CN107579233A - A kind of metal-doped silicon oxide molecular sieve/sulphur carbon complex and its preparation method and application - Google Patents
A kind of metal-doped silicon oxide molecular sieve/sulphur carbon complex and its preparation method and application Download PDFInfo
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Abstract
A kind of metal-doped silicon oxide molecular sieve/sulphur carbon complex and its preparation method and application, it is related to a kind of nano composite material and its preparation method and application.The dissolution of polysulfide can not effectively be limited by preparing sulphur positive electrode and existing the invention aims to solving the existing carrier material based on porous carbon materials and porous oxide material, cause that battery capacity reduces rapidly and porous metal oxide prepares the problem of difficult power consumption is big.A kind of metal-doped silicon oxide molecular sieve/sulphur carbon complex, it is prepared by the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve and the aqueous dispersions of carbon material.Preparation method：First, metal-doped silicon oxide molecular sieve is prepared；2nd, embedding sulfur metal doped silicon oxide molecular sieve is prepared；3rd, carbon material is impregnated, obtains metal-doped silicon oxide molecular sieve/sulphur carbon complex.Metal-doped silicon oxide molecular sieve/sulphur carbon complex is used for the positive pole for preparing lithium-sulfur cell as positive electrode.
Description
Technical field
It is more particularly to a kind of to be applied to lithium sulphur electricity the present invention relates to a kind of nano composite material and its preparation method and application
Nano composite material of pond positive electrode and its preparation method and application.
Background technology
Rechargeable Li-S batteries have high theoretical specific energy density, are 3~5 times of intercalation lithium ion battery, Li-
S batteries are likely to the developing direction of energy-storage system of future generation, particularly with large-scale application, have bright prospects.But
Its wide variety of factor is limited to still have, for example, high internal resistance, self-discharge phenomenon, circulation volume rapidly decline etc. cause it is high
Theoretical energy density has very big difference with actual energy density.Improve these problems, can by design it is new have it is excellent
The mode of the S electrodes of diverse structure.
Lithium ion battery develops by 20 years of researches, has reached the limit of energy density, in general, intercalation
The capacity of material is not over 300mAhg-1.Pure lithium battery electrical automobile range also can only achieve 300km, make electronic
The development of automobile is restricted, and the extensive, energy-storage system of high-energy-density, economy is urgently developed.1962, Herbet and
Element S is used as anode electrode material by Ulam first because S has many excellent properties, as chemical equivalent it is small, it is cheap,
It is non-toxic.There are many researchs for alkali metal-S batteries, such as in temperature can be 300~350 DEG C and work at room temperature
The Na-S batteries of work.The total reaction equation of LI-S batteries is：S8+16Li++16e-→8Li2S, average voltage are 2.15V corresponding
In Li+/ Li, it is the 1/2~2/3 of existing intercalation anode material voltage, theoretical capacity is 1672mAhg-1, in solid-state anode
It is highest in material, therefore is probably obtained most with minimum cost relative to common lithium ion battery, Li-S batteries
Big energy density.Its energy density and bulk density can reach 2500Whkg in theory-1And 2800WhL-1。
It is to add electric conductor adding additives, organic bath handle using S in nineteen sixty, anode that Li-S batteries are formed earliest
The two poles of the earth are separated.This model also provides platform for subsequent research.In the electrolyte, S electrodes mainly undergo 3 mistakes
Journey, under high potential, it happens is that S0→S0.5-Transformation, form solvable polysulfide ions S4 2-.Due to reaction molecular
Attribute, this process is very fast, followed by S0.5-→S1-Transformation, this process can form insoluble Li2S2Solid.
Phase III is Li2S2To Li2S transformation, and the step carried out is most difficult to, because this process needs the transmission of solid phase,
It is relatively slow.Discharge process but only needs step oxidation to complete, and final product is S8 2-.It should be noted that charging
Cheng Zhong, S active material can expand, because Li2S density is smaller, and can reduce in discharge process volume, and this point is in actual design
During should be noted.
And due to doing negative pole using lithium metal, Li in charging process+It is easy to be formed in negative terminal surface generation electroplating deposition
Dendrites lithium metal, when lithium dendrite growth to a certain extent, eventually pass through barrier film and positive contact and cause internal short-circuit of battery,
This is a major reason for causing lithium-sulfur cell poor circulation.Li-S battery positive electrode active materials elemental sulfur be electronics and from
The insulator of son, it is necessary to reversible electrochemical reaction could be completed with conductive agent close contact, but the addition of conductive agent can increase
Passive weight, reduce the energy density of battery.Dispersity of the active material sulphur in conductive agent skeleton also determines electrochemistry
The mass transfer rate and electronics conduction velocity of reaction, if active material disperse it is uneven, it will reduce active material utilization, from
And influence the discharge capacity and cycle performance of battery.In addition, Li-S batteries in charge and discharge process because sulphur is just having two
Discharge platform, the high poly- more lithium sulfides of state of high voltage platform product are soluble in electrolyte, the higher poly- state sulphion (S of dissolving8 2-S6 2-
S4 2-) negative pole can be diffused into, directly react, generated compared with lower valency sulphion with lithium metal, then sulphur positive pole is spread back, then it is secondary
Into higher valence state sulphion, here it is distinctive shuttle effect in Li-S batteries.Presence just because of shuttle effect causes electricity
Pond has the ability of anti-overcharge.But it is due to this effect also to stop simultaneously, and polysulfide ion is diffused into cathode of lithium and will generated not
Molten product, they will not spread back positive pole again, and be deposited on negative terminal surface, and the performance on the one hand causing cathode of lithium is disliked
Change, on the other hand will also cause the irreversible loss of battery capacity, be i.e. cycle performance declines.
A variety of methods are employed at present to improve the chemical property of sulphur positive pole, such as, by sulphur and there is highly conductive material
Expect it is compound come improve electronics conduction, polysulfide ion is limited to electrolyte main body using porous material absorption or polymer overmold
Scatter and disappear, using the flexible material with stable cavity and porous material as sulfur-donor come sulphur positive polar body during buffer cycles
Product strain.It is exactly that sulphur and conductive porous material are compound wherein for improving the widest method of lithium-sulfur cell, on the one hand can carries
The electric conductivity of high electrode, more lithium sulfide dissolutions on the other hand can also be limited to a certain extent.Wherein porous material includes more
Hole carbon material, metal oxide materials etc., although porous carbon materials improve to electric conductivity, but due to non-pole
Property essence so that when it is applied to lithium sulfur battery anode material, it is impossible to effectively adsorb polarity the more lithium sulfides of intermediate product；
And metal oxide especially porous metal oxide, not only prepare difficult power consumption greatly, and low electric conductivity can improve overall electricity
The impedance of pole, therefore report seldom.
The content of the invention
The invention aims to solve the existing carrier material based on porous carbon materials and porous oxide material
The dissolution of polysulfide can not effectively be limited by preparing sulphur positive electrode and existing, and cause battery capacity to reduce rapidly and porous metals oxygen
Compound prepares the problem of difficult power consumption is big, there is provided a kind of metal-doped silicon oxide molecular sieve/sulphur carbon complex and its preparation side
Method and application.
