CN117855594A - In-situ preparation method of solid polymer electrolyte, recovery method of solid polymer electrolyte and lithium ion battery - Google Patents
In-situ preparation method of solid polymer electrolyte, recovery method of solid polymer electrolyte and lithium ion battery Download PDFInfo
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 97
- 239000007787 solid Substances 0.000 title claims abstract description 79
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 65
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000011084 recovery Methods 0.000 title claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 47
- 239000003999 initiator Substances 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 36
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 30
- 239000011265 semifinished product Substances 0.000 claims abstract description 11
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims abstract description 6
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 37
- 239000000047 product Substances 0.000 claims description 11
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 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
- 229920000573 polyethylene Polymers 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
- MBVGJZDLUQNERS-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound FC(F)(F)C1=NC(C#N)=C(C#N)N1 MBVGJZDLUQNERS-UHFFFAOYSA-N 0.000 claims description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 4
- IYOMQTGPEVJQDR-UHFFFAOYSA-N B([O-])(O)O.[Li+].C(CC(=O)O)(=O)O.C(CC(=O)O)(=O)O Chemical compound B([O-])(O)O.[Li+].C(CC(=O)O)(=O)O.C(CC(=O)O)(=O)O IYOMQTGPEVJQDR-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 4
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 3
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000011152 fibreglass Substances 0.000 claims 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 238000004064 recycling Methods 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000003912 environmental pollution Methods 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- CHZUADMGGDUUEF-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Co+2] Chemical compound [Mn](=O)(=O)([O-])[O-].[Co+2] CHZUADMGGDUUEF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
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Abstract
The invention belongs to the field of lithium ion batteries, and particularly relates to an in-situ preparation method of a solid polymer electrolyte, a recovery method of the solid polymer electrolyte and a lithium ion battery. The preparation method provided by the invention comprises the following steps: a) Loading an electrolyte precursor on the surface of a battery diaphragm, and then assembling the electrolyte precursor with a positive electrode of a lithium ion battery and a negative electrode of the lithium ion battery to obtain a semi-finished product of the lithium ion battery; in the step a), the electrolyte precursor comprises a polymerization monomer, lithium salt and an initiator, wherein the lithium salt is lithium perchlorate, lithium hexafluorophosphate, lithium difluorophosphate and the like; b) And under the heating condition, the electrolyte precursor in the semi-finished product of the lithium ion battery is polymerized in situ on the battery diaphragm to obtain the solid polymer electrolyte loaded on the battery diaphragm. The preparation method provided by the invention does not need to add a catalyst, and the prepared solid polymer electrolyte can be depolymerized in a heating mode, so that the preparation method has good environmental benefit and economic benefit.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to an in-situ preparation method of a solid polymer electrolyte, a recovery method of the solid polymer electrolyte and a lithium ion battery.
Background
Lithium ion batteries have been widely used in various fields such as new energy vehicles, consumer electronics and energy storage. The lithium battery has higher energy density and longer cycle life, the energy density can reach 100-200Wh/kg, the cycle life is more than 1000 times, and the lithium battery is far higher than other secondary batteries, and is the object of great development at present. Most of the lithium ion batteries commercialized in the market at present are liquid lithium ion batteries, wherein the electrolyte used is low-boiling point and easy-to-burn organic liquid such as carbonic ester, ether and the like. Once the internal short circuit of the liquid battery generates a large amount of heat, the safety accident of battery burning and even explosion is very easy to occur. Compared with the traditional electrolyte lithium ion battery with an amateur state, the solid polymer battery has higher safety, better mechanical property and stronger processability, and can use high-energy-density electrode materials such as metal lithium and the like to further improve the energy density of the battery. Therefore, the solid polymer battery has very wide application prospect.
Compared with the liquid electrolyte 10 -2 ～10 -3 S·cm -1 The development of solid polymer electrolytes is limited by their low ionic conductivity (typically at 10 -5 ～10 -6 S·cm -1 ). Because of its low ionic conductivity, solid polymer batteries are difficult to use at room temperature, difficult to implement fast charge techniques, and because of their high internal resistance, irreversible energy loss can be caused during charging, resulting in capacity degradation. In addition, the preparation process of the solid polymer battery is complex, and the solid polymer electrolyte needs to be prepared in advance and then assembled with the positive and negative plates of the battery in a winding or lamination mode. The all-solid-state battery inner electrode obtained by the ectopic preparation method,The poor interfacial compatibility of the solid electrolyte results in very high interfacial impedance, severely affects the power density of the battery, and has complex preparation process and high cost.
