CN108695497A - A kind of preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery - Google Patents
A kind of preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery Download PDFInfo
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Abstract
The present invention relates to electrochemical energy storage materials technical fields, and in particular to a kind of preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery;The present invention utilizes from foaming and constructs a kind of three-dimensional carbon skeleton with hierarchical porous structure, as the carrier of active material elemental sulfur, with elemental sulfur it is compound after, by the way of in situ, it is formed on its surface conducting high polymers object coating modification, lithium-sulphur cell positive electrode is used for as combination electrode material;The multi-element composite material of the application can promote ion to transmit, and its three dimensional skeletal structure provides continuous electronic access, thus there is excellent storage lithium performance, high molecular polymer in-stiu coating forms effective three-dimensional conductive network structure, there is certain suction-operated to elemental sulfur and battery intermediate product, the volume expansion problem generated during discharge and recharge reaction can be alleviated, improve the cycle performance of lithium-sulfur cell, new approaches are provided for lithium sulfur battery anode material design construction.
Description
Technical field
The present invention relates to electrochemical energy storage materials technical fields, and in particular to a kind of conductive polymer is polymer three-dimensional porous
The preparation method of carbon structure anode composite material of lithium sulfur battery.
Background technology
In many energy storage modes, lithium ion battery is high with energy density, self-discharge rate is low, has extended cycle life, without note
Outstanding advantages of recalling effect, environment friendly etc., oneself is widely used in consumption electronic product.But Current commercial lithium electricity product energy
Metric density is low, is only capable of meeting low-power consumption, the requirement of portable equipment.Electrode material be lithium ion battery core also, energy storage component, just
Pole material is the bottleneck for restricting its energy density and improving.The embedding lithium ternary metal oxide positive electrode of tradition is such as;Cobalt acid lithium, phosphoric acid
The specific capacities such as iron lithium, LiMn2O4 are relatively low (100-140mAh g-1), made by the improvement difficulty to its composed structure and technology
Battery energy density has breakthrough raising again (energy density at most improves 30%).Sulphur be attract attention in recent years it is novel just
Pole material, different from based on traditional positive electrode of single electron energy storage mechanism, the reversible transition that polyelectron participates in reacts (16Li+
S8=8Li2S) specific capacity that sulphur positive electrode is up to 1672140mAh g-1 is assigned, when using lithium metal as cathode, structure
Lithium-sulfur cell theoretical energy density up to 2567Wh kg-1(conventional lithium ion battery only 100-150 Wh kg-1), simultaneously
Its of low cost, low toxic and environment-friendly, therefore, it has also become the energy storage that current national governments greatly develop and power battery hot spot technology it
One.
High energy energy storage and electrokinetic cell system one of of the lithium-sulfur cell as most foreground, are usually made by S-containing composite
For anode.Sulphur anode the simplest is mixed by sulphur powder and conductive additive, binder, however, by by bright sulfur powder with
The positive electrode that preparation is simply mixed in conductive additive, binder is difficult to effectively fetter the loss of active material sulphur, to carry
The utilization rate of high-sulfur, reaching improves lithium-sulfur cell performance.During lithium-sulfur cell charge and discharge cycles, anode is several under will facing
The problem of aspect:First, the sulfur granules of insulating properties agglomerate into cluster and the active material inside cluster are made to be difficult to effectively connect
It is reduced by electronics, converts chemical energy to electric energy, cause the inactivation of active material;Second, battery discharge intermediate product is readily soluble
Active material is caused to be lost in organic electrolyte, charge and discharge coulombic efficiency declines;Third, final discharging product Li2Sn (n=
1-2) there is insulating properties, be deposited on and form inactive particle on conducting base, hinder electronics conduction, ion transmission;4th,
In the phase transition process of sulphur and lithium sulfide, there can be about 79% volume change, huge volume expansion or contraction cause activity
Material is detached from conducting base, causes the rapid decay of battery specific capacity.
For above-mentioned lithium-sulphur cell positive electrode problem encountered, to sulphur anode carry out physics, chemistry and structural modification oneself
Through the effective measures as development lithium-sulfur cell.To improve the conductivity of anode and inhibiting more sulphion diffusions, in anode initially
Bright sulfur substituted by various porous carbon/sulphur, conducting polymer/sulphur nanocomposite.However, additional conductive addition
The addition of agent not only reduces the content of active material sulphur, and increases the difficulty that battery large-scale promotion uses.Therefore, just
The content of extremely middle sulphur and electrode electro Chemical performance this conflict need researcher carefully to weigh.With belong to deintercalation mechanism
Positive electrode is compared, and anode belongs to electrochemical reaction mechanism in lithium-sulfur cell, by being optimized to battery component and battery structure
To improve a kind of efficient strategy of lithium-sulfur cell performance.