A kind of metal-doped silicon oxide molecular sieve/sulphur carbon complex, it by embedding sulfur metal doped silicon oxide molecular sieve water
The aqueous dispersions of dispersion liquid and carbon material are prepared, embedding sulphur in the aqueous dispersions of the embedding sulfur metal doped silicon oxide molecular sieve
The mass ratio of carbon material is (4~10) in the aqueous dispersions of metal-doped silicon oxide molecular sieve and carbon material:1；The embedding sulphur gold
Category doped silicon oxide molecular sieve is prepared by metal-doped silicon oxide molecular sieve and elemental sulfur, and the embedding sulfur metal doping oxygen
The mass fraction of elemental sulfur is 10%~80% in SiClx molecular sieve.
A kind of preparation method of metal-doped silicon oxide molecular sieve/sulphur carbon complex, it is completed according to the following steps：
First, metal-doped silicon oxide molecular sieve is prepared：
A, surfactant is dissolved in deionized water, it is water-soluble obtains the surfactant that concentration is 0.3g/L~10g/L
Liquid, the pH for the aqueous surfactant solution that concentration is 0.3g/L~10g/L is then adjusted to 1~6 using acid medium, obtains acid
Property aqueous surfactant solution；
B, acid surface active agent aqueous temperature is adjusted to 20~60 DEG C, and silicon is added at being 20~60 DEG C in temperature
Source, stirring reaction 1h~12h, stand 12h~48h, product after being stood；Surface in the acid surface active agent aqueous solution
The mol ratio of activating agent and element silicon in silicon source is (0.05~1):1；
C, product after standing is transferred in autoclave, insulation ageing 1h~72h, is obtained at being 35~200 DEG C in temperature
Reactant after ageing；
D, reactant after ageing is filtered, the solid being filtrated to get is washed and dried successively, obtains drying
Solid afterwards, solid carries out calcination process after drying, that is, obtains mesopore silicon oxide；
E, source metal solution and mesopore silicon oxide are added in isopropanol solvent, stirred and evenly mixed, and be 25~200 in temperature
12h~72h is incubated at DEG C, sediment is obtained after filtering, sediment is washed and dried successively, obtains metal-doped oxidation
Si molecular sieves；The mass ratio (5~80) of the mesopore silicon oxide and source metal GOLD FROM PLATING SOLUTION category element:1；The mesopore silicon oxide
Quality and the volume ratio of isopropanol solvent be (0.1~1) g:40mL；
2nd, embedding sulfur metal doped silicon oxide molecular sieve is prepared：
Elemental sulfur is filled in metal-doped silicon oxide molecular sieve using melt impregnation, obtains embedding sulfur metal doping oxygen
SiClx molecular sieve, the mass fraction of elemental sulfur is 10%~80% in the embedding sulfur metal doped silicon oxide molecular sieve；
3rd, carbon material is impregnated：
Embedding sulfur metal doped silicon oxide molecular sieve is scattered in deionized water, and magnetic agitation 0.5h~12h, obtain embedding
The aqueous dispersions of sulfur metal doped silicon oxide molecular sieve, then the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve are added
In the aqueous dispersions of carbon material, continue to stir 12h~48h, centrifuged after precipitation, solid reactant is obtained, to solid reaction
Thing is washed and dried successively, obtains metal-doped silicon oxide molecular sieve/sulphur carbon complex；The embedding sulfur metal doping oxidation
In the aqueous dispersions of si molecular sieves in the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve and carbon material carbon material quality
Than for (4~10):1.
A kind of application of metal-doped silicon oxide molecular sieve/sulphur carbon complex, metal-doped silicon oxide molecular sieve/sulphur carbon are answered
Compound is used for the positive pole for preparing lithium-sulfur cell as positive electrode.
Advantage of the present invention：
First, using metal-doped silicon oxide molecular sieve as S carriers.Cost is low.Technique is simple, energy consumption is low, can realize
Large-scale production.
2nd, metal-doped silicon oxide molecular sieve/sulphur carbon complex surface prepared by the present invention carries oh group, with liquid
S has good wetability, is easy to impregnate S；For lithium-sulfur rechargeable battery, in charge and discharge process, by Si-S keys and can mix
The effectively low absorption electric discharge poly- lithium sulfide of intermediate product of the metal-O polar bonds formed after miscellaneous metallic element, reduces shuttle effect, because
This shows higher utilization efficiency and electric conductivity, battery is shown high specific capacity and good stable circulation performance；And
And Ti introducing also improves the electric conductivity of material in itself to a certain extent.
3rd, the carbon material on metal-doped silicon oxide molecular sieve/sulphur carbon complex surface prepared by the present invention can provide very
Good electric conductivity, such as graphene oxide, weak redox graphene are advantageous to adsorb the poly- lithium sulfide of back dissolving solution, reach dual
The purpose of confinement.
4th, metal-doped silicon oxide molecular sieve/sulphur carbon complex prepared by the present invention has as lithium sulfur battery anode material
There are very high specific capacity and cyclical stability.Lithium battery anode composition battery is prepared using the material, the battery discharges in 0.1C,
Discharge capacity is up to 1638mAhg-1, capacity remains to be maintained at 800mAhg after the circulation of 200 circles-1~
850mA·h·g-1。
5th, the aperture of metal-doped silicon oxide molecular sieve prepared by step 1 of the present invention is 2nm~9nm, and pore volume exists
0.8cm3/ g~4cm3/ g, specific surface area 500m2/ g~1600m2/g。
Brief description of the drawings
Fig. 1 is Fe-SiO prepared by embodiment 12/ S/GO composites SEM schemes；
Fig. 2 is Ti-SiO prepared by embodiment 22/ S/BC composites SEM schemes；
Fig. 3 is Ni-SiO prepared by embodiment 32/ S/CNT composites SEM schemes；
Fig. 4 is Co-SiO prepared by embodiment 42/ S/rGO composites SEM schemes；
Fig. 5 is XRD curve maps, and A represents Fe2O3 doping SiO prepared by embodiment 1 in figure2Composite XRD curves, B in figure
Represent titanium doped SiO prepared by embodiment 22Composite XRD curves, C represents nickel doping SiO prepared by embodiment 3 in figure2It is multiple
Condensation material XRD curves, D represents cobalt doped SiO prepared by embodiment 4 in figure2Composite XRD curves；
Fig. 6 is pore size distribution curve figure, and 1 represents Fe2O3 doping SiO prepared by embodiment 1 in figure2Composite pore-size distribution
Curve map, 2 represent titanium doped SiO prepared by embodiments 2 in figure2Composite pore size distribution curve figure, 3 represent embodiments in figure
The 3 nickel doping SiO prepared2Composite pore size distribution curve figure, 4 represent cobalt doped SiO prepared by embodiments 4 in figure2Composite wood
Blanking aperture scatter chart；
Fig. 7 is GO button cell cycle charge-discharge curve maps；
Fig. 8 is BC button cell cycle charge-discharge curve maps, and A represents charging curve in figure, and B represents discharge curve in figure；
Fig. 9 is CNT button cells cycle charge-discharge curve map under different multiplying, and A represents charging curve in figure, B tables in figure
Show discharge curve.
