CN110611120A - Single-ion conductor polymer all-solid-state electrolyte and lithium secondary battery comprising same - Google Patents
Single-ion conductor polymer all-solid-state electrolyte and lithium secondary battery comprising same Download PDFInfo
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- CN110611120A CN110611120A CN201910271090.0A CN201910271090A CN110611120A CN 110611120 A CN110611120 A CN 110611120A CN 201910271090 A CN201910271090 A CN 201910271090A CN 110611120 A CN110611120 A CN 110611120A
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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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
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- 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
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Abstract
The invention relates to a single-ion conductor all-solid-state polymer electrolyte and an all-solid-state secondary lithium battery formed by the same. The single-ion conductor all-solid-state polymer electrolyte comprises: polyanion lithium salt, matrix organic polymer and inorganic filler; the room temperature ionic conductivity is 2 multiplied by 10‑4S/cm～1.2×10‑3S/cm, and the electrochemical oxidation window is more than 4V. The single-ion conductor all-solid-state polymer electrolyte is simple to prepare, good in mechanical property, high in ionic conductivity and wide in electrochemical oxidation window; meanwhile, the growth of dendritic crystals in the circulation process of the lithium metal negative electrode can be effectively inhibited, and the interface stability and the long circulation performance are improved.
Description
Technical Field
The invention relates to a solid electrolyte, in particular to a single-ion conductor polymer all-solid-state electrolyte and an all-solid-state lithium secondary battery formed by the same.
Background
The power battery is the core of the electric automobile, and the development of the efficient power battery system plays an extremely important role in getting rid of the dependence on external petroleum in China, improving the urban air environment and realizing the renewable utilization of energy resources, and has great economic and social benefits. The lithium battery is the most important power battery path direction due to the characteristics of light weight, high specific energy and specific power, long service life and the like, and the current power lithium battery mainly comprises five parts in structure: positive electrode, negative electrode, electrolyte, diaphragm, shell and electrode lead. The electrolyte is one of the important components of the battery, and the performance of the electrolyte directly influences the optimization and improvement of the performance of the lithium ion battery. As an electrolyte with excellent performance, at least three conditions should be met: (1) high ionic conductivity: (2) the electrochemical stability is good, namely the electrochemical electrode has good compatibility and stability with electrode materials: (3) the heat resistance is excellent. Research shows that the composition, chemical ratio and structure of the electrolyte determine the performance of the electrolyte, and therefore the performance of the lithium ion battery is finally influenced. Therefore, the research on the electrolyte is very important to improve the comprehensive performance of the battery.
The electrolyte of the existing electrochemical power lithium ion battery comprises a liquid organic solvent, lithium salt and a polyolefin diaphragm. When in use, the electrolyte is easy to leak and volatilize, so that the dry zone phenomenon of the battery is caused, the performance of the battery is further limited and influenced, and the service life of the battery is shortened. Meanwhile, the thermal stability of the size of the polyolefin diaphragm is poor, and when the battery is heated or in an extreme case, the diaphragm shrinks or melts to cause short circuit, so that explosion occurs. The solid electrolyte is used for replacing an organic liquid electrolyte, so that the safety problem of the battery can be solved completely while the two key problems of low energy density and short service life of the traditional lithium ion battery are solved, and the development direction of a novel high-capacity chemical energy storage technology in the future is met. Compared with liquid electrolyte, the battery using all-solid polymer as electrolyte has the following advantages: the all-solid polymer electrolyte can inhibit the growth of dendrites; the liquid leakage can be avoided, and the safety is improved; the shape adaptability of the battery is enhanced, the battery can adapt to the personalized development of the battery in the future, and the overall manufacturing of the battery can be carried out through a coating process, a laminating process and the like.
The research make internal disorder or usurp on all solid-state lithium secondary batteries mainly includes two major categories by electrolyte distinction: one type of lithium secondary battery is composed of an organic polymer electrolyte, also called a polymer all-solid-state lithium battery; the other type is a lithium secondary battery composed of an inorganic solid electrolyte, which is also called an inorganic all-solid-state lithium battery. In the polymer electrolyte, the organic polymer forming the matrix includes polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, and polyvinylidene chloride. Examples of the disclosed polymer electrolytes are as follows: the invention patent publication US 4792504(a) describes a polymer electrolyte containing polyethylene dimethacrylate/polyethylene oxide, but not high in mechanical properties. The invention patent with application number CN200710144760 describes an electrolyte with polyethylene oxide added with ultra-fine powder filler, which has good mechanical properties, but the ionic conductivity is not very high. Patent publication CN1411475A describes a polymer electrolyte comprising an amphiphilic graft copolymer. The invention patent publication CN 1428363a describes a nanoporous polymer electrolyte membrane with superior charge and discharge performance and cycle performance, and both of these membrane properties are good but gel polymer electrolytes.
Polyethylene oxide (PEO)/lithium salt type electrolytes have been used in all solid-state lithium polymer batteries, but there are still some problems to be solved from the practical viewpoint: the linear and grafted polymers have poor mechanical properties, and are not easy to prepare independently supported polymer films, while the conductivity of the network polymer is too low. Therefore, the electrolyte system is only suitable for working under the condition of high temperature or micro current, and is practically applied to the lithium battery which is difficult to work at normal temperature.
