CN105924665B - A kind of preparation method and applications of superhigh cross-linking layering microporous polymer - Google Patents

A kind of preparation method and applications of superhigh cross-linking layering microporous polymer Download PDF

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CN105924665B
CN105924665B CN201610261239.3A CN201610261239A CN105924665B CN 105924665 B CN105924665 B CN 105924665B CN 201610261239 A CN201610261239 A CN 201610261239A CN 105924665 B CN105924665 B CN 105924665B
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microporous polymer
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CN105924665A (en
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韩生
陈红艳
常兴
刘凡
韩治亚
蔺华林
艾亚妮
陈达明
刘平
薛原
赵志成
周嘉伟
黄奇
李勇
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Shanghai Institute of Technology
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Abstract

The present invention relates to the preparation methods that a kind of superhigh cross-linking is layered microporous polymer, include the following steps：It is respectively first that molybdenum source and sulphur source prepare flaky molybdenum disulfide with sodium molybdate and thiocarbamide, so that diazol is grown on flaky molybdenum disulfide using the method directly grafted, MoS is formed by diazol functionalization2- PANI conducting polymers, the copolymer of organic matter polyvinyl alcohol, vinylimidazolium chloride benzyl, divinylbenzene is further added under the action of azodiisobutyronitrile polymeric initiator, the longer chain conducting polymer of superhigh cross-linking is obtained, finally by control reaction time and temperature, in FeCl3Catalytic action under Fu Lide-Kerafyrm thatch occurs layering superhigh cross-linking microporous polymer conductive material MoHCPs is obtained by the reaction；Compared with the existing technology, which has preparation process and required equipment simple to the present invention, and the advantage that reaction temperature is substantially reduced, raw material are easy to get, it is easy to accomplish the features such as large-scale production.

Description

A kind of preparation method and applications of superhigh cross-linking layering microporous polymer
[technical field]
The invention belongs to materialogy fields, are related to a kind of preparation of polymer, specifically a kind of superhigh cross-linking layering The preparation method and applications of microporous polymer.
[background technology]
Peace and development is the common aspiration and the objective of the struggle of the whole mankind, and the energy is to influence human society survival and development Important proposition.However since the 21th century, with the development of the progress of the mankind and society, fossil energy is constantly consumed, by This energy crisis caused and problem of environmental pollution are more and more prominent, become the huge challenge of scientific technological advance, while complete The climatic environment of ball, which constantly deteriorates, makes the development of modern society face a severe challenge.Therefore, from the sustainable development of socio-economy Strategic angle from the point of view of, traditional energy system just gradually hampers socio-economic development, develops safe and clean green energy resource System (such as solar energy, wind energy, biomass energy, geothermal energy and tide energy etc.) is used in people, it has also become world today's energy profit Development trend, and electrochmical power source is one of the most important research direction to solve the above problems.
Traditional lead-acid battery in electrochmical power source, nickel-cadmium cell have been difficult because of the problems such as energy density is relatively low, environmental pollution Meets the needs of market, compared with above-mentioned battery, the lithium ion battery to come into being is with bigger than energy, operating voltage is high, puts Piezoelectric voltage curve is steady, high temperature performance is good, self-discharge rate is small, outstanding advantages of having extended cycle life, is pollution-free, rapidly develop at The ideal source of a variety of lightweight compact electronic devices is widely used in the various electronic equipments of information age today, such as moves Mobile phone, digital camera, video camera and digital processor etc..In recent years, lithium ion battery is in hybrid vehicle of new generation Application on (hybrid electrical vehicle, HEV) and pure electric automobile (electrical vehicle, HEV) It is of increasing concern.
At present, the lithium ion battery negative material of research mainly has：Carbon based negative electrodes material and non-carbon negative material.Wherein Carbon based negative electrodes material includes graphite-like carbon, hard carbon and soft carbon, carbon nanotube and graphene.Non-carbon negative material is concentrated mainly on The composite wood that tin-based material, silica-base material, transition metal oxide and sulfide material and graphite are dilute, carbon nanotube is matrix Material.Most of composite materials are in longer lithium ion diffusion path length, especially hollow residual volume space, in storage lithium Inevitable large volume variation when repeated charge is withstood during ion, and common material holds during storing up lithium Easy avalanche, loses electro-chemical activity.