Invention content
The present invention is in order to solve the above technical problems, provide a kind of three-dimensional porous carbon structure anode composite material of lithium sulfur battery
Preparation method.
The present invention is achieved by the following technical programs:
A kind of preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery, comprises the steps of:
First stage:Carbon/sulphur composite material powder is prepared, the three-dimensional carbon with hierarchical porous structure is constructed using from foaming
Skeleton, it is using fusion method that elemental sulfur is compound in the three-D nano of carbon skeleton, to form three with nano-scale
Tie up carbon/sulphur composite material powder of multi-stage artery structure;
Second stage:Conducting polymer coats, and obtained carbon/sulphur composite material is added in dispersion liquid, suspension is made
Liquid is sufficiently stirred, and adds oxidant, is stirred, and is filtered, cleaning, and the more of high score conducting polymer cladding are obtained after vacuum drying
Hole carbon/sulphur multi-element composite positive pole material;
Specific preparation method includes the following steps:
A, the iron compound superfines of polymer overmold:In the high molecular weight water soluble polymer of a concentration of 10-30mg/ml
Middle addition foaming agent, 5-10min is ultrasonically treated after mixing thoroughly, and 10-14h is dried at 60-80 DEG C to get the iron of polymer overmold
Close object superfines;
B, three-dimensional porous carbon nanomaterial is prepared:Powder made from step a is put into quartz boat, in nitrogen atmosphere condition
Under, it is warming up to 600-800 DEG C with the rate of 5-10 DEG C/min, 0.8-1.2h is to get three-dimensional porous carbon nanomaterial for processing;
C, secondary heat treatment:Under the conditions of 110-130 DEG C, three-dimensional porous carbon nanomaterial prepared by step b is immersed in
8-12h in the hydrochloric acid solution of a concentration of 1-2mol/L, taking-up are washed with deionized to neutrality;
D, carbon/sulphur composite material powder is prepared:The material that step c is obtained is with distillation sulphur powder by 1:The mass ratio of (1-3)
Mixing grinding is placed on the small-sized reaction kettle of sealing and in taking a breath in glove box, finally handles 10-14h under the conditions of 150-160 DEG C,
Carbon/sulphur composite material powder is obtained after cooling;
E, suspension is prepared:Polymer monomer and template are pressed 1:It is dissolved in redistilled water after 2 mass ratio mixing
It is configured to the homogeneous solution of mass fraction 2-5%, solution is placed in -1~1 DEG C of cryogenic box, is added solution quality 2-5%'s
Carbon/sulphur composite material powder, stirs evenly to obtain suspension;
F, oxidant is prepared:P-methyl benzenesulfonic acid is dissolved in, quality depth is made in redistilled water as the molten of 0.3-0.5%
Liquid presses 1 with p-methyl benzenesulfonic acid iron ethanol solution:1 volume ratio is mixed to get solution, adds the 0.3-0.5% of solution quality
Imidazoles, mixing is up to oxidant;
G, conducting polymer coats:Under conditions of temperature is -1~1 DEG C, suspension and oxidant are pressed into (1-3):1
Volume ratio weighs measurement oxidant, is added by several times into suspension, is filtered by vacuum after reacting 12-24h, the solid first that will be obtained
Alcohol and distilled water elute repeatedly successively, and the multi-element composite positive pole material of high score conducting polymer cladding is obtained after vacuum drying.
The high molecular weight water soluble polymer is one or both of polyvinylpyrrolidone, polyvinyl alcohol.
The foaming agent is ferric nitrate, FePC one or two.
The polymer monomer is one kind in aniline, pyrroles, thiophene or polyethylene dioxythiophene.
The template is polystyrenesulfonate.
The carbon/sulphur composite material powder, for apparent size in 150-350nm, interior three-dimensional mesopore size is 5-
10nm。
The gradation is added to suspension, every to be added every other hour specifically when oxidant is added into suspension
Once until whole additions, each addition is the 10% of residual oxidizing agent total amount.
The vacuum drying, drying temperature are 55-65 DEG C, drying time 6-12h.
The multi-element composite positive pole material, as preparing lithium-sulfur cell.
