CN108808092B - Active electrolyte, preparation method and application - Google Patents
Active electrolyte, preparation method and application Download PDFInfo
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- CN108808092B CN108808092B CN201811028193.6A CN201811028193A CN108808092B CN 108808092 B CN108808092 B CN 108808092B CN 201811028193 A CN201811028193 A CN 201811028193A CN 108808092 B CN108808092 B CN 108808092B
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- 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 belongs to the technical field of lithium-sulfur batteries, and discloses an active electrolyte, a preparation method and application thereof: 40-85 parts of ether solvent, 5-15 parts of lithium salt, 5-20 parts of thiophenyl ether auxiliary agent and 15-30 parts of polysulfide active component. The preparation method comprises the following steps: A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution; B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1). Use of an active electrolyte for the preparation of a lithium sulphur battery. The invention has higher reaction activity and stability, and can greatly improve the cycling stability of the lithium-sulfur battery.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to an active electrolyte, a preparation method and application thereof.
Background
In recent years, the lithium ion battery is successfully applied and popularized in the fields of electric automobiles, electric bicycles, energy storage batteries and the like, so that the lithium ion battery is convenient for people to go out and live and makes great contribution to the sustainable development of social energy. However, the energy density of the rocking chair type lithium ion battery system based on the graphite and metal oxide system reaches the theoretical limit, the space for further promotion is small, and the requirement of people for high-energy density energy storage devices can not be met gradually. The lithium-sulfur battery takes metal lithium as a negative electrode and sulfur as a positive electrode, the theoretical energy density can reach 2600Wh/kg, which is 3-5 times of the theoretical energy density of the lithium ion battery, and the sulfur material is low in price, easy to process and environment-friendly, so that the lithium-sulfur battery is considered as a novel energy storage system which is most hopeful to replace the lithium ion battery in the near term.
However, compared with the mature battery system of lithium ion battery, although the lithium sulfur battery has been developed as early as the nineteenth century and the fifties, the scale commercialization of the lithium sulfur battery has not been realized yet, which is mainly because the system still has more technical problems to be solved. Firstly, elemental sulfur and the discharge product lithium sulfideIs an electronic and ionic insulator at room temperature, limits the utilization rate and rate capability of sulfur in the discharge process of the battery, especially at high sulfur content of the electrode (sulfur content on the electrode)>80% wt) and high sulfur loading (sulfur loading on electrode)>5mg/cm2) The problems of pole piece cracking, low sulfur utilization rate, poor circulation stability and the like exist under the condition. Secondly, 17% volume expansion and contraction of sulfur can occur in the charging and discharging process, and the volume effect is more obvious under the condition of high loading capacity, so that the electrode material structure is changed, and the electrode material is easy to separate from a metal current collector, so that capacity attenuation is caused. Therefore, obtaining high sulfur capacity per unit area and high capacity per unit area for lithium sulfur battery positive electrodes to obtain lithium sulfur battery devices with higher energy density remains an important technical issue facing the commercialization of lithium sulfur batteries. On the other hand, in order to solve the problem of poor conductivity of sulfur materials, sulfur and carbon materials are generally melt-mixed to obtain a sulfur-carbon composite material so as to improve the conductivity thereof, and sulfur and carbon powders are generally solid-phase mixed and subjected to high-temperature heat treatment during the processing. Because the chemical activity of the sulfur powder and the carbon powder is high, the process has the risk of explosion under the condition of mass production, and the mixing efficiency is low, so that the sulfur is unevenly distributed in the electrode, and the consistency of the battery is poor.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide an active electrolyte, a preparation method and application thereof. The active electrolyte can be used for obtaining the active electrolyte capable of being charged and discharged by dissolving the sulfur active material in the electrolyte in a higher proportion, so that the positive electrode of the lithium-sulfur battery realizes a non-vulcanized structure, the control of the design capacity of the battery is realized by controlling the adding amount of the electrolyte in the battery assembling process, and the consistency of the battery assembling is improved. In addition, the reaction activity and stability of sulfur in the electrolyte can be improved under the action of the auxiliary agent, and a lithium-sulfur battery device with high unit area capacity and stable circulation can be prepared.
