CN113178617A - Flame-retardant solid-liquid mixed solid electrolyte, preparation method thereof and lithium battery containing same - Google Patents

Flame-retardant solid-liquid mixed solid electrolyte, preparation method thereof and lithium battery containing same Download PDF

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CN113178617A
CN113178617A CN202110418861.1A CN202110418861A CN113178617A CN 113178617 A CN113178617 A CN 113178617A CN 202110418861 A CN202110418861 A CN 202110418861A CN 113178617 A CN113178617 A CN 113178617A
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郭玉国
谭双杰
辛森
殷雅侠
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The application discloses a flame-retardant solid-liquid mixed solid electrolyte, a preparation method thereof and a lithium battery containing the same. The flame-retardant solid-liquid mixed solid electrolyte comprises a flame-retardant liquid phase component, lithium salt and a polymer network structure, wherein the flame-retardant liquid phase component and the lithium salt are dispersed in the polymer network structure; wherein the flame retardant liquid phase component comprises a phosphorus-containing organic compound; the phosphorus-containing organic compound comprises phosphate, phosphite and phosphonate and halides thereof, and is a high-efficiency flame-retardant liquid; the polymer network structure is obtained by polymerizing a polymer network structure monomer; the polymer network structure monomer is at least one selected from ester compounds containing C ═ C, and has high mechanical strength. The electrolyte obtained by the invention can better improve the cycle performance and the safety performance of the battery.

Description

Flame-retardant solid-liquid mixed solid electrolyte, preparation method thereof and lithium battery containing same
Technical Field
The application relates to a flame-retardant solid-liquid mixed solid electrolyte, a preparation method and application thereof, belonging to the technical field of electrolytes.
Background
In recent yearsWith the rapid development of electric vehicles and distributed energy storage, people have more urgent pursuits for energy storage systems with high specific energy. It has high specific capacity (3860mAh g) due to the metallic lithium negative electrode-1) And a low electrochemical reduction potential (-3.04V vs. standard hydrogen electrode), the battery based on metal lithium as a negative electrode theoretically has high energy density, but the application of the metal lithium battery is greatly limited due to unstable chemical action between the metal lithium and the liquid electrolyte and serious potential safety hazard existing in the traditional metal lithium battery based on the organic liquid electrolyte. With the solid electrolyte, dendritic growth and side reactions of metallic lithium are expected to be suppressed, so that the battery exhibits higher safety and longer cycle life. Currently, solid electrolytes are mainly classified into inorganic ceramics and polymers. The inorganic ceramic-based solid electrolyte can provide Li equivalent to liquid electrolyte at room temperature+But most of ceramic particles have poor interface contact with battery electrodes and poor mechanical properties, and cannot be matched with the existing lithium ion battery manufacturing process. While polymer-based solid electrolytes have good mechanical properties, can accommodate the manufacture of conventional batteries, and some of them have been successfully applied to electric vehicles. However, polymer-based solid electrolytes exhibit lower Li at room temperature+Conductivity, the cell typically requires a higher operating temperature (e.g.,>60 ℃ C.). To increase Li of polymer solid electrolyte+Conductivity, it is feasible to introduce an organic liquid electrolyte into the polymer matrix to obtain a solid-liquid mixed solid electrolyte.
The liquid content in the solid-liquid mixed solid electrolyte significantly affects the performance of the electrolyte. At high liquid content, the solid-liquid mixed solid electrolyte shows higher Li+The conductivity, but the mechanical properties are greatly reduced. Meanwhile, the flammability of hydrocarbon-based liquid solvents (or plasticizers) can also pose a serious safety hazard. The introduction of flame retardant groups into the solid polymer matrix may improve its thermal stability to some extent. However, current work has been directed to the use of flammable carbonate/ether electrolytes as the liquid phase, so that the overall electrolyte remains flammable. Also have partial workmanshipFlame-retardant liquids (such as phosphate esters) are introduced into solid-liquid mixed solid electrolytes in a swelling manner, but free phosphate esters may cause deterioration of the electrode-electrolyte interface and decrease the mechanical strength of the electrolyte. Therefore, it is very important to develop a solid-liquid mixed solid electrolyte having high ionic conductivity, excellent mechanical properties, good interfacial compatibility and safety.
This patent is through the liquid phase composition who uses fire-retardant type phosphate ester to mix solid-state electrolyte for solid-liquid, through the in situ polymerization polymer monomer in the battery monomer, has developed a series of fire-retardant type solid-state electrolyte that mixes that can be used to the lithium cell. When the electrolyte works, the metal lithium and various anode materials are matched to show higher safety performance and stable cycle performance, and meanwhile, the cathode materials matched with the flame-retardant solid-liquid mixed solid electrolyte are not limited to the metal lithium, but can be matched with other cathode materials, so that the flame-retardant solid-liquid mixed solid electrolyte has wide application prospect and advantages.
Disclosure of Invention
According to one aspect of the application, the flame-retardant solid-liquid mixed solid electrolyte is provided, and a specific type of flame-retardant phosphorus-containing organic compound is selected to be packaged in a high-strength polymer framework in an in-situ polymerization mode, so that the solid-liquid mixed solid electrolyte with high strength, high ionic conductivity, high ion migration number and good interface compatibility can be obtained. The preparation method is easy to regulate and control, can flexibly match the types and proportions of the solvent, the lithium salt and the additive, is used as the electrolyte of the lithium battery, and has high safety and application prospect. The preparation method is simple, the raw materials are easy to obtain, and the preparation method is suitable for large-scale production.
