CN106571460B - A kind of binder free, selenium positive electrode of self supporting structure and preparation method thereof - Google Patents
A kind of binder free, selenium positive electrode of self supporting structure and preparation method thereof Download PDFInfo
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- CN106571460B CN106571460B CN201510650140.8A CN201510650140A CN106571460B CN 106571460 B CN106571460 B CN 106571460B CN 201510650140 A CN201510650140 A CN 201510650140A CN 106571460 B CN106571460 B CN 106571460B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- 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 present invention relates to a kind of binder frees, the selenium positive electrode of self supporting structure and preparation method thereof, include: step 1) obtains uniform selenous acid solution for selenium dioxide dissolution in deionized water, reducing agent is dissolved in selenous acid solution, obtain uniformly mixed solution, wherein, the molar concentration of the selenium dioxide is 0.01~1 mol/L, and the molar concentration of the reducing agent is 0.01~0.5 mol/L；Solution obtained in step 1) and conductive network structured substrate are placed in reaction kettle and heat 1~96 hour at a temperature of 50~250 DEG C by step 2；Step 3) will have the conductive network structured substrate dehydrated alcohol of deposit obtained in step 2 and deionized water is washed at least once, dry at a temperature of 40~100 DEG C, obtains the selenium material of binder free, self supporting structure.Have the characteristics that simple process, at low cost and morphology controllable, is a kind of preparation method for being expected to large-scale production.
Description
Technical field
The present invention relates to a kind of binder frees, the selenium positive electrode of self supporting structure and preparation method thereof, belong to energy wood
Material field.
Background technique
With the rapid development of economy, energy consumption is increasingly sharpened, lithium secondary battery is since it is with open-circuit voltage height, energy
Many advantages, such as metric density is big, has extended cycle life, pollution-free, memory-less effect is increasingly valued by people.With various
Development of the electronic product to " light, small, thin " direction, the serondary lithium battery of high-energy density are always the target that people pursue.But
Current commercialized anode material for lithium-ion batteries is concentrated mainly on the embedding lithium mechanism of lamellar compound, therefore capacity density has
Limit, is such as presently considered to the positive electrode LiFePO for most having business application future4, theoretical capacity density only has 170mAh/g.Cause
This, developing, there is the positive electrode of high-energy density to have great importance to the energy density for improving lithium ion battery.
In recent years, lithium-sulfur cell becomes the research hotspot in secondary cell field due to its high specific capacity.But sulphur is just
The disadvantages of there is also electronic isolation, shuttle effects for pole seriously, electrode volume effect is obvious.Elemental selenium as lithium secondary battery just
Pole material, since it has the electronic conductivity for being higher by than sulphur nearly 10 orders of magnitude, and advantages such as the comparable volume and capacity ratio of sulphur,
Gradually cause researcher concern (Cui Y, Abouimrane A, Lu J, etal.J Am Chem Soc, 2013,135
(21):8047-8056.).It has up to 3268mAh/ (cm3) volume and capacity ratio and 678mAh/g specific discharge capacity
(Luo C, Xu Y H, Zhu Y J, etal.Acs Nano, 2013,7 (9): 8003-8010.), are much higher by several frequently seen
Traditional positive electrode.Abouimrane etc. is put forward for the first time and confirms, selenium simple substance can be used as rechargeable lithium ion batteries and sodium from
Sub- battery positive electrode (Abouimrane A, Dambournet D, Chapman K W, etal.J Am Chem Soc,
2012,134(10):4505-8.).They have extensively studied the electrochemical reaction process of lithium anode Yu seleno anode, are putting
When electric, elemental selenium is gradually reduced to Li by lithium2Sen(n≥4)、Li2Se2And Li2Se；Charging process is then in contrast.
