CN111342121A - Pre-lithiated polyphenylene sulfide with high solid lithium solubility, and preparation method and application thereof - Google Patents
Pre-lithiated polyphenylene sulfide with high solid lithium solubility, and preparation method and application thereof Download PDFInfo
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- 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
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- H—ELECTRICITY
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Abstract
The invention provides a pre-lithiated polyphenylene sulfide with high lithium solid solubility, a preparation method and application, wherein the preparation method comprises the following steps: adding NMP and Li2S, p-DCB and LiOH are dehydrated, polymerized at 220 deg.C, neutralized and evaporated to remove NMP and H2O, the conversion from the product to a reactant of pre-lithiation is realized in one step, the nano-scale mixing of the polyphenylene sulfide and the lithium salt is realized in situ, the added chloride ion complexing agent is used for effectively separating lithium ions and chloride ions and capturing the chloride ions, the capture of sulfur sites on a polyphenylene sulfide chain to the lithium ions is promoted, and the solid solubility of lithium is improved; the lithium ion conductivity of the pre-lithiated polyphenylene sulfide is further improved due to the pinning effect of the chloride ion complexing agent on chloride ions. The solid solubility of lithium in the crystal structure of the prepared pre-lithiated polyphenylene sulfide is high, and the material contains lithiumThe chloride ions of (a) are effectively bound and are excellent conductors of single lithium ions.
Description
Technical Field
The invention relates to a pre-lithiated polyphenylene sulfide with high lithium solid solubility, a preparation method and application thereof, belonging to the technical field of new energy material preparation.
Background
All-solid-state lithium ion batteries are receiving increasing attention from the industry and academia due to their excellent safety performance and potentially high energy density. However, the low power density of all solid-state lithium ion batteries greatly limits their commercial popularization and application. The key problem to be broken through urgently is to develop a novel solid electrolyte material with high conductivity and excellent processability. Current inorganic ceramic/glass electrolytes, e.g. Li5La3Zr2O12，Li3xLa2/3-xTiO3And sulfide electrolyte at its high lithium ion conductivity (10)-4～10-2S cm-1) The materials are widely concerned, but the materials have poor mechanical processing performance and difficult film formation, particularly the processing environment of the sulfide electrolyte is extremely strict, and engineering and commercialization need a long way. The other is organic electrolyte, such as PEO, PVDF and the like, which is easy to process into film and can be processed and produced in a roll-to-roll manner, but the conductivity of the organic electrolyte is lower and is only 10-8～10-5S cm-1And the material cannot be normally applied at room temperature, so that the further large-scale popularization of the material is also limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the pre-lithiated polyphenylene sulfide with high lithium solid solubility, the preparation method and the application thereof.
The purpose of the invention is realized by the following technical scheme:
a method for preparing pre-lithiated polyphenylene sulfide with high solid lithium solubility is characterized by comprising the following steps:
(1) n-methyl pyrrolidone (NMP) and lithium sulfide Li2S, placing lithium hydroxide LiOH in a high-pressure reaction kettle with a stirring function, and heating to 150-250 ℃ for high-temperature dehydration for 2-5h to obtain a dehydration system A;
(2) cooling the dehydration system A to 100 ℃, adding 1, 4-dichlorobenzene (p-DCB), and reacting for 80-200 minutes at the temperature of 150-;
(3) dropwise adding a certain amount of hydrochloric acid into the mixed slurry B, wherein the amount of HCl and the LiOH is the same as that of substances, just neutralizing the LiOH, and removing NMP and H in the mixed slurry B by adopting an evaporation or sublimation method2O, NMP and H in Mixed slurry B2O, obtaining dry mixed powder C;
(4) adding a chloride ion complexing agent into the mixed powder C, uniformly stirring, placing in a closed reaction kettle, and preserving the heat for 80-200 minutes at the temperature of 150-; and washing and drying the powder D to obtain the pre-lithiated polyphenylene sulfide with high lithium solid solubility.
