WO2022011980A1 - 不可燃凝胶电解质前驱体、改性固态电解质、锂电池及其制备方法 - Google Patents
不可燃凝胶电解质前驱体、改性固态电解质、锂电池及其制备方法 Download PDFInfo
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- WO2022011980A1 WO2022011980A1 PCT/CN2020/139669 CN2020139669W WO2022011980A1 WO 2022011980 A1 WO2022011980 A1 WO 2022011980A1 CN 2020139669 W CN2020139669 W CN 2020139669W WO 2022011980 A1 WO2022011980 A1 WO 2022011980A1
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- Prior art keywords
- electrolyte
- solution
- lithium
- flammable
- gel electrolyte
- Prior art date
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- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 62
- 239000002243 precursor Substances 0.000 title claims abstract description 57
- 239000003792 electrolyte Substances 0.000 title claims abstract description 49
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 31
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 150000003904 phospholipids Chemical class 0.000 claims abstract description 17
- 239000007784 solid electrolyte Substances 0.000 claims description 73
- 239000000243 solution Substances 0.000 claims description 40
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 239000007773 negative electrode material Substances 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 8
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- -1 lithium tetrafluoroborate Chemical compound 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 description 13
- 239000007772 electrode material Substances 0.000 description 9
- 238000011065 in-situ storage Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention relates to the technical field of battery preparation, in particular to a nonflammable gel electrolyte precursor, a modified solid electrolyte, a lithium battery and a preparation method thereof.
- the present invention also provides a modified solid electrolyte and a preparation method thereof.
- a preparation method of a non-flammable gel electrolyte precursor comprising the following steps:
- the lithium salt and the organic phospholipid solvent are mixed to form a basic electrolyte solution
- the thermal initiator and the first solution are mixed to form a non-flammable gel electrolyte precursor.
- the step of mixing the lithium salt and the organic phospholipid solvent to form the basic electrolyte solution includes: mixing the lithium salt and the organic phospholipid solvent, and stirring at a temperature of 25 to 45 ° C for 0.5 to 2 h , forming the base electrolyte solution.
- the lithium salt is selected from lithium bis(fluorosulfonyl)imide, lithium perchlorate, lithium tetrafluoroborate, lithium bistrifluoromethanesulfonimide, and lithium bisoxalatoborate at least one of.
- the organic phospholipid solvent is selected from at least one of trimethyl phosphate and triethyl phosphate.
- the step of mixing methyl methacrylate and the base electrolyte to form the first solution includes: mixing methyl methacrylate and the base electrolyte, and mixing the methyl methacrylate and the base electrolyte at a temperature of 25° C. to 45° C. Stir at the temperature for 0.25-2.5 h to form the first solution.
- the step of mixing the thermal initiator and the first solution to form a non-flammable gel electrolyte precursor includes: mixing the thermal initiator and the first solution, and heating at 0-25° C. Stir for 0.25-2.5h to form a non-flammable gel electrolyte precursor.
- the thermal initiator is selected from at least one of azobisisobutyronitrile and benzoyl peroxide.
- the concentration of lithium salt in the base electrolyte is 3-7 mol/L, and in the first solution, the methyl methacrylate and the The mass percentage of the basic electrolyte is 25%-28.57%; in the non-flammable gel, the mass percentage of the thermal initiator and the non-flammable gel precursor is 0.14%-0.29%.
- An incombustible gel electrolyte precursor is prepared by the preparation method of the incombustible gel electrolyte precursor.
- a method for preparing a modified solid electrolyte comprising the steps of:
- the modified solid electrolyte is obtained after coating the non-flammable gel electrolyte precursor on the surface of the solid electrolyte and curing.
- the solid electrolyte is an inorganic solid electrolyte
- a modified solid electrolyte includes a solid electrolyte and a modified layer arranged on the solid electrolyte, and the material of the modified layer is the non-flammable gel electrolyte precursor.
- a preparation method of a lithium battery comprising the following steps:
- the positive electrode material and the negative electrode material are respectively attached to both sides of the modified solid electrolyte, and heated and polymerized to obtain the lithium battery.
- the heating polymerization temperature is 50°C-70°C, and the heating time is 6-10 h.
- a lithium battery includes the modified solid-state electrolyte and a positive electrode material and a negative electrode material attached to both sides of the modified solid-state electrolyte.
