CN109686981B - Composite binder applied to lithium-sulfur battery and preparation method thereof - Google Patents

Composite binder applied to lithium-sulfur battery and preparation method thereof Download PDF

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CN109686981B
CN109686981B CN201811592627.5A CN201811592627A CN109686981B CN 109686981 B CN109686981 B CN 109686981B CN 201811592627 A CN201811592627 A CN 201811592627A CN 109686981 B CN109686981 B CN 109686981B
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lithium
transition metal
component
sulfur
binder
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CN109686981A (en
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杨书廷
张孟雷
孙志贤
王秋娴
岳红云
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Battery Research Institute Of Henan Co ltd
Henan Normal University
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Henan Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a composite binder applied to a lithium-sulfur battery and a preparation method thereof, belonging to the technical field of lithium-sulfur batteries. The composite binder applied to the lithium-sulfur battery comprises a transition metal organic coordination compound and a binder; the transition metal organic coordination compound is prepared by reacting an organic ligand with a soluble transition metal salt. The transition metal organic coordination compound applied to the composite binder of the lithium-sulfur battery forms an organic-inorganic hybrid material with intramolecular pores through self-assembly in the drying process of the pole piece, so that an electrolyte can well permeate the pole piece through the pores, the ion conductivity of the pole piece is improved, and the ion conductivity can reach the whole active layer under the condition that the active layer of the pole piece is thicker; meanwhile, the metal elements in the formed organic-inorganic hybrid material have catalytic effect on the chemical reaction of sulfides, and the energy density of the battery can be improved.

Description

Composite binder applied to lithium-sulfur battery and preparation method thereof
Technical Field
The invention relates to a composite binder applied to a lithium-sulfur battery and a preparation method thereof, belonging to the technical field of lithium-sulfur batteries.
Background
The theoretical specific capacity of sulfur reaches 1675mAh/g, which is far higher than that of the anode material (the theoretical specific capacity of ternary material is 280mAh/g) in the current commercial application, and the lithium-sulfur battery is widely researched as a new generation of lithium ion battery. In order to realize the commercial application of the lithium-sulfur battery, the mass energy density of the lithium-sulfur battery is required to be more than or equal to 350Wh/kg (the energy density of the lithium-ion battery which is commercially applied at present is 220Wh/kg), and the realization of the aim needs to use the high sulfur-carrying capacity (more than or equal to 4 mg/cm) of the pole piece2) On the premise, the sulfur-carrying capacity of the pole piece of the lithium sulfur battery with high specific capacity (more than or equal to 1300mAh/g) reported at present is lower (less than or equal to 2 mg/cm)2) In proportion to the sulfur loading of the electrode plate required for commercial applicationThe distance is large, so that the realization of high specific capacity exertion of the pole piece under high sulfur carrying capacity has important practical application value.
At present, researches on improving the sulfur carrying capacity of a pole piece mainly focus on the synthesis aspect of positive pole materials, such as: although significant progress is made in different support materials of sulfur, morphology/structure control of composite particles, element doping and the like, the sulfur-containing composite particles do not have practical application value due to high cost, complex process, harsh synthesis conditions and the like. And for the common mesoporous carbon/sulfur composite material with simple synthesis conditions and low cost, the sulfur-carrying capacity (not less than 4 mg/cm) of the pole piece is high2) The high capacity performance is rarely reported. This is mainly because of the sulfur and the reaction product Li2S/Li2S2The conductivity is poor, and under the condition of high sulfur-carrying capacity of the pole piece, the influence of the intrinsic defects on the electrical property of the pole piece is more obvious by adopting a common carbon material. Because the conductivity of electrons on the pole piece is low and the internal resistance is large, the voltage of the No. 2 discharge voltage platform (2.05V) is suddenly reduced, and the capacity is low.
