1. Ein Kathodenverbundwerkstoff auf Basis von ternärem Oxid für eine Lithium-Schwefel-Batterie, beinhaltend: Schwefel und LiNi0,8Co0,15Al0,05O2 oder LiNixCoyMn1-x-yO2 (0 < x < 1, 0 < y< 1, 0 < x + y < 1) als einen Wirt, wobei ein Schwefelgehalt 50 Gew.-% bis 80 Gew.-% beträgt.

2. Kathodenverbundwerkstoff auf Basis von ternärem Oxid gemäß Anspruch 1, wobei das LiNi0,8Co0,15Al0,05O2 eine Schichtstruktur aufweist, die ein sekundäres kugelförmiges Teilchen ist, das durch Akkumulieren von primären plattenförmigen Teilchen gebildet wird; ein Partikeldurchmesser des LiNi0,8Co0,15Al0,05O2 2-25 µm beträgt und eine Klopfdichte 2,0-2,6 g cm-3 beträgt.

3. Kathodenverbundwerkstoff auf Basis von ternärem Oxid gemäß Anspruch 1, wobei das LiNixCoyMn1-x-yO2 eine Schichtstruktur aufweist, die ein sekundäres Teilchen ist, das durch Akkumulieren von primären Teilchen gebildet wird; die sekundären Teilchen kugelförmig mit einem Durchmesser von 2-25 µm sind; das LiNixCoyMn1-x-yO2 eine spezifische Oberfläche von 10,0-100 m2 g-1 und eine Klopfdichte von 2,0-2,6 g cm-3 aufweist.

4. Ein Verfahren zum Herstellen eines Kathodenverbundwerkstoffs auf Basis von ternärem Oxid für eine Lithium-Schwefel-Batterie gemäß Anspruch 1, 2 oder 3, beinhaltend einen folgenden Schritt: Verbinden von Schwefel und einem Wirt durch ein einfaches Mischverfahren, ein Schmelzverfahren, ein Gasabscheidungsverfahren, ein Auflösungskristallisationsverfahren oder ein chemisches Abscheidungsverfahren.

5. Verfahren gemäß Anspruch 4, wobei das einfache Mischverfahren die folgenden Schritte beinhaltet: Mischen von Schwefel und LiNi0,8Co0,15Al0,05O2 oder LiNixCoyMn1-x-yO2 (0 < x < 1, 0 < y < 1, 0 < x + y < 1) im Verhältnis und anschließend Zermahlen, um den Kathodenverbundwerkstoff auf Basis von ternärem Oxid zu erhalten.

6. Verfahren gemäß Anspruch 4, wobei das Schmelzverfahren die folgenden Schritte beinhaltet: Mischen von Schwefel und LiNi0,8Co0,15Al0,05O2 oder LiNixCoyMn1-x-yO2 (0 < x < 1, 0 < y < 1, 0 < x + y < 1) im Verhältnis und Zermahlen, anschließend Platzieren einer erhaltenen Mischung in einem Reaktionskessel, der mit einem Gas gefüllt ist, das aus der Gruppe ausgewählt ist, die aus Stickstoff, Argon, Helium und Kohlenstoffdioxid besteht; Erhitzen des Reaktionskessels bei 100-200 °C über 2-20 h und Kühlen auf eine Raumtemperatur, um den Kathodenverbundwerkstoff auf Basis von ternärem Oxid zu erhalten.

7. Verfahren gemäß Anspruch 4, wobei das Gasabscheidungsverfahren die folgenden Schritte beinhaltet: Mischen von Schwefel und LiNi0,8Co0,15Al0,05O2 oder LiNixCoyMn1-x-yO2 (0 < x < 1, 0 < y < 1, 0 < x + y < 1) im Verhältnis und Zermahlen, anschließend Platzieren einer erhaltenen Mischung in einem Reaktionskessel, der mit einem Gas gefüllt ist, das aus der Gruppe ausgewählt ist, die aus Stickstoff, Argon, Helium und Kohlenstoffdioxid besteht; Erhitzen des Reaktionskessels bei 100-200 °C über 2-20 h und anschließend Erhitzen bei 250-350 °C über 2-12 h und Kühlen auf eine Raumtemperatur, um den Kathodenverbundwerkstoff auf Basis von ternärem Oxid zu erhalten.

