CN106784761B - A kind of Ti3C2TxThe preparation method of/sulphur carbon composite - Google Patents
A kind of Ti3C2TxThe preparation method of/sulphur carbon composite Download PDFInfo
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- CN106784761B CN106784761B CN201710229281.1A CN201710229281A CN106784761B CN 106784761 B CN106784761 B CN 106784761B CN 201710229281 A CN201710229281 A CN 201710229281A CN 106784761 B CN106784761 B CN 106784761B
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000005864 Sulphur Substances 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 35
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 235000019441 ethanol Nutrition 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 230000007797 corrosion Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- -1 Oxygen alkane Chemical class 0.000 claims 1
- 238000005255 carburizing Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000003303 reheating Methods 0.000 claims 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005077 polysulfide Substances 0.000 abstract description 6
- 229920001021 polysulfide Polymers 0.000 abstract description 6
- 150000008117 polysulfides Polymers 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021389 graphene Inorganic materials 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of Ti3C2TxThe preparation method of/sulphur carbon composite, carbon material of the composite material by spherical porous structure, the Ti that is dispersed in porous structure carbon material3C2TxIt is formed with elemental sulfur, porous carbon materials are in outer layer to elemental sulfur and Ti3C2TxIt is coated, wherein Ti3C2Tx: carbon: the mass ratio of sulphur is 0.1-0.3:0.1-0.3:1.Ti in the composite material3C2TxOn T be-F group or-OH group, oxygen with surface of graphene oxide is highly polar group, strong chemisorption can be formed to the polysulfide formed in charge and discharge process, the micropore of porous carbon materials also can carry out physical absorption to polysulfide simultaneously, it is this while there is the ability of physics and chemisorption effectively polysulfide can be prevented to move, the generation for reducing shuttle effect, improves the service life of lithium-sulfur cell.
Description
Technical field
The present invention relates to nano material synthesis, in particular to a kind of preparation method of lithium sulfur battery anode material.
Background technique
Lithium-sulfur cell is using lithium metal as cathode, and elemental sulfur is the battery system of anode.There are two put the tool of lithium-sulfur cell
Level platform (about 2.4 V and 2.1 V), but its electrochemical reaction mechanism is more complicated.Lithium-sulfur cell has specific energy high
(2600 Wh/kg), specific capacity height (1675 mAh/g), it is at low cost the advantages that, it is considered to be very promising a new generation's electricity
Pond.But there is the problems such as active material utilization is low, cycle life is low and safety is poor at present, this seriously restricts lithium
The development of sulphur battery.The main reason for causing the above problem has the following aspects: (1) elemental sulfur is electronics and ion insulation
Body, room-temperature conductivity low (5 × 10-30S·cm-1), since the sulphur of not no ionic state exists, thus it is tired as positive electrode activation
It is difficult；(2) the poly- more lithium sulfide Li of state of height generated in electrode process2Sn(8 n >=4 >) are soluble in electrolyte, positive and negative
Concentration difference is formed between pole, cathode is moved under the action of concentration gradient, and the high poly- more lithium sulfides of state are reduced into low by lithium metal
The poly- more lithium sulfides of state.With the progress reacted above, the oligomeric more lithium sulfides of state are assembled in cathode, are finally formed between electrodes
Concentration difference, and move to anode and be oxidized to the high poly- more lithium sulfides of state.This phenomenon is referred to as shuttle effect, reduces sulphur activity
The utilization rate of substance.Insoluble Li simultaneously2S and Li2S2It is deposited on cathode of lithium surface, is further degrading lithium-sulfur cell
Performance；(3) final product Li is reacted2S is equally electronic body, can be deposited on sulfur electrode, and lithium ion vulcanizes in solid-state
Migration velocity is slow in lithium, keeps electrochemical reaction kinetic rate slack-off；(4) sulphur and final product Li2The density of S is different, works as sulphur
It is lithiated rear volume expansion about 79%, easily leads to Li2The dusting of S causes the safety problem of lithium-sulfur cell.Above-mentioned insufficient restriction
The development of lithium-sulfur cell, this is also the Important Problems that the research of current lithium-sulfur cell needs to solve.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Ti3C2Tx/ sulphur carbon composite, the composite material is by spherical shape
The carbon material of porous structure, the Ti being dispersed in porous structure carbon material3C2TxIt is formed with elemental sulfur, porous carbon materials are in outer layer
To elemental sulfur and Ti3C2TxIt is coated, wherein Ti3C2Tx: carbon: the mass ratio of sulphur is 0.1-0.3:0.1-0.3:1.