[invention content]
A kind of system of superhigh cross-linking layering microporous polymer is provided present invention aim to solve above-mentioned deficiency Preparation Method not only solves simple MoS2Easily reunite and the problems such as volume expansion in charge and discharge process, also solves polyphenyl The instability problem of amine, the synergistic effect that can make full use of the two obtain electrochemistry under the action of crosslinking agent PVD It can good layering microporous polymer.
A kind of preparation method of superhigh cross-linking layering microporous polymer is designed to achieve the above object, is included the following steps：
1) at room temperature, deionized water, ethyl alcohol, oleic acid are added to the container it is uniformly mixed, then be added sodium molybdate, thiocarbamide And enuatrol, ultrasonic 30-40min to solution are clarified completely, it is molten then with the HCl tune pH value of solution of prepared 2.0M to acidity Liquid gradually becomes bottle green by milky, eventually becomes blackish green, obtains reaction solution；
2) the above-mentioned reaction solution prepared is poured into polytetrafluoroethyllining lining stainless steel autoclave, reaction for 24 hours, is taken out Cooled to room temperature afterwards, filtering, is washed successively with deionized water and ethyl alcohol, is repeated 3-5 times, by filtration product in 60 DEG C of dryings 8h obtains sheet MoS2Powder；
3) MoS for taking a certain amount of step 2) to obtain2Powder is dissolved in dimethylformamide, ultrasonic disperse, to scattered molten Nitrobenzene diazonium tetrafluoroborate and tetrabutylammonium chloride are added in liquid, forms the mixed liquor of stable and uniform, magnetic force is bathed under room temperature Stirring, is washed 3-5 times with acetonitrile and acetone, and dry 4h, obtains nitrobenzene/vulcanization molybdenum composite material N-MoS under the conditions of 80 DEG C2；
4) a certain amount of above-mentioned N-MoS is weighed2It is dissolved in the mixed liquor of acetic acid and water, ultrasound is complete to disperseing, then The mixed liquor of a certain amount of metallic zinc, ammonium chloride and acetic acid is added, flow back 3h at 60 DEG C, cooled to room temperature, centrifugation, Three times with the hydrochloric acid and milli-Q water of 0.1M, it is dried in vacuo 4h under the conditions of 60 DEG C, obtains aminobenzene/molybdenum sulfide composite A- MoS2；
5) by a certain amount of above-mentioned A-MoS2It is dispersed in the mixing liquid of aniline and sulfuric acid, adds a certain amount of over cure Sour ammonium stirs to being completely dissolved, polymerisation is then carried out under condition of ice bath, filters, 3 are washed with deionized water and ethyl alcohol Secondary, dry 6h, obtains polyaniline-vulcanization molybdenum composite material MoS under the conditions of 60 DEG C2/PANI；
6) by a certain amount of MoS2/ PANI, vinylimidazolium chloride benzyl VBC, divinylbenzene DVB and polymeric initiator azo Bis-isobutyronitrile AIBN is added in the mixed solution of PVAC polyvinylalcohol, sodium chloride and deionized water, stirring to being completely dissolved, 80 DEG C of stirring 8h, then cool to room temperature filtering, are washed three times with deionized water, methanol and ether successively, done under the conditions of 60 DEG C Dry 12h, obtains MoS2/PANI/PVD；
7) MoS for taking a certain amount of step 6) to obtain2/ PANI/PVD is dissolved in 1,2- dichloroethanes, and the two comes into full contact with Ice bath cools down after 3h, and a certain amount of FeCl is then added3Catalyst is made, after mixing complete 2h, 12h is heated under the conditions of 80 DEG C Carry out Fu Lide-Kerafyrm thatch reaction, filtered after being cooled to room temperature, successively with methanol, acetone and 0.5M hydrochloric acid mixture, go Ion water washing three times, is dried in vacuo under the conditions of 60 DEG C, obtains superhigh cross-linking microporous polymer MoHCPs.
Further, in step 1), pH value of solution is adjusted to 1.0.
Further, in step 1), the deionized water, ethyl alcohol, oleic acid volume ratio be 15:15:2.
