CN110690500A - Polymer electrolyte with high voltage window - Google Patents
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- CN110690500A CN110690500A CN201910975284.9A CN201910975284A CN110690500A CN 110690500 A CN110690500 A CN 110690500A CN 201910975284 A CN201910975284 A CN 201910975284A CN 110690500 A CN110690500 A CN 110690500A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A polymer electrolyte with a high voltage window relates to the field of lithium ion battery electrolytes. The preparation method comprises the following steps of taking a hydrogen-containing organic silicon compound as a main chain, taking ethylene carbonate as a side chain, conducting lithium salt, an organic solvent and an initiator, carrying out graft polymerization by a chemical method, and taking the hydrogen-containing organic silicon compound as the main chain to construct a framework, so that the electrochemical stability window, the mechanical property and the thermal stability of the polymer electrolyte are improved, and an ion channel can also be provided; the side chain ethylene carbonate is used as a main ion channel of the polymer electrolyte, so that the ionic conductivity and the ionic migration number of the polymer electrolyte are improved, the interface compatibility of the polymer electrolyte and an electrode material is improved, and the charge and discharge performance of the solid lithium ion battery is improved.
Description
Technical Field
The invention relates to the field of lithium ion battery electrolytes, in particular to a novel polymer electrolyte with a high voltage window.
Background
The lithium ion battery is applied to electric vehicles and mobile electronic equipment more and more widely by virtue of the advantages of high energy density, quick charging, convenient carrying and the like, and a zero-carbon emission plan can be realized. However, the conventional lithium ion battery separator generally adopts a polyolefin polymer (polypropylene (PP)) and a liquid electrolyte (lithium hexafluorophosphate + ethylene carbonate/propylene carbonate) is added, but the polymer separator has poor wettability to the electrolyte, is easily decomposed at high pressure to generate gas, and causes liquid side leakage. In addition, when metal lithium is used as a negative electrode, lithium dendrites are generated on the surface of the metal lithium as lithium ions are continuously inserted and extracted. The formation of lithium dendrites not only causes the occurrence of dead lithium regions, which degrades the cycle performance of the battery, but also pierces the separator, which causes short-circuiting of the battery, severely limiting the development and application of high energy density lithium metal batteries. Therefore, the lithium ion polymer electrolyte replaces the traditional liquid electrolyte and has epoch-making significance for the development of the lithium secondary battery. The solid electrolyte can effectively prevent the generation of metallic lithium dendrites, so that the lithium metal with high energy and large specific power can be used as a negative electrode; can be made into a multi-layer ultrathin structure in any shape and is miniaturized, and is easier to assemble with a battery. An ideal solid electrolyte should possess the following advantages: 1. approaching the ionic conductivity of the liquid electrolyte; 2. wide electrochemical window (> 5V); 3. the electrode has good compatibility with the electrode; 4. the preparation process is simple and can be industrialized; 5. environment-friendly and pollution-free.
A mixture of polyethylene oxide (PEO) and an electrolyte salt has ionic conductivity, making it the earliest investigated polymer electrolyte. However, the ionic conductivity of the PEO-based polymer electrolyte was low (the room temperature conductivity of PEO was about 10)-6S cm-1) The electrochemical window is narrow. Therefore, many researchers have been working on developing polymer electrolytes containing highly polar carbonate groups [ -O- (C ═ O) -O-]Polymers and wide electrochemical windows, organosilicon compounds with good interfacial compatibility have attracted considerable attention from researchers. The patent No. CN105591154A provides a polycarbonate all-solid-state polymer electrolyte, the room-temperature ionic conductivity of the polymer electrolyte is 2 x 10-5S cm-1～1×10-3S cm-1The electrochemical window is greater than 4V. Patent No. CN105702919A provides a method for preparing an electrode for a lithium battery comprising an interface-stable polymer material and its use in a solid state lithium battery. The polymer electrolyte is prepared by adopting the poly (ethylene carbonate) (PVCA) or the copolymer thereof, a covering film can be formed on the surface of an electrode, and the damage of the electrode material and the damage of the solid electrolyte on the surfaces of a positive electrode and a negative electrode in the charge-discharge process can be effectively inhibitedAnd (5) decomposing. The two carbonate-based polymer electrolytes have low electrochemical window (less than 4.7V) and are not suitable for a high-voltage positive electrode material system. The patent No. 201010607369.0 provides an organic silicon amine electrolyte material containing polyether chain and its application in lithium battery, the synthesized organic silicon amine electrolyte material containing polyether chain has good electrochemical performance; poor mechanical property, unstable size property and the danger of side leakage of electrolyte. Patent No. CN 109802174A discloses a polycarbonate-based polymer electrolyte having an ionic conductivity > 10 at room temperature-3S cm-1Electrochemical window is only 4.7V, and cannot be applied to LiNi0.5Mn1.5O4And high-voltage anode materials.