The flame-retardant solid-liquid mixed solid electrolyte is characterized by comprising a flame-retardant liquid phase component, lithium salt and a polymer network structure, wherein the flame-retardant liquid phase component and the lithium salt are dispersed in the polymer network structure;
wherein the flame retardant liquid phase component comprises a phosphorus-containing organic compound;
the phosphorus-containing organic compound contains any one of groups shown in formulas I and II, and is characterized by low-viscosity liquid with efficient flame-retardant property:
Figure BDA0003027014960000031
the polymer network structure is obtained by polymerizing a polymer network structure monomer;
the high molecular network structure monomer is selected from at least one of ester compounds containing C ═ C, and is characterized in that the high molecular network structure monomer with high Young modulus can be obtained through in-situ polymerization;
wherein, in the formulas I and II, R1、R2、R3Is selected from C1～C8Alkyl radical, C1～C8Any of the halogen-substituted alkyl groups.
The preferred C ═ C ester compound includes any of C ═ C ester cyclic organic compounds and C ═ C ester linear organic compounds.
Preferably, the polymer network structure is prepared by in-situ polymerization of a C ═ C ester cyclic organic compound.
Preferably, the volume ratio of the phosphorus-containing organic compound to the high molecular network structure monomer is 1-10: 1.
Including, but not limited to, triethyl phosphate, trimethyl phosphate, tripropyl phosphate, methylethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (2-ethylhexyl) phosphate, tris (2,2, 2-trifluoroethyl) phosphate, tris- (. beta. -chloroethyl) -phosphate, tris- (chloroisopropyl) -phosphate; tris (1, 3-dichloropropyl) phosphate, dimethyl methylphosphonate, diethyl ethylphosphate, diethyl methylphosphonate, bis (2,2, 2-trifluoroethyl) ethylphosphonate, alkylene phosphonates, amide phosphonates, cyclic phosphonates.
Optionally, the chain or cyclic mono-olefin compound containing C ═ C is an ester organic compound. For example, one or more of vinylene carbonate, polyethylene glycol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-decanediol diacrylate. Vinylene carbonate is preferred.
The lithium salt is one or more of bis (trifluoromethanesulfonyl) imide lithium, bis (fluorosulfonyl) imide lithium, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium difluorooxalato borate and lithium perchlorate. Preferably, one or more of lithium bistrifluoromethanesulfonimide, lithium bistrifluorosulfonimide and lithium hexafluorophosphate.
The initiator is one or more of substances capable of initiating polymerization of high molecular monomers, and comprises azo initiators capable of initiating free radical polymerization (such as azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate), redox initiators (such as benzoyl peroxide/N, N-dimethylaniline, ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite, hydrogen peroxide/tartaric acid and the like), and the like.
Preferably, the initiator is an azo-type initiator, including azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, and the like.
Optionally, the flame-retardant solid-liquid mixed solid electrolyte further comprises at least one of a functionalized polymer, a functionalized filler and a functionalized additive.
Optionally, the functionalized polymer includes at least one of polyethylene oxide, polyvinylidene fluoride, poly (vinylidene fluoride-co-hexafluoropropylene), polydimethylsiloxane, poly-p-styrene, and polyacetylene.
The functionalized filler comprises any one of inorganic inactive ceramic fillers and lithium ion conductive active fillers;
the functional additive comprises any one of a film forming additive and an anti-overcharge additive.
Specifically, the functionalized polymer is a polymer capable of improving the physicochemical properties of the in-situ polymerization flame-retardant solid-liquid mixed solid electrolyte, and includes polyethylene oxide, polyvinylidene fluoride, poly (vinylidene fluoride-co-hexafluoropropylene), polydimethylsiloxane and the like which are used for enhancing flexibility, and poly (p-styrene), polyacetylene and the like which are used for enhancing rigidity.
The above-mentionedThe functional filler is a compound which can be used for improving the physicochemical property of the in-situ polymerization flame-retardant solid-liquid mixed solid electrolyte and comprises inorganic inactive ceramic fillers Si and B4C，SiO2，Al2O3，TiO2，ZrO2，BaTiO3And active lithium ion-conducting filler Li3N,Li1.3Al0.3Ti1.7(PO4)3、Li7La3Zr2O12、Li0.33La0.557TiO3、Li1.4Al0.4Ge1.6(PO4)3,Li10GeP2S12、Li2S–P2S5And the like.
The functional additive is a compound which can be used for assisting in improving the electrochemical performance of the system in an electrochemical reaction system, and comprises a film forming additive, an anti-overcharge additive and the like. Preferably, unsaturated cyclic carbonates (including halogen), saturated cyclic carbonates (including halogen), cyclic ethers, sultones, vinyl sulfite, vinyl sulfates, and the like.
According to another aspect of the present application, there is also provided a method of preparing the flame-retardant solid-liquid mixed solid electrolyte of any one of the above, the method comprising:
carrying out in-situ polymerization reaction on a mixture containing a phosphorus-containing organic compound, a high molecular network structure monomer and a lithium salt in the presence of an initiator to obtain the flame-retardant solid-liquid mixed solid electrolyte;
the high molecular network structure monomer is selected from at least one of ester compounds containing C ═ C.
