CN111244492B - High-specific-energy primary lithium-sulfur battery and application thereof - Google Patents
High-specific-energy primary lithium-sulfur battery and application thereof Download PDFInfo
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- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
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Abstract
The invention relates to a high-specific-energy primary lithium-sulfur battery and application thereof, wherein the battery comprises a negative electrode, a positive electrode, a diaphragm and electrolyte, the positive electrode is made of a sulfur-carbon composite positive electrode material, the sulfur-carbon composite positive electrode material comprises a sulfur simple substance, conductive carbon black and a binder, the electrolyte comprises lithium salt, a solvent and a diluent, the solvent is acetonitrile, and the addition ratio of the electrolyte to the sulfur simple substance is (0.2-3) mL:1 g. Compared with the prior art, the lithium-sulfur battery provided by the invention has the advantages that the dissolution of polysulfide is greatly inhibited, the addition of electrolyte in the lithium-sulfur battery is reduced, the utilization rate of positive active substances in the lithium-sulfur battery is improved, and the lithium-sulfur battery has extremely high energy density compared with the traditional lithium-ion battery.
Description
Technical Field
The invention relates to the technical field of lithium metal batteries, in particular to a high-specific-energy primary lithium-sulfur battery and application thereof.
Background
The lithium ion battery is inseparable from the human society, is widely applied to aspects of human production and life, and is widely used in the fields of energy storage power grids, mobile communication, electric automobiles, aerospace and the like. Conventional lithium ion batteries use lithium metal oxides (e.g., lithium cobaltate LiCoO)2LiNi, a ternary materialxCoyMn1-x-yO2) Or lithium iron phosphate (LiFePO)4) As the anode and the graphite as the cathode, the theoretical specific capacity of the electrode material is lower, the theoretical energy density is relatively lower, and the wide application of the lithium ion battery in the emerging application field requiring high specific energy and high energy density is limited. The lithium-sulfur battery uses sulfur as a positive electrode and lithium metal as a negative electrode, since sulfur and lithium metal have 1672mAh g, respectively-1And 3860mAh g-1Has a theoretical specific capacity of approximately 2600Wh kg-1The theoretical energy density of the energy storage system attracts people's extensive attention and is considered as a new generation energy storage system with great application prospect.
However, the lithium sulfur battery still has many problems, which limit the practical application of the lithium sulfur battery, and firstly, the elemental sulfur of the positive electrode in the lithium sulfur battery is not conductive, and a large amount of conductive carbon needs to be added, so that the content of the active material of the positive electrode is low. Secondly, the electrolyte in the lithium-sulfur battery is usually an ether electrolyte, in the electrolyte, the discharging process of the lithium-sulfur battery is divided into two stages, in the first stage, sulfur is converted into soluble polysulfide and is dissolved in the electrolyte, so that a relatively serious shuttle effect is caused, and the battery needs a large amount of electrolyte to meet the dissolution of the polysulfide, and the excessive electrolyte is added, so that the actual energy density of the lithium-sulfur battery is severely limited, the actual energy density of the lithium-sulfur battery is far lower than that of the traditional lithium-ion battery, and the commercialization of the lithium-sulfur battery is difficult to realize.
Patent CN104143614A discloses a new system of lithium-sulfur battery, which comprises an electrolyte and a separator matched with the electrolyte. The electrolyte is a lithium salt solution with the concentration of 0.1-3mol/L, and a lithium salt solute in the lithium salt solution is one or a mixture of more than two of lithium fluoride, lithium chloride, lithium bromide or lithium iodide; the solvent is one or a mixture of more than two of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetramethylsulfone, tetrahydrofuran, N-methylpyrrolidone and acetonitrile; the diaphragm is a microporous membrane with the aperture of 0.5-10 nanometers or a compact membrane containing anions. In this patent, the use of a lithium salt solution with a lower concentration as the electrolyte results in the reaction of the electrolyte with the negative lithium metal, corrosion consuming the negative metal, and the need for a large amount of electrolyte to ensure the normal dissolution of polysulfides, limiting the practical energy density of the lithium sulfur battery.