Embodiment
Embodiment one：Present embodiment is a kind of metal-doped silicon oxide molecular sieve/sulphur carbon complex, its feature
It is that it is prepared by the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve and the aqueous dispersions of carbon material, the embedding sulphur
In the aqueous dispersions of metal-doped silicon oxide molecular sieve in the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve and carbon material
The mass ratio of carbon material is (4~10):1；The embedding sulfur metal doped silicon oxide molecular sieve is by metal-doped silicon oxide molecular sieve
Be prepared with elemental sulfur, and in the embedding sulfur metal doped silicon oxide molecular sieve elemental sulfur mass fraction for 10%~
80%.
Embedding sulfur metal doped silicon oxide in the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve described in present embodiment
The concentration of molecular sieve is 0.5mg/mL~5mg/mL.
The concentration of carbon material is 0.2mg/mL~2mg/mL in the aqueous dispersions of carbon material described in present embodiment.
Embodiment two：The difference of present embodiment and embodiment one is：The metal-doped oxidation
The aperture of si molecular sieves is 2nm~9nm, and pore volume is in 0.8cm3/ g~4cm3/ g, specific surface area 500m2/ g~1600m2/g。
Other are identical with embodiment one.
Embodiment three：Present embodiment is with one of embodiment one or two difference：The metal is mixed
Spherical, hexagon or rod is presented in the particle of miscellaneous silicon oxide molecular sieve.Other are identical with embodiment one or two.
Embodiment four：Present embodiment is with one of embodiment one to three difference：The metal is mixed
Metallic element is Ti elements, Fe elements, Co elements or Ni elements in miscellaneous silicon oxide molecular sieve.Other with embodiment one to
Three is identical.
Embodiment five：Present embodiment is with one of embodiment one to four difference：The carbon material
Aqueous dispersions in carbon material be carbon black, graphene oxide, weak redox graphene or carbon Micro/nanotubes.Other with it is specific
Embodiment one to four is identical.
Weak redox graphene described in present embodiment is by by vacuum of the graphene oxide at 200~1000 DEG C
Under the conditions of be thermally treated resulting in, heat treatment time is 0.5~10 hour.
Embodiment six：Present embodiment is a kind of preparation of metal-doped silicon oxide molecular sieve/sulphur carbon complex
Method, it is completed according to the following steps：
First, metal-doped silicon oxide molecular sieve is prepared：
A, surfactant is dissolved in deionized water, it is water-soluble obtains the surfactant that concentration is 0.3g/L~10g/L
Liquid, the pH for the aqueous surfactant solution that concentration is 0.3g/L~10g/L is then adjusted to 1~6 using acid medium, obtains acid
Property aqueous surfactant solution；
B, acid surface active agent aqueous temperature is adjusted to 20~60 DEG C, and silicon is added at being 20~60 DEG C in temperature
Source, stirring reaction 1h~12h, stand 12h~48h, product after being stood；Surface in the acid surface active agent aqueous solution
The mol ratio of activating agent and element silicon in silicon source is (0.05~1):1；
C, product after standing is transferred in autoclave, insulation ageing 1h~72h, is obtained at being 35~200 DEG C in temperature
Reactant after ageing；
D, reactant after ageing is filtered, the solid being filtrated to get is washed and dried successively, obtains drying
Solid afterwards, solid carries out calcination process after drying, that is, obtains mesopore silicon oxide；
E, source metal solution and mesopore silicon oxide are added in isopropanol solvent, stirred and evenly mixed, and be 25~200 in temperature
12h~72h is incubated at DEG C, sediment is obtained after filtering, sediment is washed and dried successively, obtains metal-doped oxidation
Si molecular sieves；The mass ratio (5~80) of the mesopore silicon oxide and source metal GOLD FROM PLATING SOLUTION category element:1；The mesopore silicon oxide
Quality and the volume ratio of isopropanol solvent be (0.1~1) g:40mL；
2nd, embedding sulfur metal doped silicon oxide molecular sieve is prepared：
Elemental sulfur is filled in metal-doped silicon oxide molecular sieve using melt impregnation, obtains embedding sulfur metal doping oxygen
SiClx molecular sieve, the mass fraction of elemental sulfur is 10%~80% in the embedding sulfur metal doped silicon oxide molecular sieve；
3rd, carbon material is impregnated：
Embedding sulfur metal doped silicon oxide molecular sieve is scattered in deionized water, and magnetic agitation 0.5h~12h, obtain embedding
The aqueous dispersions of sulfur metal doped silicon oxide molecular sieve, then the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve are added
In the aqueous dispersions of carbon material, continue to stir 12h~48h, centrifuged after precipitation, solid reactant is obtained, to solid reaction
Thing is washed and dried successively, obtains metal-doped silicon oxide molecular sieve/sulphur carbon complex；The embedding sulfur metal doping oxidation
In the aqueous dispersions of si molecular sieves in the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve and carbon material carbon material quality
Than for (4~10):1.
The detailed process of melt impregnation is as follows described in present embodiment step 2：By elemental sulfur and metal-doped oxidation
Si molecular sieves are mixed, and under nitrogen or argon gas atmosphere protection, 6h~20h, Ran Housheng are first incubated at 158~160 DEG C of temperature
Temperature is incubated 0.5h~3h to 250~300 DEG C at being 250~300 DEG C in temperature, that is, obtains embedding sulfur metal doped silicon oxide point
Son sieve, and the mass fraction of elemental sulfur is 10%~80% in the embedding sulfur metal doped silicon oxide molecular sieve.
Acid medium described in present embodiment step 1 a is that concentration is 1mol/L~2mol/L hydrochloric acid solutions or concentration
For 1mol/L~2mol/ sulfuric acid solutions.
Embedding sulfur metal is mixed in the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve described in present embodiment step 3
The concentration of miscellaneous silicon oxide molecular sieve is 0.5mg/mL~5mg/mL.
The concentration of carbon material is 0.2mg/mL~2mg/ in the aqueous dispersions of carbon material described in present embodiment step 3
mL。
The aperture of metal-doped silicon oxide molecular sieve prepared by present embodiment step 1 is 2nm~9nm, and pore volume exists
0.8cm3/ g~4cm3/ g, specific surface area 500m2/ g~1600m2/g。
Research at present is most widely that carrier material improves based on the porous carbon materials and porous oxide material
Electric conductivity and limitation sulphur dissolution.1st, coated using flexible material merely, although improving electric conductivity, but can not effectively limited
The dissolution of polysulfide.2nd, most of carbon materials are very difficult without the synthesis of 3, porous oxide, are generally required by high anneal crack
Solution, or complicated step could be realized.Present embodiment solves the problems, such as polarity absorption problem, conductivity issues and volumetric expansion,
And preparation method is simple.