Further, the NMP and the lithium sulfide Li2The molar ratio of S to lithium hydroxide LiOH is 1-5: 1: 0.05-0.2.
Further, said Li2S is the high-temperature reaction of metallic lithium powder and sulfur powder or lithium sulfate (Li)2SO4) And (3) carrying out a carbothermic reduction reaction.
Further, the Li2The molar ratio of S to p-DCB is 1.3-0.8: 1.
further, the evaporation or sublimation method is a hot air drying method, a rotary evaporation method or a freeze drying method, so that solid phase components are retained to the maximum extent, and only NMP and H are removed2O。
Furthermore, the chloride ion complexing agent is an organic metal-free complexing agent with a chloride ion binding effect.
Further, the chloride ion complexing agent is calixarene crown ether, calixazole, calixarene or calixarene.
Furthermore, the amount of the added substance of the chloride ion complexing agent is 0.01 to 0.2 times of that of the p-DCB.
The pre-lithiated polyphenylene sulfide with high lithium solid solubility is prepared by the preparation method of the pre-lithiated polyphenylene sulfide with high lithium solid solubility.
The application of the pre-lithiated polyphenylene sulfide with high solid lithium solubility is characterized in that: mixing the pre-lithiated polyphenylene sulfide powder with high lithium solid solubility and PTFE powder, and grinding the mixed powder in a stainless steel closed bin body by adopting dry compressed air with the air flow rate reaching supersonic speed; and then the continuous cake-shaped wide band is prepared by an extruder, and then the film material for the all-solid-state lithium ion battery is prepared by rolling by a hot roller press.
In the invention, LiOH is added first, for the purpose of better dehydration of the system, Li2The reaction of S with p-DCB is a nucleophilic substitution reaction, and the aprotic polarity facilitates the reaction. But H2O may react with Li2S has solvation effect, so that nucleophilic action is weakened, monomer reaction activity is reduced, yield of a linear crystallization zone of the polyphenylene sulfide can be improved through dehydration, and a linear zone with a high enough ratio can ensure that a large number of lithium ion fast migration channels exist in the structure. Then, the solvent and water are directly evaporated or sublimated, the conversion from the product in the previous step to the reactant of the prelithiation is realized in one step, and the nano-scale mixing of the polyphenylene sulfide and the lithium salt is realized in situ, so that the subsequent high-temperature solid solution reaction is promoted to be sufficient. And the added chloride ion complexing agent can effectively separate lithium ions and chloride ions, promote capture of sulfur positions on the polyphenylene sulfide chain on the lithium ions, and improve the solid solubility of lithium, so that the conductivity of the pre-lithiated polyphenylene sulfide is improved. Meanwhile, due to the pinning effect of the chloride ion complexing agent on chloride ions, only lithium ions can be directionally transferred in the crystal structure of the pre-lithiated polyphenylene sulfide under the action of an electric field, and the chloride ions cannot move, so that the pre-lithiated polyphenylene sulfide becomes an excellent conductor of single lithium ions, and the lithium ion conductivity of the pre-lithiated polyphenylene sulfide is further improved. The pinning effect of the chloride ion complexing agent on chloride ions can also prevent the chloride ions from participating in electrochemical reaction to corrode a current collector, so that the capacity of the battery is reduced.
Meanwhile, the manufacturing equipment used in the manufacturing method is simple and convenient to operate, the whole process is free of pollution to the environment, the recovered NMP can be recycled after purification, and the cleaning filtrate is an excessive LiCl solution and also has high recovery value.
