CN112072175B - Polymer electrolyte and preparation method and application thereof - Google Patents

Polymer electrolyte and preparation method and application thereof Download PDF

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CN112072175B
CN112072175B CN202010947306.3A CN202010947306A CN112072175B CN 112072175 B CN112072175 B CN 112072175B CN 202010947306 A CN202010947306 A CN 202010947306A CN 112072175 B CN112072175 B CN 112072175B
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谭强强
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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Abstract

The invention relates to a polymer electrolyte, a preparation method and an application thereof. According to the invention, the polyfluoroether chain segment is introduced into the polyethylene glycol, the fluorine atom in the molecule replaces a hydrogen atom, and the fluorine atom has strong electronegativity, so that the bond energy is as high as 418kJ/mol to 502.08kJ/mol, so that the polyfluoroether chain segment has high thermal stability and oxidation stability and good chemical inertness and insulating property, the high-pressure resistance and high-temperature resistance of the battery are improved, combustion and explosion are not easy to occur, the safety performance of the battery is improved, and meanwhile, the polyfluoroether chain segment has good electrochemical performance.

Description

Polymer electrolyte and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a polymer electrolyte, and a preparation method and application thereof.
Background
With the development of lithium battery technology and the increase of market demand, the safety problem of lithium batteries draws extensive attention. The high-energy density lithium battery has a series of potential safety hazards such as easy leakage, ignition, explosion and the like due to the use of the organic electrolyte. One of the effective ways to improve the safety of the battery is to use a polymer electrolyte instead of a conventional organic electrolyte. However, it is a great technical challenge to prepare a solid polymer electrolyte material with high ionic conductivity, low electrode/electrolyte interface impedance and good mechanical strength. Therefore, the novel polymer electrolyte for the high-energy-density lithium battery system is developed, the energy density and the safety guarantee of the existing lithium battery are expected to be greatly improved, and the method has important practical significance and scientific research value.
Patent application CN106785032A discloses a polymer electrolyte prepared by crosslinking and curing terminated polyether with terminated silane as oligomer, conductive lithium salt as lithium source, organic solvent as plasticizer and tin salt as catalyst, and its application in lithium ion polymer battery, wherein the polymer electrolyte has the characteristics of polypropylene oxide and silicon rubber, and has excellent mechanical properties;
patent application CN106898812A discloses a solid polymer electrolyte, which is a network polymer formed by cross-linking comb polymer and lithium salt, wherein the main chain of the polymer is polyethylene glycol connected by boron atom and silicon atom, and the side chain is polyethylene glycol monomethyl ether connected to silicon or boron atom on the main chain. The polymer has high conductivity, good battery rate performance, high low-temperature cycle performance and high coulombic efficiency.
At present, the research on polymer electrolytes is not comprehensive enough, and the high temperature and high pressure resistance of the polymer electrolytes in the above patent applications still needs to be further improved, and at the same time, the electrochemical performance also needs to be improved.
Therefore, there is a need in the art to develop a polymer electrolyte that is resistant to high temperature and high pressure, and can improve the safety of a battery while ensuring good electrochemical performance.
Disclosure of Invention
One of the objects of the present invention is to provide a polymer electrolyte which can be used as an electrolyte of a chemical battery, has improved high temperature and high pressure resistance, is highly safe, has a good ion mobility, and has good electrochemical properties.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a polymer electrolyte, which comprises lithium salt and a polyfluoroether-polyethylene glycol block copolymer.
The invention provides a novel block polymer electrolyte, wherein a polyfluoroether chain segment is introduced into polyethylene glycol, and because fluorine atoms in molecules replace hydrogen atoms and have strong electronegativity, the bond energy is as high as 418kJ/mol to 502.08kJ/mol, the polyfluoroether chain segment has higher thermal stability and oxidation stability, so that the high pressure resistance and high temperature resistance of a battery are improved, combustion and explosion are not easy to occur, the safety performance of the battery is improved, and the block polymer electrolyte has better ion migration number and good electrochemical performance.