First, by business molysite (ferric nitrate, FePC one or two kinds of) and high molecular weight water soluble polymer be dissolved in from
Sub- water, high molecular weight water soluble polymer as carbon matrix precursor, molysite as foaming agent, after mixed aqueous solution evaporates deionized water,
The co-precipitation object for forming high molecular polymer and molysite, during evaporating deionized water, due to polar molysite and polymerization
Highly polar > C=O functional groups have very strong compatibility, the Fe (NO of crystallization in object3)3Nano-particle is by a large amount of polymer
It is coated with.High-temperature heat treatment Fe salt polymer powders form three-dimensional honeycomb shape structure under the conditions of nitrogen atmosphere.Since ferric nitrate decomposes
Temperature and polyvinylpyrrolidone softening temperature section overlap, and heat treatment process can occur from foamed phenomenon, and ferric nitrate decomposes production
The polymer that raw gas can advertise softening forms bubble, and foam gradually damaged can form three-dimensional honeycomb shape afterwards to a certain extent greatly
Skeleton structure.There is a large amount of Fe nanometer particles insertion (PCF/Fe) in the carbon plate of sheet, PCF/Fe is by the macropore structure that is mutually communicated
At, be similar to it is cellular.Fe nanometer particles embedded in carbon plate are removed with hydrochloric acid, the original pattern of material and microstructure energy structure obtain
It is kept to fine.Due to the removing of embedded Fe nanometer particles, abundant micropore/mesoporous, final step is introduced in carbon plate,
Diffusion method is melted under the conditions of 155 DEG C and fills sulphur, since viscosity is minimum under the conditions of 155 DEG C for elemental sulfur, in three-dimensional multistage pore passage structure
Liquid sulfur is adsorbed in duct under micropore/mesoporous capillary force in carbon skeleton, realizes the evenly dispersed of elemental sulfur, to
Obtain three-dimensional multistage pore structure carbon/sulphur composite material.
The temperature that the monomer of the application high-molecular compound polymerize is relatively low (usually less than 100 DEG C), this feature is protected
It has demonstrate,proved and has coated the feasibility of one layer of protective shell in sulphur carbon complex surface in situ under cryogenic conditions;High score as Physical barriers
Proton conducting polymer with excellent mechanical flexibility due to that can be effectively relieved the volume effect that anode occurs in charge and discharge process
It answers.
Porous carbon nanometer matrix has high conductivity, high-specific surface area and abundant pore structure, can effectively facilitate charge biography
Defeated, stress variation still will be single caused by volume change in the intermediate discharging product diffusion of limitation, buffering elemental sulfur cyclic process
Matter sulphur, which is encapsulated in the single porous carbon base body of pore-size distribution, can cause porous carbon base body to be in partly or entirely filling elemental sulfur
State.On the one hand, if nano pore is partially filled with the decline that elemental sulfur can cause porous carbon matrix hole to hold utilization rate, another party
Li+ is caused to exist if nano pore is filled up completely full elemental sulfur and electrolyte can be caused effectively parent not moisten all active materials in face
Dynamics diffusion in carbon base body is suppressed.It is limited so as to cause specific discharge capacity and the high rate performance promotion of electrode material.
Therefore, it is considered as a kind of effective raising electrode ion transmission dynamics to prepare the carbon base body with multi-stage artery structure
Method.
Porous carbon materials have high specific surface area and flourishing pore structure can adequately meet just high electronics, from
The requirement of sub- conduction velocity, conducting polymer cladding can effectively fetter more sulphions in anode composite;Improving active matter
On the basis of matter utilization rate, porous, electrically conductive matrix and flexible conductive polymer can the volume of effective buffers active material sulphur become
Change stress.In addition, by can further limit the migrating of more sulphions, efficiently solid to nanocomposite is surface-functionalized
Sulphur.
