CN115678000B - Polytrimethylene carbonate electrolyte, lithium ion battery and preparation method - Google Patents
Polytrimethylene carbonate electrolyte, lithium ion battery and preparation method Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 86
- -1 Polytrimethylene carbonate Polymers 0.000 title claims abstract description 59
- 229920000166 polytrimethylene carbonate Polymers 0.000 title claims abstract description 51
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000005496 eutectics Effects 0.000 claims abstract description 34
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000012656 cationic ring opening polymerization Methods 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 29
- 238000011065 in-situ storage Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 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 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 8
- 239000004014 plasticizer Substances 0.000 claims description 7
- FKOASGGZYSYPBI-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)alumanyl trifluoromethanesulfonate Chemical compound [Al+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F FKOASGGZYSYPBI-UHFFFAOYSA-K 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 4
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 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
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 7
- 230000000977 initiatory effect Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 12
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 7
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
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- Secondary Cells (AREA)
Abstract
The invention discloses a polytrimethylene carbonate electrolyte, a lithium ion battery and a preparation method. The preparation method of the polytrimethylene carbonate electrolyte comprises the following steps: uniformly mixing trimethylene carbonate and lithium salt to obtain a deep eutectic electrolyte, wherein the trimethylene carbonate and unavoidable water existing in the lithium salt are used as an initiator, and under the heating condition, the trimethylene carbonate undergoes cationic ring-opening polymerization to obtain the polytrimethylene carbonate electrolyte. The invention overcomes the defects of severe preparation conditions, difficult removal of non-electrolyte components and the like of the traditional polytrimethylene carbonate electrolyte by designing the deep eutectic electrolyte with double functions of catalysis and initiation as the polymerization reaction precursor liquid for preparing the polytrimethylene carbonate electrolyte.
Description
Technical Field
The invention belongs to the technical field of polymer electrolytes, and particularly relates to a polytrimethylene carbonate electrolyte, a lithium ion battery and a preparation method.
Background
The solid polymer-based lithium ion battery can simultaneously meet the requirements of energy storage equipment on high energy density and safety, so that the solid polymer-based lithium ion battery becomes a research hot spot in the field of energy. However, the most widely studied polyether electrolyte systems are limited by ionic conductivity and electrochemical stability window, and cannot meet the practical application requirements of lithium batteries. Compared with polyether electrolyte matrix, the polycarbonate has more excellent comprehensive performance, and is one of the most potential matrix materials in the field of polymer electrolytes. The polytrimethylene carbonate has the advantages of good biocompatibility, low crystallinity, high thermodynamic and electrochemical stability and the like, and is an excellent lithium ion carrier. However, the preparation of polytrimethylene carbonate generally adopts a ring-opening reaction catalyzed by a transition metal complex or an organic compound containing an ionic hydrogen bond (see non-patent document 1, prog. Polym. Sci.,2022,125,101484), and has disadvantages such as severe reaction conditions, difficult removal of non-electrolyte components such as solvents and catalysts, and the like.
In addition, the polytrimethylene carbonate obtained by the above method is further mixed with lithium salt by a solution casting film forming method to prepare an electrolyte. However, the solvent remaining during the preparation process is liable to react with the electrode material, and the prepared polytrimethylene carbonate electrolyte is poor in contact and compatibility with the electrode interface, and it is difficult to realize a long-term stable cycle of the lithium battery (see non-patent documents 2,Solid State Ionics,2014,262,738-742).
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a polytrimethylene carbonate electrolyte, a lithium ion battery and a preparation method thereof, and aims to overcome the defects of severe preparation conditions, impurity introduction and the like of the conventional polytrimethylene carbonate electrolyte and solve the defects of poor compatibility between a polymer electrolyte and electrodes, large interface impedance, poor cycling stability and the like in the ex-situ lithium battery assembly technology.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a polytrimethylene carbonate electrolyte, which is a novel deep eutectic electrolyte having both catalytic and initiating functions based on coordination of trimethylene carbonate and lithium salt, uniformly mixing trimethylene carbonate and lithium salt to obtain the deep eutectic electrolyte, wherein unavoidable water present in the trimethylene carbonate and the lithium salt is used as an initiator, and the trimethylene carbonate undergoes cationic ring-opening polymerization under heating to obtain the polytrimethylene carbonate electrolyte.
