CN114864902A - Lithium-sulfur battery positive electrode material and preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery - Google Patents
Lithium-sulfur battery positive electrode material and preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 51
- 239000011701 zinc Substances 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 44
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000000197 pyrolysis Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- -1 cobalt metal compound Chemical class 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000010406 cathode material Substances 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 5
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 235000004416 zinc carbonate Nutrition 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 24
- 239000011593 sulfur Substances 0.000 abstract description 24
- 230000001351 cycling effect Effects 0.000 abstract description 16
- 239000010405 anode material Substances 0.000 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920001021 polysulfide Polymers 0.000 description 7
- 239000005077 polysulfide Substances 0.000 description 7
- 150000008117 polysulfides Polymers 0.000 description 7
- 239000011796 hollow space material Substances 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910013553 LiNO Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910018091 Li 2 S Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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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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- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lithium-sulfur battery anode material, which comprises the following steps: and uniformly mixing the trivalent cobalt metal compound, the divalent zinc metal compound and the organic solvent to obtain a mixed solution. Adjusting the pH value of the mixed solution to 13-14 to obtain a raw material solution. And (3) carrying out reflux heating treatment on the raw material solution, carrying out solid-liquid separation after full reaction, and retaining the solid to obtain the precursor. And carrying out pyrolysis reaction on the precursor to obtain the zinc cobaltate nano thin cage material. And mixing the zinc cobaltate nano thin cage material with elemental sulfur, then carrying out heat treatment, and fully reacting to obtain the lithium-sulfur battery cathode material. The lithium-sulfur battery cathode material prepared by the method is used for a lithium-sulfur battery, has high sulfur capacity and high specific capacity and cycling stability. Correspondingly, the invention also provides a lithium-sulfur battery positive electrode material prepared by the preparation method of the lithium-sulfur battery positive electrode material, a lithium-sulfur battery positive electrode and a lithium-sulfur battery.
Description
Technical Field
The invention relates to the field of energy material preparation, in particular to a lithium-sulfur battery positive electrode material and a preparation method thereof, a lithium-sulfur battery positive electrode and a lithium-sulfur battery.
Background
With the development of economy and science and technology, the energy structure of human beings is continuously changing towards a clean and sustainable direction. At present, lithium ion batteries with high energy density, long cycle stability, and other characteristics have become the main power source of consumer electronics products, playing an important role. However, with the development of high specific energy mobile devices, lithium ion batteries have been difficult to meet the current market demand. Compared with the traditional lithium ion battery, the lithium-sulfur battery has the advantages of ultrahigh theoretical specific capacity (1675mAh/g), theoretical energy density (2600Wh/kg), abundant sulfur storage capacity, low price and the like, so the lithium-sulfur battery is considered to be one of novel energy storage systems with development potential, and can be applied to the fields of portable electronic products, power automobiles, large-scale energy storage and the like. However, lithium sulfur batteries still have many problems and challenges, such as elemental S reactant for the battery system 8 And the final reduction product Li 2 S 2 And Li 2 S has the defects of extremely low electronic and ionic conductivity, volume expansion and shrinkage of electrodes in the charging and discharging processes, shuttle effect of polysulfide and the like, and the defects cause low utilization rate of active substances of the lithium-sulfur battery and poor battery cycle stability, so that the development and application of the lithium-sulfur battery are restricted.
The addition of sulfur framework materials into the positive electrode of the lithium-sulfur battery can effectively improve the electrical conductivity of the electrode, inhibit the shuttle effect of polysulfide and catalyze sulfur conversion reaction, and a great deal of work is developed around the problem at present. The hollow material is used as one of main solving means, polysulfide can be effectively adsorbed on the surface of the hollow material, and the volume expansion effect of the battery can be inhibited by the hollow space inside the hollow material, so that the cycling stability of the battery is improved. However, the hollow material has a large amount of hollow structures which cannot store sulfur inside, which results in a large amount of wasted battery space, and the electrode thickness is too large under high sulfur loading, which results in too far electrodes and current collectors, limiting the transmission of ions and electrons on the electrodes. If the thickness is forcibly reduced by increasing the pressure, pore channels in the electrode are blocked, and the pore channels cannot be infiltrated by the electrolyte, so that the performance of the battery is influenced.
