CN114249356B - Double-metal hydroxide composite graphene catalyst, positive electrode material and lithium sulfur battery - Google Patents
Double-metal hydroxide composite graphene catalyst, positive electrode material and lithium sulfur battery Download PDFInfo
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- CN114249356B CN114249356B CN202111451519.8A CN202111451519A CN114249356B CN 114249356 B CN114249356 B CN 114249356B CN 202111451519 A CN202111451519 A CN 202111451519A CN 114249356 B CN114249356 B CN 114249356B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 31
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 description 12
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 11
- 239000005077 polysulfide Substances 0.000 description 9
- 229920001021 polysulfide Polymers 0.000 description 9
- 150000008117 polysulfides Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 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 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000004108 freeze drying 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000014233 sulfur utilization Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a double-metal hydroxide composite graphene catalyst, a positive electrode material and a lithium sulfur battery, wherein the preparation method of the composite catalyst comprises the following steps: s1: preparing graphene oxide; s2: preparation of the composite catalyst: s21: dispersing graphene oxide prepared in the step S1 in 50% formamide solution, adding a metal source for stirring reaction, adding sodium hydroxide solution in the reaction process to maintain the pH of the solution at 9.5-10.5, and cleaning the precipitate collected after the reaction; s22: and (3) dispersing the precipitate cleaned in the step (S21) in deionized water, and adding a strong reducing agent for reaction to obtain the composite catalyst. The lithium sulfur battery prepared by the catalyst has good specific capacity and cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium sulfur batteries, in particular to a double-metal hydroxide composite graphene catalyst, a positive electrode material and a lithium sulfur battery.
Background
Lithium sulfur batteries are considered as one of the new generation of high performance battery systems, but they have the following drawbacks: (1) the utilization rate of the active material is low; (2) Dissolution of the higher polysulfide in the electrolyte through the separator to react with the lithium negative electrode to form the lower polysulfide and back to the positive electrode results in the formation of a "shuttle effect" which severely reduces sulfur utilization.
In order to solve the above problems, a functional main material is combined with sulfur, and the layered double hydroxide is widely focused due to its unique two-dimensional constraint structure and catalytic performance. The double metal hydroxide and the carbon material are compounded to form an ideal material, but for the common stripping intercalation preparation method, on one hand, the active sites are fewer due to insufficient stripping, so that the shuttle effect inhibition effect is poorer, and on the other hand, the preparation method is more complicated.
Disclosure of Invention
The invention provides a double-metal hydroxide composite graphene catalyst, a positive electrode material and a lithium sulfur battery, and the prepared lithium sulfur battery has good specific capacity and cycle performance.
The preparation method of the double-metal hydroxide composite graphene catalyst provided by the invention comprises the following steps:
S1: preparation of graphene oxide
Preparing required graphene oxide by using natural graphite powder as a raw material through a Hummer's method;
S2: preparation of composite catalyst
S21: dispersing graphene oxide prepared in the step S1 in formamide aqueous solution with the volume ratio of 1:1, adding a metal source for stirring reaction, adding sodium hydroxide solution in the reaction process to maintain the pH of the solution at 9.5-10.5, and cleaning the precipitate collected after the reaction;
S22: and (3) dispersing the precipitate cleaned in the step (S21) in deionized water, adding a strong reducing agent for reaction, washing and drying the precipitate after reaction to obtain the composite catalyst.
Preferably, the metal source is two of nickel salt, iron salt, cobalt salt, manganese salt, magnesium salt, aluminum salt, copper salt and zinc salt.
Preferably, the mass ratio of graphene oxide to the metal source in S21 is 4-6:1.
Preferably, the reaction conditions of S22 are: the temperature is 85-95 ℃ and the time is 1-2h.
The double-metal hydroxide composite graphene catalyst prepared by the method provided by the invention.
The invention provides application of the double-metal hydroxide composite graphene catalyst in a positive electrode material.
