CN111952664A - Solid polymer electrolyte and preparation method and application thereof - Google Patents

Solid polymer electrolyte and preparation method and application thereof Download PDF

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Publication number
CN111952664A
CN111952664A CN202010825384.6A CN202010825384A CN111952664A CN 111952664 A CN111952664 A CN 111952664A CN 202010825384 A CN202010825384 A CN 202010825384A CN 111952664 A CN111952664 A CN 111952664A
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polymer electrolyte
polyethylene glycol
solid polymer
polyorganosiloxane
lithium
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谭强强
娄平平
王鹏飞
董子杰
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Institute of Process Engineering of CAS
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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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2200/00—Safety devices for primary or secondary batteries
    • 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
    • H01M2300/0088—Composites
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Silicon Polymers (AREA)

Abstract

The invention relates to a solid polymer electrolyte and a preparation method and application thereof. According to the invention, the organic siloxane chain segment is introduced to the polyethylene glycol to form a block copolymer, and the block copolymer is mixed with the lithium salt and vulcanized to obtain the solid polymer electrolyte, so that the high-temperature-resistant and high-pressure-resistant solid polymer electrolyte has excellent high-temperature-resistant performance and high-pressure-resistant performance, is not easy to combust or explode, has high safety and simultaneously has good electrochemical performance.

Description

Solid polymer electrolyte and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a solid polymer electrolyte and a preparation method and application thereof.
Background
At present, some applications of lithium ion batteries with liquid electrolytes in electric vehicles, intelligent electronic products and other aspects are more and more difficult to meet the long-term endurance requirements of consumers. To produce higher energy density batteries, researchers have combined Li metal as the negative electrode with a positive electrode of sulfur, air (oxygen), or high content layered nickel oxide. At this time, since organic solvent electrolytes present safety hazards themselves, research on solid electrolytes, ionic liquids, polymers and combinations thereof has been accelerated.
The high polymer solid electrolyte is a compound of high polymer with high ion conductivity and metal salt, and is mainly used for dry batteries, electrochromic devices, sensors, large-capacity capacitors and the like. Although the polymer material is solid, the polymer material has the characteristics of dissolving metal salt in a liquid electrolyte and transferring ion migration. Generally, a polymer material with a low glass transition temperature, a high polarity and an amorphous structure is selected, and polyether polymers and derivatives thereof are the most common. The salts are mostly alkali metal salts and alkaline earth metal salts with low dissociation energy. Compared with liquid electrolytes and inorganic solid electrolytes, the high polymer solid electrolyte has the advantages of easy processing and forming, capability of preparing large-area uniform films and light weight; no leakage, good flexibility, impact resistance, good contact performance with electrode materials and the like. However, there are currently less solid polymer electrolyte products on the market and electrochemical performance is greatly compromised.
CN110518282A discloses a solid polymer electrolyte, solid-state lithium ion battery. The solid polymer electrolyte includes: a lithium salt; the copolymer, the monomers forming the copolymer include vinylene carbonate and glycol acrylate. According to the solid polymer electrolyte provided by the invention, the carbonate monomer can enable the solvation and the mobility of the polymer to lithium ions to be higher, and the flexible monomer glycol acrylate is introduced into the copolymer chain, so that the chain flexibility of the copolymer is better, and the coordination effect and the conductivity of the lithium ions are improved. But the high voltage resistance and high temperature resistance of the solid polymer electrolyte still need to be improved.
CN107851837A discloses a silicone polyether for forming a solid polymer electrolyte membrane, which contains a heterocyclic moiety. The silicone polyethers comprising heterocyclic moieties are useful in providing electrolyte compositions suitable for use in electrochemical devices. The silicone polyether containing a heterocyclic moiety can also be used to form a solid polymer electrolyte that can be used to form a solid polymer electrolyte membrane that can be suitable for use in an electrochemical device. But the high temperature and high pressure resistance and the electrochemical performance of the solid polymer electrolyte are all required to be further improved.