The technical scheme adopted by the invention is as follows:
the active electrolyte comprises the following components in parts by weight: 40-85 parts of ether solvent, 5-15 parts of lithium salt, 5-20 parts of thiophenyl ether auxiliary agent and 15-30 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 1 to 4; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 1-4.
Further, the value of y is 2 to 3; the value of x is 2-3.
Further, the ether solvent is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane or tetrahydrofuran.
Further, the lithium salt is one or more of bis (trifluoromethyl) sulfonyl imide lithium, bis (fluoro) sulfonyl imide lithium, trifluoromethyl sulfonic acid lithium and lithium nitrate.
Further, the active electrolyte comprises the following components in parts by weight: 50-65 parts of ether solvent, 8-12 parts of lithium salt, 10-15 parts of thiophenyl ether auxiliary agent and 18-25 parts of polysulfide active component.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1).
Further, the heating temperature of the step B is 40-70 ℃.
Use of an active electrolyte for the preparation of a lithium sulphur battery.
Use of an active electrolyte for the preparation of a lithium-sulfur battery comprising a carbon material positive electrode, an active electrolyte, a separator and a lithium metal negative electrode; the carbon material anode, the diaphragm and the lithium metal cathode are stacked layer by layer in a lamination or winding mode; the active electrolyte is filled in the gap between the carbon material positive electrode, the separator and the lithium metal negative electrode.
The active electrolyte is used for preparing the lithium-sulfur battery, and the material of the positive electrode of the carbon material is one or more of active carbon, carbon nano tubes or graphene; the diaphragm is a non-woven fabric diaphragm; the porosity of the non-woven fabric diaphragm is 40% -90%.
The invention has the beneficial effects that: according to the active electrolyte, the preparation method and the application, the thiophenyl ether auxiliary agent is added into the electrolyte to promote the dissolution of the polysulfide active component in the electrolyte, so that the reaction activity of the polysulfide component is improved, the electrolyte has extremely high reaction activity and energy density, the battery can be assembled for charging and discharging without adding extra sulfur active components to the positive electrode of the corresponding lithium-sulfur battery, and the battery assembly process is simplified. In addition, as the active components of the battery are dissolved in the liquid electrolyte, compared with the conventional lithium-sulfur battery, the lithium-sulfur battery has higher reaction activity and stability, and the cycle stability of the lithium-sulfur battery can be greatly improved.
Drawings
FIG. 1 shows the cell of the comparative example at 2mA/cm2And (4) a cycle test curve diagram under charge and discharge current.
FIG. 2 shows the cell of example 1 with active electrolyte 1# at 2mA/cm2And (4) a cycle test curve diagram under charge and discharge current.
FIG. 3 shows the cell of example 2 with active electrolyte 2# at 2mA/cm2And (4) a cycle test curve diagram under charge and discharge current.
FIG. 4 shows the cell of example 3 with active electrolyte 2# at 2mA/cm2And (4) a cycle test curve diagram under charge and discharge current.
Fig. 5 is a graph showing charge and discharge curves of comparative example, example 1, example 2, and example 3.
Detailed Description
The present invention is further illustrated below with reference to specific examples.
The active electrolyte comprises the following components in parts by weight: 40-85 parts of ether solvent, 5-15 parts of lithium salt, 5-20 parts of thiophenyl ether auxiliary agent and 15-30 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 1 to 4; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 1-4.
Further, the value of y is 2 to 3; the value of x is 2-3.
Further, the ether solvent is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane or tetrahydrofuran.
Further, the lithium salt is one or more of bis (trifluoromethyl) sulfonyl imide lithium, bis (fluoro) sulfonyl imide lithium, trifluoromethyl sulfonic acid lithium and lithium nitrate.
Further, the active electrolyte comprises the following components in parts by weight: 50-65 parts of ether solvent, 8-12 parts of lithium salt, 10-15 parts of thiophenyl ether auxiliary agent and 18-25 parts of polysulfide active component.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1).
Further, the heating temperature of the step B is 40-70 ℃.
Use of an active electrolyte for the preparation of a lithium sulphur battery.