Embodiment seven：The difference of present embodiment and embodiment six is：Silicon described in step 1 b
Source is methyl silicate, tetraethyl orthosilicate or butyl silicate.Other are identical with embodiment six.
Embodiment eight：Present embodiment is with one of embodiment six or seven difference：It is sharp in step 1 a
The pH for the aqueous surfactant solution that concentration is 0.3g/L~10g/L is adjusted to 2~6 with acid medium.Other and specific implementation
Mode six or seven is identical.
Embodiment nine：Present embodiment is with one of embodiment six to eight difference：It is sharp in step 1 a
The pH for the aqueous surfactant solution that concentration is 0.3g/L~10g/L is adjusted to 3~5 with acid medium.Other and specific implementation
Mode six to eight is identical.
Embodiment ten：Present embodiment is with one of embodiment six to nine difference：Institute in step 1 e
The concentration for stating source metal GOLD FROM PLATING SOLUTION category source be 0.1mg/mL~3mg/mL, and the source metal be titanium compound, iron compound,
Cobalt compound or nickel compound.Other are identical with embodiment six to nine.
Embodiment 11：Present embodiment is with one of embodiment six to ten difference：In step 1 a
The surfactant is triblock copolymer P123 or triblock copolymer F127.Other and the phase of embodiment six to ten
Together.
Embodiment 12：Present embodiment is with the difference of embodiment six to one of 11：Step 1 b
Described in the acid surface active agent aqueous solution mol ratio of surfactant and element silicon in silicon source be (0.05~0.7):1.
Other are identical with embodiment six to 11.
Embodiment 13：Present embodiment is with the difference of embodiment six to one of 12：Step 1 b
Described in the acid surface active agent aqueous solution mol ratio of surfactant and element silicon in silicon source be (0.2~0.5):1.Its
He is identical with embodiment six to 12.
Embodiment 14：Present embodiment is with the difference of embodiment six to one of 13：Step 1 a
It is middle that surfactant is dissolved in deionized water, obtain the aqueous surfactant solution that concentration is 0.5g/L~5g/L.Other with
Embodiment six to 13 is identical.
Embodiment 15：Present embodiment is with the difference of embodiment six to one of 14：Step 1 a
It is middle that surfactant is dissolved in deionized water, obtain the aqueous surfactant solution that concentration is 1g/L~4g/L.Other and tool
Body embodiment six to 14 is identical.
Embodiment 16：Present embodiment is with the difference of embodiment six to one of 15：Step 1 b
It is middle that acid surface active agent aqueous temperature is adjusted to 30~50 DEG C, and add silicon source at being 30~50 DEG C in temperature.Other with
Embodiment six to 15 is identical.
Embodiment 17：Present embodiment is with the difference of embodiment six to one of 16：Step 1 b
It is middle that acid surface active agent aqueous temperature is adjusted to 35~40 DEG C, and add silicon source at being 35~40 DEG C in temperature.Other with
Embodiment six to 16 is identical.
Embodiment 18：Present embodiment is with the difference of embodiment six to one of 17：Step 1 b
Middle stirring reaction 3h~10h, stand 12h~48h.Other are identical with embodiment six to 17.
Embodiment 19：Present embodiment is with the difference of embodiment six to one of 18：Step 1 b
Middle stirring reaction 4h~6h, stand 12h~48h.Other are identical with embodiment six to 18.
Embodiment 20：Present embodiment is with the difference of embodiment six to one of 19：Step 1 c
In temperature be 35~200 DEG C at insulation ageing 12h~48h.Other are identical with embodiment six to 19.
Embodiment 21：Present embodiment is with the difference of embodiment six to one of 20：Step
The sintering temperature that solid carries out calcination process after being dried described in one d is 150~600 DEG C.Other with embodiment six to
20 is identical.
Embodiment 22：Present embodiment is with the difference of embodiment six to one of 21：Step
The sintering temperature that solid carries out calcination process after being dried described in a rapid d is 200~500 DEG C.Other and embodiment six
It is identical to 21.
Embodiment 23：Present embodiment is with the difference of embodiment six to one of 22：Step
The sintering temperature that solid carries out calcination process after being dried described in a rapid d is 400~500 DEG C.Other and embodiment six
It is identical to 22.
Embodiment 24：Present embodiment is with the difference of embodiment six to one of 23：Step
The roasting time that solid carries out calcination process after being dried described in a rapid d is 1h~10h.Other and embodiment six to two
13 is identical.
Embodiment 25：Present embodiment is with the difference of embodiment six to one of 24：Step
The roasting time that solid carries out calcination process after being dried described in a rapid d is 3h~8h.Other and embodiment six to two
14 is identical.
Embodiment 26：Present embodiment is with the difference of embodiment six to one of 25：Step
The roasting time that solid carries out calcination process after being dried described in a rapid d is 4h~6h.Other and embodiment six to two
15 is identical.
Embodiment 27：Present embodiment is with the difference of embodiment six to one of 26：Step
Described in rapid three in the aqueous dispersions of carbon material carbon material be carbon black, graphene oxide, weak redox graphene or carbon it is micro-/receive
Mitron.Other are identical with embodiment six to 26.
Weak redox graphene described in present embodiment be by by graphene oxide under 200 DEG C of vacuum condition
It is thermally treated resulting in, heat treatment time 0.5~10 hour.
Embodiment 28：A kind of application of metal-doped silicon oxide molecular sieve/sulphur carbon complex, its feature exist
It is used for the positive pole of lithium-sulfur cell as positive electrode in metal-doped silicon oxide molecular sieve/sulphur carbon complex.
In the lithium-sulfur cell lithium salts be lithium hexafluoro phosphate, lithium perchlorate, hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium or
Di-trifluoromethyl sulfonic acid imide li.
