CN111653826A - Lithium-sulfur battery electrolyte and application thereof - Google Patents
Lithium-sulfur battery electrolyte and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium-sulfur battery electrolyte, and particularly discloses a lithium-sulfur battery electrolyte which comprises conductive lithium salt, an organic solvent and an additive A, wherein the additive A is one or two or more of a sulfhydryl compound, sodium borohydride, vitamin C and tributyl phosphine; the mass percentage of the additive in the electrolyte is 0.1-5 wt%. The additive A can effectively reduce a charging and discharging product of the lithium-sulfur battery, namely a disulfide bond of lithium polysulfide, promote the conversion of long-chain polysulfide to short chain, effectively relieve the diffusion of polysulfide to an electrolyte body and the shuttle effect caused by the diffusion, and improve the specific discharge capacity and the cycling stability of the battery.
Description
Technical Field
The invention relates to the field of lithium-sulfur batteries, in particular to an electrolyte for a lithium-sulfur battery and the lithium-sulfur battery using the electrolyte.
Background
In recent years, lithium sulfur batteries have attracted attention from researchers because of their advantages such as high energy density (2500Wh/kg, 2800Wh/L), wide sulfur source as an active material, and low cost, and are considered to be one of the most promising next-generation high energy density energy storage devices. However, some problems are serious due to its complicated electrochemical reaction mechanism
Limiting the practical application of lithium-sulfur batteries. Long-chain polysulphides Li as intermediate products of the discharge2SX(X4-8) is easily dissolved in ether electrolyte, so that the actual utilization rate of the positive active material is not high, and the actual specific capacity of the first loop is far lower than the theoretical capacity (1675mAh/g) of elemental sulfur; under the action of electric field force and concentration gradient, long-chain lithium polysulfide can diffuse to the lithium metal negative electrode, on one hand, the lithium metal negative electrode is corroded to react to generate short-chain lithium polysulfide and insulated Li2S, the former in turn diffuses into the positive electrode region and is oxidized to long-chain lithium polysulphides, which are cyclically repeated, the so-called "shuttle effect", leading to a severe reduction in coulombic efficiency and irreversible loss of active material, and thus to a constant decline in battery capacity.
Researchers have adopted many different strategies and achieved certain results in response to the shuttling problem of polysulfides in lithium sulfur batteries. In the positive electrode aspect, the most common strategy is to use a nano-structured carbon material with high specific surface area, to adsorb sulfur in the carbon material pores, and to prevent polysulfide shuttling by physical confinement. In patent CN102208645A, amorphous carbon is coated on the surface of the sulfur-based cathode active material, the particles of the cathode material are 10 nm-10 μm, and the thickness of the amorphous carbon layer is 1-5 nm, which significantly improves the conductivity of the cathode material. The carbon material coating has a certain effect on inhibiting polysulfide shuttling, but with repeated dissolution and deposition of sulfur in the charging and discharging processes, sulfur active substances gradually migrate from the interior of the carbon to the surface, so that the carbon material loses the effect. Considering that the polysulfide ions have polarity, and thus the nonpolar carbon material has very limited physical adsorption effect on the multiple lithium ions, researchers further propose that some polar metal compounds (oxides, sulfides, nitrides and the like) are loaded on the carbon material or the battery diaphragm, and the shuttling of the carbon material or the battery diaphragm is inhibited by utilizing the chemical adsorption effect of the compounds and the polysulfide ions, for example, CN201810129954 can effectively limit the shuttling effect of the polysulfide by adding tungsten disulfide with a lamellar structure into the lithium-sulfur battery diaphragm, and thus the battery performance of the lithium-sulfur battery is improved. On the other hand, a layer of relatively stable artificial SEI film is formed through surface treatment of the negative electrode, so that the reaction of electrolyte, polysulfide and lithium metal caused by instability of an intrinsic SEI film is avoided, and the influence of a shuttle effect can be relieved to a certain extent. For the characteristic of high solubility of polysulfide in a conventional ether electrolyte system, researchers propose a novel solvent component to reduce the dissolution of polysulfide by electrolyte, for example, CN201710807396 adopts ionic liquid and fluoroether as basic solvents, and utilizes the complementary synergistic effect of the ionic liquid and fluoroether to enhance the capability of the electrolyte for inhibiting the dissolution and shuttling of lithium polysulfide, but the ionic liquid and fluoroether tend to have higher viscosity and low conductivity, so the rate capability of the battery is greatly reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an electrolyte of a lithium-sulfur battery, which aims to solve the problem of shuttle of polysulfide and improve the specific discharge capacity and the cycling stability of the lithium-sulfur battery.
