CN113707936A - Gel polymer electrolyte for soft package lithium battery and preparation method thereof - Google Patents
Gel polymer electrolyte for soft package lithium battery and preparation method thereof Download PDFInfo
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 66
- 239000003960 organic solvent Substances 0.000 claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 239000003999 initiator Substances 0.000 claims abstract description 38
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 31
- 159000000002 lithium salts Chemical class 0.000 claims description 31
- 239000013538 functional additive Substances 0.000 claims description 27
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 25
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 18
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 11
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 9
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical group O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 7
- 125000005587 carbonate group Chemical group 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910010941 LiFSI Inorganic materials 0.000 claims description 4
- 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 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011244 liquid electrolyte Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000011056 performance test Methods 0.000 description 6
- 238000004880 explosion Methods 0.000 description 4
- 239000011245 gel electrolyte Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 230000000391 smoking effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009778 extrusion testing Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
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Abstract
The invention discloses a gel polymer electrolyte for a soft package lithium battery, which comprises a gel polymer and an organic electrolyte; the gel polymer is obtained by chain polymerization of polymer monomers under the action of initiator. The invention has the beneficial effects that: the polymer monomer selected by the invention can rapidly generate chain polymerization reaction under the action of a thermal initiator, the gel polymer with a long-chain structure is obtained through the polymerization reaction, the gel polymer mainly plays a role in supporting a skeleton in a gel polymer electrolyte, an organic solvent is contained in gaps of the polymer, and the gel polymer electrolyte has a jelly-like appearance at normal temperature, cannot freely flow, has good mechanical property and space size stability and has good room-temperature ionic conductivity.
Description
Technical Field
The invention relates to the field of gel polymer electrolytes, in particular to a gel polymer electrolyte for a soft package lithium battery and a preparation method thereof.
Background
Lithium ion batteries have become the mainstream power source for portable electronic devices due to their high energy density, long cycle life, and environmental friendliness. Structurally, a lithium ion battery is composed of positive and negative electrode materials and an electrolyte intermediate layer. The electrolyte of the lithium ion battery commercialized at present is an organic liquid electrolyte, and although the electrolyte has high conductivity at room temperature, the organic liquid electrolyte contains a large amount of flammable and explosive organic solvents which can freely flow, and has great potential safety hazards of liquid leakage and volatilization, so that the development of a safe electrolyte is urgent.
In order to solve the potential safety hazard of the electrolyte, the development trend in the field of lithium ion batteries is to replace liquid electrolyte with safe, efficient and environment-friendly polymer electrolyte. The early proposal is to add lithium salt electrolyte into PEO and other polymers to prepare pure solid polymer electrolyte, and the prepared polymer electrolyte has high mechanical strength, but has low ionic conductivity and poor electrolyte and electrode interface, thereby influencing the cycle performance of the battery. Recent studies have shown that the use of polymer gel electrolytes provides a compromise to the above-mentioned problems. The polymer gel electrolyte generally consists of a solid polymer and a liquid organic electrolyte, and has the processability of the polymer electrolyte and the excellent interface property of the liquid electrolyte/electrode. Due to the fixing action of the polymer, the volatilization of the liquid electrolyte during thermal runaway is inhibited, and the interface reaction between the liquid electrolyte and the electrode is reduced, so that the occurrence of thermal runaway is reduced or delayed to a certain extent, and the safety of the battery can be obviously improved.
