CN105470570A - Polymer electrolyte, preparation method therefor and application thereof - Google Patents
Polymer electrolyte, preparation method therefor and application thereof Download PDFInfo
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- CN105470570A CN105470570A CN201510945378.3A CN201510945378A CN105470570A CN 105470570 A CN105470570 A CN 105470570A CN 201510945378 A CN201510945378 A CN 201510945378A CN 105470570 A CN105470570 A CN 105470570A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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Abstract
The invention provides a polymer electrolyte, a preparation method therefor and an application thereof. The polymer electrolyte comprises a lithium salt-containing non-aqueous solvent, and further comprises an cationic grafted modified polymer, wherein the cationic grafted modified polymer is prepared by a ring-opening polymerization reaction of a polymer matrix, amine monomers and epoxy monomers, and the polymer matrix is prepared by a curing reaction of ether monomers, a cross-linking agent and an initiator. The polymer electrolyte has relatively high ionic conductivity and good mechanical property, and is more environmentally-friendly and safe in comparison with an organic electrolyte solution; and meanwhile, positive ions are introduced in the polymer electrolyte, so that the charge interaction of the positive ions and polysulfide ions can suppress the dissolution of active sulfur of an electrode material and the flying shuttle effect of the polysulfide ions, remarkably expand the discharge specific capacity of a lithium-sulfur battery and remarkably prolong the cycle life of the lithium-sulfur battery.
Description
Technical field
The present invention relates to can charging and discharging secondary battery field, is specifically related to a kind of polymer dielectric and its preparation method and application.
Background technology
Along with mobile communication, developing rapidly of the portable electric appts such as electronic instrument and electric tool, and the raising of people's energy-conserving and environment-protective consciousness, can the secondary cell of repeatedly discharge and recharge be widely applied.Wherein, the lithium rechargeable battery coming across the nineties in 20th century is the chemical power source of new generation of generally acknowledging in the world at present, viable commercial product develop rapidly in field of portable devices.But in fields such as electric automobile, Aero-Space and defence equipments, current commercialization lithium rechargeable battery is limited to theoretical capacity, cannot significantly improve its energy density further, far can not meet the demand of technical development.Therefore, eager research and development are needed to have the mechanism of new electrochemical power sources of the features such as more high-energy-density, more long circulation life, low cost and environmental friendliness.
Take lithium metal as negative pole, elemental sulfur is in the lithium-sulfur rechargeable battery (abbreviation lithium-sulfur cell) of positive active material, S
8theoretical specific capacity be 1675mAh/g, the theoretical discharge voltage of Li/S battery is 2.287V, then theoretical energy density is 3825Wh/kg, contrast energy density and the relative price of various material in secondary cell, elemental sulfur is the positive electrode that current energy density is the highest, compared with the lithium ion battery of main flow on market, lithium-sulfur cell has the former theoretical specific capacity of 2 ~ 5 times, and sulphur is nontoxic, inexpensive, lithium-sulfur cell also has environmentally friendly, the advantages such as fail safe is high, it is desirable battery material of new generation, thus the domestic and international attention to lithium-sulfur cell day by day improves, this also promotes the fast development of lithium-sulfur cell.
But, the high power capacity of lithium-sulfur cell and S can be derived from by charge-discharge performance
8the electrochemical cleavage of S-S key and bonding again in molecule, in cell operations, intermediate product Li
2s
n(4≤n≤8) are soluble in organic electrolyte, deposit in case in concentration gradient, will in organic electrolyte free diffusing, thus produce " flying shuttle phenomenon ", finally cause lithium-sulfur cell coulombic efficiency to decline; And end product Li
2s
2/ Li
2s is insoluble to organic electrolyte, will respectively at both positive and negative polarity surface deposition, is difficult to be electrochemically oxidized completely become Li under rich lithium state
2s
n(4≤n≤8), thus cause active material inactivation.Therefore, lithium-sulfur cell is difficult to reach long cycle life and high efficiency for charge-discharge, which greatly limits the application of lithium-sulfur cell.
In order to solve the problem, major part research all concentrates on the structural research of lithium sulfur battery anode material, reduces Li to the special construction by positive pole
2s
n(4≤n≤8) are to the dissolving of electrolyte.At present, about by introducing cation in polymer dielectric, Li is suppressed by charge interaction
2s
nthe research that (4≤n≤8) dissolve migratory behaviour has no report.