In the prior art, the main means for solving the problem of shuttle of polysulfide is to limit shuttle of polysulfide by a physical adsorption or chemical adsorption method, which can play a certain role, but the effect needs to be improved. The other idea is to adopt ionic liquid or fluoroether and the like as solvents to reduce the solubility of the electrolyte to polysulfide, but also greatly reduce the conductivity of the electrolyte and influence the rate performance of the battery.
In order to solve the problems of the prior art, the invention provides an electrolyte for a lithium-sulfur battery, which comprises a conductive lithium salt, an organic solvent and an additive A:
the additive A is one or more than two of sulfhydryl compound, borohydride, vitamin C and tributyl phosphine.
The invention aims to provide a novel technical idea for solving the shuttle effect of polysulfide, namely, a reducing material capable of reducing disulfide bonds of the polysulfide is added into an electrolyte, and the problem of the shuttle effect puzzling the industry of lithium-sulfur batteries is solved by utilizing the reaction between the reducing material and the polysulfide. However, the discharging process of the lithium-sulfur battery has its particularity, and in the early development of the technology, it is often difficult to successfully implement the innovative technical idea. Through intensive research, the inventor finds that in order to successfully implement the innovative technical idea of the invention in the lithium-sulfur battery, the compatibility problem of materials in a lithium-sulfur electrolyte system and a lithium negative electrode needs to be solved. Through further research, the additive A in the category can unexpectedly reduce sulfur-sulfur bonds of polysulfide under the cycling condition of a lithium-sulfur battery, so that the sulfur-sulfur bonds of long-chain polysulfide are broken and rapidly converted into short chains, thereby effectively inhibiting the shuttle effect and improving the capacity and cycling stability of the positive electrode.
Preferably, the mercapto compound includes at least one of mercaptoethanol, potassium thioglycolate, sodium thioglycolate, ammonium thioglycolate, dithioerythritol, dithiothreitol, reduced glutathione, N 'N-dimethyl-N' N-dimercaptoacetylhydrazine; further preferred is mercaptoethanol and/or dithiothreitol. It has been found that the preferred mercapto compounds unexpectedly further enhance the cycling performance and initial specific capacity of lithium sulfur batteries.
Preferably, the borohydride salt is sodium borohydride and/or potassium borohydride.
Preferably, the additive A is at least one of dithiothreitol, mercaptoethanol and vitamin C.
In the invention, the electrical performance of the additive A in the lithium-sulfur battery can be further improved by controlling the addition amount of the additive A in the electrolyte.
Preferably, the mass percentage of the additive A in the electrolyte is 0.1-5 wt%; preferably 0.5 to 1 wt%. At the preferable addition amount, the electrical performance of the lithium-sulfur battery can be further improved.
In the present invention, the organic solvent may be a solvent well known in the art of lithium sulfur battery electrolytes.
Preferably, the organic solvent is at least one of polyether compound, carbonate compound, alkyl ester compound, sulfone and sulfoxide compound.
Preferably, the organic solvent is 1, 3-Dioxolane (DOL), 1, 4-Dioxane (DX), ethylene glycol dimethyl ether (DME), and diethylene glycol dimethyl ether (G)2) Trimeric ethylene glycol dimethyl ether (G)3) Tetraglyme (G)4) Tetrahydrofuran (THF), Ethylmethylsulfone (EMS), sulfolane (TMS), Methylisopropylsulfone (MiPS), Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC).