How to enable the lithium-sulfur battery added with the hollow-structure sulfur framework material to have higher specific capacity and cycling stability is a research hotspot in the field.
Disclosure of Invention
The technical problem to be solved by the embodiment of the invention is how to make the lithium-sulfur battery added with the hollow-structure sulfur framework material have higher specific capacity and cycling stability.
In order to solve the technical problems, the invention provides a preparation method of a lithium-sulfur battery positive electrode material, which comprises the following steps:
and uniformly mixing the trivalent cobalt metal compound, the divalent zinc metal compound and the organic solvent to obtain a mixed solution.
Adjusting the pH value of the mixed solution to 13-14 to obtain a raw material solution.
And (3) carrying out reflux heating treatment on the raw material solution, carrying out solid-liquid separation after full reaction, and retaining the solid to obtain the precursor.
And carrying out pyrolysis reaction on the precursor to obtain the zinc cobaltate nano thin cage material.
And mixing the zinc cobaltate nano thin cage material with elemental sulfur, then carrying out heat treatment, and fully reacting to obtain the lithium-sulfur battery cathode material.
In one possible implementation, the mass ratio of the trivalent cobalt metal compound, the divalent zinc metal compound and the organic solvent is (3-8): (500-.
In one possible implementation, the mass ratio of the zinc cobaltate nano thin cage material to the elemental sulfur is (10-40): (60-90).
In one possible implementation, the temperature of the reflux heat treatment is 120 ℃ to 200 ℃.
In a feasible implementation mode, the temperature of the pyrolysis reaction is 500-950 ℃, the heating rate of the pyrolysis reaction is 1-5 ℃/min, and the pyrolysis time of the pyrolysis reaction is 2-12 h.
In a feasible realization mode, the zinc cobaltate nano thin cage material and elemental sulfur are uniformly mixed and then subjected to heat treatment, wherein the heat treatment temperature is 140-180 ℃, and the heat treatment time is 4-6 h.
In one possible implementation, the trivalent cobalt metal compound is selected from at least one of cobalt acetylacetonate, cobalt acetate, cobalt nitrate, and cobalt carbonate.
In one possible implementation, the divalent zinc metal compound is selected from at least one of zinc acetylacetonate, zinc acetate, zinc nitrate, and zinc carbonate. In one possible implementation, the organic solvent is selected from at least one of ethanol, acetone, ethylene glycol, and glycerol.
In one possible implementation, the pH of the mixed solution is adjusted using an alkaline solution, the alkaline solution being selected from at least one of ammonia, sodium hydroxide solution, and potassium hydroxide solution.
In one possible implementation, the pyrolysis reaction is carried out under an air atmosphere or an oxygen atmosphere.
The implementation of the invention has the following beneficial effects:
the lithium-sulfur battery positive electrode material prepared by the method can effectively adsorb polysulfide and catalyze sulfur conversion reaction, has a certain hollow structure, occupies a very small space, can reduce the distance between the lithium-sulfur battery positive electrode material and a current collector, improves the transmission efficiency of ions and electrons on an electrode, reduces unused space on the basis of inhibiting the battery volume expansion of the lithium-sulfur battery, and improves the specific capacity and the cycling stability of the lithium-sulfur battery.
The preparation method adopts a non-template method to prepare a precursor, then obtains a zinc cobaltate nano thin cage material through a pyrolysis reaction, and then obtains the lithium-sulfur battery anode material provided by the invention through hot melting compounding with elemental sulfur. The method has the advantages of simple and convenient operation, low temperature, simple post-treatment, simple equipment requirement and moderate cost, and is suitable for large-scale production.
Correspondingly, the invention also provides a lithium-sulfur battery cathode material prepared by the preparation method of the lithium-sulfur battery cathode material.
The lithium-sulfur battery positive electrode material is used for the lithium-sulfur battery and has high specific capacity and cycling stability.