Summary of the invention
For the deficiencies in the prior art, the invention discloses a kind of polymer dielectric and its preparation method and application.
First aspect, the invention provides a kind of polymer dielectric, comprises the nonaqueous solvents containing lithium salts, also comprises cation graft polymer-modified; Wherein, described cation graft is polymer-modified to be obtained through ring-opening polymerization by polymeric matrix, amine monomers, epoxy monomer, and described polymeric matrix is obtained through curing reaction by ether type monomer, crosslinking agent, initator.
Preferably, the mass ratio of described ether type monomer, crosslinking agent, initator is 100:(10 ~ 20): (1 ~ 5).
Preferably, described amine monomers and polymeric matrix end group mol ratio are (0.1 ~ 10): 1.
Preferred further, described amine monomers and polymeric matrix end group mol ratio are (1 ~ 5): 1.
Preferably, described epoxy monomer and the mol ratio of amine monomers are (0.1 ~ 10): 1.
Preferred further, described epoxy monomer and the mol ratio of amine monomers are (0.1 ~ 5): 1.
Preferably, described cation graft is polymer-modified is (0.05 ~ 10) with the mass ratio of the nonaqueous solvents containing lithium salts: 1.
Preferably, described contains in the nonaqueous solvents of lithium salts, and the concentration of lithium salts is 0.5 ~ 2.0mol/L.
Preferred further, described contains in the nonaqueous solvents of lithium salts, and the concentration of lithium salts is 0.5 ~ 1.0mol/L.
Preferably, described ether type monomer comprises the linear ether type monomer containing double bond functional group and/or has the ether type monomer of branched structure.
Further preferably, described ether type monomer includes but not limited to one or more in polysorbas20, polysorbate40, polysorbate60, Tween 80, sorbimacrogol oleate100, polysorbate85.
Preferably, described crosslinking agent include but not limited in pentaerythrite three methyl acrylate, ethylene glycol dimethacrylate, dimethacrylate, TEGDMA, TEG dimethylacrylate, lauryl methacrylate, triethylene glycol diacrylate, neopentylglycol diacrylate one or more.
Preferably, described initator includes but not limited to styrax ethers or benzophenone.
Further preferably, described styrax ethers includes but not limited to one or more in dimethoxybenzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether.
Further preferably, described benzophenone includes but not limited to one or more in benzophenone, 2,4-DihydroxyBenzophenone, Michler's keton.
Preferably, described amine monomers include but not limited in dimethylamine, ethylenediamine, diethylenetriamine, TEPA, diphenylamines, 1,2-propane diamine one or more.
Preferably, described epoxy monomer include but not limited in epoxychloropropane, epoxy bromopropane one or more.
Preferably, described lithium salts includes but not limited to LiClO
4, LiCF
3sO
3, LiPF
6, LiBF
4, LiAsF
6, LiSbF
6, LiCF
3cF
2sO
3, LiN (CF
3sO
2)
2, LiNO
3, one or more in di-oxalate lithium borate.
Preferably, described nonaqueous solvents comprises linear ethers and/or ring-type ethers.
Further preferably, described linear ethers includes but not limited to one or more in glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, ethylene glycol diethyl ether.
Further preferably, described ring-type ethers includes but not limited to one or more in Isosorbide-5-Nitrae-dioxane, oxolane, dioxolanes.
Preferably, described polymeric matrix is obtained through curing reaction by acrylic ester monomer, ether type monomer, crosslinking agent, initator.
Further preferred, the mass ratio of the quality summation of described acrylic ester monomer and ether type monomer and crosslinking agent, initator is 100:(10 ~ 20): (1 ~ 5).
Further preferred, described acrylic ester monomer and the mass ratio of ether type monomer are 1:(0.25 ~ 4).
Further preferably, described acrylic ester monomer includes but not limited to one or more in methyl methacrylate, methyl acrylate, EMA, butyl acrylate.
