CN114142081B - Ion-selective gel-state electrolyte, preparation method and lithium-sulfur battery - Google Patents
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Abstract
The invention discloses an ion selective gel electrolyte, a preparation method and a lithium-sulfur battery, wherein the electrolyte comprises a polymer matrix and liquid electrolyte held in the polymer matrix; the polymer matrix is prepared by performing sulfonation and crosslinking reaction on polyether-ether-ketone; the preparation method comprises the following steps: preparing a sulfonated polyether-ether-ketone solution system, and adding a cross-linking agent for cross-linking reaction to obtain a cross-linked sulfonated polyether-ether-ketone mixed solution; cooling and precipitating in ice-water bath, filtering and washing to obtain crosslinked sulfonated polyether-ether-ketone; dissolving in a mixed solution of an organic solvent and water to obtain a polymer precursor solution; coating on a glass plate to obtain a wet film, standing for defoaming, and then drying in vacuum to obtain a cross-linked sulfonated polymer matrix; and cutting, immersing into lithium sulfur electrolyte, and removing the redundant electrolyte on the surface to obtain the ion selective gel electrolyte membrane. The gel-state polymer electrolyte membrane does not contain free electrolyte, can reduce the solubility of polysulfide ions, and is favorable for weakening the shuttle behavior of the polysulfide ions.
Description
Technical Field
The invention relates to the field of lithium-sulfur batteries, in particular to an ion-selective gel-state electrolyte, a preparation method and a lithium-sulfur battery.
Background
Lithium-sulfur secondary battery (lithium-sulfur battery for short) using metal lithium as negative electrode and elemental sulfur as positive electrode active material, and LiCoO 2 、LiMn 2 O 4 、LiFePO 4 Compared with the lithium ion battery taking ternary materials and the like as anode materials, the lithium ion battery has remarkable advantages in the aspects of specific capacity, energy density, power density and the like, and the theoretical specific capacity of elemental sulfur is 1675mAh g -1 The theoretical specific capacity of the catalyst is 3861mAh g -1 The theoretical specific energy of the assembled battery of the lithium metal can reach 2600Wh kg -1 In addition, the elemental sulfur also hasThe method has the advantages of rich resources, low cost, environmental friendliness and the like, meets the requirements of electric vehicles on power batteries, and also meets the requirements of portable electronic products on light weight, miniaturization, low cost and no toxicity of chemical power supplies. However, lithium-sulfur batteries also have some non-negligible problems: first, the electronic insulating property inherent to elemental sulfur (5 × 10) -30 S cm -1 At 25 ℃) to render it chemically inert; in addition, an intermediate polysulfide generated in the charging and discharging reaction of the lithium-sulfur battery is easily dissolved in the organic electrolyte, so that the loss of active substances is caused, and the viscosity of the electrolyte is increased after the lithium polysulfide is dissolved in the electrolyte, so that the ionic conductivity of the electrolyte is influenced; meanwhile, polysulfide dissolved in the electrolyte diffuses through the separator to the negative electrode, reacts with metallic lithium to form low-valent polysulfide, and then diffuses back to the sulfur positive electrode, thereby causing corrosion of the lithium negative electrode. This phenomenon of the reciprocal migration of the polysulphide anion between the positive and negative electrodes is called "shuttle effect". The shuttle effect can lead to the phenomena that the charging time of the battery is prolonged, the charging capacity is far larger than the discharging capacity and the internal heating of the battery, and the cycle performance of the sulfur electrode and the development of a practical battery system are restricted.
In order to solve the above problems, in recent years, research on separators for lithium-sulfur batteries is in a growing trend, and mainly the commercial separators are modified or directly coated with carbon-based materials with strong conductivity, polymers or other materials capable of adsorbing polysulfide ions, so that the cycle stability of the lithium-sulfur batteries can be improved to a certain extent, but the matrix structure of the separators is not controllable, and the electrolyte still needs to be used excessively, so that the exertion of the inhibition effect on the shuttle effect of the polysulfide ions is limited. Therefore, the electrolyte or electrolyte membrane is designed to be optimized from the viewpoint of the fundamental problem, i.e., the reduction of the solubility of polysulfide and the inhibition of shuttling thereof, thereby improving the capacity and cycle performance of the lithium-sulfur battery.