The zinc cobaltate nano thin cage material has a good adsorption effect on polysulfide, can effectively improve the sulfur loading capacity of the lithium-sulfur battery anode material, and can effectively inhibit the shuttle effect. Meanwhile, the zinc cobaltate nano thin cage material has good catalytic action on the electrochemical conversion reaction of sulfur, and can effectively improve the utilization rate of active substance sulfur in the lithium-sulfur battery.
Correspondingly, the invention also provides a lithium-sulfur battery positive electrode, and the material for preparing the lithium-sulfur battery positive electrode comprises the lithium-sulfur battery positive electrode material.
The positive electrode of the lithium-sulfur battery is used for the lithium-sulfur battery and has higher specific capacity and cycling stability.
Correspondingly, the invention also provides a lithium-sulfur battery which comprises the lithium-sulfur battery positive electrode.
The lithium-sulfur battery has high specific capacity and cycling stability.
When the prepared lithium-sulfur battery had a density of 1.5mg/cm 2 When the sulfur capacity is increased, the capacity of the lithium-sulfur battery is still kept at a higher level of 700mAh/g after the lithium-sulfur battery is circulated for 1000 circles under the high current density of 2C, and the specific capacity attenuation rate is only 0.016 percent per circle.
Further, the lithium-sulfur battery provided by the invention can keep higher specific capacity and cycling stability under higher sulfur loading. When the obtained lithium-sulfur battery has a capacity of 10mg/cm 2 When the sulfur capacity is higher than the preset value, the lithium-sulfur battery can still release specific capacity of over 1000mAh/g after circulating for 50 circles, which is equivalent to 10mAh/cm 2 High specific capacity of area. High specific capacity and low capacity decay rate.
Drawings
FIG. 1 is a scanning electron microscope image of the zinc cobaltate nano thin cage material prepared in example 1;
FIG. 2 is a scanning electron micrograph and EDS scan data of the zinc cobaltate nano thin cage material prepared in example 1;
FIG. 3 is an X-ray diffraction pattern of the zinc cobaltate nano thin cage material prepared in example 1;
FIG. 4 is a battery cycle test chart of the lithium sulfur battery prepared in example 1;
fig. 5 is a battery cycle test chart of the lithium sulfur battery prepared in example 2 and the lithium sulfur battery prepared in comparative example 1;
fig. 6 is a battery cycle test chart of the lithium sulfur battery prepared in example 3.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
A preparation method of a lithium-sulfur battery positive electrode material comprises the following steps:
uniformly mixing a trivalent cobalt metal compound, a divalent zinc metal compound and an organic solvent to obtain a mixed solution.
Adjusting the pH value of the mixed solution to 13-14 to obtain a raw material solution.
And (3) carrying out reflux heating treatment on the raw material solution, carrying out solid-liquid separation after full reaction, and retaining the solid to obtain the precursor.
And carrying out pyrolysis reaction on the precursor to obtain the zinc cobaltate nano thin cage material.
And uniformly mixing the zinc cobaltate nano thin cage material with elemental sulfur, and then carrying out heat treatment to obtain the lithium-sulfur battery positive electrode material after full reaction.
The lithium-sulfur battery positive electrode material prepared by the method can effectively adsorb polysulfide and catalyze sulfur conversion reaction, has a certain hollow structure, occupies a very small space, can reduce the distance between the lithium-sulfur battery positive electrode material and a current collector, improves the transmission efficiency of ions and electrons on an electrode, reduces unused space on the basis of inhibiting the battery volume expansion of the lithium-sulfur battery, and improves the specific capacity and the cycling stability of the lithium-sulfur battery.
Furthermore, the hollow structure of the lithium-sulfur battery cathode material prepared by the method is only one fifth of that of the traditional hollow material, and the transmission capability of ions and electrons on the electrode can be greatly improved.
In one possible implementation, the mass ratio of the trivalent cobalt metal compound, the divalent zinc metal compound and the organic solvent is (3-8): (500-.
In one possible implementation, the mass ratio of the zinc cobaltate nano thin cage material to the elemental sulfur is (10-40): (60-90).
In one possible implementation, the temperature of the reflux heat treatment is 120 ℃ to 200 ℃.
