CN106450205A - Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof - Google Patents
Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof Download PDFInfo
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- 239000011593 sulfur Substances 0.000 title claims abstract description 99
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 99
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 86
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000011238 particulate composite Substances 0.000 title abstract description 4
- 150000004767 nitrides Chemical class 0.000 title abstract 7
- 150000003624 transition metals Chemical class 0.000 title abstract 7
- 239000002245 particle Substances 0.000 claims abstract description 60
- 239000002131 composite material Substances 0.000 claims abstract description 59
- 239000000725 suspension Substances 0.000 claims abstract description 56
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005119 centrifugation Methods 0.000 claims abstract description 15
- 235000019253 formic acid Nutrition 0.000 claims abstract description 15
- 239000002356 single layer Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims abstract description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 3
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 8
- 229910010067 TiC2 Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920001021 polysulfide Polymers 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910019762 Nb4C3 Inorganic materials 0.000 claims description 3
- 229910004472 Ta4C3 Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims 1
- 210000000481 breast Anatomy 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 3
- 239000006258 conductive agent Substances 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract 5
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 45
- -1 Transition Metals Carbides Chemical class 0.000 description 43
- 239000000243 solution Substances 0.000 description 27
- 238000003760 magnetic stirring Methods 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 14
- 230000004888 barrier function Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000010955 niobium Substances 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000004087 circulation Effects 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 6
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ZLANVVMKMCTKMT-UHFFFAOYSA-N methanidylidynevanadium(1+) Chemical class [V+]#[C-] ZLANVVMKMCTKMT-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01—ELECTRIC ELEMENTS
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- 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
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- H—ELECTRICITY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/624—Electric conductive fillers
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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
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Abstract
The invention relates to a two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof. The composite is formed by two-dimensional transition metal carbide (nitride) MXene nanosheets and nano sulfur particles, wherein the nano sulfur particles grow on the surface of the two-dimensional transition metal carbide (nitride) MXene nanosheets in an in-situ manner, marked as S@MXene. The stable suspension of a single layer or a few layers of two-dimensional transition metal carbide (nitride) MXene nanosheets is mixed with a sodium thiosulfate or sodium polysulfide solution; with formic acid as a reducing agent, the nano sulfur generated by the reaction uniformly grows on the surface of the two-dimensional MXene nanosheet; and the two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite is obtained through neutralization, washing and centrifugation and serves as the anode of a lithium-sulfur battery. According to the invention, a high-conductivity two-dimensional transition metal carbide (nitride) MXene nanosheet carrier is uniformly compounded with nano sulfur particles, introduction of a binder and a conductive agent is not needed, and the composite has excellent electrochemical performance as the anode of a lithium-sulfur battery; and moreover, the technology is simple and can meet the requirements of large-scale production.
Description
Technical field
The invention belongs to nano composite material technical field and in particular to a kind of two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound with
Nano-sulfur particles composite and its preparation and application.
Background technology
Lithium sulfur (Li-S) battery is the novel high-capacity energy storage system of the great development prospect of a class, has theoretical energy density
The outstanding advantages such as high and low cost, environmental protection, its theoretical specific capacity is up to 1675mAh g-1, the lithium secondary battery system of composition
Theoretical specific energy density is up to 2600Wh kg-1, it is 7 times of current commercial Li-ion battery, in new-energy automobile power current
The emerging technology areas such as pond show wide application prospect.But its positive active material sulfur poorly conductive, charge and discharge process
Change in volume is big, and during many lithium sulfides of being formed easily deviate from and be dissolved in electrolyte the problems such as cause " shuttle effect " urgently
Need to solve.