In order to improve the conductivity of sulfur particles, the compounding of sulfur with a conductive polymer is widely studied. Polythiophene, polyaniline, polymer 3, 4-ethylenedioxythiophene and the like are compounded with sulfur, and the sandwich-structure polyaniline/sulfur composite material reported in the Chinese invention patent application with the application publication number of CN 106356513A achieves the specific capacity of more than 800mAh/g, but the sulfur proportion of the high-molecular/sulfur composite material is only about 50% (the sulfur proportion of the mesoporous carbon/sulfur composite material can reach about 70%), which is not beneficial to realizing the high sulfur-carrying capacity of the pole piece. The Chinese invention patent application with application publication number CN105655593A adopts a high-molecular conductive adhesive to replace the traditional adhesive (PVDF, CMC/SBR, LA132 and the like), improves the specific capacity of the battery by reducing the internal resistance, but the specific capacity is still lower under the condition of high sulfur-carrying capacity of a pole piece. This is because the electron conduction of the electrode sheet is improved, but the ion conduction of the electrode sheet is not changed, and the electrode sheet is thicker under high sulfur loading of the electrode sheet, and the ion conduction cannot go deep into the bottom of the electrode sheet, resulting in lower battery capacity.
Disclosure of Invention
The invention aims to provide a composite binder applied to a lithium-sulfur battery, which can promote the conduction of ions in a pole piece.
The invention also provides a preparation method of the composite binder applied to the lithium-sulfur battery, which is simple in process.
In order to achieve the above object, the composite binder for a lithium-sulfur battery according to the present invention employs the following technical solutions:
a composite binder applied to a lithium-sulfur battery comprises a transition metal organic coordination compound and a binder; the transition metal organic coordination compound is prepared by the reaction of an organic ligand and a soluble transition metal salt; the mass ratio of the binder to the organic ligand to the soluble transition metal salt is 1.5-20: 0.5-10: 0.25-2.5.
The composite binder applied to the lithium-sulfur battery contains a transition metal organic coordination compound generated by coordination reaction of an organic ligand and a soluble transition metal salt, and forms an organic-inorganic hybrid material with intramolecular pores along with volatilization self-assembly of a solvent in the drying process of a pole piece, and an electrolyte can well soak the pole piece through the pores, so that the ion conductivity of the pole piece is improved, and under the condition that an active layer of the pole piece is thicker, the ion conductivity can reach the whole active layer, so that the first discharge specific capacity and the circulation specific capacity of the lithium-sulfur battery are improved; meanwhile, the metal elements in the formed organic-inorganic hybrid material have a certain catalytic action on the chemical reaction of sulfides, so that the energy density of the battery can be further improved.
The binder component in the composite binder for the lithium-sulfur battery is not particularly limited, and conventional binders for the positive electrode of the lithium-sulfur battery, such as polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC) and the like, can be adopted. In order to reduce the influence of the conventional binder on electrons and ions in the pole piece, the binder is preferably a conductive high molecular material.
Preferably, the conductive polymer material is selected from at least one of polyaniline, polypyrrole, polythiophene, polyfuran, polyselenophene, polyparaphenylene and polyphenylene sulfide. The conductive polymer materials not only have good conductivity, but also have high cohesiveness.
When the conductive polymer material is used as the binder, in order to avoid the chelating reaction between the conductive polymer material and the metal salt in the preparation process of the composite binder applied to the lithium-sulfur battery and influence the generation of organic-inorganic hybrid material gaps, the composite binder applied to the lithium-sulfur battery is prepared into two components to be stored respectively. Preferably, the composite binder for lithium-sulfur batteries comprises a component A and a component B; the component A comprises the transition metal organic coordination compound and a solvent A; the component B comprises the conductive polymer material and a solvent B. The component A and the component B are mixed in the using process of the bi-component composite binder applied to the lithium-sulfur battery, and at the moment, the soluble transition metal salt and the conductive polymer material generate chelation reaction, so that the conductive polymer material is doped with metal, and the conductivity of the conductive polymer material can be further improved.
The preparation method of the composite binder applied to the lithium-sulfur battery adopts the technical scheme that:
a preparation method of a composite binder applied to a lithium-sulfur battery comprises the following steps: uniformly mixing an organic ligand and soluble transition metal salt in a solvent A to obtain a component A; uniformly mixing the binder and the solvent B to obtain a component B; the mass ratio of the binder to the organic ligand to the soluble transition metal salt is 1.5-20: 0.5-10: 0.25-2.5.
