CN117558983A - Low-temperature electrolyte, preparation method and lithium battery - Google Patents
Low-temperature electrolyte, preparation method and lithium battery Download PDFInfo
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- CN117558983A CN117558983A CN202311674139.XA CN202311674139A CN117558983A CN 117558983 A CN117558983 A CN 117558983A CN 202311674139 A CN202311674139 A CN 202311674139A CN 117558983 A CN117558983 A CN 117558983A
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- temperature
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000654 additive Substances 0.000 claims abstract description 47
- 230000000996 additive effect Effects 0.000 claims abstract description 43
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims abstract description 12
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 100
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 90
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000002243 precursor Substances 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 45
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 40
- VATYWCRQDJIRAI-UHFFFAOYSA-N p-aminobenzaldehyde Chemical compound NC1=CC=C(C=O)C=C1 VATYWCRQDJIRAI-UHFFFAOYSA-N 0.000 claims description 40
- 235000019441 ethanol Nutrition 0.000 claims description 33
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 22
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 22
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 20
- KZLDGFZCFRXUIB-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC(C=2C=C(N)C(O)=CC=2)=C1 KZLDGFZCFRXUIB-UHFFFAOYSA-N 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- MEXUTNIFSHFQRG-UHFFFAOYSA-N 6,7,12,13-tetrahydro-5h-indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one Chemical compound C12=C3C=CC=C[C]3NC2=C2NC3=CC=C[CH]C3=C2C2=C1C(=O)NC2 MEXUTNIFSHFQRG-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- KQIGMPWTAHJUMN-VKHMYHEASA-N 3-aminopropane-1,2-diol Chemical compound NC[C@H](O)CO KQIGMPWTAHJUMN-VKHMYHEASA-N 0.000 claims description 11
- RPFXMKLCYJSYDE-UHFFFAOYSA-N 3-fluoropropanoic acid Chemical compound OC(=O)CCF RPFXMKLCYJSYDE-UHFFFAOYSA-N 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 150000002825 nitriles Chemical class 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 125000005587 carbonate group Chemical group 0.000 abstract description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000002262 Schiff base Substances 0.000 description 4
- 150000004753 Schiff bases Chemical class 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 238000007112 amidation reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- QGRBVOROYKMJKX-UHFFFAOYSA-M sodium;3-fluoropropanoate Chemical compound [Na+].[O-]C(=O)CCF QGRBVOROYKMJKX-UHFFFAOYSA-M 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical group 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a low-temperature electrolyte which consists of propylene carbonate, lithium hexafluorophosphate and two additives. In addition to the superior conductivity of lithium hexafluorophosphate, which increases the viscosity of the electrolyte at low temperatures, lithium dendrites are easily precipitated from the electrode when the lithium battery is operated at low temperatures. The carbonate structure of the additive 2 can be reduced preferentially on the surface of the negative electrode in the battery formation process to form an SEI film, so as to prevent damage of lithium dendrites to the electrode. The additive 2 is used as a nitrile substance, has higher conductivity, and solves the problem of conductivity reduction of electrolyte in a low-temperature environment. The phenanthrene ring structure of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide of the additive 1 reduces the flammability of the electrolyte, widens the use temperature range of the lithium battery, effectively reduces the surface tension of the electrolyte at the interface of the anode and the cathode by F-anions, obviously improves the wettability of the battery and increases the conductivity of the electrolyte.
Description
Technical Field
The invention relates to the field of electrolyte preparation, in particular to a preparation method of low-temperature electrolyte.
Background
The electrolyte is called as the 'blood' of the lithium ion battery, plays a vital role in the performance of the lithium ion battery, and particularly has an interface structure and properties of an electrode and the electrolyte, and with the rapid development of pure electric vehicles and hybrid electric vehicles, the requirements on energy density, cycle life and safety are continuously improved. However, in a low-temperature environment, the compatibility between the electrolyte and the negative electrode and the separator is poor, the viscosity of the electrolyte is increased, even the electrolyte is partially solidified, the conductivity of the lithium ion battery is reduced, the lithium is seriously precipitated from the negative electrode of the lithium ion battery in the low-temperature environment, the precipitated metallic lithium reacts with the electrolyte, and the deposition of a product of the metallic lithium leads to the increase of the interface thickness of the solid electrolyte. These problems bring great challenges to practical application, and development of an adapted electrolyte additive for improving the interface structure between an electrode and an electrolyte is one of the most economical and effective methods for improving the electrochemical performance of a lithium ion battery, and is widely focused on all the fields.