Preferably, the positive electrode material comprises the following raw materials in parts by weight: 10-30 parts of double metal hydroxide composite graphene catalyst, 70-90 parts of sulfur powder, 25-35 parts of conductive agent and 10-20 parts of binder.
Preferably, the conductive agent is one of ketjen black, conductive carbon black, acetylene black and graphene.
Preferably, the binder is one of polyvinylidene fluoride, polytetrafluoroethylene and polyvinyl alcohol.
The invention provides application of the positive electrode material in a lithium-sulfur battery.
The beneficial technical effects are as follows:
For the double-metal hydroxide composite graphene catalyst prepared by the method, partial isomorphic substitution of high-valence metal is beneficial to forming a positively charged surface, polysulfide anions can be captured by static electricity, and the utilization rate of active material sulfur is improved; the plurality of hydroxyl groups on the surface of the layered double hydroxide are highly thiophilic, and can be used as adsorption sites for polysulfide to effectively promote oxidation-reduction reaction of polysulfide, and reduce shuttle effect of polysulfide. Meanwhile, the complex and tedious stripping steps can be omitted by adopting an in-situ one-step synthesis method to synthesize the layered double hydroxide composite graphene catalyst material. The two-dimensional layered double hydroxide and the reduced graphene oxide with good conductivity and large specific surface area are assembled, so that more unsaturated coordination sites are provided to promote the catalytic activity of heterogeneous catalysis, thereby being capable of catalyzing conversion among sulfur-containing species and limiting shuttling of polysulfide. The interaction between interfaces also produces a stronger synergistic effect, thereby improving the charge and discharge efficiency and the cycling stability of the lithium-sulfur battery.
Drawings
Fig. 1 is a transmission electron micrograph of graphene oxide prepared in example 1 according to the present invention.
Fig. 2 is a transmission electron micrograph of a nickel-iron double metal hydroxide composite graphene catalyst prepared in example 1 according to the present invention.
Fig. 3 is an EDS elemental analysis chart of the nickel-iron double metal hydroxide composite graphene catalyst prepared in example 1 according to the present invention;
Fig. 4 is an X-ray diffraction pattern of the nickel-iron double metal hydroxide composite graphene catalyst prepared in example 1 according to the present invention.
Fig. 5 is a Cyclic Voltammetry (CV) curve of a lithium sulfur battery with a nickel-iron double metal hydroxide composite graphene catalyst prepared in example 4 according to the invention.
Fig. 6 is a first charge-discharge curve of a lithium sulfur battery assembled by taking a nickel-iron double metal hydroxide composite graphene catalyst as an anode, which is prepared in example 5 according to the present invention.
Fig. 7 is a cycle number-specific discharge capacity curve of a lithium sulfur battery assembled by taking a nickel-iron double metal hydroxide composite graphene catalyst as a positive electrode, prepared in example 5 according to the present invention.
Detailed Description
Example 1
The preparation method of the double-metal hydroxide composite graphene catalyst provided by the invention comprises the following steps:
S1: preparation of graphene oxide
Preparing required graphene oxide by using natural graphite powder as a raw material through a Hummer's method; the specific method comprises the following steps:
S11: mixing 1g of graphite flake, 1g of sodium nitrate and 46mL of 98% concentrated sulfuric acid, slowly stirring to obtain uniformly mixed black paste liquid, adding 6g of KMnO 4 at the temperature of not higher than 4 ℃, heating the system to 35 ℃ and stirring for reaction for 2h;
S12: continuously dropwise adding 15mL of distilled water, heating to 98 ℃ and reacting for 15min;
S13: and then 200mL of distilled water and 20mL of H 2O2 are slowly added and the reaction is stopped, the obtained product is centrifuged, the product is respectively washed 3 times by 5% of diluted hydrochloric acid and deionized water, and finally the product is washed by distilled water until the supernatant after centrifugation is neutral. Then dispersing graphene oxide in a certain amount of deionized water, and measuring the solid content; fig. 1 is a transmission electron microscope image of graphene oxide, from which it can be seen that graphene oxide has a remarkable lamellar structure.