For problem above, scientific and technical personnel have carried out substantial amounts of exploratory development to lithium sulfur battery anode material, using carbon, lead
Electric polymer and metal-oxide etc. as sulfur positive pole carrier, thus constituting anode composite.MXene is a kind of new two dimension
Magnesium-yttrium-transition metal carbon (nitrogen) compound, its chemical general formula is Mn+1XnTx(M is early stage transiting group metal elements, and X is carbon or/and nitrogen unit
Element, n=1,2 or 3, T represent the surface functional groups such as-F ,-O and-OH, monolayer Mn+1XnNanometer sheet is former by n-layer X atom and n+1 layer M
Son replaces stacking and forms, and M atomic layer is located at outermost layer).It is that (chemical formula is M from ternary layered compound MAX phasen+1AXn, its
The implication of middle M, X, n and Mn+1XnTxIn the same, A is III, IV major element) in selective corrosion go out the one of A layer atom gained
Class new class Graphene two dimensional crystal.The MXene having prepared at present has Ti3C2Tx、Ti2CTx、(Ti0.5,Nb0.5)2CTx、
(V0.5,Cr0.5)3C2Tx、Ti3CNTx、Ta4C3Tx、V2CTx、Nb2CTx、Nb4C3Tx、(Nb0.8,Ti0.2)4C3Tx、(Nb0.8,Zr0.2)4C3Tx、Mo2TiC2Tx、Mo2Ti2C3Tx、Mo2CTx、Cr2TiC2Tx、Zr3C2Tx、Ti4N3Tx[Anasori B,Xie Y,Beidaghi
M,et al.Two-Dimensional,Ordered,Double Transition Metals Carbides(MXenes),ACS
Nano,2015,9(10):9507-9516.Zhou J,Zha X-H,Chen F-Y,et al.A Two-Dimensional
Zirconium Carbide by Selective Etching of Al3C3from Nanolaminated Zr3Al3C5,
Angew Chem Int Edit,2016,55(16):5008-5013.].Ti3C2TxIt is the MXene of current most study.MXene
There is two-dimensional appearance, larger reference area and good conduction and the mechanical performance of uniqueness, therefore in energy storage, urge
The fields such as change, composite, environmental improvement have broad application prospects [Naguib M, Mochalin V N, Barsoum M
W,et al.25th Anniversary Article:MXenes:A New Family of Two-Dimensional
Materials,Advanced Materials,2014,26(7):992 1005.], especially as electrochemical energy storage
The electrode material of part such as ultracapacitor and lithium ion battery shown outstanding performance [Naguib M, Halim J, Lu J,
et al.New Two-Dimensional Niobium and Vanadium Carbides as Promising
Materials for Li-Ion Batteries,Journal of the American Chemical Society,2013,
135(43):15966–15969.Lukatskaya M R,Mashtalir O,Ren C E,et al.Cation
Intercalation and High Volumetric Capacitance of Two-dimensional Titanium
Carbide,Science,2013,341(6153):1502-1505.].Additionally, MXene nanometer sheet outer surface is magnesium-yttrium-transition metal
Atomic layer, and its surface has the surface chemistry environment similar to graphene oxide, is therefore a kind of new of Li-S battery
Positive pole sulfur active ingredient carriers material.Widely used Fluohydric acid. selective corrosion goes out A atomic layer at present, is then passed through intercalation, stripping
From etc. series of processes prepare MXene suspension [Naguib, M.et al.Two-dimensional nanocrystals
produced by exfoliation of Ti3AlC2.Adv.Mater,2011,23:4248–4253.].
Content of the invention
The invention aims to improving the deficiencies in the prior art and providing a kind of two dimension magnesium-yttrium-transition metal carbon (nitrogen)
Compound and nano-sulfur particles composite；It is a further object of the present invention to provide the preparation method of above-mentioned material, its process is simple,
The requirement of large-scale production can be met；It is the purposes providing above-mentioned material that the present invention also has a purpose.
The technical scheme is that：A kind of two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound and nano-sulfur particles composite,
It is characterized in that：This composite is by New Two Dimensional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet and nano-sulfur particles structure
Become, for reducing the nano-sulfur particles growth in situ generating on two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet surface, point
Dissipate uniformly, be expressed as S@MXene.
Preferably above-mentioned nano-sulfur particles a size of 20～500nm, mass content in S@MXene for the sulfur be 10～
80wt%.
Preferably above-mentioned two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene is：Ti3C2Tx、Ti2CTx、Ti3CNTx、(Ti0.5,
Nb0.5)2CTx、(V0.5,Cr0.5)3C2Tx、Ta4C3Tx、V2CTx、Nb2CTx、Nb4C3Tx、(Nb0.8,Ti0.2)4C3Tx、(Nb0.8,
Zr0.2)4C3Tx、Mo2TiC2Tx、Mo2Ti2C3Tx、Mo2CTx、Cr2TiC2Tx、Zr3C2TxOr Ti4N3Tx.
Present invention also offers the system of above-mentioned two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound and nano-sulfur particles composite
Preparation Method, it comprises the following steps that：
1) sodium polysulphide or hypo solution are suspended with two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet
Liquid mixes, and obtains mixing suspension；
2) while magnetic agitation, formic acid solution is slowly dropped to step 1) be obtained mixing suspension in；
3) after reacting completely, centrifugation behind pH of suspension=6.5～7.3 is neutralized to using ammonia；
4) precipitate that obtains of centrifugation is washed with deionized, be centrifuged obtain two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound with
Nano-sulfur particles composite.
