CN107946569A - A kind of N doping ordered mesopore carbon sulfur materials and its preparation method and application - Google Patents
A kind of N doping ordered mesopore carbon sulfur materials and its preparation method and application Download PDFInfo
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- CN107946569A CN107946569A CN201711150363.3A CN201711150363A CN107946569A CN 107946569 A CN107946569 A CN 107946569A CN 201711150363 A CN201711150363 A CN 201711150363A CN 107946569 A CN107946569 A CN 107946569A
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- H—ELECTRICITY
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a kind of N doping ordered mesopore carbon sulfur materials, using SBA 15, phenol, formaldehyde, guanine and sulphur as raw material, not activated N doping ordered mesopore carbon sulfur materials are obtained by the synthesising mesoporous carbon dust of soft template method, again by liquid phase in-situ compositing, finally activated with fusion method and obtain N doping ordered mesopore carbon sulfur materials, sulfur content is 60 ~ 70%.Its preparation method comprises the following steps：1）Soft template method prepares the order mesoporous carbon dust of N doping, and 2）The not activated N doping ordered mesopore carbon sulfur materials of liquid phase in-situ compositing preparation, 3）The activation of N doping ordered mesopore carbon sulfur materials.As the application of lithium-sulphur cell positive electrode, when current density is 335 mA/cm2When, first discharge specific capacity is 1100 ~ 1200 mAh/g, and after 170 circulations, special capacity fade to 600 ~ 650 mAh/g, is 50% to discharge first, and average each attenuation rate is 0.29%.The present invention has sulfur content high, suppresses the dissolving of part polysulfide, effectively suppresses the advantages of shuttle effect causes.
Description
Technical field
The invention belongs to battery technology field, and in particular to a kind of N doping ordered mesopore carbon-sulfur materials and its preparation side
Method and application.
Background technology
With social development, the mankind gradually increase for the demand of the energy.Change however as to coal, oil, natural gas etc.
The lasting acceleration of nearly 200 years of stone fuel source exploit, resource oneself progressively tend to exhaust.Accordingly, it is capable to source problem and environmental problem into
For global concern and it is in the urgent need to address the problem of.Development with high-energy, high density, high security, it is environmentally protective and it is low into
This secondary cell is of great significance in new energy field.Lithium-sulfur cell is that have higher energy density in secondary cell system
One kind, using elemental sulfur or sulphurous materials as a positive electrode active material, its theoretical energy density reaches 2600Wh/kg, and has
The advantages that Sulphur ressource enriches, is environmental-friendly, is cheap.The lithium-sulfur cell of high sulfur content is close with high capacity density and energy
Degree is conducive to the demand of electric automobile, can realize that the technology for overcoming lithium ion battery energy density to meet electric automobile is asked
Topic.
Activated carbon is to be used as the porous carbon materials compound with sulphur earliest.Early in 2002, Wang etc. was just by the sulphur of melting
Penetrated into the mode of distribution step heat treatment in the pore structure of activated carbon（Document 1：J Wang, L Liu, Z Ling, et
al. Polymer lithium cells with sulfur composites as cathode materials[J].
Electrochimica Acta, 2003,48: 1861-1867.）, 0.3 A cm-1Under current density, sulfur content is 30 wt%
When, specific capacity is 800 mAh g first-1, specific capacity is maintained at 440 mAh g after 25 circulations-1, but when sulfur content is 60.9
During wt%, specific capacity only has 180 mAh g first-1.There are problems with for the material：（1）The load sulfur content of positive electrode is relatively low；
（2）：And specific capacity is very low when carrying sulfur content and being more than 50%.
Wu Feng etc. has synthesized the ordered mesopore carbon of high-specific surface area and multi-cellular structure using optimize technique（Document 2：F
Wu, S X Wu, R J Chen, et al. Electrochemical performance of sulfur composite
Materials for rechargeable lithium batteries [J] Chinese Chemical Letters,
2009,20: 1255-1258.）, elemental sulfur is distilled by the method for heating and deposit in ordered mesopore carbon micropore, obtain
Carbon sulphur composite material sulfur content 49%, 100mA g-1, under current density, first discharge specific capacity is up to 1180.8 mAh g-1,
Specific capacity is also maintained at 720.4 mAh g after circulating 60 weeks-1.The material has the drawback that（1）：Current density is relatively low；（2）：
And carry sulfur content and be not above 50%.