Polyfluoroether (PFPE for short) is a perfluorinated polymer compound, the main chain is a C-O-C structure, and has good flexibility, the hydrogen on the carbon is completely replaced by fluorine, and the polyfluoroether is oily liquid at normal temperature. Compared with hydrocarbons, the PFPE polymer has a similar molecular structure, but fluorine atoms replace hydrogen atoms in the molecule, so that C-H bonds in the hydrocarbons are replaced by stronger C-F bonds, and the fluorine atoms have strong shielding effect on carbon chains, so that the PFPE has very good thermal stability and oxidation stability and good chemical inertness and insulating property. The high-temperature resistance of the perfluoropolyether is most excellent, the working temperature range is 50-300 ℃, and the short-term temperature can reach 350 ℃; in addition, the main chain structure of the perfluoropolyether has good flexibility, so that the perfluoropolyether also has good low-temperature resistance.
Preferably, the polyfluoroether segment is a perfluoropolyether segment.
Preferably, the polyfluoroether-polyethylene glycol block copolymer has the following structure:
Figure BDA0002675729480000031
the R is1Is selected from-OCF2CF3or-COOH;
the R is2Is selected from-OCH2CH3or-OH;
n is an integer of 5 to 50, such as 10, 15, 20, 25, 30, 35, 40, 45, etc., and m is an integer of 10 to 500, such as 50, 100, 150, 200, 250, 300, 350, 400, 450, etc.
Preferably, the mass fraction of the lithium salt in the polymer electrolyte is 1-8% of the polyfluoroether-polyethylene glycol block copolymer, such as 2%, 3%, 4%, 5%, 6%, 7%, and the like, and preferably 3-6%.
Preferably, the polyfluoroether-polyethylene glycol block copolymer is obtained by reacting an acylated polyfluoroether with a polyethylene glycol containing hydroxyl functional groups.
Preferably, the polyfluoroether is a perfluoropolyether.
Preferably, the acylated polyfluoroethers have a number average molecular weight of 6X 102～6×104E.g. 6 x 102、8×102、1×103、2×103、4×103、6×103、8×103、1×104、2×104、4×104、5×104And the like.
Preferably, the number average molecular weight of the polyethylene glycol containing the hydroxyl functional group is 500-2 x 105E.g. 1X 103、2×103、4×103、6×103、8×103、1×104、2×104、4×104、6×104、8×104、1×105And the like.
Preferably, the ratio of the amount of the acylated polyfluoroether to the amount of hydroxy-functional polyethylene glycol is (0.8-1.3): 1, for example, 0.9:1, 1:1, 1.1:1, 1.2:1, etc., preferably (0.9-1.1): 1.
In the present invention, it is preferable that the two blocks have the above-mentioned specific ratio, and at this ratio, the high-pressure resistance and high-temperature resistance can be further improved, and an excessively high ratio of the polyfluoroether causes a decrease in electrochemical properties, and an excessively low ratio of the polyfluoroether causes a decrease in high-temperature resistance and voltage resistance of the electrolyte.
Preferably, the acylated polyfluoroether and the hydroxy-functional polyethylene glycol are mixed by adding the hydroxy-functional polyethylene glycol to the acylated polyfluoroether with stirring.
Preferably, the reaction temperature is 50-90 ℃, such as 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and the like, preferably 60-80 ℃.
Preferably, the reaction time is 4-24 h, such as 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, etc., preferably 8-12 h.
Preferably, the reaction is carried out in a solvent comprising any one or a combination of at least two of nonafluoromethoxybutane, nonafluoroethoxybutane, 1, 2-trifluorotrichloroethane, pentafluoromonochloroethane, perfluoroheptane, decafluoropentane, hexafluorobenzene, diethyl ether, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, toluene, acetone, dimethylformamide or dimethylacetamide.
Preferably, the method for terminating the reaction comprises: adding a quenching agent until the reaction system is neutral, and finishing the reaction.
Preferably, the quenching agent comprises an alkaline solution.