The preparation method of the composite binder applied to the lithium-sulfur battery is simple in process and convenient to popularize and apply.
Preferably, the binder is a conductive polymer material.
Preferably, the conductive polymer material is selected from at least one of polyaniline, polypyrrole, polythiophene, polyfuran, polyselenophene, polyparaphenylene and polyphenylene sulfide.
Drawings
Fig. 1 is a graph of capacity-voltage performance of a soft-packed lithium-sulfur battery (2Ah) according to example 1 of the present invention after 100 cycles;
fig. 2 is a graph of cycle number versus specific capacity performance for button cell a1 made in experimental example 2 of the present invention;
fig. 3 is a graph of cycle number versus specific capacity performance for button cell a2 made in experimental example 2 of the present invention;
fig. 4 is a graph of cycle number versus specific capacity performance for button cell a3 made in experimental example 2 of the present invention.
Detailed Description
The composite binder applied to the lithium-sulfur battery comprises a transition metal organic coordination compound and a binder; the transition metal organic coordination compound is prepared by the reaction of an organic ligand and a soluble transition metal salt; the mass ratio of the binder to the organic ligand to the soluble transition metal salt is 1.5-20: 0.5-10: 0.25-2.5.
The binder may be selected from conventional binders. As a modification of the composite binder applied to the lithium-sulfur battery, the binder is made of a conductive polymer material.
Preferably, the composite binder applied to a lithium sulfur battery of the present invention is used for a positive electrode of a lithium sulfur battery. The positive plate of the composite binder applied to the lithium-sulfur battery can provide more channels for ion transmission in the charging and discharging processes, so that the positive plate has good ion conductivity, and the energy density of the lithium-sulfur battery is greatly improved; particularly, the conductive polymer material is used as the binder in the composite binder applied to the lithium-sulfur battery, so that the influence of the conventional binder on electron conduction can be avoided, and the electron conductivity of the pole piece is improved.
As a further modification of the composite binder applied to the lithium-sulfur battery, the conductive polymer material is selected from at least one of polyaniline, polypyrrole, polythiophene, polyfuran, polyselenophene, polyparaphenylene and polyphenylene sulfide.
The organic ligand may be at least one selected from terephthalic acid, isophthalic acid, trimesic acid, cyclodextrin, imidazole, 4-methylimidazole, 1-vinylimidazole, N' -carbonyldiimidazole, 2-methyl-5-vinylpyridine, 2-acetylpyridine, L-tryptophan, 1, 2-bis (4-pyridyl) ethylene and bipyridine.
The soluble transition metal salt may be at least one selected from soluble cobalt salt, zinc salt, chromium salt, and nickel salt. The soluble cobalt salt is preferably cobalt chloride, the soluble zinc salt is preferably at least one of zinc nitrate and zinc acetate, the soluble chromium salt is preferably chromium nitrate, and the soluble nickel salt is preferably nickel acetate.
The composite binder for a lithium-sulfur battery further includes a solvent. The solvent comprises water and an organic solvent; the organic solvent is at least one selected from ethanol, N-butanol, acetone, tetrahydrofuran, dimethyl sulfoxide, toluene, ethylene glycol, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, ethyl acetate, dibutyl phthalate, chloroform and N-methylpyrrolidone.
As a modification to a composite binder for a lithium-sulfur battery, the composite binder for a lithium-sulfur battery includes a component a and a component B; the component A comprises the transition metal organic coordination compound and a solvent A; the component B comprises the conductive polymer material and a solvent B. The preparation method of the component A comprises the following steps: and (3) uniformly mixing the organic ligand and the soluble transition metal salt in a solvent A to obtain the catalyst. When the composite binder applied to the lithium-sulfur battery is used, the component A and the component B are mixed; it is also possible to mix component A and component B before use.
