CN112968163A - Pre-lithiated tin-lithium alloy nanoparticles for lithium-sulfur battery, and preparation method and application thereof - Google Patents

Pre-lithiated tin-lithium alloy nanoparticles for lithium-sulfur battery, and preparation method and application thereof Download PDF

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CN112968163A
CN112968163A CN202110134562.5A CN202110134562A CN112968163A CN 112968163 A CN112968163 A CN 112968163A CN 202110134562 A CN202110134562 A CN 202110134562A CN 112968163 A CN112968163 A CN 112968163A
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tin
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徐士民
吕菲
徐宁
吴孟涛
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Tianjin B&M Science and Technology Co Ltd
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Abstract

The invention discloses a preparation method and application of a prelithiation tin-lithium alloy nano composite material lithium-sulfur positive electrode, which comprises the following steps: 1) preparing amorphous tin-lithium alloy nanoparticles; 2) preparing an amorphous tin-lithium alloy/conductive agent nano composite material; 3) preparing an amorphous tin-lithium alloy/conductive agent/sulfur nano composite anode material; 4) preparing a pre-lithiated tin-lithium alloy nano composite material lithium-sulfur positive electrode; 5) the pre-lithiation lithium-sulfur battery prepared by the method has good gram capacity and cycle performance, and the tin-lithium alloy has good application prospect in the lithium-sulfur battery.

Description

Pre-lithiated tin-lithium alloy nanoparticles for lithium-sulfur battery, and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a pre-lithiated tin-lithium alloy nanoparticle for a lithium-sulfur battery, and a preparation method and application thereof.
Background
Lithium ion secondary batteries have been increasingly used in the field of 3C and power batteries in recent years. Improving the energy density and cycle performance of the battery is an important direction of the lithium ion secondary battery. The elementary sulfur (S) of the positive electrode of the lithium-sulfur battery has the theoretical capacity of 1675mAh/g, the theoretical mass energy density of the lithium-sulfur battery formed by the elementary sulfur (S) and the metal lithium (Li) is 2600Wh/kg, the volume energy density of the lithium-sulfur battery is 2800Wh/L, and the lithium-sulfur battery has a good application prospect.
Lithium sulfur batteries, however, have faced a number of problems during use. First, elemental sulfur is an insulator with a normal temperature conductivity of 5 × 10-30S.cm-1Discharge product of lithium-sulfur battery, Li2Conductivity of S3.6X 10-7S.cm-1The generation of discharge products during use is very detrimental to the normal operation of the battery. Secondly, the elemental sulfur crystal density was 2.03g.cm-3Discharge product Li of positive electrode sulfur of lithium-sulfur battery in charge and discharge processes2The density of S is 1.67g.cm-3The active material is easily peeled off from the current collector due to a large volume change before and after charge and discharge. Finally, lithium polysulfide formed in the discharging process of the positive electrode of the lithium-sulfur battery is dissolved in electrode liquid, and the shuttle effect of the polysulfide is transferred to a negative electrode metal lithium sheet under the action of concentration gradient, so that reduction reaction is generated to generate lithium sulfide, and the capacity and the cycle performance of the battery are reduced.
In view of the problems of the lithium sulfur positive electrode material, many modifications have been made to the positive electrode material, in which the addition of a metal or a metal compound is one direction.
In the prior art, CN109713282A adds metal or metal compound into the positive electrode material, which can fix the intermediate product lithium polysulfide and show stronger chemical adsorption, thereby inhibiting shuttle effect of polysulfide ions and effectively improving the capacity exertion and cycling stability of the lithium-sulfur battery; in the prior art CN104752702B, metal oxide micro-nanotubes are added to the positive electrode, and the characteristic of high specific surface area of the nanotubes is utilized to better adsorb and inhibit the dissolution of polysulfide.
