CN106684355A - Metal organic framework Uio-66@ S lithium sulfur positive electrode material and preparation method thereof - Google Patents
Metal organic framework Uio-66@ S lithium sulfur positive electrode material and preparation method thereof Download PDFInfo
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- CN106684355A CN106684355A CN201611247980.0A CN201611247980A CN106684355A CN 106684355 A CN106684355 A CN 106684355A CN 201611247980 A CN201611247980 A CN 201611247980A CN 106684355 A CN106684355 A CN 106684355A
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 239000006258 conductive agent Substances 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 5
- 239000007772 electrode material Substances 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000005864 Sulphur Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910007928 ZrCl2 Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000005030 aluminium foil Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007500 overflow downdraw method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 239000011636 chromium(III) chloride Substances 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229910021389 graphene Inorganic materials 0.000 claims 1
- 239000013384 organic framework Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 229910052717 sulfur Inorganic materials 0.000 abstract 2
- 239000011593 sulfur Substances 0.000 abstract 2
- 239000010406 cathode material Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 5
- -1 sulphur anions Chemical class 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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 invention relates to a metal organic framework Uio-66@ S lithium sulfur positive electrode material and a preparation method thereof. The invention belongs to the technical field of lithium-sulfur batteries. The metal-organic framework Uio-66@ S lithium sulfur cathode material is formed by mixing a metal-organic framework Uio-66@ S composite material, a conductive agent and a binder, and the metal-organic framework Uio-66@ S composite material is formed by mixing and ball-milling a metal-organic framework material generated by metal salt and terephthalic acid and sulfur. The preparation method comprises the following steps: 1) synthesis of metal-organic framework materials Uio-66: taking metal salt to react with terephthalic acid to generate a metal-organic framework material; 2) uio-66@ S composite formation: mixing with sulfur, ball milling uniformly, and forming Uio-66@ S composite material by adopting a melting method; 3) preparing an electrode material: uniformly stirring the mixture with a conductive agent and a binder in a solvent to form slurry, coating the slurry on a current collector, and drying the cut pieces. The invention has the advantages of extremely high specific surface area, abundant mesoporous channels, simple preparation process, low cost, large-scale production and the like.
Description
Technical field
The invention belongs to lithium-sulfur cell technical field, more particularly to a kind of metal organic frame Uio-66@S lithium sulphur positive poles
Material and preparation method.
Background technology
At present, with the depleted of global fossil energy and adverse condition problem increasingly, new clean energy resource material is got over
Research and development are taken seriously to get over.Since lithium ion commercialization electrochemical cell comes out from the nineties in last century, the whole energy has been dominate always
Market, has reformed generation by generation electronic product.But electronics and power technology are developed rapidly, current commercial li-ion battery
Seem not clearly fulfilling nowadays to high power capacity, the demand of high power power.With elemental sulfur as positive pole, with lithium metal as negative pole
Lithium-sulfur cell system possesses theoretical specific capacity (the 1675mAh ﹒ g of superelevation-1) and theoretical specific energy (2600Wh ﹒ kg-1) be significantly larger than
Current various lithium-ion battery systems.In addition the advantage such as positive pole elemental sulfur rich reserves, cheap, environment-friendly causes lithium
Sulphur battery turns into study hotspot in recent years.
However, lithium-sulfur cell there is also some intrinsic defects.Such as the non-conductive property of elemental sulfur and " wearing for many sulphur anions
The problems such as shuttle effect ".The non-conductive property of elemental sulfur can cause that active material utilization is low, high rate performance is poor；And " shuttle effect "
The loss of active material can be caused, caused the rapid decay of capacity, shortened battery cycle life.
The content of the invention
The present invention provides a kind of metal organic frame Uio-66@S lithiums to solve technical problem present in known technology
Sulphur positive electrode and preparation method.
Metal-organic framework materials be a class with metal ion as node, with organic ligand be complexed and formed with week
The three-dimensional network material of phase property.This kind of material has high specific surface and abundant pore passage structure.Due to metal ion and having
Machine ligand origins enrich so that the topological structure of such material, specific surface, pore size and shape, the diversity of modification and spirit
Activity will be far superior to current all kinds of carbon materials.As pluging with molten metal sulfur-donor, by its trickle pore passage structure and metal ion
Lewis acidity, can be under the double effects of physics constraint and chemisorption, to " shuttle effect " effect of many sulphur anions
The effect of significantly inhibiting should be played, the cycle life of battery is significantly improved.