Use of an active electrolyte for the preparation of a lithium-sulfur battery comprising a carbon material positive electrode, an active electrolyte, a separator and a lithium metal negative electrode; the carbon material anode, the diaphragm and the lithium metal cathode are stacked layer by layer in a lamination or winding mode; the active electrolyte is filled in the gap between the carbon material positive electrode, the separator and the lithium metal negative electrode.
The active electrolyte is used for preparing the lithium-sulfur battery, and the material of the positive electrode of the carbon material is one or more of active carbon, carbon nano tubes or graphene; the diaphragm is a non-woven fabric diaphragm; the porosity of the non-woven fabric diaphragm is 40% -90%.
Comparative example
Selecting a graphene carbon nanotube mixed powder sample (the sample is purchased from China age nanometer) and elemental sulfur according to a mass ratio of 1: 8, placing the mixture in a sealed tank, and carrying out heat treatment in a heating furnace at 155 ℃ for 6 hours to obtain sulfur-carbon composite powder. Mixing the mixed powder with polytetrafluoroethylene according to the mass ratio of 9: 1 in N-methyl pyrrolidone (NMP), fully mechanically mixing, blade-coating on an aluminum foil current collector by using a scraper with the thickness of 400 mu m, vacuum-drying at 100 ℃, mechanically rolling to obtain an electrode plate with the thickness of 220 mu m, wherein the sulfur content on the electrode plate is 80 wt%, and the sulfur loading is 5.0mg/cm2. Cutting the pole piece to 2cm2The pole piece assembled battery of (1) is tested.
The pole piece prepared by the method is used as a cathode, the metal lithium piece is used as an anode, and the mixed solvent of ethylene glycol dimethyl ether (DME) and 1, 3-epoxy pentalene (DOXL) is used as electrolyte (containing 1.0M LiTFSI +0.5 MLiNO)3Lithium salt) in a glove box filled with argon gas, assembling the lithium salt into a miniature soft package battery, and testing the battery, wherein the testing voltage range is 1.7-2.8V. FIG. 1 shows the cell of the comparative example at 2mA/cm2The cycle test curve under the charge-discharge current shows that the discharge capacity of the first circle of the battery is 10.60mAh, and the corresponding unit area capacity is 5.30mAh/cm2The sulfur utilization rate is 66.96%, the cycle retention rate after 50 cycles is 71.60%, and the charge-discharge efficiency is 96.70%.
Example 1
Selecting graphene carbon nanotube powder described in the comparative example, wherein the graphene carbon nanotube powder and polytetrafluoroethylene are mixed according to the mass ratio of 1: 0.8 in N-methyl pyrrolidone (NMP), mechanically mixing, spreading on aluminum foil collector with 150 μm scraper, vacuum drying at 100 deg.C, mechanically rolling to obtain electrode sheet with thickness of 60 μm, and loading carbon material on the electrode sheet of 0.7mg/cm2Cutting the pole piece to 2cm2The pole piece assembled battery of (1) is tested.
The preparation process of the active electrolyte used in this example is as follows: weighing 4.5g of ethylene glycol dimethyl ether and 2.0g of 1, 3-dioxolane in a glove box protected by ArF atmosphere, mixing, adding 0.9g of lithium bistrifluoromethylsulfonyl imide, 0.1g of lithium nitrate and 1.0g of auxiliary diphenyl disulfide, adding 1.5g of mixed powder of active components of sulfur and lithium sulfide (the molar ratio of sulfur to lithium sulfide is 3: 1) into the electrolyte after complete dissolution, heating the electrolyte on a heating plate at 70 ℃, and obtaining the required active electrolyte 1# after complete dissolution.
The battery assembly process described in this embodiment is: the laminated battery is assembled by adopting the carbon electrode as the positive electrode, the metal lithium as the negative electrode and the polyimide non-woven fabric diaphragm as the diaphragm, the mass of the injected active electrolyte 1# is 65mg, and the corresponding lithium-sulfur battery is obtained by packaging. FIG. 2 shows that the battery of the active electrolyte 1# is at 2mA/cm2The cycle test curve under the charge-discharge current shows that the discharge capacity of the first circle of the battery is 12.66mAh, and the corresponding unit area capacity is 6.33mAh/cm2The sulfur utilization rate is 75.58%, the cycle retention rate after 50 cycles is 91.23%, and the charge-discharge efficiency is 99.21%. The corresponding unit area capacity exertion and sulfur utilization rate are superior to those of the batteries corresponding to the comparative examples, and the cycling stability and the charging and discharging efficiency are improved, so that the active electrolyte and the corresponding lithium-sulfur battery structure can effectively improve the energy density and the cycling stability of the batteries.