In a feasible implementation mode, the temperature of the pyrolysis reaction is 500-950 ℃, the heating rate of the pyrolysis reaction is 1-5 ℃/min, and the pyrolysis time of the pyrolysis reaction is 2-12 h.
In a feasible implementation mode, the zinc cobaltate nano thin cage material and elemental sulfur are uniformly mixed and then subjected to heat treatment, wherein the heat treatment temperature is 140-180 ℃, and the heat treatment time is 4-6 h.
In one possible implementation, the trivalent cobalt metal compound is selected from at least one of cobalt acetylacetonate, cobalt acetate, cobalt nitrate, and cobalt carbonate.
In one possible implementation, the divalent zinc metal compound is selected from at least one of zinc acetylacetonate, zinc acetate, zinc nitrate, and zinc carbonate.
The zinc cobaltate prepared from the trivalent cobalt metal compound and the divalent zinc metal compound not only can adsorb polysulfide, but also has good conductivity and electrocatalytic performance, and can effectively improve the utilization rate of active substance sulfur in the lithium-sulfur battery.
In one possible implementation, the organic solvent is selected from at least one of ethanol, acetone, ethylene glycol, and glycerol.
In one possible implementation, the pH of the mixed solution is adjusted using an alkaline solution, the alkaline solution being selected from at least one of ammonia, sodium hydroxide solution, and potassium hydroxide solution.
In one possible implementation, the pyrolysis reaction is carried out under an air atmosphere or an oxygen atmosphere.
The preparation method adopts a non-template method to prepare a precursor, then obtains a zinc cobaltate nano thin cage material through a pyrolysis reaction, and then obtains the lithium-sulfur battery anode material provided by the invention through hot melting compounding with elemental sulfur. Simple operation and easy large-scale production.
Correspondingly, the invention also provides a lithium-sulfur battery cathode material prepared by the preparation method of the lithium-sulfur battery cathode material.
The hollow structure of the lithium-sulfur battery positive electrode material inhibits the volume expansion of the lithium-sulfur battery positive electrode, and improves the utilization rate of active substances of the lithium-sulfur battery, thereby improving the specific capacity and the cycling stability of the lithium-sulfur battery.
Further, compared with the traditional cathode material with a hollow structure, the cathode material of the lithium-sulfur battery provided by the invention has fewer hollow structures and smaller volume, and can shorten the distance between the cathode material of the lithium-sulfur battery and a current collector on the lithium-sulfur battery while providing higher sulfur loading capacity, so that active substance sulfur is closer to the current collector, and the transmission efficiency of ions and electrons on an electrode is improved.
Correspondingly, the invention also provides a lithium-sulfur battery positive electrode, and the material for preparing the lithium-sulfur battery positive electrode comprises the lithium-sulfur battery positive electrode material.
The positive electrode of the lithium-sulfur battery is used for the lithium-sulfur battery, and has higher specific capacity and cycling stability.
Correspondingly, the invention also provides a lithium-sulfur battery which comprises the lithium-sulfur battery positive electrode. The lithium-sulfur battery has higher specific capacity and cycling stability.
With reference to the above implementation contents, in order to make the technical solution of the present invention more specific and clear and easy to understand, the technical solution of the present invention is exemplified, but it should be noted that the contents to be protected by the present invention are not limited to the following embodiments 1 to 5.
Example 1
0.514g of zinc acetylacetonate, 0.706g of cobalt acetylacetonate and 100mL of ethylene glycol were mixed well to obtain a mixed solution. And adding ammonia water into the mixed solution to adjust the pH value to 13 to obtain a raw material solution.
Heating the raw material solution to 170 ℃, carrying out condensation reflux for 3h, then cooling to room temperature, centrifugally separating out a solid product, washing with ethanol and deionized water, and carrying out vacuum drying at 80 ℃ overnight to obtain a precursor.
And (3) introducing air atmosphere, and carrying out pyrolysis reaction on the precursor, wherein the heating rate of the pyrolysis reaction is 5 ℃/min, the temperature of the pyrolysis reaction is 800 ℃, and the time of the pyrolysis reaction is 6h, so as to obtain the zinc cobaltate nano thin cage material.
