CN108963151A - A kind of preparation method of the functional interlayer applied to lithium-sulphur cell positive electrode - Google Patents
A kind of preparation method of the functional interlayer applied to lithium-sulphur cell positive electrode Download PDFInfo
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- CN108963151A CN108963151A CN201810687317.5A CN201810687317A CN108963151A CN 108963151 A CN108963151 A CN 108963151A CN 201810687317 A CN201810687317 A CN 201810687317A CN 108963151 A CN108963151 A CN 108963151A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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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 invention belongs to technical field of material chemistry, are related to a kind of preparation method of functional interlayer applied to the anode in lithium-sulfur cell.This method includes the preparation of electrostatic spinning precursor liquid, the preparation of titanium dioxide nanofiber film and Ag-TiO2Three steps of preparation of composite material carry out electrostatic spinning using tetraisopropyl titanate and PVP as raw material, and TiO is made after Hong Gan ﹑ calcining in the spun fiber of electrospinning2Nanofiber, then as template, photoreduction silver nitrate constructs dendroid Ag-TiO2Composite material, the composite material can improve polysulfide shuttle effect in lithium-sulfur cell of the existing technology.
Description
Technical field
The present invention relates to a kind of cell interlayer preparation method, more particularly, to it is a kind of applied in lithium-sulfur cell just
The preparation method of the functional interlayer of pole, belongs to technical field of material chemistry.
Background technique
With the rapid development of science and technology and information industry, global environmental pollution and energy crisis are on the rise, and compel
The new energy and energy storing and transporting system for so that various countries is striven to find sustainable development are to substitute traditional fossil fuel, with secondary electricity
Efficient, practical, " green " (low pollution or no pollution) the energy storage and transportation system that Chi Wei is represented has become current focus
With research hotspot.Lithium ion battery, as light, high specific energy, it is environmental-friendly, can be recycled the advantages that, become numerous energy storage
The first choice of equipment.
Positive electrode of the elemental sulfur as lithium-sulfur cell, theoretical capacity reach 1675 mAh/g, and theoretical energy density is reachable
To 2600 Wh/kg, there is critical role in the development of later lithium battery.However, the limitation of lithium-sulfur cell includes more vulcanizations
Shuttle effect, the service efficiency of sulphur in the long-term cyclic process of lithium be low and serious volume expansion (80%).In addition, more vulcanizations
The diffusion of lithium intermediate product and redox reaction will lead to serious self-discharge phenomenon and low coulombic efficiency, lead to cell reaction
It is poorly reversible.Although there are these disadvantages for lithium-sulfur cell, undeniable is the development situation for making a general survey of current battery, it
It is still a kind of most promising new energy material.
In order to be dedicated to solving the disadvantages mentioned above of lithium-sulfur cell, in recent years, researcher is in the side such as anode, cathode, electrolyte
Many effort have been done in face, and emphasis solves the conductivity of positive electrode, reduces " shuttle effect " in reaction process, to lithium metal
The several aspects of the protection of cathode.In all research, positive carbon material and the compound most study of sulphur, carbon material can be effective
The electric conductivity for improving positive electrode, also has certain inhibiting effect to the migration of polysulfide, also has one to the expansion of positive sulphur
Fixed improvement result.
Functional interlayer is a kind of next shuttle effect for directly solving lithium-sulfur cell of simple and easy method.Multi-functional interlayer
It is placed between anode and diaphragm, more sulphions is hindered to spread to cathode, inhibit " shuttle effect "；Meanwhile interlayer can adsorb electricity
More sulphions in liquid are solved, and as second level collector, reduces the loss of active material, improves the electrochemistry of lithium-sulfur cell
Energy.