In addition, in a conventional organic solid electrolyte, an electrolyte salt is generally a small-molecular lithium salt such as LiFSI (lithium LiFSI) and LiTFSI (lithium iron phosphate), anions with large volume steric hindrance can migrate together with Li ions in the charging and discharging processes, so that the problems of increased ion migration resistance, low ion mobility, aggravation of battery polarization and the like are caused, and in a polyanion lithium salt, the anions are polymerized and fixed on a polymer matrix and cannot migrate along with the Li ions, the ion migration number is close to 1.0, so that the effective conductivity is greatly improved, and the overall electrochemical performance of the battery is improved.
Disclosure of Invention
The invention aims to provide a single-ion conductor polymer all-solid-state electrolyte and an all-solid-state lithium secondary battery formed by the same; polyanion lithium salt is introduced to improve the ion mobility of electrolyte, thereby improving the electrochemical performance of the battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a single-ion conductor all-solid-state polymer electrolyte is characterized in that: comprises polyanion lithium salt, matrix organic polymer and inorganic filler;
the polyanionic lithium salt has a structure shown as general formulas Ia, Ib, ic, Id, ie and if:
the polyanionic lithium salt is one or more of Ia, Ib, ic, id, ie and if, wherein ic, id and ie are preferably used in a mixture with a mass ratio of 1:1: 1; the value of m is 1000-5000.
The all-solid-state electrolyte of the single-ion conductor polymer is obtained by combining polyanion lithium salt, matrix organic polymer and inorganic filler, and particularly is obtained by carrying out free radical copolymerization on lithium salt monomers IIa, IIb, IIc, IId, IIe and IIf corresponding to the polyanion lithium salt and monomers of the matrix organic polymer.
Wherein:
the thickness of the single-ion conductor all-solid-state polymer electrolyte is 20-100 mu m, and the room-temperature ionic conductivity is 2 multiplied by 10-4～1.2×10-3S/cm, and the electrochemical window is 2.8-5.0V.
The polyanionic lithium salt is respectively obtained by polymerizing lithium salt monomers IIa, IIb, IIc, IId, IIe and IIf containing unsaturated double bonds through free radical double bonds, and the lithium salt monomers IIa, IIb, IIc, IId, IIe and IIf have the structures shown as the following formulas:
the matrix organic polymer provided by the invention is as follows: the material is one of polymethyl methacrylate, poly ethylene carbonate, polyvinyl acetate and polyoxyethylene ether containing unsaturated double bonds, wherein the polymethyl methacrylate, the poly ethylene carbonate and the polyvinyl acetate are respectively formed by in-situ polymerization of methyl methacrylate, vinylene carbonate and vinyl acetate monomers.
The polyoxyethylene ether containing unsaturated double bonds is one of allyl alcohol polyoxyethylene ether, methallyl alcohol polyoxyethylene ether, isopentenol polyoxyethylene ether and pentaerythritol triallyl ether polyoxyethylene ether, and the structures of the polyoxyethylene ether containing unsaturated double bonds are respectively shown as IIIa, IIIb, IIIc and IIId:
mixing polyanion lithium salt monomer and matrix organic polymer monomer, adding dibenzoyl peroxide initiator to form copolymer, and forming the single-ion conductor all-solid-state polymer electrolyte by the copolymer and inorganic filler, wherein the copolymer has a structure shown in formulas IVa, IVb, IVc, IVd, IVe, IVf, IVg, IVh, IVi and IVj:
wherein m is 1000-5000, n is 10000-50000, k is 1000-5000, j is 1000-5000, and x is 2000-2500.
The inorganic filler is one of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, silicon nitride, diatomite, montmorillonite and kaolin.
The composition of the single-ion conductor all-solid-state polymer electrolyte is preferably as follows by mass percent: polyanionic lithium salt 30%; 60% of matrix organic polymer; 10% of inorganic filler.
The invention also provides a preparation method of the single-ion conductor all-solid-state polymer electrolyte, which is characterized by comprising the following specific steps of:
a) dissolving a lithium salt monomer (with a structural formula of IIa, IIb, IIc, IId, IIe and IIf) containing unsaturated double bonds in a matrix organic polymer monomer (the polymer monomer is one of the methyl methacrylate monomer, the vinylene carbonate monomer, the vinyl acetate monomer or the polyoxyethylene ether monomer containing unsaturated double bonds), wherein the addition amount of the lithium salt monomer is preferably 30% of the total mass of the electrolyte, the addition amount of the matrix organic polymer monomer is preferably 60% of the total mass of the electrolyte, and adding a dibenzoyl peroxide (BPO) initiator accounting for 0.5% of the total mass fraction, and stirring until all the components are dissolved to form a uniform pre-polymerization monomer solution;
b) adding an inorganic filler into the obtained prepolymer monomer solution, stirring and dispersing to form uniform wet electrolyte prepolymer slurry;
c) coating the slurry between positive and negative electrode plates of a lithium secondary battery, and winding, hot-pressing and standing to enable a prepolymer solution adsorbed by the inorganic filler to be fully soaked and absorbed by the positive and negative electrode plates;
d) putting the wound battery cell into an aluminum-plastic film and putting the aluminum-plastic film into a baking oven, and baking at 70-80 ℃; the initiator dibenzoyl peroxide is decomposed to initiate the free radical copolymerization of the lithium salt monomer and the organic polymer monomer solvent to form the in-situ polymerized all-solid electrolyte containing polyanion lithium salt.