Second aspect, the invention provides a kind of method for preparing polymer electrolytes, comprises the following steps:
(1) preparation of polymeric matrix: mixed with crosslinking agent, initator by ether type monomer and carry out curing reaction, product prepares polymeric matrix after extracting drying;
(2) preparation that cation graft is polymer-modified: under solvent existence and alkali condition, the polymeric matrix obtained in step (1), amine monomers mix with epoxy monomer, carry out ring-opening polymerization, after having reacted, regulate pH to neutral, except after desolventizing, drying obtains crude product, more polymer-modified by obtaining cation graft after crude product extracting drying;
(3) preparation of polymer dielectric: mix polymer-modified for the cation graft obtained in step (2) with the nonaqueous solvents containing lithium salts, obtain polymer dielectric.
Preferably, the mass ratio of the ether type monomer described in step (1), crosslinking agent, initator is 100:(10 ~ 20): (1 ~ 5).
Preferably, the ether type monomer described in step (1) comprises the linear ether type monomer containing double bond functional group and/or has the ether type monomer of branched structure.
Further preferably, the ether type monomer described in step (1) includes but not limited to one or more in polysorbas20, polysorbate40, polysorbate60, Tween 80, sorbimacrogol oleate100, polysorbate85.
Preferably, the crosslinking agent described in step (1) includes but not limited to one or more in pentaerythrite three methyl acrylate, ethylene glycol dimethacrylate, dimethacrylate, TEGDMA, TEG dimethylacrylate, lauryl methacrylate, triethylene glycol diacrylate, neopentylglycol diacrylate.
Preferably, the initator described in step (1) includes but not limited to styrax ethers or benzophenone.
Further preferably, described styrax ethers includes but not limited to one or more in dimethoxybenzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether.
Further preferably, described benzophenone includes but not limited to one or more in benzophenone, 2,4-DihydroxyBenzophenone, Michler's keton.
Preferably, the preparation method of polymeric matrix comprises acrylic ester monomer to mix with ether type monomer, crosslinking agent, initator and carries out curing reaction in step (1).
Further preferred, the mass ratio of the quality summation of described acrylic ester monomer and ether type monomer and crosslinking agent, initator is 100:(10 ~ 20): (1 ~ 5).
Further preferred, described acrylic ester monomer and the mass ratio of ether type monomer are 1:(0.25 ~ 4).
Further preferably, described acrylic ester monomer includes but not limited to one or more in methyl methacrylate, methyl acrylate, EMA, butyl acrylate.
Preferably, there is the time of curing reaction in step (1) at more than 12h.
Preferably, the solvent used of the extraction steps described in step (1) is ether or acetone.
Preferably, the time of the extracting described in step (1) is 10 ~ 15h.
Preferably, the amine monomers described in step (2) and polymeric matrix end group mol ratio are (0.1 ~ 10): 1.
Preferred further, the amine monomers described in step (2) and polymeric matrix end group mol ratio are (1 ~ 5): 1.
Preferably, the mol ratio of the epoxy monomer described in step (2) and amine monomers is (0.1 ~ 10): 1.
Preferred further, the mol ratio of the epoxy monomer described in step (2) and amine monomers is (0.1 ~ 5): 1.
Preferably, the amine monomers described in step (2) includes but not limited to one or more in dimethylamine, ethylenediamine, diethylenetriamine, TEPA, diphenylamines, 1,2-propane diamine.
Preferably, the epoxy monomer described in step (2) includes but not limited to one or more in epoxychloropropane, epoxy bromopropane.
Preferably, the solvent described in step (2) includes but not limited to one or more in water, methyl alcohol, ethanol, ethyl acetate, acetone.
Preferably, the cation graft described in step (3) is polymer-modified is (0.05 ~ 10) with the mass ratio of the nonaqueous solvents containing lithium salts: 1.
Preferably, containing in the nonaqueous solvents of lithium salts described in step (3), the concentration of lithium salts is 0.5 ~ 2.0mol/L.
Preferred further, containing in the nonaqueous solvents of lithium salts described in step (3), the concentration of lithium salts is 0.5 ~ 1.0mol/L.
Preferably, the lithium salts described in step (3) includes but not limited to LiClO
4, LiCF
3sO
3, LiPF
6, LiBF
4, LiAsF
6, LiSbF
6, LiCF
3cF
2sO
3, LiN (CF
3sO
2)
2, LiNO
3, one or more in di-oxalate lithium borate.
Preferably, the nonaqueous solvents described in step (3) comprises linear ethers and/or ring-type ethers.
Further preferably, described linear ethers includes but not limited to one or more in glycol dimethyl ether, diethylene glycol dimethyl ether, TRIGLYME, tetraethyleneglycol dimethyl ether, ethylene glycol diethyl ether.