However, the positive electrode material prepared by the prior art still has the disadvantages of large polysulfide shuttling effect and irreversible capacity, and the like, because the metal/metal oxide material is compounded with sulfur in a physical mode in the prior art, the positive electrode material is not modified fundamentally, in addition, the traditional metal/metal oxide has limited chemisorption effect, and lithium dendrite formation is induced in the actual use process, and the battery performance of the material is reduced. Therefore, it is a technical problem in the art how to prepare a novel metal/metal oxide material with strong adsorbability and select a suitable way to complex with sulfur.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the pre-lithiated tin-lithium alloy nano particles and the preparation method and application thereof. The tin-lithium alloy and the sulfur are compounded, so that the active material stripping caused by the volume change of the positive active material in the charging and discharging process of the sulfur positive electrode can be reduced.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a pre-lithiated tin-lithium alloy nanoparticle characterized by: the chemical formula of the pre-lithiated tin-lithium alloy nano particles is LiaSnxAyBzWherein A is one or more metal elements, B is one or more nonmetal elements,
Figure BDA0002925923830000021
the pre-lithiated tin-lithium alloy nanoparticlesThe pellets are for addition to the positive electrode of a lithium sulfur battery.
Furthermore, I is more than or equal to 0.3 and less than 0.5.
Preferably, a is one or more elements of cobalt (Co), indium (In), manganese (Mn), titanium (Ti), aluminum (Al), iron (Fe), nickel (Ni), magnesium (Mg), copper (Cu), zirconium (Zr), niobium (Nb), tungsten (W), antimony (Sb), bismuth (Bi), vanadium (V), zinc (Zn), germanium (Ge), palladium (Pd), barium (Ba), and molybdenum (Mo); b is one or more elements of boron (B), carbon (C), nitrogen (N), phosphorus (P) and selenium (Se).
The proper doping element types and proportions are the premise of ensuring the specific capacity and stability of the tin-lithium alloy. The added metal and non-metal elements can well stabilize the crystal structure of the tin-lithium alloy, and the metal elements and the non-metal elements have covalent bonds due to different electronegativities, so that the crystal structure of the tin-lithium alloy can be kept stable in the battery cycle process, and the cycle performance of the lithium-sulfur battery is improved.
Further, A is one or two of cobalt (Co) and titanium (Ti), and the nonmetal element is one or two of carbon (C) and phosphorus (P). Compared with other elements, the atomic radius of Co and Ti is more suitable, and the Co and Ti are easy to be embedded into the crystal lattice of the Li-Sn alloy to play a role in stabilizing the crystal structure; the electronegativity of C and P is moderate, the C and P are easy to form bonding force with Li and Sn, the crystal structure is further stabilized, and the tin-lithium alloy nano particles prepared by adopting the elements have specific capacity and stability.
Preferably, the mass ratio of Sn wt.% is more than or equal to 50%, 50% > Li wt.% is more than or equal to 1%.
The crystal structure of the tin-lithium alloy structure is unstable in the battery cycle process due to excessive Sn; too little Sn, low content of tin-lithium alloy, too much Li, low negative electrode capacity, easy formation of lithium dendrite, too little Li, and increased irreversible capacity. Therefore, the selection of proper Sn and Li contents is an important factor for ensuring the using effect of the tin-lithium alloy.
Further, the Sn content is more than or equal to 90 wt% and more than or equal to 70 wt%, and the Li content is more than or equal to 15 wt% and more than or equal to 5 wt%.
Under the proportion, the prepared tin-lithium alloy has both stability and specific capacity and better comprehensive performance.
A process for preparing the amorphous pre-lithiated Sn-Li alloy nanoparticles includes atomizing and high-energy mechanical stirring ball-milling to obtain Sn-Li alloy compound LiaSnxAyBz。
Compared with single vacuum melting or mechanical stirring, the components of the tin-lithium alloy prepared by jointly using the atomization method and the mechanical method can be mixed on an atomic scale, and the components have the acting force of chemical covalent bonds instead of pure physical mixing.