The prior gel electrolyte generally has a cross-linking reaction of a thermal cross-linking monomer, a thermal cross-linking monomer derivative, a photo-cross-linking monomer and a photo-cross-linking monomer derivative under the catalysis of light or heat, and a reticular gel electrolyte is obtained by cross-linking.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a gel polymer electrolyte for a soft package lithium battery and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme: a gel polymer electrolyte for a soft package lithium battery comprises a gel polymer and an organic electrolyte; the gel polymer is obtained by the chain polymerization reaction of polymer monomers under the action of an initiator;
further, the organic electrolyte comprises an organic solvent, a lithium salt and a functional additive;
further, according to the parts by weight, 70-85 parts of organic solvent, 10-20 parts of lithium salt, 1-5 parts of functional additive, 5-10 parts of polymer monomer and 1-2 parts of initiator are included;
further, the initiator is azobisisobutyronitrile; the polymer monomer is one or two of ethoxylated trimethylolpropane triacrylate and pentaerythritol triacrylate;
further, the organic solvent is a carbonate organic solvent;
further, the organic solvent is one or more of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate;
further, the lithium salt is LiPF6Or LiFSI;
the further technical proposal is that the functional additive is vinylene carbonate and 1, 3-propane sultone;
a preparation method of gel polymer electrolyte for soft package lithium battery comprises the following steps:
(1) mixing an organic solvent, lithium salt and a functional additive to prepare an organic electrolyte;
(2) dissolving a polymer monomer in the organic electrolyte prepared in the step (1), mixing and stirring, adding an initiator, and heating for 0.5-1h under a vacuum condition to obtain a gel polymer electrolyte;
the further technical scheme is that the organic solvent is prepared from ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to a mass ratio of 30: 50: 20 examples are prepared and mixed.
The invention has the following advantages: the polymer monomer selected by the invention can rapidly generate chain polymerization reaction under the action of a thermal initiator, the gel polymer with a long-chain structure is obtained through the polymerization reaction, the gel polymer mainly plays a role in supporting a skeleton in a gel polymer electrolyte, an organic solvent is contained in gaps of the polymer, and the gel polymer electrolyte has a jelly-like appearance at normal temperature, cannot freely flow, has good mechanical property and space size stability and has good room-temperature ionic conductivity.
The gel polymer has the advantages of both liquid electrolyte and solid electrolyte, and avoids the safety problems that the liquid electrolyte is easy to leak or release inflammable steam and the like and the defects that the solid electrolyte has low ionic conductivity and the like.
Drawings
FIG. 1 shows the results of the cycling tests for the blank and gel groups.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In addition, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, or orientations or positional relationships that the products of the present invention conventionally lay out when in use, or orientations or positional relationships that are conventionally understood by those skilled in the art, which are merely for convenience of describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used merely to distinguish one description from another, and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should also be noted that, unless otherwise explicitly specified or limited, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1: a gel polymer electrolyte for a soft package lithium battery comprises a gel polymer and an organic electrolyte; the gel polymer is obtained by the chain polymerization reaction of polymer monomers under the action of an initiator;
the organic electrolyte comprises an organic solvent, lithium salt and a functional additive;
according to the weight portion, the organic solvent comprises 70-85 portions of organic solvent, 10-20 portions of lithium salt, 1-5 portions of functional additive, 5-10 portions of polymer monomer and 1-2 portions of initiator;
the initiator is azobisisobutyronitrile; the polymer monomer is one or two of ethoxylated trimethylolpropane triacrylate and pentaerythritol triacrylate;
the action mechanism is as follows:
1) azo-bis-isobutyronitrile decomposes to generate free radicals:
2) the primary radical reacts with the monomer to form a monomeric radical:
3) chain extension reaction:
the organic solvent is a carbonate organic solvent;
the organic solvent is one or more of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate;
the lithium salt is LiPF6Or LiFSI;
the functional additives are vinylene carbonate and 1, 3-propane sultone;
the preparation method of the gel polymer electrolyte for the soft package lithium battery comprises the following steps:
(1) mixing an organic solvent, lithium salt and a functional additive to prepare an organic electrolyte;
(2) dissolving a polymer monomer in the organic electrolyte prepared in the step (1), mixing and stirring, adding an initiator, and heating for 0.5-1h under a vacuum condition to obtain a gel polymer electrolyte;
the organic solvent is prepared from ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to a mass ratio of 30: 50: 20 examples are prepared and mixed.