To solve the above-mentioned problems of the ex-situ preparation of solid polymer electrolytes, researchers have continuously issued systems for preparing solid polymer electrolytes by in-situ polymerization directly on battery modules. However, existing techniques for preparing solid polymer electrolytes by in situ polymerization generally require additional catalyst introduction, which may lead to deterioration of battery performance.
In addition, as the market share of lithium ion batteries continues to expand, the problem of disposal of batteries after use also develops. The common solid polymer electrolyte is based on polyolefin or polyether structure, and is difficult to degrade and separate from lithium salt, so that the common treatment mode of the current solid polymer electrolyte is landfill or combustion, thereby not only wasting a large amount of high-value electrolyte salt, but also possibly causing environmental pollution.
Disclosure of Invention
In view of the above, the present invention aims to provide an in-situ preparation method of a solid polymer electrolyte, a recovery method thereof and a lithium ion battery, wherein the preparation method provided by the present invention uses electrolyte salt as a catalyst, does not need an additional catalyst, and avoids the deterioration of the battery performance caused by the additional catalyst; in addition, the prepared solid polymer electrolyte can be depolymerized in a heating mode after being used, so that the recycling of the polymerized monomer and lithium salt in the solid polymer electrolyte is realized, and the solid polymer electrolyte has good environmental benefit and economic benefit.
The invention provides an in-situ preparation method of a solid polymer electrolyte, which comprises the following steps:
a) Loading an electrolyte precursor on the surface of a battery diaphragm, and then assembling the battery diaphragm loaded with the electrolyte precursor, a positive electrode of a lithium ion battery and a negative electrode of the lithium ion battery to obtain a semi-finished product of the lithium ion battery;
in the step a), the electrolyte precursor comprises a polymerization monomer, lithium salt and an initiator, wherein the polymerization monomer is one or more of cyclic carbonate, lactone, lactide and cyclic ketoacetal, the lithium salt is one or more of lithium perchlorate, lithium hexafluorophosphate, lithium difluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium tetrafluoroborate, lithium bismalonate borate, lithium hexafluoroarsonate, lithium trifluoromethylsulfonate, lithium bistrifluoromethane sulfonyl imide, lithium bistrifluoromethane sulfonyl methyl and 4, 5-dicyano-2-trifluoromethyl imidazole, and the initiator is one or more of carboxylic acid initiator, alcohol initiator, phenol initiator and amine initiator;
b) And under the heating condition, the electrolyte precursor in the semi-finished product of the lithium ion battery is polymerized in situ on the battery diaphragm to obtain the solid polymer electrolyte loaded on the battery diaphragm.
Preferably, the polymeric monomer is one or more of trimethylene carbonate, ethylene carbonate, epsilon-caprolactone, beta-butyrolactone, and lactide; the initiator is one or more of terephthalic acid, trimesic acid, terephthalyl alcohol, dipentaerythritol, 1, 4-butanediol and hydroquinone.
Preferably, the molar ratio of the polymerized monomer to the lithium salt to the initiator is 300 (20-60): 1-2.
Preferably, the heating temperature is 80-150 ℃; the heating time is 0.5-24 h.
Preferably, the material of the positive electrode of the lithium ion battery is one or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt manganate and lithium nickel cobalt oxide.
Preferably, the material of the lithium ion battery anode is one or more of lithium, graphite, soft carbon, hard carbon and silicon.
Preferably, the battery separator is one or more of a glass fiber separator, a cellulose separator, a polyethylene separator, and a polypropylene separator.
The invention provides a method for recycling solid polymer electrolyte, which comprises the following steps:
the solid polymer electrolyte prepared by the preparation method is collected, heated and depolymerized, and the product is separated and recovered to obtain the polymerized monomer and/or lithium salt.
Preferably, the temperature of the heating depolymerization is 150-200 ℃; the heating depolymerization time is 0.5-10 h.