Disclosure of Invention
The invention aims to provide a preparation method of low-temperature electrolyte, which solves the problem that the current lithium ion battery cannot adapt to low-temperature environment.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the low-temperature electrolyte specifically comprises the following steps:
in glove box (O) 2 ，H 2 O<0.1 ppm), propylene carbonate is subjected to water removal treatment by using a molecular sieve of A3+A4, lithium hexafluorophosphate is added, and the mixture is left for 10 to 12 hours to prepare a basic electrolyte, and an additive 1 and an additive 2 are added to prepare the low-temperature electrolyte.
The concentration of lithium hexafluorophosphate in the electrolyte was 1mol/L.
Further, the additive 1 is prepared by the steps of:
step A1: dissolving 4-aminobenzaldehyde in methanol, adding manganese dioxide, reacting for 1-2h at the rotation speed of 100-120rpm and the temperature of 40-50 ℃ to obtain an intermediate 1, dispersing nano alumina in ethanol, adding deionized water and KH560 at the rotation speed of 80-100rpm and the temperature of 20-25 ℃ for stirring for 30-40min, filtering to remove filtrate, dispersing a filter cake in ethanol, adding the intermediate 1, and reacting for 10-12h at the rotation speed of 100-120rpm and the temperature of 40-50 ℃ to obtain the precursor 1.
Step A2: uniformly mixing a precursor 1, pentafluorobenzoic acid, p-toluenesulfonic acid and dimethylformamide, reacting for 3-5 hours at the speed of 80-120rpm and the temperature of 80-100 ℃ to obtain a precursor 2, dissolving the precursor 2 in dimethyl sulfoxide, adding dilute sulfuric acid, reacting for 2-3 hours at the speed of 100-120rpm and the temperature of 50-60 ℃ to obtain a precursor 3, dissolving the precursor 3 and 1, 6-hexamethylenediamine in absolute ethyl alcohol, reacting for 2-3 hours at the speed of 80-120rpm and the temperature of 80-90 ℃ under the protection of nitrogen, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and reacting for 3-5 hours at the speed of 80-120rpm and the temperature of 80-90 ℃ to obtain the additive 1.
Further, the dosage ratio of the nano 4-aminobenzaldehyde to the methanol in the step A1 is 1g:20mL, 2.5% of manganese dioxide, 1g of nano aluminum oxide, ethanol, deionized water and KH 560: 50mL:50mL:10mL, cake, ethanol and intermediate 1 in an amount ratio of 1g:10mL:2.3g.
Further, the ratio of the amount of the precursor 1, pentafluorobenzoic acid and dimethylformamide in the step A2 is 1g:2.2g:15mL, the dosage of the p-toluenesulfonic acid is 1% of that of 4-aminobenzaldehyde, and the dosage ratio of the precursor 2 to the dimethyl sulfoxide to the dilute sulfuric acid is 1g:10mL:2.5mL of dilute sulfuric acid with a concentration of 40%, the dosage ratio of precursor 3, 1, 6-hexamethylenediamine, absolute ethanol and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide being 1g:0.95g:15mL:1g.
Further, the additive 2 is prepared by the steps of:
step B1: uniformly mixing 3,3 '-diamino-4, 4' -dihydroxybiphenyl, pyridine and trifluoroacetic anhydride, reacting for 2-3h at the speed of 80-100rpm and the temperature of 30-40 ℃ to obtain an intermediate 2, uniformly mixing the intermediate 2, 3-fluoropropionic acid, dimethyl sulfoxide and sodium hydroxide, reacting for 30-50min at the temperature of 25-30 ℃, heating to 70-80 ℃, reacting for 1-2h at the speed of 120-150rpm to obtain an intermediate 3, uniformly mixing the intermediate 3, (S) -3-amino-1, 2-propanediol, concentrated sulfuric acid and dimethylformamide, and reacting for 3-5h at the speed of 90-110rpm and the temperature of 50-60 ℃ to obtain the intermediate 4.
Step B2: uniformly mixing the intermediate 4, urea, zinc oxide and dimethylformamide, reacting for 3-4 hours at the rotation speed of 80-100rpm and the temperature of 145-155 ℃ to obtain an intermediate 5, dissolving the intermediate 5 in methanol, continuously introducing ammonia gas at the rotation speed of 110-120rpm and the temperature of 60-80 ℃ to react for 3-5 hours to obtain an intermediate 6, uniformly mixing the intermediate 6, 2-cyanoacrylate, ethanol and p-toluenesulfonic acid, and reacting for 2-3 hours at the rotation speed of 100-120rpm and the temperature of 70-80 ℃ to obtain the additive 2.