The conductive lithium salt of the present invention may be any known lithium salt known to those skilled in the art.
Preferably, the conductive lithium salt is lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium trifluoromethanesulfonate (LiTf), lithium difluorooxalato borate (liddob), lithium difluorobis (oxalato) phosphate (lidbop), lithium dioxalate borate (LiBOB), lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium nitrate (LiNO)3) Lithium perchlorate (LiClO)4) One or more of them.
Preferably, the concentration of the conductive lithium salt in the electrolyte is preferably 0.5-4 mol/L.
Preferably, the electrolyte solution of the present invention further comprises an additive B, wherein the additive B is preferably one or more of lithium nitrate, lithium polysulfide, potassium nitrate, cesium nitrate, barium nitrate, ammonium nitrate, lithium nitrite, potassium nitrite, cesium nitrite, ammonium nitrite, methyl nitrate, phosphorus sulfide, lithium bromide, lithium iodide, indium iodide, dibenzothiazyl disulfide, iodonitrobenzene, and triphenylphosphine; lithium nitrate is more preferable.
The additive A and the additive B have a synergistic effect, and can synergistically solve the shuttle effect, so that the initial specific capacity and the cycling stability of the lithium-sulfur battery are further improved.
Preferably, the mass percentage content of the additive B in the electrolyte is 0.1-5%; preferably 1 to 2%.
The invention also provides an application of the lithium-sulfur battery electrolyte, which is used as the electrolyte for preparing the lithium-sulfur battery.
According to another object of the present invention, there is provided a lithium sulfur battery comprising the electrolyte. The lithium-sulfur battery comprises a positive plate, a negative plate, a diaphragm for separating the positive plate from the negative plate and electrolyte, wherein the electrolyte is the lithium-sulfur battery electrolyte.
Preferably, the positive plate comprises a positive current collector and a positive material compounded on the surface of the positive current collector; the positive electrode material is obtained by solidifying slurry of a positive electrode active material, a conductive agent, a binder and a solvent.
The positive active material is one or more of elemental sulfur, sulfur-containing polymer, lithium sulfide and lithium polysulfide.
The negative plate is one of metal lithium foil, a lithium plate, a lithium alloy and a silicon-carbon compound.
A lithium-sulfur battery preferably assembled using the electrolyte, characterized in that: comprises a positive plate, a negative plate, a diaphragm and a shell package; the diaphragm is positioned between the positive plate and the negative plate, and the positive plate, the negative plate, the diaphragm and the electrolyte are sealed in the battery shell package. The positive plate is formed by coating a positive active material, a conductive agent and a binder on a current collector in proportion, wherein the positive active material is one or more of elemental sulfur, a sulfur-containing polymer, lithium sulfide and lithium polysulfide. The negative plate is one of metal lithium foil, a lithium plate, a lithium alloy and a silicon-carbon compound.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
according to the invention, the reducibility of the electrolyte additive A to sulfur-sulfur bonds is utilized, and the long-chain polysulfide sulfur-sulfur bonds are rapidly converted into short chains through breakage, so that shuttling of polysulfide between a positive electrode and a negative electrode is effectively inhibited, and the capacity and the cycling stability of the positive electrode are improved. The used electrolyte additive is convenient and easy to obtain, the process is simple, and the practicability and operability are strong.
According to the technical scheme, the problems of low initial specific capacity and unsatisfactory cycle performance, which are puzzling technicians in the lithium-sulfur battery industry, can be effectively solved, the initial specific capacity can be increased to 1120mAh/g, the retention rate of 100 cycles of constant-current charging and discharging at 0.5C can be increased to 71.07%, and the effect is remarkable.
Drawings
Fig. 1 shows the cycle curves of the lithium-sulfur battery assembled by the electrolyte provided in example 1 of the present invention and the comparative example.
Detailed Description
The following examples are intended to illustrate the invention in further detail; and the scope of the claims of the present invention is not limited by the examples.
