CN110311102A - The hollow sulfur electrode material of the conducting polymer cladding of lithium-sulfur cell is prepared using sublimate - Google Patents
The hollow sulfur electrode material of the conducting polymer cladding of lithium-sulfur cell is prepared using sublimate Download PDFInfo
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Abstract
The invention belongs to the preparation and application of chemical energy storage field more particularly to the new sulfur electrode material of lithium-sulfur cell, the hollow sulfur electrode material of specially a kind of conducting polymer cladding that lithium-sulfur cell is prepared using sublimate.The hollow sulfur electrode material that the conducting polymer cladding of lithium-sulfur cell is prepared using sublimate includes gas generation agent, surfactant and covering material；The gas generation agent is easy sublimate ADD or camphor；The surfactant is laruyl alcohol sulfate ammonium salt；The covering material is conducting polymer, specially polyaniline, polypyrrole or polythiophene.In preparation process, using heating at a temperature of not high, makes easy sublimate volatilization in intermediate and cause hole, the hollow sulfur particle material and hollow sulphur-graphene composite particulate material of conducting polymer cladding is made.This method significantly improves the specific discharge capacity and service life of sulfur electrode.Present invention process is easy, at low cost.
Description
Technical field
The invention belongs to the preparation of chemical energy storage field more particularly to the new sulfur electrode material of lithium-sulfur cell and answer
With the hollow sulfur electrode material of specially a kind of conducting polymer cladding for preparing lithium-sulfur cell using sublimate.
Background technique
High-performance lithium ion battery is the research of current electrochmical power source, developing focus.Due to the theoretical specific capacity of sulphur
(1675mAh·g-1) it is much higher than commercial li-ion cell positive material cobalt acid lithium (274mAhg-1) and LiFePO4
(170mAh·g-1), become the research and development focus of current lithium ion battery high energy positive electrode.But sulfur electrode is lacked there are following
Point: 1. sulphur and its discharging product Li2The conductivity of S is low；2. in charging process, the volume expansion of material is larger (about 80%)；3.
The polysulfide lithium that the intermediate product polysulfide ion and lithium ion of reaction generate dissolves in electrolyte, and can be threaded back through between electrodes
Shuttle, and react on the electrode, cause the charge and discharge coulombic efficiency of electrode to reduce low with cycle life.Therefore, how to overcome these
Disadvantage becomes the key for improving sulfur electrode performance.Currently, common method is to prepare hollow shell sulfur particle material, for example, passing through
Slowly hydrolysis first coats TiO in the appearance of spherical nano-sulfur2Then thin layer is dissolved the part sulphur simple substance in shell with toluene, most
Hollow core-shell structure sulfur materials (Zhi W S, Li WY, Cha J J, et al.Sulphur-TiO2yolk-shell is obtained eventually
nanoarchitecture with internal void space for long-cycle lithium-sulphur
batteries[J].Nature Communications,2013:2327.)；Or in-stiu coating is poly- on the basis of synthesizing sulphur
Aniline shell makes a part of sulphur distil, forms hollow structure (Zhou W D, Yu Y then by heating in tube furnace
C,Chen H,et al.Yolk-Shell Structure of Polyaniline-Coated Sulfur for Lithium-
Sulfur Batteries[J].J.Am.Chem.Soc.,2013,135:16736.).But these methods will lose a part
Sulphur, and technique is more complex.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of conducting polymer cladding for preparing lithium-sulfur cell using sublimate
Hollow sulfur electrode material.
To achieve the goals above, the conducting polymer packet provided by the invention that lithium-sulfur cell is prepared using sublimate
The hollow sulfur electrode material covered includes gas generation agent, surfactant and covering material；The gas generation agent is easy sublimate ADD
Or camphor；The surfactant is that laruyl alcohol sulfate ammonium salt (uses 30wt% aqueous solution, 1ml solution: (0.5~4) g
ADD dispersion)；The covering material is conducting polymer, specially polyaniline, polypyrrole or polythiophene (polymer and sublimate
Matter is according to 1:(0.5~4) mass ratio combination).
The trade name that the ADD is 2,4,6-tri (propan-2-yl) 1,3,5-trioxane, is that one kind is easy to wave
The non-toxic solid substance of hair, can be used for making scented tea, mould inhibitor etc..