Disclosure of Invention
In view of the problems, the invention develops a novel high-voltage window polymer electrolyte. The preparation method comprises the steps of selecting a hydrogen-containing organic silicon compound as a main chain, selecting ethylene carbonate as a side chain, conducting lithium salt, a porous supporting material, an organic solvent and an initiator, and carrying out graft polymerization by a chemical method to prepare the graft polymer electrolyte with a high voltage window. The hydrogen-containing organic silicon compound is used as a skeleton for constructing a main chain, so that the electrochemical stability window, the mechanical property and the thermal stability of the polymer electrolyte are improved, and an ion channel can be provided; the side chain ethylene carbonate is used as a main ion channel of the polymer electrolyte, so that the ionic conductivity and the ionic migration number of the polymer electrolyte are improved, the interface compatibility of the polymer electrolyte and an electrode material is improved, and the charge and discharge performance of the solid lithium ion battery is improved. The thickness of the polymer electrolyte is 10-500 μm; ionic conductivity 1X 10-4S cm-1～5×10-3S cm-1(25 ℃), the working temperature is-25-100 ℃; an electrochemical window > 5V (vs. Li)+/Li), has great innovation and practicability for the application of high-voltage cathode materials. In addition, when the solid lithium ion battery is assembled, the polymer electrolyte can form a protective layer on the surfaces of the electrode material of the lithium battery and the metal lithium, so that the damage of electrode crystals caused by the embedding and the separation of lithium ions can be effectively inhibited, and the long-cycle stability of the lithium battery is further improved.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the polymer electrolyte with a high voltage window is characterized in that the raw materials comprise a hydrogen-containing organic silicon compound, ethylene carbonate, a conductive lithium salt, an organic solvent, an initiator or a catalyst; wherein the mass fraction of the hydrogen-containing organosilicon compound is 5-70%, the mass fraction of the ethylene carbonate is 5-70%, the mass fraction of the conductive lithium salt is 5-60%, the mass fraction of the organic solvent is 10-80%, and the mass fraction of the initiator or the catalyst is 0.5-5%. The polymer electrolyte with the high voltage window is subjected to graft polymerization by a chemical method to prepare the graft polymer electrolyte with the high voltage window, wherein a hydrogen-containing organic silicon compound reacts with ethylene carbonate to form a polymer taking the hydrogen-containing organic silicon compound as a main chain and ethylene carbonate as a side chain. And (4) supporting and forming by adopting a porous supporting material.
The thickness of the polymer electrolyte is 20-200 μm; ionic conductivity 1X 10-4S cm-1～5×10-3Scm-1(25 ℃), and the working temperature is-25 to 100 ℃; an electrochemical window > 5V (vs. Li)+/Li), has great innovation and practicability for the application of high-voltage cathode materials.
The structure of the hydrogen-containing organosilicon compound is shown as a general formula 1:
wherein the value of n is a natural number of 1-50000; r1、R2And R3Is one selected from H, halogen, alkyl of 18 carbon or less, phenyl, cyano, epoxy, and alkyl silyl of 18 carbon or less.
The structure of the ethylene carbonate is shown as a general formula 2:
the structure of the polymer in the polymer electrolyte is shown as a general formula 3
R1、R2And R3Is one selected from H, halogen, alkyl of 18 carbon or less, phenyl, cyano, epoxy, and alkyl silyl of 18 carbon or less. The value of n is a natural number between 1 and 50000.
The conductive lithium salt is one or more of the following: lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (trifluoromethanesulfonyl) methide [ LiC (SO)2CF3)3]。
The organic solvent is one or more of the following: acetonitrile, 1, 2-dimethoxyethane, ethylene carbonate, N-methylpyrrolidone (NMP), propylene carbonate, dimethyl carbonate, butylene carbonate, methyl ethyl carbonate, ethylene carbonate, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, gamma-butyrolactone, diethylene glycol dimethyl ether, 2-methyltetrahydrofuran, tetrahydrofuran, dimethyl sulfoxide.