Example 2: a gel polymer electrolyte for a soft package lithium battery comprises a gel polymer and an organic electrolyte; the gel polymer is obtained by the chain polymerization reaction of polymer monomers under the action of an initiator;
the organic electrolyte comprises an organic solvent, lithium salt and a functional additive;
according to the parts by weight, the composite material comprises 70 parts of organic solvent, 10 parts of lithium salt, 1 part of functional additive, 5 parts of polymer monomer and 1 part of initiator;
the initiator is azobisisobutyronitrile; the polymer monomer is ethoxylated trimethylolpropane triacrylate;
the organic solvent is a carbonate organic solvent;
the organic solvent is one or more of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate;
the lithium salt is LiFSI;
the functional additives are vinylene carbonate and 1, 3-propane sultone;
the preparation method of the gel polymer electrolyte for the soft package lithium battery comprises the following steps:
(1) mixing an organic solvent, lithium salt and a functional additive to prepare an organic electrolyte;
(2) dissolving a polymer monomer in the organic electrolyte prepared in the step (1), mixing and stirring, adding an initiator, and heating for 0.5h under a vacuum condition to obtain a gel polymer electrolyte;
the organic solvent is prepared from ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to a mass ratio of 30: 50: 20 examples are prepared and mixed.
Example 3: a gel polymer electrolyte for a soft package lithium battery comprises a gel polymer and an organic electrolyte; the gel polymer is obtained by the chain polymerization reaction of polymer monomers under the action of an initiator;
the organic electrolyte comprises an organic solvent, lithium salt and a functional additive;
according to parts by weight, the composite material comprises 85 parts of organic solvent, 20 parts of lithium salt, 5 parts of functional additive, 10 parts of polymer monomer and 2 parts of initiator;
the initiator is azobisisobutyronitrile; the polymer monomer is pentaerythritol triacrylate;
the organic solvent is a carbonate organic solvent;
the organic solvent is one or more of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate;
the lithium salt is LiPF6；
The functional additives are vinylene carbonate and 1, 3-propane sultone;
the preparation method of the gel polymer electrolyte for the soft package lithium battery comprises the following steps:
(1) mixing an organic solvent, lithium salt and a functional additive to prepare an organic electrolyte;
(2) dissolving a polymer monomer in the organic electrolyte prepared in the step (1), mixing and stirring, adding an initiator, and heating for 1h under a vacuum condition to obtain a gel polymer electrolyte;
the organic solvent is prepared from ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to a mass ratio of 30: 50: 20 examples are prepared and mixed.
Example 4: a gel polymer electrolyte for a soft package lithium battery comprises a gel polymer and an organic electrolyte; the gel polymer is obtained by the chain polymerization reaction of polymer monomers under the action of an initiator;
the organic electrolyte comprises an organic solvent, lithium salt and a functional additive;
the lithium ion battery comprises 81 parts of organic solvent, 15 parts of lithium salt, 8 parts of polymer monomer and 1 part of initiator according to parts by weight; the functional additive comprises 1 part of vinylene carbonate and 1.5 parts of 1, 3-propane sultone;
the initiator is azobisisobutyronitrile; the polymer monomer is ethoxylated trimethylolpropane triacrylate or pentaerythritol triacrylate;
the organic solvent is a carbonate organic solvent;
the organic solvent is one or more of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate;
the lithium salt is LiPF6；
The preparation method of the gel polymer electrolyte for the soft package lithium battery comprises the following steps:
(1) mixing an organic solvent, lithium salt and a functional additive to prepare an organic electrolyte;
(2) dissolving a polymer monomer in the organic electrolyte prepared in the step (1), mixing and stirring, adding an initiator, and heating for 0.5 under a vacuum condition to obtain a gel polymer electrolyte;
the organic solvent is prepared and mixed by ethylene carbonate and methyl ethyl carbonate according to the mass ratio of 2: 3.