8. Verfahren gemäß Anspruch 4, wobei das Auflösungskristallisationsverfahren die folgenden Schritte beinhaltet: Auflösen von Schwefel in einem Lösungsmittel, wobei ein Konzentrationsbereich des Schwefels in einer erhaltenen Lösung 1-20 mg ml-1 beträgt; anschließend Hinzufügen von LiNi0,8Co0,15Al0,05O2 oder LiNixCoyMn1-x-yO2 (0 < x < 1, 0 < y < 1, 0 < x + y < 1) zu der Lösung im Verhältnis und Rühren, um das Lösungsmittel verdunsten zu lassen; Trocknen und Abkühlen eines erhaltenen Feststoffs, um den Kathodenverbundwerkstoff auf Basis von ternärem Oxid zu erhalten; wobei das Lösungsmittel aus der Gruppe ausgewählt ist, die aus Schwefelkohlenstoff, Kohlenstofftetrachlorid, Benzol, Toluol, o-Xylen, m-Xylen, p-Xylen, Cyclohexan, Octan, Tetrachlorethen, Trichlorethen und Tetrachlorethan besteht.

9. Verfahren gemäß Anspruch 4, wobei das chemische Abscheidungsverfahren die folgenden Schritte beinhaltet: vollständiges Mischen von LiNi0,8Co0,15Al0,05O2 oder LiNixCoyMn1-x-yO2 (0 < x < 1, 0 < y < 1, 0 < x + y < 1) mit einer Sulfidlösung und tröpfchenweises Hinzufügen einer Säurelösung, um durch Reaktion der Sulfidlösung und der Säurelösung Schwefel zu erhalten; Schleudern und Trocknen, um den Kathodenverbundwerkstoff auf Basis von ternärem Oxid zu erhalten; wobei die Sulfidlösung eine Natriumthiosulfat- oder Natriumpolysulfidlösung mit einer Konzentration von 0,01-1 mol l-1 ist; die Säurelösung aus der Gruppe ausgewählt ist, die aus Schwefelsäure, Salzsäure, Salpetersäure, Phosphorsäure, Essigsäure und Ameisensäure mit einer Konzentration von 0,1-10 mol l-1 besteht; eine Reaktionszeit 0,5-6 h beträgt.

10. Eine Lithium-Schwefel-Batterie, die eine Kathodenplatte beinhaltet, die aus dem Kathodenverbundwerkstoff auf Basis von ternärem Oxid gemäß Anspruch 1, 2 oder 3 hergestellt ist.

BACKGROUND OF THE PRESENT INVENTION

Field of Invention

[0001]The present invention relates to a technical field of electrode materials for lithium-sulfur batteries, and more particularly to a composite cathode material for lithium-sulfur battery based on nickel-cobalt-aluminum or nickel-cobalt-manganese ternary materials and a preparation method thereof.

Description of Related Arts

[0002]In recent years, more and more new energy vehicles are entering people's lives. The development of new energy vehicles can help optimize the energy structure and solve the environmental problems caused by traditional fuels. However, the development of new energy vehicles relies on the reliable power storage system with high safety. As an efficient and clean energy storage system commonly used in new energy vehicles, electrochemical batteries not only need to have high safety, but also need to have high energy density. Although the current development momentum of electric vehicles is high, the proportion is still less than 1%. One of the factors is the energy density of the battery. It is reported that the extreme value of the energy density of electric vehicles equipped with lithium-ion batteries is only about 1/40 of that of fuel vehicles. At the same time, low volumetric energy density of the battery pack will cause the battery pack to be too large and occupy a larger space in the car, which will adversely affect the design and driving experience of new energy vehicles. Conventionally, the energy density of commercial lithium-ion batteries can reach 200-250 Wh kg -1< , but it is still difficult to meet the booming needs of the industry. Therefore, in order to accelerate the development of new energy vehicles, it is urgent to optimize the conventional energy structure, and develop a new high-energy density battery system.