CN101407625A discloses a hyperbranched polyether type solid polymer electrolyte and a preparation method thereof. The polymer electrolyte material comprises a polymer matrix material (A), a polymer matrix material (B) and a lithium salt (C). The polymer matrix material A is hyperbranched polyether containing ether oxygen groups and having a completely amorphous structure, and the polymer matrix material B is a polymer matrix material with excellent mechanical properties. The solid polymer electrolyte membrane is prepared by a one-step method of a volatile solvent, has simple and convenient preparation process, higher ionic conductivity and electrochemical stability, good mechanical property and thermal stability, and can be applied to the preparation of secondary lithium ion batteries. However, the high voltage resistance of the solid polymer electrolyte prepared by the invention still needs to be improved so as to further improve the safety.
Therefore, there is a need in the art to develop a wider variety of solid polymer electrolytes with better safety performance and good electrochemical performance.
Disclosure of Invention
An object of the present invention is to provide a solid polymer electrolyte which has excellent high temperature and high pressure resistance, is not easily combustible and explosive, and has high safety.
In order to achieve the purpose, the invention adopts the following technical scheme:
the present invention provides a solid polymer electrolyte comprising a lithium salt and a vulcanized polyorganosiloxane-polyethylene glycol block copolymer.
The invention introduces organosiloxane chain segment on polyethylene glycol to form block copolymer, and mixes the block copolymer with lithium salt and vulcanizes the block copolymer to obtain the solid polymer electrolyte, because polysiloxane is a structure taking silicon-oxygen (Si-O) bond as a main chain, wherein the bond energy of the Si-O bond is 121kcal/g, and the bond energy of the C-C bond is 82.6kcal/g, the thermal stability of the polyorganosiloxane is high, and the chemical bond of the molecule is not broken and decomposed at high temperature. Therefore, the solid polymer electrolyte has excellent high temperature resistance and high pressure resistance, is not easy to combust and explode, has high safety, and does not influence the electrochemical performance.
Preferably, the polyorganosiloxane-polyethylene glycol block copolymer is obtained by hydrosilylation reaction of polyorganosiloxane containing a silicon hydride functional group and polyethylene glycol having a double bond as a terminal group.
Preferably, the polyorganosiloxane containing a hydrosilicon function has a number-average molecular weight of 5X 102～5×104E.g. 6 x 102、7×102、8×102、9×102、1×103、2×103、3×103、4×103、5×103、6×103、7×103、8×103、9×103、1×104、2×104、3×104、4×104And the like.
Preferably, the polyorganosiloxane containing a hydrosilyl functional group contains 0.1% to 0.7% of the total number of silicon hydride units (which may also be referred to simply as the hydrosilyl content), for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, etc.
Preferably, the number average molecular weight of the polyethylene glycol with the terminal group as a double bond is 2 x 102～2×104E.g. 3X 102、4×102、5×102、6×102、7×102、8×102、9×102、1×103、2×103、3×103、4×103、5×103、6×103、7×103、8×103、9×103、1×104And the like.
Preferably, the ratio of the amount of the polyorganosiloxane containing a silicon-hydrogen functional group to the amount of the polyethylene glycol having a double bond as a terminal group is (0.5 to 1.3):1, for example, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, and the like.
In a preferred embodiment of the present invention, the lithium battery prepared from the solid electrolyte can obtain the following effects: the high-pressure circulation capacity retention rate is 90-95%, the high-temperature circulation capacity retention rate is 85-92%, and the first-week capacity is 191-217mAh g-1The first week efficiency is 83-90%.
The invention preferably selects the proportion of the two polymers, and further obtains the block copolymer with the specific polyorganosiloxane and the polyethylene glycol chain segment distribution, thereby further improving the high temperature resistance and the high pressure resistance. The polyorganosiloxane chain segment accounts for too much, which can cause the conductivity of lithium ion to be reduced and the electrochemical performance to be poor; the polysiloxane chain segment accounts for too small, so that the temperature resistance and high voltage resistance of the system can not be effectively improved.
Preferably, the hydrogenation addition reaction is carried out in the presence of a platinum catalyst.
Preferably, the platinum catalyst comprises a Speier catalyst and/or a Karstedt catalyst.
Preferably, the platinum catalyst is used in an amount of 0.1 to 0.3%, for example, 0.15%, 0.2%, 0.25%, etc., based on the total mass of the polyorganosiloxane containing the silicon-hydrogen functional group and the polyethylene glycol having a double bond as a terminal group.
Preferably, the solvent for the hydrosilylation reaction comprises any one or a combination of at least two of toluene, tetrahydrofuran, dichloromethane, or n-hexane.
