CN117175000A - Zwitterionic polymer-based lithium ion battery electrolyte and preparation method thereof - Google Patents
Zwitterionic polymer-based lithium ion battery electrolyte and preparation method thereof Download PDFInfo
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- CN117175000A CN117175000A CN202311137987.7A CN202311137987A CN117175000A CN 117175000 A CN117175000 A CN 117175000A CN 202311137987 A CN202311137987 A CN 202311137987A CN 117175000 A CN117175000 A CN 117175000A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 50
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- -1 carbonate compound Chemical class 0.000 claims abstract description 17
- 239000003365 glass fiber Substances 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- 150000003254 radicals Chemical class 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 41
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229920000620 organic polymer Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- HBJICDATLIMQTJ-UHFFFAOYSA-N C(O)(O)=O.C(=C)C=CC=C Chemical compound C(O)(O)=O.C(=C)C=CC=C HBJICDATLIMQTJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- KPBSJEBFALFJTO-UHFFFAOYSA-N propane-1-sulfonyl chloride Chemical compound CCCS(Cl)(=O)=O KPBSJEBFALFJTO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000005956 quaternization reaction Methods 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 1
- 229910013063 LiBF 4 Inorganic materials 0.000 claims 1
- 229910013870 LiPF 6 Inorganic materials 0.000 claims 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 1
- 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 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000005012 migration Effects 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002001 electrolyte material Substances 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 239000012453 solvate Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 229910001220 stainless steel Inorganic materials 0.000 description 11
- 239000010935 stainless steel Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- 210000000227 basophil cell of anterior lobe of hypophysis Anatomy 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 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
- 239000000463 material Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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 belongs to the technical field of lithium ion battery electrolytes, and particularly relates to a polymer-based lithium ion battery electrolyte of amphoteric ions and a preparation method thereof. The electrolyte material can be prepared on a battery cathode material through free radical in-situ polymerization, so that interface impedance is greatly reduced, and the rate performance and the cycle performance of the battery are improved. In addition, an organic solvent is introduced as a plasticizer, so that the battery has high conductivity; introducing a zwitterion to solvate the lithium salt and dendrite-free deposition of lithium; the glass fiber is introduced so that the lithium migration number is increased. The electrolyte integrally uses the carbonate compound, has high chemical stability, and can be applied to high-voltage lithium batteries; the preparation process is favorable for battery integration and mass production; no solvent exists in the production process, so that the environmental pollution is reduced, and the cost is reduced.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery electrolytes, and particularly relates to a polymer-based lithium ion battery electrolyte of amphoteric ions and a preparation method thereof.
Background
Lithium batteries are widely used in commercial portable electronic devices, but to expand the lithium batteries to air transportation modes such as electric vehicles and unmanned aerial vehicles, very significant improvements in terms of safety and energy density are required. This is a major challenge facing current battery systems because of the volatile and flammable liquid carbonate electrolytes contained in the battery systems. Although these liquid electrolytes have high ionic conductivity, their high flammability, low thermal stability, and inability to inhibit lithium dendrite growth are causes of fire and explosion hazards of the battery, and the liquid electrolytes have low energy density, which is disadvantageous for lightweight battery systems. The replacement of conventional liquid electrolytes with polymer electrolytes has been recognized as an effective method to overcome the safety and energy density problems of lithium-based batteries. The polymer electrolyte needs to meet high performance requirements, such as high ion conductivity, high lithium ion migration number, good mechanical strength, wide electrochemical window and excellent chemical and thermal stability, for use in lithium-based batteries, however, the existing materials and techniques have difficulty in meeting the requirements at the same time.
Zwitterionic is a unique class of locally charged but globally neutral molecules in which the cationic and anionic groups are covalently linked, zwitterionic compound electrolytes have many advantages due to their unique molecular structure. First, the strong dipole moment generated by the molecular structure can promote the dissolution of lithium salts. Second, the cationic component of the zwitterionic compound can greatly inhibit movement of anions in the electrolyte, preventing depletion of anions near the anode region. Furthermore, the uniformly arranged anionic components in the zwitterionic compound can effectively regulate Li + Flux distribution, anion immobilization and Li regulation + Can achieve dendrite-free deposition. However, the molecular structure of the zwitterionic is still very limited. The cationic groups are mainly heterocyclic imidazole, and the anionic groups are mainly sulfonate, carboxylate and the like; unfortunately, these negatively charged groups have too strong coulombic interactions with lithium ions in the electrolyte, which severely impedes migration of lithium ions at potential and results in a fairly low migration number.