Further, in step 2), hydrothermal temperature is 200 DEG C in the reaction kettle.
Further, in step 3), the magnetic agitation time is for 24 hours.
Further, in step 4), the acetic acid and water volume ratio are 3:2.
Further, in step 5), the ice bath reaction time is 3h.
Further, in step 3), magnetic agitation reaction is carried out under the protection of nitrogen.
Further, in step 7), the MoS2It refers to by MoS that/PANI/PVD and 1,2- dichloroethanes, which comes into full contact with,2/ PANI/PVD is fully immersed in 1,2- dichloroethane solutions.
The present invention also provides prepared superhigh cross-linkings to be layered microporous polymer in lithium ion battery electrode material or suction Application in enclosure material.
The present invention compared with the existing technology, first by C-S covalent bond effects, allows diazol directly to graft in two-dimensional sheet Transition metal MoS2On, polyaniline-vulcanization molybdenum composite material is obtained, then under the action of crosslinking agent PVD, it is long to lengthen chain Fu Lide-Kerafyrm thatch reaction finally occurs for degree, obtains superhigh cross-linking layering microporous polymer MoHCPs, this preparation method Not only solve simple MoS2Easily reunite and the problems such as volume expansion in charge and discharge process, also solves the shakiness of polyaniline It is good to obtain chemical property under the action of crosslinking agent PVD for qualitative question, the synergistic effect that can make full use of the two It is layered microporous polymer.Compared with prior art, specific advantage is：
(1) using flaky molybdenum disulfide as substrate, using hydro-thermal-directly grafting-emulsion process, by controlling reaction time, system It is standby go out different-shape layering microporous polymer, the MoHCPs composite materials of gained not only have that thermal stability is good, crystallization degree High, large specific surface area, and the morphology controllable of molybdenum sulfide is strong, is one of ideal energy and material；
(2) preparation method has preparation process and required equipment simple, and the advantage that reaction temperature is substantially reduced, raw material It is easy to get, it is easy to accomplish the features such as large-scale production；
(3) polyaniline is directly grafted onto on molybdenum disulfide by covalent bond effect, more stable polymer can be obtained； Longer chain polymer is obtained further through crosslinking, MoHCPs, crystallization degree is obtained by the reaction Fu Lide-Kerafyrm thatch occurs Height, large specific surface area, and be the more microporous polymers of layering, electric charge transfer performance can be not only significantly increased, is shown very Good high rate performance and cycle performance, and provide contact site of more polyanilines with molybdenum sulfide.
[description of the drawings]
Fig. 1 a are scanning electron microscope (SEM) photograph of the flaky molybdenum disulfide of 1 gained of embodiment under 120000 multiplying power；
Fig. 1 b are transmission electron microscope picture of the flaky molybdenum disulfide of 1 gained of embodiment under 80000 multiplying power；
Fig. 2 a are the infrared figures of embodiment 2 gained molybdenum disulfide and N-MoS2；
Fig. 2 b are the scanning electron microscope (SEM) photographs under the multiplying power of the flaky molybdenum disulfide 50000 of 2 gained of embodiment；
Fig. 3 is scanning electron microscope (SEM) photograph of the flaky molybdenum disulfide of 3 gained of embodiment under 100000 multiplying power；
Fig. 4 is embodiment 1,2 and 3 gained MoS2/PANI cyclical stability figures.
[specific implementation mode]
The present invention provides the preparation methods that a kind of superhigh cross-linking is layered microporous polymer, first with sodium molybdate and thiocarbamide point Not Wei molybdenum source and sulphur source prepare flaky molybdenum disulfide, so that diazol is grown in flaky molybdenum disulfide using the method directly grafted On, form MoS by diazol functionalization2- PANI conducting polymers further draw in azodiisobutyronitrile (AIBN) macromolecule The copolymer of organic matter polyvinyl alcohol (PVA), vinylimidazolium chloride benzyl (VBC), divinylbenzene (DVB) is added under the action of hair agent (PVD), the longer chain conducting polymer for obtaining superhigh cross-linking, finally by control reaction time and temperature, in FeCl3Urge Layering superhigh cross-linking microporous polymer conductive material MoHCPs is obtained by the reaction in the lower generation Fu Lide-Kerafyrm thatch of change effect.Party's legal system Not only thermal stability is good, crystallization degree is high, large specific surface area for standby composite material, but also with layering microcellular structure and well Dispersibility is one of ideal energy and material.Superhigh cross-linking layering microporous polymer can be applied to lithium ion cell electrode material Material field can also be applied to sorbing material field.