In a better example, a mixture containing a phosphorus-containing organic compound, a cyclic ester polymer monomer containing C ═ C and a lithium salt is subjected to in-situ polymerization reaction in the presence of an initiator, so that the flame-retardant solid-liquid mixed solid electrolyte can be obtained.
Optionally, the method of preparing the mixture comprises: firstly, dissolving lithium salt in a phosphorus-containing organic compound, and then adding a C-containing ester polymer network structure monomer, a functional polymer, a functional filler, a functional additive and the like to obtain the mixture.
Optionally, the initiator comprises at least one of azo initiators.
The azo initiator includes any one of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
Preferably, the mass ratio of the phosphorus-containing organic compound to the material A is 5-150%.
The material A is an ester polymer network structure monomer containing C ═ C.
Preferably, the mass ratio of the initiator to the material A is 0.1-0.5%.
Preferably, the mixture further comprises at least one of a functionalized polymer, a functionalized filler and a functionalized additive.
Preferably, the conditions of the in situ polymerization reaction are: the heating temperature is 45-90 ℃.
Preferably, the molar concentration of lithium salt in the mixture is between 0.25M and 4M.
Optionally, the mixture further comprises at least one of a functionalized polymer, a functionalized filler and a functionalized additive.
Preferably, the content of the functionalized polymer in the mixture is 0-40%, preferably 2-10% of the total mass of the phosphorus-containing compound and the polymer network structure monomer.
Preferably, the content of the functionalized nano filler in the mixture is 0-15%, preferably 2-5% of the total mass of the phosphorus-containing compound and the high molecular network structure monomer.
Preferably, the content of the functionalized additive in the mixture is 0-10%, preferably 2-10% of the total volume of the phosphorus-containing compound and the high molecular network structure monomer.
Furthermore, the inventors have unexpectedly found that when the phosphorus-containing compound of formula I or II is further mixed with the compound of formula III below in an amount of 5 to 10% by mass, the ionic conductivity and the surface Young's modulus of the compound of formula I or II are further improved, possibly due to the introduction of the phosphorus-containing compound of formula III, the way of segment winding of the polymer network itself is changed, and the distribution of the compound of formula I or II in the polymer network structure is changed.
Figure BDA0003027014960000061
In formula III, R1 is selected from C1～C8Alkyl radical, C1～C8Any of substituted alkyl groups;
R2、R3independently selected from C1～C8Alkyl radical, C1～C8Any of substituted alkyl groups.
The application also provides the flame-retardant solid-liquid mixed solid electrolyte and the application of the flame-retardant solid-liquid mixed solid electrolyte obtained by the preparation method in a lithium battery.
The application also provides a lithium battery, wherein the lithium battery contains the flame-retardant solid-liquid mixed solid electrolyte;
the flame-retardant solid-liquid mixed solid electrolyte is selected from any one of the flame-retardant solid-liquid mixed solid electrolyte and the flame-retardant solid-liquid mixed solid electrolyte obtained by the preparation method.
Specifically, the non-combustible solid-liquid mixed lithium battery comprises a positive electrode, a negative electrode, a diaphragm and the flame-retardant electrolyte.
Further, the positive electrode includes, but is not limited to, a switching type S, Li2S、Se、Li2Se、O2Air, CO2、FeF3、CuF2、CoF3、CuF、BiF3、NiF2、MnF3、VF3、TiF3、CuCl2、FeCl3、MnCl2Olivine type LiMPO4(where M is Fe, Mn, Co, etc.), spinel-type LiMn2O4、LiCo2O4Layered Litis2、LiMnO2、LiNiO2、LiCoO2、Li2MnO3、LiMnO2、LiNixCoyMn(1-x-y)O2(wherein x and y are any ratio values satisfying the conditions that x is more than or equal to 0 and less than or equal to 1 and y is more than or equal to 0 and less than or equal to 1), LiNixCoyAl(1-x-y)O2(wherein x and y are selected at any ratio satisfying the conditions that x is more than or equal to 0 and less than or equal to 1 and y is more than or equal to 0 and less than or equal to 1), polyanionic LiFeSO4F、LiVPO4F. Lithium rich material xLi2MnO3·(1-x)LiMO2(M ═ Ni, Co, Mn), and the like.
The negative electrode includes but is not limited to a metallic lithium negative electrode, a silicon-based negative electrode (Si, SiO, silicon-carbon composite negative electrode), an alloy negative electrode (Sn, Al and the like), a graphite negative electrode material (artificial graphite, natural graphite, mesocarbon microbeads and the like), and lithium titanate (Li)4Ti5O12) Hard carbon, soft carbon, and the like.
The beneficial effects that this application can produce include:
1) the invention provides a flame-retardant solid-liquid mixed solid electrolyte and a lithium battery containing the flame-retardant electrolyte, wherein the liquid-phase component of the flame-retardant solid-liquid mixed solid electrolyte is one or a combination of more of phosphorus-containing organic compounds with flame-retardant property, and the liquid-phase component with flame-retardant property provides good safety for the lithium battery and simultaneously ensures high ionic conductance of the electrolyte; the solid phase component of the flame-retardant solid-liquid mixed solid electrolyte is a polymer obtained by in-situ polymerization of a polymer monomer in a battery system, and a polymer network generated by in-situ polymerization and a flame-retardant liquid phase component are well fused together, so that leakage of the system is prevented, the lithium ion migration number of the electrolyte is improved, and the high-strength polymer framework selected and used is favorable for preventing the puncture of metal lithium dendrites and reducing interface side reactions. The in-situ polymerization mode adopted by the invention can be well compatible with the existing battery production process, the solid-liquid mixed solid electrolyte formed in situ can also ensure good contact of the electrode electrolyte interface, and the in-situ polymerization mode can also well combine the solid phase and the liquid phase with each component. The functionalized polymer, the functionalized filler and the additive also play a role in improving the comprehensive performance of the electrolyte.
