CN111430696A - Yolk structure S @ Co3O4Positive electrode material of/C composite lithium-sulfur battery and preparation method thereof - Google Patents
Yolk structure S @ Co3O4Positive electrode material of/C composite lithium-sulfur battery and preparation method thereof Download PDFInfo
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- 210000002969 egg yolk Anatomy 0.000 title claims abstract description 49
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000007772 electrode material Substances 0.000 title description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000007774 positive electrode material Substances 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 31
- 239000011593 sulfur Substances 0.000 claims abstract description 31
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 25
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 25
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 25
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000137 annealing Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000001868 cobalt Chemical class 0.000 claims description 16
- 239000004005 microsphere Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 19
- 230000008859 change Effects 0.000 abstract description 16
- 229920001021 polysulfide Polymers 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000004090 dissolution Methods 0.000 abstract description 5
- 239000005486 organic electrolyte Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 19
- 239000005077 polysulfide Substances 0.000 description 14
- 150000008117 polysulfides Polymers 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000000543 intermediate Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 230000002468 redox effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013345 egg yolk Nutrition 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H01M10/052—Li-accumulators
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention relates to a yolk structure S @ Co3O4A positive electrode material of a/C composite lithium-sulfur battery and a preparation method thereof, wherein a C layer in the positive electrode material is coated on Co3O4The outside of the hollow ball is filled with S3O4The interior of the hollow sphere; the preparation method comprises (1) preparing SiO2@Co3O4A precursor; (2) to obtain Co3O4Hollow spheres; (3) preparation of Co3O4A polypyrrole intermediate; (4) the yolk structure Co is obtained3O4C; (5) obtaining S @ Co3O4the/C composite lithium-sulfur battery positive electrode material. Co3O4Hollow structure canThe yolk structure not only keeps the excellent coating of the hollow sphere on sulfur, but also further improves the slow release effect of the carbon layer outside the hollow sphere on the volume change relative to the hollow sphere structure. Co3O4The polar effect of (a) can inhibit the dissolution of polysulphides in the organic electrolyte to mitigate the shuttling effect.
Description
Technical Field
The invention relates to a yolk structure S @ Co3O4A/C composite lithium-sulfur battery positive electrode material and a preparation method thereof belong to the field of preparation of lithium-sulfur battery electrode materials.
Background
As lithium ion batteries are commercialized, disadvantages of the lithium ion batteries are also beginning to be exposed. So that attention has been focused on lithium sulfur batteries having higher specific capacities.
Compared with the traditional lithium ion anode material, the elemental sulfur is widely distributed, has low price, is very suitable for commerce, and is a high-specific-energy anode material with great prospect. Therefore, the lithium-sulfur battery has attracted great research enthusiasm of researchers, so that the lithium-sulfur battery is likely to become a substitute of the lithium-ion battery.
Although lithium-sulfur batteries are expected, their practical use is hampered by the existence of many scientific and technical problems that need to be solved. Firstly, sulfur has larger volume change in the charging and discharging process, and moreover, the shuttle effect of lithium polysulfide causes the cycle performance of the lithium sulfur battery to be poorer.
In order to relieve the volume change in the charging and discharging process, the sulfur is coated by the inner hollow of a hollow sphere structure material at present, wherein the volume change can be relieved to a certain extent by the inner space of a hollow sphere structure; the multilayer two-dimensional carbon material can be used for relieving, sulfur can be contained between layers of the two-dimensional carbon material, and meanwhile, the interlayer spacing plays a certain buffering role in the volume change process. Compared with the two modes, the two-dimensional carbon material has better conductivity due to the planar structure, but the sulfur is not coated between layers as much as a hollow sphere structure. Although the hollow sphere structure has a better coating effect on sulfur, the volume change of the hollow sphere structure is not as relieved as that of a two-dimensional material.