Example 5: electrochemical performance test of cell
Blank group: the lithium ion battery comprises an organic solvent, lithium salt and a functional additive, wherein the organic solvent is ethylene carbonate and methyl ethyl carbonate, the mass ratio of the ethylene carbonate to the methyl ethyl carbonate is 2:3, the addition amount of the ethylene carbonate to the methyl ethyl carbonate is 81 parts, and the lithium salt is LiPF615 parts of lithium salt, 1 part of vinylene carbonate and 1.5 parts of 1, 3-propane sultone as functional additives;
gel group: on the basis of a blank group, adding 8 parts of polymer monomer ethoxylated trimethylolpropane triacrylate and 1 part of initiator to obtain azobisisobutyronitrile;
control group: adding 8 parts of polymer monomer ethoxylated trimethylolpropane triacrylate on the basis of the gel group, but not adding an initiator, and heating for 5 hours to perform a crosslinking reaction;
the gel polymer electrolyte and the blank electrolyte are respectively assembled into a battery and then subjected to cycle performance test, and the method comprises the following steps: lithium cobaltate is used as a positive electrode material, a negative electrode is made of a silicon-carbon composite material, current collectors of the positive electrode and the negative electrode are distributed to be aluminum foil and copper foil, a diaphragm is made of a ceramic diaphragm to form a soft package battery, electrolyte and gel polymer electrolyte are respectively injected into the soft package battery, the soft package battery is assembled in a glove box, the blank battery is stood for 9 hours at normal temperature for testing, the gel polymer battery is heated for 1 hour at 65 ℃, and then stood for 8 hours at normal temperature for testing. The battery is activated by charging and discharging at 1/10C 3.0V to 4.2V respectively at the constant temperature of 25 ℃, and the battery is charged and discharged at 0.5C in cycles at 25 ℃ after standing for 24 h. The basic performance and cycle test results of the battery are shown in the following table 1, and after 350 cycles, the capacity retention rate of the gel battery reaches 80%, and the good electrochemical performance is shown.
TABLE 1 Battery base Performance
| Group of | Initial capacity (mAh) | First time efficiency | Internal resistance of battery (m omega) |
| Blank group | 2060 | 94％ | 28 |
| Gel polymers | 2025 | 92％ | 32 |
| Control group | 2000 | 85％ | 36 |
TABLE 2 results of the cycling tests
Example 6: effect of initiators on chain extension reactions and cell Performance
Blank group: the lithium ion battery comprises an organic solvent, lithium salt and a functional additive, wherein the organic solvent is ethylene carbonate and methyl ethyl carbonate, the mass ratio of the ethylene carbonate to the methyl ethyl carbonate is 2:3, the addition amount of the ethylene carbonate to the methyl ethyl carbonate is 81 parts, and the lithium salt is LiPF615 parts of lithium salt, 1 part of vinylene carbonate and 1.5 parts of 1, 3-propane sultone as functional additives;
gel set 1: on the basis of a blank group, adding 8 parts of polymer monomer ethoxylated trimethylolpropane triacrylate and 1 part of initiator to obtain azobisisobutyronitrile;
gel group 2: on the basis of a blank group, 8 parts of polymer monomer pentaerythritol triacrylate and 1 part of initiator are added to prepare azobisisobutyronitrile;
gel group 3: on the basis of a blank group, adding 4 parts of polymer monomer pentaerythritol triacrylate and 4 parts of polymer monomer pentaerythritol triacrylate; and 1 part of initiator is azobisisobutyronitrile;
control group 1: adding 8 parts of polymer monomer ethoxylated trimethylolpropane triacrylate on the basis of the gel group, but not adding an initiator, and heating for 5 hours to perform a crosslinking reaction;
control group 2: adding 8 parts of polymer monomer pentaerythritol triacrylate on the basis of the gel group, but not adding an initiator, and heating for 5 hours to perform a crosslinking reaction;
control group 3: adding 4 parts of polymer monomer pentaerythritol triacrylate and 4 parts of polymer monomer pentaerythritol triacrylate on the basis of the gel group, but not adding an initiator, and heating for 5 hours to perform a crosslinking reaction;
the gel polymer electrolyte and the blank electrolyte are respectively assembled into a battery and then subjected to cycle performance test, and the method comprises the following steps: lithium cobaltate is used as a positive electrode material, a negative electrode is made of a silicon-carbon composite material, current collectors of the positive electrode and the negative electrode are distributed to be aluminum foil and copper foil, a diaphragm is made of a ceramic diaphragm to form a soft package battery, electrolyte and gel polymer electrolyte are respectively injected into the soft package battery, the soft package battery is assembled in a glove box, the blank battery is stood for 9 hours at normal temperature for testing, the gel polymer battery is heated for 1 hour at 65 ℃, and then stood for 8 hours at normal temperature for testing. The battery is activated by charging and discharging at 1/10C 3.0V to 4.2V respectively at the constant temperature of 25 ℃, and the battery is charged and discharged at 0.5C in cycles at 25 ℃ after standing for 24 h. The basic performance and cycle test results of the battery are shown in the following table 1, and after 350 cycles, the capacity retention rate of the gel battery reaches 80%, and the good electrochemical performance is shown.