Example 2
The preparation process of the active electrolyte used in this example is as follows: weighing 4.0g of diethylene glycol dimethyl ether and 1.5g of 1, 3-dioxolane in an ArF atmosphere protected glove box, mixing, adding 0.8g of lithium salt trifluoromethanesulfonate, 0.2g of lithium nitrate and 2.0g of auxiliary agent diphenyl disulfide, adding 1.5g of mixed powder of active components of sulfur and lithium sulfide (the molar ratio of sulfur to lithium sulfide is 3: 1) into the electrolyte after complete dissolution, heating the electrolyte on a heating plate at 70 ℃, and obtaining the required active electrolyte 2# after complete dissolution. The battery was assembled in the same manner as in example 1, and was encapsulated with addition of 2#65mg of active electrolyte to obtain a corresponding lithium sulfur battery. FIG. 3 shows that the active electrolyte 2# cell is at 2mA/cm2A cycle test curve under the charge-discharge current, the first circle discharge capacity of the battery is 15.31mAh, and the corresponding unit area capacity is 7.65mAh/cm2The sulfur utilization rate was 91.41%, the cycle retention rate after 50 cycles was 92.71%, and the charge-discharge efficiency was 99.33%. This example illustrates that increasing the proportion of the auxiliary agent in the active electrolyte can be effective within a certain rangeThe utilization rate of the sulfur active material in the high electrolyte is high, so that the energy density of the battery is correspondingly improved. As shown in fig. 5, the charging and discharging curves of the lithium-sulfur battery corresponding to the addition of the auxiliary agent are greatly different from those of the comparative example, the capacity corresponding to the high potential plateau in the range of 2.1-2.4V is significantly increased, and the capacity is increased along with the increase of the proportion of the auxiliary agent, which indicates that the addition of the auxiliary agent can effectively increase the utilization rate of the sulfur active component, thereby improving the energy density of the battery.
Example 3
The preparation process of the active electrolyte used in this example is as follows: weighing 3.5g of tetraethylene glycol dimethyl ether and 2.0g of 1, 4-dioxane in a glove box protected by ArF atmosphere, adding 1.2g of lithium salt lithium bis (fluorosulfonyl) imide and 0.8g of auxiliary agent diphenyl disulfide, adding 2.5g of mixed powder of active components of sulfur and lithium sulfide (molar ratio of sulfur to lithium sulfide is 3: 1) into the electrolyte after complete dissolution, heating the electrolyte on a heating plate at 70 ℃, and obtaining the required active electrolyte 3# after complete dissolution. The battery was assembled in the same manner as in example 1, and was encapsulated with addition of 2#40mg of active electrolyte to obtain a corresponding lithium sulfur battery. FIG. 4 shows the state that the active electrolyte 3# cell is at 2mA/cm2The cycle test curve under the charge-discharge current shows that the discharge capacity of the first circle of the battery is 12.44mAh, and the corresponding unit area capacity is 6.22mAh/cm2The sulfur utilization rate is 74.27%, the cycle retention rate after 50 circles is 88.10%, and the charge-discharge efficiency is 99.00%.
The following are comparative data for the parameters of comparative example, example 1, example 2 and example 3, as shown in table 1 below.
TABLE 1 comparison of cell Performance data for each of the examples and comparative examples
Therefore, the active electrolyte and the battery prepared by the active electrolyte have higher unit area capacity exertion and first-turn capacity, and the first-turn sulfur utilization rate, the cycle retention rate after 50 turns and the cycle efficiency after 50 turns are also greatly improved compared with the comparative example, so that the active electrolyte has higher reaction activity and stability compared with the conventional lithium-sulfur battery, and the cycle stability of the lithium-sulfur battery can be greatly improved.