Example 1
A lithium sulfur battery was prepared as follows:
① electrolyte solution preparation in an argon atmosphere glove box (H)2O<0.1ppm), the organic solvent is ethylene glycol dimethyl ether (DME) according to volume ratio: 1, 3-Dioxolane (DOL) ═ 1: 1 and LiTFSI (1.0M), adding anhydrous lithium nitrate accounting for 2 percent of the total mass and dithiothreitol accounting for 1 percent of the total mass, and fully and uniformly stirring to obtain the electrolyte of the lithium-sulfur battery.
Preparing a sulfur positive electrode: mixing a sulfur/carbon composite material (the sulfur carrying amount is 70%), acetylene black and PVDF according to a ratio of 80:10:10, adding a proper volume of N-methylpyrrolidone (NMP), placing the mixture into a homogenizer, stirring for 15min, and forming stable and uniform anode slurry at a rotating speed of 15 kr/min. The slurry was coated on carbon-coated aluminum foil with a doctor blade and dried in an oven at 80 ℃ for 8h until the NMP was completely volatilized.
Assembling and testing the lithium-sulfur button cell: and (3) punching the prepared sulfur pole piece into a round pole piece with the diameter of 13mm, and drying in an oven at the temperature of 55 ℃ for 1 h. In argon atmosphere, a metal lithium sheet is taken as a negative electrode, a polypropylene microporous membrane with the model of Celgard 2400 is selected as a diaphragm, the using amount of electrolyte is 15 mu L/mg S, and the CR2025 lithium-sulfur battery is sequentially assembled. And (2) standing the prepared battery in a thermostatic chamber at 25 ℃ for 12h, and then performing charge-discharge cycle test on a blue test charge-discharge tester under the test conditions of constant current of 0.5C, a potential interval of 1.7-2.8V and 100 cycles (see figure 1).
Example 2
Compared with example 1, the difference is only that the addition amount of the electrolyte additive A is different; the preparation process of the electrolyte in the present case is as follows: the organic solvent is ethylene glycol dimethyl ether (DME) according to the volume ratio: 1, 3-Dioxolane (DOL) ═ 1: 1 and LiTFSI (1.0M), adding anhydrous lithium nitrate accounting for 2 percent of the total mass and dithiothreitol accounting for 0.5 percent of the total mass, and fully and uniformly stirring.
Sulfur positive electrode preparation and lithium sulfur button cell assembly testing were the same as in example 1.
Example 3
Compared with example 1, the difference is only that the electrolyte composition is different; the preparation process of the electrolyte in the present case is as follows: the organic solvent is ethylene glycol dimethyl ether (DME) according to the volume ratio: 1, 3-Dioxolane (DOL) ═ 1: 1 and LiTFSI (1.0M), only 1 percent of dithiothreitol is added without adding lithium nitrate, and the mixture is fully and evenly stirred.
Sulfur positive electrode preparation and lithium sulfur button cell assembly testing were the same as in example 1.
Example 4
Compared with example 1, the difference is only that the electrolyte composition is different; the preparation process of the electrolyte in the present case is as follows: the organic solvent is ethylene glycol dimethyl ether (DME) according to the volume ratio: 1, 3-Dioxolane (DOL) ═ 1: 1 and LiTFSI (1.0M), adding anhydrous lithium nitrate accounting for 2 percent of the total mass and mercaptoethanol accounting for 1 percent of the total mass, and fully and uniformly stirring.
Sulfur positive electrode preparation and lithium sulfur button cell assembly testing were the same as in example 1.
Example 5
Compared with example 1, the difference is only that the electrolyte composition is different; the preparation process of the electrolyte in the present case is as follows: the organic solvent is ethylene glycol dimethyl ether (DME) according to the volume ratio: 1, 3-Dioxolane (DOL) ═ 1: 1 and LiTFSI (1.0M), adding anhydrous lithium nitrate accounting for 2 percent of the total mass and reduced glutathione accounting for 1 percent of the total mass, and fully and uniformly stirring.
Sulfur positive electrode preparation and lithium sulfur button cell assembly testing were the same as in example 1.
