CN114249356A - 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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- CN114249356A CN114249356A CN202111451519.8A CN202111451519A CN114249356A CN 114249356 A CN114249356 A CN 114249356A CN 202111451519 A CN202111451519 A CN 202111451519A CN 114249356 A CN114249356 A CN 114249356A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 28
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 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 5
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 16
- 150000004692 metal hydroxides Chemical class 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 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
- 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
- 150000002505 iron 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 239000011593 sulfur Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 5
- 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
- 230000005540 biological transmission Effects 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
- 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
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium 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
- 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
- 239000002904 solvent Substances 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
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004108 freeze drying Methods 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
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 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
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 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
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
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- 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
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/052—Li-accumulators
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- 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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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 the graphene oxide prepared by S1 in 50% formamide solution, adding a metal source to perform stirring reaction, adding a 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 dispersing the precipitate cleaned in the 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 disadvantages: (1) the utilization rate of active substances is low; (2) the polysulfide in high valence state is dissolved in the electrolyte, passes through the membrane, reacts with the lithium cathode to form polysulfide in low valence state, and then returns to the anode, so that the shuttle effect is formed, and the shuttle effect seriously reduces the utilization rate of sulfur.
At present, in order to solve the problems, a functional host material is mostly adopted to be combined with sulfur, and the layered double hydroxide is widely concerned due to the unique two-dimensional constraint structure and the catalytic performance. The method for preparing the composite material by the double metal hydroxide and the carbon material is an ideal material, but for a common stripping intercalation preparation method, on one hand, insufficient stripping results in less active sites, so that the shuttle effect inhibition effect is poor, 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 bimetallic 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 the graphene oxide prepared by S1 in formamide aqueous solution with the volume ratio of 1:1, adding a metal source to carry out 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 dispersing the precipitate cleaned in the S21 in deionized water, adding a strong reducing agent for reaction, and washing and drying the precipitate after the 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 the 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 1-2 h.
The bimetallic hydroxide composite graphene catalyst prepared by the method is provided by the invention.
The invention provides an application of the double metal hydroxide composite graphene catalyst in a positive electrode material.
Preferably, the cathode 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.
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 cathode material in a lithium-sulfur battery.
The beneficial technical effects are as follows:
for the bimetallic hydroxide composite graphene catalyst prepared by the method, partial isomorphic substitution of high-valence metal is beneficial to forming a surface with positive charges, polysulfide anions can be captured by static electricity, and the utilization rate of active substance sulfur is improved; a large number 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 the redox reaction of the polysulfide and reduce the shuttle effect of the polysulfide. Meanwhile, the in-situ one-step synthesis method is adopted to synthesize the layered double hydroxide composite graphene catalyst material, so that the complicated and fussy stripping step can be omitted. The two-dimensional layered double hydroxide is assembled with the reduced graphene oxide with good conductivity and large specific surface area, so that more unsaturated coordination sites are provided to promote the catalytic activity of heterogeneous catalysis, thereby catalyzing the conversion among sulfur-containing species and limiting the shuttle of polysulfide. The interaction between the interfaces also generates a strong synergistic effect, thereby improving the charge and discharge efficiency and the cycle stability of the lithium-sulfur battery.
Drawings
Fig. 1 is a transmission electron microscope photograph of graphene oxide prepared in example 1 according to the present invention.
Fig. 2 is a transmission electron microscope photograph of the 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 nickel-iron double-metal hydroxide composite graphene catalyst lithium-sulfur battery prepared in example 4 according to the present invention.
Fig. 6 is a first charge-discharge curve of a lithium-sulfur battery assembled by using a nickel-iron double-metal hydroxide composite graphene catalyst as a positive electrode according to example 5 of the present invention.
Fig. 7 is a cycle number-specific discharge capacity curve of a lithium-sulfur battery assembled by using a nickel-iron double metal hydroxide composite graphene catalyst as a positive electrode according to example 5 of the present invention.