Preferably above-mentioned two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet suspension is prepared into by following methods
Arrive, it concretely comprises the following steps：LiF is dissolved in hydrochloric acid, then ternary layered compound MAX powder is slowly added to above-mentioned solution
In, stirring reaction at 30～40 DEG C, it is 6.2～6.5 that product is centrifuged to supernatant pH value using washing with alcohol, will do
Solid sample after dry adds in deionized water, ultrasonic stripping under flowing argon protection, is then centrifuged for obtaining few layer or monolayer
Two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet suspension；Suspension concentration is 0.2～1.5mg/ml.
Preferably above-mentioned again at 30～40 DEG C the stir speed (S.S.) of stirring reaction be 200-500rpm, mixing time is 6～24h；
The supersonic frequency of described ultrasonic stripping is 40-100kHz, and the time of ultrasonic stripping is 0.5～1.5h；It is centrifuged after ultrasonic stripping
Rotating speed be 2500～4000rpm, centrifugation time be 0.5～1.5h.
Preferably above-mentioned sodium thiosulfate or sodium polysulfide solution concentration are 0.2～1mol/L；Formic acid concn be 1～
3mol/L, the drop rate of formic acid is 0.1～0.3ml/ second, after solution is completely reformed into milky, continues to drop to pH
For 6～6.8, then neutralized with ammonia；Ammonia concn used is 0.2～1mol/L.
Present invention also offers a kind of above-mentioned two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound and nano-sulfur particles composite
Application in lithium-sulphur cell positive electrode.
A kind of described two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound is just being used for Li-S battery with nano-sulfur particles composite
Pole, can be traditionally to two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound being dried and addition in nano-sulfur particles composite
Conductive agent and binding agent and cream, be then coated on aluminium foil it is also possible to by pulp-like two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound with
Nano-sulfur particles composite is coated directly onto on aluminium foil or on PP battery diaphragm, its suspension sucking filtration is made positive pole.As
One of preferred embodiment, specially will be centrifuged pulp-like two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound obtaining and nano-sulfur
Granules composite material is coated directly onto in aluminum foil current collector (coating layer thickness is 10～40 μm), or will be golden for the two-dimentional transition group after washing
Belong to carbon (nitrogen) compound, with nano-sulfur particles composite suspension sucking filtration, anode composite/barrier film one is obtained on PP battery diaphragm
Structure (positive pole thickness is 20～50 μm), is vacuum dried 12-24h, you can assembling button 2032 lithium-sulfur cell.
Beneficial effect：
1. the present invention adopts sodium polysulphide or hypo solution and two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene
After nanometer sheet suspension mixes, Deca formic acid reducing agent, the nano-sulfur particles growth in situ that reduction generates is in two-dimentional transition group gold
Belong to carbon (nitrogen) compound MXene surface.Receive in two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound of preparation and nano-sulfur particles composite
Rice sulfur granules are combined, are uniformly dispersed with two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet, are firmly combined with, contact area
Greatly, and whole preparation process is simple, be conducive to giving full play to the solid sulfur of two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet
Effect.
2. present invention two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound and nano-sulfur particles composite are used as Li-S anode,
To have two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound of the surface chemistry environment of excellent electric conductivity, larger reference area and uniqueness
MXene, as the carrier of sulfur active substance, can improve the electric conductivity of sulfur positive pole and play the captured sulfur result of uniqueness, effectively suppress
Many lithium sulfide " shuttle effect " problems, improve the cycle performance of battery and the utilization rate of sulfur active substance.
3. pulp-like two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound is directly coated with by the present invention with nano-sulfur particles composite
In aluminum foil current collector, or its suspension sucking filtration is made positive pole on PP battery diaphragm, binding agent and conductive agent can be avoided
Introduce, reduce the internal resistance of battery further, process is simple simultaneously, easily with existing lithium-sulfur cell production technology and hardware compatibility.