Disclosure of Invention
The invention aims to provide an ion selective gel-state electrolyte, a preparation method and a lithium-sulfur battery, wherein the gel-state polymer electrolyte membrane does not contain free electrolyte, can reduce the solubility of polysulfide ions and is beneficial to weakening the shuttle behavior of the polysulfide ions; the polymer matrix contains electrons with high cloud densityThe electrolyte membrane has ion selectivity due to functional groups with strong electronegativity, such as benzene ring pi bonds, sulfonic groups and phosphate groups, so that the electrolyte membrane can promote the transmission of electropositive lithium ions and inhibit the migration behavior of polysulfide anions in the membrane, thereby inhibiting the shuttle effect of the electrolyte membrane, and improving the problems of capacity attenuation and low coulombic efficiency of lithium-sulfur batteries; the scheme is simple, convenient and controllable, the operability is strong, and the room-temperature ionic conductivity of the obtained ion selective gel electrolyte membrane is 10 -3 S cm -1 The order of magnitude is higher, the conductivity of the electrolyte is close to that of the traditional liquid electrolyte, the transference number of lithium ions is close to 1, and the electrolyte membrane has lithium ion selectivity. The lithium sulfur battery containing the ion selective electrolyte membrane is at 500mA g -1 The capacity retention rate of the capacitor can reach 80.6 percent under the current density after the cycle for 250 weeks. At 100, 200, 400, 800, 1000mA g -1 The coulomb efficiency of charging and discharging under different current densities is close to 100 percent, which shows that the shuttle effect of polysulfide ions is effectively inhibited.
The purpose of the invention can be realized by the following technical scheme:
an ion-selective gel state electrolyte comprising a polymer matrix and a liquid electrolyte held therein;
the polymer matrix is prepared by the sulfonation and crosslinking reaction of polyether-ether-ketone.
A method of preparing an ion selective gel state electrolyte, the method comprising the steps of:
s1, weighing polyether-ether-ketone, adding the polyether-ether-ketone into excessive concentrated sulfuric acid for sulfonation reaction to obtain a sulfonated polyether-ether-ketone solution system; the reaction equation is:
s2, adding a cross-linking agent into the sulfonated polyether ether ketone solution system obtained in the S1 for cross-linking reaction to obtain a cross-linked sulfonated polyether ether ketone mixed solution;
s3, placing the mixed solution obtained in the step S2 in an ice water bath for cooling and precipitating, filtering and washing until the filtrate is neutral, and performing vacuum drying and precipitation to obtain the crosslinked sulfonated polyether ether ketone;
s4, weighing the crosslinked sulfonated polyether ether ketone obtained in the S3, and dissolving the crosslinked sulfonated polyether ether ketone in a mixed solution of an organic solvent and water to obtain a polymer precursor solution;
s5, coating the polymer precursor solution obtained in the step S4 on a glass plate to obtain a wet film, standing for defoaming, and then drying in vacuum to obtain a cross-linked sulfonated polymer matrix;
and S6, cutting the polymer matrix obtained in the step S5, immersing the polymer matrix into a lithium-sulfur electrolyte, and removing the redundant electrolyte on the surface to obtain the ion-selective gel electrolyte membrane.
Further, the mass ratio of the polyether-ether-ketone to the concentrated sulfuric acid in the S1 is 1: (40-50), the sulfonation reaction condition is 55-65 ℃, 4-6 h.
Further, the cross-linking agent in S2 is sodium trimetaphosphate or sodium hexametaphosphate, the mass ratio of the cross-linking agent to the polyether-ether-ketone is 1-30%, the cross-linking reaction is kept at the sulfonation reaction temperature, and the reaction time is 10-60 min.