The invention provides a lithium ion battery, comprising: the lithium ion battery positive electrode, the lithium ion battery negative electrode, the battery diaphragm and the electrolyte are solid polymer electrolyte prepared by the preparation method according to the technical scheme.
Compared with the prior art, the invention provides an in-situ preparation method of a solid polymer electrolyte, a recovery method thereof and a lithium ion battery. The preparation method provided by the invention comprises the following steps: a) Loading an electrolyte precursor on the surface of a battery diaphragm, and then assembling the battery diaphragm loaded with the electrolyte precursor, a positive electrode of a lithium ion battery and a negative electrode of the lithium ion battery to obtain a semi-finished product of the lithium ion battery; in the step a), the electrolyte precursor comprises a polymerization monomer, lithium salt and an initiator, wherein the polymerization monomer is one or more of cyclic carbonate, lactone, lactide and cyclic ketoacetal, the lithium salt is one or more of lithium perchlorate, lithium hexafluorophosphate, lithium difluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium tetrafluoroborate, lithium bismalonate borate, lithium hexafluoroarsonate, lithium trifluoromethylsulfonate, lithium bistrifluoromethane sulfonyl imide, lithium bistrifluoromethane sulfonyl methyl and 4, 5-dicyano-2-trifluoromethyl imidazole, and the initiator is one or more of carboxylic acid initiator, alcohol initiator, phenol initiator and amine initiator; b) And under the heating condition, the electrolyte precursor in the semi-finished product of the lithium ion battery is polymerized in situ on the battery diaphragm to obtain the solid polymer electrolyte loaded on the battery diaphragm. The preparation method provided by the invention does not need to add a catalyst, and the prepared solid polymer electrolyte can be depolymerized in a heating mode, so that the preparation method has good environmental benefit and economic benefit.
More specifically, the following technical advantages are achieved:
(1) The existing technical scheme for preparing the solid polymer electrolyte by in-situ polymerization requires additional introduction of a catalyst, and the mode may deteriorate the performance of the battery; in the invention, lithium salt is used as a catalyst, so that possible adverse side reactions in the battery are avoided, and the electrolyte formula is simplified.
(2) The polymer electrolyte contains a large amount of high-value electrolyte salt, the existing solid polymer electrolyte prepared by in-situ polymerization is based on a polyolefin or polyether structure, and the polymer is difficult to degrade and separate from lithium salt, so that the polymer electrolyte can only be buried or burnt after being abandoned, thereby not only wasting a large amount of high-value electrolyte salt, but also possibly causing environmental pollution; the polymer electrolyte obtained by the invention can be depolymerized by heating after being used, and then high-value lithium salt and partial reaction monomers in the electrolyte can be recovered by simple separation steps (recrystallization, sublimation and the like), so that the problem of environmental pollution caused by the polymer electrolyte is solved, and the economic benefit is also improved.
(3) The solid polymer electrolyte prepared by the prior technical scheme depends on crosslinking reaction or cationic polymerization, the structure and molecular weight of the product are difficult to regulate and control, and the performance of the battery is difficult to optimize by regulating and controlling the polymerization reaction; the invention can precisely regulate the molecular weight and chain structure of the polymerization product by regulating the dosage of the initiator and the number of functional groups in the initiator molecule, and can prepare the solid polymer electrolyte with high ionic conductivity by optimizing the reaction conditions.
(4) The method is limited by uncontrollable polymer structure, and the ionic conductivity of the prepared all-solid polymer electrolyte is low at room temperature, and the conductivity can be improved only by adding a plasticizer and the like, so that the formula is more complex; the solid polymer electrolyte obtained by the invention can accurately regulate and control the polymerization reaction degree by adjusting the heating time and the temperature, so that the residual polymer monomer is used as an internal plasticizer, and the formula of the electrolyte is simplified.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an EIS spectrum provided in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum provided in example 1 of the present invention;
fig. 3 is a nuclear magnetic lithium spectrum provided in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an in-situ preparation method of a solid polymer electrolyte, which comprises the following steps:
a) Loading an electrolyte precursor on the surface of a battery diaphragm, and then assembling the battery diaphragm loaded with the electrolyte precursor, a positive electrode of a lithium ion battery and a negative electrode of the lithium ion battery to obtain a semi-finished product of the lithium ion battery;
b) And under the heating condition, the electrolyte precursor in the semi-finished product of the lithium ion battery is polymerized in situ on the battery diaphragm to obtain the solid polymer electrolyte loaded on the battery diaphragm.