Drawings
FIG. 1 is an XRD pattern of a prelithiated polyphenylene sulfide as described herein.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. Elements and features described in one embodiment of the invention may be combined with elements and features shown in one or more other embodiments. It should be noted that the illustration omits illustration and description of components and processes not relevant to the present invention that are known to those of ordinary skill in the art for clarity purposes. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The prelithiation polyphenylene sulfide is high-lithium solid solubility polyphenylene sulfide with a single lithium ion conduction function, contains a chloride ion complexing agent, is an organic metal-free ion complexing agent with a chloride ion binding effect, such as calixarene crown ether, calixamidazole, calixarene and the like, and can effectively bind chloride ions, so that the chloride ions cannot migrate and participate in electrochemical reaction to corrode a current collector.
The preparation method of the pre-lithiated polyphenylene sulfide with high solid lithium solubility comprises the following steps:
first, N-methylpyrrolidone (NMP) and lithium sulfide Li are added2S, lithium hydroxide Li (OH), wherein the mass ratio of substances is 1-5: 1: 0.05 to 0.2, placing the mixture into a high-pressure reaction kettle with a stirring function, and heating the mixture to the temperature of 150 ℃ and 250 ℃ for high-temperature dehydration for 2 to 5 hours to obtain a dehydration system A;
secondly, the dehydration system A is cooled to 100 ℃, and 1, 4-dichlorobenzene (p-DCB) and Li are added2The mass ratio of S is 1: 1.3-0.8. Reacting at 150 ℃ and 250 ℃ for 80-200 minutes to obtain mixed slurry B.
Thirdly, dropwise adding a certain amount of hydrochloric acid into the mixed slurry B, wherein the amount of HCl and the LiOH is the same as that of substances of the mixed slurry B, just neutralizing the LiOH, and removing NMP and H in the mixed slurry B by adopting an evaporation or sublimation method2O, NMP and H in Mixed slurry B2And O, obtaining the dry mixed powder C.
And adding a chloride ion complexing agent into the mixed powder C, wherein the amount of substances added by the chloride ion complexing agent is 0.01-0.2 times that of the p-DCB, uniformly stirring, placing in a closed reaction kettle, and preserving the heat for 80-200 minutes at the temperature of 150-.
And finally, stirring and washing the powder D obtained after the reaction for a certain time by using deionized water, filtering, washing and drying the filter cake again to obtain the pre-lithiated polyphenylene sulfide with high lithium solid solubility as a final product.
Example 1:
n-methyl pyrrolidone (NMP) and lithium sulfide Li2S, lithium hydroxide Li (OH), wherein the mass ratio of substances is 3: 1: 0.1, placing the mixture into a high-pressure reaction kettle with a stirring function, and heating the mixture to 200 ℃ for high-temperature dehydration for 4 hours to obtain a dehydration system A; secondly, the dehydration system A is cooled to 100 ℃, and 1, 4-dichlorobenzene (p-DCB) and Li are added2The mass ratio of S is 1: 1. the reaction was carried out at 220 ℃ for 130 minutes to obtain mixed slurry B. Thirdly, dropwise adding a certain amount of hydrochloric acid into the mixed slurry B, wherein the amount of HCl and the LiOH is the same as that of substances of the mixed slurry B, just neutralizing the LiOH, and removing NMP and H in the mixed slurry B by adopting an evaporation or sublimation method2O, NMP and H in Mixed slurry B2And O, obtaining the dry mixed powder C. Adding calixarene crown ether with the substance amount being 0.17 times of that of p-DCB into the mixed powder C, uniformly stirring, placing the mixture into a closed reaction kettle, and preserving the temperature at 210 ℃ for 160 minutes to obtain powder D. And finally, stirring and washing the powder D obtained after the reaction for a certain time by using deionized water, filtering, washing and drying the filter cake again to obtain the pre-lithiated polyphenylene sulfide with high lithium solid solubility as a final product. The crystal structure XRD pattern of the final product is shown in fig. 1. The product is orthorhombic and has a space group of Pbcn-D2h 14The unit cell size is 0.867nm, 0.561nm, 0.1026 nm, c (fiber axis direction)nm。