Preferably, the lithium salt includes at least one of lithium bis (trifluoromethanesulfonyl) imide, lithium difluorooxalato borate, lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, and lithium trifluoromethanesulfonate.
Preferably, the molar ratio of trimethylene carbonate to lithium salt in the deep eutectic electrolyte is 1:1 to 12:1.
Preferably, the reaction temperature of the cationic ring-opening polymerization reaction is 30-80 ℃ and the reaction time is 0.5-24 hours.
Preferably, the unavoidable water concentration present in the trimethylene carbonate and lithium salt is 0.01% -0.3% by mass.
Preferably, the preparation method further comprises adding an inorganic salt to the deep eutectic electrolyte, wherein the inorganic salt comprises at least one of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium acetate, potassium thiocyanate, tin fluoride and aluminum triflate, and preferably, the molar ratio of the lithium salt to the inorganic salt is 1: (0.01-0.1). The addition of the inorganic salt can increase the polymerization rate and improve the cycle stability of the battery.
Preferably, the preparation method further comprises adding a plasticizer to the deep eutectic electrolyte, the plasticizer comprising at least one of sulfolane and divinyl sulfone.
It should be noted that the water content in the environment affects the polymerization degree of the polymer during the preparation process of the polytrimethylene carbonate electrolyte, so that the polytrimethylene carbonate electrolyte is prepared under the anhydrous and anaerobic condition as a preferable mode, and the polymerization degree of the polymerization reaction is more controllable under the anhydrous condition.
According to another aspect of the present invention, there is provided a polytrimethylene carbonate electrolyte.
According to still another aspect of the present invention, there is provided a method for preparing a lithium ion battery, uniformly mixing trimethylene carbonate and lithium salt to obtain a deep eutectic electrolyte, assembling the lithium ion battery using the deep eutectic electrolyte, and heating the lithium ion battery to form a polytrimethylene carbonate electrolyte in situ in the lithium ion battery; preferably, the heating temperature is 30-80 ℃ and the heating time is 0.5-24 hours.
According to yet another aspect of the present invention, a lithium ion battery is provided.
In general, the above technical solutions conceived by the present invention can achieve at least the following advantageous effects compared to the prior art.
(1) In the present invention, trimethylene carbonate has a low melting point of 46 ℃ and is capable of forming a liquid deep eutectic electrolyte by coordination of electron rich carbonyl groups with lithium ions. Meanwhile, the coordination of the trimethylene carbonate and lithium ions reduces the electron cloud density of carbonyl carbon atoms, thereby catalyzing the trimethylene carbonate to undergo cationic ring-opening polymerization to form the polytrimethylene carbonate electrolyte in situ. Therefore, the invention overcomes the defects of the existing polytrimethylene carbonate electrolyte such as harsh preparation conditions and difficult removal of non-electrolyte components by designing the deep eutectic electrolyte with double functions of catalysis and initiation as the polymerization reaction precursor liquid for preparing the polytrimethylene carbonate electrolyte.
(2) The invention prepares the polytrimethylene carbonate electrolyte by an in-situ polymerization method of the deep eutectic electrolyte, overcomes the defects of poor electrolyte-electrode interface contact property and compatibility and the like existing in the polytrimethylene carbonate electrolyte prepared by an ex-situ method, thereby reducing interface impedance and promoting lithium ion conduction.
(3) According to the invention, the components of the deep eutectic electrolyte are optimized, and the inorganic salt is added to improve the polymerization reaction rate and the stability of the electrolyte-electrode interface, so that the long-time stable cycle performance of the polytrimethylene carbonate-based lithium battery is realized.
(4) According to the invention, sulfolane and divinyl sulfone plasticizers can be added to prepare the polytrimethylene carbonate gel electrolyte, so that the ionic conductivity is improved and the rate capability of the applied lithium battery is improved.