Song etc. prepares nanometer Mg using sol-gal process0.6Ni0.40 particle suppresses more vulcanizations as the additive of sulphur cathode
Dissolving and promotion redox reaction of the thing in electrolyte（Document 3：Min-Sang Song, Sang-Cheol Han, Hyun-
Seok Kim, Jin-Ho Kim, Ki-Tae Kim, Yong-Mook Kang, Hyo-Jun Ahn, S. X. Dou,
Jai-Young Lee.Effects of nanosized adsorbing material on electrochemical
properties of sulfur cathodes for Li/S second batteries. Journal of the
Electrochemical Society. 2004,151 (6):A791-A795）.The material has the drawback that（1）：Colloidal sol
Metal alkoxide cost is higher in gel method；（2）：The shortcomings of self-propagating high-temperature synthesis is difficult to control there are reaction process.
The content of the invention
The object of the present invention is to provide a kind of N doping ordered mesopore carbon-sulfur materials, solve following existing for lithium-sulfur cell
Technical problem：
First, the problem of elemental sulfur is electronics and ion insulator at room temperature；
2nd, cathode carries the problem of sulfur content is no more than 50%；
3rd, sulphur is easily soluble in organic electrolyte in the intermediate product polysulfide of electrochemical reduction and causes specific capacity and huge decay
Problem.
In order to realize foregoing invention purpose, the technical solution adopted by the present invention is：
A kind of N doping ordered mesopore carbon-sulfur materials, using SBA-15, phenol, formaldehyde, guanine and sulphur as raw material, meet raw material
SBA-15, phenolic resin, the mass ratio of guanine and sulphur are 1:（6-7）:1:（2-3）, pass through the synthesising mesoporous carbon dust of soft template method
End, obtain not activated N doping ordered mesopore carbon-sulfur materials by liquid phase in-situ compositing again, is finally activated with fusion method
Obtain N doping ordered mesopore carbon-sulfur materials, the phenolic resin be by:Phenol solution and the NaOH solution of 20wt% with（4-
5）：1 ratio mixing, stirs 10-20 min, is then added dropwise formaldehyde at 40-60 DEG C, and the ratio of formaldehyde and phenol is（4-
5）:1, temperature rises to 70-80 DEG C the reaction was continued 50-90min.After cooling, with dilute hydrochloric acid adjustment pH to pH=7-8 and then 50-60
DEG C vacuum drying, finally obtain product dissolving in ethanol, the ratio of ethanol and product is（4-5）：1, the N doping has
The sulfur content of sequence mesoporous carbon-sulfur materials is 60 ~ 70 %.
The preparation method of N doping ordered mesopore carbon-sulphur positive electrode, it is characterised in that comprise the following steps：
Step 1）Soft template method prepares the order mesoporous carbon dust of N doping, with SBA-15, phenolic resin, guanine and absolute ethyl alcohol
Mass ratio be 1:（6-7）:1:（10-20）, SBA-15, phenolic resin, guanine and absolute ethyl alcohol, room are added into beaker
When the lower magnetic stirrer 15-25 of temperature is small, drying, is then transferred in tube furnace and is passed through N2, with the heating of 3-5 DEG C/min
Speed is warming up to 750-850 DEG C of carbonization insulation 1-3 h, finally removes silica template with the HF that concentration is about 10wt%, i.e.,
It can obtain the order mesoporous carbon dust of N doping (NOMCs)；
Step 2）Liquid phase in-situ compositing prepares not activated N doping ordered mesopore carbon-sulfur materials, and a certain amount of sulphur is molten
In sodium sulfide solution, the aqueous solution of sodium polysulfide is obtained, then by step 1）The order mesoporous carbon dust of gained N doping adds
Enter the aqueous solution of sodium polysulfide, until carbon material is uniformly mixed with solution, dilute hydrochloric acid solution is slow with 1 ~ 2 drop/sec of speed
It is added dropwise in uniformly mixed solution, the reaction time after being added dropwise is 1 ~ 3 h, after complete reaction, will be obtained scattered equal
Even suspension, then filters, is dried to obtain N doping ordered mesopore carbon-sulfur materials；
Step 3）The activation of N doping ordered mesopore carbon-sulfur materials, by step 2）Obtained not activated N doping is situated between in order
Hole carbon-sulfur materials, at 150-160 DEG C keep the temperature 3~5h, be continuously heating to 280-300 DEG C insulation 30 ~ 60 minutes under the conditions of heat at
Reason obtains N doping ordered mesopore carbon-sulfur materials.