Make following further clarification below by specific embodiment and in conjunction with attached drawing to the present invention, but is not intended to limit the present invention
Embodiment 1
A kind of preparation method of superhigh cross-linking layering microporous polymer, includes the following steps：
(1) preparation of flaky molybdenum disulfide：At room temperature, 15ml deionized waters, 15ml ethyl alcohol, 2ml oleic acid are added successively Enter into 50ml beakers, be slowly added into 1.6g enuatrols, 1.0g sodium molybdates, 0.9g thiocarbamides successively after mixing, stirs 5- 10min, then ultrasound 30-40min clarified completely to solution, with the pH to 1.0 of the above-mentioned solution of hydrochloric acid tune of prepared 2.0M Left and right, solution gradually become bottle green by milky, eventually become black.Above-mentioned prepared solution is moved into poly- the four of 50ml In vinyl fluoride inner liner stainless steel water heating kettle, after being reacted for 24 hours under 180 degrees celsius, cooled to room temperature, filtering is spent Ionized water and pure ethyl alcohol wash four times, and the product being obtained by filtration is dried in vacuo 8h under the conditions of 60 DEG C, obtain sheet vulcanization Molybdenum powder.Wherein, the amount of enuatrol used in reaction process, sodium molybdate, thiocarbamide, oleic acid, ethyl alcohol, calculates in mass ratio, i.e., Enuatrol：Sodium molybdate：Thiocarbamide：Oleic acid：Ethyl alcohol is 16:10:9:18:120；The mass percent concentration of the ethyl alcohol be 75~ 99%.
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, to institute under 120000 multiplying power The flaky molybdenum disulfide obtained is scanned, and the scanning electron microscope (SEM) photograph of gained is as shown in Figure 1a, is carried out to molybdenum disulfide with transmission electron microscope Scanning such as Fig. 1 b, it can be seen that molybdenum disulfide laminated structure, has been indicated above and has successfully prepared receiving for sheet from Fig. 1 a and 1b Meter level molybdenum disulfide；
(2) molybdenum disulfide that 120mg is obtained is dissolved in 100ml dimethylformamides (DMF), ultrasonic 1h；240mg nitre Base benzene diazonium tetrafluoroborate, 3.29mg tetrabutylammonium chlorides are added sequentially in above-mentioned solution；Magnetic agitation is for 24 hours under room temperature Afterwards, filter, washed 3~5 times with acetonitrile and acetone, obtained product is dried in vacuo under the conditions of 80 DEG C 4h obtain nitrobenzene/ Molybdenum disulfide composite material (N-MoS2)；It calculates in mass ratio, MoS2:DMF:Nitrobenzene diazonium tetrafluoroborate:Tetrabutyl chlorination Ammonium is 120:94:240:3.29.
(3) by 60mg N-MoS2It is dissolved in 20ml acetic acid and the mixed liquor of deionized water, ultrasonic 2h；Into above-mentioned solution It is slowly added to 104mgZn, 1mgNH successively4Cl and 2.3ml acetic acid；Flow back after being mixed thoroughly under the conditions of 60 DEG C 3h；From The heart, with hydrochloric acid and milli-Q water 3 times, under the conditions of 60 DEG C being dried in vacuo 4h obtains aminobenzene/molybdenum disulfide composite material (A-MoS2).Wherein, the volume ratio of acetic acid and deionized water is 3:2；When washing, with the hydrochloric acid washed product of 0.1M.
(4) 34mg A-MoS are taken2It is scattered in the mixed solution of sulfuric acid and aniline, 50ml over cures is added after mixing The aqueous solution of sour ammonium (APS), stirring to mixing substantially uniformity；Ice bath reacts 3h, filtering, with water and ethyl alcohol under nitrogen protection It is dried in vacuo 6h under the conditions of 60 DEG C after washing, obtains MoS2/ PANI composite materials.A concentration of 1.0M of sulfuric acid；Aniline and mistake The molar ratio of ammonium sulfate is 4:1.
