CN114583166A - Lithium-sulfur battery and preparation method thereof - Google Patents
Lithium-sulfur battery and preparation method thereof Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002135 nanosheet Substances 0.000 claims abstract description 52
- 239000004744 fabric Substances 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000003993 interaction Effects 0.000 claims abstract description 7
- 230000002349 favourable effect Effects 0.000 claims abstract description 6
- 230000001737 promoting effect Effects 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 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 description 20
- 239000011258 core-shell material Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002985 plastic film Substances 0.000 claims description 9
- 229920006255 plastic film Polymers 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000007547 defect Effects 0.000 claims description 5
- 230000001788 irregular Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- GGPPEHZOVMWIHQ-UHFFFAOYSA-N S1C=CC=CC=CC=C1.[Li] Chemical compound S1C=CC=CC=CC=C1.[Li] GGPPEHZOVMWIHQ-UHFFFAOYSA-N 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- -1 zeolite imidazole ester Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- 229910002451 CoOx Inorganic materials 0.000 description 1
- 229910001216 Li2S Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
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Abstract
The invention provides a lithium-sulfur battery and a preparation method thereof, and belongs to the technical field of lithium-sulfur battery preparation. The invention prepares CC @ Co/CoO for the first time1‑xThe nanosheet array is used as a framework of the positive electrode structure, so that the electrochemical performance of the lithium-sulfur battery is improved. The unique 2D porous structure of the material enables CoO1‑xThe nano-sheet has a high active site, has strong chemical interaction with the LiPS, and is favorable for promoting the breakage of S-S bonds in the LiPS. In addition, the Co core on the carbon cloth forms a continuous with the Carbon Cloth (CC)The integrated conductive frame can realize rapid charge transfer and further accelerate the conversion of the immobilized LipS.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur battery preparation, and particularly relates to a lithium-sulfur battery and a preparation method thereof.
Background
With the development of lithium-sulfur batteries, CN107994251B discloses a dual-carbon cloth flexible lithium-sulfur battery and a preparation method thereof, namely carbon cloth and CC @ CoOxAnd one or more of CC @ ZIF-67 and CC @ Co/CNTs, which have higher specific surface area and conductivity compared with the raw material of carbon cloth. However, since the conductivity is still not ideal and the active sites are limited, the performance is far from meeting the requirements of commercialization.
Therefore, promoting the application of metal oxides in lithium-sulfur batteries through reasonable structural design and component design is a problem to be solved urgently at present.
Disclosure of Invention
In order to solve the technical problem, the invention provides a CC @ Co/CoO with a two-dimensional porous core-shell structure and oxygen vacancy combination1-xA lithium-sulfur battery with a nanosheet array positive electrode framework structure and a preparation method thereof.
A double-carbon cloth flexible lithium-sulfur battery is characterized in that: the lithium-sulfur battery is composed of a flexible positive electrode, a flexible negative electrode, a PP diaphragm, electrolyte and an aluminum-plastic film;
the PP diaphragm is positioned between the flexible positive electrode and the flexible negative electrode; electrolyte is filled between the flexible positive electrode and the flexible negative electrode and the PP diaphragm; and aluminum-plastic films are packaged outside the flexible positive electrode and the flexible negative electrode. The frameworks of the flexible anode and the flexible cathode are CC @ Co/CoO with a two-dimensional porous core-shell structure and oxygen vacancy combination1-xAn array of nanoplates.