In the preparation method provided by the invention, in the step a), the electrolyte precursor comprises a polymerized monomer, lithium salt and an initiator; wherein the polymeric monomer is one or more of cyclic carbonates, lactones, lactide and cyclic ketoacetals, preferably one or more of trimethylene carbonate, ethylene carbonate, epsilon-caprolactone, beta-butyrolactone and lactide; the lithium salt is one or more of lithium perchlorate, lithium hexafluorophosphate, lithium difluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium tetrafluoroborate, lithium bismalonate borate, lithium hexafluoroarsenate, lithium bistrifluoromethane sulfonyl imide, lithium bistrifluoromethane sulfonyl methyl and 4, 5-dicyano-2-trifluoromethylimidazole; the initiator is one or more of carboxylic acid initiator, alcohol initiator, phenol initiator and amine initiator, preferably one or more of terephthalic acid, trimesic acid, terephthalyl alcohol, dipentaerythritol, 1, 4-butanediol and hydroquinone. In the invention, the molar ratio of the polymerized monomer to the lithium salt to the initiator is preferably 300 (20-60): 1-2), wherein the molar ratio of the polymerized monomer to the lithium salt can be specifically 300:20, 300:25, 300:30, 300:35, 300:40, 300:45, 300:50, 300:55 or 300:60, and the molar ratio of the polymerized monomer to the initiator is preferably 300:1, 300:1.1, 300:1.2, 300:1.3, 300:1.4, 300:1.5, 300:1.6, 300:1.7, 300:1.8, 300:1.9 or 300:2.
In the preparation method provided by the invention, in the step a), the electrolyte precursor is preferably loaded on the surface of the battery separator in a solution state. In the present invention, when the electrolyte precursor is not in a solution state at room temperature, it is preferably heated to a solution state.
In the preparation method provided by the invention, in the step a), the battery separator is preferably one or more of a glass fiber separator, a cellulose separator, a polyethylene separator and a polypropylene separator.
In the preparation method provided by the invention, in the step a), the material of the positive electrode of the lithium ion battery is preferably one or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium manganese iron phosphate, lithium nickelate cobalt manganate and lithium nickelate cobalt materials.
In the preparation method provided by the invention, in the step a), the material of the lithium ion battery anode is preferably one or more of lithium, graphite, soft carbon, hard carbon and silicon.
In the preparation method provided by the invention, in the step b), before the heating, the semi-finished product of the lithium ion battery is preferably kept stand for a period of time so as to ensure that the electrolyte precursor is fully contacted with the electrode.
In the preparation method provided by the invention, in the step b), the heating temperature is preferably 80-150 ℃, and can be specifically 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃; the heating time is preferably 0.5 to 24 hours, and may be specifically 0.5 hours, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 6 hours, 8 hours, 12 hours, 16 hours or 24 hours.
The invention also provides a recovery method of the solid polymer electrolyte, which comprises the following steps:
the solid polymer electrolyte prepared by the preparation method is collected, heated and depolymerized, and the product is separated and recovered to obtain the polymerized monomer and/or lithium salt.
In the recovery method provided by the invention, the temperature of the heating depolymerization is preferably 150-200 ℃, and specifically can be 150 ℃, 155 ℃, 160 ℃, 165 ℃,170 ℃, 175 ℃,180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃; the heating depolymerization time is preferably 0.5 to 10 hours, and may specifically be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours.
In the recovery process provided by the present invention, the product is preferably isolated in a manner that is recrystallised and/or sublimated.
The invention also provides a lithium ion battery, comprising: the lithium ion battery positive electrode, the lithium ion battery negative electrode, the battery diaphragm and the electrolyte are solid polymer electrolyte prepared by the preparation method according to the technical scheme.
In the lithium ion battery provided by the invention, the positive electrode of the lithium ion battery, the negative electrode of the lithium ion battery and the battery diaphragm are already described in the in-situ preparation method of the solid polymer electrolyte described above, and are not described in detail herein.