S2: preparation of composite catalyst
S21: dispersing 45mg of graphene oxide prepared in S1 in 100mL of formamide aqueous solution with the volume ratio of 1:1, adding 4.5mg of ferric nitrate nonahydrate and 4.5mg of nickel nitrate hexahydrate for stirring reaction, adding 1M sodium hydroxide solution in the reaction process to maintain the pH of the solution at 10, collecting precipitate after the reaction is finished, and respectively cleaning three times by using absolute ethyl alcohol and deionized water to obtain a wet sample;
S22: dispersing the precipitate cleaned in S21 in deionized water, slowly adding 90uL of strong reducing agent, wherein the strong reducing agent can be sodium borohydride or hydrazine hydrate, the strong reducing agent in the embodiment is 80% hydrazine hydrate solution, reacting for 1.5 hours at 90 ℃, washing the obtained precipitate with absolute ethyl alcohol and deionized water for three times, and finally, freeze-drying in a freeze dryer to obtain the composite catalyst NiFe-LDH/rGO.
FIG. 2 is a transmission electron micrograph of the composite NiFe-LDH/rGO. From TEM electron microscope pictures, the surface of the graphene sheet is uniformly covered by LDH, and aggregation phenomenon does not occur.
Fig. 3 is an EDS elemental analysis diagram of the NiFe-LDH/rGO composite material, and it is evident from the diagram that the nickel element and the iron element are uniformly distributed on the NiFeLDH/rGO composite material.
FIG. 4 is an X-ray diffraction pattern of the composite catalyst NiFe-LDH/rGO, and it can be seen that the material has obvious LDH characteristic peaks. Furthermore, a broader, stronger peak was exhibited in the range of 22 ° to 27 °, due to the coincidence of 002 peak of rGO and 006 peak of LDH.
Example 2
The preparation method of the double-metal hydroxide composite graphene catalyst provided by the invention comprises the following steps:
S1: preparation of graphene oxide
The specific preparation method of the graphene oxide is shown in the example 1.
S2: preparation of composite catalyst
S21: dispersing 45mg of graphene oxide prepared in S1 in 100mL of 50% formamide aqueous solution, adding 5mg of ferric nitrate nonahydrate and 5mg of nickel nitrate hexahydrate, stirring for reaction, adding 1M sodium hydroxide solution in the reaction process to maintain the pH of the solution at 9.5, collecting precipitate after the reaction is finished, and cleaning by adopting the method of example 1 to obtain a wet sample;
S22: dispersing the precipitate cleaned in S21 in deionized water, slowly adding 90uL of 80% hydrazine hydrate solution, reacting for 1h at 85 ℃, and washing and drying the obtained precipitate by adopting the method of the example 1 to obtain the composite catalyst NiFe-LDH/rGO.
Example 3
The preparation method of the double-metal hydroxide composite graphene catalyst provided by the invention comprises the following steps:
S1: preparation of graphene oxide
The specific preparation method of the graphene oxide is shown in the example 1.
S2: preparation of composite catalyst
S21: dispersing 45mg of graphene oxide prepared in S1 in 100mL of 50% formamide aqueous solution, adding 4mg of ferric nitrate nonahydrate and 4mg of nickel nitrate hexahydrate, stirring for reaction, adding 1M sodium hydroxide solution in the reaction process to maintain the pH of the solution at 10.5, collecting precipitate after the reaction is finished, and cleaning by adopting the method of example 1 to obtain a wet sample;
S22: dispersing the precipitate cleaned in S21 in deionized water, slowly adding 90uL of 80% hydrazine hydrate solution, reacting for 2 hours at 95 ℃, and washing and drying the obtained precipitate by adopting the method of the example 1 to obtain the composite catalyst NiFe-LDH/rGO.