Taking copolymerization of polyanion lithium salt Ia and polyvinyl acetate as an example, coating the slurry obtained in the step 2) on the surface of an electrode plate to form a slurry film with the thickness of 20-100 microns, then winding or clamping the electrolyte prepolymer slurry by using another electrode, packaging the electrolyte prepolymer slurry in a soft package or a button cell, heating the electrolyte prepolymer slurry in an oven to 80 ℃ and baking the electrolyte prepolymer slurry for 2 hours to initiate polymerization reaction, and fully polymerizing the monomer to obtain the polyanion all-solid electrolyte with the following structure:
the polyanion is a block copolymer, polyanion lithium salt provides enough lithium ions as a current carrier, so that the electrolyte has high ionic conductivity, polyvinyl acetate is used as a high-molecular matrix organic polymer, and enough oxygen-rich carbonyl C (O) is complexed with the lithium ions, so that the lithium ions can be effectively conducted in the electrolyte, the conductivity is further improved, and the solid electrolyte has good elasticity and flexibility;
in addition, the polyanionic electrolyte has only Li as the carrier+The ionic polymer and the polymeric anion are fixed and cannot move, the radius of the lithium ion is small, and the conduction resistance is low, so that the electrolyte has the ionic mobility close to 1.0 and the effective conductivity, the polarization phenomenon of the battery in the charging process is avoided, and the overall performance of the battery is improved.
The inorganic filler is used as a polymer reinforcing agent to improve the mechanical property of the electrolyte, can effectively prevent lithium crystal branches from piercing a solid electrolyte membrane when metal lithium is used as a negative electrode material, and passes through the surface of inorganic solid particles with high surface area and Li+The polarization of ions and polyanions further improves the overall conductivity of the electrolyte, and in addition, solid particles such as aluminum oxide and the like can also absorb trace moisture and free acid in the electrolyte, reduce the corrosion of the solid particles to the surface of the electrode, and improve the cycle and storage life of the battery.
The single-ion conductor all-solid-state polymer electrolyte can be used for preparing all-solid-state lithium secondary batteries, wherein the all-solid-state lithium secondary batteries comprise all-solid-state metal lithium batteries, all-solid-state lithium ion batteries or all-solid-state lithium sulfur batteries and comprise a positive electrode, a negative electrode and an electrolyte between the positive electrode and the negative electrode, and the all-solid-state lithium secondary batteries are characterized in that: the electrolyte is a single-ion conductor all-solid-state polymer electrolyte, and the positive and negative electrode plates are separated by the electrolyte and sealed to obtain the all-solid-state lithium secondary battery.
Wherein: the positive active material is one of lithium cobaltate, lithium iron phosphate, lithium iron manganese phosphate, lithium manganate, lithium nickel manganese oxide, ternary materials, sulfur compound, lithium iron sulfate, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium iron fluorophosphate and lithium manganese oxide;
the negative active material is one of metal lithium, metal lithium alloy, graphite, hard carbon, silicon, molybdenum disulfide, lithium titanate, graphene, antimony oxide, antimony-carbon composite material, tin-antimony composite material and lithium-titanium oxide.
The positive electrode suitable for the all-solid-state secondary lithium-sulfur battery is a sulfur and sulfur compound, and the negative electrode is metal lithium and metal lithium alloy.
The invention has the advantages that:
the electrolyte lithium salt in the all-solid-state polymer electrolyte is polyanionic lithium salt, and is different from the traditional small-molecule lithium salts such as lithium hexafluorophosphate, LiTFSI, LiFSI and the like, when the polyanionic lithium salt conducts lithium ions, anions cannot migrate along with the lithium salt, the ion mobility of the polyanionic lithium salt is close to 1.0, namely only the lithium ions can migrate under the action of an electric field in the charging and discharging process, because the radius of the lithium ions is far smaller than that of the anions, the ionic conduction resistance of a single-ion conductor polymer is greatly reduced in the electrochemical process, and more excellent electrochemical performance can be obtained;
on the other hand, compared with the conventional monomer, the polymer has greatly improved thermal stability and water stability, is polymerized at the temperature of 80 ℃, does not cause the rapid decomposition of an electrolyte system, and is the traditional lithium hexafluorophosphate (LiPF)6) The lithium salt, at 50 c, will decompose and react with other components in the electrolyte, causing irreversible performance deterioration.
Meanwhile, the polyanion is a high-molecular solid polymer and is used as a part of the polymer structure, so that the integral mechanical strength of the electrolyte can be greatly improved under the condition of ensuring the same conductivity.
The electrolyte obtained by the invention is easy to prepare, can be coated between a positive pole piece and a negative pole piece, is wound and pressed, is cured at high temperature, and is polymerized in situ to form the all-solid-state battery, compared with the traditional mode that the solid electrolyte is firstly formed into a film and then is hot-pressed, the in-situ polymerization has better contact with an electrode material interface, the electrochemical performance of the all-solid-state battery can be improved, the forming is simple, the mechanical strength is 10-80 MPa, the room-temperature ionic conductivity is 2 multiplied by 10-4s/cm～1.2×10-3s/cm, electrochemical window greater than 4V. At the same time as the solid electrolyteCan effectively inhibit the growth of lithium dendrite of the negative electrode, and improves the interface stability and long cycle performance. The electrolyte does not contain flammable and explosive organic solvents after complete polymerization, thereby eliminating potential safety hazards and greatly improving the safety of the lithium battery. 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 battery systems.