Further, the vacuum drying condition in the S3 is 50-90 ℃ and 12-24 h.
Further, the organic solvent in S4 is any one of NMP, DMF, and DMSO, and the volume ratio of the organic solvent to water is 1: (1-4), the mass concentration of the cross-linked sulfonated polyether-ether-ketone is 4-10%.
Further, in the S5, the wet film standing defoaming conditions are as follows: standing for 3-6 h under room temperature regulation; the vacuum drying conditions were: 50-90 ℃ for 12-24 h.
Further, the lithium sulfur electrolyte in S6 is an ether solution or an ether-containing solution in which lithium bis-imine is dissolved: 1M LiTFSI +DOL/DME (1) 3 (ii) a The dipping time is 10-60 min.
The lithium-sulfur battery comprises the ion selective gel-state electrolyte membrane prepared by the preparation method, and the ion selective gel-state electrolyte membrane is used for inhibiting the polysulfide ion shuttling effect of the lithium-sulfur battery.
The invention has the beneficial effects that:
1. the gel-state polymer electrolyte membrane does not contain free electrolyte, can reduce the solubility of polysulfide ions and is beneficial to weakening the shuttle behavior of the polysulfide ions;
2. the polymer matrix contains functional groups with high electronegativity, such as benzene ring pi bonds with high electron cloud density, sulfonic groups and phosphate groups, so that the electrolyte membrane has ion selectivity, and on one hand, the electrolyte membrane can promote electropositive lithium ion transmission and simultaneously inhibit migration behavior of polysulfide anions in the membrane, thereby inhibiting shuttle effect of the electrolyte membrane, and improving the problems of capacity attenuation of a lithium-sulfur battery and low coulombic efficiency;
3. the method has the advantages of simple and controllable scheme and strong operability, and the room-temperature ionic conductivity of the obtained ion selective gel electrolyte membrane is 10 -3 S cm -1 The order of magnitude is higher, the conductivity of the electrolyte is close to that of the traditional liquid electrolyte, the transference number of lithium ions is close to 1, and the electrolyte membrane has lithium ion selectivity. The lithium sulfur battery containing the ion selective electrolyte membrane is at 500mA g -1 The capacity retention rate of the current density can reach 80.6 percent after the cycle of 250 weeks. At 100, 200, 400, 800, 1000mA g -1 The coulomb efficiency of charging and discharging under different current densities is close to 100 percent, which shows that the shuttle effect of polysulfide ions is effectively inhibited.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a graph showing the results of rate capability tests of lithium sulfur batteries of the present invention at different current densities;
FIG. 2 is a graph of the coulombic efficiency results for lithium sulfur batteries of the present invention at different current densities;
FIG. 3 is a SEM representation of a dry polymer film of the present invention at different magnifications;
FIG. 4 is a graph showing the results of rate capability tests of lithium sulfur batteries of the present invention at different current densities;
FIG. 5 is a graph of coulombic efficiency results for lithium sulfur batteries of the present invention at different current densities;
FIG. 6 shows the lithium sulfur battery of the present invention at 500mA g -1 And (5) a cycle performance test result chart under the current density.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following examples further illustrate the preparation of the ion-selective gel polymer electrolyte for lithium-sulfur batteries and the method of using the same according to the present invention.