The present invention provides a kind of Ti3C2Tx/ sulphur carbon composite the preparation method is as follows:
(1) eight silsesquioxane of 1.5mmol octaphenyl is added to 70mL 1, in 2- dichloroethanes, is stirred in 60 DEG C of machinery
Dissolution is mixed, Ti is added3AlC2Ceramic powders, stirring form suspension；
(2) 2mmol anhydrous aluminum chloride catalyst is added into suspension and 40 mL carbon tetrachloride crosslinking agents are added, stirring
After reaction ethanol/water solution is added, ethyl alcohol/dilute hydrochloric acid solution is washed, washes, is dried in vacuo, before obtaining in cross-linking reaction 10h
Drive body；
(3) presoma is placed in the Muffle furnace of nitrogen atmosphere protection, the reaction of 900 DEG C 3h2 °C/min high temperature cabonization；
(4) product after carbonization is placed in hydrofluoric acid and is performed etching, solution is added deionized water and is centrifuged after corrosion
Processing, then sediment is dried, obtain Ti3C2Tx/ spherical porous carbon material；
(5) by Ti3C2Tx/ spherical porous carbon material is uniformly mixed with elemental sulfur, is placed in 155- in the tube furnace of sealing
165 DEG C are reacted 12 hours, are heated to 200 DEG C and are passed through nitrogen reaction 30 minutes, after natural cooling, obtain Ti3C2Tx/ sulphur carbon is multiple
Condensation material.
Eight silsesquioxane of octaphenyl in step (1): the ratio of 1,2- dichloroethanes is 1g:50-100mL, is stirred to react
Temperature is 50-70 DEG C, eight silsesquioxane of octaphenyl and Ti3AlC2The mass ratio of ceramic powders is 1:0.05-0.5;
Catalyst is anhydrous aluminum chloride in step (2), and the quality of catalyst is the 5- of eight silsesquioxane quality of octaphenyl
10%, crosslinking agent is carbon tetrachloride, and crosslinking agent quality is eight 10-40 times of silsesquioxane quality of octaphenyl, is stirred to react the time and is
5-10 hours, ethyl alcohol in ethanol/water solution: the volume ratio of water was 2-4:1, and dilute hydrochloric acid is quality point in ethyl alcohol/dilute hydrochloric acid solution
The hydrochloric acid solution that number is 10%, ethyl alcohol and dilute hydrochloric acid volume ratio 2-4:1;
Reaction atmosphere in step (3) in Muffle furnace is nitrogen, 800-1200 DEG C of reaction temperature, reaction time 1-5 hour,
1-5 °C/minute of heating rate；
The concentration of hydrofluoric acid is 20%-50% in step (4), and the time of corrosion is 4-24 hours;
Ti in step (5)3C2TxThe mass ratio of/spherical porous carbon material and elemental sulfur is 0.1-0.3:1, in tube furnace just
Phase reaction temperature is 155-165 DEG C, and the reaction time is 10-20 hours, and the reaction temperature after being passed through nitrogen is 180-200 DEG C, instead
It is 10-30 minutes between seasonable.
The invention has the following beneficial effects: (1) Ti3C2TxThere is abundant pore structure, Ke Yiti in/sulphur carbon composite
For effectively storing up sulphur space；(2) carbon material of the composite material external sheath effectively limits the movement of sulfenyl material, makes it only
In internal motion；(3) Ti in the composite material3C2TxOn T be-F group or-OH group, the oxygen with surface of graphene oxide
It is highly polar group, strong chemisorption, while porous carbon can be formed to the polysulfide formed in charge and discharge process
The micropore of material can also carry out physical absorption to polysulfide, this while there is the ability of physics and chemisorption can effectively hinder
Only polysulfide moves, and reduces the generation of shuttle effect, improves the service life of lithium-sulfur cell.