Preferably, the temperature of the hydrosilylation reaction is 50 to 90 ℃, for example, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or the like, preferably 50 to 80 ℃, and more preferably 60 to 80 ℃.
Preferably, the hydrosilylation reaction time is 5-24 h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, and the like, and preferably 8-12 h.
Preferably, after the hydrosilylation reaction is completed, the solvent removal and drying steps are performed.
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 solid polymer electrolyte according to the first object, the method comprising the steps of: mixing the polyorganosiloxane-polyethylene glycol block copolymer with lithium salt, and carrying out vulcanization reaction to obtain the solid polymer electrolyte.
Preferably, the sulfidation reaction is carried out in the presence of a platinum catalyst, preferably the platinum catalyst comprises a Speier catalyst and/or a Karstedt catalyst.
Preferably, the amount of platinum catalyst used in the vulcanization reaction is 0.1% to 0.7%, such as 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, etc., preferably 0.2% to 0.4% of the mass of the polyorganosiloxane-polyethylene glycol block copolymer.
Preferably, the vulcanization reaction is carried out in the presence of a vulcanizing agent.
Preferably, the vulcanizing agent comprises any one or at least two of tetramethyltetravinylcyclotetrasiloxane, hydrogen-containing silicone oil or tetramethyldivinylsiloxane.
Preferably, the vulcanizing agent is used in an amount of 1% to 6%, for example 2%, 3%, 4%, 5%, etc., preferably 2% to 4%, based on the weight of the polyorganosiloxane-polyethylene glycol block copolymer.
Preferably, the temperature of the vulcanization reaction is 40 to 90 ℃, such as 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and the like, preferably 50 to 80 ℃.
Preferably, the time of the vulcanization reaction is 4-24 h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, etc., preferably 6-14 h.
Preferably, in the reaction system of the vulcanization reaction, the lithium salt accounts for 1-8% by mass of the polyorganosiloxane-polyethylene glycol block copolymer, such as 2%, 3%, 4%, 5%, 6%, 7%, and the like, and preferably 3-5%.
It is a further object of the present invention to provide a lithium battery comprising the solid polymer electrolyte according to one of the objects.
Compared with the prior art, the invention has the following beneficial effects:
the invention introduces organic siloxane chain segment on polyethylene glycol to form block copolymer, which is mixed with lithium salt and vulcanized to obtain solid polymer electrolyte, wherein the polysiloxane is silicon oxide (S)i-O) bond is a main chain structure, wherein the bond energy of Si-O bond is 121kcal/g, and the bond energy of C-C bond is 82.6kcal/g, so that the thermal stability of the polyorganosiloxane is high, and the chemical bond of the molecule is not broken and decomposed at high temperature, so that the solid polymer electrolyte has excellent high temperature resistance and high pressure resistance, is not easy to combust and explode, has high safety, and does not influence the electrochemical performance. Wherein the high-pressure circulation capacity retention rate is 82-95%, the high-temperature circulation capacity retention rate is 81-92%, and the first-week capacity is 191-217mAh g-1The first week efficiency is 79-90%.
The preparation method has the advantages of simple and easy preparation process, no side reaction, simple post-treatment steps and no pollution, and the yield is more than 80%.
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
Adding 20g of polyethylene glycol (molecular weight 2000) with double bonds as end groups, 50mL of toluene and 0.12g of Karstedt catalyst into a three-neck flask, placing the three-neck flask in an oil bath kettle at 55 ℃ under the protection of nitrogen, dropwise adding 10g of polysiloxane (molecular weight 3000, content of hydrosilation chain links is 0.2%) under magnetic stirring, wherein the mass ratio of the polysiloxane to the polyethylene glycol is 0.33:1, refluxing for 12h after dropwise adding, washing with toluene, and carrying out rotary evaporation and drying for 6h to obtain the block polymer electrolyte. Taking 10g of the block polymer, adding lithium hexafluorophosphate, wherein the lithium ion concentration is 3%, then adding 0.03g of Karstedt catalyst and 0.2g of tetramethyl tetravinylcyclotetrasiloxane, stirring uniformly, placing in a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing in a vacuum oven at 55 ℃ for 5 hours to obtain the solid polymer electrolyte (the yield is 85%).