Example 1:
mixing polyether-ether-ketone and concentrated sulfuric acid according to the mass ratio of 1:40 and reacting for 6 hours at 55 ℃. Adding a cross-linking agent with the mass ratio of 1% and sodium trimetaphosphate, continuing to react for 10min, pouring the mixed solution into an ice water bath for precipitation after the reaction is finished, filtering and washing until the filtrate is neutral, and drying in a vacuum drying oven at 50 ℃ for 24h to obtain the cross-linked sulfonated polyether ether ketone. Weighing cross-linked sulfonated polyether ether ketone, dissolving in NMP + H 2 O (the volume ratio is 1:1), the mass concentration of the cross-linked sulfonated polyether ether ketone is 4%, the obtained uniform solution is coated on a glass plate to obtain a wet film, the wet film is kept stand for 3h for defoaming at room temperature, and the wet film is transferred to a vacuum drying oven to be dried for 24h at 50 ℃ to form a film. Cutting the dry polymer film into disks of 16mm diameter, immersing in a lithium sulfur electrolyte (1M LiTFSIDOL/DME (V/V = 1:1) +0% 3 ) And after dipping for 10min, removing the redundant electrolyte on the surface to obtain the polymer electrolyte membrane. Assembling the electrolyte membrane into a lithium-sulfur battery with 100, 200, 400, 800, 1000mA g -1 The current density is charged and discharged, the discharge specific capacity of the battery is not obviously attenuated when the current density is increased, and the battery has good rate capability of 1000mA g -1 The specific discharge capacity of the battery still has 420mA g under the current density -1 . The coulombic efficiency of the battery under different current densities is close to 100 percent, which shows that the shuttle effect of polysulfide ions is inhibited.
Example 2:
mixing polyether-ether-ketone and concentrated sulfuric acid according to the mass ratio of 1:50 are mixed and reacted for 4h at 65 ℃. Adding 30 percent by mass of cross-linking agent and sodium trimetaphosphate to continue reacting 60And min, pouring the mixed solution into an ice water bath for precipitation after the reaction is finished, filtering and washing until the filtrate is neutral, and drying in a vacuum drying oven at 90 ℃ for 12h to obtain the crosslinked sulfonated polyether ether ketone. Weighing cross-linked sulfonated polyether ether ketone, and dissolving in DMF + H 2 O (the volume ratio of 1:4) in the mixed solution, making the mass concentration of the cross-linked sulfonated polyether ether ketone be 10%, coating the obtained uniform solution on a glass plate to obtain a wet film, standing for 6h at room temperature for defoaming, and transferring the wet film to a vacuum drying oven to be dried for 12h at 90 ℃ for film formation. And (4) performing SEM representation on the dry film, wherein the surface of the film is smooth, and uniform network lines can be seen on the cross section of the film. Cutting the dry polymer film into 16mm diameter disks, immersing in lithium sulfur electrolyte (1M LiTFSIDOL/DME (V/V = 1:1) +5% LiNO% 3 ) And after 60min of immersion, removing the redundant electrolyte on the surface to obtain the polymer electrolyte membrane. The battery is 100, 200, 400, 800 and 1000mA g -1 Charging and discharging at current density of 1000mA g -1 The discharging specific capacity is 311mA g under the current density -1 . The coulombic efficiency of the battery is 90% under different current densities, and the current density is increased to 800 mA g and 1000mA g -1 The coulomb efficiency approaches 100%.
Example 3:
polyether-ether-ketone and concentrated sulfuric acid are mixed according to the mass ratio of 1:40 and reacting for 6 hours at 55 ℃. Adding a cross-linking agent with the mass ratio of 5% to sodium trimetaphosphate, continuously reacting for 30min, pouring the mixed solution into ice water bath for precipitation after the reaction is finished, filtering and washing until the filtrate is neutral, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain the cross-linked sulfonated polyetheretherketone. Weighing cross-linked sulfonated polyether ether ketone, dissolving in NMP + H 2 O (1:2 in volume ratio), coating the obtained uniform solution on a glass plate to obtain a wet film, standing at room temperature for 4h for defoaming, and transferring to a vacuum drying oven for drying at 80 ℃ for 24h to form the film. Cutting the dry polymer film into 16mm diameter disks, immersing in lithium sulfur electrolyte (1M LiTFSI DOL/DME (V/V = 1:1) +1% LiNO% 3 ) And removing the redundant electrolyte on the surface to obtain the polymer electrolyte membrane. Assembling the electrolyte membrane into a lithium-sulfur battery with 500mA g -1 The capacity retention rate of the current density at 250 cycles is 80.6 percent.