The prelithiated polyphenylene sulfide powder and Polytetrafluoroethylene (PTFE) powder of example 1 were mixed in a 94% ratio: mixing 6% by weight, grinding the mixed powder in a stainless steel closed bin by dry compressed air with air flow rate reaching supersonic speed, and collecting. The powder is made into a continuous cake-shaped wide band by an extruder, and then the continuous cake-shaped wide band is compositely rolled and pressed for a plurality of times by a hot roller press to form a film, the final thickness of the film is 35 mu m, and the lithium ion conductivity of the prepared film is 7 x 10-4S·cm-1。
Example 2
N-methyl pyrrolidone (NMP) and lithium sulfide Li2S, lithium hydroxide Li (OH), wherein the mass ratio of substances is 4: 1: 0.15, placing the mixture into a high-pressure reaction kettle with a stirring function, and heating the mixture to 200 ℃ for high-temperature dehydration for 4 hours to obtain a dehydration system A; secondly, the dehydration system A is cooled to 100 ℃, and 1, 4-dichlorobenzene (p-DCB) and Li are added2The mass ratio of S is 1: 1.2. the reaction was carried out at 220 ℃ for 130 minutes to obtain mixed slurry B. Thirdly, dropwise adding a certain amount of hydrochloric acid into the mixed slurry B, wherein the amount of HCl and the LiOH is the same as that of substances of the mixed slurry B, just neutralizing the LiOH, and removing NMP and H in the mixed slurry B by adopting an evaporation or sublimation method2O, NMP and H in Mixed slurry B2And O, obtaining the dry mixed powder C. And adding calixazole with the substance amount of 0.05 p-DCB into the mixed powder C, uniformly stirring, placing into a closed reaction kettle, and keeping the temperature at 210 ℃ for 160 minutes to obtain powder D. And finally, stirring and washing the powder D obtained after the reaction for a certain time by using deionized water, filtering, washing and drying the filter cake again to obtain the pre-lithiated polyphenylene sulfide with high lithium solid solubility as a final product.
The prelithiated polyphenylene sulfide powder and PTFE powder of example 2 were mixed in a 94% ratio: mixing 6% by weight, grinding the mixed powder in a stainless steel closed bin by dry compressed air with air flow rate reaching supersonic speed, and collecting. The powder is made into a continuous cake-shaped wide band by an extruder, and then the continuous cake-shaped wide band is compositely rolled and pressed for a plurality of times by a hot roller press to form a film, the final thickness of the film is 52 mu m, and the lithium ion conductivity of the prepared film is 1 x 10-3S·cm-1。
Example 3
N-methyl pyrrolidone (NMP) and lithium sulfide Li2S, lithium hydroxide Li (OH), wherein the mass ratio of substances is 5: 1: 0.18, placing the mixture into a high-pressure reaction kettle with a stirring function, and heating the mixture to 200 ℃ for high-temperature dehydration for 4 hours to obtain a dehydration system A; secondly, the dehydration system A is cooled to 100 ℃, and 1, 4-dichlorobenzene (p-DCB) and Li are added2The mass ratio of S is 1: 0.9. the reaction was carried out at 220 ℃ for 130 minutes to obtain mixed slurry B. Thirdly, dropwise adding a certain amount of hydrochloric acid into the mixed slurry B, wherein the amount of HCl and the LiOH is the same as that of substances of the mixed slurry B, just neutralizing the LiOH, and removing NMP and H in the mixed slurry B by adopting an evaporation or sublimation method2O, NMP and H in Mixed slurry B2And O, obtaining the dry mixed powder C. And adding califorrole with the substance amount of 0.2 of p-DCB into the mixed powder C, uniformly stirring, placing into a closed reaction kettle, and preserving the temperature at 210 ℃ for 160 minutes to obtain powder D. And finally, stirring and washing the powder D obtained after the reaction for a certain time by using deionized water, filtering, washing and drying the filter cake again to obtain the pre-lithiated polyphenylene sulfide with high lithium solid solubility as a final product.