Preferably, the mass ratio of the component A to the component B is 1-1.1: 1. The mass ratio of the organic ligand used for reacting to generate the transition metal organic coordination compound in the component A to the solvent A is 1: 9-190. The mass ratio of the conductive polymer material to the solvent B in the component B is 1: 4-66.
The solvent A comprises water and an organic solvent; the organic solvent is at least one of tetrahydrofuran, ethanol and dimethylacetamide. The volume ratio of water to the organic solvent in the solvent A is 1-4: 1.
The solvent B comprises an organic solvent, and the organic solvent is at least one selected from dimethylformamide, N-butanol, dimethyl sulfoxide, chloroform, tetrahydrofuran and N-methylpyrrolidone. The solvent B also comprises water, and the volume ratio of the organic solvent to the water is 0.65-3: 1.
The invention provides a preparation method of a composite binder applied to a lithium-sulfur battery, which comprises the following steps: uniformly mixing an organic ligand and soluble transition metal salt in a solvent A to obtain a component A; uniformly mixing the binder and the solvent B to obtain a component B; the mass ratio of the binder to the organic ligand to the soluble transition metal salt is 1.5-20: 0.5-10: 0.25-2.5.
In the above method for preparing a composite binder for a lithium-sulfur battery, the organic ligand may be at least one selected from the group consisting of terephthalic acid, isophthalic acid, trimesic acid, cyclodextrin, imidazole, 4-methylimidazole, 1-vinylimidazole, N' -carbonyldiimidazole, 2-methyl-5-vinylpyridine, 2-acetylpyridine, L-tryptophan, 1, 2-bis (4-pyridyl) ethene, and bipyridine. The soluble transition metal salt may be at least one selected from soluble cobalt salt, zinc salt, chromium salt, and nickel salt. The soluble cobalt salt is preferably cobalt chloride, the soluble zinc salt is preferably at least one of zinc nitrate and zinc acetate, the soluble chromium salt is preferably chromium nitrate, and the soluble nickel salt is preferably nickel acetate.
In the preparation method of the composite binder applied to the lithium-sulfur battery, the mass ratio of the component A to the component B is preferably 1-1.1: 1. The mass ratio of the organic ligand to the solvent A is 1: 9-190. The mass ratio of the conductive polymer material to the solvent B in the component B is 1: 4-66.
In the above method for preparing a composite binder for a lithium-sulfur battery, preferably, the solvent a comprises water and an organic solvent; the organic solvent is at least one of tetrahydrofuran, ethanol and dimethylacetamide. The volume ratio of water to the organic solvent in the solvent A is 1-4: 1.
In the above method for preparing a composite binder for a lithium-sulfur battery, preferably, the solvent B includes an organic solvent selected from at least one of dimethylformamide, N-butanol, dimethyl sulfoxide, chloroform, tetrahydrofuran, and N-methylpyrrolidone. The solvent B also comprises water, and the volume ratio of the organic solvent to the water is 0.65-3: 1.
The invention also provides a preparation method of the positive plate for the lithium-sulfur battery, which comprises the following steps: preparing a sulfur-based composite material, a conductive agent and the composite binder applied to the lithium-sulfur battery into positive electrode slurry; and then coating the positive slurry on a current collector, and drying to obtain the lithium ion battery.
In the preparation method of the positive plate for the lithium-sulfur battery, the adopted sulfur-based composite material comprises sulfur and a carrier for loading sulfur; the carrier is at least one of mesoporous carbon, CNTs, graphene, carbon nanosheets, SP, KS-6, acetylene black and Ketjen black. The sulfur content of the sulfur-based composite material is 60-75% by mass, and preferably 68-70%.
The drying temperature is preferably 45-80 ℃. The drying time is preferably 8-12 h.
The technical solution of the present invention will be further described with reference to the following embodiments.
In the following examples, examples 1 to 8 are examples of a composite binder for a lithium-sulfur battery, example 9 is an example of a method for producing a composite binder for a lithium-sulfur battery, and examples 10 to 17 are methods for producing a positive electrode sheet for a lithium-sulfur battery.