Detailed Description
Example 1
The preparation method of the bimetallic 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 graphiteMixing the tablet, 1g of sodium nitrate and 46mL of 98% concentrated sulfuric acid, slowly stirring until a black slurry liquid is uniformly mixed, and adding 6g of KMnO at a temperature of not higher than 4 DEG C4Heating the system to 35 ℃ and stirring for reaction for 2 hours;
s12: continuously dropwise adding 15mL of distilled water, heating to 98 ℃, and reacting for 15 min;
s13: the slow addition of 200mL of distilled water and 20mL of H was continued2O2And stopping the reaction, centrifuging the obtained product, washing with 5% dilute hydrochloric acid and deionized water for 3 times respectively, and finally washing with distilled water until the centrifuged supernatant is neutral. Then dispersing the 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 the graphene oxide has a distinct lamellar structure.
S2: preparation of composite catalyst
S21: dispersing 45mg of graphene oxide prepared by 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 of sodium hydroxide solution in the reaction process to maintain the pH of the solution at 10, collecting precipitates after the reaction is finished, and respectively washing the precipitates with absolute ethyl alcohol and deionized water for three times to finally obtain a wet sample;
s22: dispersing the precipitate cleaned in the S21 in deionized water, slowly adding 90uL of a strong reducing agent which can be sodium borohydride or hydrazine hydrate, selecting an 80% hydrazine hydrate solution as the strong reducing agent in the embodiment, reacting at 90 ℃ for 1.5h, washing the obtained precipitate with absolute ethyl alcohol and deionized water for three times, and finally putting the precipitate into a freeze dryer for freeze drying to obtain the composite catalyst NiFe-LDH/rGO.
FIG. 2 is a transmission electron micrograph of the composite NiFe-LDH/rGO. According to a TEM image, the surface of the graphene sheet is uniformly covered by LDH, and no aggregation phenomenon occurs.
FIG. 3 is an EDS elemental analysis chart of the composite material NiFe-LDH/rGO, and it is obvious from the chart 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 the material can be seen to have obvious LDH characteristic peaks. In addition, a broader, stronger peak was shown in the range of 22 ° to 27 ° due to the coincidence of the 002 peak of rGO and the 006 peak of LDH.
Example 2
The preparation method of the bimetallic hydroxide composite graphene catalyst provided by the invention comprises the following steps:
s1: preparation of graphene oxide
The specific preparation method of graphene oxide is shown in 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 for stirring reaction, adding 1M sodium hydroxide solution during the reaction process to maintain the pH of the solution at 9.5, collecting precipitates after the reaction is finished, and cleaning by adopting the method of example 1 to finally obtain a wet sample;
s22: and dispersing the precipitate cleaned in the 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 example 1 to obtain the composite catalyst NiFe-LDH/rGO.
Example 3
The preparation method of the bimetallic hydroxide composite graphene catalyst provided by the invention comprises the following steps:
s1: preparation of graphene oxide
The specific preparation method of graphene oxide is shown in 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 for stirring reaction, adding 1M sodium hydroxide solution during the reaction process to maintain the pH of the solution at 10.5, collecting precipitates after the reaction is finished, and cleaning by adopting the method of example 1 to finally obtain a wet sample;
s22: and dispersing the precipitate cleaned in the S21 in deionized water, slowly adding 90uL of 80% hydrazine hydrate solution, reacting for 2h at 95 ℃, and washing and drying the obtained precipitate by adopting the method of the embodiment 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, 15mg of ketjen black powder and 5mg of polyvinylidene fluoride (PVDF) by taking NMP as a solvent to obtain uniform slurry, coating the uniform slurry on an aluminum foil current collector, wherein the coating thickness is 150 mu m, and drying the aluminum foil current collector at 50 ℃ for 24 hours to obtain electrode materials for positive and negative electrodes of a symmetrical battery; the dosage of NMP is not specially limited, and the NMP can meet the actual requirement. The battery separator (Celgard 2400 polypropylene film) and the electrolyte (lithium bistrifluoromethanesulfonimide, Li) of the present example2S6A mixed solution of 1, 3-dioxolane and 1, 2-dimethoxyethane), and an additive (LiNO with a mass concentration of 1%)3) By the existing scheme, wherein the lithium bis (trifluoromethanesulfonyl) imide and the Li are adopted2S6The concentration of the mixed liquid of the 1, 3-dioxolane and the 1, 2-dimethoxyethane is 0.5mol/L, and the volume ratio of the two is 1: 1.