2) When the high-molecular network structure is obtained by in-situ polymerization of a cyclic ester monomer containing C ═ C and is matched with a phosphorus-containing organic compound shown in a formula I, the phosphorus-containing organic compound has higher mechanical strength, high ionic conductivity and better flame retardance, and has good electrochemical performance, and particularly the phosphorus-containing organic compound is selected from trimethyl phosphate, triethyl phosphate and tripropyl phosphate; when the high molecular network structure monomer is selected from vinylene carbonate, experiments prove that the comprehensive performance can reach the optimal level.
Drawings
Fig. 1 is a flammability test of the flame-retardant solid-liquid mixed solid electrolyte in example 1 of the present invention.
Fig. 2 is a lithium-lithium symmetric battery cycle curve of a battery using the flame retardant solid-liquid mixed solid electrolyte of example 1 of the present invention.
FIG. 3 shows LiNi as a negative electrode made of a lithium metal foil0.8Co0.1Mn0.1O2The electrolyte of example 1, a lithium battery obtained, was used as a working electrode, and the charge-discharge curve was 0.1C.
Fig. 4 shows the charge/discharge curve at 0.1C for a lithium battery obtained using a lithium metal foil as a negative electrode and graphite as a working electrode, and the electrolyte in example 1.
Fig. 5 shows the charge/discharge curve at 0.1C for a lithium battery obtained using a metallic lithium foil as a negative electrode and SnO as a working electrode, and the electrolyte of example 1.
Fig. 6 is a first-turn charge-discharge curve of a lithium iron phosphate battery using the electrolyte of example 1.
Fig. 7 is a surface young's modulus test result of the solid electrolyte of example 1.
Fig. 8 is a surface young's modulus test result of the solid electrolyte of comparative example 1.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were all purchased commercially
The electrochemical properties of the batteries using the flame-retardant solid-liquid mixed solid electrolyte prepared in the following examples were all measured according to the following methods: and (3) mixing the prepared flame-retardant solid-liquid mixed solid electrolyte precursor with a metal lithium sheet as a reference electrode and Celgard 3501 as a diaphragm, mixing the working electrode with a slurry according to a certain ratio (the electrode active substance, the conductive agent, acetylene black and the binder, PVDF, are mixed according to a mass ratio of 8:1: 1) to obtain a positive electrode plate (the negative electrode material is coated on the aluminum foil), and assembling in a glove box to obtain the button cell.
And (3) carrying out charge and discharge tests on the assembled battery on a LAND charge and discharge tester.
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The electrochemical properties of the batteries using the flame-retardant solid-liquid mixed solid electrolyte prepared in the following examples were all measured according to the following methods: and (3) mixing the prepared flame-retardant solid-liquid mixed solid electrolyte precursor according to a certain proportion to prepare slurry, taking a metal lithium sheet as a reference electrode and Celgard 3501 as a diaphragm, uniformly coating the slurry on an aluminum foil current collector to obtain a positive electrode plate (coating the negative electrode material on the aluminum foil), and assembling in a glove box to obtain the button cell.
And (3) carrying out charge and discharge tests on the assembled battery on a LAND charge and discharge tester.
Preparation example 1 Synthesis of phosphorus-containing organic Compound No. 1
54g (0.4mo1) of pentaerythritol and 50ml of toluene as a solvent were put in a four-necked flask equipped with a stirrer, a thermometer, a constant pressure dropping funnel and a condenser, and heated to 50 ℃ to drop phosphorus trichloride, followed by heating and refluxing. During the process, a slight negative pressure is maintained in the system. After the reflux is finished, decompressing and distilling out unreacted phosphorus trichloride, solvent and hydrogen chloride to obtain yellow transparent viscous liquid, and cooling to room temperature for solidification to obtain an intermediate product (I). The yield was 95%. The molar ratio of phosphorus trichloride to pentaerythritol is selected to be 2.5: 1.
adding 60mL of solvent into the intermediate product (I) in the first step, heating to about 50 ℃, slowly introducing chlorine gas until the reaction does not release heat after the solvent is completely dissolved, stopping introducing chlorine after the solution is changed from colorless to yellow green, heating (60 ℃) again, keeping the temperature for a period of time (5 hours), and quantitatively generating an intermediate product (II) which is directly used for the reaction in the next step.