The technical scheme provided by the invention does not need to add a catalyst in the process of preparing the solid polymer electrolyte in situ, and the prepared solid polymer electrolyte can be depolymerized in a heating mode, so that the method has good environmental benefit and economic benefit. More specifically, the following technical advantages are achieved:
(1) The existing technical scheme for preparing the solid polymer electrolyte by in-situ polymerization requires additional introduction of a catalyst, and the mode may deteriorate the performance of the battery; in the invention, lithium salt is used as a catalyst, so that possible adverse side reactions in the battery are avoided, and the electrolyte formula is simplified.
(2) The polymer electrolyte contains a large amount of high-value electrolyte salt, the existing solid polymer electrolyte prepared by in-situ polymerization is based on a polyolefin or polyether structure, and the polymer is difficult to degrade and separate from lithium salt, so that the polymer electrolyte can only be buried or burnt after being abandoned, thereby not only wasting a large amount of high-value electrolyte salt, but also possibly causing environmental pollution; the polymer electrolyte obtained by the invention can be depolymerized by heating after being used, and then high-value lithium salt and partial reaction monomers in the electrolyte can be recovered by simple separation steps (recrystallization, sublimation and the like), so that the problem of environmental pollution caused by the polymer electrolyte is solved, and the economic benefit is also improved.
(3) The solid polymer electrolyte prepared by the prior technical scheme depends on crosslinking reaction or cationic polymerization, the structure and molecular weight of the product are difficult to regulate and control, and the performance of the battery is difficult to optimize by regulating and controlling the polymerization reaction; the invention can precisely regulate the molecular weight and chain structure of the polymerization product by regulating the dosage of the initiator and the number of functional groups in the initiator molecule, and can prepare the solid polymer electrolyte with high ionic conductivity by optimizing the reaction conditions.
(4) The method is limited by uncontrollable polymer structure, and the ionic conductivity of the prepared all-solid polymer electrolyte is low at room temperature, and the conductivity can be improved only by adding a plasticizer and the like, so that the formula is more complex; the solid polymer electrolyte obtained by the invention can accurately regulate and control the polymerization reaction degree by adjusting the heating time and the temperature, so that the residual polymer monomer is used as an internal plasticizer, and the formula of the electrolyte is simplified.
For clarity, the following examples are provided in detail.
Example 1
(1) Preparing a polymer electrolyte precursor solution:
1.0g of trimethylene carbonate was weighed out as a polymerization monomer, 281.2mg of lithium bistrifluoromethane sulfonyl imide was used as a catalyst and a lithium source, and 4.5mg of terephthalyl alcohol was used as an initiator, and the mixture was uniformly mixed at 45 ℃.
(2) In-situ polymerization to prepare a solid-state battery:
assembling a lithium ion button cell in an argon glove box, wherein the anode is a commercial nickel cobalt lithium manganate pole piece, the cathode is a commercial graphite pole piece, and the diaphragm is a commercial glass fiber diaphragm; and (3) dripping 100 mu L of the polymer electrolyte precursor solution onto a glass fiber diaphragm, assembling a button cell, standing for 2 hours in a glove box to ensure that the electrolyte and the electrode material are fully soaked, and then placing in a 110 ℃ oven to keep the temperature for 1 hour for in-situ polymerization to form the lithium ion button cell with the solid polymer electrolyte. Performing 0.2C constant current charge and discharge test on the prepared lithium ion button cell at room temperature, wherein the capacity retention rate is 95.0% after 50 weeks of circulation, and the capacity retention rate is 89.6% under 1C multiplying power; the solid polymer electrolyte prepared by the above method was tested for ionic conductivity, resulting in an ionic conductivity of 1.2mS/cm at room temperature (25 ℃) and an EIS spectrum as shown in FIG. 1 below.
(3) Depolymerizing and recycling high-value lithium salt:
collecting the prepared solid polymer electrolyte in a reaction tube, heating in an oil bath at 180 ℃ for 1h, adding diethyl ether into the depolymerized product for recrystallization, wherein the lower layer is prepared into trimethylene carbonate crystals, the nuclear magnetic hydrogen spectrum is shown as the following figure 2, the recovery rate is 85%, the upper layer diethyl ether solution is dried to obtain lithium bistrifluoromethane sulfonyl imide, the recovery rate is 96%, and the nuclear magnetic lithium spectrum is shown as the following figure 3.