Disclosure of Invention
Aiming at the problems or the defects, the invention provides a zwitterionic polymer-based lithium ion battery electrolyte and a preparation method thereof, which are used for solving the problem of the cycle stability of a polymer-based semi-solid electrolyte battery.
A polymer-based lithium ion battery electrolyte of amphoteric ion is composed of organic polymer, organic solvent and lithium salt, and has ionic conductivity of 8×10 at 30deg.C -4 ～1.15×10 -3 S/cm。
The organic polymer is prepared by double bond free radical polymerization of zwitterionic monomer (15-20 wt.%), carbonic ester monomer (70-80 wt.%) and polyethylene glycol acrylic ester monomer (8-15 wt.%) and the total content is 1.
Wherein the zwitterionic monomer is 3- (N, N-diallyl-N-methyl ammonium) propane sulfonate (DMA-SO) with double bond 3 - ) Or ((3- (diallyl (methyl) amino) propyl) sulfonyl) (trifluoromethyl) sulfonyl) amide (DMA-SO) 2 N - SO 2 CF 3 ) One or more of the following specific structures:
further, the polyethylene glycol acrylate monomer is one or more of polyethylene glycol dimethacrylate (PEGDMA), polyethylene glycol diacrylate (PEGDA), ethoxylated trimethylolpropane triacrylate (ETPTA) and pentaerythritol triacrylate (PETA). And the relative molecular weight of the monomers is 400-1500 g/mol.
Further, the carbonic ester monomer is one or more of ethylene carbonate (VEC) and divinyl ethylene carbonate.
Further, the organic solvent is one or more of diethyl carbonate (DEC), ethylmethyl carbonate (EMC), ethylene Carbonate (EC), propylene Carbonate (PC), fluoroethylene carbonate (FEC) and dimethyl carbonate (DMC).
Further, the lithium salt is lithium bis (trifluoromethanesulfonyl imide) (LiTFSI), lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) One or more of lithium difluorooxalato borate (LiDFOB).
The preparation method of the amphoteric ion polymer-based lithium ion battery electrolyte comprises the following steps:
step 1, preparing a zwitterionic monomer:
quaternizing N, N-diallyl-N-methylamine and 1, 3-propane sultone in acetonitrile to obtain a zwitterionic monomer DMA-SO 3 - I.e. 3- (N, N-diallyl-N-methyl-ammonium) propanesulfonate with a double bond.
Zwitterionic monomers (DMA-SO) 2 N - SO 2 CF 3 ) Is to first synthesize CF 3 SO 2 NH 2 And K is equal to 2 CO 3 Reaction to CF 3 SO 2 NHK which is then reacted with 1-propanesulfonyl chloride to form Cl-SO 2 NSO 2 CF 3 . Then N, N-diallyl-N-methylamine and Cl-SO are used 2 NSO 2 CF 3 Quaternization in acetonitrile to obtain zwitterionic monomer DMA-SO 2 N - SO 2 CF 3 。
Preparing organic solution with concentration of 0.5-2mol/L by lithium salt and organic solvent.
And step 2, mixing the zwitterionic monomer, the carbonate monomer, the polyethylene glycol acrylic ester monomer, the organic solution obtained in the step 2 and the free radical initiator together to form a uniform transparent solution.
The weight ratio of each component in the uniform transparent solution is recorded by mass fraction: 3 to 6 percent of zwitterionic monomer, 15 to 25 percent of carbonate monomer, 1 to 2.5 percent of polyethylene glycol acrylic ester monomer, 65 to 80 percent of organic solution and 1 to 2 percent of free radical initiator.
And 3, dripping the uniform transparent solution obtained in the step 2 on a glass fiber membrane of Whatman or Millipore, packaging, initiating free radical polymerization through a thermal initiator at the temperature of 50-80 ℃, and realizing in-situ curing on the surface of the negative electrode of the lithium ion battery to obtain the composite semi-solid lithium ion battery electrolyte film with the thickness of 100-200 mu m.
Further, the thermal initiator in the step 3 is one or more of Azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN) and dibenzoyl peroxide (BPO).
Further, the electrolyte of the semi-solid lithium ion battery is the polymer-based lithium ion battery electrolyte of the amphoteric ion prepared on the negative electrode in situ. Compared with the existing electrolyte, the electrolyte material has the following advantages:
1. the electrolyte can be prepared by in-situ polymerization on the battery cathode, so that the interface contact between the electrolyte and the electrode is promoted, the interface impedance of the battery is greatly reduced, and the rate capability and the cycle performance of the battery are improved.