Such as: Wang etc. is prepared for light multi-functional sulphur, nitrogen co-doped porous graphene (SNGE) interlayer, interlayer tool
There is the ability of good electric conductivity and stronger absorption polysulfide, and Li can be regulated and controled2S2/Li2Diaphragm is protected in the generation of S
Integrality.When using SNGE interlayer in porous carbon nanotube-sulphur anode, discharge capacity of the battery in 0.25 C is
1460 mAh/g, the capacity in 40 C remain to reach 130 mAh/g, and battery is still protected after recycling 1000 times under 8C multiplying power
Held good capacity attenuation rate 0.01%/time.Yu etc. is in nitrogen-doped graphene/sulphur positive electrode surface atom layer depositing Ti O2
As interlayer.20 TiO are deposited in the positive electrode surface that sulfur mass fraction is 59%2Afterwards, first, last time after being recycled 500 times when 1 C
Capacity is respectively 1069.5,918.3 mAh/g, and the raising of battery performance depends primarily on TiO2It is very strong between more lithium sulfides
In conjunction with energy.Abbas etc. by poly- 3,4- ethylenedioxythiophene (PEDOT) and sulfonated polystyrene (PSS) be sprayed to traditional PP every
Functional diaphragm is prepared on film.Using sulfonate radical in PSS come the soluble more lithium sulfides of electrostatic repulsion, and PEDOT can be with Li2S、
Li2S2Chemical action occurs, realizes double action, more lithium sulfides is effectively limited in positive side.Other than PEDOT, gather
Pyrroles can also be used as interlayer, and being based primarily upon electric polypyrrole layer can be improved the electronics and ionic conduction performance of positive electrode surface,
The polypyrrole particle of high-ratio surface can capture more sulphions by hydrogen bond action, while the flexibility of polypyrrole interlayer can also
Buffer the Volumetric expansion of sulphur anode.CN106450104A discloses a kind of interlayer applied in lithium-sulfur cell and its preparation
The fiber surface that metal oxide is attached to bacteria cellulose is carbonized by method by the method, is obtained a kind of novel
Positive interlayer.The interlayer can be used between lithium-sulphur cell positive electrode and diaphragm, can inhibit the shuttle of more sulphions well, every
Metal oxide in layer can also adsorb more sulphions；Metal oxide is also to the redox of lithium-sulfur cell simultaneously
Reaction has certain catalytic action, and the cycle performance for improving lithium-sulfur cell plays critically important effect.But above-mentioned technology
Generally existing disadvantage is: preparation process very complicated, production cost is higher, and production takes a long time, and is suitable for Laboratory Production,
It is difficult to large-scale commercial production；The interlayer prepared will appear the phenomenon that contracting by carbonization, influence it in lithium-sulfur cell
Extensive use, microscopic appearance is unable to control, and size is larger, specific surface area is small, and ideal effect is not achieved to the performance of battery
Fruit.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of functional interlayer applied to lithium-sulphur cell positive electrode, should
Method carries out electrostatic spinning using tetraisopropyl titanate and PVP as raw material, and the spun fiber of electrospinning is made after Hong Gan ﹑ calcining
Obtain TiO2Nanofiber, then as template, photoreduction silver nitrate constructs dendroid Ag-TiO2Composite material, the composite material
Polysulfide shuttle effect in lithium-sulfur cell of the existing technology can be improved.
The preparation method of multi-functional interlayer provided by the invention applied to lithium-sulphur cell positive electrode, includes the following steps:
(1) preparation of electrostatic spinning precursor liquid
The tetraisopropyl titanate for being 1:2:2 according to mass volume ratio, ethyl alcohol and acetic acid, weigh tetraisopropyl titanate be dissolved in ethyl alcohol and
In the mixed liquor of acetic acid, through 5 ~ 20 min of magnetic agitation, it is molten then to add 0.03 ~ 0.17g/ml polyvinylpyrrolidone (PVP)
Liquid continues 1 ~ 2 h of stirring；
(2) preparation of titanium dioxide nanofiber film
The obtained electrostatic spinning precursor liquid of step (1) is added in syringe, control operating voltage is 10 ~ 15 kV, and adjusting connects
It receives device and spinning syringe needle distance is 5 ~ 20 cm, the rate of outflow of solution is 0.3 ~ 0.8 ml/h, and the fiber spun is being dried in vacuo
After (120 DEG C) of case dry 12 h, in 450 DEG C of 3 h of calcining, it is then down to room temperature naturally, obtains TiO2Nanofiber；
(3) Ag-TiO2The preparation of composite material
By TiO2Nanofiber immerses 0.0005 ~ 0.002 mol/LAgNO3Solution irradiates 24 ~ 48 at high-pressure sodium lamp (100W)
Then h successively uses high purity water and ethanol washing, in 300 ~ 500 DEG C of Muffle furnace 2 ~ 5 h of calcining after drying.
The above-mentioned multi-functional interlayer Ag-TiO for lithium-sulphur cell positive electrode2The preparation method of composite material, wherein involved
To raw material be commercially available, equipment used is known to those skilled in the art.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
1、TiO2Nanofiber has big specific surface area, has high chemical stability, catalytic degradation organic matter ability strong, good
Biocompatibility, it is inexpensive nontoxic the advantages that.