Example 4
The active electrolyte comprises the following components in parts by weight: 40 parts of ether solvent, 5 parts of lithium salt, 5 parts of thiophenether auxiliary agent and 15 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 1; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 1.
The ether solvent is one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane or tetrahydrofuran.
The lithium salt is one of bis (trifluoromethyl) sulfonyl imide lithium, bis (fluoro) sulfonyl imide lithium, lithium trifluoro methyl sulfonate and lithium nitrate.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1). The heating temperature in the step B is 40 ℃.
Example 5
The active electrolyte comprises the following components in parts by weight: 85 parts of ether solvent, 15 parts of lithium salt, 20 parts of thiophenyl ether auxiliary agent and 30 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 4; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 4.
The ether solvent is a mixture obtained by mixing two of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane or tetrahydrofuran in any proportion.
The lithium salt is a mixture obtained by mixing two of lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate and lithium nitrate in any proportion.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1). The heating temperature in the step B is 70 ℃.
Example 6
The active electrolyte comprises the following components in parts by weight: 60 parts of ether solvent, 9 parts of lithium salt, 10 parts of thiophenyl ether auxiliary agent and 20 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 2; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 3.
The ether solvent is a mixture obtained by mixing three of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane or tetrahydrofuran in any proportion.
The lithium salt is a mixture obtained by mixing three of lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate and lithium nitrate in any proportion.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1). The heating temperature in the step B is 50 ℃.
Example 7
The active electrolyte comprises the following components in parts by weight: 50 parts of ether solvent, 8 parts of lithium salt, 10 parts of thiophenyl ether auxiliary agent and 18 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 3; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 2.
The ether solvent is a mixture obtained by mixing four of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane or tetrahydrofuran in any proportion.
The lithium salt is a mixture obtained by mixing lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate and lithium nitrate in any proportion.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1). The heating temperature in the step B is 60 ℃.
Example 8
The active electrolyte comprises the following components in parts by weight: 65 parts of ether solvent, 12 parts of lithium salt, 15 parts of thiophenether auxiliary agent and 25 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 2; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 3.
The ether solvent is a mixture obtained by mixing five of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane or tetrahydrofuran in any proportion.
The lithium salt is a mixture obtained by mixing four of lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate and lithium nitrate in any proportion.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1). The heating temperature in the step B is 65 ℃.
Example 9
The active electrolyte comprises the following components in parts by weight: 55 parts of ether solvent, 9 parts of lithium salt, 12 parts of thiophenyl ether auxiliary agent and 20 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 3; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 3.
The ether solvent is a mixture obtained by mixing ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane and tetrahydrofuran in any proportion.
The lithium salt is a mixture obtained by mixing bis (trifluoromethyl) sulfonyl imide lithium and bis (fluoro) sulfonyl imide lithium in any proportion.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1).
Further, the heating temperature of the step B is 58 ℃.
Use of an active electrolyte for the preparation of a lithium-sulfur battery comprising a carbon material positive electrode, an active electrolyte, a separator and a lithium metal negative electrode; the carbon material anode, the diaphragm and the lithium metal cathode are stacked layer by layer in a lamination or winding mode; the active electrolyte is filled in the gap between the carbon material positive electrode, the separator and the lithium metal negative electrode.
The active electrolyte is used for preparing the lithium-sulfur battery, and the material of the positive electrode of the carbon material is one or more of active carbon, carbon nano tubes or graphene; the diaphragm is a non-woven fabric diaphragm; the porosity of the nonwoven fabric separator was 60%.
Example 10
The active electrolyte comprises the following components in parts by weight: 62 parts of ether solvent, 11 parts of lithium salt, 13 parts of thiophenether auxiliary agent and 22 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 3; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 3.
The ether solvent is a mixture obtained by mixing ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether in any proportion.
The lithium salt is a mixture obtained by mixing lithium bistrifluoromethylsulfonyl imide, lithium bistrifluoromethylsulfonyl imide and lithium trifluoromethanesulfonate in any proportion.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1).
Further, the heating temperature of the step B is 55 ℃.