Example 2
(1) Preparing a polymer electrolyte precursor solution:
1.0g of trimethylene carbonate is respectively weighed in an argon glove box as a polymerization monomer, 182.0mg of lithium hexafluoroarsenate is used as a catalyst and a lithium source, 16.6mg of dipentaerythritol is used as an initiator, and the mixture is uniformly mixed at 45 ℃ to obtain a polymer electrolyte precursor solution ([ monomer ]/[ lithium salt ]/[ initiator ] =300/30/2).
(2) In-situ polymerization to prepare a solid-state battery:
assembling a lithium ion button cell in an argon glove box, wherein the anode is a commercial lithium iron manganese phosphate pole piece, the cathode is a commercial graphite pole piece, and the diaphragm is a commercial cellulose diaphragm; and (3) dripping 100 mu L of the polymer electrolyte precursor solution onto a cellulose diaphragm, assembling a button cell, standing for 2 hours in a glove box to ensure that the electrolyte and the electrode material are fully soaked, and then placing in a 110 ℃ oven to keep the temperature for 2 hours for in-situ polymerization to form the lithium ion button cell with the solid polymer electrolyte. Performing 0.2C constant current charge and discharge test on the prepared lithium ion button cell at room temperature, wherein the capacity retention rate is 92.8% after 50 weeks of circulation, and the capacity retention rate is 88.2% under 1C multiplying power; the ionic conductivity of the solid polymer electrolyte prepared by the above method was measured and found to be 0.95mS/cm at room temperature.
(3) Depolymerizing and recycling high-value lithium salt:
collecting the prepared solid polymer electrolyte in a reaction tube, heating in an oil bath at 180 ℃ for 1h, adding diethyl ether into a depolymerized product for recrystallization, obtaining trimethylene carbonate crystals at the lower layer, and drying an diethyl ether solution at the upper layer to obtain lithium hexafluorophosphate with a recovery rate of 96%.
Example 3
(1) Preparing a polymer electrolyte precursor solution:
1.0g epsilon-caprolactone is respectively weighed in an argon glove box as a polymerization monomer, 266.2mg lithium hexafluorophosphate is used as a catalyst and a lithium source, 4.9mg terephthalic acid is used as an initiator, and the mixture is uniformly mixed to obtain a polymer electrolyte precursor solution ([ monomer ]/[ lithium salt ]/[ initiator ] = 300/60/1).
(2) In-situ polymerization to prepare a solid-state battery:
assembling a lithium ion button cell in an argon glove box, wherein the anode is a commercial lithium iron phosphate pole piece, the cathode is a commercial graphite pole piece, and the diaphragm is a commercial polypropylene diaphragm; and (3) dripping 100 mu L of the polymer electrolyte precursor solution onto a polypropylene diaphragm, assembling a button cell, standing for 2 hours in a glove box to ensure that the electrolyte and the electrode material are fully soaked, and then placing in a 100 ℃ oven to keep the temperature for 1 hour for in-situ polymerization to form the lithium ion button cell with the solid polymer electrolyte. Performing 0.2C constant current charge and discharge test on the prepared lithium ion button cell at room temperature, wherein the capacity retention rate is 91.3% after 50 weeks of circulation, and the capacity retention rate is 84.9% under 1C multiplying power; the ionic conductivity of the solid polymer electrolyte prepared by the above method was measured and found to be 1.1mS/cm at room temperature.
(3) Depolymerizing and recycling high-value lithium salt:
collecting the prepared solid polymer electrolyte in a reaction tube, connecting a cold trap, heating in an oil bath at 150 ℃ for 1h under vacuum condition, collecting epsilon-caprolactone in the cold trap, and recrystallizing the residual solid in diethyl ether to obtain lithium hexafluorophosphate with a recovery rate of 93%.
Example 4
(1) Preparing a polymer electrolyte precursor solution:
1.0g of lactide is respectively weighed in an argon glove box as a polymerization monomer, 49.2mg of lithium perchlorate is used as a catalyst and a lithium source, 5.1mg of hydroquinone is used as an initiator, and the mixture is uniformly mixed at 95 ℃ to obtain a polymer electrolyte precursor solution ([ monomer ]/[ lithium salt ]/[ initiator ] = 300/20/2).