Brief description
Fig. 1 is the two-dimentional transition metal carbides Ti prepared by embodiment 13C2And sulfur content is the two-dimentional mistake of 70wt.%
Cross race metal carbides Ti3C2XRD spectrum with nano-sulfur particles composite；
Fig. 2 is the two-dimentional transition metal carbides Ti that sulfur content prepared by embodiment 1 is 70wt.%3C2With nano-sulfur
The scanning electron microscope (SEM) photograph of granules composite material；
Fig. 3 is the two-dimentional transition metal carbides Ti that sulfur content prepared by embodiment 2 is 70wt.%3C2With nano-sulfur
The scanning electron microscope (SEM) photograph of granules composite material；
Fig. 4 is the two-dimentional transition metal carbides Ti that sulfur content prepared by embodiment 5 is 70wt.%3CN and nano-sulfur
The scanning electron microscope (SEM) photograph of particulate composite；
Fig. 5 is the two-dimentional transition metal carbides Ti of sulfur content 70wt.% of embodiment 1 preparation3C2With nano-sulfur particles
Composite first charge-discharge curve under 0.5C multiplying power as lithium-sulphur cell positive electrode；
Fig. 6 is two-dimentional transition metal carbides Ti in the embodiment of the present invention 1,23C2Make with nano-sulfur particles composite
100 cyclical stability tests under 0.5C multiplying power for lithium-sulphur cell positive electrode.
Specific embodiment
Below in conjunction with specific embodiment, clear, complete description is carried out to technical scheme.It should be noted that
Described below is only the preferred embodiment of the present invention, is not limited to the present invention, for a person skilled in the art,
The present invention can have various modifications and variations.All any modifications made within the spirit and principles in the present invention, equivalent,
Improve retouching etc., should be included within the scope of the present invention.Embodiment 1
(1) two-dimentional transition metal carbides Ti3C2The preparation of nanometer sheet suspension：By 10mL concentration be 6M dilute HCl and
0.666g LiF is added in plastic bottle, is slowly added to the ternary layered carbide that 1g crosses 400 mesh sieves under magnetic stirring
Ti3AlC2Magnetic agitation 22h under powder, and 250r.p.m rotating speed at 35 DEG C, reaction terminate after by product washing with alcohol be centrifuged to
Supernatant pH value is 6.2, takes 0.1g to be added in 50mL deionized water after being dried under precipitation room temperature, in flowing argon protection
Under, ultrasonic stripping 1h under the supersonic frequency of 40kHz, subsequently under the rotating speed of 3500r.p.m, centrifugation 1h obtains few layer or monolayer two
Dimension transition metal carbides Ti3C2The stable suspension of nanometer sheet, suspension concentration is 0.6mg/ml.
(2) two-dimentional transition metal carbides Ti3C2Preparation with nano-sulfur particles composite：By 11mL 0.2mol
L-1Sodium polysulfide solution and 100mL Ti3C2TxNanometer sheet suspension mixes, and is stirred with 250r/min on magnetic stirring apparatuss
10min；By 2mol L-1Formic acid solution is added drop-wise in above-mentioned mixed solution with speed for 0.1ml/s, until solution all changes
After milky, continue Deca formic acid to pH=6.5, the nano-sulfur particles that reaction generates are grown in Ti3C2TxNanometer sheet surface.
Use 0.5mol L-1Ammonia is neutralized to and is centrifuged behind pH of suspension=7, and gained precipitation is washed with deionized again, be centrifuged and obtain sulfur
Content is the argillaceous two dimension transition metal carbides Ti of 70wt.%3C2With nano-sulfur particles composite (accompanying drawing 1, Fig. 2),
, at 20 to 150 nanometers, the XRD figure of the composite of following examples is basically identical with embodiment 1 for sulfur granules size.
(3) electrochemical property test：By argillaceous two dimension transition metal carbides Ti3C2With nano-sulfur particles composite wood
Material coating machine is uniformly coated in aluminum foil current collector (coating layer thickness is 17 μm), is vacuum dried 24h, and then compacting, cut-parts are made
For positive pole；With lithium piece as negative pole, using Celgard barrier film, concentration selected by electrolyte is 1mol L-1LiTFSI/DOL-DME (body
Amass and compare 1:, and add 0.1mol L 1)-1LiNO3, it is assembled into button lithium-sulfur cell.Carry out constant current charge and discharge under 0.5C multiplying power
Electricity, discharge capacity is 1035mAh g first-1(accompanying drawing 4), after 100 circulations, discharge capacity is 907mAh g-1.
Embodiment 2
(1) two-dimentional transition metal carbides Ti3C2The preparation of nanometer sheet suspension：By 10mL concentration be 6M dilute HCl and
0.666g LiF is added in plastic bottle, is slowly added to the ternary layered carbide that 1g crosses 400 mesh sieves under magnetic stirring
Ti3AlC2Stir 15h under powder, and magnetic force under 30 DEG C of 250r.p.m rotating speeds, reaction terminate after by product washing with alcohol be centrifuged to
Supernatant pH value is 6.3, takes 0.2g to be added in 150mL deionized water, protect in flowing argon under precipitation room temperature after being dried
Under shield, ultrasonic stripping 1h under the supersonic frequency of 40kHz, subsequently under the rotating speed of 3500r.p.m, centrifugation 1h obtains few layer or monolayer
Two-dimentional transition metal carbides Ti3C2The stable suspension of nanometer sheet, suspension concentration is 0.2mg/ml.