Further, the 3,3 '-diamino-4, 4' -dihydroxybiphenyl and trifluoroacetic anhydride in step B1 were used in an amount ratio of 1g:10mL of pyridine is 1.5% of 3,3 '-diamino-4, 4' -dihydroxybiphenyl mass, and the dosage ratio of the intermediate 2, 3-fluoropropionic acid, dimethyl sulfoxide and sodium hydroxide is 1g:5mL:15mL:10mL of sodium hydroxide solution with a concentration of 1mol/L, and the dosage ratio of the intermediate 3, (S) -3-amino-1, 2-propanediol, concentrated sulfuric acid and dimethylformamide is 1g:2.2g:0.2g:12mL, the mass fraction of concentrated sulfuric acid is 70%.
Further, the ratio of the amount of intermediate 4, urea and dimethylformamide in step B2 was 1g:1.5g:10mL of zinc oxide was used in an amount of 2% by mass of intermediate 4, and the ratio of intermediate 5 to methanol was 1g:10mL, the dosage ratio of intermediate 6, 2-cyanoacrylate and ethanol is 1g:5mL:10mL.
The invention has the beneficial effects that:
the invention improves the performance of the electrolyte by adding two additives. The additive 1 takes 4-aminobenzaldehyde as a raw material, a proton solvent methanol is used, under the catalysis of manganese dioxide, the methanol attacks aldehyde groups to generate two methyl ether groups, the aldehyde groups of the 4-aminobenzaldehyde are protected to prepare an intermediate 1, KH560 is used for carrying out surface modification on nano alumina to enable the epoxy groups to be functionalized, primary amino of the intermediate 1 is used for carrying out nucleophilic ring opening reaction on the epoxy groups of the modified nano alumina to prepare a precursor 1, nitrogen atoms with lone pair atoms in amino groups are used for attacking the epoxy groups to enable the epoxy groups to open rings to form a secondary amino group and an alcohol hydroxyl group, the secondary amino group is then used for attacking the epoxy groups according to the steps to form a tertiary amino group and an alcohol hydroxyl group, the alcohol hydroxyl group of the precursor 1 and the carboxyl group of pentafluorobenzoic acid are subjected to esterification reaction under the catalysis of P-toluenesulfonic acid to prepare a precursor 2, the precursor 3 is prepared by removing the aldehyde group protection under the action of dilute sulfuric acid, the precursor 3 is used for carrying out Schiff base and Schiff base reaction on the precursor 3, and the Schiff base is used for generating a Schiff base and the addition reaction of 10-H-10.
The inorganic component nano alumina of the additive 1 can inhibit hydrofluoric acid from corroding an electrode, reduce the dissolution of transition metal, improve the battery capacity, and the pentafluorobenzoic acid contains F - The negative ions can effectively reduce the surface tension of the electrolyte at the interface of the positive electrode and the negative electrode, remarkably improve the wettability of the battery, meanwhile, the pentafluorobenzoic acid contains benzene rings, has a protective effect on the positive electrode, effectively prevents the catalytic oxidation of metal ions of the positive electrode to the electrolyte, and improves the stability of the electrolyte and the circulation of the batteryThe ring performance, the phenanthrene ring structure of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, reduces the flammability of electrolyte and widens the use temperature range of the lithium battery.
The additive 2 takes 3,3 '-diamino-4, 4' -dihydroxybiphenyl as a raw material, under the action of trifluoroacetic anhydride and the catalysis of pyridine, amino is protected to form Tfa protecting groups, amino is prevented from participating in subsequent reactions, intermediate 2 is prepared, intermediate 2, 3-fluoropropionic acid firstly undergoes neutralization reaction with sodium hydroxide at room temperature to generate sodium phenolate and sodium 3-fluoropropionate, after heating, 3-fluoropropionate sodium and intermediate 2 undergo substitution reaction to generate phenolic ether to prepare intermediate 3, intermediate 3 undergoes amidation reaction with carboxylate to generate carboxylic acid under the action of concentrated sulfuric acid, carboxyl and (S) -3-amino-1, 2-propanediol undergo amidation reaction to prepare intermediate 4, intermediate 4 and urea undergo cyclization reaction with the catalysis of zinc oxide, the Tfa protecting groups of the amino are removed under the action of proton solvent methanol and continuous ammonia to prepare intermediate 6, the amino and 2-cyanoacrylate acid undergo amidation reaction under the catalysis of toluene sulfonic acid to prepare the additive 2.