In order to inhibit the shuttling effect, sulfur and polysulfide can be physically and chemically adsorbed, but the adsorption effect of the sulfur and polysulfide by single physical adsorption or single chemical adsorption is limited, and the shuttling effect is inhibited by the existing material based on the physical adsorption and the chemical adsorption, so that the preparation process is complicated, and the improvement on the electrical performance of the product is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a yolk structure S @ Co3O4a/C composite lithium-sulfur battery anode material, wherein Co is contained in the anode material3O4Is of a hollow sphere structure, and the C layer is coated on Co3O4Outside the hollow sphere, S is located at Co3O4Interior of the hollow sphere, Co3O4The hollow sphere structure can relieve volume change in the charge-discharge process, and is Co3O4The C layer is coated on the outer side of the hollow sphere, so that the volume change in the charge-discharge process can be further relieved, and the conductivity is greatly improved; co3O4The polar effect of (3) can suppress the dissolution of polysulfide in the organic electrolyte solution, and can greatly improve the capacity and cycle performance of the battery.
The invention also provides the yolk structure S @ Co3O4The preparation method of the/C composite lithium-sulfur battery positive electrode material is simple and easy to operate, and the preparation process is easy to control.
The technical scheme of the invention is as follows:
yolk structure S @ Co3O4the/C composite lithium-sulfur battery positive electrode material contains Co3O4Is of a hollow sphere structure, and the C layer is coated on Co3O4Outside the hollow sphere, S is located at Co3O4The interior of the hollow sphere.
The yolk structure S @ Co provided by the invention3O4The positive electrode material of the/C composite lithium-sulfur battery is prepared by firstly, Co in the positive electrode material3O4The unique hollow sphere structure can ensure rapid electric transmission and provide space for volume change of sulfur in the charging and discharging processes; the yolk structure is based on the hollow sphere structure, so that the excellent coating of the hollow sphere structure on sulfur is maintained, andCo3O4the carbon layer is prepared on the outer side of the hollow sphere, the space between the layers can further improve the slow release effect of the hollow sphere structure on volume change, and meanwhile, the carbon layer can greatly improve the conductivity (to make up for the low conductivity of sulfur). Secondly, the polar action of cobaltosic oxide can inhibit the dissolution of polysulfide in organic electrolyte, so as to reduce shuttle effect, accelerate the redox reaction power of polysulfide and greatly improve the capacity and cycle performance of the battery. Furthermore, the C layer and the S enable the positive electrode material to have relatively high electron and ion transmission performance, and the positive electrode shows excellent electrochemical performance under low sulfur load and high sulfur load.
The yolk structure S @ Co3O4The preparation method of the/C composite lithium-sulfur battery positive electrode material specifically comprises the following steps:
(1) mixing SiO2Mixing the microspheres, cobalt salt, urea and deionized water, uniformly stirring, placing the mixture in a high-pressure reaction kettle for reaction at the temperature of between 80 and 150 ℃ for 4 to 8 hours, and then sequentially centrifuging, drying and calcining to obtain SiO2@Co3O4；SiO2The microspheres are used as hard templates, and spherical SiO is prepared by a solvothermal method2@Co3O4And (3) precursor.
(2) SiO obtained in the step (1)2@Co3O4Placing the mixture in NaOH solution for standing to remove SiO2Hard template to obtain precursor Co3O4Hollow spheres;
(3) preparation of yolk-structured Co3O4A polypyrrole intermediate; polypyrrole has high conductivity, good environmental stability, reversible redox property and strong charge storage capacity.
(4) The yolk structure Co obtained in the step (3) is3O4Annealing the polypyrrole intermediate in inert atmosphere to prepare yolk structure Co3O4C; the annealing serves to decompose the polypyrrole intermediate to give the carbon layer.
(5) The Co obtained in the step (4) is put into3O4Mixing with sulfur, grinding, and vulcanizing in inert atmosphere to obtain yolkStructure S @ Co3O4the/C composite lithium-sulfur battery positive electrode material. Under a certain temperature and atmosphere, elemental sulfur enters Co3O4The interior of the hollow sphere.
The physical adsorption and the chemical adsorption of the anode material prepared by the invention are simultaneously applied, and the prepared Co3O4Chemical adsorption can be carried out, namely, the chemical acting force between metal Co and sulfur is utilized; the capturing capability of the adsorption effect of a relatively single aspect on sulfur and polysulfide is greatly improved, and the acting force between cobalt and sulfur in the cobaltosic oxide is stronger.
Preferably, in step (1), the cobalt salt is cobalt chloride hexahydrate, cobalt salt and SiO2The mass ratio of the microspheres is (2.3-3): (0.7-0.9), the mass ratio of the cobalt salt to the urea is (2.3-3): 1.2-1.8, and the mass volume ratio of the cobalt salt to the deionized water is (2.3-3): 100-150), unit, g/m L;
further preferably, cobalt salts are mixed with SiO2The mass ratio of the microspheres is 2.5: 0.7, the mass ratio of the cobalt salt to the urea is 2.5: 1.7, and the mass-volume ratio of the cobalt salt to the deionized water is 2.5: 140 in units of g/m L.