Preferably, the base comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide, lithium hydroxide, diethylamine or triethylamine.
Preferably, after the reaction is completed, the reaction product is washed with water, desolventized, and dried.
Preferably, the acylated polyfluoroether is obtained by acylation of a polyfluoroether containing a carboxyl end-cap with an acylating agent.
Preferably, the polyfluoroether containing carboxyl end capping comprises polyfluoroether end capping with carboxylic acid at single end and/or polyfluoroether end capping with carboxylic acid at both ends.
Preferably, the acylating agent comprises any one or a combination of at least two of oxalyl chloride, acetyl chloride, phosphorus trichloride, phosphorus pentachloride or thionyl chloride.
Preferably, the temperature of the acylation reaction is 50-85 ℃, such as 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 82 ℃ and the like, preferably 60-75 ℃.
Preferably, the time of the acylation reaction is 6-15 h, such as 8h, 9h, 10h, 11h, 12h, 13h, 14h and the like, and preferably 8-12 h.
Preferably, the ratio of the amount of the substance containing the carboxyl-terminated polyfluoroether to the amount of the acylating agent is 1 (2 to 3), for example 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, etc., preferably 1 (2.2 to 2.5).
Preferably, the acylation reaction is carried out in a solvent comprising any one or a combination of at least two of nonafluoromethoxybutane (HFE-7100), nonafluoroethoxybutane (HFE-7200), 1, 2-trifluorotrichloroethane (CFC-113), pentafluoromonochloroethane (CFC-115), perfluoroheptane, decafluoropentane, hexafluorobenzene, diethyl ether, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, toluene, acetone, dimethylformamide, or dimethylacetamide.
Preferably, the lithium salt includes lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium trifluoromethanesulfonate (LiCF)3SO3) Or lithium bis (trifluoromethylxanthylimide) (LiN (CF)3SO2)2) Any one or a combination of at least two of them.
Another object of the present invention is to provide a method for producing a polymer electrolyte according to the first object, the method comprising: and mixing the polyfluoroether-polyethylene glycol block copolymer with lithium salt, and stirring to obtain the polymer electrolyte.
Preferably, the mass fraction of the lithium salt in the polyfluoroether-polyethylene glycol block copolymer is 1-8%, such as 2%, 3%, 4%, 5%, 6%, 7%, and the like, and preferably 3-6%.
Preferably, the stirring temperature is 20-30 ℃, such as 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ and the like.
Preferably, the preparation method comprises the following steps:
1) adding polyfluoroether carboxylic acid (PFPE-COOH), a solvent and an acylation reagent into a sealable reactor, and carrying out reflux condensation reaction under the protection of inert gas to obtain an acyl chloride-terminated polymer;
2) adding hydroxyl-terminated polyethylene glycol (PEG) into the reaction system in the step 1), then refluxing for esterification, washing and drying to obtain a block polymer;
3) blending the block polymer synthesized in the step 2) with lithium salt to obtain the polymer electrolyte.
Preferably, the reflux condensation reaction time is 4-24 h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h and the like.
Preferably, the reflux condensation temperature is 50-90 deg.C, such as 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, etc.
It is a further object of the present invention to provide a lithium battery comprising the polymer electrolyte according to one of the objects.
The preparation method has the advantages of simple and easy preparation process, no side reaction, simple and convenient post-treatment steps and no pollution. The prepared block polymer electrolyte can be used as a polymer electrolyte of an electrochemical cell and is used for assembling a chemical cell.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel polymer electrolyte, wherein a polyfluoroether chain segment is introduced into polyethylene glycol, and because fluorine atoms in molecules replace hydrogen atoms and have strong electronegativity, the bond energy is as high as 418kJ/mol to 502.08kJ/mol, the polyfluoroether chain segment has higher thermal stability and oxidation stability and good chemical inertness and insulating property, so that the high-pressure resistance and high-temperature resistance of a battery are improved, combustion and explosion are not easy to occur, the safety performance of the battery is improved, and the novel polymer electrolyte has good electrochemical performance.