[0003]There are two common methods to increase the energy density of the battery. One is to reduce the parts that do not contribute to the capacity, such as current collectors and binders. The second method is to increase the capacity per unit mass or unit volume of the cathode and anode active materials. The first method has limited effect on increasing the energy density of the battery. Therefore, the cathode and anode active materials have become the key to increasing the energy density of the battery. In commercial lithium-ion batteries, the cathode materials with large molecular weight and small number of transferred electrons make little room for the improvement on energy density. Developing lightweight active materials with multi-electron reactions has become an effective way to increase the energy density of batteries (Energy & Environmental Science, 2010, 3, 174-189). Lithium-sulfur batteries, based on the two electrons reaction between the light-weight sulfur and lithium could offer a high gravimetric energy density of 2600 Wh kg -1< . And it has been regarded as one of the most promising high specific energy secondary battery systems in the future. However, the inherent insulation of sulfur and the "shuttle effect" of soluble intermediates reduce the utilization of active materials and shorten the cycle life. The elemental sulfur is usually combined with other conductive carbon materials to construct a sulfur/carbon composite cathode material to improve the conductivity of the active material, and the developed pore structure and large specific surface area of the carbon material are used to physically adsorb lithium polysulfides, thereby improving the cycle performance of the sulfur cathode to a certain extent. However, such physical adsorption cannot ensure the long-term cycle stability of the battery. At the same time, the density of carbon materials is small and the specific surface area is large, which is not conducive to the improvement of the volumetric energy density of cathode materials. Although sulfur loading of the conventional carbon based high-sulfur-loaded cathodes can be up to 10 mg cm -2< , (Advanced Materials, 2016, 28, 3374-3382), such material usually has a self-supporting structure made of carbon materials, such as graphene and carbon nanotubes. As a result, electrode sheets cannot be rolled, and gaps between the electrode sheets will increase the using of electrolyte. In addition, the dissolution and shuttle problems of lithium polysulfides still exist.

[0004]EP 3 114 721 A1 is a relevant state of the art document, disclosing active materials for Li/S batteries.

SUMMARY OF THE PRESENT INVENTION

[0005]An object of the present invention is to provide a ternary oxide based composite cathode material for lithium-sulfur battery, wherein polar adsorption and catalytic conversion of the ternary oxide on polar lithium polysulfides can slow down the diffusion and shuttle of lithium polysulfides and improve the electrochemical stability of lithium-sulfur batteries.

[0006]Accordingly, in order to accomplish the above objects, the present invention provides a ternary oxide based composite cathode material for a lithium-sulfur battery, comprising: sulfur and LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0007]Preferably, the LiNi 0.8 Co 0.15 Al 0.05 O 2 has a layered structure, which is a spherical secondary particle formed by accumulating flake primary particles; a particle diameter of the LiNi 0.8 Co 0.15 Al 0.05 O 2 is 2-25 µm, and a tap density is 2.0-2.6 g cm -3< .

[0008]Preferably, the LiNi x Co y Mn 1-x-y O 2 has a layered structure, which is a secondary particle formed by accumulating primary particles; the secondary particles are spherical with a diameter of 2-25 µm; the LiNi x Co y Mn 1-x-y O 2 is LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 or LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and specific surface areas thereof are 46.72, 10.90, 12.73 and 10.40 m 2< g -1< , while tap densities are 2.09, 2.48, 2.46 and 2.56 g cm -3< .

[0009]The present invention also provides a method for preparing a ternary oxide based composite cathode material for a lithium-sulfur battery, comprising: compositing sulfur and the host by a simple mixing method, a melting method, a vapor deposition method, a dissolution-crystallization method, or a chemical deposition method.

[0010]Preferably, the simple mixing method comprises steps of: mixing sulfur and LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0011]Preferably, the melting method comprises steps of: mixing sulfur and LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0012]Preferably, the vapor deposition method comprises steps of: mixing sulfur and LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0013]Preferably, the dissolution-crystallization method comprises steps of: dissolving sulfur in a solvent, wherein a concentration range of the sulfur in a solution obtained is 1-20 mg mL -1< ; then adding LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0014]Preferably, the chemical deposition method comprises steps of: fully mixing LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0015]The present invention also provides a lithium-sulfur battery, comprising a cathode plate made of the ternary oxide based composite cathode material as mentioned above.