And (3) uniformly mixing 0.5g of the prepared zinc cobaltate nano thin cage material and 1.5g of sublimed sulfur powder, and carrying out heat treatment at 155 ℃ for 6 hours to obtain the lithium-sulfur battery positive electrode material.
The positive electrode material of the lithium-sulfur battery, the conductive agent Sup P and the binder LA123 were mixed in a mass ratio of 7:2:1 to obtain a slurry.
Using a coater at a rate of 1.5mg/cm 2 The slurry is coated on an aluminum foil and dried to obtain the lithium-sulfur battery anode with the diameter of 14 mm.
The positive electrode of the lithium-sulfur battery, the negative electrode of the lithium-sulfur battery (a metal lithium sheet with the diameter of 14.5 mm), a diaphragm and an electrolyte (1mol/L LITFSI + 1% LiNO) 3 DOL + DME dissolved in a 1:1 volume ratio) were assembled into a 2025 type button lithium sulfur cell in a glove box filled with argon.
The prepared lithium-sulfur battery was allowed to stand for 6 hours and then tested.
Example 2
This example differs from example 1 in that the prepared lithium sulfur battery positive electrode had a sulfur loading of 6mg/cm 2 。
Example 3
This example differs from example 1 in that the prepared lithium-sulfur battery positive electrode had a sulfur loading of 10mg/cm 2 。
Example 4
0.549g of zinc nitrate, 0.725g of cobalt nitrate and 150mL of ethylene glycol were mixed uniformly to obtain a mixed solution. And adding sodium hydroxide into the mixed solution to adjust the pH value to 14 to obtain a raw material solution.
Heating the raw material solution to 180 ℃, carrying out condensation reflux for 4h, then cooling to room temperature, centrifugally separating out a solid product, washing with ethanol and deionized water, and carrying out vacuum drying at 80 ℃ overnight to obtain a precursor.
And (3) introducing air atmosphere, and carrying out pyrolysis reaction on the precursor, wherein the heating rate of the pyrolysis reaction is 5 ℃/min, the temperature of the pyrolysis reaction is 700 ℃, and the time of the pyrolysis reaction is 6h, so as to obtain the zinc cobaltate nano thin cage material.
And (3) uniformly mixing 0.5g of the prepared zinc cobaltate nano thin cage material and 1.5g of sublimed sulfur powder, and heating at 155 ℃ for 6 hours to obtain the lithium-sulfur battery positive electrode material.
The positive electrode material of the lithium-sulfur battery, the conductive agent Sup P and the binder LA123 were mixed in a mass ratio of 7:2:1 to obtain a slurry.
Using a coater at 8mg/cm 2 The slurry is coated on an aluminum foil and dried to obtain the lithium-sulfur battery anode with the diameter of 14 mm.
The positive electrode of the lithium-sulfur battery, the negative electrode of the lithium-sulfur battery (a metal lithium sheet with the diameter of 14.5 mm), a diaphragm and an electrolyte (1mol/L LITFSI + 1% LiNO) 3 DOL + DME dissolved in a 1:1 volume ratio) were assembled into a 2025 type button lithium sulfur cell in a glove box filled with argon.
The prepared lithium-sulfur battery was allowed to stand for 6 hours and then tested.
Example 5
0.514g of zinc acetylacetonate, 0.706g of cobalt acetylacetonate and 100mL of glycerol were mixed well to obtain a mixed solution. Adding potassium hydroxide into the mixed solution to adjust the pH value to 14 to obtain a raw material solution.
Heating the raw material solution to 190 ℃, carrying out condensation reflux for 3h, then cooling to room temperature, centrifugally separating out a solid product, washing with ethanol and deionized water, and carrying out vacuum drying at 80 ℃ overnight to obtain a precursor.
And (3) introducing air atmosphere, and carrying out pyrolysis reaction on the precursor, wherein the heating rate of the pyrolysis reaction is 5 ℃/min, the temperature of the pyrolysis reaction is 700 ℃, and the time of the pyrolysis reaction is 6h, so as to obtain the zinc cobaltate nano thin cage material.
And (3) uniformly mixing 0.5g of the prepared zinc cobaltate nano thin cage material and 1.5g of sublimed sulfur powder, and heating at 155 ℃ for 6 hours to obtain the lithium-sulfur battery positive electrode material.