A method for preparing a pre-lithiated lithium-sulfur battery positive electrode material comprises the following steps,
1) preparing pre-lithiated tin-lithium alloy nanoparticles having the formula LiaSnxAyBz；
2) Li prepared in the step 1)aSnxAyBzCarrying out mechanical ball milling and mixing with a conductive agent to obtain a composite material A;
3) mixing the composite material A, a sulfur source and a solvent according to a certain proportion, roasting in vacuum or inert atmosphere, and fully ball-milling a roasted product under the protection of inert atmosphere to obtain a composite material B;
4) dispersing the composite material B in a proper amount of organic solvent, adding a conductive agent, uniformly stirring and mixing, coating the mixture on a microporous copper foil, drying, and winding the dried microporous copper foil and a ceramic diaphragm coated with a binder on two sides to prepare a pre-lithiated lithium-sulfur battery anode;
5) assembling the pre-lithiation lithium sulfur battery anode and cathode obtained in the step 4), the ceramic diaphragm and the electrode solution into a lithium sulfur battery, and then carrying out formation to obtain the pre-lithiation lithium sulfur battery.
Tin sulfide (SnS and SnS)2) Has higher gram capacity (1130 mAh/g and 6400mAh/g), reacts the amorphous tin-lithium alloy with the sulfur anode to form a certain content of tin sulfide in the anode sulfur material, can reduce volume change of sulfur in the charge-discharge process, maintains the structural stability of the anode material, and improves the cycle。
Preferably, the conductive agent in step 2) is one or more of conductive carbon black, carbon nanotubes and graphene; and the mass ratio is more than 60 percent and more than 1 percent of the conductive agent/pre-lithiated tin-lithium alloy nano particles.
The capacity is reduced due to excessive conductive agent, the bonding performance of the pole piece is reduced, the conductive agent is too little, the internal resistance of the battery pole piece is increased, and the cycle performance of the battery is reduced.
Further, 20% > conductive agent/pre-lithiated tin-lithium alloy nanoparticles > 5%.
The sulfur source in the step 3) is one or more of elemental sulfur, monosulfide, chain sulfide and cyclic sulfide, and the mass percent of pure sulfur in the sulfur source is 30-100%; the ratio of the sulfur source to the composite material A is more than 95 wt% and more than or equal to 50 wt% in percentage by mass; the solvent is one or more of alkane, alcohol, ether, ketone and petroleum ether; the roasting conditions are as follows: the roasting temperature is 100-300 ℃, and the roasting time is 0.5-5 hours; the inert atmosphere is one or more of nitrogen, helium and argon.
The preferable sintering temperature in the experiment is suitable for elemental sulfur sublimation, sulfur compound pyrolysis and composite material A homogeneous reaction; the temperature is too low, and sulfur cannot be sublimated; the temperature is too high, and the sulfur can not react with the composite material A after being sublimated too fast; the sintering time is less than 0.5 hour, the reaction is insufficient, and the reaction time is more than 5 hours, so that the material is easy to sinter and is difficult to process.
Further, the mass percent of pure sulfur in the sulfur source is 80%; the roasting time is 1.5-2 hours, and the roasting time is more than 90 wt% and more than or equal to 80 wt% of the sulfur source/composite material A.
Preferably, the binder in step 4) may be selected from one or more of lithium polyacrylate, polyimide and polymethyl methacrylate; the conductive agent is one or more of conductive carbon black, carbon nano tubes and graphene; calculated by mass ratio, 20 percent more than 0.5 percent of conductive agent/composite material B;
further, the binder can be selected from one or two of lithium polyacrylate or polyimide;
preferably, the mass ratio is more than 15% and more than 5% of the conductive agent/composite material B.
Preferably, the formation conditions in step 5) are as follows: the formation temperature is 40-90 ℃, the formation pressure is 0.5-2 MPa, the formation time is 1-10 hours, the formation current is 0.1-1.5C, and the formation voltage is 1.5-2.3V.