(2) two-dimentional transition metal carbides Ti3C2Preparation with nano-sulfur particles composite：By 3.6mL 0.8mol
L-1Hypo solution and 200mL Ti3C2TxNanometer sheet suspension mixes, and is stirred with 250r/min on magnetic stirring apparatuss
10min；By 2mol L-1Formic acid solution is added drop-wise in above-mentioned mixed solution with speed for 0.2ml/s, until solution all changes
After milky, continue Deca formic acid to pH=6.5, the nano-sulfur particles that reaction generates are grown in Ti3C2TxNanometer sheet surface.
Use 0.2mol L-1Ammonia is centrifuged after being neutralized to pH of suspension=7.1, and gained precipitation is washed with deionized again and obtains sulfur content
Two-dimentional transition metal carbides Ti for 70wt.%3C2With the suspension of nano-sulfur particles composite, nano-sulfur is a size of
50～500nm.
(3) electrochemical property test：By two-dimentional transition metal carbides Ti3C2Suspend with nano-sulfur particles composite
Liquid sucking filtration on pp battery diaphragm obtains anode composite/barrier film integrative-structure (accompanying drawing 3), and anode composite thickness is 45 μm, vacuum
After 24h is dried, as positive pole, with lithium piece as negative pole, using Celgard barrier film, concentration selected by electrolyte is 1molL for cut-parts- 1LiTFSI/DOL-DME (volume ratio 1:, and add 0.1mol L 1)-1LiNO3, it is assembled into button lithium-sulfur cell.In 0.5C
Carry out constant current charge-discharge, discharge capacity is 1005mAh g first under multiplying power-1, after 100 circulations, discharge capacity is 621mAh g-1.
Embodiment 3
(1) two-dimentional transition metal carbides Ti3C2The preparation of nanometer sheet suspension：By 10mL concentration be 6M dilute HCl and
0.666g LiF is added in plastic bottle, is slowly added to the ternary layered carbide that 1g crosses 400 mesh sieves under magnetic stirring
Ti3AlC2Stir 24h under powder, and magnetic force under 35 DEG C of 300r.p.m rotating speeds, reaction terminate after by product washing with alcohol be centrifuged to
Supernatant pH value is 6.2, takes 0.3g to be added in 50mL deionized water after being dried under precipitation room temperature, in flowing argon protection
Under, ultrasonic stripping 1h under the supersonic frequency of 80kHz, subsequently under the rotating speed of 3000r.p.m, centrifugation 1h obtains few layer or monolayer two
Dimension transition metal carbides Ti3C2The stable suspension of nanometer sheet, suspension concentration is 1.1mg/ml.
(2) two-dimentional transition metal carbides Ti3C2Preparation with nano-sulfur particles composite：By 8.6mL 0.4mol
L-1Hypo solution and 100mL Ti3C2TxNanometer sheet suspension mixes, and is stirred with 250r/min on magnetic stirring apparatuss
10min；By 2mol L-1Formic acid solution is added drop-wise in above-mentioned mixed solution with speed for 0.1ml/s, until solution all changes
After milky, continue Deca formic acid to pH=6.5, the nano-sulfur particles that reaction generates are grown in Ti3C2TxNanometer sheet surface.
Use 0.7mol L-1Ammonia is neutralized to and is centrifuged behind pH of suspension=6.8, and gained precipitation is washed with deionized again, be centrifuged and obtain
Sulfur content is the argillaceous two dimension transition metal carbides Ti of 50wt.%3C2With nano-sulfur particles composite, sulfur granules chi
Very little in 20 to 200 nanometers.
(3) electrochemical property test：By argillaceous two dimension transition metal carbides Ti3C2With nano-sulfur particles composite wood
Material is uniformly coated in aluminum foil current collector (coating layer thickness is 20 μm) using coating machine, is vacuum dried 24h, then compacting, cut-parts
As positive pole；With lithium piece as negative pole, using Celgard barrier film, concentration selected by electrolyte is 1mol L-1LiTFSI/DOL-DME
(volume ratio 1:, and add 0.1mol L 1)-1LiNO3, it is assembled into button lithium-sulfur cell.Carry out constant current under 0.5C multiplying power
Discharge and recharge, discharge capacity is 1060mAh g first-1, after 100 circulations, discharge capacity is 859mAh g-1.