Example 2
30g of polyethylene glycol (molecular weight 2000) with double bonds as end groups, 50mL of toluene and 0.16g of Karstedt catalyst are added into a three-neck flask, the three-neck flask is placed in an oil bath kettle at 50 ℃ under the protection of nitrogen, 10g of polysiloxane (molecular weight 3000, the content of hydrosilation chain links is 0.4%) is dropwise added under magnetic stirring, the mass ratio of the polysiloxane to the polyethylene glycol is 0.22:1, the three-neck flask is washed by toluene after the dropwise addition is performed for 12h, and the block polymer electrolyte is obtained after rotary evaporation and drying for 6 h. Taking 10g of the block polymer, adding lithium hexafluorophosphate, wherein the lithium ion concentration is 3%, then adding 0.03g of Karstedt catalyst and 0.25g of tetramethyl tetravinylcyclotetrasiloxane, stirring uniformly, placing in a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing in a vacuum oven at 55 ℃ for 5 hours to obtain the solid polymer electrolyte (the yield is 90%).
Example 3
Adding 10g of polyethylene glycol (molecular weight 2000) with double bonds as end groups, 30mL of toluene and 0.08g of Karstedt catalyst into a three-neck flask, placing the three-neck flask in an oil bath kettle at 55 ℃ under the protection of nitrogen, dropwise adding 10g of polysiloxane (molecular weight 3000, content of hydrosilation chain links is 0.6%) under magnetic stirring, wherein the mass ratio of the polysiloxane to the polyethylene glycol is 0.67:1, refluxing for 12h after dropwise adding, washing with toluene and ethanol, and carrying out rotary evaporation and drying for 6h to obtain the block polymer electrolyte. Taking 10g of the block polymer, adding lithium bis (trifluoromethyl xanthylimide) imide, wherein the concentration of lithium ions is 3%, then adding 0.04g of Karstedt catalyst and 0.4g of tetramethyl tetravinylcyclotetrasiloxane, stirring uniformly, placing in a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing in a vacuum oven at 50 ℃ for 5 hours to obtain the solid polymer electrolyte (the yield is 94%).
Example 4
Adding 20g of polyethylene glycol (with the molecular weight of 5000) with double bonds as end groups, 50mL of toluene and 0.175g of Karstedt catalyst into a three-neck flask, placing the three-neck flask in an oil bath kettle at 55 ℃ under the protection of nitrogen, dropwise adding 15g of polysiloxane (with the molecular weight of 3000 and the content of hydrosilation chain links of 0.56%) under magnetic stirring, wherein the mass ratio of the polysiloxane to the polyethylene glycol is 1.25:1, refluxing for 12h after dropwise adding, washing with toluene, and carrying out rotary evaporation and drying for 6h to obtain the block polymer electrolyte. Taking 10g of the block polymer, adding lithium trifluoromethanesulfonate into the block polymer, wherein the lithium ion concentration is 5%, then adding 0.02g of Karstedt catalyst and 0.3g of tetramethyl-tetravinylcyclotetrasiloxane into the block polymer, uniformly stirring the mixture, placing the mixture into a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing the mixture in a vacuum oven at the temperature of 55 ℃ for 5 hours to obtain the solid polymer electrolyte (the yield is 91%).
Example 5
Adding 10g of polyethylene glycol (molecular weight is 3000) with double bonds as end groups, 60mL of n-hexane and 0.16g of Karstedt catalyst into a three-neck flask, placing the three-neck flask in a 65 ℃ oil bath kettle under the protection of nitrogen, dropwise adding 30g of polysiloxane (molecular weight is 8000 and the content of hydrosilation chain links is 0.48%) under magnetic stirring, wherein the mass ratio of the polysiloxane to the polyethylene glycol is 1.13:1, refluxing for 12h after dropwise adding, washing with toluene, and carrying out rotary evaporation and drying for 6h to obtain the block polymer electrolyte. Taking 10g of the block polymer, adding lithium hexafluorophosphate, wherein the lithium ion concentration is 3%, then adding 0.03g of Karstedt catalyst and 0.3g of tetramethyl tetravinylcyclotetrasiloxane, stirring uniformly, placing in a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing in a vacuum oven at 65 ℃ for 5 hours to obtain the solid polymer electrolyte (the yield is 92%).