[0016]The present invention uses LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0017]LiNi 0.8 Co 0.15 Al 0.05 O 2 and LiNi x Co y Mn 1-x-y O 2 (0
BRIEF DESCRIPTION OF THE DRAWINGS

[0018] FIG. 1 is a graph showing cycle performance of composite cathode materials according to examples 1-5 at 0.1C; FIG. 2 is a graph showing cycle performance of the composite cathode material according to example 1 at stepped rates; FIG. 3 is XRD patterns of the composite cathode materials according to examples 6-9; FIG. 4 is TG patterns of the composite cathode materials according to the examples 6-9 and a contrast example; FIG. 5 is a discharge specific capacity diagram of lithium-sulfur batteries according to the examples 6-9 and the contrast example at 0.1C; FIG. 7 is a graph showing volumetric capacities of the composite cathode materials according to the example 4 and the contrast example at 0.1C.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0019]Generally, the present invention provides a ternary oxide based composite cathode material for a lithium-sulfur battery, comprising: sulfur and LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0020]Accordingly, the host material is a nickel-cobalt-aluminum ternary material or a nickel-cobalt-manganese ternary material, which is a commercialized lithium-ion battery cathode material. The host material is combined with the sulfur as the cathode material of the lithium-sulfur battery. The raw materials are readily available and the method is simple.

[0021]As the sulfur host material in the cathode material of the lithium-sulfur battery, the nickel-cobalt-aluminum ternary material can provide strong adsorption and catalysis to lithium polysulfides, so as to effectively inhibit the dissolution of lithium polysulfide, alleviate the shuttle effect, and provide high specific capacity and high cycle stability to the battery.

[0022]As the sulfur host material in the cathode material of the lithium-sulfur battery, the nickel-cobalt-manganese ternary material can provide strong chemical adsorption effect on polar lithium polysulfides. At the same time, the nickel-cobalt-manganese ternary material has a catalytic conversion effect on lithium polysulfides. It can reduce lithium polysulfides to thiosulfate, promote the conversion of lithium polysulfides, inhibit the dissolution of lithium polysulfides, and slow down the "shuttle effect", thereby obtaining a lithium-sulfur battery with high capacity and high stability.

[0023]The sulfur is one or both of precipitated sulfur and sublimated sulfur, and a mesh number of sulfur powder is 100-325 meshes.

[0024]In a preferred embodiment, the nickel-cobalt-aluminum ternary material is a commercialized lithium-ion battery material Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 , and a corresponding precursor is prepared by a co-precipitation method. The process is mature and can prepare on a large scale.

[0025]The Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 ternary material has a layered structure, which is a spherical secondary particle formed by accumulating primary particles, and sphericity is sufficient. A particle diameter is 2-25 µm, and a specific surface area is small. After being combined with the sulfur, it is convenient to prepare cathode plates in industry by smearing. At the same time, it can significantly reduce the using of electrolyte, increase the energy density of the battery, reduce the manufacturing cost, and improve the energy density of the battery.

[0026]A tap density of the Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 ternary material is relatively high, and measured values are 2.0-2.6 g cm -3< . A tap density of an S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 composite material obtained by mixing the Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 ternary material and the sulfur in proportion of 30:70 (mass ratio) is 1.5-2.0 g cm -3< . For comparison, a tap density of a sulfur/bp2000 composite cathode material obtained by mixing conventional commercial conductive carbon bp2000 and sulfur in proportion of 30:70 is 0.83 g cm -3< . The tap density of the S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 composite material of the present invention is higher than that of the S/bp2000 composite cathode material. Using the nickel-cobalt-aluminum ternary material as the lithium-sulfur battery cathode host material can increase the tap density of the cathode material, thereby increasing the volumetric energy density of the lithium-sulfur battery.

[0027]In a preferred embodiment, the LiNi x Co y Mn 1-x-y O 2 (0
[0028]The nickel-cobalt-manganese ternary material is a solid sphere formed by accumulating of the primary particles, which has a small specific surface area. Compared with nanomaterials and porous materials, it uses less electrolyte and increases the energy density of the battery.

[0029]The tap densities of S/LiNi 1/3 Co 1/3 Mn 1/3 O 2 , S/LiNi 0.5 C 0.2 Mn 0.3 O 2 , S/LiNi 0.6 Co 0.2 Mn 0.2 O 2 and S/LiNi 0.8 Co 0.1 Mn 0.1 O 2 composite material obtained by mixing the nickel-cobalt-manganese ternary material and the sulfur are 1.68, 1.77, 1.77, and 1.81 g cm -3< . The above-mentioned composite materials have high tap densities, which are beneficial to obtain high volumetric energy density cathode materials.