Vinylidene is added in 1-METHYLPYRROLIDONE, is configured to the inclined fluorine second that vinylidene mass fraction is 10%
Alkene -1-METHYLPYRROLIDONE mixture, then by metal-doped silicon oxide molecular sieve/sulphur carbon complex, acetylene black and inclined fluorine second
Alkene -1-METHYLPYRROLIDONE mixture mixes, and obtains anode sizing agent, the metal-doped silicon oxide molecular sieve/sulphur carbon complex
Mass ratio with acetylene black is 8:1, the metal-doped silicon oxide molecular sieve/sulphur carbon complex and vinylidene-N- methyl pyrroles
The mass ratio of vinylidene is 8 in pyrrolidone mixture:1, anode sizing agent is scratched to aluminium foil, thickness is 50 μm~150 μm,
Anode is obtained after drying, and using lithium piece as negative pole, microporous barrier is barrier film, is assembled into button cell, tests battery performance,
0.1C discharges, and discharge capacity is up to 1638mAhg-1, capacity remains to be maintained at 800mA after the circulation of 200 circles
h·g-1~850mAhg-1。
Using following verification experimental verifications effect of the present invention
Embodiment 1：A kind of preparation method of metal-doped silicon oxide molecular sieve/sulphur carbon complex, it is according to the following steps
Complete：
First, metal-doped silicon oxide molecular sieve is prepared：
A, 2g triblock copolymer P123s are dissolved in deionized water, it is water-soluble obtains the surfactant that concentration is 0.3g/L
Liquid, the pH for the aqueous surfactant solution that concentration is 0.3g/L is then adjusted to 1 using the hydrochloric acid solution that concentration is 1mol/L, obtained
To the acid surface active agent aqueous solution；
B, acid surface active agent aqueous temperature is adjusted to 38 DEG C, and the positive silicic acid second of 4.2g is added at being 38 DEG C in temperature
Ester, stirring reaction 2h, stand 12h；
C, product after standing is transferred in autoclave, insulation ageing 12h, anti-after being aged at being 100 DEG C in temperature
Answer thing；
D, reactant after ageing is filtered, the solid being filtrated to get is cleaned repeatedly using alcohol and deionized water,
Untill deionized water after washing is in neutral, then it is dried, solid after being dried, solid is 150 in temperature after drying
1h is calcined under DEG C air atmosphere, that is, obtains mesopore silicon oxide；
E, the copperas solution that concentration is 0.1mg/mL is added in 40mL isopropanol solvents with mesopore silicon oxide, stirring
Mix, and 24h is incubated at being 200 DEG C in temperature, obtain sediment after filtering, sediment is washed and dried successively, is obtained
To metal-doped silicon oxide molecular sieve；The mass ratio 5 of the mesopore silicon oxide and Fe elements in copperas solution:1；Given an account of
The quality of hole silica and the volume ratio of isopropanol solvent are 0.1g:40mL；
2nd, embedding sulfur metal doped silicon oxide molecular sieve is prepared：
Elemental sulfur is filled in metal-doped silicon oxide molecular sieve using melt impregnation, detailed process is as follows：
Elemental sulfur is mixed with metal-doped silicon oxide molecular sieve, under nitrogen atmosphere protection, first protected at 158 DEG C of temperature
Warm 6h, 250 DEG C are then heated to, and 3h are incubated at being 250 DEG C in temperature, that is, obtain embedding sulfur metal doped silicon oxide molecular sieve,
And the mass fraction of elemental sulfur is 10% in the embedding sulfur metal doped silicon oxide molecular sieve；
3rd, carbon material is impregnated：
Embedding sulfur metal doped silicon oxide molecular sieve is scattered in deionized water, and magnetic agitation 0.5h, obtaining concentration is
The aqueous dispersions of 1mg/mL embedding sulfur metal doped silicon oxide molecular sieve, the embedding sulfur metal that concentration is 1mg/mL is then adulterated into oxygen
The aqueous dispersions of SiClx molecular sieve are added in the aqueous dispersions for the graphene oxide that concentration is 1mg/mL, continue to stir 24h, precipitation
After centrifuge, obtain solid reactant, solid reactant washed and dried successively, obtain metal-doped silica point
Sub- sieve/sulphur carbon complex (is Fe-SiO2/ S/GO composites)；The moisture of the embedding sulfur metal doped silicon oxide molecular sieve
The mass ratio of graphene oxide is 4 in the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve and graphene oxide in dispersion liquid:
1。
Fe-SiO manufactured in the present embodiment2/ S/GO composites are as shown in figure 1, Fig. 1 is Fe-SiO prepared by embodiment 12/
S/GO composites SEM schemes, and sees in figure, and spherical sieve particle is oxidized graphene and closely wrapped up, and distribution of particles is equal
It is even, there is provided effectively electronic and ionic transmission path, in addition the cladding of graphene oxide also reduce shuttle to a certain extent
Effect, improve electro-chemical activity and cycle life.
Embodiment 2：A kind of preparation method of metal-doped silicon oxide molecular sieve/sulphur carbon complex, it is according to the following steps
Complete：
First, metal-doped silicon oxide molecular sieve is prepared：
A, 2g triblock copolymer P123s are dissolved in deionized water, it is water-soluble obtains the surfactant that concentration is 10g/L
Liquid, the pH for the aqueous surfactant solution that concentration is 10g/L is then adjusted to 6 using the hydrochloric acid solution that concentration is 2mol/L, obtained
To the acid surface active agent aqueous solution；
B, acid surface active agent aqueous temperature is adjusted to 45 DEG C, and the positive silicic acid second of 3g is added at being 45 DEG C in temperature
Ester, stirring reaction 2h, stand 12h；
C, product after standing is transferred in autoclave, insulation ageing 12h, reacts after being aged at being 35 DEG C in temperature
Thing；
D, reactant after ageing is filtered, the solid being filtrated to get is cleaned repeatedly using alcohol and deionized water,
Untill deionized water after washing is in neutral, then it is dried, solid after being dried, solid is 400 in temperature after drying
6h is calcined under DEG C air atmosphere, that is, obtains mesopore silicon oxide；
E, the isopropyl titanate solution that concentration is 3mg/mL is added in 40mL isopropanol solvents with mesopore silicon oxide, stirring
Mix, and 15h is incubated at being 180 DEG C in temperature, obtain sediment after filtering, sediment is washed and dried successively, is obtained
To metal-doped silicon oxide molecular sieve；The mass ratio 80 of the mesopore silicon oxide and Ti elements in isopropyl titanate solution:1；Institute
It is 1g to state the quality of mesopore silicon oxide and the volume ratio of isopropanol solvent：40mL；
2nd, embedding sulfur metal doped silicon oxide molecular sieve is prepared：
Elemental sulfur is filled in metal-doped silicon oxide molecular sieve using melt impregnation, detailed process is as follows：
Elemental sulfur is mixed with metal-doped silicon oxide molecular sieve, under nitrogen atmosphere protection, first protected at 160 DEG C of temperature
Warm 20h, 300 DEG C are then heated to, and 0.5h is incubated at being 300 DEG C in temperature, that is, obtain embedding sulfur metal doped silicon oxide molecule
Sieve, and the mass fraction of elemental sulfur is 30% in the embedding sulfur metal doped silicon oxide molecular sieve；
3rd, carbon material is impregnated：
Embedding sulfur metal doped silicon oxide molecular sieve is scattered in deionized water, and magnetic agitation 12h, obtaining concentration is
The aqueous dispersions of 5mg/mL embedding sulfur metal doped silicon oxide molecular sieve, the embedding sulfur metal that concentration is 5mg/mL is then adulterated into oxygen
The aqueous dispersions of SiClx molecular sieve are added in the aqueous dispersions for the carbon black that concentration is 1mg/mL, are continued to stir 12h, are centrifuged after precipitation
Separation, obtain solid reactant, solid reactant washed and dried successively, obtain metal-doped silicon oxide molecular sieve/
Sulphur carbon complex (is Ti-SiO2/ S/BC composites)；In the aqueous dispersions of the embedding sulfur metal doped silicon oxide molecular sieve
The mass ratio of carbon black is 10 in the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve and carbon black:1.
Ti-SiO manufactured in the present embodiment2/ S/BC composites are as shown in Fig. 2 Fig. 2 is Ti-SiO prepared by embodiment 22/
S/BC composites SEM schemes, and sees in figure, the sieve particle surface attachment of hexagon carbon black pellet, and distribution of particles
Uniformly, there is provided effectively electronic and ionic transmission path, improve electro-chemical activity.