TABLE 3 Battery base Performance
From the results in table 3, it is known that, because it is difficult to mix two or more monomers uniformly during in-situ polymerization, the two or more monomers are not uniformly distributed on the surface of the electrode after gelation at high temperature, and the uniformity of the prepared battery is poor, resulting in large internal resistance of the control group 3, and when two monomers are polymerized, under the action of azobisisobutyronitrile as an initiator, the two monomers are not only uniformly mixed to generate a synergistic effect, but also are beneficial to cross-linking of the two monomers, and the gel battery with smaller internal resistance is obtained by polymerization. In addition, after one monomer is polymerized, the performance of the battery is better than that of two monomers in the aspects of efficiency and internal resistance of the battery, and the battery is polymerized under the initiator azodiisobutyronitrile.
Example 7: safety performance test of battery
A. High temperature testing
For comparison of high temperature resistance, the test is carried out according to 6.2.6 requirements in GB/T31485-2015 and is compared with a blank liquid battery. Experimental results as shown in the following table, the gel battery was swollen only without the occurrence of the combustion phenomenon, which indicates that no significant thermal runaway phenomenon occurred inside the gel battery, that is, the safety of the gel battery was much higher than that of the liquid battery in practical use.
TABLE 4 high temperature test results
B. Squeeze test
For comparison of the cell's resistance to deformation, reference is made to the 6.2.7 requirements of GB/T31485-2015 and comparison with a blank liquid cell. The experimental results are shown in the following table, and the gel battery is deformed only without the occurrence of the combustion phenomenon, which indicates that the gel battery will have much higher safety than the liquid battery in practical use.
TABLE 5 extrusion test results
| Item | Post hot box test condition |
| Gel battery | The 5 batteries have no phenomena of smoking, ignition and explosion |
| Blank liquid battery | 2 batteries are used for smoking, and the smoke is discharged,3 stand up to fire for explosion |
C. Needle stick test
For comparing the safety performance of the battery, 6.2.8 requirements in GB/T31485-2015 are referred to and compared with a blank liquid battery. The experimental results are shown in the following table, and no occurrence of smoke, fire, explosion, etc. after puncturing of the gel battery indicates that the gel battery will have much higher safety than the liquid battery in practical use.
TABLE 6 needling test results
| Item | Post hot box test condition |
| Gel battery | The 5 batteries have no phenomena of smoking, ignition and explosion |
| Blank liquid battery | 3 batteries smoke and 2 batteries are fired and exploded |
The cycle performance test shows that the gel battery has comparable capacity and cycle stability compared with the liquid battery, and the capacity retention rate is 80% after 350 cycles at room temperature. The safety performance test shows that the gel battery has more excellent safety performance than the liquid battery.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (10)
1. A gel polymer electrolyte for a soft package lithium battery comprises a gel polymer and an organic electrolyte; the method is characterized in that: the gel polymer is obtained by chain polymerization of polymer monomers under the action of initiator.
2. The gel polymer electrolyte for a soft packed lithium battery as claimed in claim 1, wherein: the organic electrolyte includes an organic solvent, a lithium salt and a functional additive.
3. The gel polymer electrolyte for a soft packed lithium battery as claimed in claim 3, wherein: according to the weight portion, the organic solvent comprises 70-85 portions of organic solvent, 10-20 portions of lithium salt, 1-5 portions of functional additive, 5-10 portions of polymer monomer and 1-2 portions of initiator.