In conclusion the beneficial effects of the present invention are:The present invention utilizes from foaming and constructs one kind with multi-stage porous knot
The three-dimensional carbon skeleton of structure, as the carrier of active material elemental sulfur, with elemental sulfur it is compound after, be used for lithium as combination electrode material
Sulphur cell positive electrode.Using etal molysite and high molecular polymer as presoma, being prepared by from foaming, being aided with acid etch has
Three-dimensional multistage pore passage structure and the carbon skeleton with high-specific surface area and Kong Rong, and as substrate, utilize the side of melting diffusion
Method prepares carbon/sulphur composite positive pole.The macro of porous carbon in the 3D hierarchical porous structures carbon/sulphur composite positive pole, it is mesoporous can
As lithium reaction of Salmon-Saxl nano-reactor, sulphur is consolidated in physics confinement, and macropore then promotes ion to transmit dynamics, and its three-dimensional framework knot
Structure provides continuous electronic access, thus has excellent storage lithium performance.Lid is coated with conducting high polymers object to be modified, macromolecule
Conducting polymer not only could be formed with the three-dimensional conductive network structure of effect, but also the flexible chain of material is also to elemental sulfur and battery
Intermediate product has certain suction-operated, can alleviate the volume expansion problem generated during discharge and recharge reaction.In addition, polymerization
If there are positively charged amine or imine groups on object material chain, battery intermediate product can also be adsorbed by electrostatic interaction, with
This improves the cycle performance of lithium-sulfur cell, for lithium sulfur battery anode material design construction provides new approaches.
Description of the drawings
Fig. 1:Three-dimensional multistage pore structure carbon/sulphur composite material preparation flow figure;
Fig. 2:Porous carbon/sulphur multi-element composite positive pole material preparation flow figure of conducting polymer cladding;
Fig. 3:Polymer/porous carbon/S positive electrodes the scanning electron microscope and transmission electron microscope picture prepared in embodiment 1;
Fig. 4:Polymer/the porous carbon prepared in embodiment 1 /S positive electrode XRD diffraction patterns;
Fig. 5:The nitrogen Adsorption and desorption isotherms and pore analysis of the polymer/porous carbon/S positive electrodes prepared in embodiment 1;
Fig. 6:The characteristic of the polymer/porous carbon/S positive electrodes prepared in embodiment 1 and the charge-discharge performance under 0.5C
Fig. 7:The characteristic and 0.5C of the polymer/porous carbon/S positive electrodes prepared in embodiment 1,2C, 5C current densities
Under cycle performance.
Specific implementation mode
Specific embodiments of the present invention will be described in further detail below, but the invention is not limited in these realities
Mode is applied, it is claimed to still fall within the claims in the present invention for any improvement or replacement on the present embodiment essence spirit
Range.
Embodiment 1
First stage:The preparation of the carbon of three-dimensional multistage pore passage structure/sulphur composite material powder
A, the iron compound superfines of polymer overmold:Configure 200mL polyvinylpyrrolidones (K30) solution, solution
The ferric nitrate of 50g is then added in a concentration of 30mg mL-1, and ultrasound 5min, solution is transferred in convection oven after whisking uniformly
In, dry 12h under the conditions of 80 DEG C;Gained yellow product is ground with agate, obtains the ferric nitrate of polyvinylpyrrolidone cladding
Superfines.
B, three-dimensional porous carbon nanomaterial is prepared:Above-mentioned gained powder is put into quartz boat, under the conditions of nitrogen atmosphere in
700 DEG C of heat treatment 1h, heating rate is 5 DEG C/min, finally obtains black, fluffy three-dimensional porous carbon nanomaterial.
C, secondary heat treatment:By the material obtained by step b in 2mol/L aqueous hydrochloric acid solutions hydro-thermal process under the conditions of 120 DEG C
Then 10h is washed with deionized water to neutrality.
D, carbon/sulphur composite material powder is prepared:7g three-dimensional multistage pore structure carbon skeletons are uniformly mixed with 13g distillations sulphur powder
And grind, small-sized reaction kettle is so transferred to and in taking a breath in glove box, finally by the small-sized reaction kettle of sealing under the conditions of 155 DEG C
12h is handled, the composite material obtained after cooling is spare.
Second stage:Conducting polymer coats
E, suspension is prepared:Polyethylene dioxythiophene monomer (EDOT) and template polystyrenesulfonate (PSS) are pressed
Mass ratio 1:2 be dissolved in the homogeneous solution of mass fraction 2.5% is configured in redistilled water (can be a small amount of ethyl alcohol to be added in solution
To promote monomer to dissolve), solution is placed in cryogenic box, temperature is 0 DEG C, then in mass ratio 3% is added the three of step d preparations
Dimension porous structure carbon skeleton sulphur is sufficiently stirred, and forms uniformly mixed suspension.