To achieve the goals above, the present invention also provides the conducting polymer packets that lithium-sulfur cell is prepared using sublimate
The preparation method of the hollow sulfur electrode material covered, it is specific as follows: first to crush easy sublimate particle, sulphur is coated on chemical method
Outside easy sublimate particle, easy sublimate-sulphur composite particles are obtained；Use laruyl alcohol sulfate ammonium salt for surfactant,
One layer of conducting polymer is uniformly coated on easy sublimate-sulphur composite particles with chemical polymerization；Then, at lower than 65 DEG C
Heating, vapors away easy sublimate, slot milling, and the hollow sulphur composite particulate material of conducting polymer cladding is made.
In addition, the present invention also provides the hollow sulphur electricity that the conducting polymer for being prepared lithium-sulfur cell using sublimate is coated
The preparation method of pole material, it is specific as follows: first chemically to prepare a nanometer sulfur particle, then with sedimentation easy sublimate packet
It overlays on outside nano-sulfur, obtains easy sublimate-sulphur composite particles；Use laruyl alcohol sulfate ammonium salt for surfactant, with change
It learns polymerization and uniformly coats one layer of conducting polymer on sulphur-sublimate composite particles；It heats, makes easily at lower than 65 DEG C
Sublimate vapors away, slot milling, and the hollow sulphur composite particulate material of conducting polymer cladding is made.
In addition, the present invention also provides the hollow sulphur electricity that the conducting polymer for being prepared lithium-sulfur cell using sublimate is coated
The preparation method of pole material, it is specific as follows: sulphur-graphene and the easy sublimate of sulphur-being prepared using chemical deposition respectively first
Composite material；Then both materials are sufficiently mixed by granulation using ball-milling method, obtain answering for sulphur-graphene-easily sublimate
Close microparticle material；Use laruyl alcohol sulfate ammonium salt for surfactant, with chemical polymerization process again on composite particles uniformly
Coat one layer of conducting polymer.Then it is heated at lower than 65 DEG C, vapors away easy sublimate, conduction is made in slot milling
Hollow sulphur-graphene composite particulate material of polymer overmold.
Significant technical effect of the invention.
Present invention firstly provides using nontoxic easy sublimate as gas generation agent, prepare the hollow nucleocapsid electricity of lithium battery
The new method of pole material；In preparation process, using heating at a temperature of not high, wave easy sublimate in intermediate
It sends out and causes hole, the hollow sulfur particle material and hollow sulphur-graphene composite particulate material of conducting polymer cladding is made.
This method significantly improves the specific discharge capacity and service life of sulfur electrode.Present invention process is easy, at low cost.
In the present invention, the electric conductivity of material is can be improved in the addition of graphene；The cladding of conducting polymer not only increases material
The conductivity of material, and the loss of reaction process intermediate product polysulfide lithium can be suppressed, to improve putting for sulfur electrode significantly
Electric specific capacity and service life；Hole in material, in electrode charge and discharge process, the volume expansion of sulphur is allowed some leeway；Month
The application of cinnamic alcohol sulfate ammonium salt can promote the conducting polymer generated to be all deposited on the easy sublimate of solid phase-sulphur composite particles table
Face, without polymerizeing precipitation in the solution；Temperature control is heated at lower than 65 DEG C, if temperature is too high, sulphur can be lost.
Detailed description of the invention
The TEM of Fig. 1 (ADD)@S@PANI composite material schemes.
The cycle performance curve of Fig. 2 (ADD)@S@PANI (A) and (ADD)@S (B) electrode.Current density 500mAg-1。
The TEM of Fig. 3 S@(ADD)@PANI composite material schemes.
The charge-discharge performance curve of Fig. 4 S@(ADD)@PAN and S electrode, current density 200mAg-1。
Fig. 5 ADD@S (a), Gr@S (b) and the SEM of (ADD) S-Gr@PANI (c, d) hollow material figure.
The TEM of Fig. 6 (ADD) S-Gr@PANI hollow material schemes.
The charge-discharge performance curve of Fig. 7 (ADD) S-Gr@PANI hollow material and nanometer S electrode.Current density
500mA·g-1。
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment 1.
The present embodiment coats ADD with sulphur, then coats polyaniline outside, prepares the hollow sulphur composite particles of polyaniline-coated
Material.