Embodiment 4
(1) two-dimentional transition metal carbides Ti3C2The preparation of nanometer sheet suspension：By 10mL concentration be 6M dilute HCl and
0.666g LiF is added in plastic bottle, is slowly added to the ternary layered carbide that 1g crosses 400 mesh sieves under magnetic stirring
Ti3AlC2Magnetic agitation 20h under powder, and 400r.p.m rotating speed at 40 DEG C, reaction terminate after by product washing with alcohol be centrifuged to
Supernatant pH value is 6.2, takes 0.1g to be added in 50mL deionized water after being dried under precipitation room temperature, in flowing argon protection
Under, ultrasonic stripping 1h under the supersonic frequency of 50kHz, subsequently under the rotating speed of 3000r.p.m, centrifugation 1h obtains few layer or monolayer two
Dimension transition metal carbides Ti3C2The stable suspension of nanometer sheet, suspension concentration is 0.7mg/ml.
(2) two-dimentional transition metal carbides Ti3C2Preparation with nano-sulfur particles composite：By 2.7mL 0.2mol
L-1Hypo solution and 100mL Ti3C2TxNanometer sheet suspension mixes, and is stirred with 250r/min on magnetic stirring apparatuss
10min；By 2mol L-1Formic acid solution is added drop-wise in above-mentioned mixed solution with speed for 0.3ml/s, until solution all changes
After milky, continue Deca formic acid to pH=6.4, the nano-sulfur particles that reaction generates are grown in Ti3C2TxNanometer sheet surface.
Use 1mol L-1Ammonia is neutralized to and is centrifuged behind pH of suspension=6.9, and gained precipitation is washed with deionized again, be centrifuged and obtain sulfur
Content is the argillaceous two dimension transition metal carbides Ti of 20wt.%3C2With nano-sulfur particles composite, sulfur granules size
At 20 to 200 nanometers.
(3) electrochemical property test：By argillaceous two dimension transition metal carbides Ti3C2With nano-sulfur particles composite wood
Material is uniformly coated in aluminum foil current collector (coating layer thickness is 19 μm) using coating machine, is vacuum dried 24h, then compacting, cut-parts
As positive pole；With lithium piece as negative pole, using Celgard barrier film, concentration selected by electrolyte is 1mol L-1LiTFSI/DOL-DME
(volume ratio 1:, and add 0.1mol L 1)-1LiNO3, it is assembled into button lithium-sulfur cell.Carry out constant current under 0.5C multiplying power
Discharge and recharge, discharge capacity is 1275mAh g first-1, after 100 circulations, discharge capacity is 1012mAh g-1.
Embodiment 5
(1) two-dimentional transition metal carbides Ti3The preparation of CN nanometer sheet suspension：10mL concentration is dilute HCl of 6M
It is added in plastic bottle with a certain amount of LiF, be slowly added to the ternary layered carbide that 1g crosses 400 mesh sieves under magnetic stirring
Ti36h is stirred, reaction after terminating, product washing with alcohol is centrifuged to upper strata under AlCN powder, and 400r.p.m rotating speed at 30 DEG C
Stillness of night pH value is 6.5, takes 0.1g to be added in 50mL deionized water after being dried under precipitation room temperature, under flowing argon protection,
Ultrasonic stripping 1.3h under 60kHz supersonic frequency, subsequently under the rotating speed of 3000r.p.m, centrifugation 0.5h obtains few layer or monolayer two dimension
Transition metal carbides Ti3The stable suspension of C N nanometer sheet, suspension concentration is 1.2mg/ml.
(2) two-dimentional transition metal carbides Ti3CN and the preparation of nano-sulfur particles composite：By 14.6mL0.6mol
L-1Hypo solution and 100mL Ti3CNTxNanometer sheet suspension mixes, and is stirred with 250r/min on magnetic stirring apparatuss
10min；By 2mol L-1Formic acid solution is added drop-wise in above-mentioned mixed solution with speed for 0.2ml/s, until solution all changes
After milky, continue Deca formic acid to pH=6.6, the nano-sulfur particles that reaction generates are grown in Ti3C2TxNanometer sheet surface.
Use 0.5mol L-1Ammonia is neutralized to and is centrifuged behind pH of suspension=7.2, and gained precipitation is washed with deionized again, be centrifuged and obtain
Sulfur content is the argillaceous two dimension transition metal carbides Ti of 70wt.%3CN and nano-sulfur particles composite, sulfur granules chi
Very little is 20 to 300 nanometers.