[0030]The above-mentioned ternary materials can be composited with the sulfur by different preparation methods to obtain the composite cathode material for the lithium-sulfur battery with a high sulfur content. Generally, the present invention also provides a method for preparing a ternary oxide based composite cathode material for the lithium-sulfur battery, comprising: compositing sulfur and the host by a simple mixing method, a melting method, a vapor deposition method, a dissolution-crystallization method, or a chemical deposition method.

[0031]In a detailed embodiment, the simple mixing method comprises steps of: mixing sulfur and LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0032]For example, the simple mixing method can adopt one or both of grinding and ball milling, wherein a grinding time is 15-60 min; a ball milling time is 15-120 min, and a ball milling speed is 50-600 rpm. A ball-to-material ratio is 1:1-50:1, and a solvent used for ball milling is selected from the group consisting of water, methanol, ethanol, isopropanol, and butanol.

[0033]In a detailed embodiment, the melting method comprises steps of: mixing sulfur and LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0034]In a detailed embodiment, the vapor deposition method comprises steps of: mixing sulfur and LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0035]In a detailed embodiment, the dissolution-crystallization method comprises steps of: dissolving sulfur in a solvent, wherein a concentration range of the sulfur in a solution obtained is 1-20 mg mL -1< ; then adding LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0036]In a detailed embodiment, the chemical deposition method comprises steps of: fully mixing LiNi 0.8 Co 0.15 Al 0.05 O 2 or LiNi x Co y Mn 1-x-y O 2 (0
[0037]Preferably, the sulfur is one or both of precipitated sulfur and sublimated sulfur, and a mesh number of sulfur powder is 100-325 meshes.

[0038]In another typical embodiment, the present invention also provides a lithium-sulfur battery, comprising a cathode plate made of the ternary oxide based composite cathode material as mentioned above. The cathode plate can be prepared by a smear method. For example, the composite cathode material, conductive carbon black and polyvinylidene fluoride (PVdF) can be added to N-methylpyrrolidone (NMP) and stirred to obtain cathode slurry; then the cathode slurry is coated on aluminum foil and dried in a drying box; finally, the cathode plate is cut into a round plate.

[0039]The technical solutions of the present invention will be further illustrated in the examples below. However, the examples and contrast example are used to explain the embodiments of the present invention and do not exceed the scope of the present invention. The protection scope of the present invention will not be limited by the examples. Unless otherwise specified, materials and reagents used in the present invention are commercially available in this field.

[0040]Examples 1-5 relate to a preparation method of an S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 composite cathode material and a lithium-sulfur battery prepared based on the composite cathode material.

Example 1

[0041]The Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 and the sulfur were fully mixed at a mass ratio of 30:70, and then kept at 155°C for 12 h under an argon atmosphere to obtain an S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 -1 composite cathode material.

[0042]The prepared composite cathode material was made into an electrode plate according to the following method, and was assembled into a battery for testing: weighing the S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 -1 composite cathode material, Super P and PVdF according to a mass ratio of 70:20:10, and fully mixing; adding an appropriate amount of NMP, and stirring for 4 h to obtain cathode slurry with a suitable viscosity (Super P, PVdF and NMP are all conventional reagents in the field); then coating the slurry on aluminum foil, and drying in a 60°C drying oven for 12 h; cutting a cathode plate obtained into a round plate with a diameter of 10 mm, and assembling into a button cell in a glove box filled with argon while using 10 µL electrolyte (per mg of sulfur); stabling for 4 h before testing the button cell on a battery test system by a charge and discharge program with a rate of 0.1 C rate and a voltage of 1.7-2.8 V; calculating a specific discharge capacity of the button cell based on a sulfur mass, wherein changes in discharge capacity with a number of cycles is shown in FIG. 1, and relevant data are shown in Table 1. In addition, a stepped rate charge and discharge test was also performed on the button cell, and lithium-sulfur battery stepped rate cycle of the S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 -1 composite material is shown in FIG. 2.

Example 2

[0043]The Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 and the sulfur were fully mixed at a mass ratio of 30:70, and then kept at 155°C for 8 h under an argon atmosphere before being heated to 300°C to obtain an S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 -2 composite cathode material.

[0044]The S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 -2 composite cathode material was fabricated into an electrode according to the method in example 1, and assembled into a battery for testing. The electrolyte dosage was 10 µL (per mg of sulfur). A specific discharge capacity of the battery was calculated based on a sulfur mass. Electrochemical performance test of the battery was carried out according to the method in example 1, wherein changes in discharge capacity with a number of cycles is shown in FIG. 1, and relevant data are shown in Table 1.