According to the invention, in the step (1), the calcining temperature is 400-550 ℃, and the calcining time is 2-4 h; more preferably, the calcination temperature is 550 ℃ and the calcination time is 3.5 h. The calcining temperature can keep the morphological characteristics of the cobaltosic oxide from being changed greatly on the basis of ensuring the reaction.
According to a preferred embodiment of the invention, in step (1), SiO2The preparation method of the microsphere comprises the steps of placing 20-30m L deionized water, 60-80m L absolute ethyl alcohol, 2-3m L volume percent of 28% ammonia water and 2-3.5m L tetraethoxysilane in a beaker, magnetically stirring for 10 hours, and centrifugally drying to obtain SiO2And (3) microspheres. SiO prepared by the method2Good microsphere dispersibility and prepared SiO2The size of the microsphere is controllable, and the process is simple.
According to a preferred embodiment of the invention, in step (2), SiO2@Co3O4The mass/volume ratio of the solution to NaOH solution is (0.4-0.8), (50-100), unit, g/m L, and SiO is further preferable2@Co3O4The mass-to-volume ratio of the NaOH solution to the NaOH solution is 0.6: 80, unit, g/m L.
Preferably, in the step (2), the SiO is removed by standing for 18-36 h at 25 DEG C2A hard template.
According to the invention, in the step (2), the concentration of the substance of the NaOH solution is preferably 2-5 mol/L, and further preferably, the concentration of the substance of the NaOH solution is 2.5 mol/L.
Preferably, according to the present invention, in the step (3), Co of yolk structure is prepared3O4The process of the polypyrrole intermediate comprises the following steps:
A. co obtained in the step (2)3O4Adding the hollow spheres and sodium dodecyl benzene sulfonate into deionized water, and stirring for 2-4 hours; the sodium dodecyl benzene sulfonate is a surfactant or a dopant, can provide an acid environment for polypyrrole polymerization, and can improve the conductivity of polypyrrole by entering a polypyrrole framework in a form of counter ions.
B. Adding pyrrole monomer, and continuing stirring for 2-3 h;
C. transferring the mixture into a low-temperature reaction bath at the temperature of-5 to 0 ℃, and mechanically stirring the mixture for 24 to 48 hours;
D. dropping ammonium persulfate solution; ammonium persulfate is an initiator for high-molecular polymerization;
E. washing with water and ethanol alternately, centrifuging, and drying at 60-80 ℃ to obtain Co with a yolk structure3O4A polypyrrole intermediate.
Preferably, according to the invention, in step (3) A, Co3O4The mass ratio of the hollow spheres to the sodium dodecyl benzene sulfonate is 50-80: 1, Co3O4The mass volume ratio of the hollow spheres to the deionized water is (0.3-0.5): 40-70), unit, g/m L, Co3O4The mass volume ratio of the hollow spheres to the pyrrole monomers is (0.3-0.5): 80-130), unit, g/mu L;
further preferably, Co3O4The mass ratio of the hollow sphere to the sodium dodecyl benzene sulfonate is 65:1, and Co is3O4The mass volume ratio of the hollow spheres to the deionized water is 0.3: 60 in units of g/m L, and Co3O4The mass-volume ratio of the hollow spheres to the pyrrole monomers is 0.3: 120 in units of g/mu L.
Preferably, according to the invention, in step (3), Co3O4The mass volume ratio (0.3-0.5) of the hollow spheres to the ammonium persulfate solution (40-70) in units of g/m L, the mass concentration of the ammonium persulfate solution is 0.3 mol/L, and the Co solution is further preferable3O4The mass-volume ratio of the hollow sphere to the ammonium persulfate solution is 0.3: 60, unit, g/m L.
According to the invention, in the step (3) D, the dropping speed of the ammonium persulfate solution is preferably 40-80 m L within 30-50 min, and further preferably, the dropping speed of the ammonium persulfate solution is 60m L within 40 min.