Further preferably, described ring-type ethers includes but not limited to one or more in Isosorbide-5-Nitrae-dioxane, oxolane, dioxolanes.
Be understandable that, the curing reaction that in step (1), polyether prepolymer, polyacrylate and crosslinking agent occur is the Raolical polymerizable of light-initiated or hot initiation.
The third aspect, the invention provides a kind of polymer dielectric as described in relation to the first aspect or the application of method for preparing polymer electrolytes in lithium-sulfur cell, lithium battery as described in second aspect.
Preferably, described polymer dielectric is as described in relation to the first aspect preparing the application in lithium-sulfur cell or lithium battery, is specially: surface polymer dielectric being as described in relation to the first aspect coated in lithium-sulfur cell or lithium battery anode.
Fourth aspect, the invention provides the application of preparation method in lithium-sulfur cell, lithium battery that polymer-modified or as described in second aspect the cation graft of a kind of cation graft is as described in relation to the first aspect polymer-modified.
Beneficial effect of the present invention: 1, the invention provides a kind of polymer dielectric, has higher ionic conductivity, good mechanical property, compared to organic electrolyte, and more environmental protection, safety;
2, polymer dielectric provided by the invention introduces charge interaction by cationic polymer graft modification, compared with liquid electrolyte, that can suppress the stripping of electrode material activity sulphur and suppress many sulphions flies shuttle effect, significantly improves specific discharge capacity and the cycle life of lithium-sulfur cell.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present application or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the application, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the discharge curve first of the lithium-sulfur cell comprising polymer dielectric in embodiment 1;
Fig. 2 comprises the lithium-sulfur cell of polymer dielectric and the charge and discharge cycles curve of control cell in embodiment 1 and embodiment 2 respectively.
Embodiment
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite not making creative work, all belongs to the scope of protection of the invention.
Embodiment 1 one kinds of method for preparing polymer electrolytes
(1) preparation of polymeric matrix: after Tween 80, pentaerythritol triacrylate and dimethoxybenzoin are mixed according to mass ratio 100:10:1,12h is solidified under the illumination of ultraviolet (λ=254nm and/or 365nm), generate polyhydroxy branch polyether, polyhydroxy branch polyether is used after heavily steaming ether extraction 12h, by the sample drying after extracting, obtain polymeric matrix;
(2) preparation that cation graft is polymer-modified: 0.5g polymeric matrix, 0.26g dimethylamine and 0.1g epoxychloropropane are mixed, under condition of ice bath, dissolve dispersion in deionized water, the saturated lithium hydroxide solution adding certain mass carries out ring-opening polymerisation; After stirring a period of time, after being warming up to 40 ~ 50 DEG C, continue reaction 12h to complete; In reactant liquor, instill red fuming nitric acid (RFNA) regulates the pH of solution for neutral, and at 50 DEG C, solvent is removed in decompression distillation, and graft modification branch polyether is separated out, dry, grind into powder; By dried sample with heavily steaming acetonitrile extracting 24h, sample being placed in glove box dry, obtaining high-cation graft-modified polymers;
(3) preparation of polymer dielectric: by high-cation graft-modified polymers powder uniform fold obtained in step (2) on carbon sulfur electrode surface, drip a small amount of liquid electrolyte (wherein, glycol dimethyl ether/1,4-dioxane volume ratio 1/1, bis trifluoromethyl sulfimide lithium 0.5mol/L, lithium nitrate 0.1mol/L), form gel after wetting, obtain polymer dielectric.