Drawings
Fig. 1 is a charge-discharge cycle chart of a lithium-iron phosphate lithium battery based on polytrimethylene carbonate electrolyte in example 2;
FIG. 2 is an ion conductivity diagram of a lithium battery based on polytrimethylene carbonate electrolyte as in example 3;
FIG. 3 is a lithium deposition diagram of a lithium battery based on polytrimethylene carbonate electrolyte as in example 4;
fig. 4 is a graph of electrochemical stability windows for a lithium battery based on polytrimethylene carbonate electrolyte as in example 5.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
The present embodiment provides a polytrimethylene carbonate electrolyte, the preparation method of which comprises:
mixing trimethylene carbonate, lithium bistrifluoromethylsulfonyl imide and aluminum triflate under anhydrous and oxygen-isolated conditions and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium bis (trifluoromethanesulfonyl) imide and aluminum triflate is 5:1:0.1; heating at 80 ℃ for 12 hours to obtain the polytrimethylene carbonate electrolyte.
Example 2
The embodiment provides a lithium ion battery, and the preparation method thereof is as follows:
mixing trimethylene carbonate, lithium bistrifluoromethylsulfonyl imide and aluminum triflate under anhydrous and oxygen-isolated conditions and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium bis (trifluoromethanesulfonyl) imide and aluminum triflate is 5:1:0.1; adding sulfolane with the mass fraction of 20%, uniformly stirring, and dripping on a cellulose support film to assemble a lithium-iron phosphate lithium battery; the assembled battery was heated at 80 ℃ for 12 hours and subjected to battery charge-discharge cycle testing.
Fig. 1 is a charge-discharge cycle diagram of an in-situ assembled lithium polytrimethylene carbonate-based lithium iron phosphate battery as described in example 2. As can be seen from fig. 1, the polytrimethylene carbonate electrolyte prepared by the method has good interface stability with lithium metal and lithium iron phosphate electrode, and the battery can stably charge and discharge for more than 1000 times.
Example 3
The embodiment provides a lithium ion battery, and the preparation method thereof is as follows:
mixing trimethylene carbonate, lithium bistrifluoro methanesulfonimide and lithium nitrate under anhydrous and oxygen-isolated conditions and stirring at room temperature to form a deep eutectic electrolyte; trimethylene carbonate, lithium bis (trifluoromethanesulfonyl) imide and lithium nitrate were combined in a molar ratio of 5:1:0.1 with stainless steel to form a coin cell and heated at 60 ℃ for 5 hours for conductivity testing. Fig. 2 is an ion conductivity diagram of an in situ assembled polytrimethylene carbonate electrolyte coin cell as described in example 3.
Example 4
The embodiment provides a lithium ion battery, and the preparation method thereof is as follows:
mixing trimethylene carbonate and lithium bistrifluoro methanesulfonimide under the condition of no water and isolating oxygen, and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate to lithium bis (trifluoromethanesulfonyl) imide was 5:1, assembled with lithium sheets into coin lithium symmetric cells and heated at 80 ℃ for 24 hours and subjected to lithium deposition testing. Fig. 3 is a lithium deposition diagram of an in-situ assembled polytrimethylene carbonate electrolyte coin cell as described in example 4.
Example 5
The embodiment provides a lithium ion battery, and the preparation method thereof is as follows:
mixing trimethylene carbonate, lithium bistrifluoro methanesulfonimide and lithium bromide under anhydrous and oxygen-isolated conditions and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium bis (trifluoromethanesulfonyl) imide and lithium nitrate was 8:1:0.1, assembled into lithium symmetric coin cells and heated at 80 ℃ for 1 hour and tested for electrochemical stability window. Fig. 4 is a graph of electrochemical stability windows of an in-situ assembled polytrimethylene carbonate electrolyte lithium symmetric cell as described in example 5.
Example 6
The embodiment provides a lithium ion battery, and the preparation method thereof is as follows:
mixing trimethylene carbonate, lithium triflate and lithium acetate under anhydrous and oxygen-isolated conditions and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium triflate and lithium fluoride was 5:1:0.1, assembled into lithium symmetric coin cells and lithium-iron phosphate lithium cells, respectively, and heated at 80 ℃ for 24 hours to prepare polytrimethylene carbonate electrolyte in situ.