According to the invention, in the step (4), the inert atmosphere is argon, the annealing temperature is 500-600 ℃, and the annealing time is 2-4 h; more preferably, the annealing temperature is 550 ℃ and the annealing time is 3.5 h.
Preferably, according to the invention, in step (5), Co3O4The mass ratio of the/C to the sulfur is 1: 1-2, and preferably Co3O4The mass ratio of the/C to the sulfur is 2: 3.
According to the invention, in the step (5), the annealing temperature is 100-200 ℃, and the annealing time is 12-15 h; further preferably, the annealing temperature is 150 ℃ and the annealing time is 13 hours.
The invention has the beneficial effects that:
1. the invention provides S @ Co with an egg yolk structure3O4Composite of/C, unique Co3O4The hollow structure can ensure quick electric transmission, relieve volume change in the charging and discharging process, and is not only polysulfideProvides physical adsorption and passes through Co for polysulfide3O4The chemisorption and catalytic conversion of the nanospheres provide strong chemisorption and activation sites. The polar action of cobaltosic oxide can inhibit the dissolution of polysulfide in organic electrolyte, so as to reduce shuttle effect, accelerate the redox reaction power of polysulfide and greatly improve the capacity and cycle performance of the battery.
2. The yolk structure prepared by the method not only keeps the excellent coating effect of the hollow sphere structure on sulfur, but also prepares the carbon layer on the basis of the excellent coating effect, and the space between the layers is further improved relative to the slow release effect of the hollow sphere structure on volume change.
3. The lithium-sulfur battery cathode material prepared by the invention has higher electron and ion transmission performance and good electrochemical performance, the capacity is basically stable after 200 times of circulation under 1C, and the capacity is 466mAh g after 200 times of circulation-1。
4. The preparation method provided by the invention is simple, and the preparation process is easy to control; and relative to other metal oxides (e.g., TiO)2Etc.) the raw materials are cheap and widely available; waste liquid and waste materials which cannot be treated are not generated in the preparation process, the energy consumption is low, the environment is friendly, the operability is strong, and a new direction is provided for preparing the lithium-sulfur battery cathode material.
Drawings
Fig. 1 is an XRD pattern of cobaltosic oxide having a hollow sphere structure prepared in example 2.
Fig. 2 is a graph showing rate performance curves of the positive electrode material of the lithium sulfur battery in example 2.
Detailed Description
The invention is further described below, but not limited thereto, with reference to the following examples and the accompanying drawings.
Example 1
Yolk structure S @ Co3O4The preparation method of the/C composite lithium-sulfur battery positive electrode material specifically comprises the following steps:
(1) 0.7g of SiO2Uniformly stirring microspheres, 2.5g of cobalt chloride hexahydrate, 1.7g of urea and 140m of L deionized water, and placing the mixture at a high temperaturePressing the mixture in a reaction kettle for 6 hours at 120 ℃ to obtain a pink purple mixed turbid liquid; drying at 80 ℃ for 5h after centrifugation, and calcining at 550 ℃ for 3.5h in air to obtain SiO2@Co3O4，SiO2@Co3O4Represents SiO2Coating Co outside3O4A layer; SiO 22The microspheres are used as hard templates, and spherical SiO is prepared by a solvothermal method2@Co3O4And (3) precursor.
In step (1), SiO2The preparation method of the microsphere comprises placing 20-30m L deionized water, 60-80m L anhydrous ethanol, 2-3m L% ammonia water, and 2-3.5m L ethyl orthosilicate in a beaker, magnetically stirring for 10h, centrifuging, and drying to obtain SiO2And (3) microspheres.
(2) SiO obtained in the step (1)2@Co3O4Placing in 2.5 mol/L NaOH solution, wherein SiO is2@Co3O4The mass is 0.6g, the volume of NaOH solution is 80m L, and the mixture is kept stand at 25 ℃ for 18-36 h to obtain a precursor Co3O4Hollow spheres; mixing SiO2@Co3O4Placing in NaOH solution for removing SiO2A hard template.