The prelithiated polyphenylene sulfide powder and PTFE powder of example 3 were mixed in a 94% ratio: mixing 6% by weight, grinding the mixed powder in a stainless steel closed bin by dry compressed air with air flow rate reaching supersonic speed, and collecting. The powder is made into a continuous cake-shaped wide band by an extruder, and then the continuous cake-shaped wide band is compositely rolled and pressed for a plurality of times by a hot roller press to form a film, the final thickness of the film is 42 mu m, and the lithium ion conductivity of the prepared film is 3.3 x 10-4S·cm-1。
Example 4:
n-methyl pyrrolidone (NMP) and lithium sulfide Li2S, lithium hydroxide Li (OH), wherein the mass ratio of substances is 3.5: 1: 0.05, placing the mixture into a high-pressure reaction kettle with a stirring function, heating the mixture to 200 ℃, and dehydrating the mixture for 4 hours to obtain a dehydration system A; secondly, the dehydration system A is cooled to 100 ℃, and 1, 4-dichlorobenzene (p-DCB) and Li are added2The mass ratio of S is 1: 1.1. the reaction was carried out at 220 ℃ for 130 minutes to obtain mixed slurry B. Thirdly, a fixed amount of the slurry B is added dropwise to the mixed slurry BHydrochloric acid, HCl and LiOH are in the same amount, just neutralize LiOH, and NMP and H in the mixed slurry B are removed by evaporation or sublimation2O, NMP and H in Mixed slurry B2And O, obtaining the dry mixed powder C. Adding calixarene into the mixed powder C, wherein the mass amount of the calixarene is 0.03 of p-DCB, uniformly stirring, placing the mixture into a closed reaction kettle, and preserving the temperature at 210 ℃ for 160 minutes to obtain powder D. And finally, stirring and washing the powder D obtained after the reaction for a certain time by using deionized water, filtering, washing and drying the filter cake again to obtain the pre-lithiated polyphenylene sulfide with high lithium solid solubility as a final product.
The prelithiated polyphenylene sulfide powder and PTFE powder of example 3 were mixed in a 94% ratio: mixing 6% by weight, grinding the mixed powder in a stainless steel closed bin by dry compressed air with air flow rate reaching supersonic speed, and collecting. The powder is made into a continuous cake-shaped wide band by an extruder, and then the continuous cake-shaped wide band is compositely rolled and pressed for a plurality of times by a hot roller press to form a film, the final thickness of the film is 37 mu m, and the lithium ion conductivity of the prepared film is 8.2 x 10-4S·cm-1。
The above examples are some embodiments of the present invention, but the present invention is not limited to the above embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A method for preparing pre-lithiated polyphenylene sulfide with high solid lithium solubility is characterized by comprising the following steps:
(1) n-methyl pyrrolidone (NMP) and lithium sulfide Li2S, placing lithium hydroxide LiOH in a high-pressure reaction kettle with a stirring function, and heating to 150-250 ℃ for high-temperature dehydration for 2-5h to obtain a dehydration system A;
(2) cooling the dehydration system A to 100 ℃, adding 1, 4-dichlorobenzene (p-DCB), and reacting for 80-200 minutes at the temperature of 150-;
(3) dripping hydrochloric acid with the same amount as the substance of the LiOH into the mixed slurry B to just neutralize the LiOH, and adopting evaporation or sublimationMethod (2) for removing NMP and H from mixed slurry B2O, obtaining dry mixed powder C;
(4) adding a chloride ion complexing agent into the mixed powder C, uniformly stirring, placing in a closed reaction kettle, and preserving the heat for 80-200 minutes at the temperature of 150-; and washing and drying the powder D to obtain the pre-lithiated polyphenylene sulfide with high lithium solid solubility.