In the description herein, references to the description of "one embodiment," "an example," "a specific example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (9)
1. An ion-selective gel-state electrolyte, comprising a polymer matrix and a liquid electrolyte held therein;
the polymer matrix is prepared by taking polyether-ether-ketone as a raw material and performing sulfonation and crosslinking reactions, and a crosslinking agent used in the crosslinking reaction is sodium trimetaphosphate or sodium hexametaphosphate;
adding the polyether-ether-ketone into excessive concentrated sulfuric acid for sulfonation reaction to obtain a sulfonated polyether-ether-ketone solution system; the reaction equation is as follows:
the ion-selective gel state electrolyte is used in a lithium sulfur battery.
2. A method for preparing the ion-selective gel electrolyte of claim 1, comprising the steps of:
s1, weighing polyether-ether-ketone, adding the polyether-ether-ketone into excessive concentrated sulfuric acid for sulfonation reaction to obtain a sulfonated polyether-ether-ketone solution system; the reaction equation is as follows:
s2, adding a cross-linking agent into the sulfonated polyether ether ketone solution system obtained in the S1 for cross-linking reaction, wherein the cross-linking agent is sodium trimetaphosphate or sodium hexametaphosphate to obtain a cross-linked sulfonated polyether ether ketone mixed solution;
s3, placing the mixed solution obtained in the step S2 in an ice water bath for cooling and precipitating, filtering and washing until the filtrate is neutral, and performing vacuum drying and precipitation to obtain the crosslinked sulfonated polyether ether ketone;
s4, weighing the crosslinked sulfonated polyether ether ketone obtained in the step S3, and dissolving the crosslinked sulfonated polyether ether ketone in a mixed solution of an organic solvent and water to obtain a polymer precursor solution;
s5, coating the polymer precursor solution obtained in the step S4 on a glass plate to obtain a wet film, standing for defoaming, and then drying in vacuum to obtain a cross-linked sulfonated polymer matrix;
and S6, cutting the polymer matrix obtained in the step S5, immersing the polymer matrix into a lithium-sulfur electrolyte, and removing the redundant electrolyte on the surface to obtain the ion-selective gel electrolyte membrane.
3. The preparation method according to claim 2, wherein the mass ratio of the polyetheretherketone to the concentrated sulfuric acid in the S1 is 1: (40-50), the sulfonation reaction condition is 55-65 ℃, 4-6 h.
4. The preparation method according to claim 2, wherein the mass ratio of the cross-linking agent to the polyetheretherketone in the S2 is 1-30%, and the cross-linking reaction is carried out at the sulfonation reaction temperature for 10-60 min.
5. The method according to claim 2, wherein the vacuum drying in S3 is performed at 50-90 ℃ for 12-24 h.
6. The preparation method according to claim 2, wherein the organic solvent in S4 is any one of NMP, DMF and DMSO, and the volume ratio of the organic solvent to water is 1: (1-4), the mass concentration of the cross-linked sulfonated polyether-ether-ketone is 4-10%.
7. The preparation method according to claim 2, wherein the wet film standing defoaming conditions in S5 are as follows: standing for 3-6 h under room temperature regulation; the vacuum drying conditions were: 50-90 ℃ for 12-24 h.
8. The preparation method according to claim 2, wherein the lithium sulfur electrolyte in S6 is an ether solution or an ether-containing solution in which lithium diimine is dissolved: 1MLiTFSI +DOL/DME (1); the dipping time is 10-60 min.
9. A lithium-sulfur cell comprising the ion-selective gel electrolyte membrane prepared by the preparation method according to any one of claims 2 to 8, wherein the ion-selective gel electrolyte membrane is used for inhibiting polysulfide ion "shuttling effect" of the lithium-sulfur cell.
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