Disclosure of Invention
The invention aims to solve the problems and provide a primary lithium-sulfur battery with high specific energy and application thereof, which overcome the defects of low sulfur content of a positive electrode and high addition amount of electrolyte in the lithium-sulfur battery.
The purpose of the invention is realized by the following technical scheme:
the high-specific-energy primary lithium-sulfur battery comprises a negative electrode, a positive electrode, a diaphragm and electrolyte, wherein the positive electrode is made of a sulfur-carbon composite positive electrode material, and the sulfur-carbon composite positive electrode material contains sulfurThe electrolyte comprises a lithium salt, a solvent and a diluent, wherein the solvent is acetonitrile, and the addition ratio (E/S) of the electrolyte to the elemental sulfur is (0.2-3) mL:1 g. The energy density of the obtained lithium-sulfur battery is 500-1200 Wh kg-1The negative electrode is a lithium metal material, the positive electrode is a flexible self-supporting pole piece consisting of a sulfur-carbon composite material and an adhesive, and the diaphragm is a commercial diaphragm which is a 2500-type diaphragm produced by Celgard corporation.
Preferably, the conductive carbon black is selected from one or more of ketjen black, acetylene black or Super P.
Preferably, in the sulfur-carbon composite positive electrode material, the mass ratio of the sulfur simple substance to the conductive carbon black to the polytetrafluoroethylene is (30-95): (3-40): (2-10). Further preferably, the mass ratio of the elemental sulfur, the conductive carbon black and the polytetrafluoroethylene is 50:10: 9.
Preferably, the sulfur-carbon composite cathode material is prepared by the following preparation method:
(a) uniformly mixing a sulfur simple substance and conductive carbon black, and then sealing and sintering in an inert atmosphere to obtain a precursor of the positive electrode material, wherein the inert atmosphere is an argon atmosphere;
(b) adding the precursor of the positive electrode material obtained in the step (a) and a binder into ethanol, and uniformly stirring the mixture to be in a bulk shape to obtain a crude product of the positive electrode material, wherein the binder is polytetrafluoroethylene dispersion liquid;
(c) and (c) repeatedly rolling and molding the crude product of the cathode material obtained in the step (b) by using a roller press, continuously reducing the rolling distance, and drying to obtain the sulfur-carbon composite cathode material.
Preferably, in the step (a), the sintering temperature is 140-170 ℃, and the sintering time is 10-14 h.
Preferably, in step (c), the drying process is specifically: firstly, the rolled crude product of the anode material is hung and dried, and then the dried product is placed in an oven to be dried for 8-18 h at the temperature of 60-80 ℃.
Preferably, the lithium salt is lithium bistrifluoromethanesulfonylimide (expressed as LiTFSI) and the diluent is hydrofluoroether.
Preferably, the hydrofluoroether is selected from one or more of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (CAS:16627-68-2), 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether (CAS:406-78-0), 1,2, 2-tetrafluoroethyl ethyl ether (CAS: 512-51-6).
Preferably, in the electrolyte, the molar ratio of the acetonitrile to the lithium salt is (1-9): 1, and the volume ratio of the acetonitrile to the diluent is (4-9): 1-6.
Preferably, the electrolyte is obtained by the following preparation method: firstly, preparing acetonitrile and lithium bis (trifluoromethane sulfonyl) imide into a uniform solution according to a molar ratio, then adding hydrofluoroether, uniformly mixing, and standing to obtain the electrolyte for the primary lithium-sulfur battery.
An application of a primary lithium-sulfur battery with high specific energy. The battery can be made into a columnar battery, a single-layer soft package battery and a 2032 type button cell battery.
According to the invention, the sulfur-carbon anode with high sulfur capacity and the acetonitrile system electrolyte are prepared, the addition amount of the electrolyte is reduced, the preparation of the primary lithium-sulfur battery with high specific energy is realized, the prepared anode plate has good ductility, conductivity and high active substance capacity, the prepared electrolyte has high ionic conductivity and good rate capability at high temperature (60 ℃) and low temperature (minus 40 ℃), and the prepared primary lithium-sulfur battery has extremely high energy density (400-1200 Wh kg)-1) Excellent high-temperature and low-temperature performance, and excellent discharge capability at high current density.