4. The gel polymer electrolyte for a soft packed lithium battery as claimed in claim 3, wherein: the initiator is azobisisobutyronitrile; the polymer monomer is one or two of ethoxylated trimethylolpropane triacrylate and pentaerythritol triacrylate.
5. The gel polymer electrolyte for a soft packed lithium battery as claimed in claim 3, wherein: the organic solvent is a carbonate organic solvent.
6. The gel polymer electrolyte for a soft packed lithium battery as claimed in claim 5, wherein: the organic solvent is one or more of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate.
7. The gel polymer electrolyte for a soft packed lithium battery as claimed in claim 3, wherein:the lithium salt is LiPF6Or LiFSI.
8. The gel polymer electrolyte for a soft packed lithium battery as claimed in claim 3, wherein: the functional additive is vinylene carbonate and 1, 3-propane sultone.
9. A method for preparing a gel polymer electrolyte for a lithium pouch battery as claimed in any one of claims 1 to 8, comprising the steps of:
(1) mixing an organic solvent, lithium salt and a functional additive to prepare an organic electrolyte;
(2) and (2) dissolving a polymer monomer in the organic electrolyte prepared in the step (1), mixing and stirring, adding an initiator, and heating for 0.5-1h under a vacuum condition to obtain the gel polymer electrolyte.
10. The method for preparing the gel polymer electrolyte for the soft package lithium battery as claimed in claim 9, wherein the organic solvent is prepared from ethylene carbonate, ethyl methyl carbonate and diethyl carbonate in a mass ratio of 30: 50: 20 examples are prepared and mixed.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114221021A (en) * | 2021-12-10 | 2022-03-22 | 惠州亿纬锂能股份有限公司 | In-situ cured polymer electrolyte, preparation method thereof and lithium ion battery |
| CN114335700A (en) * | 2022-01-13 | 2022-04-12 | 湖南立方新能源科技有限责任公司 | Solid electrolyte membrane and preparation method thereof, secondary battery and preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101563808A (en) * | 2006-12-21 | 2009-10-21 | 株式会社Lg化学 | Gel polymer electrolyte composition, gel polymer electrolyte and electrochemical device comprising the same |
| CN103840198A (en) * | 2012-11-20 | 2014-06-04 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery gel polymer electrolyte and preparation method thereof |
| CN106532115A (en) * | 2016-11-25 | 2017-03-22 | 张家港市国泰华荣化工新材料有限公司 | Gel electrolyte and lithium-sulfur secondary battery |
| CN111490287A (en) * | 2020-04-09 | 2020-08-04 | 湖南立方新能源科技有限责任公司 | Solid electrolyte, solid battery and preparation method thereof |
| CN111816925A (en) * | 2020-08-14 | 2020-10-23 | 中南大学 | Solid-state battery and preparation method thereof |
-
2021
- 2021-08-27 CN CN202110992703.7A patent/CN113707936A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101563808A (en) * | 2006-12-21 | 2009-10-21 | 株式会社Lg化学 | Gel polymer electrolyte composition, gel polymer electrolyte and electrochemical device comprising the same |
| CN103840198A (en) * | 2012-11-20 | 2014-06-04 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery gel polymer electrolyte and preparation method thereof |
| CN106532115A (en) * | 2016-11-25 | 2017-03-22 | 张家港市国泰华荣化工新材料有限公司 | Gel electrolyte and lithium-sulfur secondary battery |
| CN111490287A (en) * | 2020-04-09 | 2020-08-04 | 湖南立方新能源科技有限责任公司 | Solid electrolyte, solid battery and preparation method thereof |
| CN111816925A (en) * | 2020-08-14 | 2020-10-23 | 中南大学 | Solid-state battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114221021A (en) * | 2021-12-10 | 2022-03-22 | 惠州亿纬锂能股份有限公司 | In-situ cured polymer electrolyte, preparation method thereof and lithium ion battery |
| CN114335700A (en) * | 2022-01-13 | 2022-04-12 | 湖南立方新能源科技有限责任公司 | Solid electrolyte membrane and preparation method thereof, secondary battery and preparation method |
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