How the disadvantages of selenium anode equally exists shuttle effect during the work time, and capacity attenuation is fast slows down capacity attenuation
It is the key that improve lithium selenium secondary cell chemical property.Zhang etc. is prepared for mesoporous TiO 2-selenium combination electrode, utilizes
The meso-hole structure of titanium dioxide adsorbs more lithium selenides, and all discharge capacities of head of the battery under 0.1C multiplying power reach 481mAh/g, and 50
Zhou Houwei 158mAh/g (Zhang Zhian, Yang Xing, Wang Xiwen, etal.Solid State Ionics.2014,
260:101-106.).Kundu etc. is prepared for the selenium fiber that the diameter of in-stiu coating polypyrrole and graphene is 20~50 nanometers,
Reduce activation polarization using the cladding of polypyrrole, slows down the bulk effect of electrode using the cladding of graphene, improve battery
Capacity (Kundu Dipan, Krumeich Frank, Nesper Reinhard.Journal of Power Sources,
2013,236:112-117.).Liu et al. uses mechanical attrition method, prepares a kind of nanoporous selenium by template of calcium carbonate, follows
Specific capacity remains 230mAh/g (Liu L L, Hou Y Y, Wu X W, etal.Chemical after ring 20 weeks
Communications,2013,49(98):11515-11517.)。
But since the method for modifying of above-mentioned several pairs of selenium still cannot largely improve its cycle performance, to this
There are also very big rooms for promotion for the chemical property of kind material.For this purpose, exploring novel selenium anode structure and effectively to selenium
Method of modifying has great importance to cathode plate for lithium secondary battery performance is improved.
Summary of the invention
The purpose of the present invention is to provide a kind of high-performance binder free, the selenium positive electrode of self supporting structure and its preparations
Method.
Here, the present invention provide a kind of binder free, self supporting structure selenium positive electrode preparation method, feature exists
In, which comprises
Selenium dioxide dissolution is obtained uniform selenous acid solution by step 1) in deionized water, and reducing agent is dissolved in Asia
In selenic acid solution, uniformly mixed solution is obtained, wherein the molar concentration of the selenium dioxide is 0.01~1 mol/L, institute
The molar concentration for stating reducing agent is 0.01~0.5 mol/L；
Solution obtained in step 1) and conductive network structured substrate are placed in reaction kettle 50~250 by step 2)
It is heated 1~96 hour at a temperature of DEG C；
Step 3) by obtained in step 2) have deposit conductive network structured substrate dehydrated alcohol and go from
Sub- water washing is at least once, dry at a temperature of 40~100 DEG C, obtains the selenium material of binder free, self supporting structure.
It is substrate using conductive network structure in the present invention, it is sharp under hydrothermal conditions using selenium dioxide as selenium source
It by selenium dioxide in-situ reducing is elemental selenium with suitable reducing agent, and in-situ deposition is in conductive network structured substrate, from
And prepare the selenium positive electrode of a kind of binder free, self-supporting.The present invention essentially consists in, using selenium dioxide and and suitably
Reducing agent is raw material, by the reaction temperature of control system, reaction time, reducing agent type and reactant concentration, prepares nothing
The elemental selenium material of binder, self supporting structure, realizes the controlledly synthesis of its pattern and object phase.Then, it then is applied in lithium
Very high specific capacity, good cycle performance and rate capability are obtained in anode.Preparation method of the invention has technique
Simply, the features such as at low cost and morphology controllable is a kind of preparation method for being expected to large-scale production.This method without dispersing agent or
Selenium dioxide is reduced to elemental selenium using suitable reducing agent under hydrothermal conditions, and is deposited on electric conductivity by surfactant
On network structure substrate, obtain pattern uniformly, the elemental selenium deposited particles of size uniformity.The anti-of control reaction system can be passed through
Answer temperature, reaction time, reducing agent type and reactant concentration control the object phase and pattern of product.Utilize conductive network
The network structure and high conductivity of structured substrate can also serve as the conductive agent and collector of selenium anode, and directly by elemental selenium original position
It is deposited on carbon paper, removes the use of binder from, obtain the selenium anode of self supporting structure, mitigate the weight of positive electrode.It is made
The elemental selenium material of standby binder free, self supporting structure applies the positive electrode in lithium battery, do not need cladding carbon material or
Conductive polymer material can obtain very high capacity density, and cycle performance and rate capability well, in energy and material
Application field shows good application prospect.
In the present invention, reducing agent described in step 1) be hydrazine, it is ethylenediamine tetra-acetic acid, glucose, vitamin C, anti-bad
At least one of hematic acid.