Example 6
Compared with example 1, the difference is only that the electrolyte composition is different; the preparation process of the electrolyte in the present case is as follows: the organic solvent is ethylene glycol dimethyl ether (DME) according to the volume ratio: 1, 3-Dioxolane (DOL) ═ 1: 1 and LiTFSI (1.0M), adding anhydrous lithium nitrate accounting for 2 percent of the total mass and vitamin C accounting for 1 percent of the total mass, and fully and uniformly stirring.
Sulfur positive electrode preparation and lithium sulfur button cell assembly testing were the same as in example 1.
Comparative example 1
The only difference compared to example 1 is that the electrolyte is not supplemented with additive a. The electrolyte preparation process of this comparative example was: in an argon atmosphere glove box (H)2O<0.1ppm), the organic solvent is ethylene glycol dimethyl ether (DME) according to volume ratio: 1, 3-Dioxolane (DOL) ═ 1: 1 and LiTFSI (1.0M), adding anhydrous lithium nitrate with the total mass of 2 percent, and fully and uniformly stirring to obtain the electrolyte of the lithium-sulfur battery.
Sulfur positive electrode preparation and lithium sulfur button cell assembly testing were the same as in example 1.
Comparative example 2
The only difference compared to example 1 is that the electrolyte was not supplemented with additive a and lithium nitrate. The electrolyte preparation process of this comparative example was: in an argon atmosphere glove box (H)2O<0.1ppm), the organic solvent is ethylene glycol dimethyl ether (DME) according to volume ratio: 1, 3-Dioxolane (DOL) ═ 1: 1 and LiTFSI (1.0M), and fully and uniformly stirring to obtain the lithium-sulfur battery electrolyte.
Sulfur positive electrode preparation and lithium sulfur button cell assembly testing were the same as in example 1.
Comparative example 3
The only difference compared to example 1 is that the additive a of the invention is replaced by a reducing material that can reduce disulfide bonds: the method comprises the following specific steps: the electrolyte preparation process of this comparative example was: in an argon atmosphere glove box (H)2O<0.1ppm), the organic solvent is ethylene glycol dimethyl ether (DME) according to volume ratio: 1, 3-Dioxolane (DOL) ═ 1: 1 and LiTFSI (1.0M), adding anhydrous lithium nitrate and tris (2-carbonyl ethyl) phosphate which account for 2 percent of the total mass, and fully and uniformly stirring to obtain the lithium-sulfur battery electrolyte.
Sulfur positive electrode preparation and lithium sulfur button cell assembly testing were the same as in example 1.
TABLE 1 test results of examples 1-6 and comparative examples 1-3
As can be seen from table 1, the addition of additive a required by the present invention to the electrolyte of a lithium-sulfur battery can bring about better initial capacity and cycle stability, and the research also finds that the combination of additive a and additive B can produce synergistic effect, which can further improve cycle performance.
The study of the invention also finds that the batteries without the additive A (comparative examples 1 and 2) provided by the invention have low coulombic efficiency and rapid battery capacity decay; the electrolyte added with the additive provided by the invention is used, so that the capacity, the circulation and the coulombic efficiency of the battery are improved.
The electrolyte additive A provided by the invention can quickly reduce long-chain polysulfide into short chains through spontaneous reduction of sulfur-sulfur bonds, so that shuttling of polysulfide between a positive electrode and a negative electrode is effectively inhibited. Therefore, the electrolyte of the present invention further improves the capacity, efficiency, and cycle performance of the battery on the basis of the comparative example. However, in order to solve the performance of the lithium-sulfur battery, the additive A has special requirements, and the compound which can reduce the disulfide bond can solve the shuttling problem of the lithium-sulfur battery. For example, in comparative example 3, which is an arrangement of the present invention, the added tris (2-carbonylethyl) phosphate can theoretically reduce the disulfide bond as well, but the actual addition deteriorates the cell performance instead. Therefore, the additive A required by the invention can be used for unexpectedly solving the polysulfide shuttling problem of the lithium-sulfur battery and improving the electrical performance.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. An electrolyte for a lithium-sulfur battery, comprising a conductive lithium salt, an organic solvent, and an additive a: the additive A is one or more than two of sulfhydryl compound, borohydride, vitamin C and tributyl phosphine.