Preparation step is as follows: weighing ADD 2g and is dissolved in 10ml ethanol solution, then pours into solution containing 1ml laruyl alcohol
In the 20ml deionized water of sulfate ammonium salt, tiny ADD crystallization can be precipitated suddenly；This suspension ball milling is after 12 hours, dispersion
In contain 2wt%PVP (polyvinylpyrrolidone) and 0.1molL-1In the 400ml solution of sodium thiosulfate, it is added dropwise
The 1molL of amount-1Dilute hydrochloric acid, sulphur is precipitated in the reaction；It reacts and completes after 2 hours, through multiple eccentric cleaning, obtain ADD
The composite material of upper cladding sulphur, is denoted as ADD@S.
It disperses materials A DD@S in the hydrochloric acid solution of the sulfate ammonium salt of laruyl alcohol containing 1ml, 0.6g aniline monomer is added,
Magnetic agitation dispersion；Place the beaker in ice bath, using ammonium persulfate solution as oxidant, be added dropwise to be dispersed with aniline monomer and
In the suspension of ADD@S, react 4 hours；Then gained suspension is centrifugated and is washed repeatedly to neutral (pH value=7),
Obtain polyaniline-coated object；Then 12 hours dry at 60 DEG C, at this point, ADD meeting nature volatilization, obtains polyaniline shell cladding
Hollow sulfur compound, the compound are denoted as (ADD)@S@PAN.Formula bracket indicates that wherein ADD has distilled and vapors away；Preparation
When, the mass ratio of material therefor is sulphur: ADD: polyaniline=12.8:20:6.
(ADD) the TEM photo of@S@PANI material is shown in Fig. 1, and shape keeps ADD grain shape.As it can be seen that sulphur-cake in figure
Intermediate site color is shallower, shows since ADD volatilization is formed by space, there is also gap between sulphur and polyaniline film, this
The expansion slot milling of sulphur when a bit can be to discharge.A ghost is also shown in figure, this may be the sulphur due to depositing on ADD
Very little reason.
Use N methyl pyrrolidone (NMP) for solvent, PVDF is binder, and ((ADD)@S@PANI) ﹕ is led with active material
(S.P) ﹕ binder (PVDF)=7:2:1 mass ratio tune cream is coated on aluminium foil for electric agent；After being dried under the conditions of 60 DEG C, it is washed into
The circle electrode slice of diameter 14mm；For electrode slice after 60 DEG C are dried in vacuo 12 hours, the anode as lithium-sulfur cell is stand-by.With lithium piece
For to electrode, using polypropylene micropore diaphragm (Celgard 2300) and 1molL-1LiTFSI/DME:DOL=1:1 (v/v)+
0.2mol·L-1LiNO3Electrolyte is assembled into CR2025 type button cell in argon gas glove box.Use LAND charge-discharge system
Electrode performance is tested, in 500mAhg-1Charge and discharge are carried out under electric current, (ADD)@S@PAN electrode and do not wrap PANI's
(ADD) charge-discharge performance of@S electrode is shown in Fig. 2.In 100 charge and discharge cycles, the electric discharge ratio of (ADD)@S@PAN electrode
Capacity is 444.6mAhg-1, it is only 207.5mAhg without wrapping the specific discharge capacity of (ADD)@S electrode of PANI-1。
(ADD) specific discharge capacity of@S@PAN electrode and charge-discharge performance are apparently higher than (ADD)@S electrode for not wrapping PANI.Thus
As it can be seen that due to the loss that the hollow core-shell structure of polyaniline-coated can increase electric conductivity, inhibit polysulfide lithium, and part provides and fills
The expansion space of sulphur in discharge process, so as to make charge/discharge capacity and the stability of sulfur electrode be significantly improved.
Embodiment 2.
The present embodiment coats nano-sulfur with ADD, then coats polyaniline outside, and the hollow sulphur for preparing polyaniline-coated is compound
Microparticle material.
Preparation step is as follows: surfactant polyethylene pyrrole is added in configuration 0.1mol/L 400ml hypo solution
Pyrrolidone (PVP) 2wt% then configures the 1molL of equivalent-1Hydrochloric acid weak solution, dropwise plus hypo solution；Reaction 2
After hour, it is centrifuged using supercentrifuge, it is multiple with deionized water and alcohol washes, until supernatant is neutral (PH=7), 60
DEG C vacuum drying 12 hours, obtain a nanometer sulfur materials；Then it is molten the nanometer sulfur materials of drying to be placed in the acetone dissolved with ADD material
In liquid, grinding does not stop to stir mixture, until acetone sufficiently volatilizees, cladding obtains in nano-sulfur surface after ADD is precipitated
Even ADD coats nanometer sulfur materials, is denoted as S ADD.