The preparation process of the polymer electrolyte is simple and easy to implement, has no side reaction, and has simple and convenient post-treatment steps and no pollution. The prepared polymer electrolyte can be used as a polymer electrolyte of an electrochemical cell and is used for assembling a chemical cell.
The lithium ion battery provided by the invention has the high-pressure cycle capacity retention rate of 82-95% and the high-temperature cycle capacity retention rate of 83-92%, first week capacity 194-217mAh g-1The first week efficiency is 80-90%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
0.01mol of perfluoropolyether (molecular weight 1000, purchased from Henan Hengjing chemical Co., Ltd., Hubei), 30mL of perfluorohexane, 10mL of chloroform solvent and 3.80g of oxalyl chloride are added into a single-neck bottle, placed into an oil bath kettle at 55 ℃ under the protection of nitrogen, magnetically stirred and refluxed for 12 hours, then 0.022mol of polyethylene glycol (molecular weight 2000, purchased from Inoka, and the product number is A35872) is added into the system, and stirring is continued for 12 hours at 55 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium bis (trifluoromethyl xanthylimide) into the block polymer, wherein the mass fraction of lithium salt in the block polymer is 4%, and fully stirring the mixture at 25 ℃ to obtain the block polymer electrolyte.
Example 2
0.01mol of perfluoropolyether (molecular weight 5000, purchased from Henan Hengjing chemical Co., Ltd., Hubei), 50mL of perfluorohexane, 10mL of chloroform solvent and 3.80g of oxalyl chloride are added into a single-neck bottle, placed into a 65 ℃ oil bath kettle under the protection of nitrogen, magnetically stirred and refluxed for 12 hours, then 0.022mol of polyethylene glycol (molecular weight 2000, purchased from Inoka, and the product number is A35872) is added into the system, and stirring is continued for 12 hours at 65 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium bis (trifluoromethyl xanthylimide) into the block polymer, wherein the mass fraction of lithium salt in the block polymer is 4%, and fully stirring the mixture at 25 ℃ to obtain the block polymer electrolyte.
Example 3
0.01mol of perfluoropolyether (with a molecular weight of 5000, purchased from Henan constant Jing chemical Co., Ltd., Hubei), 30mL of perfluorohexanone, 10mL of chloroform solvent and 2.854g of thionyl chloride are added into a single-mouth bottle, placed into an oil bath kettle at 60 ℃ under the protection of nitrogen, magnetically stirred and refluxed for 12 hours, then 0.018mol of polyethylene glycol (with a molecular weight of 2000, purchased from Inoka, and the product number is A35872) is added into the system, and stirring is continued for 12 hours at 60 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium trifluoromethanesulfonate, wherein the lithium salt accounts for 4% of the mass fraction of the block polymer, and fully stirring at 25 ℃ to obtain the block polymer electrolyte.
Example 4
0.01mol of perfluoropolyether (molecular weight 5000, purchased from Henan Hengjing chemical Co., Ltd., Hubei), 50mL of perfluorohexane, 20mL of chloroform solvent and 3.80g of oxalyl chloride are added into a single-neck bottle, placed into a 65 ℃ oil bath kettle under the protection of nitrogen, magnetically stirred and refluxed for 12 hours, then 0.012mol of polyethylene glycol (molecular weight 2000, purchased from Inokay, and the product number is A35872) is added into the system, and stirring is continued for 12 hours at 65 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium hexafluoroarsenate, wherein the lithium salt accounts for 4% of the mass fraction of the block polymer, and fully stirring at 25 ℃ to obtain the block polymer electrolyte.
Example 5
0.01mol of perfluoropolyether (molecular weight 4000, available from Henan Hengjing chemical Co., Ltd., Hubei), 40mL of perfluorohexane, 20mL of chloroform solvent and 3.80g of oxalyl chloride are added into a single-neck bottle, placed into an oil bath kettle at 55 ℃ under the protection of nitrogen, magnetically stirred and refluxed for 12 hours, then 0.01mol of polyethylene glycol (molecular weight 2000, available from Inoka, with the product number of A35872) is added into the system, and stirring is continued for 12 hours at 55 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium bis (trifluoromethyl xanthylimide) into the block polymer, wherein the mass fraction of lithium salt in the block polymer is 3%, and fully stirring the mixture at 25 ℃ to obtain the block polymer electrolyte.