Compared with the prior art, the invention has the beneficial effects that: the primary lithium-sulfur battery disclosed by the invention uses the novel system electrolyte, so that the dissolution of polysulfide is greatly inhibited, the addition of the electrolyte in the lithium-sulfur battery is reduced, the utilization rate of the positive active substance in the lithium-sulfur battery is improved, and the primary lithium-sulfur battery has extremely high energy density compared with the traditional lithium-ion battery.
Drawings
FIG. 1 is a graph comparing discharge curves of examples 1 and 2 and comparative examples 1 and 2;
FIG. 2 is a graph comparing the discharge curves of example 3 and comparative example 3;
FIG. 3 is a graph comparing the discharge curves of examples 4 and 5 and comparative example 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A high specific energy primary lithium-sulfur battery is prepared by the following preparation method: weighing 500g of sulfur powder and 100g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 90g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive electrode plate with the thickness of 0.9mm, then placing the malleable positive electrode plate in an oven to be dried for 12 hours at the temperature of 60 ℃, and then cutting the malleable positive electrode plate into the pole piece with the size of 285 multiplied by 37.5 multiplied by 0.9 mm.
Dissolving acetonitrile solvent and LiTFSI according to a molar ratio of 2:1, taking 20mL of acetonitrile solvent, adding 55g of LiTFSI, stirring until the acetonitrile solvent is completely dissolved (the volume is expanded to about 40mL after the acetonitrile solvent is completely dissolved, the same below), taking 30mL of mixed solution after the acetonitrile solvent is dissolved, adding 30mL of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether into the mixed solution, and obtaining electrolyte, wherein the ionic conductivity of the electrolyte at 60 ℃ is 2 x 10-3S cm-1And an ionic conductivity at 40 ℃ of 1.3X 10-3S cm-1And an ionic conductivity at-40 ℃ of 0.2X 10-3S cm-1。
Winding the positive pole piece, the diaphragm and the lithium belt into a 26500 cylindrical battery, and adding the electrolyte according to the proportion that E/S is 1mL:1g to obtain a primary lithium-sulfur battery, wherein the energy density of the primary lithium-sulfur battery is 610Wh kg-1The lithium sulfur battery is discharged at C/1000 multiplying power, and as can be seen from figure 1, the battery has higher discharge capacity and higher energy density under the same discharge condition than the lithium sulfur battery using ether electrolyte.
Example 2
A high specific energy primary lithium-sulfur battery is prepared by the following preparation method: weighing 500g of sulfur powder and 100g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 90g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive electrode plate with the thickness of 0.9mm, then placing the malleable positive electrode plate in an oven to be dried for 12 hours at the temperature of 60 ℃, and then cutting the malleable positive electrode plate into the pole piece with the size of 285 multiplied by 37.5 multiplied by 0.9 mm.
Dissolving acetonitrile solvent and LiTFSI according to the molar ratio of 2:1, taking 20mL of acetonitrile solvent, adding 55g of LiTFSI, stirring until the acetonitrile solvent is completely dissolved, taking 30mL of dissolved mixed solution, adding 30mL of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether into the mixed solution to obtain electrolyte, wherein the ionic conductivity of the electrolyte at 60 ℃ is 2 x 10-3S cm-1And an ionic conductivity at 40 ℃ of 1.3X 10-3S cm-1And an ionic conductivity at-40 ℃ of 0.2X 10-3S cm-1。
Winding the positive pole piece, the diaphragm and the lithium belt into a 26500 cylindrical battery, and adding the electrolyte according to the proportion that E/S is 1mL:1g to obtain a primary lithium-sulfur battery, wherein the energy density of the primary lithium-sulfur battery is 610Wh kg-1The lithium sulfur battery is discharged at C/500 multiplying power, and as can be seen from figure 1, the battery has higher discharge capacity and higher energy density under the same discharge condition than the lithium sulfur battery using ether electrolyte.