Introducing N into the reaction liquid in the second step to purge chlorine and hydrogen chloride in the reaction liquid, and adding certain catalyst AlCl3(the addition amount of the catalyst is 0.5 wt% of the intermediate product (II)), stirring, slowly introducing ethylene oxide (the mass ratio of the ethylene oxide to the intermediate product (II) is 1.5:1) at room temperature, and heating (60 ℃) for keeping the temperature for a period of time (5 hours) after the introduction is finished. Decompressing, desolventizing and washing with water to be neutral to obtain a liquid-phase product, wherein the structural formula is shown as follows:
Figure BDA0003027014960000091
preparation example 2 Synthesis of phosphorus-containing organic Compound No. 2
2, 2-bis (bromomethyl) -1, 3-bis [ (2-bromopropyl-2-chloropropyl) phosphate ] propane
In a four-necked beaker equipped with a stirrer, a thermometer, a dropping funnel and a condenser, 34g (0.25mo1) of pentaerythritol and toluene as a solvent were charged. And (3) dropwise adding 1/2 mass of phosphorus trichloride, and slowly raising the temperature to 50 ℃ to react for 2 h. Then the temperature was raised to reflux. Simultaneously, another 1/2 amounts of phosphorus trichloride were added dropwise. A low vacuum is maintained indefinitely during this process. Refluxing for 3h, filtering while hot, and distilling out unreacted phosphorus trichloride, solvent and hydrogen chloride under reduced pressure to obtain yellow transparent viscous liquid, which is marked as an intermediate (I), wherein the crude yield is 98%, and refining is not needed, and the molar ratio of phosphorus trichloride to pentaerythritol is 4: 1.
Weighing an intermediate (I), dissolving the intermediate (I) in 48ml of carbon tetrachloride solvent at 50 ℃, uniformly stirring, slowly dropwise adding a certain amount of bromine (the mass ratio of the bromine to the intermediate (I) is 2:1) at 28 ℃, keeping the temperature and stirring after the reaction does not release heat any more, and generating an intermediate (II) which is directly used for the next synthesis.
Putting a certain amount of intermediate (II) into a three-neck flask, and adding a certain amount of catalyst AlCl3(the addition amount of the catalyst is 0.5 wt% of the intermediate (II)), stirring for 10min, and slowly dropping a certain amount of propylene oxide (the mass ratio of the propylene oxide to the intermediate (II) is 2: 1). After the dripping is finished, the temperature is kept (60 ℃) for reacting for certain 3 hours. The solvent and unreacted materials were distilled off under reduced pressure. Washing with water to neutrality to obtain a liquid-phase product, wherein the structural formula is as follows:
Figure BDA0003027014960000101
example 1
Dissolving lithium bistrifluoromethanesulfonylimide in a mixed solution (volume ratio: 1.5:1) of triethyl phosphate and vinylene carbonate at a molar concentration of 1mol/L, stirring under a dry condition to completely dissolve the lithium bistrifluoromethanesulfonylimide, adding azobisisobutyronitrile (0.1% in molar ratio to vinylene carbonate) into the mixed solution, and stirring and dissolving to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution at 45 ℃ to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution at 45 ℃ to initiate the polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 2
Dissolving lithium bistrifluoromethanesulfonylimide in a mixed solution (volume ratio: 1: 1) of triethyl phosphate and vinylene carbonate according to a molar concentration of 1mol/L, stirring under a dry condition to completely dissolve the lithium bistrifluoromethanesulfonylimide, adding azobisisobutyronitrile (0.1% in molar ratio to the vinylene carbonate) into the mixed solution, and stirring and dissolving to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution at 45 ℃ to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution at 45 ℃ to initiate the polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 3
Dissolving lithium hexafluorophosphate in a mixed solution (volume ratio: 1.5:1) of triethyl phosphate and vinylene carbonate according to the molar concentration of 1mol/L, stirring to completely dissolve the lithium hexafluorophosphate under a dry condition, adding azobisisobutyronitrile (0.1 percent of the molar ratio of the lithium hexafluorophosphate to the vinylene carbonate) into the mixed solution, and stirring to dissolve the mixture to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution at 45 ℃ to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution at 45 ℃ to initiate the polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 4
Dissolving lithium bis (trifluoromethanesulfonyl) imide into a mixed solution (volume ratio: 1.5:1) of dimethyl methylphosphonate and vinylene carbonate at a molar concentration of 1mol/L, stirring under a drying condition to completely dissolve the lithium bis (trifluoromethanesulfonyl) imide, adding azobisisobutyronitrile (0.1 percent, molar ratio to vinylene carbonate) into the mixed solution, and stirring and dissolving to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution at 45 ℃ to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution at 45 ℃ to initiate the polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 5
Dissolving polyvinylidene fluoride with the molar concentration of 1mol/L and 5% (mass ratio, relative to the mixed solution of triethyl phosphate and vinylene carbonate) of lithium bistrifluoromethanesulfonylimide in the mixed solution of triethyl phosphate and vinylene carbonate (volume ratio: 1.5:1), stirring under a dry condition to completely dissolve the polyvinylidene fluoride, then adding azobisisobutyronitrile (0.1%, molar ratio to vinylene carbonate) into the mixed solution, and stirring and dissolving to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution at 45 ℃ to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution at 45 ℃ to initiate the polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 6
Dissolving polyvinylidene fluoride of lithium bistrifluoromethanesulfonylimide in a mixed solution (volume ratio: 1.5:1) of triethyl phosphate and vinylene carbonate at a molar concentration of 1mol/L and 5% (relative to the mixed solution of triethyl phosphate and vinylene carbonate), stirring under a dry condition to completely dissolve the polyvinylidene fluoride, adding azobisisobutyronitrile (0.1% in molar ratio to the vinylene carbonate) into the mixed solution, stirring and dissolving to obtain a transparent and uniform solution, and adding nano B (2% by mass relative to the mixed solution) into the solution4And C, uniformly stirring and dispersing the particles to obtain a precursor solution. And initiating the precursor solution to polymerize at 45 ℃ to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution at 45 ℃ to initiate the polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 7