Use of an active electrolyte for the preparation of a lithium-sulfur battery comprising a carbon material positive electrode, an active electrolyte, a separator and a lithium metal negative electrode; the carbon material anode, the diaphragm and the lithium metal cathode are stacked layer by layer in a lamination or winding mode; the active electrolyte is filled in the gap between the carbon material positive electrode, the separator and the lithium metal negative electrode.
The active electrolyte is used for preparing the lithium-sulfur battery, and the material of the positive electrode of the carbon material is one or more of active carbon, carbon nano tubes or graphene; the diaphragm is a non-woven fabric diaphragm; the porosity of the nonwoven fabric separator was 60%. The diaphragm is a non-woven fabric diaphragm which has larger porosity and is made of polyolefin, polyvinyl alcohol, polyimide or cellulose.
Example 11
The active electrolyte comprises the following components in parts by weight: 62 parts of ether solvent, 11 parts of lithium salt, 13 parts of thiophenether auxiliary agent and 22 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 3; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 3.
The ether solvent is a mixture obtained by mixing 1, 3-dioxolane, 1, 4-dioxane and tetrahydrofuran in any proportion.
The lithium salt is a mixture obtained by mixing lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate and lithium nitrate in any proportion.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1).
Further, the heating temperature of the step B is 55 ℃.
Use of an active electrolyte for the preparation of a lithium-sulfur battery comprising a carbon material positive electrode, an active electrolyte, a separator and a lithium metal negative electrode; the carbon material anode, the diaphragm and the lithium metal cathode are stacked layer by layer in a lamination or winding mode; the active electrolyte is filled in the gap between the carbon material positive electrode, the separator and the lithium metal negative electrode.
The application of the active electrolyte in preparing the lithium-sulfur battery is characterized in that the material of the positive electrode of the carbon material is one of active carbon, carbon nano tubes or graphene; the diaphragm is a non-woven fabric diaphragm; the porosity of the nonwoven fabric separator was 40%. The diaphragm is a non-woven fabric diaphragm which has larger porosity and is made of polyolefin, polyvinyl alcohol, polyimide or cellulose.
Example 12
The active electrolyte comprises the following components in parts by weight: 62 parts of ether solvent, 11 parts of lithium salt, 13 parts of thiophenether auxiliary agent and 22 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 3; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 3.
The ether solvent is a mixture obtained by mixing tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane and tetrahydrofuran in any proportion.
The lithium salt is a mixture obtained by mixing lithium bistrifluoromethylsulfonyl imide, lithium trifluoromethanesulfonate and lithium nitrate in any proportion.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1).
Further, the heating temperature of the step B is 55 ℃.
Use of an active electrolyte for the preparation of a lithium-sulfur battery comprising a carbon material positive electrode, an active electrolyte, a separator and a lithium metal negative electrode; the carbon material anode, the diaphragm and the lithium metal cathode are stacked layer by layer in a lamination or winding mode; the active electrolyte is filled in the gap between the carbon material positive electrode, the separator and the lithium metal negative electrode.
The use of an active electrolyte for preparing a lithium-sulfur battery, wherein the material of the carbon material anode is a mixture of activated carbon and carbon nanotubes, a mixture of carbon nanotubes and graphene or a mixture of graphene and activated carbon; the diaphragm is a non-woven fabric diaphragm; the porosity of the nonwoven fabric separator was 90%. The diaphragm is a non-woven fabric diaphragm which has larger porosity and is made of polyolefin, polyvinyl alcohol, polyimide or cellulose.
Example 13
The active electrolyte comprises the following components in parts by weight: 63 parts of ether solvent, 10 parts of lithium salt, 14 parts of thiophenether auxiliary agent and 23 parts of polysulfide active component.
Wherein the structural formula of the polysulfide active component is Li2SyY has a value of 2; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 2.
The ether solvent is a mixture obtained by mixing ethylene glycol dimethyl ether, 1, 3-dioxolane and 1, 4-dioxane in any proportion.
The lithium salt is a mixture obtained by mixing lithium bistrifluoromethylsulfonyl imide, lithium difluorosulfonyl imide and lithium nitrate in any proportion.
A preparation method of an active electrolyte comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1).