Example 3
A high specific energy primary lithium-sulfur battery is prepared by the following preparation method: weighing 500g of sulfur powder and 100g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 90g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive electrode plate with the thickness of 0.9mm, then placing the malleable positive electrode plate in an oven to be dried for 12 hours at the temperature of 60 ℃, and then cutting the malleable positive electrode plate into a pole piece with the size of 30 multiplied by 40 multiplied by 0.9 mm.
Dissolving acetonitrile solvent and LiTFSI according to the molar ratio of 2:1, taking 20mL of acetonitrile solvent, adding 55g of LiTFSI, stirring until the acetonitrile solvent is completely dissolved, taking 30mL of dissolved mixed solution, adding 30mL of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether into the mixed solution to obtain electrolyte, wherein the ionic conductivity of the electrolyte at 60 ℃ is 2 x 10-3S cm-1And an ionic conductivity at 40 ℃ of 1.3X 10-3S cm-1And an ionic conductivity at-40 ℃ of 0.2X 10-3S cm-1。
Assembling the positive pole piece, the diaphragm and the lithium belt into a single-layer soft package battery, and adding electrolyte according to the proportion that E/S is 1.6mL:1g to obtain a primary lithium-sulfur battery, wherein the energy density of the primary lithium-sulfur battery is 600Wh kg-1When the lithium-sulfur battery is discharged at a rate of C/1000, it can be seen from fig. 2 that the battery using the acetonitrile electrolyte has a higher discharge capacity and a higher energy density under the same electrolyte addition condition and discharge point condition.
Example 4
A high specific energy primary lithium-sulfur battery is prepared by the following preparation method: weighing 50g of sulfur powder and 10g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 9g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive plate with the thickness of 0.9mm, then placing the malleable positive plate in an oven to be dried for 12 hours at the temperature of 60 ℃, and then cutting the malleable positive plate into a pole piece with the size of phi 12 mm.
Dissolving acetonitrile solvent and LiTFSI according to the molar ratio of 2:1, taking 2mL of acetonitrile solvent, adding 5.5g of LiTFSI, stirring until the acetonitrile solvent is completely dissolved, taking 3mL of dissolved mixed solution, adding 3mL of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether into the mixed solution to obtain electrolyte, wherein the ionic conductivity of the electrolyte at 60 ℃ is 2 x 10-3S cm-1And an ionic conductivity at 40 ℃ of 1.3X 10-3S cm-1And an ionic conductivity at-40 ℃ of 0.2X 10-3S cm-1。
Assembling a positive pole piece, a diaphragm and a lithium belt into a 2032 type button cell, adding electrolyte according to the proportion of E/S to 1mL to 1g to obtain a primary lithium-sulfur battery, wherein the theoretical energy density of the primary lithium-sulfur battery is 685Wh kg-1(ignoring battery case mass), the lithium sulfur battery was discharged at C/1000 rate, and as can be seen from fig. 3, the battery had a higher specific discharge capacity than the lithium sulfur battery using the ether electrolyte under the condition that E/S is 1mL:1 g.
Example 5
A high specific energy primary lithium-sulfur battery is prepared by the following preparation method: weighing 50g of sulfur powder and 10g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 9g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive plate with the thickness of 0.9mm, then placing the malleable positive plate in an oven to be dried for 12 hours at the temperature of 60 ℃, and then cutting the malleable positive plate into a pole piece with the size of phi 12 mm.
Dissolving acetonitrile solvent and LiTFSI according to the molar ratio of 2:1, taking 2mL of acetonitrile solvent, adding 5.5g of LiTFSI, stirring until the acetonitrile solvent is completely dissolved, taking 3mL of dissolved mixed solution, adding 3mL of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether into the mixed solution to obtain electrolyte, wherein the ionic conductivity of the electrolyte at 60 ℃ is 2 x 10-3S cm-1And an ionic conductivity at 40 ℃ of 1.3X 10-3S cm-1And an ionic conductivity at-40 ℃ of 0.2X 10-3S cm-1。
Assembling the positive pole piece, the diaphragm and the lithium belt into a 2032 type button cell, adding electrolyte according to the proportion of E/S2 mL:1g to obtain a primary lithium-sulfur battery, wherein the theoretical energy density of the primary lithium-sulfur battery is 580Wh kg-1(ignoring battery case mass), the lithium sulfur battery was discharged at a rate of C/500, and as can be seen from fig. 3, the battery had a higher specific discharge capacity than the lithium sulfur battery using the ether electrolyte under the condition that E/S was 2mL:1 g.