Example 4
Mixing 35mg of the nickel-iron double-metal hydroxide composite graphene catalyst prepared in the embodiment 1 with 15mg of ketjen black powder and 5mg of polyvinylidene fluoride (PVDF) to obtain uniform slurry, coating the uniform slurry on an aluminum foil current collector, coating the uniform slurry with a thickness of 150um, and drying the uniform slurry at 50 ℃ for 24 hours to obtain an electrode material for the positive electrode and the negative electrode of the symmetrical battery; the amount of NMP is not particularly limited, and can meet the actual needs. The battery separator (Celgard 2400 polypropylene film), the electrolyte (mixed solution of lithium bis (trifluoromethanesulfonyl) imide, 1, 3-dioxolane of Li 2S6 and 1, 2-dimethoxyethane) and the additive (LiNO 3 with the mass concentration of 1%) of the embodiment adopt the existing scheme, wherein the concentration of the mixed solution of lithium bis (trifluoromethanesulfonyl) imide, the 1, 3-dioxolane of Li 2S6 and the 1, 2-dimethoxyethane is 0.5mol/L, and the volume ratio of the two is 1:1.
2032 Symmetrical battery is assembled from the above materials. An electrochemical workstation (PARSTAT, 4000) was used to test the catalytic performance of a nickel iron double metal hydroxide composite graphene catalyst (Co-NG), and the Cyclic Voltammetry (CV) curve of a symmetric cell was tested at a sweep rate of 10mV s-1 in the voltage range of-1.4 to 1.4V, and the results are shown in FIG. 5.
As can be seen from fig. 5, the Cyclic Voltammetry (CV) curve of the symmetrical battery assembled in example 4 of the present invention has obvious oxidation-reduction peak, wide peak shape, large peak current and small polarization, which indicates that the nickel-iron double metal hydroxide composite graphene catalyst in the symmetrical battery assembled in example 4 of the present invention has good capability of catalyzing oxidation-reduction reaction of sulfur-containing species, and can effectively reduce shuttle effect of polysulfide.
Example 5
Weighing 20mg of nickel-iron double metal hydroxide composite graphene catalyst and 80mg of sulfur powder, manually grinding, and heating the ground mixture at 155 ℃ for 10 hours to obtain a catalyst-sulfur composite material; uniformly mixing 70mg of catalyst-sulfur composite material, 20mg of ketjen black and 10mg of polyvinylidene fluoride (PVDF) by taking NMP as a solvent to obtain slurry, then coating the slurry on a carbon cloth current collector, and drying the carbon cloth current collector at 50 ℃ for 24 hours to obtain a positive electrode material; taking a metal lithium sheet as a negative electrode material; the battery separator, electrolyte and additive of this example were the same as in example 4.
A 2032 lithium sulfur battery was assembled from the above materials. A blue electric testing system (model CT 2011A) was used to test the performance of lithium sulfur batteries of nickel-iron double metal hydroxide composite graphene catalysts (Co-NG).
According to the method of the technical scheme, the discharge capacity of the lithium sulfur battery assembled in the embodiment 5 of the invention at the charge-discharge rate of 0.2C and the discharge capacity of the battery after 200 cycles are tested, and the test results are shown in fig. 6 and 7. As can be seen from fig. 6 and 7, the lithium sulfur battery assembled in example 5 of the present invention has a discharge capacity of 1353mAh/g at a charge-discharge rate of 0.2C, a discharge capacity of 929mAh/g after 100 cycles, and has a higher discharge capacity and a more stable cycle performance.
In summary, according to the layered double hydroxide composite graphene catalyst material disclosed by the invention, the two-dimensional layered double hydroxide and the reduced graphene oxide with good conductivity and large specific surface area are assembled, so that more unsaturated coordination sites are provided to promote the catalytic activity of heterogeneous catalysis, thereby being capable of catalyzing conversion among sulfur-containing species and limiting shuttling of polysulfide; the interaction between interfaces also produces a stronger synergistic effect, thereby improving the charge and discharge efficiency and the cycling stability of the lithium-sulfur battery.