The initiator or catalyst is one of the following: dibutyl tin dilaurate, dibutyl tin bis (acetylacetonate), platinum water (Pt), Azobisisoheptonitrile (ABVN), Azobisisobutyronitrile (AIBN), dimethyl Azobisisobutyrate (AIBME), Benzoyl Peroxide (BPO).
The preparation of the polymer electrolyte with the high voltage window comprises the following steps: preparing an electrolyte from an organic silicon compound, ethylene carbonate, a conductive lithium salt and an organic solvent according to the corresponding mass fraction, and uniformly stirring; adding initiator or catalyst with corresponding mass fraction and stirring uniformly; coating or immersing the electrolyte into a polytetrafluoroethylene mould containing a porous support material, and heating and curing at 60-120 ℃ for 2-24 hours to form a film.
The porous supporting material is one or more of polypropylene non-woven fabric, glass fiber non-woven fabric, polyethylene non-woven fabric, polytetrafluoroethylene non-woven fabric and cellulose non-woven fabric.
The polymer electrolyte with high voltage window can be used for a separator between a positive electrode and a negative electrode.
A polymer lithium ion battery comprising: the electrolyte comprises a positive electrode, a negative electrode and a diaphragm arranged between the positive electrode and the negative electrode, wherein the diaphragm is the polymer electrolyte.
The polymer lithium ion battery has a positive active material of lithium manganate or lithium iron phosphate (LiFeO)4) Lithium Nickel Cobalt Aluminate (NCA), lithium manganese oxide, lithium manganese iron phosphate, and lithium cobaltate (LiCoO)2) Lithium nickel manganese oxide, lithium rich materials (LLOs), lithium nickel cobalt manganese oxide, lithium ion fluorophosphate, and lithium nickelate (LiNiO)2) One or more of the above; the negative active material is one or more of metal lithium, metal lithium alloy, carbon-silicon composite material, lithium titanate, graphite, lithium metal nitride, antimony oxide, carbon-germanium composite material and lithium-titanium oxide. The preparation of the positive electrode comprises the following steps: the preparation method of the cathode material comprises the following steps: grinding and mixing a positive electrode active material accounting for 50-90% by mass and a conductive agent acetylene black accounting for 5-30% by mass, adding polyvinylidene fluoride (PVDF) accounting for 1-15% by mass, an electrolyte mixed solution accounting for 1-15% by mass and 1-methyl-2 pyrrolidone (NMP), grinding and mixing to obtain a positive electrode material, wherein the 1-methyl-2 pyrrolidone (NMP) is used for adjusting viscosity and is not counted in the mass percentage composition of the positive electrode material; and coating the anode material on the surface of the aluminum foil, and drying to obtain the anode. The metal lithium and the metal lithium alloy can be directly used as corresponding negative electrodes. The preparation of the negative electrode comprises the following steps: : grinding and mixing 30-80% by mass of a negative electrode active material and 5-30% by mass of a conductive agent acetylene black; adding polyvinylidene fluoride (PVDF) accounting for 5-25% of the mass fraction, electrolyte mixed liquor accounting for 1-15% of the mass fraction and 1-methyl-2-pyrrolidone (NMP) to be ground and mixed to obtain a negative electrode material; wherein, the 1-methyl-2 pyrrolidone (NMP) is used for adjusting the viscosity and is not counted in the mass percentage composition of the cathode material; and coating the copper foil surface, and drying to obtain the cathode.
The polymer lithium ion battery comprises: the electrolyte mixed liquid in the anode material and the cathode material comprises the following components: 5-70% of hydrogen-containing organic silicon compound, 5-70% of ethylene carbonate, 5-60% of conductive lithium salt, 10-80% of organic solvent and 0.5-5% of initiator or catalyst (the specific selection range of each substance in the electrolyte mixed solution is the same as that of each substance in the polymer electrolyte raw material component of the high-voltage window).
The polymer lithium ion battery is characterized in that: the battery can be prepared as follows (1): ex-situ assembly process-positive and negative electrodes and the above composite solid electrolyte; (2): and (3) in-situ assembly technology, namely injecting the electrolyte mixed solution into a battery system of a positive electrode, a diaphragm and a negative electrode, and curing for 2-24 hours at the temperature of 60-120 ℃.