Embodiment 3：A kind of preparation method of metal-doped silicon oxide molecular sieve/sulphur carbon complex, it is according to the following steps
Complete：
First, metal-doped silicon oxide molecular sieve is prepared：
A, 2g triblock copolymer P123s are dissolved in deionized water, it is water-soluble obtains the surfactant that concentration is 0.5g/L
Liquid, the pH for the aqueous surfactant solution that concentration is 0.5g/L is then adjusted to 3 using the hydrochloric acid solution that concentration is 1mol/L, obtained
To the acid surface active agent aqueous solution；
B, acid surface active agent aqueous temperature is adjusted to 50 DEG C, and the positive silicic acid second of 5g is added at being 50 DEG C in temperature
Ester, stirring reaction 2h, stand 24h；
C, product after standing is transferred in autoclave, insulation ageing 24h, anti-after being aged at being 180 DEG C in temperature
Answer thing；
D, reactant after ageing is filtered, the solid being filtrated to get is cleaned repeatedly using alcohol and deionized water,
Untill deionized water after washing is in neutral, then it is dried, solid after being dried, solid is 200 in temperature after drying
8h is calcined under DEG C air atmosphere, that is, obtains mesopore silicon oxide；
E, the nickel sulfamic acid solution that concentration is 2mg/mL is added in 40mL isopropanol solvents with mesopore silicon oxide, stirring
Mix, and 24h is incubated at being 120 DEG C in temperature, obtain sediment after filtering, sediment is washed and dried successively, is obtained
To metal-doped silicon oxide molecular sieve；The mass ratio 20 of the mesopore silicon oxide and Ni elements in nickel sulfamic acid solution:1；Institute
It is 0.2g to state the quality of mesopore silicon oxide and the volume ratio of isopropanol solvent:40mL；
2nd, embedding sulfur metal doped silicon oxide molecular sieve is prepared：
Elemental sulfur is filled in metal-doped silicon oxide molecular sieve using melt impregnation, detailed process is as follows：
Elemental sulfur is mixed with metal-doped silicon oxide molecular sieve, under nitrogen atmosphere protection, first protected at 150 DEG C of temperature
Warm 10h, 250 DEG C are then heated to, and 2h are incubated at being 250 DEG C in temperature, that is, obtain embedding sulfur metal doped silicon oxide molecular sieve,
And the mass fraction of elemental sulfur is 60% in the embedding sulfur metal doped silicon oxide molecular sieve；
3rd, carbon material is impregnated：
Embedding sulfur metal doped silicon oxide molecular sieve is scattered in deionized water, and magnetic agitation 10h, obtaining concentration is
The aqueous dispersions of 2mg/mL embedding sulfur metal doped silicon oxide molecular sieve, then the embedding sulfur metal that concentration is 0.5mg/mL is adulterated
The aqueous dispersions of silicon oxide molecular sieve are added in the aqueous dispersions for the CNT that concentration is 1mg/mL, continue to stir 24h, precipitation
After centrifuge, obtain solid reactant, solid reactant washed and dried successively, obtain metal-doped silica point
Sub- sieve/sulphur carbon complex (is Ni-SiO2/ S/CN composites)；The moisture of the embedding sulfur metal doped silicon oxide molecular sieve
The mass ratio of CNT is 6 in the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve and CNT in dispersion liquid:1.
Ni-SiO manufactured in the present embodiment2/ S/CNT composites are as shown in figure 3, Fig. 3 is Ni- prepared by embodiment 3
SiO2/ S/CNT composites SEM schemes, and sees in figure, and bar-shaped sieve particle and CNT are dispersed, there is provided
Effectively electronic and ionic transmission path, improve electro-chemical activity.
Embodiment 4：A kind of preparation method of metal-doped silicon oxide molecular sieve/sulphur carbon complex, it is according to the following steps
Complete：
First, metal-doped silicon oxide molecular sieve is prepared：
A, 2g triblock copolymer P123s are dissolved in deionized water, it is water-soluble obtains the surfactant that concentration is 3g/L
Liquid, the pH for the aqueous surfactant solution that concentration is 3g/L is then adjusted to 4 using the hydrochloric acid solution that concentration is 2mol/L, obtained
The acid surface active agent aqueous solution；
B, acid surface active agent aqueous temperature is adjusted to 38 DEG C, and the positive silicic acid second of 10g is added at being 38 DEG C in temperature
Ester, stirring reaction 2h, stand 48h；
C, product after standing is transferred in autoclave, insulation ageing 48h, anti-after being aged at being 200 DEG C in temperature
Answer thing；
D, reactant after ageing is filtered, the solid being filtrated to get is cleaned repeatedly using alcohol and deionized water,
Untill deionized water after washing is in neutral, then it is dried, solid after being dried, solid is 150 in temperature after drying
5h is calcined under DEG C air atmosphere, that is, obtains mesopore silicon oxide；
E, the acetic acid cobalt liquor that concentration is 1mg/mL is added in 40mL isopropanol solvents with mesopore silicon oxide, stirring is mixed
It is even, and 12h is incubated at being 25 DEG C in temperature, sediment is obtained after filtering, sediment is washed and dried successively, obtains gold
Belong to doped silicon oxide molecular sieve；The mass ratio 60 of the mesopore silicon oxide and Co elements in acetic acid cobalt liquor:1；The mesoporous oxygen
The quality of SiClx and the volume ratio of isopropanol solvent are 0.8g:40mL；
2nd, embedding sulfur metal doped silicon oxide molecular sieve is prepared：
Elemental sulfur is filled in metal-doped silicon oxide molecular sieve using melt impregnation, detailed process is as follows：
Elemental sulfur is mixed with metal-doped silicon oxide molecular sieve, under nitrogen atmosphere protection, first protected at 159 DEG C of temperature
Warm 12h, 280 DEG C are then heated to, and 1h are incubated at being 280 DEG C in temperature, that is, obtain embedding sulfur metal doped silicon oxide molecular sieve,
And the mass fraction of elemental sulfur is 80% in the embedding sulfur metal doped silicon oxide molecular sieve；
3rd, carbon material is impregnated：
Embedding sulfur metal doped silicon oxide molecular sieve is scattered in deionized water, and magnetic agitation 8h, obtaining concentration is
The aqueous dispersions of 2mg/mL embedding sulfur metal doped silicon oxide molecular sieve, the embedding sulfur metal that concentration is 1mg/mL is then adulterated into oxygen
The aqueous dispersions of SiClx molecular sieve are added in the aqueous dispersions for the weak redox graphene that concentration is 1mg/mL, continue to stir
20h, centrifuge after precipitation, obtain solid reactant, solid reactant is washed and dried successively, is obtained metal-doped
Silicon oxide molecular sieve/sulphur carbon complex (is Co-SiO2/ S/rGO composites)；The embedding sulfur metal doped silicon oxide molecule
Embedding sulfur metal doped silicon oxide molecular sieve and weak oxygen reduction in the aqueous dispersions of weak redox graphene in the aqueous dispersions of sieve
The mass ratio of graphite alkene is 5:1.