A preparation method of the double-carbon-cloth flexible lithium-sulfur battery comprises the following specific steps:
the method comprises the following steps: preparing flexible positive and negative electrode frameworks:
1) preparing a CC @ ZIF-L precursor: growing the ZIF-L nanosheets on carbon cloth to obtain CC @ ZIF-L;
2)CC@Co3O4preparation: annealing CC @ ZIF-L for 2h at the heating rate of 2 ℃/min of 350 ℃ in the air atmosphere to obtain CC @ Co3O4I.e. Co3O4CC coated by nano sheets;
3)CC@Co/CoO1-xpreparation: h2Mixing CC @ Co with Ar in the volume ratio of 1:93O4Annealing at 240 ℃ and 260 ℃ for 2h at the heating rate of 2 ℃/min. Annealing at 250 ℃ for 2h is preferred, and CC @ Co/CoO with porous core-shell structure and oxygen vacancy combination cannot be obtained at other temperatures1-x。
Step two: preparing a flexible positive electrode and a flexible negative electrode:
the obtained CC @ Co/CoO1-xCoating a layer of 1M lithium polysulfide solution on the surface of the anode as an active substance to obtain a flexible anode; melting 0.2-20 g of metal lithium, and then obtaining CC @ Co/CoO1-xSoaking in molten lithium for 3-120 s, absorbing a lithium source, and cooling to room temperature to obtain a flexible cathode;
step three: preparing a flexible lithium-sulfur battery:
and (3) adding a PP diaphragm between the flexible positive electrode obtained in the step one and the flexible negative electrode obtained in the step two, dripping 20-150 mu L of electrolyte, and packaging by using an aluminum-plastic film to obtain the flexible lithium-sulfur battery.
The invention also provides CC @ Co/CoO with a two-dimensional porous core-shell structure and oxygen vacancy combination1-xA lithium-sulfur battery with a nanosheet array positive electrode framework and a preparation method thereof.
A lithium sulfur button cell, characterized in that: from CC @ Co/CoO1-xPositive electrode skeleton electrode plate, Celgard 2400 diaphragm, lithium metal current collector, L2S6Sulfur-based electrolyte and blank electrolyte.
A preparation method of the lithium-sulfur button battery comprises the following specific steps:
the method comprises the following steps: CC @ Co/CoO1-xPreparing a positive electrode framework structure:
1) CC @ ZIF-L precursor preparation: growing the ZIF-L nanosheets on carbon cloth to obtain CC @ ZIF-L;
2)CC@Co3O4preparation: annealing CC @ ZIF-L for 2h at the heating rate of 2 ℃/min of 350 ℃ in the air atmosphere to obtain CC @ Co3O4I.e. Co3O4Nano-meterSheet-coated CC;
3)CC@Co/CoO1-xpreparation: h2Mixing CC @ Co with Ar in the volume ratio of 1:93O4Annealing at the temperature rise rate of 2 ℃/min and the temperature of 240 ℃ and 260 ℃ for 2 h. Annealing at 250 ℃ for 2h is preferred, and CC @ Co/CoO with porous core-shell structure and oxygen vacancy combination cannot be obtained at other temperatures1-x。
Step two: the CC @ Co/CoO obtained by the step 3) is added1-xAnd the positive electrode framework structure is assembled into the lithium-sulfur button battery. The specific assembling process is as follows:
1) preparing a blank electrolyte: first 1.0M LiTFSI, 2 wt.% LiNO3Adding the mixture into a mixed solution with a volume ratio of DOL/DME of 1:1, and uniformly stirring and mixing the mixture on a magnetic stirrer to obtain a blank electrolyte.
2) Preparing a sulfur-based electrolyte: mixing sulfur powder and Li in a mass ratio of 5:12Adding the S powder into the blank electrolyte, and placing the mixture on a magnetic stirrer to be stirred and mixed uniformly to obtain L2S6A sulfur-based electrolyte.
3) Assembling the battery: mixing CC @ Co/CoO1-xDrying in a vacuum drying oven to remove water, cutting into circular electrode plate with diameter of 12mm, and drying in a vacuum drying oven2O/O2(ii) assembling the cell in an Ar-filled glove box at less than 0.1ppm, sequentially mixing CC @ Co/CoO1-xPole piece, L2S6And adding a sulfur-based electrolyte, a Celgard 2400 diaphragm, a blank electrolyte and a lithium metal current collector into the CR2032 type button battery, and packaging.
Compared with the prior art, the invention has the beneficial effects that:
oxygen vacancies as a surface defect in CoO1-xOxygen Vacancies (OVs) are introduced on the surface, so that a large number of local electrons and unsaturated cations can be generated on the surface of the oxide, which contributes to effectively increasing CoO1-xElectrical conductivity and enhanced CoO1-xThe interaction with the LiPS promotes charge transfer, and the experimental result of the predecessor proves that the strategy can obviously improve the redox kinetics of the sulfur.