Example 1
The composite binder applied to the lithium-sulfur battery in the embodiment comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1: 1;
the component A comprises a transition metal organic coordination compound and a solvent A; the transition metal organic coordination compound is prepared by the reaction of an organic ligand and soluble transition metal; the mass ratio of the organic ligand to the soluble transition metal salt to the solvent A is 5:0.5:94.5, the organic ligand is isophthalic acid, and the soluble transition metal salt is cobalt chloride; the solvent A is a mixed solution of water and tetrahydrofuran, and the volume ratio of the water to the tetrahydrofuran is 2: 1;
the component B consists of a conductive high polymer material (namely a binder) and a solvent B, the mass ratio of the conductive high polymer material to the solvent B is 5:95, and the conductive high polymer material is polyaniline; the solvent B is a mixed solution of water, dimethylformamide and n-butyl alcohol, and the volume ratio of the water, the dimethylformamide and the n-butyl alcohol is 2:2: 1.
Example 2
The composite binder applied to the lithium-sulfur battery in the embodiment comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1: 1;
the component A comprises a transition metal organic coordination compound and a solvent A; the transition metal organic coordination compound is prepared by the reaction of an organic ligand and soluble transition metal; the mass ratio of the organic ligand to the soluble transition metal salt to the solvent A is 8:0.25:91.75, the organic ligand is cyclodextrin, and the soluble transition metal salt is zinc acetate; the solvent A is a mixed solution of water and ethanol, and the volume ratio of the water to the ethanol is 1: 1;
the component B consists of a conductive high polymer material (namely a binder) and a solvent B, the mass ratio of the conductive high polymer material to the solvent B is 7:93, and the conductive high polymer material is polyphenylene sulfide; the solvent B is a mixed solution of dimethyl sulfoxide and chloroform, and the volume ratio of the dimethyl sulfoxide to the chloroform is 10: 1.
Example 3
The composite binder applied to the lithium-sulfur battery in the embodiment comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 1: 1;
the component A comprises a transition metal organic coordination compound and a solvent A; the transition metal organic coordination compound is prepared by the reaction of an organic ligand and soluble transition metal; the mass ratio of the organic ligand to the soluble transition metal salt to the solvent A is 5:0.5:94.5, the organic ligand is 1-vinyl imidazole, and the soluble transition metal salt is nickel acetate; the solvent A is a mixed solution of water, dimethylacetamide and ethanol, and the volume ratio of the water, dimethylacetamide and ethanol is 6:3: 1;
the component B consists of a conductive high polymer material (namely a binder) and a solvent B, the mass ratio of the conductive high polymer material to the solvent B is 5:95, and the conductive high polymer material is polythiophene; the solvent B is a mixed solution of water and tetrahydrofuran, and the volume ratio of the water to the tetrahydrofuran is 3: 1.
Example 4
The composite binder applied to the lithium-sulfur battery of the embodiment is composed of a component A and a component B;
the component A comprises a transition metal organic coordination compound and a solvent A; the transition metal organic coordination compound is prepared by the reaction of an organic ligand and soluble transition metal; the mass ratio of the organic ligand to the soluble transition metal salt to the solvent A is 10:2.5:94.5, the organic ligand is 2-methyl-5-vinylpyridine, and the soluble transition metal salt is chromium nitrate; the solvent A is a mixed solution of water, dimethylacetamide and ethanol, and the volume ratio of the water, dimethylacetamide and ethanol is 2:1: 1;
the component B consists of a conductive high polymer material (namely a binder) and a solvent B, the mass ratio of the conductive high polymer material to the solvent B is 20:80, and the conductive high polymer material is polypyrrole; the solvent B is a mixed solution of water and tetrahydrofuran, and the volume ratio of the water to the tetrahydrofuran is 3: 1;
the mass ratio of the metal salt in the component A to the conductive high polymer material in the component B is 2.5: 20.