(5) successively by 5mg MoS2/ PANI, 6.37g vinylimidazolium chlorides benzyl (VBC), 0.16g divinylbenzenes (DVB) and 33mg polymeric initiators azodiisobutyronitrile (AIBN) is added to the mixing of polyvinyl alcohol (PVA), sodium chloride and deionized water In solution, stirring is to being completely dissolved.8h is stirred at 80 DEG C, then cools to room temperature filtering, uses deionized water, methanol and second successively Ether washs three times, and 12h is dried in vacuo under the conditions of 60 DEG C and obtains MoS2/ PANI/PVD. is dissolved in 1,2- dichloroethanes afterwards In, ice bath cools down after the two comes into full contact with 3h, and a certain amount of FeCl is then added3Catalyst is made, after mixing complete 2h, at 80 DEG C Under the conditions of heating 12h carry out Fu Lide-Kerafyrm thatch reaction, filtered after being cooled to room temperature, use methanol, acetone and 0.5M successively The mixture of hydrochloric acid, deionized water washing are dried in vacuo three times, under the conditions of 60 DEG C obtains superhigh cross-linking microporous polymer (MoHCPs)。
Embodiment 2
A kind of preparation method of superhigh cross-linking layering microporous polymer, specifically comprises the following steps：
(1) preparation of flaky molybdenum disulfide：At room temperature, 15ml deionized waters, 15ml ethyl alcohol, 2ml oleic acid are added successively Enter into 50ml beakers, be slowly added into 1.6g enuatrols, 1.0g sodium molybdates, 0.9g thiocarbamides successively after mixing, stirs 5- 10min, then ultrasound 30-40min clarified completely to solution, with the pH to 1.0 of the above-mentioned solution of hydrochloric acid tune of prepared 2.0M Left and right, solution gradually become bottle green by milky, eventually become black.Above-mentioned prepared solution is moved into poly- the four of 50ml In vinyl fluoride inner liner stainless steel water heating kettle, after being reacted for 24 hours under 180 degrees celsius, cooled to room temperature, filtering is spent Ionized water and pure ethyl alcohol wash four times, and the product being obtained by filtration is dried in vacuo 8h under the conditions of 60 DEG C, obtain sheet vulcanization Molybdenum powder.Wherein, the amount of enuatrol used in reaction process, sodium molybdate, thiocarbamide, oleic acid, ethyl alcohol, calculates in mass ratio, i.e., Enuatrol：Sodium molybdate：Thiocarbamide：Oleic acid：Ethyl alcohol is 16:10:9:18:120；The mass percent concentration of the ethyl alcohol be 75~ 99%.
(2) molybdenum disulfide that 120mg is obtained is dissolved in 100ml dimethylformamides (DMF), ultrasonic 1h；240mg nitre Base benzene diazonium tetrafluoroborate, 3.29mg tetrabutylammonium chlorides are added sequentially in above-mentioned solution；Magnetic agitation is for 24 hours under room temperature Afterwards, filter, washed 3~5 times with acetonitrile and acetone, obtained product is dried in vacuo under the conditions of 80 DEG C 4h obtain nitrobenzene/ Molybdenum disulfide composite material (N-MoS2)；It calculates in mass ratio, MoS2:DMF:Nitrobenzene diazonium tetrafluoroborate:Tetrabutyl chlorination Ammonium is 120:94:240:3.29.
(3) by 60mg N-MoS2It is dissolved in 20ml acetic acid and the mixed liquor of deionized water, ultrasonic 2h；Into above-mentioned solution It is slowly added to 104mgZn, 1mgNH successively4Cl and 2.3ml acetic acid；Flow back after being mixed thoroughly under the conditions of 60 DEG C 3h；From The heart, with hydrochloric acid and milli-Q water 3 times, under the conditions of 60 DEG C being dried in vacuo 4h obtains aminobenzene/molybdenum disulfide composite material (A-MoS2).The volume ratio of acetic acid and deionized water is 3:2；With the hydrochloric acid washed product of 0.1M.