Weak redox graphene described in the present embodiment step 3 is by by vacuum of the graphene oxide at 500 DEG C
Under the conditions of be thermally treated resulting in, heat treatment time is 10 hours.
Co-SiO manufactured in the present embodiment2/ S/rGO composites are as shown in figure 4, Fig. 4 is Co- prepared by embodiment 4
SiO2/ S/rGO composites SEM schemes, there is provided the cladding of effectively electronic and ionic transmission path, in addition redox graphene
Also reduce shuttle effect to a certain extent, improve electro-chemical activity and cycle life.
The metal-doped silicon oxide molecular sieve obtained using low-angle X-ray powder diffraction detection embodiment 1-4, detection knot
Fruit is as shown in figure 5, Fig. 5 is XRD curve maps, and A represents Fe2O3 doping SiO prepared by embodiment 1 in figure2Composite XRD curves, figure
Middle B represents titanium doped SiO prepared by embodiment 22Composite XRD curves, C represents nickel doping SiO prepared by embodiment 3 in figure2
Composite XRD curves, D represents cobalt doped SiO prepared by embodiment 4 in figure2Composite XRD curves, as seen in Figure 5,
In the XRD spectrum of small angle range, all there is the peak for meeting Bragg equation in 4 samples, represent prepared metal and mix
The pore structure of the miscellaneous regular removal of mines of molecular sieve.
The metal-doped silicon oxide molecular sieve of detection embodiment 1-4 step 1 preparations is tested using isothermal nitrogen adsorption desorption,
Testing result is as shown in fig. 6, Fig. 6 is pore size distribution curve figure, and 1 represents Fe2O3 doping SiO prepared by embodiment 1 in figure2Composite wood
Blanking aperture scatter chart, 2 represent titanium doped SiO prepared by embodiments 2 in figure2Composite pore size distribution curve figure, 3 in figure
Represent nickel doping SiO prepared by embodiment 32Composite pore size distribution curve figure, the cobalt that prepared by 4 expression embodiments 4 in figure are mixed
Miscellaneous SiO2Composite pore size distribution curve figure, it can be seen that 4 samples remain in that 2~9nm aperture point after overdoping
Cloth, be advantageous to penetrate into sulphur in duct.
Embodiment 5：GO button cells assemble：
Vinylidene is added in 1-METHYLPYRROLIDONE, is configured to the inclined fluorine second that vinylidene mass fraction is 10%
Alkene -1-METHYLPYRROLIDONE mixture, the metal-doped silicon oxide molecular sieve/sulphur carbon complex for then preparing embodiment 1, second
Acetylene black mixes with vinylidene -1-METHYLPYRROLIDONE mixture, obtains anode sizing agent, the metal-doped silica molecule
Sieve/sulphur carbon complex and the mass ratio of acetylene black are 8:1, the metal-doped silicon oxide molecular sieve/sulphur carbon complex and inclined fluorine
The mass ratio of vinylidene is 8 in ethene -1-METHYLPYRROLIDONE mixture:1, anode sizing agent is scratched to aluminium foil, thickness
To obtain anode after 50 μm of drying, and using lithium piece as negative pole, microporous barrier is barrier film, is assembled into GO button cells,
Cycle charge discharge electro-detection is carried out to GO button cells, multiplying power electric current is 0.1C, and testing result is as shown in fig. 7, Fig. 7 is
GO button cell cycle charge-discharge curve maps, as seen in Figure 7, charging curve and discharge curve overlap, and battery is initial
Discharge capacity is in 1600mA h g-1Left and right, close to theoretical capacity.After 500 circle cycle charge-discharges, 800mA is remained in that
h g-1Capacity, illustrate that battery has very high cyclical stability.
Embodiment 6：BC button cells assemble：
Vinylidene is added in 1-METHYLPYRROLIDONE, is configured to the inclined fluorine second that vinylidene mass fraction is 10%
Alkene -1-METHYLPYRROLIDONE mixture, the metal-doped silicon oxide molecular sieve/sulphur carbon complex for then preparing embodiment 2, second
Acetylene black mixes with vinylidene -1-METHYLPYRROLIDONE mixture, obtains anode sizing agent, the metal-doped silica molecule
Sieve/sulphur carbon complex and the mass ratio of acetylene black are 8:1, the metal-doped silicon oxide molecular sieve/sulphur carbon complex and inclined fluorine
The mass ratio of vinylidene is 8 in ethene -1-METHYLPYRROLIDONE mixture:1, anode sizing agent is scratched to aluminium foil, thickness
To obtain anode after 100 μm of drying, and using lithium piece as negative pole, microporous barrier is barrier film, is assembled into BC button cells,
Cycle charge discharge electro-detection is carried out to BC button cells, multiplying power electric current is 0.1C, and testing result is as shown in figure 8, Fig. 8 is
BC button cell cycle charge-discharge curve maps, A represents charging curve in figure, and B represents discharge curve in figure, can be seen by Fig. 8
Go out, charging curve and discharge curve almost overlap, and battery initial discharge capacity is in 1500mA h g-1Left and right, hold close to theoretical
Amount.After 200 circle cycle charge-discharges, 500mA h g are remained in that-1Capacity, illustrate that battery has higher circulation steady
It is qualitative, it is shorter than GO battery cycle lifes prepared by embodiment 5 the reason for be, GO flexible cladding, not only to a certain degree
The upper more lithium sulfide dissolvings of limitation, and GO surface functional groups also provide suction-operated of the part to more lithium sulfides.But material
The ratio of charge/discharge capacity close to 100%, illustrates that this material has very high reaction power activity very strong always.
Embodiment 7：CNT button cells assemble：
Vinylidene is added in 1-METHYLPYRROLIDONE, is configured to the inclined fluorine second that vinylidene mass fraction is 10%
Alkene -1-METHYLPYRROLIDONE mixture, the metal-doped silicon oxide molecular sieve/sulphur carbon complex for then preparing embodiment 3, second
Acetylene black mixes with vinylidene -1-METHYLPYRROLIDONE mixture, obtains anode sizing agent, the metal-doped silica molecule
Sieve/sulphur carbon complex and the mass ratio of acetylene black are 8:1, the metal-doped silicon oxide molecular sieve/sulphur carbon complex and inclined fluorine
The mass ratio of vinylidene is 8 in ethene -1-METHYLPYRROLIDONE mixture:1, anode sizing agent is scratched to aluminium foil, thickness
To obtain anode after 150 μm of drying, and using lithium piece as negative pole, microporous barrier is barrier film, is assembled into BC button cells,
Charge and discharge electro-detection under different multiplying is carried out to CNT button cells, testing result is as shown in figure 9, Fig. 9 is different times
CNT button cells cycle charge-discharge curve map under rate, A represents charging curve in figure, and B represents discharge curve in figure, electric current from
0.1C increases process progressively diminishes to 2C, the capacity of material, and when electric current reduces back 0.1C again, the capacity of material responds immediately to
To initial level, illustrate that material has very high reaction power.