F, oxidant is prepared:Weigh a certain amount of p-methyl benzenesulfonic acid (TSA) be dissolved in redistilled water be configured to quality depth
Degree mixes for 0.3% solution with the p-methyl benzenesulfonic acid iron ethanol solution (Xin Zhou nations company OX-100B) of 40% quality depth
Even (volume ratio 1:1) 0.4% imidazoles, is added as oxidation retarder, solution is stirred evenly;
G, conducting polymer coats:By oxidizing agent solution 100mL that above-mentioned steps f is prepared 0 DEG C of condition be slowly added dropwise into
In the monomer mix suspending liquor (200mL) that above-mentioned steps e is prepared, it is kept stirring, oxidizing agent solution will be added by several times, every
The 10% of one hour addition total amount carries out this reaction for 24 hours until whole additions at 0 DEG C.After reaction stops, vacuum is taken out
Filter, obtained solid methanol and distilled water are eluted repeatedly successively;
H, it is dried in vacuo:It is placed into later in vacuum drying chamber and keeps 12h at 60 DEG C, obtain navy blue polymerization cladding
Multi-element composite material can be used as the positive electrode of lithium-sulfur cell.
Embodiment 2
First stage:The preparation of the carbon of three-dimensional multistage pore passage structure/sulphur composite material powder
A, the iron compound superfines of polymer overmold:Configure 240mL poly-vinyl alcohol solutions, solution concentration 20mg
The FePC of 60g is then added in mL-1, ultrasound 10min after whisking uniformly, during solution is transferred in convection oven, 70 DEG C of items
Dry 14h under part;Gained yellow product is ground with agate, obtains the ferric nitrate superfines of polyvinylpyrrolidone cladding.
B, three-dimensional porous carbon nanomaterial is prepared:Above-mentioned gained powder is put into quartz boat, under the conditions of nitrogen atmosphere in
800 DEG C of heat treatment 1.2h, heating rate is 10 DEG C/min, finally obtains black, fluffy three-dimensional porous carbon nanomaterial.
C, secondary heat treatment:By the material obtained by step b in 1.5mol/L aqueous hydrochloric acid solutions under the conditions of 130 DEG C at hydro-thermal
8h is managed, is then washed to neutrality with deionized water.
D, carbon/sulphur composite material powder is prepared:5g three-dimensional multistage pore structure carbon skeletons are uniformly mixed with 10g distillations sulphur powder
And grind, small-sized reaction kettle is so transferred to and in taking a breath in glove box, finally by the small-sized reaction kettle of sealing under the conditions of 160 DEG C
10h is handled, the composite material obtained after cooling is spare.
Second stage:Conducting polymer coats
E, suspension is prepared:By aniline monomer and template polystyrenesulfonate (PSS) in mass ratio 1:2 are dissolved in two
The homogeneous solution (can be a small amount of ethyl alcohol to be added in solution to promote monomer to dissolve) of mass fraction 3% is configured in secondary distilled water,
Solution is placed in cryogenic box, temperature is 1 DEG C, and the composite material that then prepared by mass ratio 2% addition step d is sufficiently stirred,
Form uniformly mixed suspension.
F, oxidant is prepared:Weigh p-methyl benzenesulfonic acid (TSA) be dissolved in redistilled water be configured to quality depth be 0.5%
Solution be uniformly mixed (volume ratio with the p-methyl benzenesulfonic acid iron ethanol solution (Xin Zhou nations company OX-100B) of 40% quality depth
1:1) 0.3% imidazoles, is added as oxidation retarder, solution is stirred evenly;
G, conducting polymer coats:The oxidizing agent solution that above-mentioned steps f is prepared is slowly added dropwise under the conditions of 1 DEG C
It states in the monomer mix suspending liquor that step e is prepared, is kept stirring, oxidizing agent solution will be added by several times, every to add every other hour
Enter the 10% of total amount until whole additions, this reaction is carried out for 24 hours at -1 DEG C, after reaction stops, vacuum filtration will obtain
Solid methanol and distilled water elute repeatedly successively;
H, it is dried in vacuo:Be placed into later in vacuum drying chamber in, keep 8h at 65 DEG C, obtain navy blue polymerization cladding
Multi-element composite material can be used as the positive electrode of lithium-sulfur cell.
Embodiment 3
First stage:The preparation of the carbon of three-dimensional multistage pore passage structure/sulphur composite material powder
A, the iron compound superfines of polymer overmold:Configure 200mL polyvinylpyrrolidones (K30) solution, solution
The FePC of 50g is then added in a concentration of 15mg mL-1, and ultrasound 8min, solution is transferred in convection oven after whisking uniformly
In, dry 10h under the conditions of 60 DEG C;Gained yellow product is ground with agate, obtains the ferric nitrate of polyvinylpyrrolidone cladding
Superfines.