It disperses S ADD material in the 0.2mol/L hydrochloric acid solution of the laurel alcohol sulfuric ester of surfactant containing 1ml；It is added
0.4g aniline monomer, is dispersed with stirring under magnetic stirring；It places the beaker in ice bath, with molar ratio (C6H7N:(NH4)2S2O4=
Ammonium persulfate solution 1:2) is oxidant, is added dropwise in the suspension for being dispersed with aniline monomer and S@ADD, is reacted 4 hours；
Then gained suspension is centrifugated and is washed repeatedly to neutrality, obtain polyaniline-coated object.It is 12 hours dry at 60 DEG C,
At this temperature, ADD meeting nature volatilization, obtains the hollow core-shell structure sulfur compound of polyaniline shell cladding, and compound is denoted as
S@(ADD)@PANI.Bracket indicates that wherein ADD has distilled and vapors away.When preparing S@(ADD)@PANI, the matter of material therefor
Measuring ratio is sulphur: ADD: polyaniline=10:15:4.
The TEM picture of S@(ADD)@PANI material is shown in Fig. 3, can measure, the thickness of polyaniline film is about 50nm.It can from figure
To find out, due to the volatilization of ADD, there are gaps between sulphur and polyaniline film.The expansion of sulphur leaves when these gaps are electric discharge
Space.
CR2025 type button cell is made with method similar in embodiment 1.Electrode is tested using LAND charge-discharge system
Performance.In 200mAhg-1Under electric current, the charge-discharge performance of S@(ADD)@PAN and S electrode is shown in Fig. 4.By 100 charge and discharges
Electricity circulation, the specific discharge capacity of S@(ADD)@PAN electrode are positively retained at 503mAhg-1.And then with the S electrode of chemical method production
Drop to 221.9mAhg-1.As can be seen that since the hollow core-shell structure of polyaniline-coated can increase electric conductivity, inhibition gathers
The loss of sulphur lithium, and part provides the expansion space of sulphur in charge and discharge process, so that the charge/discharge capacity and stability of sulfur electrode
It is significantly improved.
Embodiment 3.
Sulphur, ADD and graphene are first mixed and made into composite particles using ball-milling method by the present embodiment, then coat polyphenyl outside
Amine prepares hollow sulphur-graphene composite particulate material of polyaniline-coated.
Preparation step is as follows: weighing 2.0g ADD and is dissolved in 10ml ethyl alcohol, ultrasonic 10min；Then the deionization of 20ml is added
Tiny ADD crystal grain is precipitated in water；Again plus 6.0g polyvinylpyrrolidone (2wt.%) and 7.8g sodium thiosulfate (0.1mol/
L), " solution A " is obtained；Using peristaltic pump by 0.6mol/L HCl (amount of hydrochloric acid by the molar ratio of HCl and sodium thiosulfate be 2:
1 relationship is calculated) solution is added dropwise to dropwise in " solution A "；After reacting 2h, centrifuge washing obtains sulphur cladding ADD material, note
For ADD@S.
0.04g graphene is weighed, successively with ethyl alcohol and the processing of the hydrochloric ultrasonic wave of 8wt.% to clean impurity；300ml is added
Deionized water in, and stir evenly；Plus 6.0g polyvinylpyrrolidone (2wt.%) and 7.8g sodium thiosulfate then
(0.1mol/L) obtains " solution B "；Using peristaltic pump, by 0.6mol/L HCl solution, (amount of hydrochloric acid is by HCl and sodium thiosulfate
Molar ratio be 2:1 relationship be calculated) be added dropwise in " solution B " dropwise；After reacting 2h, centrifuge washing obtains sulphur cladding stone
Black alkene material is denoted as Gr@S.
ADD@S and Gr@two kinds of materials of S are sufficiently mixed using ball-milling method, obtain the composite construction of sulphur, graphene and ADD
Product.It disperses above-mentioned material in the hydrochloric acid solution of the sulfate ammonium salt of laruyl alcohol containing 1ml, 0.4g aniline monomer, magnetic force is added
It is dispersed with stirring；It places the beaker in ice bath, using ammonium persulfate solution as oxidant, is added dropwise to and is dispersed with aniline monomer and ADD@
In the suspension of S, react 4 hours；Then gained suspension is centrifugated and is washed repeatedly to neutral (PH=7), gathered
Hollow structure sulphur-graphene composite material of aniline cladding is denoted as (ADD) S-Gr@PANI, and formula bracket indicates ADD, and oneself volatilizees.