Example 6
0.01mol of perfluoropolyether (molecular weight 2000, purchased from Henan constant Jing chemical Co., Ltd., Hubei), 30mL of perfluorohexanone, 10mL of chloroform solvent and 1.427g of thionyl chloride are added into a single-neck bottle, the single-neck bottle is placed into an oil bath kettle at 60 ℃ under the protection of nitrogen, 0.009mol of polyethylene glycol (molecular weight 2000, purchased from Inoka, and the product number is A35872) is added into the system after magnetic stirring reflux is carried out for 12 hours, and stirring is continued for 12 hours at 60 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium trifluoromethanesulfonate, wherein the lithium salt accounts for 4% of the mass fraction of the block polymer, and fully stirring at 25 ℃ to obtain the block polymer electrolyte.
Example 7
0.01mol of perfluoropolyether (molecular weight 1000, purchased from Henan Hespan chemical Co., Ltd.), 30mL of perfluorohexanone, 10mL of dichloromethane solvent and 4.10g of oxalyl chloride are added into a single-mouth bottle, placed into a 45 ℃ oil bath kettle under the protection of nitrogen, magnetically stirred and refluxed for 12 hours, then 0.01mol of polyethylene glycol (molecular weight 1000, purchased from Inoka, and with the product number of A82102) is added into the system, and stirred for 12 hours at 55 ℃. Then washing with dichloromethane solution, and obtaining the block polymer electrolyte after rotary steaming and drying for 5 h. Taking 10g of the block polymer, adding lithium hexafluorophosphate, wherein the lithium salt accounts for 3 percent of the mass of the block polymer, and fully stirring at 25 ℃ to obtain the block polymer electrolyte.
Example 8
0.01mol of perfluoropolyether (with a molecular weight of 5000, purchased from Henan Hengjing chemical Co., Ltd., Hubei), 40mL of perfluorohexanone, 10mL of chloroform solvent and 1.427g of thionyl chloride are added into a single-mouth bottle, the single-mouth bottle is placed into a 60 ℃ oil bath kettle under the protection of nitrogen, 0.009mol of polyethylene glycol (with a molecular weight of 10000, purchased from InonoKa and a product number of A86517) is added into the system after magnetic stirring and refluxing for 12h, and stirring is continued for 12h at 60 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium trifluoromethanesulfonate, wherein the lithium salt accounts for 4% of the mass fraction of the block polymer, and fully stirring at 25 ℃ to obtain the block polymer electrolyte.
Example 9
0.01mol of perfluoropolyether (molecular weight 2000, purchased from Henan Hengjing chemical Co., Ltd., Hubei), 30mL of perfluorohexanone, 10mL of chloroform solvent and 2.88g of phosphorus trichloride are added into a single-mouth bottle, the single-mouth bottle is placed into an oil bath kettle at 60 ℃ under the protection of nitrogen, 0.021mol of polyethylene glycol (molecular weight 4000, purchased from Inoka, and the product number is A83412) is added into the system after magnetic stirring and refluxing for 12h, and stirring is continued for 12h at 60 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium hexafluoroarsenate, wherein the mass fraction of lithium salt in the block polymer is 3%, and fully stirring at 25 ℃ to obtain the block polymer electrolyte.
Example 10
0.01mol of perfluoropolyether (with a molecular weight of 5000, purchased from Hechenne chemical Co., Ltd., North lake), 30mL of perfluorohexanone, 10mL of chloroform solvent and 2.88g of phosphorus trichloride are added into a single-mouth bottle, the single-mouth bottle is placed into an oil bath kettle at 60 ℃ under the protection of nitrogen, 0.009mol of polyethylene glycol (with a molecular weight of 10000, purchased from InonoKa, and the product number of A86517) is added into the system after magnetic stirring and refluxing for 12h, and stirring is continued for 12h at 60 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium tetrafluoroborate, wherein the lithium salt accounts for 4 percent of the mass of the block polymer, and fully stirring at 25 ℃ to obtain the block polymer electrolyte.