Example 7
The embodiment provides a lithium ion battery, and the preparation method thereof is as follows:
mixing trimethylene carbonate, lithium triflate and lithium acetate under anhydrous and oxygen-isolated conditions and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium bistrifluoro methanesulfonimide and lithium acetate was 5:1:0.1, assembled into lithium symmetric coin cells and lithium-iron phosphate lithium cells, respectively, and heated at 80 ℃ for 24 hours to prepare polytrimethylene carbonate electrolyte in situ.
Example 8
The embodiment provides a lithium ion battery, and the preparation method thereof is as follows:
mixing trimethylene carbonate, lithium perchlorate and potassium thiocyanate under anhydrous and oxygen-isolated conditions and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate to lithium bis (trifluoromethanesulfonyl) imide to potassium thiocyanate is 5:1:0.1, divinyl sulfone plasticizer is added, and the lithium symmetrical button cell and the lithium-ferric phosphate lithium cell are respectively assembled and heated at 80 ℃ for 10 hours to prepare the polymer in situ
Trimethylene carbonate gel electrolyte.
Example 9
The embodiment provides a lithium ion battery, and the preparation method thereof is as follows:
mixing trimethylene carbonate, lithium difluorooxalato borate and lithium iodide under anhydrous and oxygen-isolated conditions and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate to lithium difluorooxalato borate to lithium iodide is 10:1:0.1, a divinyl sulfone plasticizer is added, and the lithium symmetric button cell and the lithium-iron phosphate lithium cell are respectively assembled and heated at 80 ℃ for 5 hours to prepare the polytrimethylene carbonate gel electrolyte in situ.
Example 10
The embodiment provides a lithium ion battery, and the preparation method thereof is as follows:
mixing trimethylene carbonate, lithium hexafluorophosphate and lithium chloride under anhydrous and oxygen-isolated conditions and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium hexafluorophosphate and lithium chloride was 5:1:0.05, assembled into lithium symmetric coin cells and lithium-iron phosphate lithium cells, respectively, and heated at 80 ℃ for 12 hours to prepare polytrimethylene carbonate electrolyte in situ.
Example 11
The embodiment provides a lithium ion battery, and the preparation method thereof is as follows:
mixing trimethylene carbonate, lithium tetrafluoroborate and tin fluoride under anhydrous and oxygen-isolated conditions and stirring at room temperature to form a deep eutectic electrolyte; the molar ratio of trimethylene carbonate, lithium tetrafluoroborate and tin fluoride was 5:1:0.1, assembled into lithium symmetric coin cells and lithium-nickel cobalt manganese cells, respectively, and heated at 80 ℃ for 12 hours to prepare polytrimethylene carbonate electrolyte in situ.
The invention prepares the polytrimethylene carbonate electrolyte based on in-situ polymerization of the deep eutectic electrolyte by designing the trimethylene carbonate based deep eutectic electrolyte with double functions of catalysis and initiation, and is applied to a lithium ion battery, and the polytrimethylene carbonate electrolyte with excellent comprehensive electrochemical performance is obtained by improving the overall synthesis route design of the corresponding preparation method, parameter conditions of each process step (such as the types and the proportion of reactants in each reaction step, the reaction temperature and the reaction time) and the like, and compared with the prior art, on one hand, the design of the deep eutectic electrolyte with the integrated catalysis initiation can solve the defects of rigor preparation condition, difficult removal of non-electrolyte components and the like of the traditional polytrimethylene carbonate electrolyte, and reduce the reaction cost; on the other hand, the in-situ polymerization method can obviously reduce the interface impedance between the electrolyte and the electrode, and can obviously improve the interface stability of the electrolyte and the electrode by optimizing the components of the deep eutectic precursor liquid, thereby endowing the lithium battery with ultra-long charge-discharge cycle performance.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A method for preparing a polytrimethylene carbonate electrolyte, comprising:
uniformly mixing trimethylene carbonate and lithium salt to obtain deep eutectic electrolyte, wherein the trimethylene carbonate and unavoidable water existing in the lithium salt are used as an initiator, and the trimethylene carbonate undergoes cationic ring-opening polymerization under a heating condition, so that the polytrimethylene carbonate electrolyte is obtained, and the heating condition is that the temperature is 60-80 ℃ for 5-24 hours.