(3) Preparation of yolk-structured Co3O4Polypyrrole intermediates, Co3O4The polypyrrole intermediate represents Co3O4Coating a polypyrrole intermediate; the polypyrrole has higher conductivity, good environmental stability, reversible redox property and stronger charge storage capacity; the method comprises the following specific steps:
A. co obtained in the step (2)3O4The mass of the hollow sphere is 0.3g, and the mass of the sodium dodecyl benzene sulfonate is 4.6mg, the hollow sphere is added into 60m L deionized water, and the mixture is magnetically stirred for 3 hours, wherein the sodium dodecyl benzene sulfonate is not only a surfactant but also a dopant, so that on one hand, an acid environment can be provided for polypyrrole polymerization, and on the other hand, the sodium dodecyl benzene sulfonate enters a polypyrrole framework in a form of balanced ions, and the conductivity of the polypyrrole can be improved.
B. 120 mu L of pyrrole monomer, which is the basis for the formation of polypyrrole, was added and stirring was continued for 2.5 h.
C. Transferring the mixture into a low-temperature reaction bath at the temperature of-5 ℃, and mechanically stirring the mixture for 36 hours;
D. and (3) dripping 60m L ammonium persulfate solution within 40min, wherein the mass concentration of the ammonium persulfate solution is 0.3 mol/L, the ammonium persulfate is a high-molecular polymerization initiator, the ammonium persulfate is excessively fast and violently reacts and is likely to cause explosion, and the reaction rate is slowed or even cannot occur due to excessively slow dripping.
E. Washing with water and ethanol, centrifuging, and drying at 70 deg.C to obtain Co with yolk structure3O4A polypyrrole intermediate.
(4) The yolk structure Co obtained in the step (3) is3O4Putting the polypyrrole intermediate into a tube furnace, and annealing at 550 ℃ for 3.5h in argon atmosphere to obtain Co with a yolk structure3O4C, yolk structure Co3O4C represents Co3O4An outer layer is coated with a C layer, and Co3O4The layer is of a hollow sphere structure; the annealing serves to decompose the polypyrrole intermediate to give the carbon layer.
(5) The Co obtained in the step (4) is put into3O4Mixing the/C and sulfur in a mass ratio of 2:3, uniformly grinding, and annealing at 150 ℃ for 13h in an inert atmosphere to obtain a yolk structure S @ Co3O4the/C composite lithium-sulfur battery positive electrode material.
The yolk structure S @ Co prepared by the steps3O4Positive electrode material of/C composite lithium-sulfur battery, and Co in positive electrode material3O4Is of a hollow sphere structure, and the C layer is coated on Co3O4Outside the hollow sphere, S is located at Co3O4The interior of the hollow sphere.
The yolk structure S @ Co provided by the invention3O4Firstly, in the positive electrode material, the unique hollow sphere structure of cobaltosic oxide can ensure rapid electric transmission and provide space for volume change of sulfur in the charge and discharge processes; the yolk structure is based on the hollow sphere structure, so that the excellent coating of the hollow sphere structure on sulfur is reserved, and the yolk structure is coated on Co3O4A carbon layer is prepared on the outer side of the hollow sphere, and the space between the layers can be formedThe slow release effect of the structure of the relative hollow sphere on the volume change is further improved. Secondly, the polar action of cobaltosic oxide can inhibit the dissolution of polysulfide in organic electrolyte, so as to reduce shuttle effect, accelerate the redox reaction power of polysulfide and greatly improve the capacity and cycle performance of the battery. Furthermore, the C layer and the S enable the cathode material to have relatively high electron and ion transmission performance, and enable the cathode to show excellent electrochemical performance under low sulfur load and high sulfur load.
Characterization of XRD
For the precursor Co obtained in the step (2)3O4Analyzing the crystal phase of the hollow sphere, and obtaining a precursor Co in the step (2) according to an XRD (X-ray diffraction) spectrum as shown in figure 13O4Characteristic peak of hollow sphere and Co3O4(JCPDS No.42-1467) and step (2) gives the precursor Co3O4The corresponding peak of the hollow sphere is obvious, which indicates that the precursor Co3O4The hollow spheres have good crystallinity.
Electrical Performance testing
For the prepared yolk structure S @ Co3O4Performing electrical performance test on the positive electrode of the/C composite lithium-sulfur battery, and obtaining the yolk structure S @ Co3O4the/C composite lithium-sulfur battery is used as a positive electrode material of the lithium-sulfur battery, the positive electrode material is mixed with acetylene black and PVDF according to a certain proportion, a certain amount of solvent N-methyl pyrrolidone is dripped into the mixture, and the mixture is uniformly mixed, and then the processes of ball milling, drying, slicing, weighing and the like are carried out, so that the electrode plate used for testing is finally obtained. Finally, the prepared electrode plate is used for assembling the battery, and then the cycling stability performance of the battery is tested on a blue test system, wherein the charging and discharging voltage range is 1.5-3.0V.