The invention firstly provides a synergistic reaction which combines a two-dimensional core-shell heterostructure and Oxygen Vacancies (OVs) to enhance the strength to the maximum extentCatalytic activity of metal oxide, converting ZIF-L array vertically grown on Carbon Cloth (CC) into two-dimensional core-shell Co/CoO with large amount of oxygen vacancy by two-step simple heat treatment1-xNanosheet array (CC @ Co/CoO)1-x). CoO with abundant OVs1-xThe porous shell and the LiPS have strong chemical interaction, can promote the fracture of S-S in the LiPS, and simultaneously has strong adsorption capacity of the LiPS. In addition, the Co core at the bottom of the nanosheet is combined with the carbon cloth to form a complete and continuous conductive framework network, so that the carbon cloth and CoO can be realized1-xThe surface is fast in electron transfer, and reaction kinetics of sulfur are enhanced. Due to these synergistic effects, Co/CoO1-xThe nanosheet can simultaneously realize strong LipS adsorption, rapid LipS conversion and Li2Rapid nucleation of S. Thus, CC @ Co/CoO is used1-xPositive electrode skeleton structure, even at sulfur loading up to 5.1mg cm-2Also in the case of (2), the electrochemical performance is excellent.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a CC @ Co/CoO representation of an embodiment of the present invention1-xSEM picture of (1);
FIG. 2 is a CC @ Co/CoO representation of an embodiment of the present invention1-xA) STEM and b) EDS line scan, c) HRTEM image corresponding to the lower left square area in a) image;
FIG. 3 is CC @ Co/CoO of an embodiment of the present invention1-xA) an XRD pattern and b) a SAED diffraction pattern;
FIG. 4 is a CC @ Co/CoO representation of an embodiment of the present invention1-xAt 3.35A g-1(2C) Cyclic characteristics at current density;
FIG. 5 is a CC @ Co/CoO representation of an embodiment of the present invention1-xAt 167.5mA g-1-3.35A g-1(0.1-2C) rate characteristics at current density;
FIG. 6 shows CC @ Co/CoO according to an embodiment of the present invention1-xCycling profile at different sulfur loading per unit area.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments are further described in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and that the invention is not limited in this regard.
[ example 1]
A double-carbon cloth flexible lithium-sulfur battery is characterized in that: the lithium-sulfur battery is composed of a flexible positive electrode, a flexible negative electrode, a PP diaphragm, electrolyte and an aluminum-plastic film; the PP diaphragm is positioned between the flexible positive electrode and the flexible negative electrode; electrolyte is filled between the flexible positive electrode and the flexible negative electrode and the PP diaphragm; and aluminum-plastic films are packaged outside the flexible positive electrode and the flexible negative electrode. The frameworks of the flexible positive electrode and the flexible negative electrode are CC @ Co/CoO with two-dimensional porous core-shell structure and oxygen vacancy combination1-xA nanosheet array.
The CC @ Co/CoO1-xIs a nanosheet array with a two-dimensional porous core-shell structure and oxygen vacancy combination, and is characterized in that the nanosheet array is CC @ Co/CoO as shown in figure 11-xHaving a uniform nanosheet array structure, the CC @ Co/CoO1-xThe appearance is uniform; the CC @ Co/CoO1-xThe nano-sheet has nano-pores, and the nano-pores are derived from Co3O4The huge volume shrinkage during the conversion of the particles to Co (about 49%); the unique 2D porous structure makes CoO1-xThe nano-sheet has a high active site, has strong chemical interaction with the LiPS, and is favorable for promoting the breakage of S-S bonds in the LiPS. Co/CoO1-xIs formed by a plurality of irregular nano-sheets which are seamlessly connected together and are derived from H2Reduction of Co3O4Co atoms obtained by the nano particles are polymerized, and the structure is favorable for accelerating charge transfer and enhancing the structural stability. As shown in FIGS. 2a and 2b, STEM and line scan results indicate Co/CoO1-xThe nano sheet has a core-shell structure, and the metal Co at the bottom of the nano sheet is mainly distributed on the surface of the nano carbon cloth sheet and forms a continuous integrated conductive frame with the carbon cloth, so that rapid charge transmission can be realized, and the immobilized LiPS conversion can be accelerated. Due to thiophilic CoO1-xSynergism between the shell and the Co conductive core, CC @ Co/CoO1-xThe lithium-sulfur battery positive electrode framework structure has excellent rate performance and long cycle stability; HRTEM patternSolid Co/CoO1-xThe nanosheets have a core-shell structure, and the lattice spacing of 0.204nm corresponds to the (002) plane of crystalline Co (JCPDS No. 05-0727). At a thin outer shell with a thickness of about 2.5nm, 2 completely different lattice spacings were found: 0.240and 0.211nm correspond to the (111) face of CoO and the (200) face of CoO, respectively (JCPDS No. 48-1719). As shown in FIG. 3a, the CC @ Co/CoO1-xHas good crystallinity and has obvious characteristic peaks of Co and CoO. As shown in fig. 3b, can be in the CoO1-xMany lattice defects caused by oxygen vacancies, Co/CoO, were found in the shell1-xHas diffraction rings belonging to hcp Co and CoO, respectively.