Dissolving lithium bis (trifluoromethanesulfonyl) imide into a mixed solution (volume ratio: 1.5:1) of triethyl phosphate and polyethylene glycol diacrylate with a molar concentration of 1mol/L, stirring the solution under a dry condition to completely dissolve the lithium bis (trifluoromethanesulfonyl) imide, adding dibenzoyl peroxide (0.1 percent, molar ratio of the dibenzoyl peroxide to vinylene carbonate) into the mixed solution, and stirring the solution to dissolve the dibenzoyl peroxide to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution at 55 ℃ to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution at 55 ℃ to initiate the polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 8
Dissolving lithium bis (trifluoromethanesulfonyl) imide into a mixed solution (volume ratio: 1: 1: 1) of triethyl phosphate, polyethylene glycol diacrylate and polyethylene glycol diglycidyl ether at a molar concentration of 1mol/L, stirring the solution under a drying condition to completely dissolve the lithium bis (trifluoromethanesulfonyl) imide, adding dibenzoyl peroxide (0.1 percent, molar ratio of the dibenzoyl peroxide to the polyethylene glycol diacrylate) into the mixed solution, and stirring the solution to dissolve the dibenzoyl peroxide to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution at 55 ℃ to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution at 55 ℃ to initiate the polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 9
Dissolving lithium bistrifluoromethanesulfonylimide in a mixed solution (volume ratio: 1.5:1) of triethyl phosphate and vinylene carbonate at a molar concentration of 1mol/L, stirring the solution under a dry condition to completely dissolve the lithium bistrifluoromethanesulfonylimide, adding azobisisobutyronitrile (0.1% in molar ratio to the vinylene carbonate) into the mixed solution, adding fluoroethylene carbonate accounting for 2% of the volume fraction of the mixed solution as an additive, and stirring the solution to dissolve the fluoroethylene carbonate to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution at 45 ℃ to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution at 45 ℃ to initiate the polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 10
Dissolving lithium bistrifluoromethanesulfonylimide in a mixed solution (volume ratio: 2:1) of triethyl phosphate and 3- (propoxy) glycerol triacrylate at a molar concentration of 1mol/L, stirring under a drying condition to completely dissolve the lithium bistrifluoromethanesulfonylimide, adding 2-hydroxy-2-methyl-1-phenyl-1-acetone (1%, molar ratio of 3- (propoxy) glycerol triacrylate) into the mixed solution, and stirring and dissolving to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution under ultraviolet light to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution under ultraviolet light to initiate polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 11
Dissolving lithium bistrifluoromethanesulfonylimide with the molar concentration of 1mol/L in a mixed solution (volume ratio: 2:1) of triethyl phosphate and 3- (propoxy) glycerol triacrylate, and stirring under a drying condition to completely dissolve the lithium bistrifluoromethanesulfonylimide so as to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution by ionizing radiation to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) initiating the polymerization of the precursor electrolyte by ionizing radiation of the battery filled with the precursor solution to obtain the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 12
Dissolving lithium bistrifluoromethanesulfonylimide in a mixed phosphorus-containing compound of triethyl phosphate and the phosphorus-containing compound obtained in preparation example 1 at a molar concentration of 1mol/L, preparing a mixed solution (volume ratio: 1.5:1) containing the mixed phosphorus-containing compound and vinylene carbonate, stirring under a dry condition to completely dissolve the mixed phosphorus-containing compound and the vinylene carbonate, adding azobisisobutyronitrile (0.1% in molar ratio to the vinylene carbonate) into the mixed solution, and stirring and dissolving to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution at 45 ℃ to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution at 45 ℃ to initiate the polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 13
Dissolving lithium bistrifluoromethanesulfonylimide in a mixed phosphorus-containing compound of triethyl phosphate and the phosphorus-containing compound obtained in preparation example 2 at a molar concentration of 1mol/L, preparing the mixed phosphorus-containing compound and vinylene carbonate into a mixed solution (volume ratio: 1.5:1), stirring under a dry condition to completely dissolve the mixed phosphorus-containing compound and the vinylene carbonate, adding azobisisobutyronitrile (0.1% in molar ratio to the vinylene carbonate) into the mixed solution, and stirring and dissolving to obtain a transparent and uniform solution, namely a precursor solution. And initiating polymerization of the precursor solution at 45 ℃ to obtain the flame-retardant solid-liquid mixed solid electrolyte. And (3) placing the battery injected with the precursor solution at 45 ℃ to initiate the polymerization of the precursor electrolyte, thus obtaining the battery using the flame-retardant solid-liquid mixed solid electrolyte.
Example 14 Performance testing
Ignition experiments were carried out using the flame-retardant solid-liquid mixed solid electrolytes obtained in sample examples 1 to 13, and it was found that they were all incombustible. The incombustibility of the flame retardant was found in FIG. 1, which is a typical example of example 1. The results are similar for the remaining examples.
Deposition experiments were performed on lithium-lithium symmetric batteries prepared using the flame-retardant solid-liquid mixed solid electrolytes of examples 1 to 13, respectively, at a current density of 0.5mA/cm2After the battery is charged and discharged, no obvious potential polarization increase is observed after the battery is cycled for 500 hours. As a representative example of the symmetrical cell obtained with the solid electrolyte in example 1, no significant increase in potential polarization was observed as shown in fig. 2. The results are similar for the remaining examples.
