly dripping 57ml concentration is the ammonium persulfate solution of 0.1mol/L, polymerization reaction take place 3h under Keep agitation condition, can obtain polypyrrole/SnSe xnano flower anode material.
The sode cell composite negative pole material adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and its material list seeks peace chemical property as shown in the figure:
Fig. 1 contrast standard diffracting spectrum is known, polypyrrole/SnSe xdiffraction maximum main in nano flower composite material and the SnSe of rhombic system match (JCPDSNO.48 ~ 1224); All the other use peaks of " " mark corresponding be the SnSe of hexagonal crystal system 2(JCPDSNO.48 ~ 1224), illustrate SnSe in composite material xby SnSe and SnSe 2two kinds of compound compositions.
Can find out in Fig. 2 and successfully synthesize flower-shaped polypyrrole/SnSe xcomposite material, this material is assembled by nanometer sheet, and the thickness of nanometer sheet is about 30nm.
Show in Fig. 3 to adopt polypyrrole/SnSe xthe electrode that nano flower anode material is made, at room temperature when 500mA/g constant-current discharge, circulation 200 circle specific capacity still can remain on 350mAh/g; Show good cycle performance.
Show in Fig. 4 to adopt polypyrrole/SnSe xthe high rate performance figure of electrode respective battery under different discharge-rate that nano flower anode material is made, can find that this composite material has excellent high rate performance, under large multiplying power 1600mA/g, capacity still can remain on 358mAh/g, and after current density slowly gets back to 200mA/g by big current, capacity is returned to 450mAh/g again.
Embodiment 2
First taking 0.175g Tin tetrachloride pentahydrate, 0.055g selenium oxide and 0.018g Phen joins in 40ml oleyl amine, at 70 DEG C, the solution that 2h obtains transparent clarification is stirred in oil bath, then solution is transferred in autoclave, at 180 DEG C, carry out solvent thermal reaction 24h, cooling is centrifugal afterwards and drying obtains SnSe xnano flower.
Take 0.2gSnSe xnano flower and 0.02g softex kw join deionized water for ultrasonic 3h, then under 0 DEG C of condition of ice bath, add 0.4ml pyrrole monomer continue to stir 1h, then slowly dripping 57ml concentration is the ammonium persulfate solution of 0.1mol/L, polymerization reaction take place 3h under Keep agitation condition, can obtain polypyrrole/SnSex nano flower anode material.
Phosphorization tin/Graphene the anode material adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and at room temperature, during with 500mA/g constant-current discharge, circulation 80 circle specific capacity still can remain on 400mAh/g; Show good cycle performance.
Embodiment 3
First taking 0.175g Tin tetrachloride pentahydrate, 0.055g selenium oxide and 0.035g Phen joins in 40ml oleyl amine, at 75 DEG C, the solution that 2h obtains transparent clarification is stirred in oil bath, then solution is transferred in autoclave, at 180 DEG C, carry out solvent thermal reaction 24h, cooling is centrifugal afterwards and drying obtains SnSe xnano flower.
Take 0.2gSnSe xnano flower and 0.02g softex kw join deionized water for ultrasonic 5h, then under 0 DEG C of condition of ice bath, add 0.8ml pyrrole monomer continue to stir 2h, then slowly dripping 114ml concentration is the ammonium persulfate solution of 0.1mol/L, polymerization reaction take place 6h under Keep agitation condition, can obtain polypyrrole/SnSe xnano flower anode material.
Phosphorization tin/Graphene the anode material adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and at room temperature, during with 500mA/g constant-current discharge, circulation 80 circle specific capacity still can remain on 420mAh/g; Show good cycle performance.
Embodiment 4
First taking 0.175g Tin tetrachloride pentahydrate, 0.11g selenium oxide and 0.035g Phen joins in 40ml oleyl amine, at 70 DEG C, the solution that 2h obtains transparent clarification is stirred in oil bath, then solution is transferred in autoclave, at 180 DEG C, carry out solvent thermal reaction 24h, cooling is centrifugal afterwards and drying obtains SnSe xnano flower.
Take 0.2gSnSe xnano flower and 0.02g softex kw join deionized water for ultrasonic 5h, then under 0 DEG C of condition of ice bath, add 0.4ml pyrrole monomer continue to stir 2h, then slowly dripping 57ml concentration is the ammonium persulfate solution of 0.1mol/L, polymerization reaction take place 3h under Keep agitation condition, can obtain polypyrrole/SnSe xnano flower anode material.
Embodiment 5
First taking 0.175g Tin tetrachloride pentahydrate, 0.055g selenium oxide and 0.035g Phen joins in 40ml oleyl amine, at 65 DEG C, the solution that 2h obtains transparent clarification is stirred in oil bath, then solution is transferred in autoclave, at 185 DEG C, carry out solvent thermal reaction 24h, cooling is centrifugal afterwards and drying obtains SnSe xnano flower.
Take 0.2gSnSe xnano flower and 0.04g softex kw join deionized water for ultrasonic 5h, then under 0 DEG C of condition of ice bath, add 0.4ml pyrrole monomer continue to stir 2h, then slowly dripping 57ml concentration is the ammonium persulfate solution of 0.1mol/L, polymerization reaction take place 3h under Keep agitation condition, can obtain polypyrrole/SnSe xnano flower anode material.
Phosphorization tin/Graphene the anode material adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and at room temperature, during with 500mA/g constant-current discharge, circulation 80 circle specific capacity still can remain on 450mAh/g; Show good cycle performance.