Example 6
Adding 20g of polyethylene glycol (with the molecular weight of 4000) with double bonds as end groups, 80mL of toluene and 0.08g of Karstedt catalyst into a three-neck flask, placing the three-neck flask in an oil bath kettle at 55 ℃ under the protection of nitrogen, dropwise adding 20g of polysiloxane (with the molecular weight of 10000 and the content of hydrosilation chain links of 0.36%) under magnetic stirring, wherein the mass ratio of the polysiloxane to the polyethylene glycol is 0.4:1, refluxing for 12h after dropwise adding, washing with toluene, and carrying out rotary evaporation and drying for 6h to obtain the block polymer electrolyte. Taking 10g of the block polymer, adding lithium hexafluorophosphate, wherein the lithium ion concentration is 5%, then adding 0.04g of Karstedt catalyst and 0.3g of tetramethyl tetravinylcyclotetrasiloxane, stirring uniformly, placing in a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing in a vacuum oven at 65 ℃ for 5 hours to obtain the solid polymer electrolyte (the yield is 90%).
Example 7
Adding 20g of polyethylene glycol (molecular weight of 8000) with double bonds as end groups, 50mL of toluene and 0.15g of Karstedt catalyst into a three-neck flask, placing the three-neck flask in an oil bath kettle at 55 ℃ under the protection of nitrogen, dropwise adding 10g of polysiloxane (molecular weight of 4000 and content of hydrosilation chain links of 0.45%) under magnetic stirring, wherein the mass ratio of the polysiloxane to the polyethylene glycol is 1:1, refluxing for 12h after dropwise adding, washing with toluene, and carrying out rotary evaporation and drying for 6h to obtain the block polymer electrolyte. Taking 10g of the block polymer, adding lithium trifluoromethanesulfonate into the block polymer, wherein the lithium ion concentration is 5%, then adding 0.05g of Karstedt catalyst and 0.3g of tetramethyl-tetravinylcyclotetrasiloxane into the block polymer, uniformly stirring the mixture, placing the mixture into a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing the mixture in a vacuum oven at the temperature of 55 ℃ for 5 hours to obtain the solid polymer electrolyte (the yield is 93%).
Example 8
Adding 20g of polyethylene glycol (with the molecular weight of 10000) with double bonds as end groups, 50mL of toluene and 0.175g of Karstedt catalyst into a three-neck flask, placing the three-neck flask in an oil bath kettle at 70 ℃ under the protection of nitrogen, dropwise adding 15g of polysiloxane (with the molecular weight of 4000 and the content of hydrosilation chain links of 0.52%) under magnetic stirring, wherein the mass ratio of the polysiloxane to the polyethylene glycol is 1.9:1, refluxing for 12h after dropwise adding, washing with toluene, and carrying out rotary evaporation and drying for 6h to obtain the block polymer electrolyte. Taking 10g of the block polymer, adding lithium trifluoromethanesulfonate into the block polymer, wherein the lithium ion concentration is 4%, then adding 0.04g of Karstedt catalyst and 0.3g of tetramethyl-tetravinylcyclotetrasiloxane into the block polymer, uniformly stirring the mixture, placing the mixture into a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing the mixture in a vacuum oven at 70 ℃ for 5 hours to obtain the solid polymer electrolyte (the yield is 92%).
Example 9
Adding 20g of polyethylene glycol (with the molecular weight of 10000) with double bonds as end groups, 50mL of toluene and 0.12g of Karstedt catalyst into a three-neck flask, placing the three-neck flask in a 65 ℃ oil bath kettle under the protection of nitrogen, dropwise adding 10g of polysiloxane (with the molecular weight of 4000 and the content of hydrosilation chain links of 0.46%) under magnetic stirring, wherein the mass ratio of the polysiloxane to the polyethylene glycol is 1.25:1, refluxing for 14h after dropwise adding, washing with toluene, and carrying out rotary evaporation and drying for 4h to obtain the block polymer electrolyte. Taking 10g of the block polymer, adding lithium hexafluorophosphate, wherein the lithium ion concentration is 4%, then adding 0.04g of Karstedt catalyst and 0.4g of tetramethyl tetravinylcyclotetrasiloxane, stirring uniformly, placing in a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing in a vacuum oven at 70 ℃ for 5 hours to obtain the solid polymer electrolyte (the yield is 90%).