Also, the ratio of the molar concentration of selenium dioxide described in step 1) and the reducing agent is 1:0.5~1:10, it is excellent
Select 1:0.5~1:5.
In the present invention, conductive network structured substrate described in step 2) is carbon fiber paper, carbon cloth, carbon nanotube
At least one of network, the film of graphene assembling, conducting polymer film, stainless (steel) wire, nickel foam, copper mesh.
In the present invention, step 2) further includes the preparation process of conductive network structured substrate: conductive network structure is served as a contrast
At least once, each ultrasonic time 5~60 minutes is rushed ultrasound with dehydrated alcohol and deionized water in dehydrated alcohol or acetone at bottom
It washes.
The present invention also provides a kind of binder frees of above-mentioned preparation method preparation, the selenium positive electrode of self supporting structure.Institute
The object phase and pattern for stating selenium positive electrode can be controlled by adjusting experiment condition, and pattern is uniform, even size distribution.
In the present invention, the object phase composition of the selenium positive electrode is monoclinic system elemental selenium, hexagonal crystal system elemental selenium or nothing
Shape elemental selenium.
In the present invention, the pattern of the selenium positive electrode is granules of selenium or aggregate, and the granule-morphology is spherical selenium
At least one of grain, regular polyhedron granules of selenium, the dendritic selenium of irregular tree, the fibrous selenium of dispersion, cotton-shaped selenium, having a size of 0.01
~50 microns.
Also, the spatial position of simple substance granules of selenium and conductive network structure is granules of selenium in conduction in the selenium positive electrode
Property network structure surface deposition or granules of selenium be interspersed in conductive network structure and deposit, the settled density of selenium simple substance is 0.01~
5 millis gram/cm.
Also, the granules of selenium deposited in the selenium positive electrode is at least one of brownish red, black, silver gray.
Detailed description of the invention
Fig. 1 a is the XRD diagram of the selenium positive electrode prepared in example 1；
Fig. 1 b is the SEM picture of the selenium positive electrode prepared in example 1；
Fig. 2 a is the XRD diagram of the selenium positive electrode prepared in example 2；
Fig. 2 b is the SEM picture of the selenium positive electrode prepared in example 2.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that following embodiments are only used for
Illustrate the present invention, is not intended to limit the present invention.
The present invention provides a kind of high-performance binder free, selenium positive electrode of self supporting structure and preparation method thereof.It is described
High-performance binder free, self supporting structure selenium positive electrode object phase and pattern can be controlled by adjusting experiment condition
System, and pattern is uniform, even size distribution；The preparation method is substrate using conductive network structure, using selenium dioxide
As selenium source, selenium dioxide is reduced to elemental selenium using suitable reducing agent under hydrothermal conditions, is deposited on conductive network
In structured substrate, to prepare the selenium positive electrode of a kind of binder free, self-supporting.The present invention essentially consists in, and utilizes dioxy
Change selenium with and suitable reducing agent be raw material, pass through the reaction temperature of control system, reaction time, reducing agent type and reaction
Object concentration prepares the elemental selenium material of binder free, self supporting structure, realizes the controlledly synthesis of its pattern and object phase.Then, then
It is applied and obtains very high specific capacity in lithium battery anode, good cycle performance and rate capability.
Preparation method of the invention includes: that the dissolution of a certain amount of selenium dioxide is obtained uniform sub- selenium in deionized water
Then suitable reducing agent is dissolved in uniform selenous acid solution by acid solution, stir 5~120 minutes at room temperature
Obtain uniform solution.Meanwhile conductive network structured substrate is cut into sizeable strip, in dehydrated alcohol or acetone
It middle ultrasonic 5~60 minutes, repeats ultrasound 1~5 time, is then rinsed again with dehydrated alcohol and deionized water.Then by above-mentioned mixing
Solution and substrate are placed in reaction kettle, are reacted under hydrothermal conditions, wherein the hydro-thermal heating temperature range is 50~250
DEG C, the hydro-thermal heating time range is 1~96 hour.After reaction, the substrate nothing with deposit that will be obtained
Water-ethanol and deionized water washing for several times, obtain binder free, self-supporting knot after dry several hours in 40~100 DEG C of baking ovens
The selenium material of structure.