Example 5
The composite binder applied to the lithium-sulfur battery of the embodiment is composed of a component A and a component B;
the component A comprises a transition metal organic coordination compound and a solvent A; the transition metal organic coordination compound is prepared by the reaction of an organic ligand and soluble transition metal; the mass ratio of the organic ligand to the soluble transition metal salt to the solvent A is 0.5:0.25:99.75, the organic ligand is 1-vinylimidazole, and the soluble transition metal salt is zinc nitrate; the solvent A is a mixed solution of water, dimethylacetamide and ethanol, and the volume ratio of the water, dimethylacetamide and ethanol is 2:1: 1;
the component B consists of a conductive high polymer material (namely a binder) and a solvent B, the mass ratio of the conductive high polymer material to the solvent B is 1.5:98.5, and the conductive high polymer material is polyfuran; the solvent B is a mixed solution of water and tetrahydrofuran, and the volume ratio of the water to the tetrahydrofuran is 3: 1;
the mass ratio of the metal salt in the component A to the conductive polymer material in the component B is 0.25: 1.5.
Example 6
The composite binder applied to the lithium-sulfur battery of the embodiment is composed of a component A and a component B;
the component A comprises a transition metal organic coordination compound and a solvent A; the transition metal organic coordination compound is prepared by the reaction of an organic ligand and soluble transition metal; the mass ratio of the organic ligand to the soluble transition metal salt to the solvent A is 5:0.5:94.5, the organic ligand is 1-vinyl imidazole, the soluble transition metal salt is nickel acetate, the solvent A is a mixed solution of water, dimethylacetamide and ethanol, and the volume ratio of the water to the dimethylacetamide to the ethanol is 2:1: 1;
the component B consists of a conductive high polymer material (namely a binder) and a solvent B, the mass ratio of the conductive high polymer material to the solvent B is 5:95, the conductive high polymer material is polyselenophene, the solvent B is a mixed solution of water and dimethylformamide, and the volume ratio of the water to the dimethylformamide is 4: 1;
the mass ratio of the metal salt in the component A to the conductive high polymer material in the component B is 0.5: 5.
Example 7
The positive electrode binder for lithium-sulfur batteries of the present example is different from the composite binder applied to lithium-sulfur batteries in example 1 only in that: the conductive polymer material (i.e., binder) in component B is poly-p-phenylene.
Example 8
The composite binder applied to the lithium sulfur battery of the present example is different from the composite binder applied to the lithium sulfur battery of example 1 only in that: the conductive polymer material in the component B is replaced by polyvinylidene fluoride (PVDF, namely a binder), and the solvent B is replaced by N-methyl pyrrolidone.
The composite binder applied to the lithium-sulfur battery in the embodiment is a bi-component composite binder, and when the composite binder is used, the component A and the component B are mixed; these two-component composite binders were prepared by the following preparation method of example 9.
Example 9
The preparation method of the composite binder applied to the lithium-sulfur battery of the embodiment comprises the following steps:
1) taking an organic ligand, a soluble transition metal salt and a solvent A according to the formula amount, adding the organic ligand and the soluble transition metal salt into the solvent A, and carrying out ball milling until the organic ligand and the soluble transition metal salt are completely dispersed to obtain a component A;
2) taking the binder and the solvent B according to the formula amount, adding the binder into the solvent B, and ball-milling until the binder is completely dispersed to obtain the component B.
Example 10
The preparation method of the positive plate for the lithium-sulfur battery comprises the following steps: mixing a sulfur-based composite material, acetylene black and a binder according to a mass ratio of 8:1:1, adding the mixture into deionized water for ball milling to prepare anode slurry, coating the anode slurry on an aluminum foil, then placing the aluminum foil in a vacuum drying box, drying the aluminum foil at 60 ℃ for 12 hours after vacuumizing to prepare the sulfur-carrying capacity of about 4mg/cm2Obtaining the pole piece; the adopted sulfur-based composite material is a mesoporous carbon/sulfur composite material, and the mass percentage of sulfur is 69.5%; the binder used was the composite binder applied to the lithium-sulfur battery in example 1, and when the positive electrode slurry was prepared, component a and component B of the composite binder applied to the lithium-sulfur battery were uniformly mixed, and then mixed with the sulfur-based composite material and acetylene black.