And (3) bonding the double-sided adhesive-ceramic diaphragm and the microporous copper foil of the pre-lithiated tin-lithium alloy nano composite material together to prepare a pre-lithiated lithium-sulfur positive electrode, and applying the pre-lithiated lithium-sulfur positive electrode in a lithium-sulfur battery after formation in the step 5). The microporous copper foil can reduce the stress generated by volume change in the charge and discharge process of the anode material and reduce the stripping of the active substance.
Furthermore, the formation temperature is 60-90 ℃, the formation pressure is 1.0-1.5 MPa, the formation time is 3-5 hours, the formation current is 0.1-0.7C, and the voltage is 1.7-2.1V.
Use of prelithiated tin-lithium alloy nanoparticles in a lithium-sulfur battery.
A pre-lithiated lithium sulfur battery prepared according to the pre-lithiated lithium sulfur battery preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1. the gram capacity of the tin lithium is 990mAh/g, the tin alloy has a high-capacity lithium storage function, and the specific capacity of the lithium-sulfur battery can be effectively improved by adopting the tin-lithium alloy as an additive; and due to the covalent bond between the doped metal and the non-metal element, the amorphous tin alloy has better reversible cycle performance.
2. The prelithiation tin-lithium alloy is innovatively adopted as the positive electrode additive, and the prelithiation tin-lithium alloy optimized in components and proportion is adopted as the additive, so that the first coulombic efficiency of the lithium-sulfur battery can be effectively improved, the shuttle effect of the lithium-sulfur battery is reduced, the positive electrode conductivity of the lithium-sulfur battery is improved, and the cycle performance of the lithium-sulfur battery is improved.
3. The tin-lithium sulfide alloy and the sulfur powder are uniformly roasted at high temperature to react to synthesize an alloy-S compound, but are not purely physically mixed, so that the coulomb efficiency of the sulfur anode and the gram capacity of the electrode can be effectively improved, the volume change of the sulfur anode material in the charging and discharging process is reduced, and the battery cycle is improved.
4. The microporous copper is selected as the current collector in the preparation process of the lithium-sulfur battery, so that the stress generated by volume change in the charge and discharge process of the positive electrode material can be reduced, and the stripping of active substances is reduced.
5. The adhesive on the double-sided gluing ceramic diaphragm permeates among the active substance of the positive electrode material, the diaphragm and the current collector, can permeate and fix the gaps among the active substance of the positive electrode material, the diaphragm and the current collector, and can solidify the diaphragm, the active substance and the current collector, thereby improving the structural stability of the material, reducing the shuttling effect of lithium sulfide and the volume change of the positive electrode material, and improving the gram capacity of the material and the battery cycle.
6. The preparation process of the material is simple, flexible and easy to control, has good gram capacity, cycle performance and safety in the lithium ion secondary battery, and is suitable for industrial production.
Drawings
FIG. 1 is an XRD pattern of amorphous tin-lithium alloy powder prepared in example 1;
FIG. 2 is a capacity cycle decay curve of the pre-lithiated lithium sulfur soft package battery prepared in example 1 under the conditions of normal temperature, 25 ℃ and 0.5C charge and discharge;
FIG. 3 is an SEM image of an amorphous tin-lithium alloy prepared in example 2;
FIG. 4 is TEM and SAED images of amorphous tin-lithium sulfide alloy/single-walled carbon nanotube/sulfur nanocomposite cathode material prepared in example 5;
FIG. 5 is a particle size distribution diagram of tin-lithium alloy powder prepared in example 7;
FIG. 6 is an AFM image of a pre-physical lithium sulfur positive electrode piece prepared in example 9.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited thereto.
The raw materials used in the examples are all analytically pure, and the content is more than or equal to 99.9 percent.
Example 1
The preparation and application of the prelithiation tin-lithium alloy nano composite material lithium-sulfur positive electrode comprise the following steps:
according to the mass percentage of 70: 10: 25: 3: 5: 5 weighing simple substances of tin, lithium, cobalt, titanium, zinc and manganese, placing the simple substances into a vacuum smelting furnace, and then introducing high-speed 99.99% nitrogen through an aerosol method to prepare the tin-lithium alloy powder with uniform components. And placing the prepared tin-lithium alloy powder in a stirring ball mill, and carrying out ball milling for 50 hours under the protection of 99.99% nitrogen to prepare black amorphous tin-lithium alloy powder.