Example 6
A high specific energy primary lithium-sulfur battery is prepared by the following preparation method: weighing 50g of sulfur powder and 10g of super P, uniformly mixing, sintering at 155 ℃ for 12h in an argon sealed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 9g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive plate with the thickness of 0.9mm, then placing the malleable positive plate in an oven to dry for 10 hours at the temperature of 80 ℃, and then cutting the malleable positive plate into a pole piece with the size of phi 12 mm.
Dissolving acetonitrile solvent and LiTFSI according to the molar ratio of 2:1, taking 2mL of acetonitrile solvent, adding 5.5g of LiTFSI, stirring until the acetonitrile solvent is completely dissolved, taking 3mL of dissolved mixed solution, adding 3mL of 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether into the mixed solution to obtain electrolyte, wherein the ionic conductivity of the electrolyte at 60 ℃ is 2 x 10-3S cm-1And an ionic conductivity at 40 ℃ of 1.3X 10-3S cm-1And an ionic conductivity at-40 ℃ of 0.2X 10-3S cm-1。
Assembling the positive pole piece, the diaphragm and the lithium belt into a 2032 type button cell, adding electrolyte according to the proportion of E/S to 1mL to 1g to obtain a primary lithium-sulfur battery, wherein the theoretical energy density of the primary lithium-sulfur battery is 660Wh kg-1(battery case mass is ignored).
Example 7
A high specific energy primary lithium-sulfur battery is prepared by the following preparation method: weighing 30g of sulfur powder and 20g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 9g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive plate with the thickness of 0.9mm, then placing the malleable positive plate in an oven to dry for 8 hours at the temperature of 80 ℃, and then cutting the malleable positive plate into a pole piece with the size of phi 12 mm.
B is to beDissolving nitrile solvent and LiTFSI according to the molar ratio of 2:1, taking 2mL of acetonitrile solvent, adding 5.5g of LiTFSI, stirring until the acetonitrile solvent is completely dissolved, taking 3mL of mixed solution after dissolution, and adding 3mL of 1,1,2, 2-tetrafluoroethylethyl ether into the mixed solution to obtain electrolyte, wherein the ionic conductivity of the electrolyte at 60 ℃ is 2 x 10-3S cm-1And an ionic conductivity at 40 ℃ of 1.3X 10-3S cm-1And an ionic conductivity at-40 ℃ of 0.2X 10-3S cm-1。
Assembling the positive pole piece, the diaphragm and the lithium belt into a 2032 type button cell, adding electrolyte according to the proportion of E/S2 mL:1g to obtain a primary lithium-sulfur battery, wherein the energy density of the primary lithium-sulfur battery is 400Wh kg-1。
Example 8
A high specific energy primary lithium-sulfur battery is prepared by the following preparation method: weighing 950g of sulfur powder and 400g of acetylene black, uniformly mixing, sintering at 170 ℃ for 10h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 10g of polytetrafluoroethylene dispersion liquid (the solid content is 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive electrode plate with the thickness of 0.9mm, then placing the malleable positive electrode plate in an oven to be dried for 18 hours at the temperature of 60 ℃, and then cutting the malleable positive electrode plate into the pole piece with the size of 285 multiplied by 37.5 multiplied by 0.9 mm.
Dissolving an acetonitrile solvent and LiTFSI according to a molar ratio of 9:1, taking 20mL of the acetonitrile solvent, adding 55g of LiTFSI, stirring until the acetonitrile solvent is completely dissolved, taking a mixed solution after all the solvents are dissolved, and adding 5mL of 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether into the mixed solution to obtain the electrolyte.