(2) In-situ polymerization to prepare a solid-state battery:
assembling a lithium metal button cell in an argon glove box, wherein the anode is a commercial lithium cobaltate pole piece, the cathode is a commercial lithium cobaltate piece, and the diaphragm is a commercial polypropylene diaphragm; and (3) dripping 100 mu L of the polymer electrolyte precursor solution onto a polypropylene diaphragm, assembling a button cell, standing for 2 hours in a glove box to ensure that the electrolyte and the electrode material are fully soaked, and then placing in a 120 ℃ oven to keep the temperature for 0.5 hour for in-situ polymerization to form the cell with the solid polymer electrolyte. Performing 0.2C constant current charge and discharge test on the prepared lithium ion button cell at room temperature, wherein the capacity retention rate is 79.6% after 50 weeks of circulation, and the capacity retention rate is 74% under 1C multiplying power; the ionic conductivity of the solid polymer electrolyte prepared by the above method was measured and found to be 0.76mS/cm at room temperature.
(3) Depolymerizing and recycling high-value lithium salt:
collecting the prepared solid polymer electrolyte in a reaction tube, heating in 170 ℃ oil bath for 1h, adding diethyl ether into the depolymerized product for recrystallization, obtaining lactide at the lower layer, obtaining lithium hexafluorophosphate with the recovery rate of 85%, and drying the diethyl ether solution at the upper layer to obtain lithium hexafluorophosphate with the recovery rate of 89%.
Example 5
(1) Preparing a polymer electrolyte precursor solution:
1.0g of ethylene carbonate is respectively weighed in an argon glove box as a polymerization monomer, 177.4mg of lithium tetrafluoroborate is used as a catalyst and a lithium source, 8.0mg of trimesic acid is used as an initiator, and the mixture is uniformly mixed, so that a polymer electrolyte precursor solution ([ monomer ]/[ lithium salt ]/[ initiator ] = 300/50/1) is obtained.
(2) In-situ polymerization to prepare a solid-state battery:
assembling a lithium metal button cell in an argon glove box, wherein the anode is a commercial lithium nickelate pole piece, the cathode is a commercial lithium nickelate piece, and the diaphragm is a commercial polyethylene diaphragm; and (3) dripping 100 mu L of the polymer electrolyte precursor solution onto a polyethylene diaphragm, assembling a button cell, standing for 2 hours in a glove box to ensure that the electrolyte and the electrode material are fully soaked, and then placing in a baking oven at 150 ℃ for heat preservation for 1 hour to perform in-situ polymerization to form the cell with the solid polymer electrolyte. Performing 0.1C constant current charge and discharge test on the prepared lithium ion button cell at room temperature, wherein the capacity retention rate is 90.6% after 50 weeks of circulation, and the capacity retention rate is 86.5% under 1C multiplying power; the ionic conductivity of the solid polymer electrolyte prepared by the above method was measured and found to be 0.88mS/cm at room temperature.
(3) Depolymerizing and recycling high-value lithium salt:
collecting the prepared solid polymer electrolyte in a reaction tube, connecting a cold trap, heating in an oil bath at 200 ℃ under vacuum for 1h, collecting ethylene carbonate in the cold trap, and recrystallizing the residual solid in diethyl ether to obtain lithium tetrafluoroborate with a recovery rate of 94 percent.
Example 6
(1) Preparing a polymer electrolyte precursor solution:
1.0g of beta-butyrolactone is respectively weighed in an argon glove box as a polymerization monomer, 181.2mg of lithium trifluoromethane sulfonate is used as a catalyst and a lithium source, 3.5mg of 1, 4-butanediol is used as an initiator, and the mixture is uniformly mixed, so that a polymer electrolyte precursor solution ([ monomer ]/[ lithium salt ]/[ initiator ] =300/30/1) is obtained.