- the above-mentioned non-flammable gel electrolyte precursor in an oxygen-free atmosphere, is mixed with lithium salt and organic phospholipid solvent to form a basic electrolyte solution, and methyl methacrylate and the basic electrolyte are mixed to form a first solution.
- the first solution is mixed to form an incombustible gel electrolyte precursor, the preparation process is simple, the raw material sources are wide, the cost is low, and it is suitable for industrial production.
- the non-flammable gel electrolyte precursor is coated on the surface of the existing solid electrolyte, and the gel electrolyte can well infiltrate the surface of the active material and the solid electrolyte, Improve the inherent point-to-point contact between the solid electrolyte and the electrode material, so that the electrode material can well contact the solid electrolyte, thereby reducing the interface impedance between the positive electrode material and the negative electrode material and the solid electrolyte, and at the same time, it can suppress the side reaction between the solid electrolyte and the electrode material, effectively Improve the electrochemical performance of solid-state batteries.
- FIG. 1 is a flow chart of steps of a non-flammable gel electrolyte precursor according to an embodiment
- FIG. 2 is a schematic structural diagram of a modified solid electrolyte provided by an embodiment
- FIG. 3 is a schematic structural diagram of a lithium battery provided by an embodiment
- Fig. 4 is the charge-discharge curve of the solid-state battery of the sample of Example 4 at different rates, and the test temperature is 25°C;
- Figure 5 shows the cycle performance of the LFP/GEL-LLZTO-GEL/Li solid-state battery provided in Example 4 at 0.1C, and the test temperature is 25°C.
- Figure 6 shows the cycle performance of the LFP/GEL-LLZTO-GEL/Li solid-state battery provided in Example 1 at 0.1C, and the test temperature is 25°C.
- first and second are only used for descriptive purposes, and should not be construed as indicating or implying relative importance or implying the number of indicated technical features. Thus, a feature defined as “first” or “second” may expressly or implicitly include one or more of that feature.
- “plurality” means two or more, unless otherwise expressly and specifically defined.
- the preparation method for the non-flammable gel electrolyte precursor includes the following steps:
- the step of mixing the lithium salt and the organic phospholipid solvent to form the basic electrolyte solution includes: mixing the lithium salt and the organic phospholipid solvent, and stirring at a temperature of 25 to 45 ° C for 0.5 to 2 h , so that it is fully dissolved to form a basic electrolyte solution.
- the lithium salt is selected from lithium bis(fluorosulfonyl)imide, lithium perchlorate, lithium tetrafluoroborate, lithium bistrifluoromethanesulfonimide, and lithium bisoxalatoborate at least one of.
- the amount of free Li+ in the electrolyte can be increased, thereby improving the ionic conductivity of the electrolyte at room temperature.
- the organic phospholipid solvent is selected from at least one of trimethyl phosphate and triethyl phosphate.
- the step of mixing methyl methacrylate and the base electrolyte to form the first solution includes: mixing methyl methacrylate and the base electrolyte, and mixing the methyl methacrylate and the base electrolyte at a temperature of 25° C. to 45° C. Stir at the temperature for 0.25-2.5 h to form the first solution.
- the step of mixing the thermal initiator and the first solution to form a non-flammable gel electrolyte precursor includes: mixing the thermal initiator and the first solution, and heating at 0-25° C. Stir for 0.25-2.5h to form a non-flammable gel electrolyte precursor.
- the thermal initiator is selected from at least one of azobisisobutyronitrile and benzoyl peroxide.
- the above thermal initiator will initiate the polymerization of methyl methacrylate monomer to form polymethyl methacrylate.
- the concentration of lithium salt in the base electrolyte is 3-7 mol/L; in the first solution, the methyl methacrylate and The mass percentage of the basic electrolyte is 25%-28.57%; in the non-flammable gel, the mass of the thermal initiator and the non-flammable gel precursor percentage are 0.14%-0.29%.
- the wettability will be poor, and it will be difficult to wet the active material well. If the concentration is low, the ionic conductivity will be low; The gel electrolyte can not achieve the flame retardant effect, the content is too low, the gel texture is too soft, it is difficult to form, and it is easy to cause leakage; the thermal initiator is too small, and the methyl methacrylate cannot be completely polymerized, Too much will cause waste of reagents.
- a suitable material ratio range can be used to avoid the defects and improve the electrical performance.