A preparation method of the double-carbon-cloth flexible lithium-sulfur battery comprises the following specific steps:
the method comprises the following steps: preparing flexible positive and negative electrode frameworks:
1) 2.60g of 2-methylimidazole, 1.17g of Co (NO)3)2·6H2O is respectively dispersed in 80ml of deionized water, and then the two precursor solutions are uniformly mixed under magnetic stirring; putting a clean Carbon Cloth (CC) sheet into the mixed solution, storing for 4h at room temperature, taking out, washing with deionized water, and drying at 80 ℃ to obtain a CC @ ZIF-L precursor;
2) annealing CC @ ZIF-L for 2h at the heating rate of 2 ℃/min of 350 ℃ in the air atmosphere to obtain CC @ Co3O4Nanosheets;
3) mixing CC @ Co3O4In H2Annealing at 250 ℃ for 2h at the heating rate of 2 ℃/min under the mixed atmosphere of which the volume ratio of/Ar is 1:9 to obtain CC @ Co/CoO1-xA nanosheet array.
Step two: preparing a flexible positive electrode and a flexible negative electrode:
the obtained CC @ Co/CoO1-xCoating a layer of 1M lithium polysulfide solution on the surface of the anode as an active substance to obtain a flexible anode; melting 0.2-20 g of metal lithium, and then obtaining CC @ Co/CoO1-xSoaking in molten lithium for 3-120 s, absorbing a lithium source, and cooling to room temperature to obtain a flexible cathode;
step three: preparing a flexible lithium-sulfur battery:
and (3) adding a PP diaphragm between the flexible positive electrode obtained in the step one and the flexible negative electrode obtained in the step two, dripping 20-150 mu L of electrolyte, and packaging by using an aluminum-plastic film to obtain the flexible lithium-sulfur battery.
[ example 2]
A lithium-sulfur button cell, characterized in that: from CC @ Co/CoO1-xElectrode pole piece, Celgard 2400 diaphragm, lithium metal current collector and Li2S6Base electrolyte and blank electrolyte.
The CC @ Co/CoO1-xIs a nanosheet array with a two-dimensional porous core-shell structure and oxygen vacancy combination, and is characterized in that the nanosheet array is CC @ Co/CoO as shown in figure 11-xA plurality of irregular nano-sheets are connected together in a seamless way to form a uniform nano-sheet array, and the irregular nano-sheets are derived from H2Reduction of Co3O4Co atoms obtained by the nano particles are polymerized, and the structure is favorable for accelerating charge transfer and enhancing the structural stability. The CC @ Co/CoO1-xBeing porous nanoplatelets, the nanopores being of Co origin3O4The particles undergo a large volume shrinkage during the conversion to Co (about 49%). As shown in FIGS. 2a and 2b, STEM and line scan results indicate Co/CoO1-xThe nano sheet has a core-shell structure, and the metal Co at the bottom of the nano sheet is mainly distributed on the surface of the nano carbon cloth sheet and forms a continuous integrated conductive frame with the carbon cloth; as shown in FIG. 2c, HRTEM results confirmed that Co/CoO1-xThe nanosheets have a core-shell structure, and the lattice spacing of 0.204nm corresponds to the (002) plane of crystalline Co (JCPDS No. 05-0727). At a thin outer shell with a thickness of about 2.5nm, 2 completely different lattice spacings were found: 0.240and 0.211nm correspond to the (111) face of CoO and the (200) face of CoO, respectively (JCPDS No. 48-1719). As shown in FIG. 3a, the CC @ Co/CoO1-xThe crystallinity is good, and the characteristic peaks of metal Co and CoO are obvious; as shown in fig. 3b, can be in the CoO1-xMany lattice defects caused by oxygen vacancies, Co/CoO, were found in the shell1-xHas diffraction rings belonging to hcp Co and CoO, respectively. The CC @ Co/CoO1-xThe unique 2D porous structure of the nanosheet array enables CoO1-xThe nano-sheet has higher active site, has strong chemical interaction with the LiPS, and is beneficial to promoting the LiPSCleavage of the S-S bond. In addition, the Co at the bottom and the carbon cloth form a continuous integrated conductive framework, so that rapid charge transfer can be realized, and the conversion of the immobilized LiPS can be accelerated. Due to CoO1-xSynergistic interaction between the thiophilic shell and the Co conductive core, CC @ Co/CoO1-xThe lithium-sulfur button cell positive electrode framework structure has excellent rate performance and long cycle stability.