2. The method for producing a prelithiated polyphenylene sulfide with high solid lithium solubility according to claim 1, wherein: the NMP and the lithium sulfide Li2The molar ratio of S to lithium hydroxide LiOH is 1-5: 1: 0.05-0.2.
3. The method for producing a prelithiated polyphenylene sulfide with high solid lithium solubility according to claim 1, wherein: said Li2S is the high-temperature reaction of metallic lithium powder and sulfur powder or lithium sulfate (Li)2SO4) And (3) carrying out a carbothermic reduction reaction.
4. The method for producing a prelithiated polyphenylene sulfide with high solid lithium solubility according to claim 1, wherein: the Li2The molar ratio of S to p-DCB is 1.3-0.8: 1.
5. the method for producing a prelithiated polyphenylene sulfide with high solid lithium solubility according to claim 1, wherein: the evaporation or sublimation method is hot air drying, rotary evaporation or freeze drying, and can maximally retain solid phase components and remove NMP and H2O。
6. The method for producing a prelithiated polyphenylene sulfide with high solid lithium solubility according to claim 1, wherein: the chloride ion complexing agent is an organic metal-free complexing agent with a chloride ion binding effect.
7. The method for producing a prelithiated polyphenylene sulfide with high solid lithium solubility according to claim 1, wherein: the chloride ion complexing agent is calixarene crown ether, calixamidazole, calixarene or calixarene.
8. The method for producing a prelithiated polyphenylene sulfide with high solid lithium solubility according to claim 1, wherein: the amount of the substances added into the chloride ion complexing agent is 0.01 to 0.2 time of that of the p-DCB.
9. The pre-lithiated polyphenylene sulfide with high lithium solid solubility prepared by the method for preparing the pre-lithiated polyphenylene sulfide with high lithium solid solubility according to any one of claims 1 to 8.
10. The use of the pre-lithiated polyphenylene sulfide with high solid solubility in lithium as claimed in claim 9, wherein: mixing the pre-lithiated polyphenylene sulfide powder with high lithium solid solubility and PTFE powder, and grinding the mixed powder in a stainless steel closed bin body by adopting dry compressed air with the air flow rate reaching supersonic speed; and then the continuous cake-shaped wide band is prepared by an extruder, and then the film material for the all-solid-state lithium ion battery is prepared by rolling by a hot roller press.
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| PCT/CN2020/099141 WO2021098215A1 (en) | 2019-11-21 | 2020-06-30 | High-safety high-volume-energy-density quasi-solid-state lithium-ion battery and manufacturing method therefor |
| US17/413,960 US11289737B2 (en) | 2019-11-21 | 2020-11-20 | Pre-lithiated polyphenylene sulfide, polyphenylene sulfide-based solid electrolyte membrane, battery electrode sheet, quasi-solid-state lithium ion battery and method for manufacturing same |
| PCT/CN2020/130376 WO2021098820A1 (en) | 2019-11-21 | 2020-11-20 | Pre-lithiated polyphenylene sulfide, polyphenylene sulfide solid-state electrolyte membrane, battery electrode plate, quasi-solid-state lithium-ion battery, and method for manufacture thereof |
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| CN112290081A (en) * | 2020-09-22 | 2021-01-29 | 江苏大学 | Manufacturing method of high-energy-density quasi-solid sodium ion battery |
| WO2021098215A1 (en) * | 2019-11-21 | 2021-05-27 | 江苏大学 | High-safety high-volume-energy-density quasi-solid-state lithium-ion battery and manufacturing method therefor |
| WO2021098820A1 (en) * | 2019-11-21 | 2021-05-27 | 江苏大学 | Pre-lithiated polyphenylene sulfide, polyphenylene sulfide solid-state electrolyte membrane, battery electrode plate, quasi-solid-state lithium-ion battery, and method for manufacture thereof |
| CN116031479A (en) * | 2023-01-16 | 2023-04-28 | 江苏大学 | Polymer solid electrolyte slurry and film for lithium ion battery, preparation method and application |
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