Example 11
The preparation method of the positive plate for the lithium-sulfur battery comprises the following steps: mixing the sulfur-based composite material, the superconducting carbon and the binder according to the mass ratio of 8:1:1, adding the mixture into deionized water for ball milling to prepare anode slurry, coating the anode slurry on an aluminum foil, then placing the aluminum foil in a vacuum drying box, drying the aluminum foil at 60 ℃ for 12 hours after vacuumizing to prepare the sulfur-carrying capacity of about 5mg/cm2Obtaining the pole piece; the adopted sulfur-based composite material is a mesoporous carbon/sulfur composite material, and the mass percentage of sulfur is 69.5%; the binder used was the composite binder applied to the lithium-sulfur battery in example 2, and when the positive electrode slurry was prepared, component a and component B of the composite binder applied to the lithium-sulfur battery were uniformly mixed, and then mixed with the sulfur-based composite material and acetylene black.
Example 12
The preparation method of the positive plate for the lithium-sulfur battery comprises the following steps: adding the sulfur-based composite material, the superconducting carbon and the binder into deionized water according to the mass ratio of 8:1:1 for ball milling to prepare anode slurry, coating the anode slurry on an aluminum foil, then placing the aluminum foil in a vacuum drying box, drying the aluminum foil at 60 ℃ for 12 hours after vacuumizing to prepare the sulfur-carrying capacity of about 6mg/cm2Obtaining the pole piece; the sulfur-based composite material is mesoporousThe carbon/sulfur composite material contains 69.5 percent of sulfur by mass; the binder used was the composite binder applied to the lithium-sulfur battery in example 3, and when the positive electrode slurry was prepared, component a and component B of the composite binder applied to the lithium-sulfur battery were uniformly mixed, and then mixed with the sulfur-based composite material and acetylene black.
Examples 13 to 17
The preparation methods of the positive electrode sheets for lithium-sulfur batteries of examples 13 to 17 are shown in Table 1, and the same contents as those in example 10 are not described:
TABLE 1 examples 13 to 17 of the method for producing positive electrode sheet for lithium-sulfur battery
Figure BDA0001920641000000081
Figure BDA0001920641000000091
Comparative example
The preparation method of the positive plate for the lithium-sulfur battery of the comparative example comprises the following steps:
1) dissolving isophthalic acid and cobalt chloride in a water/tetrahydrofuran mixed solution, and performing ball milling until the isophthalic acid and the cobalt chloride are completely dispersed to obtain a mixed solution, wherein the mass fractions of the isophthalic acid and the cobalt chloride in the mixed solution are 5% and 0.5% respectively;
2) then reacting the obtained mixed solution at 60 ℃ for 5h, carrying out suction filtration and drying to obtain an organic-inorganic hybrid material;
3) treating sulfur and an organic-inorganic hybrid material at 155 ℃ for 6 hours to obtain a sulfur-based composite material; the mass percent of sulfur in the sulfur-based composite material is 68 percent;
4) the positive electrode sheet for a lithium-sulfur battery was prepared according to the method for preparing the positive electrode sheet for a lithium-sulfur battery in example 10 using the sulfur-based composite material prepared in this comparative example.
Experimental example 1
In this example, the positive electrode sheet for lithium-sulfur battery obtained in example 10 was used as a positive electrode sheet, metallic lithium was used as a negative electrode sheet, and LiNO was used in an amount of 0.1mol/L3The solution (the adopted solvent is obtained by mixing 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) according to the volume ratio of 1: 1) is used as electrolyte to assemble the soft package lithium-sulfur battery (2 Ah); the assembled soft package lithium sulfur battery is subjected to an electrical property test at 25 ℃ and a charge-discharge rate of 0.1C/0.1C, and the result is shown in figure 1.