2, the Ag-TiO after compound2Not only maintain TiO2The advantages that nanofiber bigger serface, and due to metal Ag
Compound generation broadband plasma absorption, so that it is extended to visible light region to the absorption of light, thus be conducive to charge load
The generation of son is flowed, and dendroid Ag is more advantageous to TiO2The interface charge of composite material is transmitted, to improve the electrification of battery
Learn performance.Applied to multi-functional interlayer, being placed among anode and diaphragm can hinder more sulphions to spread to cathode, inhibit
" shuttle effect ", improves the utilization rate of positive active material.
Detailed description of the invention
Fig. 1 is scanning (SEM) figure of titanium dioxide nanofiber obtained by embodiment 1.
Fig. 2 is the X-ray diffraction (XRD) figure of titanium dioxide nanofiber obtained by embodiment 1.
Fig. 3 is circulation volume figure of the multi-functional interlayer of carbon dioxide fiber anode at 0.1 C obtained by embodiment 1.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method
And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available
Embodiment 1:
The first step prepares electrostatic spinning precursor liquid:
1.5 g tetraisopropyl titanates, 3 ml ethyl alcohol and 3 ml acetic acid are added in beaker, then 10 min of magnetic agitation is added
PVP solution (0.45 gPVP is dissolved in 3 ml ethyl alcohol) continues to stir 1 h.
Second step prepares titanium dioxide nanofiber film:
Mixed solution is added in syringe, control operating voltage is 10 kV, and adjusting receiver and spinning syringe needle distance is 10
Cm, the rate of outflow of solution are 0.5 ml/h.The fiber spun is after (120 DEG C) of vacuum oven dry 12 h, at 450 DEG C
Calcine 3 h.It is then down to room temperature naturally, obtains TiO2Nanofiber.
Third step prepares Ag-TiO2Composite material:
By TiO2Nanofiber immerses 0.001 mol/LAgNO3Solution irradiates 36 h at high-pressure sodium lamp (100W) respectively, then
High purity water and ethanol washing 3 times are used respectively, it is spare after 450 DEG C of Muffle furnace 3 h of calcining after dry.
Embodiment 2:
The first step prepares electrostatic spinning precursor liquid:
It is added 1.5 g tetraisopropyl titanates, 3 ml ethyl alcohol and 3 ml acetic acid in beaker, 10 min of magnetic agitation or so, then
It adds PVP solution (0.45 gPVP is dissolved in 3 ml ethyl alcohol), continues to stir 1 h.
Second step prepares titanium dioxide nanofiber film:
Mixed solution is added in syringe, control operating voltage is 15 kV, and adjusting receiver and spinning syringe needle distance is 10
Cm, the rate of outflow of solution are 0.8 ml/h.The fiber spun is after (120 DEG C) of vacuum oven dry 12 h, at 300 DEG C
Calcine 3 h.It is then down to room temperature naturally, obtains TiO2Nanofiber.
Third step prepares Ag-TiO2Composite material:
By TiO2Nanofiber immerses 0.001 mol/LAgNO3Solution irradiates 36 h at high-pressure sodium lamp (100W) respectively, then
High purity water and ethanol washing 3 times are used respectively, it is spare after 450 DEG C of Muffle furnace 3 h of calcining after dry.
Embodiment 3:
The first step prepares electrostatic spinning precursor liquid:
It is added 1.5 g tetraisopropyl titanates, 3 ml ethyl alcohol and 3 ml acetic acid in beaker, 10 min of magnetic agitation or so, then
It adds PVP solution (0.45 gPVP is dissolved in 3 ml ethyl alcohol), continues to stir 1 h.
Second step prepares titanium dioxide nanofiber film:
Mixed solution is added in syringe, control operating voltage is 10 kV, and adjusting receiver and spinning syringe needle distance is 10
Cm, the rate of outflow of solution are 0.5 ml/h.The fiber spun is after (120 DEG C) of vacuum oven dry 12 h, at 450 DEG C
Calcine 3 h.It is then down to room temperature naturally, obtains TiO2Nanofiber.
Third step prepares Ag-TiO2Composite material:
By TiO2Nanofiber immerses 0.001 mol/LAgNO3Solution irradiates 36 h at high-pressure sodium lamp (100W) respectively, then
High purity water and ethanol washing 3 times are used respectively, it is spare after 450 DEG C of Muffle furnace 3 h of calcining after dry.
Case study on implementation 4:
The first step prepares electrostatic spinning precursor liquid:
It is added 1.5 g tetraisopropyl titanates, 3 ml ethyl alcohol and 3 ml acetic acid in beaker, 10 min of magnetic agitation or so, then
It adds PVP solution (0.45 gPVP is dissolved in 3 ml ethyl alcohol), continues to stir 1 h.