B, three-dimensional porous carbon nanomaterial is prepared:Above-mentioned gained powder is put into quartz boat, under the conditions of nitrogen atmosphere in
650 DEG C of heat treatment 1h, heating rate is 8 DEG C/min, finally obtains black, fluffy three-dimensional porous carbon nanomaterial.
C, secondary heat treatment:By the material obtained by step b in 1mol/L aqueous hydrochloric acid solutions hydro-thermal process under the conditions of 110 DEG C
Then 10h is washed with deionized water to neutrality.
D, carbon/sulphur composite material powder is prepared:8g three-dimensional multistage pore structure carbon skeletons are uniformly mixed with 18g distillations sulphur powder
And grind, small-sized reaction kettle is so transferred to and in taking a breath in glove box, finally by the small-sized reaction kettle of sealing under the conditions of 160 DEG C
14h is handled, the composite material obtained after cooling is spare.
Second stage:Conducting polymer coats
E, suspension is prepared:By thiophene monomer and template polystyrenesulfonate (PSS) in mass ratio 1:2 be dissolved in it is secondary
The homogeneous solution (can be a small amount of ethyl alcohol to be added in solution to promote monomer to dissolve) of mass fraction 4% is configured in distilled water, it will
Solution is placed in cryogenic box, and temperature is 0 DEG C, then in mass ratio 3% three-dimensional porous structure carbon skeleton sulphur prepared by step d is added
It is sufficiently stirred, forms uniformly mixed suspension.
F, oxidant is prepared:Weigh p-methyl benzenesulfonic acid (TSA) be dissolved in redistilled water be configured to quality depth be 0.5%
Solution be uniformly mixed (volume ratio with the p-methyl benzenesulfonic acid iron ethanol solution (Xin Zhou nations company OX-100B) of 40% quality depth
1:1) 0.3% imidazoles, is added as oxidation retarder, solution is stirred evenly;
G, conducting polymer coats:The oxidizing agent solution that above-mentioned steps f is prepared is slowly added dropwise in -1 DEG C of condition into above-mentioned
It in the monomer mix suspending liquor that step e is prepared, is kept stirring, oxidizing agent solution will be added by several times, every to be added every other hour
The 10% of total amount carries out this reaction for 24 hours until whole additions at 0 DEG C.After reaction stops, vacuum filtration, by what is obtained
Solid methanol and distilled water elute repeatedly successively;
H, it is dried in vacuo:It is placed into later in vacuum drying chamber and keeps 10h at 55 DEG C, obtain navy blue polymerization cladding
Multi-element composite material can be used as the positive electrode of lithium-sulfur cell.
Test to resulting materials performance:
Material physical property is tested:
(1) scanning electron microscope (SEM)
Using 450 field emission scanning electron microscopes (FESEM) of U.S. FEI NOVA Nano SEM to the surface of material
Pattern is characterized.It needs sample being adhesive on sample stage using conduction before characterizing sample, is purged through nitrogen and ensure powder
End is not fallen off, in addition, sample chamber need to be then placed into through metal spraying to improve its electric conductivity for the bad sample of electric conductivity, profit
The secondary electron signal being excited with sample is imaged to observe the surface topography of sample;
By taking multi-element composite material prepared by embodiment 1 as an example, Fig. 3 left figures are multi-element composite material scanning electron microscope (SEM) photographs;
(2) transmission electron microscope (TEM):The Tecnai produced using Philips companies of transmission electron microscope model Holland
G220 type transmission electron microscopes, test sample process are:A small amount of solid powder sample is taken to be scattered in the liquor-saturated solution of second, ultrasonic 10min takes
A few drop sample suspensions drop on the copper mesh grid of plating carbon, and drying places it in transmission electron microscope vacuum chamber, vacuumizes, and carries out sample
Characterization;
By taking multi-element composite material prepared by embodiment 1 as an example, Fig. 3 right figures are multi-element composite material transmission electron microscope pictures;
(3) X-ray diffraction (XRD):Using Japan Ricoh (Rigaku) company D/max-2400 model X-ray diffractions
Instrument, x-ray source CnKa, test angle is ranging from:5≤2 θ≤90 °, it is 10 ° of min-1 to sweep speed.Sample Scan ranging from 5-
80 °, sweep speed is 10 ° of min-1, tube current 100mA, voltage 40kV;
By taking multi-element composite material prepared by embodiment 1 as an example, Fig. 4 is multi-element composite material XRD diffraction patterns;
(4) isothermal nitrogen adsorption desorption:It is filled using U.S.'s Micrometries ASAP2020 type nitrogen physisorption isothermal adsorption desorptions
Tatami characterizes specific surface area, Kong Rong and the pore-size distribution of making each electrode base material.It is needed before to sample test by sample