Electrochemical analysis tests were carried out using the flame-retardant solid-liquid mixed solid electrolytes obtained in examples 1 to 13, respectively, and using a lithium metal sheet as a negative electrode and LiNi0.8Co0.1Mn0.1O2Is the anode. Typically, the solid-liquid mixed solid electrolyte in example 1 is used as an electrolyte, and a non-combustible lithium battery is assembled. At 0.1C, the capacity of the material can reach 205mAh/g (as shown in figure 3). The results are similar for the remaining examples.
Electrochemical analysis tests were performed on the flame-retardant solid-liquid mixed solid electrolytes obtained in examples 1 to 13, respectively, using a lithium metal sheet as a reference electrode and graphite as a working electrode. Typically, the solid-liquid mixed solid electrolyte described in example 1 is an electrolyte, and a non-combustible lithium battery is assembled. At 0.1C, the capacity of the material can reach 356.5mAh/g (as shown in figure 4). The results are similar for the remaining examples.
Electrochemical analysis tests were carried out using the flame-retardant solid-liquid mixed solid electrolytes obtained in examples 1 to 13, respectively, using a lithium metal sheet as a reference electrode and using silica as a working electrode. Typically, the solid-liquid mixed solid electrolyte in example 1 is used as an electrolyte, and a non-combustible lithium battery is assembled. At 0.1C, the capacity of the material can reach 2248mAh/g (as shown in figure 5). The results are similar for the remaining examples.
LiFePO using metallic lithium sheet as negative electrode4As a positive electrode, the solid-liquid mixed solid electrolytes obtained in examples 1 to 13 were each used as an electrolyte, and a non-combustible lithium battery was assembled. The cycle performance and surface young's modulus were tested at 0.5C current and the results are shown in table 1.
Surface Young's modulus test Using an atomic force microscope, model Bruker DIMENSION ICON.
Comparative example 1
The phosphate swollen PVDF-HFP solid-liquid mixed solid electrolyte is prepared by mixing a solid electrolyte having an average molecular weight of Mw400000 PVDF-HFP powder and 1M lithium bis (trifluoromethanesulfonyl) imide are dissolved in N, N-dimethylformamide, the polymer solution is spread into a film by a scraper, then the film is dried in a 75 ℃ oven for 72 hours, and the film is taken out and soaked in 1M lithium bis (trifluoromethanesulfonyl) imide phosphate electrolyte for swelling.
The comparative example was subjected to a cycle performance and a surface Young's modulus test at a current of 50. mu.A/g, and the test results are shown in Table 1.
TABLE 1 comparison table of electrochemical properties of products obtained in examples and comparative examples
Figure BDA0003027014960000161
The first charge and discharge data of example 1 are shown in fig. 6.
The flame-retardant solid-liquid mixed solid electrolyte in example 1 is typically used as a representative, fig. 7 is a surface young's modulus test result thereof, and fig. 8 is a surface young's modulus test result of the phosphate-swollen PVDF-HFP solid-liquid mixed solid electrolyte in comparative example 1. As can be seen from fig. 7 and 8, the surface of the flame-retardant solid-liquid mixed solid electrolyte of example 1 of the present invention has an average young's modulus of 12.4GPa (fig. 7), which is significantly higher than that of the ex-situ polymerized swelling electrolyte (80MPa, fig. 8), and is also higher than the theoretical value (7.98-10.64GPa) required for the resistance to penetration of lithium dendrites (this theoretical value can be seen in chem. rev.,2020,120, 6820-.
Conductivity test
The conductivity was measured by the ac impedance method at 25 c using an electrochemical workstation with a frequency ranging from 100KHz to 0.01Hz and a perturbation voltage of 10mV, and then calculated using the formula σ ═ L/(rxs) to obtain the conductivity, the data of which are shown in table 2. Where σ is the ionic conductivity, L is the thickness of the electrolyte, R is the resistance value of the electrolyte, and S is the contact area of the electrolyte and the electrode.
Table 2 ionic conductivity results for the products obtained in examples and comparative examples
Sample (I) Conductivity (S/cm)
Comparative example 1 2.2E-03
Example 1 4.4E-03
Example 2 2.3E-03
Example 3 4.5E-03
Example 4 4.55E-03
Example 5 4.52E-03
Example 6 4.62E-03
Example 7 6.17E-03
Example 8 5.35E-03
Example 9 4.31E-03
Example 10 1.21E-03
Example 11 1.24E-03
Example 12 4.9E-03
Example 13 4.95E-03
Flame retardancy test
The flame retardant property test shows that the Limiting Oxygen Index (LOI) of the electrolyte is tested according to the national standard GB/T2406-1993 shown in Table 3, and the examples 1-13 have better flame retardant property.
TABLE 3 flame retardancy of the products obtained in the examples
Figure BDA0003027014960000171
Figure BDA0003027014960000181
According to the embodiment and the comparative example, the flame retardance of the electrolyte can be improved while the solid-liquid mixed solid electrolyte obtained by packaging the flame-retardant phosphate ester by in-situ polymerization of the polymer monomer in the battery monomer by adopting an in-situ polymerization strategy, so that the safety and the cycle performance of the battery are improved. In the invention, the liquid phase component with flame retardant property provides good safety for the battery, and simultaneously ensures high ionic conductance of the electrolyte; the polymer network generated by in-situ polymerization can well encapsulate flame-retardant liquid phase components, so that leakage of a system is prevented, the lithium ion migration number of the electrolyte is increased, and the high-strength polymer framework is favorable for preventing the penetration of metal lithium dendrites. The in-situ polymerization mode can be well compatible with the existing battery production process, and the solid-liquid mixed solid electrolyte formed in situ can also ensure good contact of the electrode electrolyte interface. The functionalized polymer, the functionalized filler and the additive also play a role in improving the comprehensive performance of the electrolyte.