An object of the present invention be to provide it is a kind of with high specific surface area, abundant mesopore orbit, to many sulphur from
Son plays the dual suction-operated of physics and chemistry, and metal the features such as can effectively suppress " the shuttle effect " of lithium-sulfur cell has
Machine frame Uio-66@S lithium sulphur positive electrodes.
Metal organic frame Uio-66@S lithium sulphur positive electrodes of the present invention are adopted the technical scheme that：
A kind of metal organic frame Uio-66@S lithium sulphur positive electrodes, are characterized in：Metal-organic framework Uio-66@S
Lithium sulphur positive electrode is mixed by metal-organic framework Uio-66@S composites and conductive agent, binding agent, metal-have
Machine frame Uio-66@S composites are the metal-organic framework materials and sulphur mixing ball that slaine is generated with terephthalic acid (TPA)
Mill is formed.
Metal organic frame Uio-66@S lithium sulphur positive electrodes of the present invention can also be adopted the following technical scheme that：
Described metal organic frame Uio-66@S lithium sulphur positive electrodes, are characterized in：Slaine is ZrCl2、TiCl4、
AlCl3、FeCl2、FeCl3、CuCl2、ZnCl2、CrCl3、Zr(NO3)2、Al(NO3)3、Fe(NO3)2、Fe(NO3)3、Ni(NO3)2、
Cu(NO3)2、Zn(NO3)2、Cr(NO3)3、Co(NO3)2In one or more.
The second object of the present invention is to provide a kind of preparation process is simple, with low cost, can be mass-produced, and product has
Many sulphions are played the dual suction-operated of physics and chemistry by high specific surface area, abundant mesopore orbit, can be effective
The preparation method of the metal organic frame Uio-66@S lithium sulphur positive electrodes of the features such as suppressing " the shuttle effect " of lithium-sulfur cell.
Metal organic frame Uio-66@S lithium sulphur method for preparing anode material of the present invention is adopted the technical scheme that：
A kind of preparation method of metal organic frame Uio-66@S lithium sulphur positive electrodes, it is characterized in that：Metal organic frame
The preparation process of Uio-66@S lithium sulphur positive electrodes is comprised the following steps that：
1) synthesis of metal-organic framework materials Uio-66：Take slaine and be dissolved in N-N dimethyl formyls with terephthalic acid (TPA)
In amine solvent, generation metal-organic framework materials are reacted under the conditions of 100 DEG C -120 DEG C；
2) formation of Uio-66@S composites：Metal-organic framework Uio-66 materials and sulphur mixing and ball milling is uniform, adopt
Sulphur is diffused into the endoporus duct of metal-organic framework materials with fusion method, forms Uio-66@S composites；
3) preparation of electrode material：Uio-66@S composites and conductive agent, binding agent are stirred shape in a solvent
Into slurry and coat on a current collector, 8-12h and cut-parts are dried under vacuum.
Metal organic frame Uio-66@S lithium sulphur method for preparing anode material of the present invention can also be adopted the following technical scheme that：
The preparation method of described metal organic frame Uio-66@S lithium sulphur positive electrodes, is characterized in：Uio-66@S are answered
Condensation material is 6-8 with the part by weight of conductive agent, binding agent:1-3:1, during current collector material is aluminium foil, nickel foam, conductive carbon paper
One kind, vacuum drying condition is 60-80 DEG C or to be placed with the vacuum environment of drier.
The preparation method of described metal organic frame Uio-66@S lithium sulphur positive electrodes, is characterized in：Metal-have machine frame
During the synthesis of frame material Uio-66, reaction 20-30h generation metal-organic framework materials in 100 DEG C -120 DEG C of oil bath are placed on
Material.
The preparation method of described metal organic frame Uio-66@S lithium sulphur positive electrodes, is characterized in：Uio-66@S are answered
During the formation of condensation material, metal-organic framework Uio-66 is 1 with the mixed proportion of sulphur:1-3, the rotating speed of ball milling is 200-380r/
Min, the time of ball milling is 2-6h, and the temperature of fusion method is 120-240 DEG C.