It deaerates 6 hours under the conditions of 120 DEG C, then carries out the test of nitrogen physisorption isothermal adsorption desorption.It is bent according to obtained isothermal adsorption desorption
Line, specific surface area, the Kong Rong of sample are calculated using BET models, and DFT models obtain the pore-size distribution of sample;
By taking multi-element composite material prepared by embodiment 1 as an example, Fig. 5 is multi-element composite material nitrogen Adsorption and desorption isotherms and aperture
Analysis chart;
The performance test of chemical property:
By the preparation-obtained composite material of 1 second stage of embodiment, conductive agent Ketjen black and binder PVDF are pressed respectively
7:2:1 ratio is placed in mortar and is fully ground that (about 1h obtains uniform pasty slurry, then after being evenly coated in precompressed
Nickel foam disk on, then in vacuum drying chamber under the conditions of 60 DEG C drying weighed afterwards for 24 hours, gained anode electrode piece
Active material is about 2-4mg.Make the anode of button cell with above-mentioned made electrode sliceMetal lithium sheetAs cathode, the polypropylene microporous barrier of model Celgard 2400 makees battery diaphragm1M
LiN (CF3SO2) 2 (LiTFSI)/DOL (1,3- dioxolanes)+DME (Yi glycol Er Jia Ugly) (volume ratio 1:1)+1wt%
LiNO3 (lithium nitrate) is electrolyte, and press-button type battery packaging technology carries out CR2032 type buttons in the glove box full of nitrogen
The assembling of battery.After cell package is complete, it is sealed and removed glove box in sample sack, is existed with sealing machine rapidly
Battery is subjected to pressurization under 80MPa, electrolyte is made to be sufficiently submerged in active material, last battery stands 12h at room temperature
Carry out various performance tests again afterwards.
(5) cyclic voltammetric (CV) is tested:It is enterprising in the CHI660D electricity work stations of Shanghai Chen Hua Instrument Ltd. production
Row, voltage window are 0.0-3.0 (lithium-sulfur cell 1.5-3.0V), and it is 0.1mVS-1 to sweep speed;
By taking multi-element composite material prepared by embodiment 1 as an example, Fig. 6 left figures are multi-element composite material performance plots;Right figure is more
Charge-discharge performance figure of first composite material at 0.5C;
(6) battery charging and discharging loop test:Using the CT-3008 charge and discharges of the new Weir Electronics Co., Ltd. production in Shenzhen
Electric tester TC53 systems carry out at room temperature.To battery under required different current densities and 1.5-3.0V voltage ranges
Charge and discharge cycles test is carried out, specific charge-discharge test program is as follows:(5min) → constant-current discharge is shelved to 1.5V
(180min) → it shelves (5min);
By taking multi-element composite material prepared by embodiment 1 as an example, Fig. 7 left figures are charge and discharge of the multi-element composite material at 0.5C
Cycle performance figure;Right figure is charge-discharge performance figure of the multi-element composite material at 2C, 5C;
The micropore of porous carbon, mesoporous Zuo Wei Li reaction of Salmon-Saxl nanometers are anti-in three-dimensional multistage pore structure carbon/sulphur composite positive pole
Device, physics confinement is answered to consolidate sulphur, macropore then promotes ion to transmit dynamics, and its Wang Wei skeleton structure provides continuous electronic and leads to
Road, the application composite material have excellent storage lithium performance, and by test, under the conditions of current density is 0.5C, electrode is for the first time
Electric discharge specific volume is up to 990mAh g-1, under 2-5C current densities, the specific capacity conservation rate of anode composites is up to after recycling 500 times
70% or more.
Finally illustrate, the above material prepared using embodiment 1 is similarly directed to as experimental performance test object
Embodiment 2, embodiment 3 are equally applicable, and above example, are merely illustrative of the technical solution of the present invention and unrestricted, to the greatest extent
Pipe has been described in detail the present invention by above-described embodiment, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (10)
1. a kind of preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery, which is characterized in that include following step
Suddenly:
First stage:Carbon/sulphur composite material powder is prepared, using constructing the three-dimensional carbon bone with hierarchical porous structure from foaming
Frame, it is using fusion method that elemental sulfur is compound in the three-D nano of carbon skeleton, to form the three-dimensional with nano-scale
The carbon of multi-stage artery structure/sulphur composite material powder;
Second stage:Conducting polymer coats, and obtained carbon/sulphur composite material is added in dispersion liquid, suspension is made, filled
Point stirring, add oxidant, stir, filter, cleaning, obtained after vacuum drying high score conducting polymer cladding porous carbon/
Sulphur multi-element composite positive pole material.