Detailed description of the invention
Fig. 1 is preparation technology flow chart of the invention.
Fig. 2 is the charge-discharge performance figure of composite material of the present invention.
Specific embodiment
With reference to the accompanying drawing, preferably embodiment of the invention is described in further detail:
Embodiment 1
(1) eight silsesquioxane of 1g octaphenyl is added to 50mL 1, it is molten in 50 DEG C of mechanical stirrings in 2- dichloroethanes
Solution, adds 0.05gTi3AlC2Ceramic powders, stirring form suspension；
(2) 0.05g anhydrous aluminum chloride catalyst is added into suspension and 10g carbon tetrachloride crosslinking agent is added, stirring is handed over
After reaction ethanol/water solution is added, ethyl alcohol/dilute hydrochloric acid solution is washed, washes, is dried in vacuo, before obtaining in connection reaction 5 hours
Drive body；
(3) presoma is placed in the Muffle furnace of nitrogen atmosphere protection, 800 DEG C of calcinings 5h, 1 °C/min of heating rate；
(4) by the product after carbonization be placed in concentration be 20% hydrofluoric acid in etch 24 hours, after corrosion solution be added go from
Sub- water carries out centrifugal treating, then dries sediment, obtains Ti3C2Tx/ spherical porous carbon material；
(5) by 0.1g Ti3C2Tx/ spherical porous carbon material is uniformly mixed with 1g elemental sulfur, is placed in the tube furnace of sealing
Interior 165 DEG C are reacted 10 hours, are heated to 200 DEG C and are passed through nitrogen reaction 10 minutes, after natural cooling, obtain Ti3C2Tx/ sulphur carbon
Composite material.
Embodiment 2
(1) eight silsesquioxane of 1g octaphenyl is added to 100mL 1, it is molten in 70 DEG C of mechanical stirrings in 2- dichloroethanes
Solution, adds 0. 5gTi3AlC2Ceramic powders, stirring form suspension；
(2) 0.1g anhydrous aluminum chloride catalyst is added into suspension and 40g carbon tetrachloride crosslinking agent is added, stirring crosslinking
After reaction ethanol/water solution is added, ethyl alcohol/dilute hydrochloric acid solution is washed, washes, is dried in vacuo, before obtaining in reaction 10 hours
Drive body；
(3) presoma is placed in the Muffle furnace of nitrogen atmosphere protection, 1200 DEG C of calcinings 1h, 5 °C/min of heating rate；.
(4) product after carbonization is placed in concentration is to etch 4 hours in 50% hydrofluoric acid, and deionization is added in solution after corrosion
Water carries out centrifugal treating, then dries sediment, obtains Ti3C2Tx/ spherical porous carbon material；
(5) by 0.3g Ti3C2Tx/ spherical porous carbon material is uniformly mixed with 1g elemental sulfur, is placed in the tube furnace of sealing
Interior 155 DEG C are reacted 20 hours, are heated to 180 DEG C and are passed through nitrogen reaction 30 minutes, after natural cooling, obtain Ti3C2Tx/ sulphur carbon
Composite material.
Embodiment 3
(1) eight silsesquioxane of 1g octaphenyl is added to 70mL 1, it is molten in 60 DEG C of mechanical stirrings in 2- dichloroethanes
Solution, adds 0.1gTi3AlC2Ceramic powders, stirring form suspension；
(2) 0.08g anhydrous aluminum chloride catalyst is added into suspension and 20g carbon tetrachloride crosslinking agent is added, stirring is handed over
After reaction ethanol/water solution is added, ethyl alcohol/dilute hydrochloric acid solution is washed, washes, is dried in vacuo, before obtaining in connection reaction 8 hours
Drive body；
(3) presoma is placed in the Muffle furnace of nitrogen atmosphere protection, 1000 DEG C of calcinings 3h, 3 °C/min of heating rate；.