Claims (4)
1. The application of the double-metal hydroxide composite graphene catalyst in the positive electrode material of the lithium-sulfur battery is characterized in that the positive electrode material comprises the following raw materials in parts by weight: 10-30 parts of a double-metal hydroxide composite graphene catalyst, 70-90 parts of sulfur powder, 25-35 parts of a conductive agent and 10-20 parts of a binder;
the preparation method of the double-metal hydroxide composite graphene catalyst comprises the following steps:
S1: preparation of graphene oxide
Preparing required graphene oxide by using natural graphite powder as a raw material through a Hummer's method;
S2: preparation of composite catalyst
S21: dispersing graphene oxide prepared in the step S1 in formamide aqueous solution, adding a metal source for stirring reaction, adding sodium hydroxide solution in the reaction process to maintain the pH of the solution at 9.5-10.5, and cleaning the precipitate collected after the reaction;
s22: dispersing the precipitate cleaned in the step S21 in deionized water, adding a strong reducing agent for reaction, washing the precipitate after the reaction, and drying to obtain a composite catalyst;
the metal source is two of nickel salt, ferric salt, cobalt salt, manganese salt, magnesium salt, aluminum salt, copper salt and zinc salt;
and the mass ratio of the graphene oxide to the metal source in the S21 is 4-6:1.
2. The application of the double-metal hydroxide composite graphene catalyst in the positive electrode material of the lithium-sulfur battery according to claim 1, wherein the reaction conditions of the S22 are as follows: the temperature is 85-95 ℃ and the time is 1-2h.
3. The application of the double-metal hydroxide composite graphene catalyst in the positive electrode material of the lithium-sulfur battery according to claim 1, wherein the conductive agent is one of ketjen black, conductive carbon black, acetylene black and graphene.
4. The application of the double-metal hydroxide composite graphene catalyst in the positive electrode material of the lithium-sulfur battery according to claim 1, wherein the binder is one of polyvinylidene fluoride, polytetrafluoroethylene and polyvinyl alcohol.
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| CN109012675A (en) * | 2018-08-14 | 2018-12-18 | 青岛科技大学 | The method that one-step method prepares the difunctional VPO catalysts of graphene/nickel iron acrylic/hydrotalcite-like nano piece |
| CN109273703A (en) * | 2018-12-10 | 2019-01-25 | 山东大学 | A kind of lithium-sulphur cell positive electrode graphene/sulphur/nickel hydroxide self-supporting composite material and preparation method |
| CN110433810A (en) * | 2019-08-15 | 2019-11-12 | 青岛科技大学 | Preparation method of copper oxide doped nickel-iron hydrotalcite nanosheet/graphene bifunctional water decomposition catalyst |
| CN112531281A (en) * | 2020-09-25 | 2021-03-19 | 山东大学 | Preparation method of modified diaphragm for lithium-sulfur battery based on nano metal hydroxide-carbon composite material |
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| CN109012675A (en) * | 2018-08-14 | 2018-12-18 | 青岛科技大学 | The method that one-step method prepares the difunctional VPO catalysts of graphene/nickel iron acrylic/hydrotalcite-like nano piece |
| CN109273703A (en) * | 2018-12-10 | 2019-01-25 | 山东大学 | A kind of lithium-sulphur cell positive electrode graphene/sulphur/nickel hydroxide self-supporting composite material and preparation method |
| CN110433810A (en) * | 2019-08-15 | 2019-11-12 | 青岛科技大学 | Preparation method of copper oxide doped nickel-iron hydrotalcite nanosheet/graphene bifunctional water decomposition catalyst |
| CN112531281A (en) * | 2020-09-25 | 2021-03-19 | 山东大学 | Preparation method of modified diaphragm for lithium-sulfur battery based on nano metal hydroxide-carbon composite material |
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