Wherein, the preferred molar concentration of the selenium dioxide is 0.01~0.05 mol/L.Used reducing agent can
Think hydrazine, ethylenediamine tetra-acetic acid, glucose, ascorbic acid and other it is all be soluble in used in having in solvent
The compound of reproducibility, the molar concentration of reducing agent are 0.01~0.05 mol/L.
Also, the ratio of the molar concentration of selenium dioxide and used reducing agent be 1:0.5~1:10, preferably 1:0.5~
1:5。
Wherein, the substrate of material can be simple carbon fiber paper, cloth, carbon nano tube network, and the film of graphene assembling is led
Electric polymeric membrane, stainless (steel) wire, nickel foam, the high conductive network such as copper mesh.
Also, the substrate of material can be it is each after the modifying and decoratings such as N element doping, noble metal, polyaniline, polypyrrole
Kind high conductivity network.
Also, after obtaining self-supporting selenium anode one layer of conductive polymer material, carbon material or oxygen can be modified again on selenium surface
Compound etc..
Binder free provided by the invention, self supporting structure the feature of selenium positive electrode include:
(1) the object phase composition of material is monoclinic system elemental selenium, hexagonal crystal system elemental selenium or amorphous elemental selenium；
(2) pattern of material is granules of selenium or aggregate, which can be spherical granules of selenium, regular polyhedron selenium
The dendritic selenium of particle, irregular tree, the fibrous selenium of dispersion, cotton-shaped selenium, size is in 0.01-50 microns；
(3) spatial position of simple substance granules of selenium and carbon fiber can deposit for granules of selenium in carbon fiber surface in the material,
Granules of selenium is interspersed to be deposited in the carbon fibers；
(4) settled density of selenium simple substance can be 0.01~5.0 milli gram/cm in the material；
(5) granules of selenium deposited in the material can be brownish red, black, silver gray.
Compared with existing elemental selenium positive electrode and preparation method thereof, present invention is characterized in that simple process, cost
The features such as low and morphology controllable is a kind of preparation method for being expected to large-scale production；This method is not necessarily to dispersing agent or surface-active
Selenium dioxide is reduced to elemental selenium using suitable reducing agent under hydrothermal conditions, and is deposited on conductive network structure by agent
On substrate, obtain pattern uniformly, the elemental selenium deposited particles of size uniformity；Can by control reaction system reaction temperature,
Reaction time, reducing agent type and reactant concentration control the object phase and pattern of product, utilize conductive network structure lining
The network structure and high conductivity at bottom can also serve as the conductive agent and collector of selenium anode, and directly elemental selenium in-situ deposition exist
On carbon paper, remove the use of binder from, obtains the selenium anode of self supporting structure, mitigate the weight of positive electrode；Prepared nothing
Binder, self supporting structure elemental selenium material apply the positive electrode in lithium battery, do not need cladding carbon material or conductive high
Molecular material can obtain very high capacity density, and cycle performance and rate capability well, lead in energy and material application
Domain shows good application prospect.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then by 2mmol second
Ethylenediamine tetraacetic acid (EDTA) is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile carbon fiber paper being cut into greatly
Small suitable strip, ultrasound 10 minutes in dehydrated alcohol, repeats ultrasound 3 times, is then rinsed well again with dehydrated alcohol.So
Above-mentioned mixed solution and carbon fiber paper are placed in reaction kettle afterwards, 150 DEG C hydro-thermal reaction 24 hours.After reaction, it incites somebody to action
The dehydrated alcohol of the carbon fiber paper with deposit and deionized water arrived washs for several times, dry several hours in 60 DEG C of baking ovens
The selenium material of binder free, self supporting structure is obtained afterwards.
The sample is subjected to XRD and SEM characterization, respectively such as Fig. 1 a, shown in 1b.It can be seen that prepared sample from XRD result
Product are the monoclinic form of elemental selenium.SEM photograph shows that carbon paper is the carbon fiber network that diameter is 7 microns, simple substance granules of selenium
Be deposited on every carbon fiber surface, the pattern of granules of selenium is smooth spherical in surface, the diameter dimension of ball in 3-4 microns,
Depositing homogeneous, and settled density is 2 millis gram/cm, settled density is larger.