The positive electrode material of the lithium-sulfur battery, the conductive agent Sup P and the binder LA123 were mixed in a mass ratio of 7:2:1 to obtain a slurry.
Using a coater at 8mg/cm 2 The slurry is coated on an aluminum foil and dried to prepare the lithium-sulfur battery anode with the diameter of 14 mm.
The positive electrode of the lithium-sulfur battery, the negative electrode of the lithium-sulfur battery (a metal lithium sheet with the diameter of 14.5 mm), a diaphragm and an electrolyte (1mol/L LITFSI + 1% LiNO) 3 DOL + DME dissolved in a 1:1 volume ratio) were assembled into a 2025 type button lithium sulfur cell in a glove box filled with argon.
The prepared lithium-sulfur battery was allowed to stand for 6 hours and then tested.
Comparative example 1
Sup P-S, a conductive agent and a binder LA123 are mixed according to a mass ratio of 7:2:1 to obtain slurry.
Using a coater at 6mg/cm 2 The slurry was coated on aluminum foil to prepare a lithium-sulfur battery positive electrode having a diameter of 14 mm.
The positive electrode of the lithium-sulfur battery, the negative electrode of the lithium-sulfur battery (a metal lithium sheet with the diameter of 14.5 mm), a diaphragm and an electrolyte (1mol/L LITFSI + 1% LiNO) 3 DOL + DME dissolved in a 1:1 volume ratio) were assembled into a 2025 type button lithium sulfur cell in a glove box filled with argon.
The prepared lithium-sulfur battery was allowed to stand for 6 hours and then tested.
And (3) performance testing:
the appearance of the zinc cobaltate nano thin cage material is characterized:
scanning the zinc cobaltate nano thin cage material prepared in the example 1 by an electron microscope, and the result is shown in fig. 1;
performing energy spectrum line scanning analysis on the zinc cobaltate nano thin cage material prepared in the example 1 to obtain electron microscope image EDS line scanning data, wherein the result is shown in a figure 2;
x-ray diffraction was performed on the zinc cobaltate nano thin cage material prepared in example 1 to obtain a diffraction pattern, and the result is shown in fig. 3;
specific capacity and cycling stability of lithium-sulfur batteries:
the lithium sulfur battery prepared in example 1 was subjected to a battery cycle test at a current density of 2C, and the results are shown in fig. 4;
the lithium sulfur batteries manufactured in example 2 and comparative example 1 were subjected to a battery cycle test at a current density of 1C, and the results are shown in fig. 5;
the lithium sulfur battery prepared in example 3 was subjected to a battery cycle test at a current density of 0.1C, and the results are shown in fig. 6.
The battery cycle tests of example 4 and example 5 showed the results shown in table 1.
TABLE 1 specific capacity after fading of lithium-sulfur batteries prepared in example 4 and example 5
As can be seen from fig. 1 and 2a, the zinc cobaltate nano thin cage material prepared in example 1 has a thick sheet structure with a size of 1 micron and a thickness of about 300 nm.
Fig. 2b and 2c are EDS scan data of cobalt element and zinc element in the zinc cobaltate nano thin cage material prepared in example 1, which shows that the content of zinc and cobalt element at two sides of the zinc cobaltate nano thin cage material is higher than that at the middle, and it indicates that a hollow structure exists in the middle of the zinc cobaltate nano thin cage material prepared in example 1.
Fig. 3 is an X-ray diffraction pattern of the zinc cobaltate nano thin cage material prepared in example 1, and a diffraction peak is consistent with the X-ray diffraction pattern of zinc cobaltate.
As can be seen from fig. 4, the initial specific capacity of the lithium-sulfur battery prepared in example 1 was greater than 800mAh/g, the capacity was still maintained at a high level of 700mAh/g after 1000 cycles at a high current density of 2C, and the capacity fade rate was only 0.016% per cycle. The lithium-sulfur battery cathode material prepared by the invention has higher battery cycle stability.