- the preparation method of the non-flammable gel electrolyte precursor has the advantages of simple preparation process, wide source of raw materials and low cost, and is suitable for industrial production.
- the solid electrolyte is an inorganic solid electrolyte
- FIG. 2 is a schematic structural diagram of a modified solid electrolyte provided in an embodiment, including a solid electrolyte 110 and a modified layer 120 disposed on the solid electrolyte 110 , and the modified layer 120 is made of any material.
- the above-mentioned modified solid electrolyte is coated with the non-flammable gel electrolyte precursor on the surface of the existing solid electrolyte, thereby reducing the interface impedance between the positive electrode material and the negative electrode material and the solid electrolyte, and simultaneously suppressing the side effects of the solid electrolyte and the electrode material.
- the reaction can effectively improve the electrochemical performance of solid-state batteries.
- the heating polymerization temperature is 50°C-70°C, and the heating time is 6-10 h.
- FIG. 3 is a schematic structural diagram of a lithium battery provided in an embodiment, including the modified solid electrolyte 210 and a positive electrode material 220 and a negative electrode material 230 attached to both sides of the modified solid electrolyte 210 .
- the positive electrode material 220 and the negative electrode material 230 are the positive electrode material and the negative electrode material commonly used in existing lithium batteries.
- the non-flammable gel electrolyte precursor is coated on the surface of the existing solid electrolyte, and the gel electrolyte can well infiltrate the surface of the active material and the solid electrolyte, thereby improving the inherent point-to-point contact between the solid electrolyte and the electrode material,
- the electrode material can be in good contact with the solid electrolyte, thereby reducing the interface impedance between the positive electrode material and the negative electrode material and the solid electrolyte, and at the same time, it can suppress the side reaction between the solid electrolyte and the electrode material, and effectively improve the electrochemical performance of the solid state battery.
- the heating temperature is 50 ° C
- heating The time is 10h.
- thermal initiator 0.010g thermal initiator to the first solution, stir at 20°C for 1 hour, until the thermal initiator is uniformly dispersed in the first solution to form a non-flammable gel electrolyte precursor .
- the mass ratio of the thermal initiator to the non-flammable gel electrolyte precursor is 0.25%, and the thermal initiator is azobisisobutyronitrile and benzoyl peroxide mixed in a mass ratio of 1:1.
- thermal initiator ( ) additive 0.010g thermal initiator ( ) into the first solution, and stir at 20°C for 1 h until the thermal initiator is uniformly dispersed in the first solution to form a non-flammable gel electrolyte Precursor.
- the mass ratio of thermal initiator to non-flammable gel precursor is 0.29%, and the thermal initiator is azobisisobutyronitrile and benzoyl peroxide mixed in a mass ratio of 1:1.
- the interface of the existing inorganic solid electrolyte is used without any modification to assemble the full battery.
- the non-flammable gel interface modified solid electrolyte provided in the above embodiment is assembled in a lithium battery for electrochemical testing, as follows:
- the specific battery structure can be a Swagelok cell mold, which includes a positive electrode, a negative electrode, and a non-flammable gel interface modified solid electrolyte electrolyte disposed between the positive electrode and the negative electrode.
- the electrode sheet of the positive electrode adopts an electrode sheet formed by coating an aluminum foil current collector with lithium iron phosphate
- the electrode sheet of the negative electrode adopts a lithium metal electrode, and the following electrochemical properties are obtained.
- Figure 4 shows the charge-discharge curves of the solid-state battery of the sample of Example 4 at different rates.
- the discharge capacities of 0.1C, 0.2C, 0.5C, and 1C are 136, 118, 96, and 77mAh g -1, respectively.
- Figure 5 it can be seen that the capacity remains above 140mAh/g after 60 cycles at a rate of 0.1C, and combined with Table 1, it can be seen that the use of non-flammable gel interface modification solid electrolyte can effectively reduce the interface impedance, inorganic solid electrolyte
- the interface area specific impedance of the solid-state battery without any interface modification is as high as 7500 ⁇ .cm 2 .
- Figure 6 the capacity of the solid-state battery of the sample of Example 1 remains around 80 mAh/g after 60 cycles at a rate of 0.1 C.