Claims (10)
1. a kind of metal-doped silicon oxide molecular sieve/sulphur carbon complex, it is characterised in that it is by embedding sulfur metal doped silicon oxide point
The aqueous dispersions of son sieve and the aqueous dispersions of carbon material are prepared, and the moisture of the embedding sulfur metal doped silicon oxide molecular sieve dissipates
The mass ratio of carbon material is (4~10) in the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve and carbon material in liquid:1；Institute
Embedding sulfur metal doped silicon oxide molecular sieve is stated to be prepared by metal-doped silicon oxide molecular sieve and elemental sulfur, and the embedding sulphur gold
The mass fraction for belonging to elemental sulfur in doped silicon oxide molecular sieve is 10%~80%.
A kind of 2. metal-doped silicon oxide molecular sieve/sulphur carbon complex according to claim 1, it is characterised in that the gold
The aperture for belonging to doped silicon oxide molecular sieve is 2nm~9nm, and pore volume is in 0.8cm3/ g~4cm3/ g, specific surface area 500m2/g
~1600m2/g；Spherical, hexagon or rod is presented in the particle of the metal-doped silicon oxide molecular sieve；It is described metal-doped
Metallic element is Ti elements, Fe elements, Co elements or Ni elements in silicon oxide molecular sieve.
A kind of 3. metal-doped silicon oxide molecular sieve/sulphur carbon complex according to claim 1, it is characterised in that the carbon
Carbon material is carbon black, graphene oxide, weak redox graphene or carbon Micro/nanotubes in the aqueous dispersions of material.
4. a kind of preparation method of metal-doped silicon oxide molecular sieve/sulphur carbon complex as claimed in claim 1, its feature exist
Completed according to the following steps in it：
First, metal-doped silicon oxide molecular sieve is prepared：
A, surfactant is dissolved in deionized water, obtains the aqueous surfactant solution that concentration is 0.3g/L~10g/L, so
The pH for the aqueous surfactant solution that concentration is 0.3g/L~10g/L is adjusted to 1~6 using acid medium afterwards, obtains acid table
Face aqueous surfactant solutions；
B, acid surface active agent aqueous temperature is adjusted to 20~60 DEG C, and silicon source is added at being 20~60 DEG C in temperature, stirred
Reaction 1h~12h is mixed, stands 12h~48h, product after being stood；Surface-active in the acid surface active agent aqueous solution
Agent and the mol ratio of element silicon in silicon source are (0.05~1):1；
C, product after standing is transferred in autoclave, insulation ageing 1h~72h, is aged at being 35~200 DEG C in temperature
Reactant afterwards；
D, reactant after ageing is filtered, the solid being filtrated to get is washed and dried successively, it is solid after being dried
Body, solid carries out calcination process after drying, that is, obtains mesopore silicon oxide；
E, source metal solution and mesopore silicon oxide are added in isopropanol solvent, stirred and evenly mixed, and in the case where temperature is 25~200 DEG C
12h~72h is incubated, sediment is obtained after filtering, sediment is washed and dried successively, obtains metal-doped silica point
Son sieve；The mass ratio (5~80) of the mesopore silicon oxide and source metal GOLD FROM PLATING SOLUTION category element:1；The matter of the mesopore silicon oxide
Amount and the volume ratio of isopropanol solvent are (0.1~1) g:40mL；
2nd, embedding sulfur metal doped silicon oxide molecular sieve is prepared：
Elemental sulfur is filled in metal-doped silicon oxide molecular sieve using melt impregnation, obtains embedding sulfur metal doped silicon oxide
Molecular sieve, the mass fraction of elemental sulfur is 10%~80% in the embedding sulfur metal doped silicon oxide molecular sieve；
3rd, carbon material is impregnated：
Embedding sulfur metal doped silicon oxide molecular sieve is scattered in deionized water, and magnetic agitation 0.5h~12h, obtain embedding sulphur gold
Belong to the aqueous dispersions of doped silicon oxide molecular sieve, the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve are then added into carbon materials
In the aqueous dispersions of material, continue to stir 12h~48h, centrifuge after precipitation, obtain solid reactant, to solid reactant according to
It is secondary to be washed and dried, obtain metal-doped silicon oxide molecular sieve/sulphur carbon complex；The embedding sulfur metal doped silicon oxide point
The mass ratio of carbon material is in the aqueous dispersions of embedding sulfur metal doped silicon oxide molecular sieve and carbon material in the aqueous dispersions of son sieve
(4~10):1.
5. a kind of preparation method of metal-doped silicon oxide molecular sieve/sulphur carbon complex according to claim 4, its feature
It is methyl silicate, tetraethyl orthosilicate or butyl silicate to be the silicon source described in step 1 b.
6. a kind of preparation method of metal-doped silicon oxide molecular sieve/sulphur carbon complex according to claim 4, its feature
The concentration for being the category of source metal GOLD FROM PLATING SOLUTION described in step 1 e source is 0.1mg/mL~3mg/mL, and the source metal is titanium
Compound, iron compound, cobalt compound or nickel compound.
7. a kind of preparation method of metal-doped silicon oxide molecular sieve/sulphur carbon complex according to claim 4, its feature
It is triblock copolymer P123 or triblock copolymer F127 to be surfactant described in step 1 a.
8. a kind of preparation method of metal-doped silicon oxide molecular sieve/sulphur carbon complex according to claim 4, its feature
It is that the sintering temperature that solid carries out calcination process after being dried described in step 1 d is 150~600 DEG C；Roasting time be 1h~
10h。
9. a kind of preparation method of metal-doped silicon oxide molecular sieve/sulphur carbon complex according to claim 6, its feature
In the aqueous dispersions of the carbon material described in step 3 carbon material be carbon black, graphene oxide, weak redox graphene or
Carbon Micro/nanotubes.
A kind of 10. application of metal-doped silicon oxide molecular sieve/sulphur carbon complex as claimed in claim 1, it is characterised in that
Metal-doped silicon oxide molecular sieve/sulphur carbon complex is used for the positive pole for preparing lithium-sulfur cell as positive electrode.
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| US12034157B2 (en) | 2019-03-08 | 2024-07-09 | Lg Energy Solution, Ltd. | Sulfur-doped silicon negative electrode material, method for producing same, lithium secondary battery negative electrode including negative electrode material, and lithium secondary battery comprising negative electrode |
| CN110380052A (en) * | 2019-07-19 | 2019-10-25 | 田韬 | One kind being based on the highly conductive sulfenyl composite material of lithium-sulphur cell positive electrode |
| CN110931752A (en) * | 2019-12-09 | 2020-03-27 | 华南师范大学 | Nitrogen-doped porous carbon loaded metal nickel lithium-sulfur battery positive electrode material and preparation method and application thereof |
| CN115072696A (en) * | 2022-04-29 | 2022-09-20 | 西安交通大学苏州研究院 | Co-NCNT @ HC hierarchical porous carbon material and preparation method and application thereof |
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