2032 symmetric batteries are assembled from the above materials. An electrochemical workstation (PARSTAT4000) is adopted to test the catalytic performance of the nickel-iron double-metal hydroxide composite graphene catalyst (Co-NG), and the Cyclic Voltammetry (CV) curve of the symmetrical battery is tested at a sweep rate of 10mV s < -1 > within the voltage range of-1.4 to 1.4V, and the result is shown in FIG. 5.
As can be seen from fig. 5, the redox peak of the Cyclic Voltammetry (CV) curve of the symmetric battery assembled in example 4 of the present invention is obvious, and has a wide peak shape, a large peak current, and a small polarization, which indicates that the nickel-iron double-metal hydroxide composite graphene catalyst in the symmetric battery assembled in example 4 of the present invention has a good ability of catalyzing the redox reaction of sulfur-containing species, and can effectively reduce the shuttle effect of polysulfides.
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 for 24 hours at 50 ℃ to obtain a positive electrode material; taking a metal lithium sheet as a negative electrode material; the battery separator, electrolyte, and additives of this example were the same as those of example 4.
The 2032 lithium-sulfur battery is assembled by the materials. A blue test system (model CT2011A) was used to test the performance of a nickel-iron double metal hydroxide composite graphene catalyst (Co-NG) lithium sulfur battery.
The lithium-sulfur battery assembled in example 5 of the present invention was tested for discharge capacity at a charge-discharge rate of 0.2C and for discharge capacity after 200 cycles according to the method described in the above technical solutions, and the test results are shown in fig. 6 and 7. As can be seen from fig. 6 and 7, the discharge capacity of the lithium-sulfur battery assembled in example 5 of the present invention at the charge and discharge rate of 0.2C was 1353mAh/g, and the discharge capacity after 100 cycles was 929mAh/g, which has a higher discharge capacity and a more stable cycle performance.
In conclusion, the layered double hydroxide composite graphene catalyst material provided by the invention assembles the two-dimensional layered double hydroxide with the reduced graphene oxide with good conductivity and large specific surface area, so that more unsaturated coordination sites are provided to promote the catalytic activity of heterogeneous catalysis, thereby catalyzing the conversion between sulfur-containing species and limiting the shuttling of polysulfide; the interaction between the interfaces also generates a strong synergistic effect, thereby improving the charge and discharge efficiency and the cycle stability of the lithium-sulfur battery.
Claims (10)
1. The preparation method of the double metal hydroxide composite graphene catalyst is characterized by comprising 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 the graphene oxide prepared by S1 in formamide aqueous solution, adding a metal source to perform stirring reaction, adding a 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 dispersing the precipitate cleaned in the S21 in deionized water, adding a strong reducing agent for reaction, and washing and drying the precipitate after the reaction to obtain the composite catalyst.
2. The method of claim 1, wherein the metal source is two of nickel salt, iron salt, cobalt salt, manganese salt, magnesium salt, aluminum salt, copper salt, and zinc salt.
3. The method for preparing the double metal hydroxide composite graphene catalyst according to claim 1, wherein the mass ratio of the graphene oxide to the metal source in S21 is 4-6: 1.
4. The method for preparing the double metal hydroxide composite graphene catalyst according to claim 1, wherein the reaction conditions of S22 are as follows: the temperature is 85-95 ℃ and the time is 1-2 h.
5. The double metal hydroxide composite graphene catalyst prepared according to the method of any one of claims 1 to 4.
6. The use of the double metal hydroxide composite graphene catalyst according to claim 6 in a positive electrode material.
7. The application of the double metal hydroxide composite graphene catalyst in the positive electrode material according to claim 6, wherein 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.
8. The application of the double metal hydroxide composite graphene catalyst in the positive electrode material is characterized in that the conductive agent is one of Ketjen black, conductive carbon black, acetylene black and graphene.
9. The application of the double metal hydroxide composite graphene catalyst in the positive electrode material is characterized in that the binder is one of polyvinylidene fluoride, polytetrafluoroethylene and polyvinyl alcohol.
10. Use of a positive electrode material according to any one of claims 7 to 9 in a lithium-sulphur battery.
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