2. The electrolyte provided by the invention introduces the organic solvent as the plasticizer, so that the battery has high conductivity; introducing a zwitterion to solvate the lithium salt and dendrite-free deposition of lithium; the glass fiber is introduced so that the lithium migration number is increased. This achieves a lithium ion battery with better performance.
3. The electrolyte integrally uses the carbonate compound, has high chemical stability, and can be applied to high-voltage lithium batteries; the preparation process is favorable for battery integration and mass production; no solvent exists in the production process, so that the environmental pollution is reduced, and the cost is reduced.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a zwitterionic monomer prepared in the example.
Fig. 2 is a fourier infrared spectrum of the electrolyte prepared in examples 1, 2.
Fig. 3 is a Nyquist impedance plot at 30 ℃ for the Stainless Steel (SS) symmetric cells of the electrolytes prepared in examples 1, 2.
FIG. 4 is a graph showing the results of linear sweep voltammetry at 30℃for Li/SS cells of the electrolytes prepared in examples 1 and 2.
FIG. 5 is a graph showing the cycle performance of the electrolyte Li/LFP batteries prepared in examples 1 and 2, wherein the cut-off voltage is 2.5 to 3.9V at 30℃and the rate is 1C.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following further details of the present invention will be described by means of the accompanying drawings and examples. It should be noted that the examples given are not to be construed as limiting the invention. Insubstantial modifications and variations of the invention as would be apparent to a person skilled in the art in light of the teachings of this invention are intended to be within the scope of this invention.
First, preparation of zwitterionic monomer 3- (N, N-diallyl-N-methyl ammonium) propane sulfonate:
n, N-diallyl-N-methylamine (0.09 mol) and 1, 3-propanesultone (0.1 mol) were reacted in 40ml of acetonitrile at room temperature for 5 hours with stirring. During this time, the product formed a white precipitate. It was then filtered and washed with three portions of 40mL diethyl ether.
Secondly, preparing a positive electrode of the button cell: the positive electrode active material is lithium iron phosphate LiFePO 4 Lithium manganate LiMn 2 O 4 Lithium cobaltate LiCoO 2 Layered high nickel material LiNi 0.8 Co 0.15 Al 0.05 O 2 One or more of them. The negative electrode material is one or more of metallic lithium, silicon carbon negative electrode material and graphite.
In this embodiment: weigh 0.16g LiFePO 4 0.02g of Super-P and 0.02g of PVDF, and 1ml of N-methylpyrrolidone are added and magnetically stirred at a speed of 120r/min for 12h; then the obtained slurry was smeared on an aluminum foil with a doctor blade, and the aluminum foil was dried in a vacuum oven at 80 ℃ for 12 hours to obtain a positive electrode material. The obtained positive electrode active material has a load surface density of 1.13mg/cm 2 。
Example 1
Step 1, placing the Whatman glass fiber membrane in a vacuum drying oven at 60 ℃ for 12 hours to remove adsorbed water. Then, the dried glass fiber film was cut into a 16mm diameter disc, and the disc was put into a glove box filled with argon gas for storage.
And 2, preparing an organic solution with a solute of LiTFSI, a solvent of FEC/DMC (1:4 Vol) and a concentration of 1 mol/L. 0.058g LiTFSI was weighed and dissolved in 0.4ml FEC, 1.6ml DMC mixed solution, and shaken to form a homogeneous transparent solution for use.
Step 3, weighing 0.005g of DMA-SO in a glove box filled with argon 3 - 0.016g of VEC, 0.002g of PEGDMA and 0.002g of Azobisisobutyronitrile (AIBN) were added to 0.75g of the solution prepared in step 2 and dissolved by shaking to form a clear solution.
And 4, in a glove box filled with argon, the electrolyte is polymerized in situ to assemble the stainless steel/electrolyte/stainless steel CR2030 button cell. Firstly, a stainless steel gasket is placed in a positive electrode shell, then the gasket is aligned and covered with the glass fiber film in the step 1, the transparent solution in the step 3 is dripped on the glass fiber film, and then a stainless steel sheet, a spring piece and a negative electrode shell are covered in sequence. Further, the negative side of the coin cell was placed up on a coin cell hydraulic press with insulated tweezers and held at a pressure of 800psi for 20s. Then the mixture is put into a vacuum drying oven to react for 8 hours at 60 ℃. Finally obtaining the polymer base lithium ion battery containing the amphoteric ions.