The black amorphous tin-lithium alloy powder is prepared by adding Single-walled Carbon nanotubes (SCNT) into 5 mass percent of the black amorphous tin-lithium alloy powder, and performing ball milling for 50 hours under the protection of 99.99 percent of nitrogen to prepare black powder.
Mixing the prepared mixed powder with elemental sulfur according to the mass percentage of 40%, adding NMP solvent, stirring uniformly at a high speed, placing the mixed solution in a vacuum oven, evaporating and recovering the NMP solvent under the protection of 99.99% nitrogen, stirring and heating the solid mixture to 200 ℃ under the protection of 99.99% nitrogen, reacting for 3 hours to obtain a partial vulcanized product, cooling the mixture to room temperature under the protection of 99.99% nitrogen, stirring and ball-milling for 10 hours under the protection of 99.99% nitrogen, and preparing the amorphous tin-lithium sulfide alloy/conductive agent/sulfur nano composite anode material.
Mixing the prepared composite positive electrode material, a conductive agent (SP) and a binder Polyimide (PI) according to the mass percentage of 90: 2: adding a certain mass of NMP, uniformly mixing in a vacuum constant-temperature high-speed stirrer, preparing to obtain pre-lithiation amorphous tin lithium sulfide alloy/conductive agent/sulfur nano composite anode material slurry, coating and drying the prepared slurry in a copper foil with the aperture of 8 microns and 30 microns, rolling, and winding by using a double-sided adhesive-coated ceramic PE diaphragm, wherein the specifications of the double-sided adhesive-coated ceramic PE diaphragm are that a single-sided adhesive PAALi is coated with 0.5 micron in thickness, the thickness of the diaphragm is 5 microns, and a single-sided adhesive PAALi is coated with 2 micron nano aluminum oxide and 0.5 micron in thickness. And (4) winding the lithium-sulfur battery to a thickness of 0.5 cm to prepare the pre-lithiated lithium-sulfur battery positive pole piece. In a 99.99% argon glove box, preparing a positive pole piece, forming a soft package battery by a 9-micron ceramic diaphragm and a lithium piece, and injecting electrolyte (volume ratio) EC: EMC: DEC: FEC (30: 40:20: 10), wherein 2 percent of FEC is addedVinylene Carbonate (VC), 3% Succinonitrile (SN), 1.0M lithium hexafluorophosphate (LiPF)6) 0.2M lithium bistrifluoromethanesulfonylimide (LiTFSI). And (3) after the pre-lithiation tin-lithium alloy nano composite material lithium-sulfur soft package battery is formed at 80 ℃ and under 1.0MPa, carrying out 0.5C charge-discharge cycle test on a charge-discharge test cabinet at 25 ℃.
Example 1 the test results are as follows:
FIG. 1 is an XRD pattern of amorphous tin-lithium alloy powder obtained by preparation;
fig. 2 is a 50-cycle capacity retention for soft-packed lithium sulfur cells prepared in example 1.
Example 2
The preparation conditions of the prelithiated tin-lithium alloy nanocomposite lithium-sulfur positive electrode are the same as example 1, except that: according to the mass percentage of 80: 5: 10: and 5, weighing the simple substances of tin, lithium, cobalt and iron, and preparing the tin-lithium alloy powder with uniform components. Other pole piece fabrication and cell assembly were the same as in example 1.
Fig. 3 is an SEM image of amorphous tin-lithium alloy prepared in example 2.
Example 3
The preparation conditions of the prelithiated tin-lithium alloy nanocomposite lithium-sulfur positive electrode are the same as example 1, except that: according to the mass percentage of 60: 20: 15: and 5, weighing simple substances of tin, lithium, cobalt and aluminum, and preparing the tin-lithium alloy powder with uniform components. Other pole piece fabrication and cell assembly were the same as in example 1.