Example 3

[0045]The Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 and the sulfur were fully mixed at a mass ratio of 30:70, and then ground for 15-60 min to obtain an S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 -3 composite cathode material.

[0046]The S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 -3 composite cathode material was fabricated into an electrode according to the method in example 1, and assembled into a battery for testing. The electrolyte dosage was 10 µL (per mg of sulfur). A specific discharge capacity of the battery was calculated based on a sulfur mass. Electrochemical performance test of the battery was carried out according to the method in example 1, wherein changes in discharge capacity with a number of cycles is shown in FIG. 1, and relevant data are shown in Table 1.

Example 4

[0047]The sulfur was dissolved in CS 2 at a ratio of 5 mg mL -1< by stirring, and then the Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 was added with a mass ratio of 30:70 to sulfur, and stirred slowly at 60°C to evaporate solvent; a solid obtained was dried in vacuum and cooled to obtain an S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 -4 composite cathode material.

[0048]The S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 -4 composite cathode material was fabricated into an electrode according to the method in example 1, and assembled into a battery for testing. The electrolyte dosage was 10 µL (per mg of sulfur). A specific discharge capacity of the battery was calculated based on a sulfur mass. Electrochemical performance test of the battery was carried out according to the method in example 1, wherein changes in discharge capacity with a number of cycles is shown in FIG. 1, and relevant data are shown in Table 1.

Example 5

[0049]0.03 mol sodium thiosulfate was dissolved in 200 mL water (containing 1 wt.% PVP), then 0.24 g Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 was added, and 30mL dilute hydrochloric acid (5 wt.% ) was added drop by drop; sodium thiosulfate reacted with hydrochloric acid to obtain the sulfur, which was then deposited on a surface of the Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 ; the solution was centrifuged, washed and dried to obtain an S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 -5 composite cathode material.

[0050]The S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 -5 composite cathode material was fabricated into an electrode according to the method in example 1, and assembled into a battery for testing. The electrolyte dosage was 10 µL (per mg of sulfur). A specific discharge capacity of the battery was calculated based on a sulfur mass. Electrochemical performance test of the battery was carried out according to the method in example 1, wherein changes in discharge capacity with a number of cycles is shown in FIG. 1, and relevant data are shown in Table 1.

[0051]Referring to a graph showing cycle performance of composite cathode materials according to examples 1-5 at 0.1C (FIG. 1), the S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 composite cathode materials prepared by the melting method, the vapor deposition method, the simple mixing method, the dissolution-crystallization method, and the chemical deposition method all have excellent cycle performance, which shows that the nickel-cobalt-aluminum ternary material as the host material of the sulfur cathode of lithium-sulfur batteries can effectively fix sulfur. This is mainly due to the nickel-cobalt-aluminum ternary material is a polar oxide, which can absorb polysulfide ions with the help of chemical bonding, inhibit the "shuttle effect", and improve the cycle stability of the battery. FIG. 2 is a graph showing cycle performance of the composite cathode material according to the example 1 at stepped rates, which shows that the rate performance of the S/Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 composite cathode material for lithium-sulfur batteries is superior. At the same time, due to the high tap density, the nickel-cobalt-aluminum ternary material can improve the tap density of the cathode material after being combined with the sulfur, thereby increasing the energy density of the battery. The battery still achieves sufficient cycle performance at a lower electrolyte dosage (10 µL), indicating that the small specific surface area of the nickel-cobalt-aluminum ternary material is beneficial to reduce the using of electrolyte and increase the energy density of the battery as a whole.

[0052]Examples 6-11 relate to a preparation method of a sulfur/ LiNi x Co y Mn 1-x-y O 2 (0
Example 6

[0053]The nickel-cobalt-manganese ternary material used was a commercialized lithium-ion battery cathode material LiNi 1/3 Co 1/3 Mn 1/3 O 2 , in which a ratio of nickel, cobalt and manganese was 1:1:1. An XRD spectrum of the material is shown in FIG. 3. The LiNi 1/3 Co 1/3 Mn 1/3 O 2 and the sulfur was mixed at a mass ratio of 30:70, then ground and transferred to a reactor. After sealing, the reactor was placed in a muffle furnace and heated to 155°C at a rate of 2°C min -1< , and the temperature was kept for 12 h before cooling to a room temperature to obtain an S/LiNi 1/3 Co 1/3 Mn 1/3 O 2 composite cathode material for the lithium-sulfur battery. The sulfur content measured by TG was 69.67 wt.%, as shown in FIG. 4.