Drawings
FIG. 1 is a charge-discharge curve of a block-copolymerized single-ion conductor polymer all-solid-state battery of lithium polymethacrylate trifluroborate Ia and polymethyl methacrylate provided in example 1 of the present invention;
FIG. 2 is a charge-discharge curve of a single-ion conductor polymer all-solid-state 5V lithium battery prepared by block copolymerization of a polymer lithium salt Ib and polyvinyl acetate provided in example 2 of the present invention;
FIG. 3 is a charge-discharge curve of a single-ion conductor polymer all-solid-state lithium-sulfur battery prepared by block copolymerization of polymer lithium salts ic, id and ie and polyvinyl acetate provided in example 6 of the present invention;
FIG. 4 shows monomer IIa NMR1H NMR(solvent＝DMSO 300MHz)；
FIG. 5 is monomer IIb NMR1H NMR(solvent＝DMSO 300MHz)；
FIG. 6 is monomer IIc NMR1H NMR(solvent＝DMSO 300MHz)；
FIG. 7 shows monomer IId NMR1H NMR(solvent＝DMSO 300MHz)；
FIG. 8 is monomer IIe NMR1H NMR(solvent＝DMSO 300MHz)；
FIG. 9 is monomer IIf NMR1H NMR(solvent＝DMSO 300MHz)。
Detailed Description
The invention provides a single-ion conductor all-solid-state polymer electrolyte, which is used for solving the problems that the existing electrochemical energy storage lithium ion battery system adopts a liquid electrolyte, is easy to leak and corrode and has potential safety hazards, or the problems that the gel electrolyte has poor mechanical properties and is difficult to form.
The solid electrolyte conductivity test mode is as follows:
uniformly coating the slurry on a stainless steel sheet, wherein the coating thickness of one surface is 20-100 mu m, then clamping the stainless steel sheet by another stainless steel sheet, sealing the stainless steel sheet in a 2032 type battery case, heating the stainless steel sheet for 10min at 80 ℃ to initiate polymerization, and then keeping the temperature for 20min to ensure that the monomer is fully polymerized to form polyanionic electrolyte;
then measuring the ionic conductivity by electrochemical AC impedance spectroscopy, and adopting the formula of sigma-L/ARbWherein L is the electrolyte thickness, A is the stainless steel sheet area, RbThe resulting impedance is measured.
The electrochemical window test method is as follows:
the slurry before electrolyte polymerization was coated between a stainless steel sheet and a lithium sheet, and placed in a 2032 type battery case. The electrochemical window was measured using a linear voltammetric scan measurement using an electrochemical workstation at an initial potential of 2.5V, a maximum potential of 5.5V, and a scan rate of 1mV/s, and the results are shown in Table 1.
The method for testing the performance of the battery comprises the following steps:
(1) preparation of positive plate
Dissolving polyvinylidene fluoride (PVdF) in N, N-2-methyl pyrrolidone to obtain a concentration of 0.1 mol/L.
B, mixing the PVdF solution, the positive electrode active material and the conductive carbon black in a mass ratio of 10:80:10, and grinding for 1 hour.
And C, uniformly coating the slurry obtained in the previous step on an aluminum foil with the thickness of 100-120 microns, drying at 60 ℃, drying in a vacuum oven at 120 ℃, rolling, punching, weighing, continuously drying in the vacuum oven at 120 ℃, and putting into a glove box for later use.
And D, cutting according to the size.
(2) Preparing a negative plate:
a PVdF was dissolved in N, N-2-methylpyrrolidone at a concentration of 0.1 moI/L.
B, mixing the PVdF solution, the negative electrode active material and the conductive carbon black in a mass ratio of 10:80:10, and grinding for 1 hour.
And C, uniformly coating the slurry obtained in the previous step on a copper foil with the thickness of 100-120 microns, drying at 60 ℃, drying in a vacuum oven at 120 ℃, rolling, punching, weighing, continuously drying in the vacuum oven at 120 ℃, and putting in a glove box for later use.
(3) And (6) assembling the battery.
(4) Testing of battery charging and discharging performance
The test mode of the charge and discharge performance of the battery is as follows: the charge-discharge curve of the all-solid-state secondary lithium battery at different temperatures is tested by the LAND battery charge-discharge instrument for the assembled button cell battery.
Example 1:
weighing 30g of lithium methacrylate trifluoroborate IIa, 60g of methyl methacrylate and 0.5g of benzoyl peroxide, and stirring at room temperature until the lithium methacrylate, the methyl methacrylate and the benzoyl peroxide are completely dissolved; then 10g of aluminium oxide powder is added into the mixture and is continuously stirred to form uniform and stable slurry;
uniformly coating the slurry on a stainless steel sheet with a coating thickness of 20 μm, then clamping with another stainless steel sheet, sealing in a 2032 type battery case, heating at 80 deg.C for 10min to initiate polymerization, and then maintaining the temperature for 20min to ensure that the monomer is fully polymerized to form polyanionic electrolyte;
obtaining the single-ion conductor polymer all-solid-state electrolyte with the block copolymerization structure of lithium polymethacrylate trifluoroborate and polymethyl methacrylate shown as the following formula:
wherein m is 3000-5000, m is 15000-25000, and the measured room temperature ionic conductivity is 2.35 multiplied by 10 at 25 DEG C-4S/cm, electrochemical oxidation window is: 4.0V, the charge-discharge curve is shown in figure 1.