The preparation method of described metal organic frame Uio-66@S lithium sulphur positive electrodes, is characterized in：Conductive agent is stone
One or more in black alkene, CNT, KB, Super P, acetylene black, VGCF；Binding agent is organic binder bond or aqueous viscous
One kind in knot agent；Solvent is deionized water or NMP.
The present invention has the advantages and positive effects that：
Metal organic frame Uio-66@S lithium sulphur positive electrodes are and existing as a result of the brand-new technical scheme of the present invention
Technology is compared, and the present invention has following evident characteristic.
1st, the preparation technology of lithium sulphur positive electrode of the present invention first require it is safe and simple, it is with low cost, it is involved
Harmfulness very little of the medicine of reaction to environment.It is applicable to scale industrial production.
2nd, present invention synthesis metal framework material Uio-66 has very high mechanical properties and heat endurance, and acid-alkali-resistant degree
Height, the structural framing of safety and stability is provided for the charge and discharge cycles of lithium sulfur battery anode material.
3rd, the relative porous carbon materials for being currently used for lithium-sulfur cell of the metal framework material Uio-66 of present invention synthesis have
High-specific surface area, abundant pore passage structure, high porosity.Sulphur content in the substrate is effectively increased, metal ion is added
Louis is acid to be had compared with extensive chemical absorption and mesopore size duct to sulphur physical limit to many sulphur anions.Effectively improve lithium sulphur
The cycle performance and high rate performance of battery.
Brief description of the drawings
Fig. 1 is the SEM figures of the metal-organic framework materials Uio-66 (Zr) of the embodiment of the present invention 2
Fig. 2 is the embodiment of the present invention 2 metal-organic framework materials Uio-66 (Zr)@S positive electrodes preceding 100 under 0.5C
The charging and discharging curve and coulombic efficiency figure of circle.
Fig. 3 is present example 2 metal-organic framework materials Uio-66 (Zr)@S positive electrodes preceding 300 circle under 1C
Charging and discharging curve and coulombic efficiency figure.
Specific embodiment
For the content of the invention of the invention, feature and effect can be further appreciated that, following examples are hereby enumerated, and coordinate accompanying drawing
Describe in detail as follows：
Refering to accompanying drawing 1, Fig. 2 and Fig. 3.
Embodiment 1
A kind of metal organic frame Uio-66@S lithium sulphur positive electrodes, by metal-organic framework Uio-66@S composites
Mixed with conductive agent, binding agent, metal-organic framework Uio-66@S composites are slaine ZrCl2With terephthaldehyde
The metal-organic framework materials of acid generation are formed with sulphur mixed melting.
Embodiment 2
A kind of preparation method of metal organic frame Uio-66@S lithium sulphur positive electrodes, comprises the following steps that：
The synthesis of step (1) Uio-66 (Zr)：The synthesis of Uio-66 (Zr)：Take 1.0g ZrCl2It is dissolved in 240ml N, N bis-
In NMF ultrasound 10min, 0.5g terephthalic acid (TPA)s are added, after ultrasonic 10min is uniform.Add 50 times of moles
(with respect to ZrCl2Consumption) benzoic acid.Mixed liquor is transferred to four-hole boiling flask and is placed in 120 DEG C of oil bath and reacts 24h, wait to drop
To room temperature, washed with enough DMFs and ethanol, suction filtration, be finally placed in 80 DEG C of vacuum drying chamber and dry 3h.
The preparation of step (2) Uio-66 (Zr)@S materials：In taking 0.6g Uio-66 (Zr) and 1.4g sublimed sulfur Place grinding jars
Batch mixing ball milling, rotational speed of ball-mill is 360r/min, and Ball-milling Time is 3h.Then Uio-66 (Zr) loads small glass with the uniform powder of sulphur
Glass bottle sealing carries out melting sulphuring treatment 12h under being placed in 155 DEG C of environment.Obtain Uio-66 (Zr)@S materials.
The preparation of step (3) electrode material：Take the conductive agent (graphite of 0.1g of 0.7g Uio-66 (Zr)@S materials, 0.2g
Alkene and 0.1g CNTs), the binding agent of 0.334g LA132 mixed with deionized water, stirring 4h sizes mixing uniformly.Slurry is applied
Overlay on aluminium foil, the cut-parts after 6h drying under the conditions of 60 DEG C, then pole piece is put into is equipped with P2O5Vacuum drying chamber dry 12h.