Winding the positive pole piece, the diaphragm and the lithium belt into a 26500 cylindrical battery, and adding electrolyte according to the proportion that E/S is 0.2mL:1g to obtain a primary lithium-sulfur battery, wherein the energy density of the primary lithium-sulfur battery is 720Wh kg-1。
Example 9
A high specific energy primary lithium-sulfur battery is prepared by the following preparation method: weighing 500g of sulfur powder and 3g of super P, uniformly mixing, sintering for 14h at 140 ℃ in an argon sealed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 2g of polytetrafluoroethylene dispersion liquid (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive electrode plate with the thickness of 0.9mm, then placing the malleable positive electrode plate in an oven to be dried for 8 hours at the temperature of 80 ℃, and then cutting the malleable positive electrode plate into the pole piece with the size of 285 multiplied by 37.5 multiplied by 0.9 mm.
Dissolving acetonitrile solvent and LiTFSI according to the molar ratio of 7:1, taking 20mL of acetonitrile solvent, adding 55g of LiTFSI, stirring until the acetonitrile solvent is completely dissolved, taking a mixed solution after all the acetonitrile solvent is dissolved, adding 13.3mL of 1,1,2, 2-tetrafluoroethyl ethyl ether into the mixed solution, winding a positive pole piece, a diaphragm and a lithium belt into a 26500 cylindrical battery, and adding electrolyte according to the ratio of E/S to 3mL to 1g to obtain a primary lithium-sulfur battery, wherein the energy density of the primary lithium-sulfur battery is 400Wh kg-1。
As can be seen from examples 1 to 9 and FIGS. 1 to 3, when the addition ratio (E/S) of the electrolyte to the elemental sulfur is (0.2 to 3) mL:1g, and acetonitrile is contained in the electrolyte, the electrical properties of the primary lithium-sulfur battery obtained are very excellent.
Comparative example 1
A common primary lithium-sulfur battery is prepared by adopting the following preparation method: weighing 500g of sulfur powder and 100g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 90g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; and repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive electrode plate, wherein the thickness of the malleable positive electrode plate is 0.9mm, and cutting the malleable positive electrode plate into pole pieces with the sizes of 285 multiplied by 37.5 multiplied by 0.9 mm.
Winding the positive electrode piece, the diaphragm and the lithium belt into a 26500 cylindrical battery, and adding an ether electrolyte at the ratio of E/S (1 mL:1 g), wherein the ionic conductivity of the ether electrolyte at 60 ℃ is 1.8 multiplied by 10-3S cm-1And an ionic conductivity at 40 ℃ of 1.4X 10-3S cm-1Is obtained onceA lithium-sulfur battery having an energy density of 120Wh kg-1. The lithium sulfur battery was discharged at a rate of C/1000, and as can be seen from FIG. 1, the lithium sulfur battery using the ether electrolyte had an electrolyte addition amount of E/S of 1mL g-1The ether electrolyte is LS-009 provided by a multi-reagent network and contains LiTFSI, 1, 3-Dioxolane (DOL), 1, 2-Dimethoxyethane (DME) and LiNO3Wherein the concentration of LiTFSI is 1.0M, the volume ratio of DOL to DME is 1:1, LiNO3The content of (b) was 2.0% by volume.
Comparative example 2
A common primary lithium-sulfur battery is prepared by adopting the following preparation method: weighing 500g of sulfur powder and 100g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 90g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; and repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive electrode plate, wherein the thickness of the malleable positive electrode plate is 0.9mm, and cutting the malleable positive electrode plate into pole pieces with the sizes of 285 multiplied by 37.5 multiplied by 0.9 mm.
Winding the positive pole piece, the diaphragm and the lithium belt into a 26500 cylindrical battery, adding ether electrolyte according to the proportion that E/S is 1mL:1g, wherein the ionic conductivity of the ether electrolyte at 60 ℃ and the ionic conductivity of the ether electrolyte at-40 ℃ are the same as those of the ether electrolyte in the comparative example 1, and obtaining the primary lithium-sulfur battery, wherein the energy density of the primary lithium-sulfur battery is 120Wh kg-1. The lithium sulfur cell was discharged at C/500 rate. As can be seen from fig. 1, the discharge capacity of the lithium sulfur battery using the ether electrolyte, which is the electrolyte LS-009 provided by the multidrug network, is far inferior to that of the acetonitrile electrolyte when the amount of the electrolyte added is 1mL:1 g.