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Abstract
Description
样品 | 0.1C倍率下循环60次后容量(mAh/g) | 界面面积比阻抗(Ω.cm2) |
实施例1 | 78 | 245 |
实施例2 | 73 | 287 |
实施例.3 | 50 | 440 |
实施例4 | 145 | 150 |
对比例1 | 0 | 7500 |
Claims (15)
- 一种不可燃凝胶电解质前驱体的制备方法,其特征在于,包括下述步骤:在无氧气氛中,将锂盐及有机磷脂溶剂混合形成基础电解质溶液;保持无氧气氛,将甲基丙烯酸甲酯及所述基础电解质混合形成第一溶液;保持无氧气氛,将热引发剂及所述第一溶液混合形成不可燃凝胶电解质前驱体。
- 如权利要求1所述的不可燃凝胶电解质前驱体的制备方法,其特征在于,所述在无氧气氛中,将锂盐及有机磷脂溶剂混合形成基础电解质溶液的步骤包括:将锂盐及有机磷脂溶剂混合,并在25℃~45℃的温度下搅拌0 .5~2h,使其充分溶解,形成基础电解质溶液。
- 如权利要求1所述的不可燃凝胶电解质前驱体的制备方法,其特征在于,所述锂盐选自双(氟磺酰)亚胺锂、高氯酸锂、四氟硼酸锂、双三氟甲烷磺酰亚胺锂和双乙二酸硼酸锂中的至少一种。
- 如权利要求1所述的不可燃凝胶电解质前驱体的制备方法,其特征在于,所述有机磷脂溶剂选自磷酸三甲酯、磷酸三乙酯中的至少一种。
- 如权利要求1所述的不可燃凝胶电解质前驱体的制备方法,其特征在于,所述将甲基丙烯酸甲酯及所述基础电解质混合形成第一溶液的步骤包括:将甲基丙烯酸甲酯及所述基础电解质混合,并在25℃~45℃的温度下搅拌0.25~2.5h,形成第一溶液。
- 如权利要求1所述的不可燃凝胶电解质前驱体的制备方法,其特征在于,所述将热引发剂及所述第一溶液混合形成不可燃凝胶电解质前驱体的步骤包括:将热引发剂及所述第一溶液混合,并在0-25℃搅拌0.25-2.5h,形成不可燃凝胶电解质前驱体。
- 如权利要求1所述的不可燃凝胶电解质前驱体的制备方法,其特征在于,所述热引发剂选自偶氮二异丁腈和过氧苯甲酰中的至少一种。
- 如权利要求1~7任一项所述的不可燃凝胶电解质前驱体的制备方法,其特征在于,所述不可燃凝胶电解质前驱体中,所述基础电解质中锂盐的浓度为3-7mol/ L;在所述第一溶液中,所述甲基丙烯酸甲酯的质量百分含量为25%~28.57%;在不可燃凝胶中,所述热引发剂与不可燃凝胶前驱体质量百分比为0.14%~0.29%。
- 一种不可燃凝胶电解质前驱体,其特征在于,由权利要求1-8任一项所述的不可燃凝胶电解质前驱体的制备方法制备而成。
- 一种改性固态电解质的制备方法,其特征在于,包括下述步骤:在固态电解质表面涂覆权利要求9所述的不可燃凝胶电解质前驱体经固化后得到改性的固态电解质。
- 如权利要求10所述的改性固态电解质的制备方法,其特征在于,所述固态电解质为无机固态电解质,所述无机固态电解质的材料选自Li 7La 3Zr 2-xSn xO 12、Li 6.25La 3Sn 1.25Bi 0.75O 12、Li 7La 3Zr 1.7Ge 0.3O 12、Li 6.75La 3Zr 1.75Ta 0.25O 12及LiTa 2PO 8中的一种,其中,x=0~1。
- 一种改性固态电解质,其特征在于,包括固态电解质及设置在所述固态电解质上的改性层,所述改性层的材料为权利要求9所述的不可燃凝胶电解质前驱体。
- 一种锂电池的制备方法,其特征在于,包括下述步骤:将正极材料和负极材料分别贴合在权利要求12所述的改性固态电解质两面,经加热聚合,得到所述锂电池。
- 如权利要求13所述的锂电池的制备方法,其特征在于,所述的加热聚合的温度为50℃~70℃,时间为6~10h。
- 一种锂电池,其特征在于,包括权利要求12所述的改性固态电解质以及设置在所述改性固态电解质两面的正极材料和负极材料。
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