The invention has the innovativeness and practicability that:
the invention takes a hydrogen-containing organic silicon compound as a main chain, ethylene carbonate as a side chain, conductive lithium salt, a porous support material, an organic solvent and an initiator for the first time, and graft polymerization is carried out by a chemical method to prepare the graft polymer electrolyte with a high voltage window. The hydrogen-containing organic silicon compound is used as a skeleton for constructing a main chain, so that the electrochemical stability window, the mechanical property and the thermal stability of the polymer electrolyte are improved, and an ion channel can be provided; the side chain ethylene carbonate is used as a main ion channel of the polymer electrolyte, so that the ionic conductivity and the ionic migration number of the polymer electrolyte are improved, the interface compatibility of the polymer electrolyte and an electrode material is improved, and the charge and discharge performance of the solid lithium ion battery is improved. The thickness of the polymer electrolyte is 20-200 μm; ionic conductivity 1X 10-4S cm-1～5×10-3S cm-1(25 ℃), the working temperature is-25-100 ℃; an electrochemical window > 5V (vs. Li)+/Li), has great innovation and practicability for the application of high-voltage cathode materials. When the solid lithium ion battery is assembled, the polymer electrolyte can form a protective layer on the surfaces of the electrode material of the lithium battery and the metal lithium, so that the damage of electrode crystals caused by the embedding and the separation of lithium ions can be effectively inhibited, and the long-cycle stability of the lithium battery is further improved. In addition, the polymer electrolyte of the present invention may not be added during the preparation processThe organic solvent is used for preparing the polymer electrolyte by in-situ polymerization, the preparation process is simple, the quantitative production can be realized, the potential safety hazard and the environmental pollution are eliminated, and the safety and the practicability of the lithium battery are greatly improved. The method can be applied to all-solid-state lithium batteries (including lithium-sulfur batteries), all-solid-state lithium ion batteries and other secondary high-energy lithium batteries.
Drawings
FIG. 1 is a voltammetric linear scan of a polymer electrolyte in example 1.
Detailed Description
The present invention is illustrated below by specific examples, which are provided for better understanding of the present invention and are not intended to limit the scope of the present invention in any way.
Preparation of graft polymer electrolyte:
example 1
1.3g of ethylene carbonate, 1.5g of phenyl hydrogen silicone oil, 0.65g of lithium bistrifluoromethanesulfonylimide (LiTFSI) perchlorate (LiClO)4) Dissolving in 4ml acetonitrile, stirring at room temperature to completely dissolve; adding 0.015g of azodiisobutyronitrile, uniformly stirring, and uniformly coating the mixture on a polytetrafluoroethylene mold cavity; heating the mixture in a vacuum drying oven at 90 ℃ for 12 hours to solidify and form a film.
Example 2
2g of ethylene carbonate, 2g of methyl hydrosilicone resin, 0.8g of lithium perchlorate (LiClO)4) Dissolving in 4ml NMP, stirring at room temperature to make it completely dissolve; adding 0.02g of dibutyltin bis (acetyl acetonate) and uniformly stirring, and uniformly coating the mixture on a polytetrafluoroethylene mold cavity; heating the mixture in a vacuum drying oven at 90 ℃ for 12 hours to solidify and form a film.
Example 3
1.8g of ethylene carbonate, 2g of methyl hydrogen-containing silicone resin and 0.7g of lithium bistrifluoromethanesulfonimide (LiTFSI) were dissolved in 4ml of tetrahydrofuran, and the mixture was stirred at room temperature to be completely dissolved; adding 0.02g of platinum catalyst, uniformly stirring, and uniformly coating the mixture on a polytetrafluoroethylene die cavity; heating the mixture in a vacuum drying oven at 90 ℃ for 12 hours to solidify and form a film.
Example 4
2.5g of ethylene carbonate, 2.5g of cyano hydrogen-containing silicone resin and 1.25g of lithium bistrifluoromethanesulfonimide (LiTFSI) were dissolved in 4ml of tetrahydrofuran, and the mixture was stirred at room temperature to be completely dissolved; adding 0.03g of foil catalyst, stirring, and uniformly coating the mixture on a polytetrafluoroethylene die cavity; heating the mixture in a vacuum drying oven at 90 ℃ for 12 hours to solidify and form a film.
Example 5
2.5g of ethylene carbonate, 1.8g of methyl hydrogen-containing silicone resin and 1g of lithium bistrifluoromethanesulfonimide (LiTFSI) were dissolved in 4ml of acetonitrile, and the mixture was stirred at room temperature to be completely dissolved; adding 0.03g of azobisisobutyronitrile, stirring, and uniformly coating the mixture on a polytetrafluoroethylene die cavity; heating the mixture in a vacuum drying oven at 90 ℃ for 12 hours to solidify and form a film.