(3) electrochemical property test：By two-dimentional transition metal carbides Ti3CN is applied with nano-sulfur particles composite
Cloth machine is uniformly coated in aluminum foil current collector (coating layer thickness is 14 μm), and cut-parts after vacuum drying 24h, as positive pole, with lithium piece are
Negative pole, using Celgard barrier film, concentration selected by electrolyte is 1molL-1LiTFSI/DOL-DME (volume ratio 1:, and add 1)
0.1mol L-1LiNO3, it is assembled into button lithium-sulfur cell.Carry out constant current charge-discharge under 0.5C multiplying power, discharge capacity is first
930mAh g-1, after 100 circulations, discharge capacity is 812mAh g-1.
Embodiment 6
(1) two-dimentional transition metal carbides Ti3The preparation of CN nanometer sheet suspension：10mL concentration is dilute HCl of 6M
It is added in plastic bottle with 0.662g LiF, be slowly added to the ternary layered carbide that 1g crosses 400 mesh sieves under magnetic stirring
Ti3Stir 8h under AlCN powder, and magnetic force under 30 DEG C of 250r.p.m rotating speeds, reaction terminate after by product washing with alcohol be centrifuged to
Supernatant pH value is 6.6, takes 0.2g to be added in 150mL deionized water, protect in flowing argon under precipitation room temperature after being dried
Under shield, ultrasonic stripping 1h under the supersonic frequency of 80kHz, subsequently under the rotating speed of 3000r.p.m, centrifugation 1h obtains few layer or monolayer
Two-dimentional transition metal carbides Ti3The stable suspension of CN nanometer sheet, suspension concentration is 1.8mg/ml.
(2) two-dimentional transition metal carbides Ti3CN and the preparation of nano-sulfur particles composite：By 16.4mL0.8mol
L-1Hypo solution and 100mL Ti3CN nanometer sheet suspension mixes, and is stirred with 250r/min on magnetic stirring apparatuss
10min；By 3mol L-1Formic acid solution is added drop-wise in above-mentioned mixed solution with speed for 0.2ml/s, until solution all changes
After milky, continue Deca formic acid to pH=6.5, the nano-sulfur particles that reaction generates are grown in Ti3CN nanometer sheet surface.With
0.2mol L-1Ammonia is neutralized to and is centrifuged behind pH of suspension=7.1, and gained precipitation is washed with deionized again and obtains sulfur content and be
The two-dimentional transition metal carbides Ti of 70wt.%3The suspension of CN and nano-sulfur particles composite, sulfur granules size is 20
To 400 nanometers.
(3) electrochemical property test：By two-dimentional transition metal carbides Ti3CN is suspended with nano-sulfur particles composite
Liquid sucking filtration on pp battery diaphragm obtains anode composite/barrier film integrative-structure, and anode composite thickness is 21 μm, is vacuum dried 24h
As positive pole, with lithium piece as negative pole, using Celgard barrier film, concentration selected by electrolyte is 1molL for cut-parts afterwards-1LiTFSI/DOL-
DME (volume ratio 1:, and add 0.1mol L 1)-1LiNO3, it is assembled into button lithium-sulfur cell.Carry out perseverance under 0.5C multiplying power
Stream discharge and recharge, discharge capacity is 1057mAh g first-1, after 100 circulations, discharge capacity is 846mAh g-1.
Embodiment 7
(1) two-dimentional transition metal carbides Ti2The preparation of C nano piece suspension：By 10mL concentration be 6M dilute HCl and
A certain amount of LiF is added in plastic bottle, is slowly added to the ternary layered carbide that 1g crosses 400 mesh sieves under magnetic stirring
Ti2AlC powder, and 220r.p.m stirring 15h at 40 DEG C, reaction after terminating, product washing with alcohol is centrifuged to supernatant pH
It is worth for 6.3,0.2g will be taken to be added in 50mL deionized water after being dried under precipitation room temperature, under flowing argon protection, 80kHz surpasses
Ultrasonic stripping 1.25h under acoustic frequency, subsequently under the rotating speed of 3000r.p.m, centrifugation 1h obtains few layer or monolayer two dimension transition group gold
Belong to carbide Ti2The stable suspension of C nano piece, suspension concentration is 0.9mg/ml.