(4) 34mg A-MoS are taken2It is scattered in the mixed solution of sulfuric acid and aniline, 50ml over cures is added after mixing The aqueous solution of sour ammonium (APS), stirring to mixing substantially uniformity；Ice bath reacts 3h, filtering, with water and ethyl alcohol under nitrogen protection It is dried in vacuo 6h under the conditions of 60 DEG C after washing, obtains MoS2/ PANI composite materials；A concentration of 1.0M of sulfuric acid；Aniline and mistake The molar ratio of ammonium sulfate is 4:1.
(5) successively by 5mg MoS2/ PANI, 6.37g vinylimidazolium chlorides benzyl (VBC), 0.16g divinylbenzenes (DVB) and 33mg polymeric initiators azodiisobutyronitrile (AIBN) is added to the mixing of polyvinyl alcohol (PVA), sodium chloride and deionized water In solution, stirring is to being completely dissolved.8h is stirred at 80 DEG C, then cools to room temperature filtering, uses deionized water, methanol and second successively Ether washs three times, and 12h is dried in vacuo under the conditions of 60 DEG C and obtains MoS2/ PANI/PVD. is dissolved in 1,2- dichloroethanes afterwards In, ice bath cools down after the two comes into full contact with 3h, and a certain amount of FeCl is then added3Catalyst is made, after mixing complete 2h, at 80 DEG C Under the conditions of heating 12h carry out Fu Lide-Kerafyrm thatch reaction, filtered after being cooled to room temperature, use methanol, acetone and 0.5M successively The mixture of hydrochloric acid, deionized water washing are dried in vacuo three times, under the conditions of 60 DEG C obtains superhigh cross-linking microporous polymer (MoHCPs)。
The FT-IR of Fig. 2 a shows diazol successfully to grow on sheet molybdenum sulfide；Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, is scanned the flaky molybdenum disulfide of gained under 50000 multiplying power, gained is swept Electron microscope is retouched as shown in attached drawing 2b, has been indicated above the nanometer class molybdenum disulfide for successfully preparing sheet.
Embodiment 3
A kind of preparation method of superhigh cross-linking layering microporous polymer, specifically comprises the following steps：
(1) preparation of flaky molybdenum disulfide：At room temperature, 15ml deionized waters, 15ml ethyl alcohol, 2ml oleic acid are added successively Enter into 50ml beakers, be slowly added into 1.6g enuatrols, 1.0g sodium molybdates, 0.9g thiocarbamides successively after mixing, stirs 5- 10min, then ultrasound 30-40min clarified completely to solution, with the pH to 1.0 of the above-mentioned solution of hydrochloric acid tune of prepared 2.0M Left and right, solution gradually become bottle green by milky, eventually become black.Above-mentioned prepared solution is moved into poly- the four of 50ml In vinyl fluoride inner liner stainless steel water heating kettle, after being reacted for 24 hours under 180 degrees celsius, cooled to room temperature, filtering is spent Ionized water and pure ethyl alcohol wash four times, and the product being obtained by filtration is dried in vacuo 8h under the conditions of 60 DEG C, obtain sheet vulcanization Molybdenum powder.Wherein, the amount of enuatrol used in reaction process, sodium molybdate, thiocarbamide, oleic acid, ethyl alcohol, calculates in mass ratio, i.e., Enuatrol：Sodium molybdate：Thiocarbamide：Oleic acid：Ethyl alcohol is 16:10:9:18:120；The mass percent concentration of the ethyl alcohol be 75~ 99%.
(2) molybdenum disulfide that 120mg is obtained is dissolved in 100ml dimethylformamides (DMF), ultrasonic 1h；240mg nitros Benzene diazonium tetrafluoroborate, 3.29mg tetrabutylammonium chlorides are added sequentially in above-mentioned solution；Under room temperature magnetic agitation for 24 hours after, Filtering, is washed 3~5 times with acetonitrile and acetone, and obtained product is dried in vacuo under the conditions of 80 DEG C to 4h and obtains the sulphur of nitrobenzene/bis- Change molybdenum composite material (N-MoS2)；It calculates in mass ratio, MoS2:DMF:Nitrobenzene diazonium tetrafluoroborate:Tetrabutylammonium chloride It is 120:94:240:3.29.