Likewise, the methods of making lithium/electrolyte/stainless steel cells and lithium/electrolyte/lithium iron phosphate cells are consistent. The difference is that:
and (3) sequentially placing a stainless steel gasket and a lithium negative plate in the positive electrode shell, covering the glass fiber film in the step (1) on the gasket in an aligned manner, dripping the transparent solution in the step (3) on the glass fiber film, and sequentially covering a stainless steel sheet (or a lithium iron phosphate positive plate), a spring piece and the negative electrode shell.
Example 2
This embodiment differs from embodiment 1 in that:
step 3 in a glove box filled with argon, 0.021g VEC, 0.002g PEGDMA and 0.002g Azobisisobutyronitrile (AIBN) were weighed and added to 0.75g of the solution prepared in step 2, and dissolved by shaking to form a clear solution. Example 2 was synthesized without the addition of a zwitterionic monomer polymer-based electrolyte and used as a control experiment.
FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum of the prepared zwitterionic monomer, wherein the assignment of the individual peaks is 1H NMR (400 MHz, D 2 O) delta 6.03 (ddt, j=17.4, 10.3,7.4hz, 2H), 5.78-5.57 (m, 4H), 4.02-3.84 (m, 4H), 3.48-3.34 (m, 2H), 3.02 (s, 3H), 2.96 (t, j=7.2 hz, 2H), 2.32-2.16 (m, 2H). The results indicated that DMA-SO 3 - Is a successful synthesis of (a).
Fig. 2 is a fourier infrared spectrum of the electrolyte prepared in examples 1, 2. Polymer electrolyte IR spectra with zwitterionic monomer added at 1030 and 1151cm -1 Sulfonate SO 3 - And at 1600-1680 cm -1 Between DMA-SO 3 - The disappearance of the carbon-carbon double bonds of VEC and PEGDMA indicates successful polymerization of the individual monomers to form the electrolyte.
Fig. 3 is a Nyquist impedance plot at 30 ℃ for the Stainless Steel (SS) symmetric cells of the electrolytes prepared in examples 1, 2. According to the formula:
wherein l is electrolyte thickness, R b And S is the effective contact area of the electrode and the electrolyte.
Example 2 (0 wt.% DMA-SO) 3 - ) Conductivity at 30℃was 2.09X 10 -3 S/cm, example 1 (5 wt.% DMA-SO) 3 - ) Conductivity at 30℃was 1.15X10 -3 S/cm. The results show that DMA-SO 3 - The addition of the monomer causes a decrease in conductivity due to DMA-SO 3 - Acting as a cross-linking agent increases the degree of cross-linking of the polymer, making the segments more difficult to move.
FIG. 4 is a graph showing the results of linear sweep voltammetry at 30℃for Li/SS cells of the electrolytes prepared in examples 1 and 2. Example 2 (0 wt.% DMA-SO) 3 - ) Oxidation potential reached 4.6V at 30℃at the introduction of 5wt.% DMA-SO 3 - The post oxidation potential was raised to 5.15V, indicating good electrochemical stability.
Fig. 5 (a) shows the Li/LFP battery of the electrolyte prepared in example 2, and fig. 5 (b) shows the cycle performance of example 1, with a cut-off voltage of 2.5 to 3.9V at 30 ℃ and a rate of 0.5C. It can be seen that examples 1 and 2 have a capacity of 160mAh g at 0.5C -1 The average coulombic efficiency exceeds 99.7%, exhibiting excellent battery performance. But example 2 (0 wt.% DMA-SO) 3 - ) After 200 cycles, the capacity retention was 96.58%, while example 1 (5 wt.% DMA-SO) 3 - ) After 200 cycles, the capacity retention was 99.18%. This is a result of regulating the uniform deposition of lithium due to the uniform distribution of the zwitterion.
According to the test results of the above examples and comparative examples, the electrolyte material of the present invention can be prepared on a battery anode material by radical in-situ polymerization, so that the interface impedance is greatly reduced, and the rate performance and the cycle performance of the battery are improved. In addition, an organic solvent is introduced as a plasticizer, so that the battery has high conductivity; introducing a zwitterion to solvate the lithium salt and dendrite-free deposition of lithium; the glass fiber is introduced so that the lithium migration number is increased. In addition, the electrolyte disclosed by the invention integrally uses the carbonate compound, has high chemical stability, and can be applied to a high-voltage lithium battery. The results also confirm that the electrolyte of the present invention has excellent properties, and the conductivity at 30℃is 1.15X10 -3 S/cm, oxidation potential 5.15V, capacity 160mAh g at 0.5C -1 The average coulombic efficiency exceeded 99.7% with a capacity retention of 99.18% after 200 cycles.