Example 10
Adding 20g of polyethylene glycol (with the molecular weight of 5000) with double bonds as end groups, 50mL of toluene and 0.12g of Karstedt catalyst into a three-neck flask, placing the three-neck flask in an oil bath kettle at 55 ℃ under the protection of nitrogen, dropwise adding 15g of polysiloxane (with the molecular weight of 5000 and the content of hydrosilation chain links of 0.62%) under magnetic stirring, wherein the mass ratio of the polysiloxane to the polyethylene glycol is 0.75:1, refluxing for 8h after dropwise adding, washing with toluene, and carrying out rotary evaporation and drying for 4h to obtain the block polymer electrolyte. Taking 10g of the block polymer, adding lithium hexafluorophosphate, wherein the lithium ion concentration is 3%, then adding 0.02g of Karstedt catalyst and 0.2g of tetramethyl tetravinylcyclotetrasiloxane, stirring uniformly, placing in a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing in a vacuum oven at 55 ℃ for 8h to obtain the solid polymer electrolyte (the yield is 94%).
Example 11
Adding 20g of polyethylene glycol (molecular weight 2000) with double bonds as end groups, 50mL of toluene and 0.15g of Karstedt catalyst into a three-neck flask, placing the three-neck flask in an oil bath kettle at 55 ℃ under the protection of nitrogen, dropwise adding 20g of polysiloxane (molecular weight 12000 and content of hydrosilation chain links of 0.54%) under magnetic stirring, wherein the mass ratio of the polysiloxane to the polyethylene glycol is 0.16:1, refluxing for 16h after dropwise adding, washing with toluene, and carrying out rotary evaporation and drying for 8h to obtain the block polymer electrolyte. Taking 10g of the block polymer, adding lithium hexafluorophosphate, wherein the lithium ion concentration is 3%, then adding 0.03g of Karstedt catalyst and 0.3g of tetramethyl tetravinylcyclotetrasiloxane, stirring uniformly, placing in a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing in a vacuum oven at 75 ℃ for 5 hours to obtain the solid polymer electrolyte (the yield is 94%).
Example 12
The difference from example 4 is that the amount of polysiloxane added is 9.6g and the ratio of the amount of polysiloxane to polyethylene glycol is 0.5: 1.
Example 13
The difference from example 4 is that the amount of polysiloxane added is 6g and the ratio of the amount of polysiloxane to polyethylene glycol is 0.3: 1.
Example 14
The difference from example 4 is that the amount of polysiloxane added is 18g and the ratio of the amount of polysiloxane to polyethylene glycol is 1.5: 1.
Comparative example 1
Taking 10g of polyethylene glycol (molecular weight 2000) with double bonds as end groups, adding lithium hexafluorophosphate, wherein the lithium ion concentration is 3%, then adding 0.03g of Karstedt catalyst and 0.2g of tetramethyl tetravinylcyclotetrasiloxane, uniformly stirring, placing in a mold with the thickness of 10cm multiplied by 2mm, and vulcanizing in a vacuum oven at 55 ℃ for 5 hours to obtain the solid polymer electrolyte.
Performance testing
The solid polymer electrolytes obtained in the above examples and comparative examples were respectively prepared into lithium ion batteries by the following methods:
pressing the prepared solid polymer electrolyte material into a film with the thickness of 50 um; NCM811 positive electrode material, polyvinylidene fluoride (PVDF), and acetylene black were mixed in a ratio of 9: 0.5: preparing slurry according to the proportion of 0.5, and coating the slurry on an Al current collector to prepare a positive electrode; and sequentially stacking the positive plate, the solid electrolyte film and the lithium plate, pressing at 120 ℃ under 20MPa, packaging by using an aluminum-plastic bag, assembling into an NCM (negative polarity) solid polymer electrolyte lithium battery system, and carrying out performance test.
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 80 ℃ 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 BDA0002636006310000121
As can be seen from the data in table 1, the solid polymer electrolyte provided by the present invention has excellent high temperature resistance and high pressure resistance, and at the same time, the electrochemical performance is improved compared to the solid polymer electrolyte in the prior art.