The Electrochemical Characterization of its lithium ion battery is displayed referring to the following table 1:
Table 1
。
Embodiment 2
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then by 2mmol second
Ethylenediamine tetraacetic acid (EDTA) is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile carbon fiber paper being cut into greatly
Small suitable strip, ultrasound 10 minutes in dehydrated alcohol, repeats ultrasound 3 times, is then rinsed well again with dehydrated alcohol.So
Above-mentioned mixed solution and carbon fiber paper are placed in reaction kettle afterwards, 180 DEG C hydro-thermal reaction 24 hours.After reaction, it incites somebody to action
The dehydrated alcohol of the carbon fiber paper with deposit and deionized water arrived washs for several times, dry several hours in 60 DEG C of baking ovens
The selenium material of binder free, self supporting structure is obtained afterwards.
The sample is subjected to XRD and SEM characterization, respectively such as Fig. 2 a, shown in 2b.It can be seen that prepared sample from XRD result
Product are the monoclinic form of elemental selenium.SEM photograph shows that carbon paper is the carbon fiber network that diameter is 7 microns, simple substance granules of selenium
It is deposited on carbon fiber surface, the pattern of granules of selenium is radial fiber, and the diameter dimension of selenium fiber is deposited in 2 microns
Density is 2 millis gram/cm, and settled density is moderate.
The Electrochemical Characterization of its lithium ion battery is displayed in table 1.
Embodiment 3
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then by 2mmol second
Ethylenediamine tetraacetic acid (EDTA) is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile carbon fiber paper being cut into greatly
Small suitable strip, ultrasound 10 minutes in dehydrated alcohol, repeats ultrasound 3 times, is then rinsed well again with dehydrated alcohol.So
Above-mentioned mixed solution and carbon fiber paper are placed in reaction kettle afterwards, 120 DEG C hydro-thermal reaction 24 hours.After reaction, it incites somebody to action
The dehydrated alcohol of the carbon fiber paper with deposit and deionized water arrived washs for several times, dry several hours in 60 DEG C of baking ovens
The selenium material of binder free, self supporting structure is obtained afterwards.
Embodiment 4
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then by 2mmol second
Ethylenediamine tetraacetic acid (EDTA) is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile carbon fiber paper being cut into greatly
Small suitable strip, ultrasound 10 minutes in dehydrated alcohol, repeats ultrasound 3 times, is then rinsed well again with dehydrated alcohol.So
Above-mentioned mixed solution and carbon fiber paper are placed in reaction kettle afterwards, 150 DEG C hydro-thermal reaction 12 hours.After reaction, it incites somebody to action
The dehydrated alcohol of the carbon fiber paper with deposit and deionized water arrived washs for several times, dry several hours in 60 DEG C of baking ovens
The selenium material of binder free, self supporting structure is obtained afterwards.
Embodiment 5
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then by 2mmol second
Ethylenediamine tetraacetic acid (EDTA) is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile carbon fiber paper being cut into greatly
Small suitable strip, ultrasound 10 minutes in dehydrated alcohol, repeats ultrasound 3 times, is then rinsed well again with dehydrated alcohol.So
Above-mentioned mixed solution and carbon fiber paper are placed in reaction kettle afterwards, 150 DEG C hydro-thermal reaction 36 hours.After reaction, it incites somebody to action
The dehydrated alcohol of the carbon fiber paper with deposit and deionized water arrived washs for several times, dry several hours in 60 DEG C of baking ovens
The selenium material of binder free, self supporting structure is obtained afterwards.
Embodiment 6
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then by 1mmol second
Ethylenediamine tetraacetic acid (EDTA) is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile carbon fiber paper being cut into greatly
Small suitable strip, ultrasound 10 minutes in dehydrated alcohol, repeats ultrasound 3 times, is then rinsed well again with dehydrated alcohol.So
Above-mentioned mixed solution and carbon fiber paper are placed in reaction kettle afterwards, 150 DEG C hydro-thermal reaction 12 hours.After reaction, it incites somebody to action
The dehydrated alcohol of the carbon fiber paper with deposit and deionized water arrived washs for several times, dry several hours in 60 DEG C of baking ovens
The selenium material of binder free, self supporting structure is obtained afterwards.