Comparative example 3
A common primary lithium-sulfur battery is prepared by adopting the following preparation method: weighing 500g of sulfur powder and 100g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 90g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; and repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive electrode plate, wherein the thickness of the malleable positive electrode plate is 0.9mm, and cutting the malleable positive electrode plate into a pole piece with the size of 30 multiplied by 40 multiplied by 0.9 mm.
Assembling a positive pole piece, a diaphragm and a lithium belt into a single-layer soft package battery, adding ether electrolyte according to the proportion that E/S is 1.6mL:1g, wherein the ionic conductivity of the ether electrolyte at 60 ℃ and the ionic conductivity of the ether electrolyte at-40 ℃ are the same as those of the ether electrolyte in the comparative example 1, and obtaining a primary lithium-sulfur battery, wherein the energy density of the primary lithium-sulfur battery is 70Wh kg-1. The lithium sulfur battery was discharged at a rate of C/1000, and as can be seen from FIG. 2, the amount of the electrolyte added in the lithium sulfur battery using the ether electrolyte was 1.6mL g/S-1The discharge capacity is far inferior to that of acetonitrile electrolyte, and the ether electrolyte is provided as the electrolyte LS-009 of the lithium-sulfur battery provided by a multi-reagent network.
Comparative example 4
A common primary lithium-sulfur battery is prepared by adopting the following preparation method: weighing 50g of sulfur powder and 10g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 9g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive electrode plate with the thickness of 0.9mm, and cutting the malleable positive electrode plate into a pole piece with the size of phi 12 mm.
Assembling a positive pole piece, a diaphragm and a lithium belt into a 2032 type button cell, adding ether electrolyte according to the proportion that E/S is 1mL:1g, wherein the ionic conductivity of the ether electrolyte at 60 ℃ and the ionic conductivity of the ether electrolyte at-40 ℃ are the same as those of the ether electrolyte in a comparative example 1, and obtaining a primary lithium-sulfur cell, wherein the theoretical energy density of the primary lithium-sulfur cell is 200Wh kg-1(battery case mass is ignored). When the lithium-sulfur battery is discharged at a rate of C/1000, as can be seen from FIG. 3, the discharge capacity of the lithium-sulfur battery using the ether electrolyte is far less than that of the acetonitrile electrolyteLithium sulfur battery electrolyte LS-009 provided for a multi-reagent grid.
Comparative example 5
A common primary lithium-sulfur battery is prepared by adopting the following preparation method: weighing 500g of sulfur powder and 100g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 90g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; and repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive electrode plate, wherein the thickness of the malleable positive electrode plate is 0.9mm, and cutting the malleable positive electrode plate into pole pieces with the sizes of 285 multiplied by 37.5 multiplied by 0.9 mm.
Dissolving acetonitrile solvent and LiTFSI according to the molar ratio of 2:1, taking 20mL of acetonitrile solvent, adding 55g of LiTFSI, stirring until the acetonitrile solvent is completely dissolved, taking 30mL of dissolved mixed solution, adding 30mL of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether into the mixed solution to obtain electrolyte, wherein the ionic conductivity of the electrolyte at 60 ℃ is 2 x 10-3S cm-1And an ionic conductivity at-40 ℃ of 0.2X 10-3S cm-1。
Winding the positive pole piece, the diaphragm and the lithium belt into a 26500 cylindrical battery, and adding electrolyte according to the proportion that E/S is 0.1mL:1g to obtain a primary lithium-sulfur battery, wherein the energy density of the primary lithium-sulfur battery is 240Wh kg-1。
Comparative example 6
A common primary lithium-sulfur battery is prepared by adopting the following preparation method: weighing 500g of sulfur powder and 100g of Ketjen black, uniformly mixing, sintering at 155 ℃ for 12h in an argon gas closed environment to obtain a precursor of the positive electrode material, adding the precursor of the positive electrode material and 90g of polytetrafluoroethylene dispersion (with the solid content of 60%) into an ethanol solvent, and uniformly mixing to obtain a crude product of the powdery positive electrode material; and repeatedly rolling the prepared crude product of the positive electrode material on a rolling machine to obtain a malleable positive electrode plate, wherein the thickness of the malleable positive electrode plate is 0.9mm, and cutting the malleable positive electrode plate into pole pieces with the sizes of 285 multiplied by 37.5 multiplied by 0.9 mm.