Example 4
The preparation conditions of the prelithiated tin-lithium alloy nanocomposite lithium-sulfur positive electrode are the same as example 1, except that: according to the mass percentage of 60: 25: 10: and 5, weighing simple substances of tin, lithium, cobalt and aluminum, and preparing the tin-lithium alloy powder with uniform components. Other pole piece fabrication and cell assembly were the same as in example 1.
Example 5
The preparation conditions of the prelithiated tin-lithium alloy nanocomposite lithium-sulfur positive electrode are the same as example 1, except that: according to mass percentage 55: 30: 10: and 5, weighing simple substances of tin, lithium, cobalt and aluminum, and preparing the tin-lithium alloy powder with uniform components. Other pole piece fabrication and cell assembly were the same as in example 1.
The table is a comparison of first charge and discharge coulombic efficiencies and discharge capacities for examples 1, 2, 3, 4 and 5.
FIG. 4 is TEM and SAED images of amorphous tin-lithium sulfide alloy/single-walled carbon nanotube/sulfur nanocomposite cathode material prepared in example 5;
example 6
The preparation conditions of the prelithiated tin-lithium alloy nanocomposite lithium-sulfur positive electrode are the same as example 1, except that: adding 5 mass percent of Graphene (Graphene) into the black amorphous tin-lithium alloy powder, and carrying out ball milling for 50 hours under the protection of 99.99 mass percent of nitrogen to prepare black powder. Other pole piece fabrication and cell assembly were the same as in example 1.
Example 7
The preparation conditions of the prelithiated tin-lithium alloy nanocomposite lithium-sulfur positive electrode are the same as example 1, except that: the black amorphous tin-lithium alloy powder is prepared by adding 10 mass percent of multi-walled Carbon nanotubes (MCNT, multiple Wall Carbon Nanotube) and ball milling for 50 hours under the protection of 99.99 mass percent of nitrogen to prepare black powder. Other pole piece fabrication and cell assembly were the same as in example 1.
Mixing the prepared mixed powder with elemental sulfur according to the mass percentage of 55%.
FIG. 5 is a particle size distribution diagram of tin-lithium alloy powder particles prepared in example 7.
Example 8
The preparation conditions of the prelithiated tin-lithium alloy nanocomposite lithium-sulfur positive electrode were the same as in example 7, except that: and mixing the prepared amorphous tin-lithium alloy and multi-wall carbon nano tube mixed powder with elemental sulfur according to the mass percentage of 20%. Other pole piece fabrication and cell assembly were the same as in example 1.
Example 9
The preparation conditions of the prelithiated tin-lithium alloy nanocomposite lithium-sulfur positive electrode were the same as in example 7, except that: mixing the prepared amorphous tin-lithium alloy and multi-wall carbon nano tube mixed powder with elemental sulfur according to the mass percentage of 10%. Other pole piece fabrication and cell assembly were the same as in example 1.
FIG. 6 is an AFM image of a pre-physical lithium sulfur positive electrode piece prepared in example 9.
Example 10
The preparation conditions of the prelithiated tin-lithium alloy nanocomposite lithium-sulfur positive electrode were the same as in example 7, except that: and mixing the prepared amorphous tin-lithium alloy and multi-wall carbon nano tube mixed powder with elemental sulfur according to the mass percentage of 30%. Other pole piece fabrication and cell assembly were the same as in example 1.
Second table shows the first discharge capacity and first charge-discharge coulombic efficiency comparison of examples 1, 7, 8, 9 and 10.
Results of the experiment
Characterization of Material Properties
1) The crystal structure test is carried out on a Japan Shimadzu X-ray diffractometer XRD-7000, the copper target has the scanning speed of 2 degrees/minute, the test precision of +/-0.04 degrees and the scanning range of 10-90 degrees.