As can be seen from Table 1, the high specific capacity of 600mAh/g can be achieved after the lithium-sulfur battery positive electrode material prepared in the invention is cycled for 500 cycles under the high current density of 1C in the examples 4 and 5, which shows that the lithium-sulfur battery positive electrode material prepared in the invention has higher battery cycling stability.
As can be seen from fig. 5, the initial specific capacity and the specific capacity after 50 cycles of the lithium-sulfur battery prepared in example 2 are much larger than the initial specific capacity and the specific capacity after 50 cycles of the lithium-sulfur battery prepared in comparative example 1, which indicates that the positive electrode material of the lithium-sulfur battery prepared in the present invention has a higher specific capacity compared to the conventional Sup P-S material under the same sulfur loading capacity.
As can be seen from FIG. 6, the lithium sulfur battery prepared in example 3 has a high sulfur loading of 10mg/cm 2 The lithium-sulfur battery can still release specific capacity of over 1000mAh/g after circulating for 50 circles, which is equivalent to 10mAh/cm 2 High areal capacity density and coulombic efficiency of about 100%. The lithium-sulfur battery prepared by the invention can keep higher specific capacity and cycling stability when having higher sulfur carrying capacity.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a lithium-sulfur battery positive electrode material is characterized by comprising the following steps:
uniformly mixing a trivalent cobalt metal compound, a divalent zinc metal compound and an organic solvent to obtain a mixed solution;
adjusting the pH value of the mixed solution to 13-14 to obtain a raw material solution;
carrying out reflux heating treatment on the raw material solution, carrying out solid-liquid separation after full reaction and retaining solids to obtain a precursor;
carrying out pyrolysis reaction on the precursor to obtain a zinc cobaltate nano thin cage material;
and uniformly mixing the zinc cobaltate nano thin cage material with elemental sulfur, then carrying out heat treatment, and fully reacting to obtain the lithium-sulfur battery cathode material.
2. The method of claim 1, wherein the mass ratio of the trivalent cobalt metal compound, the divalent zinc metal compound and the organic solvent is (3-8): (3-8): 500-.
3. The method for preparing the positive electrode material of the lithium-sulfur battery as claimed in claim 1, wherein the mass ratio of the zinc cobaltate nano thin cage material to the elemental sulfur is (10-40): (60-90).
4. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 1, wherein the temperature of the reflow heating treatment is 120 ℃ to 200 ℃.
5. The method for preparing the positive electrode material for the lithium-sulfur battery according to claim 1, wherein the temperature of the pyrolysis reaction is 500 ℃ to 950 ℃, the temperature rise rate of the pyrolysis reaction is 1 ℃/min to 5 ℃/min, and the time of the pyrolysis reaction is 2h to 12 h.
6. The method for preparing the positive electrode material of the lithium-sulfur battery according to claim 1, wherein in the step of uniformly mixing the zinc cobaltate nano thin cage material with elemental sulfur and then performing heat treatment, the temperature of the heat treatment is 140-180 ℃, and the time of the heat treatment is 4-6 h.
7. The method of manufacturing a positive electrode material for a lithium-sulfur battery according to claim 1, wherein the trivalent cobalt metal compound is at least one selected from cobalt acetylacetonate, cobalt acetate, cobalt nitrate, and cobalt carbonate; and/or
The divalent zinc metal compound is at least one selected from zinc acetylacetonate, zinc acetate, zinc nitrate and zinc carbonate; and/or
The organic solvent is at least one of ethanol, acetone, ethylene glycol and glycerol; and/or
Adjusting the pH value of the mixed solution by adopting an alkaline solution, wherein the alkaline solution is selected from at least one of ammonia water, a sodium hydroxide solution and a potassium hydroxide solution; and/or
The pyrolysis reaction is carried out in an air atmosphere or an oxygen atmosphere.
8. A positive electrode material for a lithium-sulfur battery, which is produced by the method for producing a positive electrode material for a lithium-sulfur battery according to any one of claims 1 to 7.
9. A lithium sulfur battery positive electrode, characterized in that a material for preparing the lithium sulfur battery positive electrode comprises the lithium sulfur battery positive electrode material according to claim 8.
10. A lithium sulfur battery comprising the lithium sulfur battery positive electrode of claim 9.
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