Example 2:
weighing 30g of lithium salt monomer IIb and 60g of vinyl acetate, adding 0.5g of dibenzoyl peroxide, and stirring at room temperature until the lithium salt monomer IIb and the vinyl acetate are completely dissolved; then 10g of nano silicon dioxide is added into the slurry as a filler, and the mixture is stirred again to form uniform and stable slurry;
uniformly coating the slurry on a stainless steel sheet, wherein the coating thickness is 40 mu m, then clamping the stainless steel sheet by another stainless steel sheet, sealing the stainless steel sheet in a 2032 type battery case, heating the stainless steel sheet at 80 ℃ for 10min to initiate polymerization, and then preserving the temperature for 20min to ensure that the monomers are fully polymerized to form polyanion electrolyte, thus obtaining the all-solid-state electrolyte of the single-ion conductor polymer with the block copolymerization structure of polymer lithium salt Ib and polyvinyl acetate shown as the following formula:
wherein the value range of m is 3000-5000, and the value of m is 20000-40000; the ionic conductivity at room temperature at 25 ℃ was measured to be 4.74X 10-4S/cm, electrochemical oxidation window of 5.0V, charge and discharge curve as shown in figure 2.
Example 3:
weighing 30g of lithium salt monomer IIb and 60g of vinylene carbonate, adding 0.5g of benzoyl peroxide, and stirring at room temperature until the lithium salt monomer IIb and the vinylene carbonate are completely dissolved; then 10g of nano titanium dioxide is added into the slurry as a filler, and the mixture is stirred again to form uniform and stable slurry;
uniformly coating the slurry on a stainless steel sheet, wherein the coating thickness is 60 mu m, then clamping the stainless steel sheet by another stainless steel sheet, sealing the stainless steel sheet in a 2032 type battery case, heating the stainless steel sheet at 80 ℃ for 10min to initiate polymerization, and then preserving the heat for 20min to ensure that monomers are fully polymerized to form polyanion electrolyte, thereby obtaining the all-solid-state electrolyte of the single-ion conductor polymer with the block copolymerization structure of polymer lithium salt Ib and poly (ethylene carbonate) shown as the following formula:
wherein the value range of m is 3000-5000, the value of m is 25000-50000, and the measured room temperature ionic conductivity of the material at 25 ℃ is 5.19 multiplied by 10-4S/cm, electrochemical oxidation window is 5.0V.
Example 4:
weighing 30g of lithium methacrylate trifluoroborate IIa, 60g of allyl alcohol polyoxyethylene ether IIIa and 0.5g of benzoyl peroxide, and stirring under a heating and melting condition until lithium salt monomers are completely dissolved in the melted polyoxyethylene ether; then 10g of aluminium oxide powder is added into the mixture and is continuously stirred to form uniform and stable slurry;
uniformly coating the slurry on a stainless steel sheet with a coating thickness of 50 μm, then clamping with another stainless steel sheet, sealing in a 2032 type battery case, heating at 80 deg.C for 10min to initiate polymerization, and then maintaining the temperature for 20min to ensure that the monomer is fully polymerized to form polyanionic electrolyte;
obtaining the single-ion conductor polymer all-solid-state electrolyte with the block copolymerization structure of the lithium polymethacrylate trifluoroborate Ia and the polyallyl polyoxyethylene ether shown in the following formula:
wherein m is 1000-2000, n is 10000-20000, x is 2000-2500, and the room-temperature ionic conductivity is 2.29 x 10 at 25 deg.C-4S/cm, electrochemical oxidation window is 3.8V.
Example 5:
weighing 30g of lithium salt monomer IIb, 60g of methyl allyl alcohol polyoxyethylene ether IIIb and 0.5g of benzoyl peroxide, and stirring under a heating and melting condition until the lithium salt monomer is completely dissolved in the melted polyoxyethylene ether; then adding 10g of titanium dioxide powder into the mixture, and continuously stirring the mixture to form uniform and stable slurry;
uniformly coating the slurry on a stainless steel sheet with a coating thickness of 50 μm, then clamping with another stainless steel sheet, sealing in a 2032 type battery case, heating at 80 deg.C for 10min to initiate polymerization, and then maintaining the temperature for 20min to ensure that the monomer is fully polymerized to form polyanionic electrolyte;
obtaining the single-ion conductor polymer all-solid-state electrolyte with a polymer lithium salt Ib and a polymethylallyl alcohol polyoxyethylene ether block copolymerization structure shown as the following formula:
wherein m is 1000-2000, n is 10000-20000, x is 2000-2500, and the room-temperature ionic conductivity is 2.54 × 10 at 25 deg.C-4S/cm, electrochemical oxidation window is 3.8V.
Example 6:
weighing 10g of lithium salt monomers IIc, IId and IIe, 60g of isopentenol polyoxyethylene ether IIIc and 0.5g of benzoyl peroxide respectively, and stirring under a heating and melting condition until the lithium salt monomers are completely dissolved in the molten isopentenol polyoxyethylene ether; then adding 10g of titanium dioxide powder into the mixture, and continuously stirring the mixture to form uniform and stable slurry;
uniformly coating the slurry on a stainless steel sheet with a coating thickness of 50 μm, then clamping with another stainless steel sheet, sealing in a 2032 type battery case, heating at 80 deg.C for 10min to initiate polymerization, and then maintaining the temperature for 20min to ensure that the monomer is fully polymerized to form polyanionic electrolyte;
obtaining the single-ion conductor polymer all-solid-state electrolyte with a block copolymerization structure of polyanion lithium salt monomers ic, id and ie and poly (isopentenol polyoxyethylene ether) shown as the following formula:
wherein m is 1000-2000, k is 1000-2000, j is 1000-2000, n is 20000-40000, x is 2000-2500, and the room-temperature ionic conductivity at 25 ℃ is 3.77 x 10- 4S/cm, the electrochemical oxidation window is 2.8V, and the charge-discharge curve is shown in figure 3.