Embodiment 2 one kinds of method for preparing polymer electrolytes
(1) preparation of polymeric matrix: after Tween 80, pentaerythritol triacrylate and dimethoxybenzoin are mixed according to mass ratio 100:10:1,12h is solidified under the illumination of ultraviolet (λ=254nm and/or 365nm), generate polyhydroxy branch polyether, polyhydroxy branch polyether is used after heavily steaming ether extraction 12h, by the sample drying after extracting, obtain polymeric matrix;
(2) preparation that cation graft is polymer-modified: 0.5g polymeric matrix, 0.05g dimethylamine and 0.02g epoxychloropropane are mixed, dissolves dispersion in deionized water under condition of ice bath.The saturated lithium hydroxide solution adding certain mass carries out ring-opening polymerisation; After stirring a period of time, after being warming up to 40 ~ 50 DEG C, continue reaction 12h to complete; In reactant liquor, instill red fuming nitric acid (RFNA) regulates the pH of solution for neutral, and at 50 DEG C, solvent is removed in decompression distillation, and graft modification branch polyether is separated out, dry, grind into powder; By dried sample with heavily steaming acetonitrile extracting 24h, sample being placed in glove box dry, obtaining low cationic polymer graft-modified polymers;
(3) preparation of polymer dielectric: low cation graft modified polymer powders uniform fold obtained in step (2) is on carbon sulfur electrode surface, drip a small amount of liquid electrolyte (wherein, glycol dimethyl ether/1,4-dioxane volume ratio 1/1, bis trifluoromethyl sulfimide lithium 0.5mol/L, lithium nitrate 0.1mol/L), form gel after wetting, obtain polymer dielectric.
The preparation of embodiment 3 lithium-sulfur cell and the mensuration of discharge capacity
In order to further illustrate beneficial effect of the present invention, the polymer dielectric prepared using embodiment 1 and embodiment 2 is respectively as lithium-sulfur cell electrolyte, lithium metal is negative pole, and carbon sulfur electrode is that sulphur positive pole is assembled into button cell, called after lithium-sulfur cell 1 and lithium-sulfur cell 2.Assemble successfully, place 12h, test lithium-sulfur cell 1 discharge curve first, discharge and recharge interval is 1.5 ~ 2.8V, as shown in Figure 1, with the lithium-sulfur cell of liquid electrolyte assembling for control cell, as discharging current 0.1C, test the discharge capacity of lithium-sulfur cell 1, lithium-sulfur cell 2 and control cell respectively, charge and discharge cycles curve as shown in Figure 2.
Experimental result: the discharge capacity first of control cell is 97.2mAh/g, after 20 circulations, discharge capacity is 25.3mAh/g; Adopt the lithium-sulfur cell 1 of the polymer dielectric assembling of preparation in embodiment 1, the discharge capacity first of battery system is 764.2mAh/g, and after 20 circulations, discharge capacity is 218.3mAh/g; Adopt the lithium-sulfur cell 2 of the polymer dielectric assembling of preparation in embodiment 2, the discharge capacity first of battery system is 682.1mAh/g, and after 20 circulations, discharge capacity is 119.7mAh/g.
Discharge capacity after the discharge capacity first of lithium-sulfur cell 1 and circulation 20 times is all better than lithium-sulfur cell 2, this is because on polymer dielectric in embodiment 1 cations higher than the polymer dielectric in embodiment 2, cation flies shuttle effect by what suppress the dissolving of sulphur active material and many sulphions with the charge interaction of many sulphions, the larger inhibition of cations might as well, thus the discharge capacity of battery and cycle performance better.
Embodiment 4 one kinds of method for preparing polymer electrolytes
In order to further illustrate beneficial effect of the present invention, repeating the step in embodiment 1, adopting different reaction monomers to prepare polymer dielectric, and experimental group is numbered, as shown in table 1.Repeat the step of embodiment 3, the polymer dielectric prepared using A, B, C, D group respectively, as lithium-sulfur cell electrolyte, is assembled into lithium-sulfur cell, and characterize the discharge capacity after discharge capacity first and circulation 20 times, result is as shown in table 2.
The polymer dielectric that table 1 differential responses monomer prepares
Table 2 comprises the discharge capacity of the lithium-sulfur cell of different polymer dielectric
| Numbering | Discharge capacity (mAh/g) first | Circulate discharge capacity (mAh/g) after 20 times |
| A | 770.8 | 223.5 |
| B | 755.1 | 211.6 |
| C | 678.3 | 110.5 |
| D | 670.5 | 103.2 |
Embodiment 5 one kinds of method for preparing polymer electrolytes
In order to further illustrate beneficial effect of the present invention, repeat the step in embodiment 1, " mass ratio 100:10:1 " in step (1) is replaced with " mass ratio 100:15:3 ", " 0.26g dimethylamine and 0.1g epoxychloropropane " in step (2) is replaced with " 0.2g dimethylamine and 0.4g epoxychloropropane ", prepares a kind of polymer dielectric.