As shown in FIG. 2, the yolk structure S @ Co of the lithium sulfur battery3O4The capacity of the/C composite positive electrode material is basically stable after being circulated for 200 times under 1C, and the capacity is 466mAh g after being circulated for 200 times-1And is 52% of the initial discharge capacity. By preparing SiO2The microsphere designs Co3O4The hollow nanosphere structure, the unique hollow structure, can ensure rapid electrical transmission,not only being Co3O4the/C polysulfide provides physical containment and provides for polysulfide to pass through the Co3O4The chemical adsorption and catalytic conversion of the hollow spheres provide stronger chemical adsorption and activation sites. In addition, unique Co3O4The hollow sphere structure provides enough space for volume change of sulfur in the charging and discharging process, and promotes rapid electron/ion transmission so as to continuously activate the active material, thereby improving the electrochemical performance of the lithium-sulfur battery.
Comparative example 1
S @ Co3O4The preparation method of the composite lithium-sulfur battery positive electrode material comprises the following steps:
co preparation according to the procedures described in example 1, Steps (1), (2)3O4Hollow spheres; mixing the obtained Co3O4Mixing the hollow spheres with sulfur in a mass ratio of 2:3, uniformly grinding, and annealing at 150 ℃ for 13h in an inert atmosphere to obtain S @ Co3O4Composite lithium-sulfur battery positive electrode material, S @ Co3O4Co in positive electrode material of composite lithium-sulfur battery3O4Is of a hollow sphere structure, S is located in Co3O4In the structure of a hollow sphere.
The lithium sulfur battery prepared from the cathode material of comparative example 1 according to the method provided in example 1 has a cycling stability performance tested on a blue light test system, a charging and discharging voltage range of 1.5-3.0V, and a capacity of 210mAh g after 200 cycles at 1C-1。
From the comparison of the electrical properties of comparative example 1 and example 1, it can be seen that the positive electrode material of comparative example 1 was prepared into a lithium-sulfur battery having a capacity of 210mAh g after 200 cycles-1The cycle performance is much smaller than the electrical performance of the invention, and the yolk structure in example 1 is based on the hollow sphere structure, so that the superior coating of the hollow sphere structure on sulfur is maintained, and the yolk structure in Co is better than the yolk structure in the prior art3O4The carbon layer is prepared outside the hollow sphere, and the space between the layers can further improve the slow release effect of the hollow sphere structure on the volume change, so that the capacity and the cycle performance of the battery are greatly improved.
Claims (10)
1. Yolk structure S @ Co3O4the/C composite lithium-sulfur battery positive electrode material is characterized in that Co in the positive electrode material3O4Is of a hollow sphere structure, and the C layer is coated on Co3O4Outside the hollow sphere, S is located at Co3O4The interior of the hollow sphere.
2. The yolk structure S @ Co of claim 13O4The preparation method of the/C composite lithium-sulfur battery positive electrode material is characterized by comprising the following steps:
(1) mixing SiO2Mixing the microspheres, cobalt salt, urea and deionized water, uniformly stirring, placing the mixture in a high-pressure reaction kettle for reaction at the temperature of between 80 and 150 ℃ for 4 to 8 hours, and then sequentially centrifuging, drying and calcining to obtain SiO2@Co3O4；
(2) SiO obtained in the step (1)2@Co3O4Placing the mixture in NaOH solution for standing to remove SiO2Hard template to obtain precursor Co3O4Hollow spheres;
(3) preparation of yolk-structured Co3O4A polypyrrole intermediate;
(4) the yolk structure Co obtained in the step (3) is3O4Annealing the polypyrrole intermediate in inert atmosphere to prepare yolk structure Co3O4/C；
(5) The Co obtained in the step (4) is put into3O4mixing/C with sulfur, grinding uniformly, and vulcanizing in inert atmosphere to obtain yolk structure S @ Co3O4the/C composite lithium-sulfur battery positive electrode material.