Example 7:
(1) preparation of positive plate
Dissolving polyvinylidene fluoride (PVdF) in N, N-2-methyl pyrrolidone to obtain a concentration of 0.1 mol/L.
B, mixing the PVdF solution, the lithium iron phosphate powder and the conductive carbon black in a mass ratio of 10:80:10, and grinding for 1 hour.
And C, uniformly coating the slurry obtained in the previous step on an aluminum foil with the thickness of 100-120 microns, drying at 60 ℃, drying in a vacuum oven at 120 ℃, rolling, punching, weighing, continuously drying in the vacuum oven at 120 ℃, and putting into a glove box for later use.
And D, cutting according to the size of the 2032 button cell.
(2) Preparing a negative plate:
a PVdF was dissolved in N, N-2-methylpyrrolidone at a concentration of 0.1 moI/L.
And B, mixing the PVdF solution, the passivated metal lithium powder and the conductive carbon black in a mass ratio of 10:80:10, and grinding for 1 hour.
And C, uniformly coating the slurry obtained in the previous step on copper foil with the thickness of 100-120 microns, drying at 60 ℃, drying in a vacuum oven at 120 ℃, rolling, punching, weighing, continuously drying in the vacuum oven at 120 ℃, cutting according to the size of a 2032 button cell, and placing in a glove box for later use.
(3) Preparing solid electrolyte prepolymer slurry: weighing 30g of lithium methacrylate trifluoroborate IIa, 60g of allyl alcohol polyoxyethylene ether and 0.5g of benzoyl peroxide, and stirring the mixture at a melting state of 60 ℃ until the mixture is completely dissolved; then 10g of aluminium oxide powder is added into the mixture and is continuously stirred to form uniform and stable slurry;
(4) assembling the battery:
uniformly coating the solid electrolyte prepolymer slurry on the surface of the cut positive plate, wherein the coating thickness is 30 mu m,
then clamping by using a negative plate, sealing in a 2032 type battery case, heating for 10min at 80 ℃ to initiate polymerization, and then preserving heat for 20min to ensure that the monomer is fully polymerized to form polyanionic electrolyte;
the in-situ polymerization is carried out to form the single-ion conductor polymer all-solid-state electrolyte with the block copolymerization structure of the lithium polymethacrylate trifluoroborate and the polyallyl alcohol polyoxyethylene ether shown as the following formula between a positive electrode and a negative electrode:
wherein: the value of m is 1000-2000, the value of m is 10000-15000, and the value of x is 2000-2500; the room-temperature ionic conductivity at 25 ℃ was found to be 3.52X 10-4S/cm, electrochemical oxidation window is 2.8V.
Example 8:
(1) preparation of positive plate
Dissolving polyvinylidene fluoride (PVdF) in N, N-2-methyl pyrrolidone to obtain a concentration of 0.1 mol/L.
And B, mixing the PVdF solution, the lithium nickel manganese oxide material powder and the conductive carbon black in a mass ratio of 10:80:10, and grinding for 1 hour.
And C, uniformly coating the slurry obtained in the previous step on an aluminum foil with the thickness of 100 microns, drying at 60 ℃, drying in a vacuum oven at 120 ℃, rolling, punching, weighing, continuously drying in the vacuum oven at 120 ℃, and putting into a glove box for later use.
And D, cutting according to the size of the 2032 button cell.
(2) The negative plate is made of a metal plate;
(3) preparing solid electrolyte prepolymer slurry: weighing 30g of lithium methacrylate trifluoroborate IIa, 60g of vinylene carbonate and 0.5g of benzoyl peroxide, and stirring at room temperature until the lithium methacrylate, the vinylene carbonate and the benzoyl peroxide are completely dissolved; then 10g of silicon dioxide powder is added into the mixture and is continuously stirred to form uniform and stable slurry;
(4) assembling the battery:
uniformly coating the solid electrolyte prepolymer slurry on the surface of a cut positive plate, wherein the coating thickness is 50 microns, then clamping by using a negative plate, sealing in a 2032 type battery case, heating for 10min at 80 ℃ to initiate polymerization, and then preserving heat for 20min to ensure that monomers are fully polymerized to form polyanionic electrolyte;
the in-situ polymerization is carried out to form the single-ion conductor polymer all-solid-state electrolyte with the block copolymerization structure of lithium polymethacrylate trifluoroborate and poly ethylene carbonate shown as the following formula between a positive electrode and a negative electrode:
wherein the value of m is 1000-3000, and the value of m is 10000-15000.
(5) Testing a battery charging and discharging curve:
the ionic conductivity at room temperature at 25 ℃ was found to be 3.57X 10-4S/cm, and the electrochemical oxidation window is 4.2V.
Example 9:
(1) preparation of positive plate
A, mixing prenyl alcohol polyoxyethylene ether, elemental sulfur and conductive carbon black in a mass ratio of 10:80:10, and grinding for 1 hour.
And B, heating the powdery material obtained in the previous step to 60 ℃ for melting, then uniformly coating the melted powdery material on an aluminum foil, cooling the melted powdery material for re-solidification to a thickness of 100-120 mu m, then rolling, punching and placing the punched sheet into a glove box for later use.