Example 11
0.01mol of perfluoropolyether (molecular weight 2000, purchased from Henan constant Jing chemical Co., Ltd., Hubei), 30mL of perfluoroheptane, 10mL of chloroform solvent and 2.854g of thionyl chloride are added into a single-neck bottle, placed in a 60 ℃ oil bath kettle under the protection of nitrogen, magnetically stirred and refluxed for 12 hours, then 0.009mol of polyethylene glycol (molecular weight 2000, purchased from Inoka, and the commercial number is A35872) is added into the system, and stirring is continued for 12 hours at 60 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium hexafluorophosphate, wherein the lithium salt accounts for 5 percent of the mass of the block polymer, and fully stirring at 25 ℃ to obtain the block polymer electrolyte.
Example 12
0.01mol of perfluoropolyether (molecular weight 2000, purchased from Hebei Hengjing chemical Co., Ltd.), 30mL of perfluorohexanone, 10mL of chloroform solvent and 1.427g of thionyl chloride are added into a single-neck bottle, placed in a 60 ℃ oil bath kettle under the protection of nitrogen, magnetically stirred and refluxed for 12h, then 0.01mol of polyethylene glycol (molecular weight 3000, purchased from Sigma, and the product number is 81227) is added into the system, and stirring is continued for 12h at 60 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium tetrafluoroborate, wherein the lithium salt accounts for 6 percent of the mass of the block polymer, and fully stirring at 25 ℃ to obtain the block polymer electrolyte.
Example 13
0.01mol of perfluoropolyether (molecular weight 2000, purchased from Henan constant Jing chemical Co., Ltd., Hubei), 30mL of nonafluoromethoxybutane and 10mL of chloroform solvent, 1.427g of thionyl chloride are added into a single-neck bottle, the single-neck bottle is placed into an oil bath kettle at 60 ℃ under the protection of nitrogen, 0.009mol of polyethylene glycol (molecular weight 2000, purchased from Inoka, and the product number is A35872) is added into the system after magnetic stirring reflux for 12 hours, and stirring is continued for 12 hours at 60 ℃. Then washing with chloroform solution, and obtaining the block polymer electrolyte after rotary evaporation and drying for 5 h. Taking 10g of the block polymer, adding lithium trifluoromethanesulfonate, wherein the lithium salt accounts for 4% of the mass fraction of the block polymer, and fully stirring at 25 ℃ to obtain the block polymer electrolyte.
Example 14
The difference from example 5 is that the amount of the substance of polyethylene glycol is 0.0125mol, and the ratio of the amounts of the substance of perfluoropolyether and polyethylene glycol is 0.8: 1.
Example 15
The difference from example 5 is that the amount of the substance of polyethylene glycol was 0.0077mol and the ratio of the amounts of the substances of perfluoropolyether and polyethylene glycol was 1.3: 1.
Example 16
The difference from example 5 is that the amount of the substance of polyethylene glycol was 0.014mol and the ratio of the amounts of the substances of perfluoropolyether and polyethylene glycol was 0.7: 1.
Example 17
The difference from example 5 is that the amount of the substance of polyethylene glycol is 0.0067mol and the ratio of the amounts of the substances of perfluoropolyether and polyethylene glycol is 1.5: 1.
Comparative example 1
10g of polyethylene glycol (molecular weight 2000, available from Itoka under trade name A35872) was added to lithium bis (trifluoromethylxanthylimide) at a lithium ion concentration of 3%, and the mixture was stirred thoroughly at 25 ℃ to obtain a block polymer electrolyte.