2. the preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery as described in claim 1, feature exist
In specific preparation method includes the following steps:
A, the iron compound superfines of polymer overmold:Add in the high molecular weight water soluble polymer of a concentration of 10-30mg/ml
Enter foaming agent, 5-10min is ultrasonically treated after mixing thoroughly, 10-14h is dried at 60-80 DEG C to get the iron compound of polymer overmold
Superfines;
B, three-dimensional porous carbon nanomaterial is prepared:Powder made from step a is put into quartz boat, under the conditions of nitrogen atmosphere, with
The rate of 5-10 DEG C/min is warming up to 600-800 DEG C, and 0.8-1.2h is to get three-dimensional porous carbon nanomaterial for processing;
C, secondary heat treatment:Under the conditions of 110-130 DEG C, three-dimensional porous carbon nanomaterial prepared by step b is immersed in concentration
For 8-12h in the hydrochloric acid solution of 1-2mol/L, taking-up is washed with deionized to neutrality;
D, carbon/sulphur composite material powder is prepared:The material that step c is obtained is with distillation sulphur powder by 1:The quality of (1-3) compares mixing
Grinding is placed on the small-sized reaction kettle of sealing and in taking a breath in glove box, and 10-14h is finally handled under the conditions of 150-160 DEG C, is cooled down
After obtain carbon/sulphur composite material powder;
E, suspension is prepared:Polymer monomer and template are pressed 1:It is dissolved in redistilled water and preparing after 2 mass ratio mixing
At the homogeneous solution of mass fraction 2-5%, solution is placed in -1~1 DEG C of cryogenic box, be added the carbon of solution quality 2-5%/
Sulphur composite material powder stirs evenly to obtain suspension;
F, oxidant is prepared:P-methyl benzenesulfonic acid is dissolved in the solution for being made that quality depth is 0.3-0.5% in redistilled water, with
P-methyl benzenesulfonic acid iron ethanol solution presses 1:1 volume ratio is mixed to get solution, adds the miaow of the 0.3-0.5% of solution quality
Azoles, mixing is up to oxidant;
G, conducting polymer coats:Under conditions of temperature is -1~1 DEG C, suspension and oxidant are pressed into (1-3):1 volume
Than weighing measurement oxidant, be added into suspension, be filtered by vacuum after reacting 12-24h by several times, by obtained solid methanol and
Distilled water elutes repeatedly successively, and the multi-element composite positive pole material of high score conducting polymer cladding is obtained after vacuum drying.
3. the preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery as claimed in claim 2, feature exist
In the high molecular weight water soluble polymer is one or both of polyvinylpyrrolidone, polyvinyl alcohol.
4. the preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery as claimed in claim 2, feature exist
In the foaming agent is ferric nitrate, FePC one or two.
5. the preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery as claimed in claim 2, feature exist
In the polymer monomer is one kind in aniline, pyrroles, thiophene or polyethylene dioxythiophene.
6. the preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery as claimed in claim 2, feature exist
In the template is polystyrenesulfonate.
7. the preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery as claimed in claim 2, feature exist
In the carbon/sulphur composite material powder, for apparent size in 150-350nm, interior three-dimensional mesopore size is 5-10nm.
8. the preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery as claimed in claim 2, feature exist
In the gradation is added to suspension, primary straight per being added every other hour specifically when oxidant is added into suspension
To whole additions, each addition is the 10% of residual oxidizing agent total amount.
9. the preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery as claimed in claim 2, feature exist
In the vacuum drying, drying temperature is 55-65 DEG C, drying time 6-12h.
10. the preparation method of three-dimensional porous carbon structure anode composite material of lithium sulfur battery as claimed in claim 1 or 2, special
Sign is, the multi-element composite positive pole material, as preparing lithium-sulfur cell.
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| EP3503265A1 (en) * | 2017-12-20 | 2019-06-26 | Ricoh Company, Ltd. | Active material, electrode, and power storage element |
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