A preparation method of the lithium-sulfur button battery comprises the following specific steps:
the method comprises the following steps: CC @ Co/CoO1-xThe preparation of (1):
1) 2.60g of 2-methylimidazole, 1.17g of Co (NO)3)2·6H2O is respectively dispersed in 80mL deionized water, and then the two precursor solutions are uniformly mixed under magnetic stirring; putting a clean Carbon Cloth (CC) sheet into the mixed solution, preserving at room temperature for 4h, taking out, washing with deionized water, and drying at 80 ℃ to obtain a CC @ ZIF-L precursor; (ii) a
2) Annealing CC @ ZIF-L for 2h at the heating rate of 2 ℃/min of 350 ℃ in the air atmosphere to obtain CC @ Co3O4Nanosheets;
3) mixing CC @ Co3O4Is arranged at H2Annealing at 250 ℃ for 2h at the heating rate of 2 ℃/min under the mixed atmosphere of which the volume ratio of/Ar is 1:9 to obtain CC @ Co/CoO1-xA nanosheet array.
Step two: the CC @ Co/CoO obtained by the steps1-xAnd assembling the lithium-sulfur button battery. The specific assembling process is as follows:
1) preparing a blank electrolyte: first 1.0M LiTFSI, 2 wt.% LiNO3Adding the mixture into a mixed solution with a volume ratio of DOL/DME of 1:1, and placing the mixture on a magnetic stirrer to be uniformly stirred and mixed to obtain blank electrolyte.
2) Preparing a sulfur-based electrolyte: mixing sulfur powder and Li in a mass ratio of 5:12Adding the S powder into the blank electrolyte, and placing the mixture on a magnetic stirrer to be stirred and mixed uniformly to obtain L2S6A sulfur-based electrolyte.
3) Assembling the battery: mixing CC @ Co/CoO1-xDrying in a vacuum drying oven to remove water, cutting into circular electrode plate with diameter of 12mmH2O/O2(ii) assembling the cell in an Ar-filled glove box at less than 0.1ppm, sequentially mixing CC @ Co/CoO1-xPole piece, L2S6And adding a sulfur-based electrolyte, a Celgard 2400 diaphragm, a blank electrolyte and a lithium metal current collector into the CR2032 type button battery, and packaging.
The lithium-sulfur button cell, deposited Li2S completely covers Co/CoO1-xNanopores on nanosheets, Li2The S is uniformly deposited, so that ions/electrons can be rapidly transmitted in the circulating process, and the S plays an important role in excellent electrochemical performance. The excellent cycling stability is due to CC @ Co/CoO1-xThe positive electrode framework structure can realize excellent structural stability and Li at the same time2Controlled deposition of S.
The lithium-sulfur button cell is shown in figure 1, and the metal/metal oxide CC @ Co/CoO1-xIs an array structure consisting of uniform self-supporting porous nano sheets.
The lithium-sulfur button cell, shown in FIG. 2, is Co/CoO1-xThe nano-sheet has a core-shell structure, and Co is mainly distributed in Co/CoO1-xThe core of the nanosheet.