Embodiment 7
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then by 1mmol second
Ethylenediamine tetraacetic acid (EDTA) is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile carbon fiber paper being cut into greatly
Small suitable strip, ultrasound 10 minutes in dehydrated alcohol, repeats ultrasound 3 times, is then rinsed well again with dehydrated alcohol.So
Above-mentioned mixed solution and carbon fiber paper are placed in reaction kettle afterwards, 150 DEG C hydro-thermal reaction 24 hours.After reaction, it incites somebody to action
The dehydrated alcohol of the carbon fiber paper with deposit and deionized water arrived washs for several times, dry several hours in 60 DEG C of baking ovens
The selenium material of binder free, self supporting structure is obtained afterwards.
Embodiment 8
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then by 1mmol second
Ethylenediamine tetraacetic acid (EDTA) is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile carbon fiber paper being cut into greatly
Small suitable strip, ultrasound 10 minutes in dehydrated alcohol, repeats ultrasound 3 times, is then rinsed well again with dehydrated alcohol.So
Above-mentioned mixed solution and carbon fiber paper are placed in reaction kettle afterwards, 150 DEG C hydro-thermal reaction 36 hours.After reaction, it incites somebody to action
The dehydrated alcohol of the carbon fiber paper with deposit and deionized water arrived washs for several times, dry several hours in 60 DEG C of baking ovens
The selenium material of binder free, self supporting structure is obtained afterwards.
Embodiment 9
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then ties up 2mmol
Raw element C is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile carbon fiber paper is cut into size and is closed
Suitable strip, ultrasound 10 minutes in dehydrated alcohol, repeats ultrasound 3 times, is then rinsed well again with dehydrated alcohol.Then will
Above-mentioned mixed solution and carbon fiber paper are placed in reaction kettle, 150 DEG C hydro-thermal reaction 12 hours.After reaction, it will obtain
Carbon fiber paper dehydrated alcohol and deionized water with deposit wash for several times, in 60 DEG C of baking ovens after dry several hours
To binder free, the selenium material of self supporting structure.
Embodiment 10
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then ties up 2mmol
Raw element C is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile carbon fiber paper is cut into size and is closed
Suitable strip, ultrasound 10 minutes in dehydrated alcohol, repeats ultrasound 3 times, is then rinsed well again with dehydrated alcohol.Then will
Above-mentioned mixed solution and carbon fiber paper are placed in reaction kettle, 150 DEG C hydro-thermal reaction 24 hours.After reaction, it will obtain
Carbon fiber paper dehydrated alcohol and deionized water with deposit wash for several times, in 60 DEG C of baking ovens after dry several hours
To binder free, the selenium material of self supporting structure.
Embodiment 11
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then ties up 2mmol
Raw element C is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile carbon fiber paper is cut into size and is closed
Suitable strip, ultrasound 10 minutes in dehydrated alcohol, repeats ultrasound 3 times, is then rinsed well again with dehydrated alcohol.Then will
Above-mentioned mixed solution and carbon fiber paper are placed in reaction kettle, 150 DEG C hydro-thermal reaction 36 hours.After reaction, it will obtain
Carbon fiber paper dehydrated alcohol and deionized water with deposit wash for several times, in 60 DEG C of baking ovens after dry several hours
To binder free, the selenium material of self supporting structure.
Embodiment 12
1mmol selenium dioxide is dissolved in 40ml deionized water and obtains uniform selenous acid solution, then by 2mmol second
Ethylenediamine tetraacetic acid (EDTA) is dissolved in above-mentioned selenous acid solution, is stirred 60 minutes at room temperature.Meanwhile stainless (steel) wire being cut into greatly
Small suitable strip, ultrasound 10 minutes first in dilute hydrochloric acid, then ultrasound 10 minutes in dehydrated alcohol, then again with anhydrous second
Alcohol is rinsed well.Then above-mentioned mixed solution and stainless (steel) wire are placed in reaction kettle, 150 DEG C hydro-thermal reaction 24 hours.Instead
After answering, the obtained dehydrated alcohol of the stainless (steel) wire with deposit and deionized water are washed for several times, in 60 DEG C of baking ovens
The selenium material of binder free, self supporting structure is obtained after middle drying several hours.