N doping ordered mesopore carbon-application of the sulphur positive electrode as lithium-sulphur cell positive electrode, when current density is 335 mA/
cm2When, first discharge specific capacity is 1100 ~ 1200 mAh/g, after 170 circulations, special capacity fade to 600 ~ 650 mAh/
G, for 50 % to discharge first, average each attenuation rate is 0.29%.
The present invention has the following advantages relative to the prior art：
1st, material of the present invention the experiment proved that sulfur content greatly improves, reachable 60 ~ 70%, specific discharge capacity also greatly improves,
Under 335 mA/ g current densities, up to 1100mAh/g-1200mAh/g, cycle performance also greatly improves, cycle charge-discharge 170
After secondary, specific discharge capacity 600mAh/g-650mAh/g, coulombic efficiency is relatively stablized close to 100%, has preferable cycle performance；
2nd, material of the present invention is improved its electrochemistry and is followed by the dissolving of N doping ordered mesopore carbon success absorbed portion polysulfide
Ring performance；
3rd, N doping ordered mesopore carbon-sulphur composite material compositions that prepared by the present invention are very uniform, and sulphur can sufficiently enter Jie
Inside the carbon of hole, compound is highly uniform.So as to which the active material for suppressing electrode gradually decreases the generation of phenomenon, also effectively suppress by
The polysulfide dissolved caused by shuttle principle reaches caused negative plate and electricity in the anode lithium piece of battery through membrane
The increased phenomenon of pond internal resistance occurs, and then improves the cycle performance of lithium-sulfur cell, reduces the speed of battery capacity decay；
4th, the present invention by the use of N doping ordered mesopore carbon as carrier cost it is low, have a safety feature, repeatability is high, production efficiency height and
Can be with large-scale commercial production.
Brief description of the drawings：
The thermogravimetric curve of Fig. 1 N dopings ordered mesopore carbon-sulphur；
Fig. 2 is N doping ordered mesopore carbon, sublimed sulfur, the XRD curves of N doping ordered mesopore carbon-sulphur；
Fig. 3 is prepared lithium-sulfur cell test loop capacity curve figure.
Embodiment
The present invention is described in further detail present invention with reference to Figure of description, but be not pair by embodiment
The restriction of the present invention.
Embodiment
A kind of preparation method of N doping ordered mesopore carbon-sulphur positive electrode, includes the following steps：
Step 1）Soft template method prepares the order mesoporous carbon dust of N doping, and the ethanol of 18 g is added to 0.66 g SBA-15 of template
In, then be separately added into 6 g phenolic resin, 0.66 g guanines, using magnetic stirrer 12 it is small when, gone to after drying
At 60 DEG C insulation 6 it is small when evaporate water, be then warming up to 100 DEG C insulation 6 it is small when, be then transferred in tube furnace and be passed through
N2And with the speed of 3 DEG C/min be warming up to 800 DEG C carbonization insulation 2 it is small when, finally with concentration be about 10wt% HF remove
Silica template, you can obtain N doping ordered mesopore carbon (NOMCs)；
Step 2）Liquid phase in-situ compositing prepares not activated N doping ordered mesopore carbon-sulfur materials, and 0.6 g sublimed sulfurs is molten
In the sodium sulfide solution of 200 mL, being sufficiently stirred ultrasound again is completely dissolved sulphur, obtains the aqueous solution of sodium polysulfide, then
By step 1）The order mesoporous carbon dust of gained N doping adds the aqueous solution of sodium polysulfide, ultrasonic again after magnetic agitation, until carbon
Material is uniformly mixed with solution, in fume hood, under the conditions of being stirred at room temperature, with peristaltic pump by 200 mL, 0.2 mo1L-1's
Dilute hydrochloric acid solution is slowly added dropwise in the solution that 200 mL are uniformly mixed with a drop speed per second to react, after complete reaction after
2 h of continuous stirring obtain finely dispersed suspension, then filter, are dried to obtain N doping ordered mesopore carbon-sulfur materials；
Step 3）The activation of N doping ordered mesopore carbon-sulfur materials, by step 2）Obtained not activated N doping is situated between in order
Hole carbon-sulfur materials, keeps the temperature 3 h under the conditions of argon gas, 155 DEG C, is continuously heating to 290 DEG C of insulations and obtains N doping in 30 minutes to have
Sequence mesoporous carbon-sulfur materials.