The lithium-sulfur button cell is shown in figure 3, and the metal/metal oxide CC @ Co/CoO1-xThe crystalline property was good, and the diffraction peak included (002) plane of Co, (111) plane of CoO and (200) plane of CoO. A number of lattice defects caused by oxygen vacancies, Co/CoO, were found in the CoO shell1-xHas diffraction rings belonging to hcp Co and CoO, respectively.
The lithium sulfur button cell, as shown in FIG. 4, is at 3.35A g-1(2C) Has a reversible capacity of 527mAh g after circulating for 400 weeks at a high current density-1The coulombic efficiency is as high as 99.8%, the capacity decline of each week is only 0.023%, and the long-cycle performance is excellent.
The lithium sulfur button cell was operated at 167.5mA g as shown in FIG. 5-1(0.1C)、502.5mA g-1(0.3C)、837.5mA g-1(0.5C)、1.675A g-1(1C) And 3.35A g-1(2C) At current density, the reversible capacities were 1167, 1136, 1047, 897 and 701mAh g, respectively-1The current density was recovered to 167.5mA g-1After (0.1C) the capacity was 1204mAh g-1It was demonstrated that the reversible capacity retention rate was excellent.
The lithium sulfur button cell, as shown in FIG. 6, increases the sulfur loading per unit area from 2.03 to 5.10mg cm-2At 837.5mA g-1The excellent cycling stability is still achieved under the current density of (0.5C).
Claims (10)
1. A lithium-sulfur battery is composed of a flexible positive electrode, a flexible negative electrode, a PP diaphragm, electrolyte and an aluminum-plastic film; the PP diaphragm is positioned between the flexible positive electrode and the flexible negative electrode; electrolyte is filled between the flexible positive electrode and the flexible negative electrode and the PP diaphragm; the flexible anode and the flexible cathode are externally packaged with an aluminum-plastic film, and the flexible anode and the flexible cathode are characterized in that: the frameworks of the flexible positive electrode and the flexible negative electrode are CC @ Co/CoO with two-dimensional porous core-shell structure and oxygen vacancy combination1-xA nanosheet array.
2. A preparation method of a lithium-sulfur battery comprises the following specific steps:
the method comprises the following steps: preparing flexible positive and negative electrode frameworks:
1) preparing a precursor of a zeolite imidazole ester (ZIF-L) framework structure CC @ ZIF-L: growing the ZIF-L nanosheets on carbon cloth to obtain CC @ ZIF-L;
2)CC@Co3O4the preparation of (1): annealing CC @ ZIF-L for 2h at the heating rate of 2 ℃/min and the temperature of 350 ℃ in the air atmosphere to obtain CC @ Co3O4I.e. Co3O4Coating CC by nanosheets;
3)CC@Co/CoO1-xthe preparation of (1): h2Mixing CC @ Co with Ar in the volume ratio of 1:93O4Annealing at the temperature rise rate of 2 ℃/min and the temperature of 240 ℃ and 260 ℃ for 2 h. Annealing at 250 ℃ for 2h is preferred, and CC @ Co/CoO with porous core-shell structure and oxygen vacancy combination cannot be obtained at other temperatures1-x；
Step two: preparing a flexible positive electrode and a flexible negative electrode:
the obtained CC @ Co/CoO1-xCoating a layer of 1M lithium polysulfide solution on the surface of the flexible film as an active substance to obtain the flexible filmA positive electrode; melting 0.2-20 g of metal lithium, and then obtaining CC @ Co/CoO1-xSoaking in molten lithium for 3-120 s, absorbing a lithium source, and cooling to room temperature to obtain a flexible cathode;
step three: preparing a flexible lithium-sulfur battery:
and (3) adding a PP diaphragm between the flexible positive electrode obtained in the step one and the flexible negative electrode obtained in the step two, dripping 20-150 mu L of electrolyte, and packaging by using an aluminum-plastic film to obtain the flexible lithium-sulfur battery.
3. A lithium sulfur button cell, characterized in that: from CC @ Co/CoO1-xFramework electrode pole piece, Celgard 2400 diaphragm, lithium metal current collector and Li2S6Sulfur-based electrolyte and blank electrolyte.