Claims (10)

1. sodium-ion battery conducting polymer/SnSe xnano flower anode material, is characterized in that, this composite material is evenly coated on SnSe by conducting polymer xthe three-dimensional flower-shaped compound structure that nano flower surface is formed, X is 1 ~ 2, described SnSe xnano flower is by SnSe xnanometer sheet is assembled into three-dimensional flower shape.
2. conducting polymer/SnSe according to claim 1 xnano flower anode material, is characterized in that, described SnSe xnano flower Tin tetrachloride pentahydrate, selenium oxide and Phen is joined in oleyl amine solution to be obtained by solvent structure.
3. conducting polymer/SnSe according to claim 1 xnano flower anode material, is characterized in that, described conducting polymer is polypyrrole, polyaniline or polythiophene.
4. conducting polymer/SnSe according to claim 1 xnano flower anode material, is characterized in that, described conducting polymer is polypyrrole, and described three-dimensional flower-shaped compound structure is that pyrrole monomer is coated on SnSe by chemistry polymerizing in situ reaction xnano flower surface obtains.
5. conducting polymer/SnSe according to claim 1 xnano flower anode material, is characterized in that, described SnSe xthe lamellar spacing of nanometer sheet is 25 ~ 50nm; The granular size of described composite material is 500 ~ 1000nm.
6. the method for the anode material of preparation described in claim 4 or 5, is characterized in that, comprise the following steps:
1) Tin tetrachloride pentahydrate, selenium oxide and Phen are joined in oleyl amine solution, the solution obtaining transparent clarification is stirred at 65 ~ 75 DEG C, then transfer in autoclave by solution, at 175 ~ 185 DEG C, carry out solvent thermal reaction, after cooling, centrifugal drying obtains SnSe xnano flower;
2) step 1 is taken) SnSe of gained xthe deionized water for ultrasonic that joins nano flower and surfactant stirs and obtains even suspension-turbid liquid, then add after pyrrole monomer stirs at 0 ~ 5 DEG C, slow dropping ammonium persulfate solution, polymerization reaction take place under Keep agitation condition, can obtain polypyrrole/SnSe finally by centrifugal drying xnano flower anode material.
7. method according to claim 6, is characterized in that, step 1) described in Tin tetrachloride pentahydrate be 1:1 ~ 2 with the ratio of the amount of substance of selenium oxide; Described Tin tetrachloride pentahydrate and the mass ratio of Phen are 10 ~ 5:1.
8. method according to claim 6, is characterized in that, step 2) described in surfactant be one in softex kw, neopelex, polyvinylpyrrolidone.
9. method according to claim 6, is characterized in that, step 2) described in SnSe xthe mass ratio of nano flower and surfactant is 10 ~ 5:1, SnSe xthe solid-to-liquid ratio of nano flower and pyrrole monomer is 1g:0.2 ~ 5ml, and the mol ratio of pyrrole monomer and ammonium persulfate is 0.8 ~ 1.2:1.
10. method according to claim 6, is characterized in that, step 1) middle solvent thermal reaction 22 ~ 26h;
Step 2) middle polymerization reaction 3 ~ 6h.
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CN106058213A (en) * 2016-08-03 2016-10-26 中南大学 Tin diselenide/polyethyleneimine composite material and preparation method and application thereof
CN106058213B (en) * 2016-08-03 2018-05-25 中南大学 A kind of two stannic selenides/polyethyleneimine composite material and its preparation method and application
CN106430998A (en) * 2016-09-28 2017-02-22 陕西科技大学 Bi mixed SnSe/oxidation-reduction graphite composite film and preparation method thereof
CN106430998B (en) * 2016-09-28 2019-03-05 陕西科技大学 Bi adulterates SnSe/ redox graphene complex film and preparation method thereof
CN107171019A (en) * 2017-04-18 2017-09-15 陕西科技大学 A kind of method that microwave-hydrothermal method prepares SnSe nano particles
CN109698326A (en) * 2017-10-23 2019-04-30 中国石油大学(华东) A kind of organic phosphorization tin/oxidized graphite composite material for sodium-ion battery cathode
CN109698326B (en) * 2017-10-23 2021-04-02 中国石油大学(华东) Organic tin phosphide/graphite oxide composite material for negative electrode of sodium-ion battery
CN110006959A (en) * 2019-04-12 2019-07-12 南京工业大学 A kind of p-n heterojunction structure SnSe/SnSe2Nanocomposite and its preparation method and application
CN110707308A (en) * 2019-10-23 2020-01-17 湖南立方新能源科技有限责任公司 Negative electrode sodium supplement additive, negative electrode material and sodium ion battery
CN110707308B (en) * 2019-10-23 2022-09-16 湖南钠方新能源科技有限责任公司 Negative electrode sodium supplement additive, negative electrode material and sodium ion battery

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