Embodiment 6 one kinds of method for preparing polymer electrolytes
In order to further illustrate beneficial effect of the present invention, repeat the step in embodiment 1, " mass ratio 100:10:1 " in step (1) is replaced with " mass ratio 100:20:5 ", " 0.26g dimethylamine and 0.1g epoxychloropropane " in step (2) is replaced with " 0.15g dimethylamine and 2g epoxychloropropane ", prepares a kind of polymer dielectric.
The preparation of embodiment 7 lithium-sulfur cell and the mensuration of discharge capacity
In order to further illustrate beneficial effect of the present invention, repeat the step in embodiment 3, the polymer dielectric prepared using embodiment 5,6 is respectively as the electrolyte of lithium-sulfur cell.Characterize the discharge capacity after discharge capacity first and circulation 20 times, result is as shown in table 3.
Table 3 comprises the discharge capacity of the lithium-sulfur cell of different polymer dielectric
| Numbering | Discharge capacity (mAh/g) first | Circulate discharge capacity (mAh/g) after 20 times |
| Embodiment 5 | 732.6 | 186.7 |
| Embodiment 6 | 711.8 | 162.1 |
Embodiment 8 one kinds of method for preparing polymer electrolytes
(1) preparation of polymeric matrix: after Tween 80, methyl methacrylate, pentaerythritol triacrylate and dimethoxybenzoin are mixed according to mass ratio 80:20:10:1,12h is solidified under the illumination of ultraviolet (λ=254nm and/or 365nm), generate polyhydroxylated polymer, polyhydroxylated polymer is used after heavily steaming ether extraction 12h, by the sample drying after extracting, obtain polymeric matrix;
(2) preparation that cation graft is polymer-modified: 0.5g polymeric matrix, 0.26g dimethylamine and 0.1g epoxychloropropane are mixed, under condition of ice bath, dissolve dispersion in deionized water, the saturated lithium hydroxide solution adding certain mass carries out ring-opening polymerisation; After stirring a period of time, after being warming up to 40 ~ 50 DEG C, continue reaction 12h to complete; In reactant liquor, instill red fuming nitric acid (RFNA) regulates the pH of solution for neutral, and at 50 DEG C, solvent is removed in decompression distillation, and graft modification branch polyether is separated out, dry, grind into powder; By dried sample with heavily steaming acetonitrile extracting 24h, sample being placed in glove box dry, obtaining high-cation graft-modified polymers;
(3) preparation of polymer dielectric: by high-cation graft-modified polymers powder uniform fold obtained in step (2) on carbon sulfur electrode surface, drip a small amount of liquid electrolyte (wherein, glycol dimethyl ether/1,4-dioxane volume ratio 1/1, bis trifluoromethyl sulfimide lithium 0.5mol/L, lithium nitrate 0.1mol/L), form gel after wetting, obtain polymer dielectric.
Be negative pole with lithium metal, the carbon sulfur electrode being coated with polymer dielectric is sulphur positive pole, is assembled into button cell.Assemble successfully, place 12h..Test battery charge-discharge performance, discharge and recharge interval is 1.5 ~ 2.8V.During discharging current 0.1C, the discharge capacity first of battery system is 1470.8mAh/g, and after 20 circulations, discharge capacity is 732.1mAh/g.
Last it is noted that above each embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a polymer dielectric, is characterized in that, comprises the nonaqueous solvents containing lithium salts, also comprises cation graft polymer-modified; Wherein, described cation graft is polymer-modified to be obtained through ring-opening polymerization by polymeric matrix, amine monomers, epoxy monomer, and described polymeric matrix is obtained through curing reaction by ether type monomer, crosslinking agent, initator.
2. polymer dielectric according to claim 1, is characterized in that, described ether type monomer comprises the linear ether type monomer containing double bond functional group and/or has the ether type monomer of branched structure.
3. polymer dielectric according to claim 1, is characterized in that, described ether type monomer include but not limited in polysorbas20, polysorbate40, polysorbate60, Tween 80, sorbimacrogol oleate100, polysorbate85 one or more.
4. polymer dielectric according to claim 1, it is characterized in that, described crosslinking agent include but not limited in pentaerythrite three methyl acrylate, ethylene glycol dimethacrylate, dimethacrylate, TEGDMA, TEG dimethylacrylate, lauryl methacrylate, triethylene glycol diacrylate, neopentylglycol diacrylate one or more.