And C, cutting according to the size of a 2032 button cell.
(2) The negative plate is made of a metal plate;
(3) preparing solid electrolyte prepolymer slurry: weighing 30g of lithium salt monomer IIb, 60g of isopentenol polyoxyethylene ether IIIc and 0.5g of benzoyl peroxide, and stirring at the molten state of 60 ℃ until the lithium salt monomer IIb, the isopentenol polyoxyethylene ether IIIc and the benzoyl peroxide are completely dissolved; then adding 10g of titanium dioxide powder into the mixture, and continuously stirring the mixture to form uniform and stable slurry;
(4) assembling the battery:
heating and melting the solid electrolyte prepolymer slurry, uniformly coating the molten solid electrolyte prepolymer slurry on the surface of a cut positive plate, wherein the coating thickness is 50 microns, then clamping the positive plate by using a negative plate, sealing the negative plate in a 2032 type battery case, heating the battery case for 10min at 80 ℃ to initiate polymerization, and then preserving the temperature for 20min to ensure that a monomer is fully polymerized to form polyanionic electrolyte;
the in-situ polymerization is carried out to form the single-ion conductor polymer all-solid-state electrolyte with the segmented copolymerization structure of the lithium trichloro-aluminate polymethacrylate and the isopentenol polyoxyethylene ether shown as the following formula between a positive electrode and a negative electrode:
wherein the value of m is 1000-3000, and the value of m is 10000-20000.
(5) Testing the charge and discharge performance of the battery:
it was found to have an ionic conductivity of 4.86X 10 at room temperature at 25 ℃-4S/cm, and the electrochemical oxidation window is 4.2V.
As can be seen from the results in Table 1, the range of the ionic conductivity at room temperature using the polycarbonate-based all-solid polymer electrolyte provided by the present invention is 2X 10-4S/cm～1×10-3S/cm, can be charged and discharged with large multiplying power: the electrochemical oxidation window is larger than 4V, and the charging and discharging can be carried out at higher voltage, so that the energy density is improved.
Table 1: electrochemical Oxidation Window measurement
Example 10:
weighing 30g of lithium crotonate trifluoroborate IIf, 60g of methyl methacrylate and 0.5g of benzoyl peroxide, and stirring at room temperature until the lithium crotonate trifluoroborate IIf, the methyl methacrylate and the benzoyl peroxide are completely dissolved; then 10g of aluminium oxide powder is added into the mixture and is continuously stirred to form uniform and stable slurry;
uniformly coating the slurry on a stainless steel sheet with a coating thickness of 20 μm, then clamping with another stainless steel sheet, sealing in a 2032 type battery case, heating at 80 deg.C for 10min to initiate polymerization, and then maintaining the temperature for 20min to ensure that the monomer is fully polymerized to form polyanionic electrolyte;
obtaining the single-ion conductor polymer all-solid-state electrolyte with the block copolymerization structure of lithium polymethacrylate trifluoroborate and polymethyl methacrylate shown as the following formula:
wherein m is 1000-3000, n is 10000-12000, and the room temperature is measured at 25 deg.CThe ionic conductivity was 2.85X 10-4S/cm, electrochemical oxidation window is: 4.2V.
Example 11:
synthesis of methacrylic acid lithium trifluoroborate IIa monomer:
adding 50g (0.543mmol) of lithium methacrylate and 500g of dimethyl carbonate solvent into a 1500mL reaction bottle, introducing 36.84g of boron trifluoride gas (0.543mol), starting stirring at normal temperature until all solid reactants are dissolved completely; and then distilling and concentrating the material under reduced pressure at 80 ℃, cooling to 20 ℃, filtering after crystals are separated out, and drying to finally obtain 85g of white powdery solid lithium methacrylate trifluoroborate with the yield of 97.88%.
Example 12:
synthesizing a monomethylallyl alcohol maleic acid lithium trifluoroborate IIb monomer:
adding 176.5g (1mol) of monomethyl allyl alcohol lithium maleate and 500g of dimethyl carbonate solvent into a 1500mL reaction bottle, introducing 67.96g of boron trifluoride gas (1mol), starting stirring at normal temperature until all solid reactants are dissolved completely; and then, distilling and concentrating the material under reduced pressure at 80 ℃, cooling to 20 ℃, filtering after crystals are separated out, and drying to finally obtain 240g of white powdery solid with the yield of 97.99%.
Example 13:
synthesis of monomer lithium salt IIc:
50g (300mmol) of methacrylamide fluorosulfonyl imide and 200g of dimethyl carbonate solvent are added into a 500mL reaction flask, 11.05g of lithium carbonate (149.56mmol) is added, and stirring is started at normal temperature until all solid reactants are dissolved; and then distilling and concentrating the material under reduced pressure at 80 ℃, cooling to 20 ℃, filtering after crystals are separated out, and drying to finally obtain 50g of white powdery solid with the yield of 96.58%.
Example 14:
synthesis of monomer lithium salt Id:
the synthesis method is the same as that of monomer lithium salt IIc, except that the raw material of the lithium methacryloyl fluorosulfonyl imide is replaced by the following structure
And obtaining a monomer lithium salt IId after reaction.
Example 15:
synthesis of monomer lithium salt IIe:
the synthesis method is the same as that of monomer lithium salt IIc, except that raw material lithium methacryloyl fluorosulfonyl imide is replaced by allyl fluorosulfonyl imide
Obtaining monomer lithium salt IIe after reaction.