Second step prepares titanium dioxide nanofiber film:
Mixed solution is added in syringe, control operating voltage is 10 kV, and adjusting receiver and spinning syringe needle distance is 10
Cm, the rate of outflow of solution are 0.5 ml/h.The fiber spun is after (120 DEG C) of vacuum oven dry 12 h, at 450 DEG C
Calcine 3 h.It is then down to room temperature naturally, obtains TiO2 nanofiber.
Third step prepares Ag-TiO2Composite material:
By TiO2Nanofiber immerses 0.005 mol/LAgNO3Solution irradiates 48 h at high-pressure sodium lamp (100W) respectively, then
High purity water and ethanol washing 3 times are used respectively, it is spare after 450 DEG C of Muffle furnace 3 h of calcining after dry.
Unaccomplished matter of the present invention is well-known technique.
Claims (7)
1. a kind of preparation method of the functional interlayer applied to lithium-sulphur cell positive electrode, which is characterized in that including (1) electrostatic spinning
The preparation of precursor liquid, the preparation of (2) titanium dioxide nanofiber film and (3) Ag-TiO2Three steps of preparation of composite material.
2. the preparation method of the functional interlayer according to claim 1 applied to lithium-sulphur cell positive electrode, which is characterized in that
Described (1) the electrostatic spinning precursor liquid the preparation method comprises the following steps: according to mass volume ratio be 1:2:2 tetraisopropyl titanate, ethyl alcohol
And acetic acid, it weighs tetraisopropyl titanate and is dissolved in the mixed liquor of ethyl alcohol and acetic acid, through 5 ~ 20 min of magnetic agitation, then addition is poly-
Vinylpyrrolidone solution continues 1 ~ 2 h of stirring.
3. the preparation method of the functional interlayer according to claim 2 applied to lithium-sulphur cell positive electrode, which is characterized in that
The polyvinylpyrrolidonesolution solution concentration is 0.03 ~ 0.17g/ml.
4. the preparation method of the functional interlayer according to claim 1 applied to lithium-sulphur cell positive electrode, which is characterized in that
Described (2) the titanium dioxide nanofiber film is infused the preparation method comprises the following steps: the obtained electrostatic spinning precursor liquid of step (1) is added
In emitter, after the fiber that Static Spinning silk spinning is obtained dries 12 h at 120 DEG C of vacuum oven, in 450 DEG C of 3 h of calcining, then
Naturally it is down to room temperature, obtains TiO2Nanofiber.
5. the preparation method of the functional interlayer according to claim 4 applied to lithium-sulphur cell positive electrode, which is characterized in that
The electrostatic spinning process parameter are as follows: operating voltage is 10 ~ 15 kV, and adjusting receiver and spinning syringe needle distance is 5 ~ 20
Cm, the rate of outflow of solution are 0.3 ~ 0.8 ml/h.
6. the preparation method of the functional interlayer according to claim 1 applied to lithium-sulphur cell positive electrode, which is characterized in that
Described (3) Ag-TiO2Composite material the preparation method comprises the following steps: by TiO2Nanofiber immerses AgNO3High-pressure mercury of the solution in 100W
24 ~ 48 h are irradiated under lamp, are then successively used high purity water and ethanol washing, are calcined 2 ~ 5 at 300 ~ 500 DEG C of Muffle furnace after drying
h。
7. the preparation method of the functional interlayer according to claim 6 applied to lithium-sulphur cell positive electrode, which is characterized in that
The AgNO3Solution concentration is 0.0005 ~ 0.002 mol/L.
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| JP2017004605A (en) * | 2015-06-04 | 2017-01-05 | 株式会社アルバック | Method for manufacturing lithium sulfur secondary battery and separator |
| CN107394256A (en) * | 2017-07-18 | 2017-11-24 | 天津工业大学 | A kind of long-acting lithium-sulfur cell and preparation method thereof |
| CN108172796A (en) * | 2017-12-27 | 2018-06-15 | 肇庆市华师大光电产业研究院 | A kind of preparation method of nanometer fibrous niobium pentaoxide/sulphur composite positive pole |
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2018
- 2018-06-28 CN CN201810687317.5A patent/CN108963151B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104300112A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Positive electrode for lithium sulfur battery |
| CN103490027A (en) * | 2013-08-12 | 2014-01-01 | 中国科学院化学研究所 | Membrane for lithium-sulfur battery and preparation method of membrane |
| US20150318532A1 (en) * | 2014-05-05 | 2015-11-05 | Board Of Regents, The University Of Texas System | Bifunctional separators for lithium-sulfur batteries |
| JP2017004605A (en) * | 2015-06-04 | 2017-01-05 | 株式会社アルバック | Method for manufacturing lithium sulfur secondary battery and separator |
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