5. polymer dielectric according to claim 1, is characterized in that, described initator includes but not limited to styrax ethers or benzophenone.
6. polymer dielectric according to claim 1, is characterized in that, described amine monomers include but not limited in dimethylamine, ethylenediamine, diethylenetriamine, TEPA, diphenylamines, 1,2-propane diamine one or more.
7. polymer dielectric according to claim 1, is characterized in that, described epoxy monomer include but not limited in epoxychloropropane, epoxy bromopropane one or more.
8. a method for preparing polymer electrolytes, is characterized in that, comprises the following steps:
(1) preparation of polymeric matrix: mixed with crosslinking agent, initator by ether type monomer and carry out curing reaction, product prepares polymeric matrix after extracting drying;
(2) preparation that cation graft is polymer-modified: under solvent existence and alkali condition, the polymeric matrix obtained in step (1), amine monomers mix with epoxy monomer, carry out ring-opening polymerization, after having reacted, regulate pH to neutral, except after desolventizing, drying obtains crude product, more polymer-modified by obtaining cation graft after crude product extracting drying;
(3) preparation of polymer dielectric: mix polymer-modified for the cation graft obtained in step (2) with the nonaqueous solvents containing lithium salts, obtain polymer dielectric.
9. a polymer dielectric as claimed in claim 1 or method for preparing polymer electrolytes as claimed in claim 8 are preparing the application in lithium-sulfur cell, lithium battery.
10. the polymer-modified application in lithium-sulfur cell, lithium battery of cation graft in the polymer-modified or as claimed in claim 8 method for preparing polymer electrolytes of cation graft as claimed in claim 1 prepared by step (2).
Priority Applications (1)
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| CN106252087A (en) * | 2016-09-21 | 2016-12-21 | 中山大学 | A kind of photocuring gel electrolyte and its preparation method and application |
| CN111933881A (en) * | 2020-10-15 | 2020-11-13 | 河南银金达新材料股份有限公司 | Microporous polymer membrane |
| CN113956478A (en) * | 2021-10-29 | 2022-01-21 | 汕头大学 | Polymer solid electrolyte and preparation method and application thereof |
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| JP2003077539A (en) * | 2001-09-04 | 2003-03-14 | Mitsubishi Materials Corp | Gel polymer electrolyte and lithium polymer battery using the same |
| CN102097653A (en) * | 2011-01-18 | 2011-06-15 | 中国人民解放军国防科学技术大学 | Electrolyte used for Li-S battery, Li-S battery and method for preparing electrolyte membrane contained in same |
| CN102318125A (en) * | 2009-02-11 | 2012-01-11 | 陶氏环球技术有限责任公司 | High conductivity polymer electrolyte and comprise its secondary battery |
| WO2015085519A1 (en) * | 2013-12-11 | 2015-06-18 | Dow Global Technologies Llc | Composition for highly conductive polymer electrolytes |
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| JP2003077539A (en) * | 2001-09-04 | 2003-03-14 | Mitsubishi Materials Corp | Gel polymer electrolyte and lithium polymer battery using the same |
| CN102318125A (en) * | 2009-02-11 | 2012-01-11 | 陶氏环球技术有限责任公司 | High conductivity polymer electrolyte and comprise its secondary battery |
| CN102097653A (en) * | 2011-01-18 | 2011-06-15 | 中国人民解放军国防科学技术大学 | Electrolyte used for Li-S battery, Li-S battery and method for preparing electrolyte membrane contained in same |
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| CN106252087A (en) * | 2016-09-21 | 2016-12-21 | 中山大学 | A kind of photocuring gel electrolyte and its preparation method and application |
| CN106252087B (en) * | 2016-09-21 | 2018-09-04 | 中山大学 | A kind of photocuring gel electrolyte and its preparation method and application |
| CN111933881A (en) * | 2020-10-15 | 2020-11-13 | 河南银金达新材料股份有限公司 | Microporous polymer membrane |
| CN113956478A (en) * | 2021-10-29 | 2022-01-21 | 汕头大学 | Polymer solid electrolyte and preparation method and application thereof |
| CN113956478B (en) * | 2021-10-29 | 2023-05-16 | 汕头大学 | Polymer solid electrolyte and preparation method and application thereof |
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| CN105470570B (en) | 2018-05-22 |
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