In conclusion, the flame-retardant phosphate is encapsulated in the macromolecular framework in an in-situ polymerization manner, so that the solid-liquid mixed solid electrolyte with high strength, high ionic conductivity, high ion migration number and good interface compatibility can be obtained, and the cycle performance and the safety performance of the battery can be better improved. The preparation method is easy to regulate and control, can flexibly match the types and proportions of the solvent, the lithium salt and the additive, is used as the electrolyte of the lithium battery, and has high safety and application prospect. The preparation method is simple, the raw materials are easy to obtain, and the preparation method is suitable for large-scale production.
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the embodiments of the present invention, and those skilled in the art can easily make various changes or modifications according to the main concept and spirit of the present invention, so the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. The flame-retardant solid-liquid mixed solid electrolyte is characterized by comprising a flame-retardant liquid phase component, lithium salt and a polymer network structure, wherein the flame-retardant liquid phase component and the lithium salt are dispersed in the polymer network structure;
wherein the flame retardant liquid phase component comprises a phosphorus-containing organic compound;
the phosphorus-containing organic compound contains any one of groups shown in formulas I and II, and is characterized by low-viscosity liquid with efficient flame-retardant property:
Figure FDA0003027014950000011
the polymer network structure is obtained by polymerizing a polymer network structure monomer;
the high-molecular network structure monomer is selected from at least one of ester compounds containing C ═ C, and can be polymerized in situ to obtain a high-Young modulus high-molecular network structure monomer;
wherein, in the formulas I and II, R1、R2、R3Is selected from C1～C8Alkyl radical, C1～C8Any of the halogen-substituted alkyl groups.
2. The flame-retardant solid-liquid mixed solid electrolyte according to claim 1, wherein the C-C ester compound includes any one of a C-C ester cyclic organic compound and a C-C ester linear organic compound;
preferably, the polymer network structure is prepared by in-situ polymerization of a C ═ C ester cyclic organic compound.
3. The solid-liquid mixed flame-retardant solid electrolyte according to claim 1, wherein the phosphorus-containing organic compound is a mixture of a phosphorus-containing organic compound and a polymer network monomer
The volume ratio is 1-10: 1.
4. The fire retardant solid-liquid mixed solid electrolyte of claim 1 wherein the phosphorus containing organic compound is selected from trimethyl phosphate, triethyl phosphate, tripropyl phosphate; the high molecular network structure monomer is selected from vinylene carbonate.
5. The flame-retardant solid-liquid mixed solid electrolyte according to claim 3, wherein the volume ratio of the phosphorus-containing organic compound to vinylene carbonate is 0.5-3:1, preferably 1-1.5: 1.
6. The flame-retardant solid-liquid mixed solid electrolyte according to claim 1, wherein the lithium salt comprises at least one of lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium difluorooxalato borate, lithium perchlorate.
7. The fire-retardant solid-liquid mixed solid electrolyte according to claim 1, further comprising at least one of a functionalized polymer, a functionalized filler, and a functionalized additive;
preferably, the functionalized polymer comprises at least one of polyethylene oxide, polyvinylidene fluoride, poly (vinylidene fluoride-co-hexafluoropropylene), polydimethylsiloxane, poly (styrene) and polyacetylene;
the functionalized filler comprises any one of inorganic inactive ceramic fillers and lithium ion conductive active fillers;
the functional additive comprises any one of a film forming additive and an anti-overcharge additive.
8. The method for preparing a flame-retardant solid-liquid mixed solid electrolyte according to any one of claims 1 to 7, characterized by comprising:
the flame-retardant solid-liquid mixed solid electrolyte can be obtained by injecting a mixture containing a phosphorus-containing organic compound, a polymer network structure monomer, a lithium salt and optionally at least one of a functional polymer, a functional filler and a functional additive into a battery for in-situ polymerization reaction in the presence of an initiator.
9. The method of claim 8, wherein the in situ polymerization is carried out under the following conditions: heating at the temperature of 45-90 ℃; the molar concentration of lithium salt in the mixture is between 0.25M and 4M;
preferably, the content of the functionalized polymer in the mixture is 0-40%, preferably 2-10% of the total mass of the phosphorus-containing compound and the polymer network structure monomer;
preferably, the content of the functionalized nano filler in the mixture is 0-15%, preferably 2-5% of the total mass of the phosphorus-containing compound and the high molecular network structure monomer;
preferably, the content of the functionalized additive in the mixture is 0-10%, preferably 2-10% of the total volume of the phosphorus-containing compound and the high molecular network structure monomer.
10. A lithium battery is characterized in that the lithium battery contains a flame-retardant solid-liquid mixed solid electrolyte;
the flame-retardant solid-liquid mixed solid electrolyte is selected from any one of the flame-retardant solid-liquid mixed solid electrolyte as defined in any one of claims 1 to 8 and the flame-retardant solid-liquid mixed solid electrolyte obtained by the preparation method as defined in claim 9.
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