Claims (8)
1. A zwitterionic polymer-based lithium ion battery electrolyte, characterized by: is prepared from organic polymer, organic solvent and lithium salt, and has ionic conductivity of 8×10 at 30deg.C -4 ～1.15×10 -3 S/cm；
The organic polymer is prepared by polymerizing 15-20 wt.% of zwitterionic monomer, 70-80 wt.% of carbonate monomer and 8-15 wt.% of polyethylene glycol acrylate monomer through double bond free radical, wherein the total content is 1;
wherein the zwitterionic monomer is 3- (N, N-diallyl-N-methyl ammonium) propane sulfonate (DMA-SO) with double bond 3 - ) Or ((3- (diallyl (methyl) amino) propyl) sulfonyl) (trifluoromethyl) sulfonyl) amide (DMA-SO) 2 N - SO 2 CF 3 ) One or more of the following specific structures:
2. the zwitterionic polymer-based lithium-ion battery electrolyte of claim 1, wherein: the polyethylene glycol acrylic ester monomer is one or more of polyethylene glycol dimethacrylate PEGDMA, polyethylene glycol diacrylate PEGDA, ethoxylated trimethylolpropane triacrylate ETPTA and pentaerythritol triacrylate PETA; and the relative molecular weight of the monomers is 400-1500 g/mol.
3. The zwitterionic polymer-based lithium-ion battery electrolyte of claim 1, wherein: the carbonic ester monomer is one or more of ethylene carbonate VEC and divinyl ethylene carbonate.
4. The zwitterionic polymer-based lithium-ion battery electrolyte of claim 1, wherein: the organic solvent is one or more of diethyl carbonate DEC, methyl ethyl carbonate EMC, ethylene carbonate EC, propylene carbonate PC, fluoroethylene carbonate FEC and dimethyl carbonate DMC.
5. The zwitterionic polymer-based lithium-ion battery electrolyte of claim 1, wherein: the lithium salt is bis (trifluoromethanesulfonyl imide) lithium LiTFSI, lithium hexafluorophosphate LiPF 6 Lithium tetrafluoroborate LiBF 4 One or more of lithium difluorooxalato borate LiDFOB。
6. The method for preparing the zwitterionic polymer-based lithium ion battery electrolyte according to claim 1, comprising the steps of:
step 1, preparing a zwitterionic monomer and an organic solution;
quaternizing N, N-diallyl-N-methylamine and 1, 3-propane sultone in acetonitrile to obtain a zwitterionic monomer DMA-SO 3 - I.e. 3- (N, N-diallyl-N-methyl ammonium) propanesulfonate with a double bond;
zwitterionic monomer DMA-SO 2 N - SO 2 CF 3 Is to first synthesize CF 3 SO 2 NH 2 And K is equal to 2 CO 3 Reaction to CF 3 SO 2 NHK which is then reacted with 1-propanesulfonyl chloride to form Cl-SO 2 NSO 2 CF 3 The method comprises the steps of carrying out a first treatment on the surface of the Then N, N-diallyl-N-methylamine and Cl-SO are used 2 NSO 2 CF 3 Quaternization in acetonitrile to obtain zwitterionic monomer DMA-SO 2 N - SO 2 CF 3 ；
Preparing an organic solution with the concentration of 0.5-2mol/L by using lithium salt and an organic solvent;
step 2, mixing a zwitterionic monomer, a carbonic ester monomer, a polyethylene glycol acrylic ester monomer, an organic solution and a free radical initiator together to form a uniform transparent solution;
the weight ratio of each component in the uniform transparent solution is recorded by mass fraction: 3 to 6 percent of zwitterionic monomer, 15 to 25 percent of carbonate monomer, 1 to 2.5 percent of polyethylene glycol acrylic ester monomer, 65 to 80 percent of organic solution and 1 to 2 percent of free radical initiator;
and 3, dripping the uniform transparent solution obtained in the step 2 on a glass fiber membrane of Whatman or Millipore, packaging, initiating free radical polymerization through a thermal initiator at the temperature of 50-80 ℃, and realizing in-situ curing on the surface of the negative electrode of the lithium ion battery to obtain the composite semi-solid lithium ion battery electrolyte film with the thickness of 100-200 mu m.
7. The method for preparing the zwitterionic polymer-based lithium ion battery electrolyte according to claim 6, wherein: the thermal initiator in the step 3 is one or more of azodiisobutyronitrile AIBN, azodiisoheptonitrile ABVN and dibenzoyl peroxide BPO.
8. A semi-solid lithium ion battery is characterized in that: the electrolyte of the polymer-based lithium ion battery electrolyte of the amphoteric ion in claim 1, which is prepared on a negative electrode in situ.
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