3. The yolk structure S @ Co of claim 23O4The preparation method of the/C composite lithium-sulfur battery positive electrode material is characterized in that in the step (1), the cobalt salt is cobalt chloride hexahydrate, cobalt salt and SiO2The mass ratio of the microspheres is (2.3-3): (0.7-0.9), wherein the mass ratio of the cobalt salt to the urea is (2.3-3): (1.2-1.8); quality of cobalt salt and deionized waterThe volume ratio is (2.3-3): 100-150, unit, g/m L;
further preferably, cobalt salts are mixed with SiO2The mass ratio of the microspheres is 2.5: 0.7, the mass ratio of the cobalt salt to the urea is 2.5: 1.7, and the mass-volume ratio of the cobalt salt to the deionized water is 2.5: 140 in units of g/m L.
4. The yolk structure S @ Co of claim 23O4The preparation method of the/C composite lithium-sulfur battery positive electrode material is characterized in that in the step (1), the calcining temperature is 400-550 ℃, and the calcining time is 2-4 hours; more preferably, the calcination temperature is 550 ℃ and the calcination time is 3.5 h.
5. The yolk structure S @ Co of claim 23O4The preparation method of the/C composite lithium-sulfur battery positive electrode material is characterized in that in the step (2), SiO is adopted2@Co3O4The mass/volume ratio of the solution to NaOH solution is (0.4-0.8), (50-100), unit, g/m L, and SiO is further preferable2@Co3O4The mass-to-volume ratio of the NaOH solution to the NaOH solution is 0.6: 80, unit, g/m L.
6. The yolk structure S @ Co of claim 23O4The preparation method of the/C composite lithium-sulfur battery positive electrode material is characterized in that in the step (3), Co with a yolk structure is prepared3O4The process of the polypyrrole intermediate comprises the following steps:
A. co obtained in the step (2)3O4Adding the hollow spheres and sodium dodecyl benzene sulfonate into deionized water, and stirring for 2-4 hours;
B. adding pyrrole monomer, and continuing stirring for 2-3 h;
C. transferring the mixture into a low-temperature reaction bath at the temperature of-5 to 0 ℃, and mechanically stirring the mixture for 24 to 48 hours;
D. dropping ammonium persulfate solution;
E. washing with water and ethanol alternately, centrifuging, and drying at 60-80 ℃ to obtain Co with a yolk structure3O4A polypyrrole intermediate.
7. The yolk structure S @ Co of claim 63O4The preparation method of the/C composite lithium-sulfur battery positive electrode material is characterized in that in the step (3), Co is used as the material3O4The mass ratio of the hollow spheres to the sodium dodecyl benzene sulfonate is 50-80: 1, Co3O4The mass volume ratio of the hollow spheres to the deionized water is (0.3-0.5): 40-70), unit, g/m L, Co3O4The mass volume ratio of the hollow spheres to the pyrrole monomers is (0.3-0.5): 80-130), unit, g/mu L;
further preferably, Co3O4The mass ratio of the hollow sphere to the sodium dodecyl benzene sulfonate is 65:1, and Co is3O4The mass volume ratio of the hollow spheres to the deionized water is 0.3: 60 in units of g/m L, and Co3O4The mass-volume ratio of the hollow spheres to the pyrrole monomers is 0.3: 120 in units of g/mu L.
8. The yolk structure S @ Co of claim 63O4The preparation method of the/C composite lithium-sulfur battery positive electrode material is characterized in that in the step (3), Co is used3O4The mass volume ratio (0.3-0.5) of the hollow spheres to the ammonium persulfate solution (40-70) in units of g/m L, the mass concentration of the ammonium persulfate solution is 0.3 mol/L, and the Co solution is further preferable3O4The mass-volume ratio of the hollow sphere to the ammonium persulfate solution is 0.3: 60, unit, g/m L.
9. The yolk structure S @ Co of claim 23O4The preparation method of the/C composite lithium-sulfur battery positive electrode material is characterized in that in the step (5), Co is used3O4The mass ratio of the/C to the sulfur is 1: 1-2, and preferably Co3O4The mass ratio of the/C to the sulfur is 2: 3.
10. The yolk structure S @ Co of any of claims 2-93O4The preparation method of the/C composite lithium-sulfur battery anode material is characterized in thatIn the step (5), the annealing temperature is 100-200 ℃, and the annealing time is 12-15 h; further preferably, the annealing temperature is 150 ℃ and the annealing time is 13 hours.
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