(4) product after carbonization is placed in concentration is to etch 16 hours in 30% hydrofluoric acid, and deionization is added in solution after corrosion
Water carries out centrifugal treating, then dries sediment, obtains Ti3C2Tx/ spherical porous carbon material；
(5) by 0.2g Ti3C2Tx/ spherical porous carbon material is uniformly mixed with 1g elemental sulfur, is placed in the tube furnace of sealing
Interior 160 DEG C are reacted 15 hours, are heated to 190 DEG C and are passed through nitrogen reaction 20 minutes, after natural cooling, obtain Ti3C2Tx/ sulphur carbon
Composite material.
Embodiment 4
(1) eight silsesquioxane of 1g octaphenyl is added to 80mL 1, it is molten in 65 DEG C of mechanical stirrings in 2- dichloroethanes
Solution, adds 0.2gTi3AlC2Ceramic powders, stirring form suspension；
(2) 0.07g anhydrous aluminum chloride catalyst is added into suspension and 30g carbon tetrachloride crosslinking agent is added, stirring is handed over
After reaction ethanol/water solution is added, ethyl alcohol/dilute hydrochloric acid solution is washed, washes, is dried in vacuo, before obtaining in connection reaction 6 hours
Drive body；
(3) presoma is placed in the Muffle furnace of nitrogen atmosphere protection, 900 DEG C of calcinings 4h, 2 °C/min of heating rate；.
(4) product after carbonization is placed in concentration is to etch 10 hours in 40% hydrofluoric acid, and deionization is added in solution after corrosion
Water carries out centrifugal treating, then dries sediment, obtains Ti3C2Tx/ spherical porous carbon material；
(5) by 0.15g Ti3C2Tx/ spherical porous carbon material is uniformly mixed with 1g elemental sulfur, is placed in the tubular type of sealing
It is reacted 18 hours for 158 DEG C in furnace, is heated to 185 DEG C and is passed through nitrogen reaction 25 minutes, after natural cooling, obtain Ti3C2Tx/ sulphur
Carbon composite.
Embodiment 5
(1) eight silsesquioxane of 1g octaphenyl is added to 60mL 1, it is molten in 55 DEG C of mechanical stirrings in 2- dichloroethanes
Solution, adds 0.3gTi3AlC2Ceramic powders, stirring form suspension；
(2) 0.09g anhydrous aluminum chloride catalyst is added into suspension and 25g carbon tetrachloride crosslinking agent is added, stirring is handed over
After reaction ethanol/water solution is added, ethyl alcohol/dilute hydrochloric acid solution is washed, washes, is dried in vacuo, before obtaining in connection reaction 7 hours
Drive body；
(3) presoma is placed in the Muffle furnace of nitrogen atmosphere protection, 1100 DEG C of calcinings 2h, 4 °C/min of heating rate；.
(4) product after carbonization is placed in concentration is to etch 12 hours in 35% hydrofluoric acid, and deionization is added in solution after corrosion
Water carries out centrifugal treating, then dries sediment, obtains Ti3C2Tx/ spherical porous carbon material；
(5) by 0.25g Ti3C2Tx/ spherical porous carbon material is uniformly mixed with 1g elemental sulfur, is placed in the tubular type of sealing
It is reacted 13 hours for 1625 DEG C in furnace, is heated to 195 DEG C and is passed through nitrogen reaction 20 minutes, after natural cooling, obtain Ti3C2Tx/ sulphur
Carbon composite.