Thickness of electrolyte: the thickness of the block polymer electrolyte was measured using a micrometer (precision 0.01 mm), and 3 points on the film were arbitrarily removed for measurement, and the average value was determined.
Ionic conductivity: the impedance of the button cell of 2032 was measured by assembling two stainless steel gaskets sandwiching the polymer electrolyte according to the formula
Wherein L is the thickness of the polymer electrolyte and S is the area of the stainless steel gasket (1.76 cm)-2) And R is the measured impedance value.
Electrochemical window: clamping polymer electrolyte by stainless steel and lithium sheets, assembling 2032 button cell, and performing linear volt-ampere scanning measurement at initial voltage of 2.7V, maximum potential of 5.5V and scanning speed of 1mV s-1。
| Examples | Average thickness (μm) | Ion conductivity (S cm)-1,25℃) | Electrochemical window (V) |
| 1 | 157 | 9.56×10-4 | 5.07 |
| 2 | 182 | 1.12×10-3 | 5.10 |
| 3 | 173 | 8.82×10-4 | 5.12 |
| 4 | 168 | 1.03×10-3 | 5.22 |
| 5 | 178 | 9.27×10-4 | 5.21 |
。
Claims (10)
1. The polymer electrolyte with a high voltage window is characterized in that the raw materials comprise a hydrogen-containing organic silicon compound, ethylene carbonate, a conductive lithium salt, an organic solvent, an initiator or a catalyst; wherein the mass fraction of the hydrogen-containing organosilicon compound is 5-70%, the mass fraction of the ethylene carbonate is 5-70%, the mass fraction of the conductive lithium salt is 5-60%, the mass fraction of the organic solvent is 10-80%, and the mass fraction of the initiator or the catalyst is 0.5-5%. The polymer electrolyte with the high voltage window is subjected to graft polymerization by a chemical method to prepare the graft polymer electrolyte with the high voltage window, wherein a hydrogen-containing organic silicon compound reacts with ethylene carbonate to form a polymer taking the hydrogen-containing organic silicon compound as a main chain and ethylene carbonate as a side chain; and (4) supporting and forming by adopting a porous supporting material.
2. A high voltage window polymer electrolyte as defined in claim 1,
the structure of the hydrogen-containing organosilicon compound is shown as a general formula 1:
wherein the value of n is a natural number of 1-50000; r1、R2And R3One of H, halogen, alkyl with less than 18 carbon atoms, phenyl, cyano, epoxy and alkyl silyl with less than 18 carbon atoms;
the structure of the ethylene carbonate is shown as a general formula 2:
the polymer structure which takes the hydrogen-containing organosilicon compound as the main chain and the ethylene carbonate group as the side chain is formed by the reaction of the hydrogen-containing organosilicon compound and the ethylene carbonate, and is shown as a general formula 3:
R1、R2and R3Is one of H, halogen, alkyl with less than 18 carbon atoms, phenyl, cyano, epoxy and alkyl silyl methyl with less than 18 carbon atoms, and n is a natural number of 1-50000.
3. In accordance with claim 1The polymer electrolyte of the voltage window is characterized in that the conductive lithium salt is one or more of the following: lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium bis (trifluoromethanesulfonyl) methide [ LiC (SO)2CF3)3]。
4. The high voltage window polymer electrolyte of claim 1 wherein the organic solvent is one or more of the following: acetonitrile, 1, 2-dimethoxyethane, ethylene carbonate, N-methylpyrrolidone (NMP), propylene carbonate, dimethyl carbonate, butylene carbonate, methyl ethyl carbonate, ethylene carbonate, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, gamma-butyrolactone, diethylene glycol dimethyl ether, 2-methyltetrahydrofuran, tetrahydrofuran, dimethyl sulfoxide.
5. The high voltage window polymer electrolyte of claim 1 wherein the initiator or catalyst is one of the following: dibutyl tin dilaurate, dibutyl tin bis (acetylacetonate), platinum water (Pt), Azobisisoheptonitrile (ABVN), Azobisisobutyronitrile (AIBN), dimethyl Azobisisobutyrate (AIBME), Benzoyl Peroxide (BPO).