(2) two-dimentional transition metal carbides Ti2C and the preparation of nano-sulfur particles composite：By 21.1mL 0.2mol
L-1Hypo solution and 100mL Ti2CTxNanometer sheet suspension mixes, and is stirred with 250r/min on magnetic stirring apparatuss
10min；By 1mol L-1Formic acid solution is added drop-wise in above-mentioned mixed solution with speed for 0.1ml/s, until solution all changes
After milky, continue Deca formic acid to pH=6.3, the nano-sulfur particles that reaction generates are grown in Ti2CTxNanometer sheet surface.With
0.7mol L-1Ammonia is neutralized to and is centrifuged behind pH of suspension=7.1, and gained precipitation is washed with deionized again, be centrifuged and obtain sulfur
Content is the argillaceous two dimension transition metal carbides Ti of 60wt.%2C and nano-sulfur particles composite, sulfur granules size
For 20 to 300 nanometers.
(3) electrochemical property test：By two-dimentional transition metal carbides Ti2C is applied with nano-sulfur particles composite
Cloth machine is uniformly coated in aluminum foil current collector (coating layer thickness is 11 μm), and cut-parts after vacuum drying 14h, as positive pole, with lithium piece are
Negative pole, using Celgard barrier film, concentration selected by electrolyte is 1molL-1LiTFSI/DOL-DME (volume ratio 1:, and add 1)
0.1mol L-1LiNO3, it is assembled into button lithium-sulfur cell.Carry out constant current charge-discharge under 0.5C multiplying power, discharge capacity is first
1080mAh g-1, after 100 circulations, discharge capacity is 875mAh g-1.
Claims (8)
1. a kind of two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound and nano-sulfur particles composite it is characterised in that：This composite
It is made up of with nano-sulfur particles two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet, the nano-sulfur particles generating for reduction
Growth in situ, on two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet surface, is expressed as S@MXene.
2. two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound as claimed in claim 1 and nano-sulfur particles composite, its feature exists
In：Nano-sulfur particles a size of 20～500nm, mass content in S@MXene for the sulfur is 10～80wt%.
3. two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound as claimed in claim 1 and nano-sulfur particles composite, its feature exists
In：Described two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene is：Ti3C2Tx、Ti2CTx、Ti3CNTx、(Ti0.5,Nb0.5)2CTx、
(V0.5,Cr0.5)3C2Tx、Ta4C3Tx、V2CTx、Nb2CTx、Nb4C3Tx、(Nb0.8,Ti0.2)4C3Tx、(Nb0.8,Zr0.2)4C3Tx、
Mo2TiC2Tx、Mo2Ti2C3Tx、Mo2CTx、Cr2TiC2Tx、Zr3C2TxOr Ti4N3Tx.
4. one kind prepares two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound and nano-sulfur particles composite as claimed in claim 1,
It comprises the following steps that：
1) sodium polysulphide or hypo solution are mixed with two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet suspension
Close, obtain mixing suspension；
2) while magnetic agitation, formic acid solution is added drop-wise to step 1) be obtained mixing suspension in；
3) after reacting, centrifugation behind pH of suspension=6.5～7.3 is neutralized to using ammonia；
4) precipitate that obtains of centrifugation is washed with deionized, is centrifuged and obtains two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound and nanometer
Sulfur granules composite.
5. as requested the method described in 4 it is characterised in that described two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheet
Suspension is prepared by following methods, and it concretely comprises the following steps：LiF is dissolved in hydrochloric acid, then by ternary layered compound
MAX powder adds in above-mentioned solution, stirring reaction at 30～40 DEG C, and product is centrifuged to supernatant pH using washing with alcohol
It is worth for 6.2～6.5, dried solid sample is added in deionized water, ultrasonic stripping under flowing argon protection, Ran Houli
Gains in depth of comprehension are to two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) the compound MXene nanometer sheet suspension of few layer or monolayer；Suspension concentration be 0.2～
1.5mg/ml.
6. as requested the method described in 5 it is characterised in that at 30～40 DEG C stirring reaction stir speed (S.S.) be 200-500rpm,
Mixing time is 6～24h；The supersonic frequency of described ultrasonic stripping is 40-100kHz, time of ultrasonic stripping is 0.5～
1.5h；After ultrasonic stripping, the rotating speed of centrifugation is 2500～4000rpm, and centrifugation time is 0.5～1.5h.
7. method as claimed in claim 4 it is characterised in that：The concentration of sodium thiosulfate or sodium polysulfide solution be 0.2～
1mol/L；Formic acid concn is 1～3mol/L, and the drop rate of formic acid is 0.1～0.3ml/ second, until solution is completely reformed into breast
After white, continuing to drop to pH is 6～6.8, is then neutralized with ammonia；Ammonia concn used is 0.2～1mol/L.
8. a kind of two dimension magnesium-yttrium-transition metal carbon (nitrogen) compound is existed one kind with nano-sulfur particles composite as claimed in claim 1
Application in lithium-sulphur cell positive electrode.
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