Example 16:
synthesis of monomer lithium salt IIf:
the synthesis was the same as for the monomeric lithium salt IIa except that the starting material lithium methacrylate was replaced with lithium crotonate
Obtaining monomer lithium salt IIf after reaction.
The invention is not the best known technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A single-ion conductor polymer all-solid-state electrolyte is characterized in that: comprises polyanion lithium salt, matrix organic polymer and inorganic filler;
the polyanionic lithium salt has a structure shown as general formulas Ia, Ib, ic, Id, ie and if:
the polyanionic lithium salt is one or more of Ia, Ib, ic, Id, ie and if, wherein m is 1000-5000.
2. The single-ion conductor all-solid-state polymer electrolyte according to claim 1, wherein: the thickness of the single-ion conductor all-solid-state polymer electrolyte is 20-100 mu m, and the room-temperature ionic conductivity is 2 multiplied by 10-4～1.2×10-3S/cm, and the electrochemical window is 2.8-5.0V.
3. The single-ion conductor all-solid-state polymer electrolyte according to claim 1, wherein: the polyanionic lithium salt is respectively obtained by polymerizing lithium salt monomers IIa, IIb, IIc, IId, IIe and IIf containing unsaturated double bonds through free radical double bonds, and the lithium salt monomers IIa, IIb, IIc, IId, IIe and IIf have structures shown as the following formulas:
4. the single-ion conductor all-solid polymer electrolyte according to claim 1, wherein the matrix organic polymer is: the material is one of polymethyl methacrylate, poly ethylene carbonate, polyvinyl acetate and polyoxyethylene ether containing unsaturated double bonds, wherein the polymethyl methacrylate, the poly ethylene carbonate and the polyvinyl acetate are respectively formed by in-situ polymerization of methyl methacrylate, vinylene carbonate and vinyl acetate monomers.
5. The single-ion conductor all-solid-state polymer electrolyte according to claim 4, wherein: the polyoxyethylene ether containing unsaturated double bonds is one of allyl alcohol polyoxyethylene ether, methallyl alcohol polyoxyethylene ether, isopentenol polyoxyethylene ether and pentaerythritol triallyl ether polyoxyethylene ether, and the structures of the polyoxyethylene ether containing unsaturated double bonds are respectively shown as IIIa, IIIb, IIIc and IIId:
6. the single-ion conductor all-solid-state polymer electrolyte according to claim 1 or 4, wherein: mixing polyanion lithium salt monomer and matrix organic polymer monomer, adding dibenzoyl peroxide initiator to form copolymer, and forming the single-ion conductor all-solid-state polymer electrolyte by the copolymer and inorganic filler, wherein the copolymer has a structure shown in formulas IVa, IVb, IVc, IVd, IVe, IVf, IVg, IVh, IVi and IVj:
wherein m is 1000-5000, n is 10000-50000, k is 1000-5000, j is 1000-5000, and x is 2000-2500.
7. The single-ion conductor all-solid-state polymer electrolyte according to claim 1, wherein: the inorganic filler is one of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, silicon nitride, diatomite, montmorillonite and kaolin.
8. The single-ion conductor all-solid-state polymer electrolyte according to claim 1, wherein the composition of the single-ion conductor polymer all-solid-state electrolyte is as follows in mass percent: polyanionic lithium salt 30%; 60% of matrix organic polymer; 10% of inorganic filler.
9. The preparation method of the single-ion conductor all-solid-state polymer electrolyte as claimed in claim 1, which is characterized by comprising the following steps:
a) dissolving a lithium salt monomer containing unsaturated double bonds in a matrix organic polymer monomer, and adding a dibenzoyl peroxide initiator accounting for 0.5 percent of the total mass fraction to form a uniform pre-polymerization monomer solution;
b) adding inorganic filler into the obtained prepolymer monomer solution, stirring and dispersing to form uniform wet electrolyte composite slurry;
c) coating the slurry between positive and negative electrode plates of a lithium secondary battery, and winding, hot-pressing and standing to enable a prepolymer solution adsorbed by the inorganic filler to be fully soaked and absorbed by the positive and negative electrode plates;
d) putting the wound battery cell into an aluminum-plastic film and putting the aluminum-plastic film into a baking oven, and baking at 70-80 ℃; the initiator dibenzoyl peroxide is decomposed to initiate the free radical copolymerization of the lithium salt monomer and the organic polymer monomer solvent to form the in-situ polymerized all-solid electrolyte containing polyanion lithium salt.
10. An all-solid lithium secondary battery comprising the single-ion conductor all-solid polymer electrolyte according to claim 1, comprising a positive electrode, a negative electrode, and an electrolyte interposed between the positive and negative electrodes, wherein: the electrolyte is a single-ion conductor all-solid-state polymer electrolyte;
wherein: the positive active material is one of lithium cobaltate, lithium iron phosphate, lithium iron manganese phosphate, lithium manganate, lithium nickel manganese oxide, ternary materials, sulfur compound, lithium iron sulfate, lithium ion fluorophosphate, lithium vanadium fluorophosphate, lithium iron fluorophosphate and lithium manganese oxide;
the negative active material is one of metal lithium, metal lithium alloy, graphite, hard carbon, molybdenum disulfide, lithium titanate, graphene, antimony oxide, antimony carbon composite material, tin antimony composite material and lithium titanium oxide.
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