6. The high voltage window polymer electrolyte of claim 1 wherein the preparation of the high voltage window polymer electrolyte comprises the steps of: preparing an organic silicon compound, ethylene carbonate, a conductive lithium salt and an organic solvent into an electrolyte according to the corresponding mass fraction, and uniformly stirring; adding initiator or catalyst with corresponding mass fraction and stirring uniformly; coating or immersing the electrolyte into a polytetrafluoroethylene mould containing a porous support material, and heating and curing at 60-120 ℃ for 2-24 hours to form a film.
7. The high voltage window polymer electrolyte as claimed in claim 1, wherein the porous support material is one or more of polypropylene non-woven fabric, glass fiber non-woven fabric, polyethylene non-woven fabric, polytetrafluoroethylene non-woven fabric, and cellulose non-woven fabric.
8. Use of a high voltage window polymer electrolyte according to any of claims 1 to 7, characterized in that it is used in a separator between a positive electrode and a negative electrode; the thickness of the polymer electrolyte is 10-500 μm.
9. A polymer lithium ion battery comprising: a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, wherein the separator is the polymer electrolyte having a high voltage window according to any one of claims 1 to 7.
10. The polymer lithium ion battery of claim 9, wherein the positive active material of the polymer lithium ion battery is lithium manganate or lithium iron phosphate (LiFeO)4) Lithium Nickel Cobalt Aluminate (NCA), lithium manganese oxide, lithium manganese iron phosphate, and lithium cobaltate (LiCoO)2) Lithium nickel manganese oxide, lithium rich materials (LLOs), lithium nickel cobalt manganese oxide, lithium ion fluorophosphate, and lithium nickelate (LiNiO)2) One or more of the above; the negative active material is one or more of metal lithium, metal lithium alloy, carbon-silicon composite material, lithium titanate, graphite, lithium metal nitride, antimony oxide, carbon-germanium composite material and lithium-titanium oxide. The preparation of the positive electrode comprises the following steps: the preparation method of the cathode material comprises the following steps: grinding and mixing a positive electrode active material accounting for 50-90% by mass and a conductive agent acetylene black accounting for 5-30% by mass, adding polyvinylidene fluoride (PVDF) accounting for 1-15% by mass, an electrolyte mixed solution accounting for 1-15% by mass and 1-methyl-2 pyrrolidone (NMP), grinding and mixing to obtain a positive electrode material, wherein the 1-methyl-2 pyrrolidone (NMP) is used for adjusting viscosity and is not counted in the mass percentage composition of the positive electrode material; and coating the anode material on the surface of the aluminum foil, and drying to obtain the anode. The metal lithium and the metal lithium alloy can be directly used as corresponding negative electrodes. The preparation of the negative electrode comprises the following steps: 30-80% of negative electrode active material and 5-30% of conductive materialGrinding and mixing acetylene black; adding polyvinylidene fluoride (PVDF) accounting for 5-25% of the mass fraction, electrolyte mixed liquor accounting for 1-15% of the mass fraction and 1-methyl-2-pyrrolidone (NMP) to be ground and mixed to obtain a negative electrode material; wherein, the 1-methyl-2 pyrrolidone (NMP) is used for adjusting the viscosity and is not counted in the mass percentage composition of the cathode material; coating the copper foil surface, and drying to obtain a negative electrode;
the electrolyte mixed liquid in the anode material and the cathode material comprises the following components: 5-70% of hydrogen-containing organic silicon compound, 5-70% of ethylene carbonate, 5-60% of conductive lithium salt, 10-80% of organic solvent and 0.5-5% of initiator or catalyst, wherein the specific selection range of each substance in the electrolyte mixed solution is the same as the selection range of each raw material substance in the polymer electrolyte of the high voltage window in any one of claims 1-5;
the preparation of the battery comprises the following steps: (1): ex-situ assembly process-positive and negative electrodes and the above composite solid electrolyte; (2): and (3) in-situ assembly technology, namely injecting the electrolyte mixed solution into a battery system of a positive electrode, a diaphragm and a negative electrode, and curing for 2-24 hours at the temperature of 60-120 ℃.
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| CN112625592A (en) * | 2020-10-26 | 2021-04-09 | 上海汽车集团股份有限公司 | Preparation method of lithium metal interface modification layer |
| CN113540574A (en) * | 2021-06-24 | 2021-10-22 | 西安交通大学 | Lithium battery assembly process for heating in-situ solidified electrolyte |
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