(3) by 60mg N-MoS2It is dissolved in 20ml acetic acid and the mixed liquor of deionized water, ultrasonic 2h；Into above-mentioned solution It is slowly added to 104mgZn, 1mgNH successively4Cl and 2.3ml acetic acid；Flow back after being mixed thoroughly under the conditions of 60 DEG C 3h；From The heart, with hydrochloric acid and milli-Q water 3 times, under the conditions of 60 DEG C being dried in vacuo 4h obtains aminobenzene/molybdenum disulfide composite material (A-MoS2).The volume ratio of acetic acid and deionized water is 3:2；With the hydrochloric acid washed product of 0.1M.
(4) 34mg A-MoS are taken2It is scattered in the mixed solution of sulfuric acid and aniline, 50ml over cures is added after mixing The aqueous solution of sour ammonium (APS), stirring to mixing substantially uniformity；Ice bath reacts 3h, filtering, with water and ethyl alcohol under nitrogen protection It is dried in vacuo 6h under the conditions of 60 DEG C after washing, obtains MoS2/ PANI composite materials；A concentration of 1.0M of sulfuric acid；Aniline and mistake The molar ratio of ammonium sulfate is 4:1.
(5) successively by 5mg MoS2/ PANI, 6.37g vinylimidazolium chlorides benzyl (VBC), 0.16g divinylbenzenes (DVB) and 33mg polymeric initiators azodiisobutyronitrile (AIBN) is added to the mixing of polyvinyl alcohol (PVA), sodium chloride and deionized water In solution, stirring is to being completely dissolved.8h is stirred at 80 DEG C, then cools to room temperature filtering, uses deionized water, methanol and second successively Ether washs three times, and 12h is dried in vacuo under the conditions of 60 DEG C and obtains MoS2/ PANI/PVD. is dissolved in 1,2- dichloroethanes afterwards In, ice bath cools down after the two comes into full contact with 3h, and a certain amount of FeCl is then added3Catalyst is made, after mixing complete 2h, at 80 DEG C Under the conditions of heating 12h carry out Fu Lide-Kerafyrm thatch reaction, filtered after being cooled to room temperature, use methanol, acetone and 0.5M successively The mixture of hydrochloric acid, deionized water washing are dried in vacuo three times, under the conditions of 60 DEG C obtains superhigh cross-linking microporous polymer (MoHCPs)。
Using field emission scanning electron microscope (German Zeiss ultra 55) instrument, to institute under 100000 multiplying power The flaky molybdenum disulfide obtained is scanned, and the scanning electron microscope (SEM) photograph of gained is as shown in Fig. 3, has been indicated above and has successfully prepared sheet Nanometer class molybdenum disulfide；
Attached drawing 4 shows the good cyclical stabilities of MoHCPs, is 1A/g in current density, is still protected after 5000 circle of cycle Hold 90% chemical property.
The present invention is simultaneously not limited to the embodiments described above, other any Spirit Essences and principle without departing from the present invention Changes, modifications, substitutions, combinations, simplifications made by lower, should be equivalent substitute mode, be included in the protection model of the present invention Within enclosing.