FIG. 1 is the XRD pattern of the amorphous tin-lithium alloy prepared in example 1.
2) The surface morphology of the material was carried out on a scanning electron microscope SEM of model EV018 from Zeiss, Germany.
Fig. 3 is an SEM image of amorphous tin-lithium alloy prepared in example 2.
3) The material morphology characterization was performed on a JEM-200CX transmission electron microscope, Japan Electron Co.
FIG. 4 is TEM and SAED images of amorphous tin-lithium sulfide alloy/single-walled carbon nanotube/sulfur nanocomposite cathode material prepared in example 5;
4) particle size characterization was performed on malvern 3000.
FIG. 5 is a particle pattern of tin-lithium alloy powder prepared in example 7.
5) Characterization of the pole piece morphology was performed in AFM mode on VEECO SPM.
FIG. 6 is an AFM image of a pre-physical lithium sulfur positive electrode piece prepared in example 9.
Battery electrical performance testing
The prepared battery cell is carried out on a soft-package battery cell test cabinet, the gram capacity of the anode material is calculated by charging and discharging at 25 ℃ and 0.2C under the test voltage of 1.55-3.0V, and the charging and discharging cycle test at 0.5C is carried out.
Fig. 2 is 50-cycle capacity retention of the soft-packed lithium sulfur cell prepared in example 1, and electrochemical properties of the materials are shown in tables 1 and 2.
TABLE 1 comparison of first discharge capacity and first charge-discharge coulombic efficiency for examples 1, 2, 3, 4 and 5
Figure BDA0002925923830000121
TABLE 2 comparison of first discharge capacity and first charge-discharge coulombic efficiency for examples 1, 7, 8, 9 and 10
Figure BDA0002925923830000122
The physical, chemical and electrical properties of the prepared material are characterized. Fig. 1 is an XRD spectrum of amorphous tin-lithium alloy powder prepared in example 1, and fig. 2 is a capacity cycling decay curve of pre-lithiated lithium-sulfur soft package battery prepared in example 1 under the conditions of normal temperature, 25 ℃ and 0.5C charge and discharge. Therefore, the capacity retention rate of the material prepared in the embodiment 1 can reach 95% after 50 cycles, and the material prepared in the invention has good stability and the first discharge gram capacity can reach 945 mAh/g. It can be seen from tables 1 and 2 that the samples prepared in the examples have higher first-time discharging gram capacity and charging and discharging efficiency, and the tin-lithium alloy particles are better applied to the lithium-sulfur battery.
Fig. 3 is an SEM image of the amorphous tin-lithium alloy prepared in example 2, which shows that the prepared tin-lithium alloy has uniform particle size and a clear interface. FIG. 4 is TEM and SAED images of amorphous tin-lithium sulfide alloy/single-walled carbon nanotube/sulfur nanocomposite cathode material prepared in example 5; FIG. 5 is a particle spectrum of tin-lithium alloy powder prepared in example 7, revealing the particle size distribution, in which the median particle size is concentrated between 20 and 30 μm. FIG. 6 is an AFM image of a pre-physical lithium sulfur positive electrode piece prepared in example 9. Therefore, the positive pole piece has uniform thickness and good uniformity.
In summary, the disclosure of the present invention is not limited to the above-mentioned embodiments, and persons skilled in the art can easily set forth other embodiments within the technical teaching of the present invention, but such embodiments are included in the scope of the present invention.

Claims (10)

1. A pre-lithiated tin-lithium alloy nanoparticle characterized by: the chemical formula of the pre-lithiated tin-lithium alloy nano particles is LiaSnxAyBzWherein A is one or more metal elements, B is one or more nonmetal elements,
Figure FDA0002925923820000011
the pre-lithiated tin-lithium alloy nanoparticles are for addition to the positive electrode of a lithium-sulfur battery.