The present embodiment lithium sulfur battery anode material (mass fraction for accounting for lithium-sulphur cell positive electrode is 80%), acetylene black is conductive
(mass fraction for accounting for lithium-sulphur cell positive electrode is 10%, is bonded for agent (mass fraction for accounting for lithium-sulphur cell positive electrode is 10%) and binding agent
Agent be 15wt% Kynoar solution) it is fully dispersed grinding uniformly obtain anode sizing agent, obtained anode sizing agent is coated in
Electrode slice is made in aluminum foil current collector, drying obtains lithium-sulphur cell positive electrode.
Lithium-sulphur cell positive electrode manufactured in the present embodiment, anode (metal lithium sheet) and membrane (polyethylene film) are assembled into together
Lithium-sulfur cell, the electrolyte solution filled in battery is 1,3 one dioxolanes, glycol dimethyl ether, trifluoromethane sulfonic acid imines
The mixed solution of lithium.
N doping ordered mesopore carbon-sulphur positive electrode of gained is tested through XRD, and the results are shown in Figure 1, and elemental sulfur has filled
The inside for entering ordered mesopore carbon divided.
In order to verify in N doping ordered mesopore carbon-sulphur positive electrode, element sulphur accounts for the content in positive electrode, and nitrogen is mixed
Miscellaneous ordered mesopore carbon-sulphur has carried out thermogravimetric analysis, and it is 60.5% to measure distillation sulfur content.
In order to verify the combining case of ordered mesopore carbon and sublimed sulfur, ordered mesopore carbon, sublimed sulfur, N doping have been done respectively
The XRD tests of ordered mesopore carbon-sulphur, N doping ordered mesopore carbon-sulphur XRD diagram show that sublimed sulfur and ordered mesopore carbon have well
Melting mixing.
Fig. 3 is test loop design sketch of the lithium-sulfur cell in lithium-sulfur cell prepared by the present embodiment, can from Fig. 3
To find out, 335mA/cm2Under current density, the lithium-sulfur cell first discharge specific capacity of the present embodiment is 1197.55mAh/g, 170
Special capacity fade is to 600.10mAh/g after secondary circulation；The lithium-sulfur cell of the present embodiment has higher specific capacity and cyclicity
Energy.
Claims (10)
- A kind of 1. N doping ordered mesopore carbon-sulfur materials, it is characterised in that：Using SBA-15, phenol, formaldehyde, guanine and sulphur as Raw material, meets certain mass ratio by the synthesising mesoporous carbon dust of soft template method, obtained again by liquid phase in-situ compositing without work N doping ordered mesopore carbon-sulfur materials of change, are finally activated with fusion method and obtain N doping ordered mesopore carbon-sulfur materials.
- 2. N doping ordered mesopore carbon-sulphur positive electrode according to claim 1, it is characterised in that：The raw material SBA- 15th, the mass ratio of phenolic resin, guanine and sulphur is 1:（6-7）:1:（2-3）.