As can be seen from FIG. 1, the charge-discharge voltage-capacity curve has typical lithium and sulfur chemical reaction characteristics, and the second discharge voltage plateau (2.05V) is smooth and long, indicating S6To S2The reaction/S is relatively sufficient because the composite adhesive applied to the lithium-sulfur battery has the double characteristics of conductivity (conductive polymer material)/ion conductivity (organic-inorganic pore structure), so that sulfur and sulfur compounds with poor conductivity are enabled to be even under the condition of high sulfur load of a pole piece (4 mg/cm)2) A more sufficient electrochemical reaction can be performed.
Experimental example 2
In the experimental example, the electrode sheets prepared in examples 10 to 17 and the positive electrode sheet for the lithium-sulfur battery in the comparative example were used as the positive electrode sheet, the lithium sheet was used as the negative electrode sheet, and 0.1mol/L LiNO was used3The solution (the adopted solvent is obtained by mixing 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) according to the volume ratio of 1: 1) is used as electrolyte and assembled into a button cell in a glove box; the assembled button cells are numbered A1-A8 and B in sequence.
The specific capacity of the button cell after the first discharge and the specific capacity after 100 cycles of the button cell are respectively tested under the charging and discharging multiplying power of 0.1C/0.1C at the temperature of 25 ℃, and the test results are shown in table 2, wherein a cycle time-specific capacity performance diagram of the button cell A1 is shown in figure 2, a cycle time-specific capacity performance diagram of the button cell A2 is shown in figure 3, and a cycle time-specific capacity performance diagram of the button cell A3 is shown in figure 4. The specific discharge capacity is the ratio of the capacitance to the mass of the active material.
TABLE 2 specific discharge capacity at first time and specific discharge capacity after 100 cycles
Figure BDA0001920641000000101
As can be seen from table 1, the first discharge specific capacity and the discharge specific capacity of the lithium-sulfur battery can be improved by using the composite binder applied to the lithium-sulfur battery of the present invention.

Claims (4)

1. A composite binder for a lithium-sulfur battery, comprising: comprises a transition metal organic coordination compound and a binder; the transition metal organic coordination compound is prepared by the reaction of an organic ligand and a soluble transition metal salt; the mass ratio of the binder to the organic ligand to the soluble transition metal salt is 1.5-20: 0.5-10: 0.25-2.5;
the binder is a conductive polymer material;
the composite binder applied to the lithium-sulfur battery comprises a component A and a component B; the component A comprises the transition metal organic coordination compound and a solvent A; the component B comprises the conductive polymer material and a solvent B;
the organic ligand is at least one selected from terephthalic acid, isophthalic acid, trimesic acid, cyclodextrin, imidazole, 4-methylimidazole, 1-vinylimidazole, N' -carbonyldiimidazole, 2-methyl-5-vinylpyridine, 2-acetylpyridine, L-tryptophan, 1, 2-bis (4-pyridyl) ethylene and bipyridine.
2. The composite binder for a lithium-sulfur battery according to claim 1, wherein: the conductive polymer material is selected from at least one of polyaniline, polypyrrole, polythiophene, polyfuran, polyselenophene, polyparaphenylene and polyphenylene sulfide.
3. A preparation method of a composite binder applied to a lithium-sulfur battery is characterized by comprising the following steps: the method comprises the following steps:
uniformly mixing an organic ligand and soluble transition metal salt in a solvent A to obtain a component A;
uniformly mixing the binder and the solvent B to obtain a component B;
the mass ratio of the binder to the organic ligand to the soluble transition metal salt is 1.5-20: 0.5-10: 0.25-2.5;
the organic ligand is selected from at least one of terephthalic acid, isophthalic acid, trimesic acid, cyclodextrin, imidazole, 4-methylimidazole, 1-vinylimidazole, N' -carbonyldiimidazole, 2-methyl-5-vinylpyridine, 2-acetylpyridine, L-tryptophan, 1, 2-bis (4-pyridyl) ethylene and bipyridine;
the binder is a conductive polymer material.
4. The method for preparing a composite binder for a lithium-sulfur battery according to claim 3, wherein: the conductive polymer material is selected from at least one of polyaniline, polypyrrole, polythiophene, polyfuran, polyselenophene, polyparaphenylene and polyphenylene sulfide.
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