The preparation and performance test of electrode；By composite material, acetylene black and PVDF 80:10:10 in mass ratio in NMP
Mixing, being coated in is electrode film on aluminium foil, and metal lithium sheet is to electrode, and CELGARD 2400 is diaphragm, the LiTFSI/ of 1mol/L
DOL-DME (volume ratio 1:1) is electrolyte, and the LiNO3 of 1mol/L is additive, electric full of button is assembled into Ar glove box
Pond carries out constant current charge-discharge test using Land battery test system.Charging/discharging voltage range is 1-3V, and current density is
0.5C, performance are as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| First discharge specific capacity (mAh/g) | 864 | 862 | 853 | 869 | 855 |
Fig. 2 is the charge-discharge performance figure that 1 composite material of the embodiment of the present invention is prepared into lithium-sulfur cell.As can be seen from the figure
Efficiency for charge-discharge can achieve 98% or more, and first charge-discharge capacity is 864 mAh/g, efficiency for charge-discharge 98.6%, fill for 500 times
After discharge cycles, capacity still possesses 70%, illustrates that the structure of the composite material can effectively inhibit shuttle effect, improves sulphur battery
Service life.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, In
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (4)
1. a kind of Ti3C2Tx/ sulphur carbon composite, which is characterized in that the Ti3C2Tx/ sulphur carbon composite is by spherical porous knot
The carbon material of structure, the Ti being dispersed in porous structure carbon material3C2TxIt is formed with elemental sulfur, porous carbon materials are in outer layer to simple substance
Sulphur and Ti3C2TxIt is coated, wherein Ti3C2Tx: carbon: the mass ratio of sulphur is 0.1-0.3:0.1-0.3:1；Ti3C2TxOn T
For-F group or-OH group；The Ti3C2TxThe preparation method of/sulphur carbon composite comprises the following steps:
Step (1): eight silsesquioxane of octaphenyl is added in 1,2- dichloroethanes, and mechanical stirring dissolution adds
Ti3AlC2Ceramic powders, stirring form suspension；
Step (2): anhydrous aluminum chloride catalyst being added into suspension and carbon tetrachloride crosslinking agent is added, stirring crosslinking reaction,
After reaction, ethanol/water solution is added, ethyl alcohol/dilute hydrochloric acid solution is washed, washes, is dried in vacuo, and presoma is obtained；
Step (3): presoma is placed in the Muffle furnace of nitrogen atmosphere protection, carburizing reagent；
Step (4): the product after carbonization being placed in hydrofluoric acid and is performed etching, and solution is added deionized water and is centrifuged after corrosion
Processing, then sediment is dried, obtain Ti3C2Tx/ spherical porous carbon material；
Step (5): by Ti3C2Tx/ spherical porous carbon material is uniformly mixed with elemental sulfur, is placed in the tubular type reaction in furnace of sealing,
Reheating is passed through nitrogen and reacts, and after natural cooling, obtains Ti3C2Tx/ sulphur carbon composite；Eight silicon of octaphenyl in the step (1)
Sesquioxyalkane: the ratio of 1,2- dichloroethanes is 1g:50-100mL, and being stirred to react temperature is 50-70 DEG C, eight silicon sesquialter of octaphenyl
Oxygen alkane and Ti3AlC2The mass ratio of ceramic powders is 1:0.05-0.5；Catalyst is anhydrous aluminum chloride, catalysis in the step (2)
The quality of agent is the 5-10% of eight silsesquioxane quality of octaphenyl, and crosslinking agent is carbon tetrachloride, and crosslinking agent quality is octaphenyl eight
10-40 times of silsesquioxane quality, being stirred to react the time is 5-10 hours, ethyl alcohol in ethanol/water solution: the volume ratio of water is 2-
4:1, dilute hydrochloric acid is the hydrochloric acid solution that mass fraction is 10%, ethyl alcohol and dilute hydrochloric acid volume ratio 2-4:1 in ethyl alcohol/dilute hydrochloric acid solution.
2. Ti as described in claim 13C2Tx/ sulphur carbon composite, which is characterized in that in the step (3) in Muffle furnace
Reaction atmosphere is nitrogen, 800-1200 DEG C of reaction temperature, reaction time 1-5 hour, and 1-5 °C/minute of heating rate.
3. Ti as described in claim 13C2Tx/ sulphur carbon composite, which is characterized in that hydrofluoric acid is dense in the step (4)
Degree is 20%-50%, and the time of corrosion is 4-24 hours.
4. Ti as described in claim 13C2Tx/ sulphur carbon composite, which is characterized in that Ti in the step (5)3C2Tx/ ball
The mass ratio of shape porous carbon materials and elemental sulfur is 0.1-0.3:1, and initial reaction temperature is 155-165 DEG C in tube furnace, reaction
Time is 10-20 hours, and the reaction temperature after being passed through nitrogen is 180-200 DEG C, and the reaction time is 10-30 minutes.
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| CN106450205A (en) * | 2016-11-02 | 2017-02-22 | 南京工业大学 | Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof |
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