Claims (10)

1. a kind of preparation method of superhigh cross-linking layering microporous polymer, which is characterized in that include the following steps：
1) at room temperature, deionized water, ethyl alcohol, oleic acid are added to the container uniformly mixed, sodium molybdate, thiocarbamide and oil is then added Sour sodium, ultrasonic 30-40min to solution are clarified completely, then with the HCl tune pH value of solution of prepared 2.0M to acidity, solution by Milky gradually becomes bottle green, eventually becomes blackish green, obtains reaction solution；
2) the above-mentioned reaction solution prepared is poured into polytetrafluoroethyllining lining stainless steel autoclave, is reacted for 24 hours, after taking-up certainly It is so cooled to room temperature, filters, washed successively with deionized water and ethyl alcohol, repeat 3-5 times, by filtration product in 60 DEG C of dry 8h, Obtain sheet MoS2Powder；
3) MoS for taking a certain amount of step 2) to obtain2Powder is dissolved in dimethylformamide, and ultrasonic disperse adds into scattered solution Enter nitrobenzene diazonium tetrafluoroborate and tetrabutylammonium chloride, form the mixed liquor of stable and uniform, magnetic force bathes stirring under room temperature, uses Acetonitrile and acetone dry 4h under the conditions of washing 3-5 times, 80 DEG C, obtain nitrobenzene/vulcanization molybdenum composite material N-MoS2；
4) a certain amount of above-mentioned N-MoS is weighed2It is dissolved in the mixed liquor of acetic acid and water, ultrasound is complete to disperseing, and is then added one The mixed liquor of quantitative metallic zinc, ammonium chloride and acetic acid, flow back 3h at 60 DEG C, cooled to room temperature, centrifugation, with 0.1M's Hydrochloric acid and milli-Q water three times, 4h are dried in vacuo under the conditions of 60 DEG C, obtain aminobenzene/molybdenum sulfide composite A-MoS2；
5) by a certain amount of above-mentioned A-MoS2It is dispersed in the mixing liquid of aniline and sulfuric acid, adds a certain amount of ammonium persulfate, Then stirring carries out polymerisation to being completely dissolved under condition of ice bath, filter, washed 3 times, 60 DEG C with deionized water and ethyl alcohol Under the conditions of dry 6h, obtain polyaniline-vulcanization molybdenum composite material MoS2/PANI；
6) by a certain amount of MoS2/ PANI, vinylimidazolium chloride benzyl VBC, divinylbenzene DVB and polymeric initiator azo two are different Butyronitrile AIBN is added in the mixed solution of PVAC polyvinylalcohol, sodium chloride and deionized water, is stirred to being completely dissolved, at 80 DEG C 8h is stirred, filtering is then cooled to room temperature, is washed three times with deionized water, methanol and ether successively, it is dry under the conditions of 60 DEG C 12h obtains MoS2What/PANI/PVD, PVD were indicated is organic matter PVAC polyvinylalcohol, vinylimidazolium chloride benzyl VBC, divinylbenzene The copolymer of DVB；
7) MoS for taking a certain amount of step 6) to obtain2/ PANI/PVD is dissolved in 1,2- dichloroethanes, and the two comes into full contact with ice after 3h Bath cooling, is then added a certain amount of FeCl3Catalyst is made, after mixing complete 2h, is heated under the conditions of 80 DEG C in 12h progress Fu Moral-Kerafyrm thatch reaction, is filtered after being cooled to room temperature, and uses methanol, the mixture of acetone and 0.5M hydrochloric acid, deionization washing successively It washs three times, is dried in vacuo under the conditions of 60 DEG C, obtain superhigh cross-linking microporous polymer MoHCPs.
2. the preparation method of superhigh cross-linking layering microporous polymer as described in claim 1, it is characterised in that:In step 1), PH value of solution is adjusted to 1.0.
3. the preparation method of superhigh cross-linking layering microporous polymer as described in claim 1, it is characterised in that:In step 1), The deionized water, ethyl alcohol, oleic acid volume ratio be 15:15:2.
4. the preparation method of superhigh cross-linking layering microporous polymer as described in claim 1, it is characterised in that:In step 2), Hydrothermal temperature is 200 DEG C in the reaction kettle.
5. the preparation method of superhigh cross-linking layering microporous polymer as described in claim 1, it is characterised in that:In step 3), The magnetic agitation time is for 24 hours.
6. the preparation method of superhigh cross-linking layering microporous polymer as described in claim 1, it is characterised in that:In step 4), The acetic acid and water volume ratio are 3:2.
7. the preparation method of superhigh cross-linking layering microporous polymer as described in claim 1, it is characterised in that:In step 5), The ice bath reaction time is 3h.
8. the preparation method of superhigh cross-linking layering microporous polymer as described in claim 1, it is characterised in that:In step 3), Magnetic agitation reaction is carried out under the protection of nitrogen.
9. the preparation method of superhigh cross-linking layering microporous polymer as described in claim 1, it is characterised in that:In step 7), The MoS2It refers to by MoS that/PANI/PVD and 1,2- dichloroethanes, which comes into full contact with,2/ PANI/PVD is fully immersed in 1,2- dichloros In ethane solution.
10. super prepared by the preparation method of superhigh cross-linking layering microporous polymer as claimed in any one of claims 1-9 wherein Application of the height crosslinking layering microporous polymer in lithium ion battery electrode material or sorbing material.
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