2. The electrolyte for a lithium sulfur battery according to claim 1, wherein: the sulfhydryl compound comprises at least one of mercaptoethanol, potassium thioglycolate, sodium thioglycolate, ammonium thioglycolate, dithioerythritol, dithiothreitol, reduced glutathione and N 'N-dimethyl-N' N-dimercaptoacetyl hydrazine.
3. The electrolyte for a lithium sulfur battery according to claim 1, wherein: the additive A is at least one of dithiothreitol, mercaptoethanol and vitamin C.
4. The electrolyte for a lithium-sulfur battery according to any one of claims 1 to 3, wherein: the mass percentage of the additive A in the electrolyte is 0.1-5 wt%; preferably 0.5 to 1 wt%.
5. The electrolyte for a lithium-sulfur battery according to any one of claims 1 to 4, wherein: also comprises an additive B; the additive B is one or more of lithium nitrate, lithium polysulfide, potassium nitrate, cesium nitrate, barium nitrate, ammonium nitrate, lithium nitrite, potassium nitrite, cesium nitrite, ammonium nitrite, methyl nitrate, phosphorus sulfide, lithium bromide, lithium iodide, indium iodide, dibenzothiazyl disulfide, iodonitrobenzene and triphenyl phosphorus.
6. The electrolyte for a lithium sulfur battery according to claim 5, wherein: the mass percentage of the additive B in the electrolyte is 0.1-5%.
7. The additive-containing electrolyte for a lithium sulfur battery according to claim 1, wherein: the organic solvent is at least one of polyether compounds, carbonate compounds, alkyl ester compounds, sulfone and sulfoxide compounds;
preferably, the organic solvent is a mixture of one or more of 1, 3-dioxolane, 1, 4-dioxane, ethylene glycol dimethyl ether, trimeric ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylmethyl sulfone, sulfolane, methyl isopropyl sulfone, ethylene carbonate, dimethyl carbonate and diethyl carbonate.
8. The electrolyte for a lithium sulfur battery according to claim 1, wherein: the conductive lithium salt is one or more of lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium trifluoromethanesulfonate, lithium difluorooxalato borate, lithium difluorobis (oxalato) phosphate, lithium dioxalate borate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium nitrate and lithium perchlorate;
preferably, the concentration of the conductive lithium salt in the electrolyte is preferably 0.5-4 mol/L.
9. Use of the lithium sulphur battery electrolyte according to any of claims 1 to 8, wherein: used as an electrolyte for preparing a lithium-sulfur battery.
10. The utility model provides a lithium sulfur battery, by positive plate, negative pole piece, be used for positive plate and negative pole piece separated diaphragm and electrolyte, its characterized in that: the electrolyte comprises the electrolyte as claimed in any one of claims 1 to 8.
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| CN112382758A (en) * | 2020-10-14 | 2021-02-19 | 温州大学 | Ferrocene/glutathione compound-containing lithium-sulfur battery positive electrode material, positive electrode piece, preparation method and lithium-sulfur battery |
| CN112952198A (en) * | 2021-03-22 | 2021-06-11 | 华中科技大学 | Sulfur energy storage battery and method for improving rate capability and cycle stability of sulfur energy storage battery |
| CN113067036A (en) * | 2021-03-30 | 2021-07-02 | 湖南师范大学 | Formula of electrolyte for lithium-sulfur battery |
| CN113067035A (en) * | 2021-03-30 | 2021-07-02 | 湖南师范大学 | Formula of lithium-sulfur battery electrolyte |
| CN113540568A (en) * | 2021-07-12 | 2021-10-22 | 吉安谊盛电子材料有限公司 | Electrolyte and high-capacity lithium ion battery |
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| CN113540568A (en) * | 2021-07-12 | 2021-10-22 | 吉安谊盛电子材料有限公司 | Electrolyte and high-capacity lithium ion battery |
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