The SEM of Uio-66 (Zr) prepared by embodiment 2 is schemed as shown in figure 1, using the button of positive electrode described in embodiment 2
Battery, its charging and discharging capacity and coulombic efficiency figure are as shown in Figures 2 and 3.As can be seen that battery charge and discharge cycles under 0.5C
100 circles remain to keep the 76.5% of discharge capacity first, and the circle of charge and discharge cycles 300 remains to keep discharge capacity first under 1C
73.6%, show that Uio-66 (Zr)@S materials have more preferable cyclical stability and high rate performance than traditional carbon material.
The present embodiment metal-organic framework materials possess high specific surface area, abundant mesopore orbit, along with metal
Many sulphur anions are played the dual suction-operated of physics and chemistry by the stronger lewis acidity of ion, can effectively suppress lithium
" the shuttle effect " of sulphur battery.The positive electrode has preparation simple, can be mass-produced, with very strong business use value
Deng good effect.
Claims (7)
1. a kind of metal organic frame Uio-66@S lithium sulphur positive electrodes, it is characterized in that：Metal-organic framework Uio-66@S lithiums
Sulphur positive electrode is mixed by metal-organic framework Uio-66@S composites and conductive agent, binding agent, metal-organic
Framework Uio-66@S composites are the metal-organic framework materials and sulphur mixed melting of slaine and terephthalic acid (TPA) generation
Form.
2. metal organic frame Uio-66@S lithium sulphur positive electrodes according to claim 1, it is characterized in that：Slaine is
ZrCl2、TiCl4、AlCl3、FeCl2、FeCl3、CuCl2、ZnCl2、CrCl3、Zr(NO3)2、Al(NO3)3、Fe(NO3)2、Fe
(NO3)3、Ni(NO3)2、Cu(NO3)2、Zn(NO3)2、Cr(NO3)3、Co(NO3)2In one or more.
3. a kind of preparation method of metal organic frame Uio-66@S lithium sulphur positive electrodes, it is characterized in that：Metal organic frame
The preparation process of Uio-66@S lithium sulphur positive electrodes is comprised the following steps that：
1) synthesis of metal-organic framework materials Uio-66：Taking slaine, to be dissolved in N-N dimethylformamides with terephthalic acid (TPA) molten
In agent, generation metal-organic framework materials are reacted under the conditions of 100 DEG C -120 DEG C；
2) formation of Uio-66@S composites：Metal-organic framework Uio-66 materials and sulphur mixing and ball milling is uniform, using molten
Melt method sulphur is diffused into the endoporus duct of metal-organic framework materials, form Uio-66@S composites；
3) preparation of electrode material：Uio-66@S composites and conductive agent, binding agent are stirred to form slurry in a solvent
Expect and coat on a current collector, under vacuum 8-12h drying cut-parts.
4. the preparation method of metal organic frame Uio-66@S lithium sulphur positive electrodes according to claim 3, it is characterized in that：
Uio-66@S composites are 6-8 with the part by weight of conductive agent, binding agent:1-3:1, current collector material be aluminium foil, nickel foam,
One kind in conductive carbon paper, vacuum drying condition is 60-80 DEG C or is placed with the vacuum environment of drier.
5. the preparation method of metal organic frame Uio-66@S lithium sulphur positive electrodes according to claim 3, it is characterized in that：
During the synthesis of metal-organic framework materials Uio-66, reaction 20-30h generation gold in 100 DEG C -120 DEG C of oil bath is placed on
Category-organic framework materials.
6. the preparation method of the metal organic frame Uio-66@S lithium sulphur positive electrodes according to claim 3,4 or 5, it is special
Levying is：During the formation of Uio-66@S composites, metal-organic framework Uio-66 is 1 with the mixed proportion of sulphur:1-3, ball milling
Rotating speed is 200-380r/min, and the time of ball milling is 2-6h, and the temperature of fusion method is 120-240 DEG C.
7. the preparation method of the metal organic frame Uio-66@S lithium sulphur positive electrodes according to claim 3,4 or 5, it is special
Levying is：Conductive agent is one or more in Graphene, CNT, KB, Super P, acetylene black, VGCF；Binding agent is have
One kind in machine binding agent or aqueous binders；Solvent is deionized water or NMP.
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