Industrial applicability: the present invention has many advantages, such as simple process, quick, at low cost, morphology controllable, is a kind of suitable rule
The preparation method of modelling production.
Claims (10)
1. a kind of preparation method of the selenium positive electrode of binder free, self supporting structure, which is characterized in that the described method includes:
Selenium dioxide dissolution is obtained uniform selenous acid solution by step 1) in deionized water, and reducing agent is dissolved in selenous acid
In solution, uniformly mixed solution is obtained, wherein the molar concentration of the selenium dioxide is 0.01~1 mol/L, described to go back
The molar concentration of former agent is 0.01~0.5 mol/L；
Solution obtained in step 1) and conductive network structured substrate are placed in reaction kettle in 50~250 DEG C of temperature by step 2
Degree lower heating 1~96 hour；
Step 3) will have deposit conductive network structured substrate dehydrated alcohol and deionized water obtained in step 2
Washing is at least once, dry at a temperature of 40~100 DEG C, obtains the selenium material of binder free, self supporting structure.
2. preparation method according to claim 1, it is characterised in that: reducing agent described in step 1) is hydrazine, ethylenediamine
At least one of tetraacethyl, glucose, vitamin C.
3. preparation method according to claim 1, it is characterised in that: selenium dioxide described in step 1) and the reduction
The ratio of the molar concentration of agent is 1:0.5~1:10.
4. preparation method according to claim 3, it is characterised in that: selenium dioxide described in step 1) and the reduction
The ratio of the molar concentration of agent is 1:0.5~1:5.
5. preparation method according to claim 1, which is characterized in that conductive network structured substrate described in step 2
For carbon fiber paper, carbon cloth, carbon nano tube network, graphene assembling film, conducting polymer film, stainless (steel) wire, nickel foam,
At least one of copper mesh.
6. preparation method according to claim 1, which is characterized in that step 2 further includes conductive network structured substrate
Preparation process: by conductive network structured substrate in dehydrated alcohol or acetone ultrasound at least once, each ultrasonic time 5~60
Minute, it is rinsed with dehydrated alcohol and deionized water.
7. it is a kind of according to claim 1~any one of 6 described in the binder free of preparation method preparation, self supporting structure selenium
Positive electrode, it is characterised in that: the object phase composition of elemental selenium is monoclinic system elemental selenium, hexagonal crystal system in the selenium positive electrode
Elemental selenium or amorphous elemental selenium.
8. selenium positive electrode according to claim 7, it is characterised in that: the pattern of elemental selenium in the selenium positive electrode
For granules of selenium or aggregate, the granule-morphology is that spherical granules of selenium, regular polyhedron granules of selenium, irregular tree are dendritic
At least one of selenium, the fibrous selenium of dispersion, cotton-shaped selenium, having a size of 0.01~50 micron.
9. selenium positive electrode according to claim 7, it is characterised in that: in the selenium positive electrode simple substance granules of selenium with lead
The spatial position of conductive network structure is that granules of selenium is deposited in conductive network body structure surface or granules of selenium is interspersed in electric conductivity net
It is deposited in network structure, the settled density of selenium simple substance is 0.01~5 milli gram/cm.
10. the selenium positive electrode according to any one of claim 7~9, it is characterised in that: sink in the selenium positive electrode
Long-pending granules of selenium is at least one of brownish red, black, silver gray.
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| CN111063868B (en) * | 2019-07-30 | 2021-07-13 | 厦门理工学院 | Self-supporting carbon-selenium material and preparation method and application thereof |
| CN110902658B (en) * | 2019-12-02 | 2021-07-13 | 厦门理工学院 | Metal selenium compound cathode material for lithium/sodium ion battery, preparation method and application |
| CN111969194B (en) * | 2020-08-27 | 2022-02-15 | 广东工业大学 | Battery positive electrode material and preparation method and application thereof |
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