As is clear from comparative examples 4 and 12 to 14, when the amounts of the polysiloxane and polyethylene glycol are controlled within the range of (0.5 to 1.3):1, the high temperature resistance, high pressure resistance and electrochemical properties are the best.
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 (10)

1. A solid polymer electrolyte, comprising a lithium salt and a vulcanized polyorganosiloxane-polyethylene glycol block copolymer.
2. The solid polymer electrolyte as claimed in claim 1, wherein the polyorganosiloxane-polyethylene glycol block copolymer is obtained by hydrosilylation reaction of polyorganosiloxane having a silicon hydrogen functional group and polyethylene glycol having a double bond as a terminal group.
3. The solid polymer electrolyte of claim 2, wherein the polyorganosiloxane containing a silicon-hydrogen functional group has a number average molecular weight of 5 x 102～5×104；
Preferably, the polyorganosiloxane containing the silicon-hydrogen functional group has silicon-hydrogen chain links accounting for 0.1-0.7% of the total chain links;
preferably, the number average molecular weight of the polyethylene glycol with the terminal group as a double bond is 2 x 102～2×104；
Preferably, the ratio of the amount of the polyorganosiloxane containing the silicon-hydrogen functional group to the amount of the polyethylene glycol having a double bond as a terminal group is (0.5-1.3): 1.
4. The solid polymer electrolyte according to claim 2 or 3, wherein the hydrogenation addition reaction is carried out in the presence of a platinum catalyst;
preferably, the platinum catalyst comprises a Speier catalyst and/or a Karstedt catalyst;
preferably, the amount of the platinum catalyst is 0.1-0.3% of the total mass of the polyorganosiloxane containing the silicon-hydrogen functional group and the polyethylene glycol with the double bond as the terminal group;
preferably, the solvent for the hydrosilylation reaction comprises any one or a combination of at least two of toluene, tetrahydrofuran, dichloromethane, or n-hexane.
5. The solid polymer electrolyte of any one of claims 2 to 4, wherein the temperature of the hydrosilylation reaction is 50 to 90 ℃, preferably 50 to 80 ℃, and more preferably 60 to 80 ℃;
preferably, the hydrosilylation reaction time is 5-24 hours, preferably 8-12 hours;
preferably, after the hydrosilylation reaction is completed, the solvent removal and drying steps are performed.
6. The solid polymer electrolyte of any one of claims 1-5, 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 (trifluoromethylxanthyl) imide.
7. A method for producing a solid polymer electrolyte according to any one of claims 1 to 6, comprising the steps of: mixing the polyorganosiloxane-polyethylene glycol block copolymer with lithium salt, and carrying out vulcanization reaction to obtain the solid polymer electrolyte.
8. The method of claim 7, wherein the sulfidation reaction is carried out in the presence of a platinum catalyst, preferably the platinum catalyst comprises a Speier catalyst and/or a Karstedt catalyst;
preferably, the amount of the platinum catalyst used in the vulcanization reaction is 0.1 to 0.7 percent, preferably 0.2 to 0.4 percent, of the mass of the polyorganosiloxane-polyethylene glycol block copolymer;
preferably, the vulcanization reaction is carried out in the presence of a vulcanizing agent;
preferably, the vulcanizing agent comprises any one or at least two of tetramethyltetravinylcyclotetrasiloxane, vinyl silicone oil or tetramethyldivinylsiloxane;
preferably, the vulcanizing agent is used in an amount of 1 to 6%, preferably 2 to 4%, based on the mass of the polyorganosiloxane-polyethylene glycol block copolymer.
9. The method according to claim 7 or 8, wherein the temperature of the vulcanization reaction is 40 to 90 ℃, preferably 50 to 80 ℃;
preferably, the time of the vulcanization reaction is 4-24 hours, preferably 6-14 hours;
preferably, in the reaction system of the vulcanization reaction, the lithium salt accounts for 1-8% by mass of the polyorganosiloxane-polyethylene glycol block copolymer, and preferably 3-5% by mass of the polyorganosiloxane-polyethylene glycol block copolymer.
10. A lithium battery comprising the solid polymer electrolyte according to any one of claims 1 to 6.
CN202010825384.6A 2020-08-17 2020-08-17 Solid polymer electrolyte and preparation method and application thereof Pending CN111952664A (en)

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