Dissolving acetonitrile solvent and LiTFSI according to the molar ratio of 2:1, taking 20mL of acetonitrile solvent, adding 55Stirring the solution to be completely dissolved by gLiTFSI, taking 30mL of dissolved mixed solution, adding 30mL of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether into the mixed solution to obtain electrolyte, wherein the ionic conductivity of the electrolyte at 60 ℃ is 2 x 10-3S cm-1And an ionic conductivity at-40 ℃ of 0.2X 10-3S cm-1。
Winding the positive pole piece, the diaphragm and the lithium belt into a 26500 cylindrical battery, and adding electrolyte according to the proportion that E/S is 4mL:1g to obtain a primary lithium-sulfur battery, wherein the energy density of the primary lithium-sulfur battery is 280Wh kg-1。
As can be seen from FIGS. 1-3, the addition ratio (E/S) of the electrolyte and the elemental sulfur is set to be (0.2-3) mL:1g, and the electrolyte contains acetonitrile, so that the obtained primary lithium-sulfur battery has very excellent electrical properties compared with the common primary lithium-sulfur battery.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (8)
1. The high-specific-energy primary lithium-sulfur battery comprises a cathode, an anode, a diaphragm and electrolyte, and is characterized in that the anode is made of a sulfur-carbon composite anode material, the sulfur-carbon composite anode material comprises elemental sulfur, conductive carbon black and a binder, the binder is polytetrafluoroethylene dispersion liquid, the electrolyte comprises lithium salt, a solvent and a diluent, the solvent is acetonitrile, the addition ratio of the electrolyte to the elemental sulfur is (0.2-3) mL:1g,
in the sulfur-carbon composite anode material, the mass ratio of the sulfur simple substance to the conductive carbon black to the polytetrafluoroethylene is (30-95) to (3-40) to (2-10),
the sulfur-carbon composite positive electrode material is prepared by adopting the following preparation method:
(a) uniformly mixing a sulfur simple substance and conductive carbon black, and then sealing and sintering in an inert atmosphere to obtain a precursor of the positive electrode material;
(b) adding the precursor of the anode material obtained in the step (a) and a binder into ethanol, and uniformly stirring to obtain a crude product of the anode material;
(c) and (c) repeatedly rolling and forming the crude product of the cathode material obtained in the step (b), and drying to obtain the sulfur-carbon composite cathode material.
2. The lithium sulfur battery as claimed in claim 1, wherein the conductive carbon black is selected from one or more of ketjen black, acetylene black or Super P.
3. The primary lithium sulfur battery with high specific energy according to claim 1, wherein in step (a), the sintering temperature is 140-170 ℃ and the sintering time is 10-14 h.
4. The high specific energy primary lithium sulfur battery as claimed in claim 1, wherein the drying process in step (c) is specifically: firstly, hanging and airing the rolled anode material crude product, and then drying the anode material crude product at the temperature of 60-80 ℃ for 8-18 h.
5. The high specific energy primary lithium sulfur battery of claim 1 wherein said lithium salt is lithium bistrifluoromethanesulfonylimide and said diluent is a hydrofluoroether.
6. The high specific energy primary lithium sulfur battery of claim 5 wherein the hydrofluoroether is selected from one or more of 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether, 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, or 1,1,2, 2-tetrafluoroethyl ethyl ether.
7. The high specific energy primary lithium sulfur battery as claimed in claim 1, wherein the molar ratio of acetonitrile to lithium salt in the electrolyte is (1-9): 1, and the volume ratio of acetonitrile to diluent is (4-9): 1-6.
8. Use of a high specific energy primary lithium sulphur battery as claimed in any one of claims 1 to 7.
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