2. The method of preparing according to claim 1, wherein the lithium salt comprises at least one of lithium bistrifluoromethane sulfonimide, lithium difluorooxalato borate, lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, and lithium trifluoromethane sulfonate.
3. The method of claim 1 or 2, wherein the molar ratio of trimethylene carbonate to lithium salt in the deep eutectic electrolyte is 1:1 to 12:1.
4. The process according to claim 1, wherein the concentration by mass of unavoidable water present in the trimethylene carbonate and lithium salt is 0.01% -0.3%.
5. The method of preparing according to claim 1, further comprising adding an inorganic salt to the deep eutectic electrolyte, the inorganic salt comprising at least one of lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium acetate, potassium thiocyanate, tin fluoride, and aluminum triflate, the molar ratio of the lithium salt to the inorganic salt being 1: (0.01-0.1).
6. The method of preparing according to claim 1, further comprising adding a plasticizer to the deep eutectic electrolyte, the plasticizer comprising at least one of sulfolane and divinyl sulfone; the polytrimethylene carbonate electrolyte is prepared under the anhydrous and anaerobic condition.
7. A polytrimethylene carbonate electrolyte prepared by the preparation process of any one of claims 1-6.
8. A preparation method of a lithium ion battery is characterized in that trimethylene carbonate and lithium salt are uniformly mixed to obtain deep eutectic electrolyte, unavoidable water existing in the trimethylene carbonate and the lithium salt is used as an initiator, the deep eutectic electrolyte is utilized to assemble the lithium ion battery, and then the lithium ion battery is heated to form polytrimethylene carbonate electrolyte in situ in the lithium ion battery; the heating temperature is 60-80 ℃ and the heating time is 5-24 hours.
9. A lithium ion battery prepared by the preparation method of claim 8.
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| CN1449422A (en) * | 2000-02-29 | 2003-10-15 | 国际壳牌研究有限公司 | Improved method for production of poly(trimethylene carbonate) |
| CN108923064A (en) * | 2018-07-10 | 2018-11-30 | 山西长韩新能源科技有限公司 | A kind of solid macromolecule electrolyte and preparation method thereof and lithium ion secondary battery |
| CN110350243A (en) * | 2019-07-30 | 2019-10-18 | 华中科技大学 | A kind of in-situ preparation method and its application of polymer dielectric |
| CN110854429A (en) * | 2019-11-18 | 2020-02-28 | 成都新柯力化工科技有限公司 | Particle composite membrane coated polymer electrolyte and preparation method thereof |
| CN111916819A (en) * | 2020-07-08 | 2020-11-10 | 成都新柯力化工科技有限公司 | Preparation method of layered polymer solid electrolyte of lithium battery |
| EP4011947A1 (en) * | 2020-12-10 | 2022-06-15 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Preparation of a solid electrolyte made of polycarbonates |
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| AU2003244476A1 (en) * | 2002-02-07 | 2003-09-02 | Ucb, S.A. | Process using a cyclic carbonate reactant |
| FR3120742B1 (en) * | 2021-03-09 | 2023-06-16 | Commissariat Energie Atomique | Composite electrode comprising a solid electrolyte based on polycarbonates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449422A (en) * | 2000-02-29 | 2003-10-15 | 国际壳牌研究有限公司 | Improved method for production of poly(trimethylene carbonate) |
| CN108923064A (en) * | 2018-07-10 | 2018-11-30 | 山西长韩新能源科技有限公司 | A kind of solid macromolecule electrolyte and preparation method thereof and lithium ion secondary battery |
| CN110350243A (en) * | 2019-07-30 | 2019-10-18 | 华中科技大学 | A kind of in-situ preparation method and its application of polymer dielectric |
| CN110854429A (en) * | 2019-11-18 | 2020-02-28 | 成都新柯力化工科技有限公司 | Particle composite membrane coated polymer electrolyte and preparation method thereof |
| CN111916819A (en) * | 2020-07-08 | 2020-11-10 | 成都新柯力化工科技有限公司 | Preparation method of layered polymer solid electrolyte of lithium battery |
| EP4011947A1 (en) * | 2020-12-10 | 2022-06-15 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Preparation of a solid electrolyte made of polycarbonates |
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