2. The prelithiated tin-lithium alloy nanoparticle of claim 1, wherein: a is one or more elements of cobalt (Co), indium (In), manganese (Mn), titanium (Ti), aluminum (Al), iron (Fe), nickel (Ni), magnesium (Mg), copper (Cu), zirconium (Zr), niobium (Nb), tungsten (W), antimony (Sb), bismuth (Bi), vanadium (V), zinc (Zn), germanium (Ge), palladium (Pd), barium (Ba) and molybdenum (Mo); the B is one or more elements of boron (B), carbon (C), phosphorus (P) and selenium (Se).
3. The prelithiated tin-lithium alloy nanoparticle of claim 1, wherein: calculated by mass ratio, more than or equal to 90% of Sn is more than or equal to 70%, and more than or equal to 15% of Li is more than or equal to 5%.
4. A method of preparing the prelithiated tin-lithium alloy nanoparticles of any of claims 1 to 3, comprising the steps of: the preparation method comprises an atomization method and a mechanical stirring ball milling method, wherein tin, lithium, metal elements and non-metal elements are mixed in the atomization melting and mechanical stirring ball milling processesUniformly mixed to form a tin-lithium alloy compound LiaSnxAyBz。
5. A method for preparing a pre-lithiated lithium-sulfur battery, comprising the steps of:
1) preparing pre-lithiated tin-lithium alloy nanoparticles having the formula LiaSnxAyBz；
2) Li prepared in the step 1)aSnxAyBzCarrying out mechanical ball milling and mixing with a conductive agent to obtain a composite material A;
3) mixing the composite material A, a sulfur source and a solvent according to a certain proportion, roasting in vacuum or inert atmosphere, and fully ball-milling a roasted product under the protection of inert atmosphere to obtain a composite material B;
4) dispersing the composite material B in a proper amount of solvent, adding a conductive agent, uniformly stirring and mixing, coating the mixture on a microporous copper foil, drying, and winding the dried microporous copper foil and a ceramic diaphragm coated with a binder on two sides to prepare a pre-lithiated lithium-sulfur battery anode;
5) assembling the pre-lithiation lithium sulfur battery anode and cathode obtained in the step 4), the ceramic diaphragm and the electrode solution into a lithium sulfur battery, and then forming to obtain the pre-lithiation lithium sulfur battery.
6. The method of preparing a pre-lithiated lithium sulfur battery of claim 5, wherein: the conductive agent in the step 2) is one or more of conductive carbon black, carbon nano tubes and graphene; and the mass ratio is more than 60 percent and more than 1 percent of the conductive agent/pre-lithiated tin-lithium alloy nano particles.
7. The method of preparing a pre-lithiated lithium sulfur battery of claim 5, wherein: the sulfur source in the step 3) is one or more of elemental sulfur, monosulfide, chain sulfide and cyclic sulfide, the mass percent of pure sulfur in the sulfur source is 30-100%, and the mass percent of the pure sulfur in the sulfur source is more than 95 wt% and more than or equal to 50 wt% of the sulfur source/composite material A; the solvent is one or more of alkane, alcohol, ether, ketone and petroleum ether; the roasting conditions are as follows: the roasting temperature is 100-300 ℃, and the roasting time is 0.5-5 hours; the inert atmosphere is one or more of nitrogen, helium and argon.
8. The method of preparing a pre-lithiated lithium sulfur battery of claim 5, wherein: the conductive agent in the step 4) is one or more of conductive carbon black, carbon nano tubes and graphene, and the weight percentage of the conductive agent/composite material B is more than 20 and 0.5; the binder is one or more of lithium polyacrylate, polyimide and polymethyl methacrylate.
9. The method of preparing a pre-lithiated lithium sulfur battery of claim 5, wherein: the formation conditions in the step 5) are as follows: the formation temperature is 40-90 ℃, the formation pressure is 0.5-2 MPa, the formation time is 1-10 hours, the formation current is 0.1-1.5C, and the formation voltage is 1.5-2.3V.
10. The pre-lithiated lithium sulfur battery prepared by the method of preparing a pre-lithiated lithium sulfur battery according to any one of claims 5 to 9.
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