Fig. 5 is the SEM photograph of ADD@S (Fig. 5 a), Gr@S (Fig. 5 b) and (ADD) S-Gr@PANI (Fig. 5 c, 5d).From Fig. 5 c
Know that (ADD) S-Gr@PANI is the particle that diameter is about 2.5 μm, in figure 5d it can be seen that (ADD) the S-Gr@of a rupture
PANI particle, wherein the particle to shed is S the and Gr particle of its package.
Fig. 6 is the TEM figure of (ADD) S-Gr@PANI, it can be seen that there are one between the intragranular particle of (ADD) S-Gr@PANI
Fixed gap.
CR2025 type button cell is made with method similar in embodiment 1.Electrode is tested using LAND charge-discharge system
Performance.In 500mAhg-1Under electric current, the charge-discharge performance of (ADD) S-Gr@PANI electrode is shown in Fig. 7.By 50 charge and discharges
Electricity circulation, the specific discharge capacity of (ADD) S-Gr@PANI electrode are positively retained at 626mAhg-1.And the S electrode made of chemical method
It is then only 336mAhg-1.As can be seen that since the hollow core-shell structure of polyaniline-coated can increase electric conductivity, inhibition polysulfide
The loss of lithium, and part provides the expansion space of sulphur in charge and discharge process, and the dilute application of graphite increases the conduction of material
Property, so as to make charge/discharge capacity and the stability of sulfur electrode be significantly improved.
Claims (6)
1. a kind of hollow sulfur electrode material for the conducting polymer cladding for being prepared lithium-sulfur cell using sublimate, feature are existed
In the hollow sulfur electrode material includes gas generation agent, surfactant and covering material.
2. the hollow sulfur electrode of the conducting polymer cladding of lithium-sulfur cell is prepared using sublimate as described in claim 1
Material, which is characterized in that the gas generation agent is easy sublimate ADD, camphor；The surfactant is laurel alcohol sulfuric ester
Ammonium salt；The covering material is conducting polymer, specially polyaniline, polypyrrole, polythiophene.
3. the hollow sulfur electrode of the conducting polymer cladding of lithium-sulfur cell is prepared using sublimate as claimed in claim 2
Material, which is characterized in that the ADD is 2,4,6-tri (propan-2-yl) 1,3,5-trioxane.
4. the hollow sulfur electrode of the conducting polymer cladding of lithium-sulfur cell is prepared using sublimate as described in claim 1
The preparation method of material, which is characterized in that specific as follows: first crushing easy sublimate particle, and sulphur is coated on easily with chemical method
Outside sublimate particle, easy sublimate-sulphur composite particles are obtained；It uses laruyl alcohol sulfate ammonium salt for surfactant, uses
Chemical polymerization uniformly coats one layer of conducting polymer on easy sublimate-sulphur composite particles；Then, add at lower than 65 DEG C
Heat vapors away easy sublimate, slot milling, and the hollow sulphur composite particulate material of conducting polymer cladding is made.
5. the hollow sulfur electrode of the conducting polymer cladding of lithium-sulfur cell is prepared using sublimate as described in claim 1
The preparation method of material, which is characterized in that specific as follows: a nanometer sulfur particle is first chemically prepared, then with sedimentation easily
Sublimate is coated on outside nano-sulfur, obtains easy sublimate-sulphur composite particles；Use laruyl alcohol sulfate ammonium salt living for surface
Property agent, uniformly coats one layer of conducting polymer with chemical polymerization process on sulphur-sublimate composite particles；At lower than 65 DEG C
Heating, vapors away easy sublimate, slot milling, and the hollow sulphur composite particulate material of conducting polymer cladding is made.
6. the hollow sulfur electrode of the conducting polymer cladding of lithium-sulfur cell is prepared using sublimate as described in claim 1
The preparation method of material, which is characterized in that specific as follows: first sulphur-graphene is prepared using chemical deposition respectively and sulphur-is easy
Sublimate composite material；Then both materials are sufficiently mixed by granulation using ball-milling method, obtain sulphur-graphene-Yi Shenghua
The composite particulate material of substance；Use laruyl alcohol sulfate ammonium salt for surfactant, with chemical polymerization process again compound micro-
One layer of conducting polymer is uniformly coated on grain.Then it is heated at lower than 65 DEG C, vapors away easy sublimate, slot milling,
Hollow sulphur-graphene composite particulate material of conducting polymer cladding is made.
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Application publication date: 20191008 |