[0054]The prepared composite cathode material was made into an electrode plate according to the following process, and was assembled into a battery for testing:

(1) preparing the electrode plate adding S/LiNi 1/3 Co 1/3 Mn 1/3 O 2 composite cathode material, conductive carbon black and polyvinylidene fluoride (PVdF) to N-methylpyrrolidone (NMP) in a mass ratio of 70:20:10, and stirring for 4 h to obtain cathode slurry (both PVdF and NMP are conventional reagents in the field); then coating the slurry on aluminum foil, and drying in a 60°C drying oven for 12 h; cutting the cathode plate into a round plate with a diameter of 10 mm; (2) assembling the battery assembling the battery assembly in a glove box with argon atmosphere, wherein a button cell (type 2032) is assembled in an order of "negative case-shrapnel-gasket-lithium sheet-diaphragm-electrolyte-cathode plate-positive case"; a dosage of the electrolyte is 10 µL (per mg of sulfur), a diameter of the cathode plate is 10 mm, a diameter of the diaphragm is 16 mm, and a diameter of the lithium sheet is 14 mm; and (3) testing cycle performance stabling the assembled battery for 6 h before performing a constant current charge and discharge test, wherein a voltage range is 1.7-2.8 V, a current density is set 0.1 C (1 C=1675 mA g -1< ); calculating a specific discharge capacity of the button cell based on a sulfur mas to obtain a cycle performance curve of the button cell, as shown in FIG. 5. Specifically, the specific discharge capacity of the composite cathode material of the example 6 was 1255.0 mAh g -1< in the first week, and the specific discharge capacity after 50 cycles was 1050.3 mAh g -1< ; the capacity retention rate was 83.7%.

Example 7

[0055]The nickel-cobalt-manganese ternary material used was a commercialized lithium-ion battery cathode material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , in which a ratio of nickel, cobalt and manganese was 5:2:3. An XRD spectrum of the material is shown in FIG. 3. The LiNi 0.5 Co 0.2 Mn 0.3 O 2 and the sulfur was mixed at a mass ratio of 30:70, then ground and transferred to a reactor. After sealing, the reactor was placed in a muffle furnace and heated to 155°C at a rate of 2°C min -1< , and the temperature was kept for 12 h before cooling to a room temperature to obtain an S/LiNi 0.5 Co 0.2 Mn 0.3 O 2 composite cathode material. The sulfur content measured by TG was 71.25 wt.%, as shown in FIG. 4.

[0056]The composite cathode material was fabricated into an electrode plate according to the method in example 6, and assembled into a battery for testing. A specific discharge capacity of the battery was calculated based on a sulfur mass. Specifically, the specific discharge capacity of the composite cathode material of the example 7 was 1308.1 mAh g -1< in the first week, and the specific discharge capacity after 50 cycles was 968.5 mAh g -1< ; the capacity retention rate was 74.0%.

Example 8

[0057]The nickel-cobalt-manganese ternary material used was a commercialized lithium-ion battery cathode material LiNi 0.6 Co 0.2 Mn 0.2 O 2 , in which a ratio of nickel,cobalt and manganese was 6:2:2. An XRD spectrum of the material is shown in FIG. 3. The LiNi 0.6 Co 0.2 Mn 0.2 O 2 and the sulfur was mixed at a mass ratio of 30:70, then ground and transferred to a reactor. After sealing, the reactor was placed in a muffle furnace and heated to 155°C at a rate of 2°C min -1< , and the temperature was kept for 12 h before cooling to a room temperature to obtain an S/LiNi 0.6 Co 0.2 Mn 0.2 O 2 composite cathode material. The sulfur content measured by TG was 69.01 wt.%, as shown in FIG. 4.

[0058]The composite cathode material was fabricated into an electrode plate according to the method in example 6, and assembled into a battery for testing. A specific discharge capacity of the battery was calculated based on a sulfur mass. Specifically, the specific discharge capacity of the composite cathode material of the example 8 was 1037.4 mAh g -1< in