Performance testing
The polymer electrolytes obtained in the above examples and comparative examples were respectively prepared into lithium ion batteries by the following methods:
and sequentially stacking the positive plate (lithium plate), the diaphragm, the prepared polymer electrolyte and the negative lithium plate, pressing at room temperature under the condition of 20MPa, and performing performance test after assembling the lithium battery.
The following tests were carried out for the lithium ion batteries prepared in the examples and comparative examples:
(1) high pressure resistance test: and standing the prepared lithium battery for 24 hours, performing 100 charge-discharge cycle tests in a voltage range of 4V-4.8V and under a current of 1C, and recording the capacity retention rate of the battery after 200 cycles.
(2) And (3) high temperature resistance test: and standing the prepared lithium battery in a thermostat at 70 ℃ for 8 hours, performing 100 charge-discharge cycle tests in a voltage range of 3.0V-4.3V and under a current of 1C, and recording the capacity retention rate of the battery after 100 cycles.
(3) And (3) electrochemical performance testing: and standing the prepared lithium battery for 24 hours, performing charge-discharge test in a voltage interval of 3.0V-4.8V and under a current of 0.2C, and recording the first-week discharge capacity and the first-week efficiency.
The results of the above tests are shown in table 1.
TABLE 1
Figure BDA0002675729480000131
Figure BDA0002675729480000141
As can be seen from the data in table 1, the polymer electrolyte provided by the present invention has excellent high temperature resistance and high pressure resistance, high safety, and good electrochemical properties.
It is understood from comparative examples 5 and 14 to 17 that when the amount ratio of the polyfluoroether to the polyethylene glycol is controlled to be within (0.8 to 1.3):1 (examples 5, 14 and 15), the high temperature resistance and the high pressure resistance can be further improved, the safety of the battery is higher, the high temperature and high pressure resistance is reduced when the amount of polyfluoroether added is too low (example 16), and the electrochemical performance is affected when the amount of polyfluoroether added is too high (example 17).
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (34)

1. A polymer electrolyte, characterized in that the polymer electrolyte comprises a lithium salt and a polyfluoroether-polyethylene glycol block copolymer;
the polyfluoroether-polyethylene glycol block copolymer has the following structure:
Figure FDA0003204892010000011
the R is1Is selected from-OCF2CF3or-COOH;
the R is2Is selected from-OCH2CH3or-OH;
n is an integer of 5-50, and m is an integer of 10-500;
the polyfluoroether-polyethylene glycol block copolymer is obtained by reacting acylated polyfluoroether with polyethylene glycol containing hydroxyl functional groups.
2. The polymer electrolyte according to claim 1, wherein the mass fraction of lithium salt in the polymer electrolyte is 1-8% of the polyfluoroether-polyethylene glycol block copolymer.
3. The polymer electrolyte according to claim 2, wherein the mass fraction of lithium salt in the polymer electrolyte is 3-6% of the polyfluoroether-polyethylene glycol block copolymer.
4. The polymer electrolyte of claim 1 wherein the acylated polyfluoroether has a number average molecular weight of 6 x 102～6×104。
5. The polymer electrolyte according to claim 1, wherein the polyfluoroether preparation monomer comprises any one or a combination of at least two of hexafluoropropylene oxide, tetrafluorooxetane, tetrafluoroethylene, or hexafluoropropylene.
6. The polymer electrolyte according to claim 1, wherein the number average molecular weight of the polyethylene glycol having a hydroxyl functional group is 500 to 2 x 105。
7. The polymer electrolyte of claim 1, wherein the amount ratio of the acylated polyfluoroether to the hydroxy-functional polyethylene glycol is (0.8-1.3): 1.
8. The polymer electrolyte of claim 7, wherein the ratio of the amount of the acylated polyfluoroether to the amount of hydroxy-functional polyethylene glycol is (0.9-1.1): 1.
9. The polymer electrolyte of claim 1, wherein the acylated polyfluoroether and the hydroxy-functional polyethylene glycol are mixed by adding the hydroxy-functional polyethylene glycol to the acylated polyfluoroether with agitation.