4. A preparation method of a lithium-sulfur button battery is characterized by comprising the following specific steps:
the method comprises the following steps: CC @ Co/CoO1-xPreparing a positive electrode framework structure:
1) preparing a CC @ ZIF-L precursor, and growing a ZIF-L nano sheet on a carbon cloth to obtain CC @ ZIF-L;
2)CC@Co3O4the preparation method comprises the steps of annealing CC @ ZIF-L for 2h at the heating rate of 2 ℃/min and the temperature of 350 ℃ in the air atmosphere to obtain CC @ Co3O4I.e. Co3O4CC coated by nano sheets;
3)CC@Co/CoO1-xpreparation: h2Mixing CC @ Co with Ar in the volume ratio of 1:93O4Annealing at the temperature rise rate of 2 ℃/min and the temperature of 240 ℃ and 260 ℃ for 2 h. Annealing at 250 ℃ for 2h is preferred, and CC @ Co/CoO with porous core-shell structure and oxygen vacancy combination cannot be obtained at other temperatures1-x；
Step two: the CC @ Co/CoO obtained by the steps1-xThe positive electrode framework structure is assembled into the lithium-sulfur button battery, and the specific assembling process comprises the following steps:
1) preparing a blank electrolyte: first 1.0M LiTFSI, 2 wt.% LiNO3Adding into mixed solution with volume ratio of DOL/DME 1:1, stirring and mixing uniformly on a magnetic stirrerA blank electrolyte was obtained.
2) Preparing a sulfur-based electrolyte: mixing sulfur powder and Li in a mass ratio of 5:12Adding the S powder into the blank electrolyte, and placing the mixture on a magnetic stirrer to be stirred and mixed uniformly to obtain Li2S6A sulfur-based electrolyte.
3) Assembling the battery: mixing CC @ Co/CoO1-xDrying in a vacuum drying oven to remove water, cutting into circular electrode plate with diameter of 12mm, and drying in a vacuum drying oven2O/O2(ii) assembling the cell in an Ar-filled glove box at less than 0.1ppm, sequentially mixing CC @ Co/CoO1-xAnd adding the pole piece, the sulfur-based electrolyte, the Celgard 2400 diaphragm, the blank electrolyte and the lithium metal current collector into the CR2032 type button battery, and packaging.
5. The method of claim 4, wherein the CC @ Co/CoO is selected from the group consisting of1-xIs a nanosheet array combining a two-dimensional porous core-shell structure and an oxygen vacancy, CC @ Co/CoO1-xHaving a uniform nanosheet array structure, said CC @ Co/CoO1-xThe appearance is uniform.
6. The method of claim 4, wherein the CC @ Co/CoO is selected from the group consisting of1-xHas obvious characteristic peaks of Co and CoO; the CC @ Co/CoO1-xThe unique 2D porous structure of the nanosheet array enables CoO1-xThe nano-sheet has a high active site, has strong chemical interaction with the LiPS, and is favorable for promoting the breakage of S-S bonds in the LiPS.
7. The method of claim 4, wherein the CC @ Co/CoO is selected from the group consisting of1-xThe bottom Co forms a continuous integral conductive frame with the carbon cloth due to the CoO1-xThe synergistic effect between the thiophilic shell and the Co conductive core can realize rapid charge transfer so as to accelerate the conversion of the immobilized LiPS.
8. The lithium thionine of claim 4The preparation method of the button cell is characterized in that the Co/CoO1-xThe nano-sheet has a core-shell structure of CC @ Co/CoO1-xIn the nano-sheet, Co at the bottom is mainly distributed on the surface of the nano-carbon cloth sheet, and the lattice spacing of 0.204nm corresponds to the (002) plane (JCPDS No.05-0727) of crystalline Co.
9. The method of claim 4, wherein the CC @ Co/CoO is selected from the group consisting of1-xCoO in nanosheets1-xHaving lattice defects in the shell caused by oxygen vacancies, Co/CoO1-xHas diffraction rings belonging to hcp Co and CoO, respectively.
10. The method of claim 4, wherein the CC @ Co/CoO is selected from the group consisting of1-xIs formed by a plurality of irregular nano-sheets which are seamlessly connected together, wherein the irregular nano-sheets are derived from H2Reduction of Co3O4Co atoms obtained by the nano particles are polymerized, and the structure is favorable for accelerating charge transfer and enhancing the structural stability. The nanopores are from Co3O4The enormous volume shrinkage during the conversion of the particles to Co.
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