(2) In-situ polymerization to prepare a solid-state battery:
assembling a lithium metal button battery in an argon glove box, wherein the anode is a commercial lithium manganate pole piece, the cathode is a commercial lithium metal pole piece, and the diaphragm is a commercial glass fiber diaphragm; and (3) dripping 100 mu L of the polymer electrolyte precursor solution onto a glass fiber diaphragm, assembling a button cell, standing for 2 hours in a glove box to ensure that the electrolyte and the electrode material are fully soaked, and then placing in a 100 ℃ oven to keep the temperature for 2 hours for in-situ polymerization to form the lithium ion button cell with the solid polymer electrolyte. Performing 0.2C constant current charge and discharge test on the prepared lithium ion button cell at room temperature, wherein the capacity retention rate is 81.6% after cycling for x weeks, and the capacity retention rate is 76% under 1C multiplying power; the ionic conductivity of the solid polymer electrolyte prepared by the above method was measured and found to be 0.61mS/cm at room temperature.
(3) Depolymerizing and recycling high-value lithium salt:
collecting the prepared solid polymer electrolyte in a reaction tube, connecting a cold trap, heating in an oil bath at 170 ℃ for 3 hours under vacuum condition, collecting beta-butyrolactone in the cold trap, and recrystallizing the residual solid in diethyl ether to obtain lithium trifluoromethylsulfonate with a recovery rate of 74% and a recovery rate of 81%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An in situ method for preparing a solid polymer electrolyte, comprising the steps of:
a) Loading an electrolyte precursor on the surface of a battery diaphragm, and then assembling the battery diaphragm loaded with the electrolyte precursor, a positive electrode of a lithium ion battery and a negative electrode of the lithium ion battery to obtain a semi-finished product of the lithium ion battery;
in the step a), the electrolyte precursor comprises a polymerization monomer, lithium salt and an initiator, wherein the polymerization monomer is one or more of cyclic carbonate, lactone, lactide and cyclic ketoacetal, the lithium salt is one or more of lithium perchlorate, lithium hexafluorophosphate, lithium difluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium tetrafluoroborate, lithium bismalonate borate, lithium hexafluoroarsonate, lithium trifluoromethylsulfonate, lithium bistrifluoromethane sulfonyl imide, lithium bistrifluoromethane sulfonyl methyl and 4, 5-dicyano-2-trifluoromethyl imidazole, and the initiator is one or more of carboxylic acid initiator, alcohol initiator, phenol initiator and amine initiator;
b) And under the heating condition, the electrolyte precursor in the semi-finished product of the lithium ion battery is polymerized in situ on the battery diaphragm to obtain the solid polymer electrolyte loaded on the battery diaphragm.
2. The in situ preparation process of claim 1, wherein the polymeric monomer is one or more of trimethylene carbonate, ethylene carbonate, epsilon-caprolactone, beta-butyrolactone, and lactide; the initiator is one or more of terephthalic acid, trimesic acid, terephthalyl alcohol, dipentaerythritol, 1, 4-butanediol and hydroquinone.
3. The in situ preparation process according to claim 1, wherein the molar ratio of the polymerized monomer, lithium salt and initiator is 300 (20-60): 1-2.
4. The in situ preparation process according to claim 1, wherein the heating temperature is 80-150 ℃; the heating time is 0.5-24 h.
5. The in-situ preparation method according to claim 1, wherein the material of the positive electrode of the lithium ion battery is one or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt manganate and lithium nickel cobaltate.
6. The in-situ preparation method according to claim 1, wherein the material of the lithium ion battery anode is one or more of lithium, graphite, soft carbon, hard carbon and silicon.
7. The in situ preparation process of claim 1, wherein the battery separator is one or more of a fiberglass separator, a cellulose separator, a polyethylene separator, and a polypropylene separator.
8. A method for recovering a solid polymer electrolyte, comprising the steps of:
the solid polymer electrolyte produced by the production method according to any one of claims 1 to 7 is collected, heated for depolymerization, and the product is separated and recovered to obtain a polymerized monomer and/or a lithium salt.
9. The recovery method according to claim 8, wherein the temperature of the thermal depolymerization is 150 to 200 ℃; the heating depolymerization time is 0.5-10 h.
10. A lithium ion battery, comprising: a positive electrode for a lithium ion battery, a negative electrode for a lithium ion battery, a battery separator, and an electrolyte, characterized in that the electrolyte is a solid polymer electrolyte produced by the production method according to any one of claims 1 to 7.
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