10. The polymer electrolyte of claim 1, wherein the reaction temperature is 50 to 90 ℃.
11. The polymer electrolyte according to claim 10, wherein the reaction temperature is 60 to 80 ℃.
12. The polymer electrolyte of claim 1, wherein the reaction time is 4 to 24 hours.
13. The polymer electrolyte of claim 12, wherein the reaction time is 8 to 12 hours.
14. The polymer electrolyte according to claim 1, wherein the reaction is carried out in a solvent comprising any one or a combination of at least two of nonafluoromethoxybutane, nonafluoroethoxybutane, 1, 2-trifluorotrichloroethane, pentafluoromonochloroethane, perfluoroheptane, decafluoropentane, hexafluorobenzene, diethyl ether, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, toluene, acetone, dimethylformamide, or dimethylacetamide.
15. The polymer electrolyte of claim 1, wherein the method of terminating the reaction comprises: adding a quenching agent until the reaction system is neutral, and finishing the reaction.
16. The polymer electrolyte of claim 15, wherein the quencher comprises a basic solution.
17. The polymer electrolyte of claim 16, wherein the base comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide, lithium hydroxide, diethylamine or triethylamine.
18. The polymer electrolyte according to claim 1, wherein after the reaction is completed, the reaction product is washed with water, desolventized, and dried.
19. The polymer electrolyte of claim 1 wherein the acylated polyfluoroether is obtained by acylation of a polyfluoroether containing a carboxyl end-cap with an acylating agent.
20. The polymer electrolyte of claim 19, wherein the polyfluoroether containing carboxyl end-caps comprises polyfluoroether end-capped with carboxylic acid at one end and/or polyfluoroether end-capped with carboxylic acid at both ends.
21. The polymer electrolyte of claim 19, wherein the acylating agent comprises any one or a combination of at least two of oxalyl chloride, acetyl chloride, phosphorus trichloride, phosphorus pentachloride, or thionyl chloride.
22. The polymer electrolyte of claim 19 wherein the temperature of the acylation reaction is 50-85 ℃.
23. The polymer electrolyte of claim 22 wherein the temperature of the acylation reaction is 60-75 ℃.
24. The polymer electrolyte of claim 19, wherein the time for the acylation reaction is 6 to 15 hours.
25. The polymer electrolyte of claim 24, wherein the time for the acylation reaction is 8 to 12 hours.
26. The polymer electrolyte of claim 19, wherein the ratio of the amount of the substance containing the carboxyl-terminated polyfluoroether to the amount of the acylating agent is 1 (2-3).
27. The polymer electrolyte of claim 26, wherein the ratio of the amount of the substance containing the carboxyl-terminated polyfluoroether to the amount of the acylating agent is 1 (2.2-2.5).
28. The polymer electrolyte of claim 19, wherein the acylation reaction is carried out in a solvent comprising any one of or a combination of at least two of nonafluoromethoxybutane, nonafluoroethoxybutane, 1, 2-trifluorotrichloroethane, pentafluoromonochloroethane, perfluoroheptane, decafluoropentane, hexafluorobenzene, diethyl ether, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, toluene, acetone, dimethylformamide, or dimethylacetamide.
29. The polymer electrolyte of claim 1, wherein the lithium salt comprises any one or a combination of at least two of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, or lithium bis (trifluoromethylsulfonyl) imide.
30. A method for preparing a polymer electrolyte according to any of claims 1-29, wherein the method comprises: and mixing the polyfluoroether-polyethylene glycol block copolymer with lithium salt, and stirring to obtain the polymer electrolyte.
31. The method according to claim 30, wherein the lithium salt is present in an amount of 1 to 8% by mass based on the mass of the polyfluoroether-polyethylene glycol block copolymer.
32. The method according to claim 31, wherein the lithium salt is present in an amount of 3 to 6% by mass based on the mass of the polyfluoroether-polyethylene glycol block copolymer.
33. The method according to claim 30, wherein the stirring temperature is 20 to 30 ℃.
34. A lithium battery comprising the polymer electrolyte according to any one of claims 1 to 29.
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