Further, the heating temperature of the step B is 69 ℃.
Use of an active electrolyte for the preparation of a lithium-sulfur battery comprising a carbon material positive electrode, an active electrolyte, a separator and a lithium metal negative electrode; the carbon material anode, the diaphragm and the lithium metal cathode are stacked layer by layer in a lamination or winding mode; the active electrolyte is filled in the gap between the carbon material positive electrode, the separator and the lithium metal negative electrode.
The use of an active electrolyte for preparing a lithium-sulfur battery, wherein the material of the carbon material anode is a mixture of activated carbon and carbon nanotubes, a mixture of carbon nanotubes and graphene or a mixture of graphene and activated carbon; the diaphragm is a non-woven fabric diaphragm; the porosity of the nonwoven fabric separator was 70%. The diaphragm is a non-woven fabric diaphragm which has larger porosity and is made of polyolefin, polyvinyl alcohol, polyimide or cellulose.
The present invention is not limited to the above-described alternative embodiments, and various other forms of products can be obtained by anyone in light of the present invention. The above detailed description should not be taken as limiting the scope of the invention, which is defined in the claims, and which the description is intended to be interpreted accordingly.
Claims (10)
1. An active electrolyte, characterized by: the active electrolyte comprises the following components in parts by weight: 40-85 parts of ether solvent, 5-15 parts of lithium salt, 5-20 parts of thiophen ether auxiliary agent and 15-30 parts of polysulfide active component;
wherein the structural formula of the polysulfide active component is Li2SyY has a value of 1 to 4; the structural formula of the phenylether auxiliary agent is Ph-Sx-Ph, x has a value of 1-4.
2. The active electrolyte of claim 1, wherein: the value of y is 2-3; the value of x is 2-3.
3. The active electrolyte of claim 2, wherein: the ether solvent is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, 1, 4-dioxane or tetrahydrofuran.
4. An active electrolyte as claimed in claim 3, wherein: the lithium salt is one or more of bis (trifluoromethyl) sulfonyl imide lithium, bis (fluoro) sulfonyl imide lithium, lithium trifluoro methyl sulfonate and lithium nitrate.
5. The active electrolyte of claim 4, wherein: the active electrolyte comprises the following components in parts by weight: 50-65 parts of ether solvent, 8-12 parts of lithium salt, 10-15 parts of thiophenyl ether auxiliary agent and 18-25 parts of polysulfide active component.
6. A method of preparing an active electrolyte as claimed in any one of claims 1 to 5, characterized in that: the method comprises the following steps:
A. uniformly mixing an ether solvent, lithium salt and a thiophenyl ether auxiliary agent to obtain a lithium salt solution;
B. adding sulfur and lithium sulfide powder into lithium salt solution according to weight ratio, and heating for reaction to obtain the lithium-containing lithium2SyThe active electrolyte of (1).
7. The method of preparing an active electrolyte according to claim 6, wherein: the heating temperature of the step B is 40-70 ℃.
8. Use of the active electrolyte according to any of claims 1 to 5 for the preparation of a lithium-sulphur battery.
9. Use of the active electrolyte according to claim 8 for the preparation of a lithium-sulfur battery, characterized in that: the lithium-sulfur battery comprises a carbon material positive electrode, an active electrolyte, a diaphragm and a lithium metal negative electrode; the carbon material anode, the diaphragm and the lithium metal cathode are stacked layer by layer in a lamination or winding mode; the active electrolyte is filled in the gap between the carbon material positive electrode, the separator and the lithium metal negative electrode.
10. Use of the active electrolyte according to claim 9 for the preparation of a lithium-sulfur battery, characterized in that: the material of the carbon material anode is one or more of activated carbon, carbon nano tubes or graphene; the diaphragm is a non-woven fabric diaphragm; the porosity of the non-woven fabric diaphragm is 40% -90%.
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| CN113540567A (en) * | 2021-07-07 | 2021-10-22 | 清华大学 | Lithium-sulfur battery electrolyte and preparation method thereof |
| CN113871719A (en) * | 2021-09-24 | 2021-12-31 | 清华大学 | Lithium-sulfur battery electrolyte containing negative electrode protection solvent |
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