- 3. N doping ordered mesopore carbon-sulphur positive electrode according to claim 1, it is characterised in that：The phenolic resin Be by:Phenol solution and the NaOH solution of 20wt% with（4-5）：1 ratio mixing, stirs 10-20 min, then in 40-60 DEG C it is added dropwise formaldehyde, the ratio of formaldehyde and phenol is（4-5）:1, temperature rises to 70-80 DEG C the reaction was continued 50-90min；Cooling Afterwards, with dilute hydrochloric acid adjustment pH to pH=7-8 and then 50-60 DEG C of vacuum drying, the product finally obtained dissolves in ethanol, ethanol Ratio with product is（4-5）：1.
- 4. N doping ordered mesopore carbon-sulphur positive electrode according to claim 1, it is characterised in that：The N doping has The sulfur content of sequence mesoporous carbon-sulfur materials is 60 ~ 70 %.
- 5. the preparation method of N doping ordered mesopore carbon-sulphur positive electrode according to claim 1, it is characterised in that including with Lower step：Step 1）Soft template method prepares the order mesoporous carbon dust of N doping, and with certain mass ratio, SBA-15, phenol are added into beaker Urea formaldehyde, guanine and absolute ethyl alcohol, are stirred, and drying, is then transferred in tube furnace and is passed through N2With the heating of 3-5 DEG C/min Speed is warming up to 750-850 DEG C of carbonization insulation 1-3 h, HF finally and removes silica template, you can obtains N doping Order mesoporous carbon dust (NOMCs)；Step 2）Liquid phase in-situ compositing prepares not activated N doping ordered mesopore carbon-sulfur materials, and a certain amount of sulphur is molten In sodium sulfide solution, the aqueous solution of sodium polysulfide is obtained, then by step 1）The order mesoporous carbon dust of gained N doping adds Enter the aqueous solution of sodium polysulfide, until carbon material is uniformly mixed with solution, by dilute hydrochloric acid solution with given pace be slowly added dropwise into Reacted in uniformly mixed solution, after complete reaction, finely dispersed suspension will be obtained, and then filter, be dried to obtain nitrogen Adulterate ordered mesopore carbon-sulfur materials；Step 3）The activation of N doping ordered mesopore carbon-sulfur materials, by step 2）Obtained not activated N doping is situated between in order Hole carbon-sulfur materials, is thermally treated resulting in N doping ordered mesopore carbon-sulfur materials under certain condition.
- 6. preparation method according to claim 5, it is characterised in that：The step 1）SBA-15, phenolic resin, bird are fast The mass ratio of purine and absolute ethyl alcohol is 1:（6-7）:1:（10-20）, the step 1）It is described when the time of stirring is 15-25 small Step 1）Carbonization Conditions be that protection gas is done with nitrogen, carburizing temperature is 750-850 DEG C.
- 7. preparation method according to claim 5, it is characterised in that：The step 2）Sulphur and step 1）N doping The mass ratio of ordered mesopore carbon is（1-2）:1, the step 2）Heating rate be 3 DEG C/min, the time of insulation is 1 ~ 3 h.
- 8. preparation method according to claim 5, it is characterised in that：The step 3）The condition of heat treatment is 150-160 3~5h is kept the temperature at DEG C, 280-300 DEG C is continuously heating to and keeps the temperature 30 ~ 60 minutes.
- 9. N doping ordered mesopore carbon according to claim 1-application of the sulphur positive electrode as lithium-sulphur cell positive electrode, It is characterized in that：When current density is 335 mA/cm2When, first discharge specific capacity is 1100 ~ 1200 mAh/g.
- 10. N doping ordered mesopore carbon according to claim 1-application of the sulphur positive electrode as lithium-sulphur cell positive electrode, It is characterized in that：After 170 circulations, special capacity fade to 600 ~ 650 mAh/g is average each for 50 % to discharge first Attenuation rate is 0.29%.
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| CN109360970B (en) * | 2018-11-20 | 2022-04-08 | 肇庆市华师大光电产业研究院 | Positive electrode material of lithium-sulfur primary battery and preparation method of positive electrode material |
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Application publication date: 20180420 |