The biphenyl structure of the additive 2 can protect a battery in an electropolymerization mode, when the voltage exceeds a certain voltage in the working process of the battery, a monomer is polymerized, a polymerization product is attached to the surface of an electrode of the battery, the internal resistance of the battery is increased, thus the charging current is limited to protect the battery, the safety performance of the battery is improved, the intermediate 4 and urea are subjected to cyclization reaction to generate a carbonic ester group, the structure can be reduced preferentially on the surface of a negative electrode in the battery formation process to form an SEI film, the intercalation reaction of a solvent on graphite is inhibited, the electrochemical performance of electrolyte is obviously improved, the 2-cyanoacrylate simultaneously introduces carbon-carbon double bonds and cyano groups, the nitrile substance has high dielectric constant and lower viscosity, so that the conductivity is higher, the nitrile substance has the defects of narrow electrochemical window and poor reduction stability, and the vinyl is subjected to reduction polymerization at a cathode under the action of electron withdrawing nitrile group in the structure, so that the problem of narrow electrochemical window and poor reduction stability of the additive 2 is solved.
When lithium ions work at low temperature, the compatibility between the electrolyte and the negative electrode and the separator is poor, the viscosity of the electrolyte is increased, even partial solidification is carried out, the conductivity of the lithium ion battery is reduced, the lithium is seriously precipitated from the negative electrode of the lithium ion battery in a low-temperature environment, the precipitated metallic lithium reacts with the electrolyte, and the deposition of a product of the metallic lithium leads to the increase of the interface thickness of the solid electrolyte. The low-viscosity solvent is selected, so that the conductivity of the electrolyte is improved, the precipitation of lithium dendrites is inhibited, the low-temperature performance of the electrolyte is improved to a certain extent, and the low-temperature performance of the electrolyte can be further improved under the synergistic effect of the low-temperature performance and the solvent. The lithium hexafluorophosphate is used as a solvent, the lithium hexafluorophosphate is lithium salt, the melting point of the propylene carbonate is-55 ℃, the flow can be kept at a lower temperature, the lithium ion migration is facilitated, the lithium hexafluorophosphate also has higher conductivity and charging and discharging performance, the strength of an SEI film of a lithium ion battery is enhanced by the two additives, precipitation of lithium dendrites in a low-temperature environment is inhibited, and meanwhile, the conductivity of the electrolyte at a low temperature is improved. Besides, the two additives can inhibit hydrofluoric acid from corroding the electrode, improve the stability of electrolyte, improve the cycle performance of the battery and improve the high temperature resistance of the electrolyte. Therefore, the electrolyte prepared by the invention not only has excellent low-temperature performance, but also has more excellent performance.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious 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.
Example 1
The preparation method of the low-temperature electrolyte specifically comprises the following steps:
in glove box (O) 2 ，H 2 O<0.1 ppm), propylene carbonate is subjected to water removal treatment by using a molecular sieve of A3+A4, lithium hexafluorophosphate is added, and the mixture is left for 12 hours to prepare a basic electrolyte, and an additive 1 is addedAnd an additive 2 to prepare a low-temperature electrolyte.
The concentration of lithium hexafluorophosphate in the electrolyte was 1mol/L.
The additive 1 is prepared by the following steps:
step A1: dissolving 4-aminobenzaldehyde in methanol, adding manganese dioxide, reacting for 2 hours at the speed of 120rpm and the temperature of 50 ℃ to obtain an intermediate 1, dispersing nano alumina in ethanol, adding deionized water and KH560 at the speed of 100rpm and the temperature of 25 ℃, stirring for 40min, filtering to remove filtrate, dispersing a filter cake in ethanol, adding the intermediate 1, and reacting for 12 hours at the speed of 120rpm and the temperature of 50 ℃ to obtain the precursor 1.
Step A2: uniformly mixing a precursor 1, pentafluorobenzoic acid, p-toluenesulfonic acid and dimethylformamide, reacting for 5 hours at the speed of 120rpm and the temperature of 100 ℃ to obtain a precursor 2, dissolving the precursor 2 in dimethyl sulfoxide, adding dilute sulfuric acid, reacting for 3 hours at the speed of 120rpm and the temperature of 60 ℃ to obtain a precursor 3, dissolving the precursor 3 and 1, 6-hexamethylenediamine in absolute ethyl alcohol, reacting for 3 hours at the speed of 120rpm and the temperature of 90 ℃ under the protection of nitrogen, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and reacting for 5 hours at the speed of 120rpm and the temperature of 90 ℃ to obtain the additive 1.
The dosage ratio of the nano 4-aminobenzaldehyde to the methanol in the step A1 is 1g:20mL, 2.5% of manganese dioxide, 1g of nano aluminum oxide, ethanol, deionized water and KH 560: 50mL:50mL:10mL, cake, ethanol and intermediate 1 in an amount ratio of 1g:10mL: the dosage ratio of 2.3g of 4-aminobenzaldehyde is 200g, the dosage of nano alumina is 20g, and the dosage of intermediate 1 is 180g.
The dosage ratio of the precursor 1, the pentafluorobenzoic acid and the dimethylformamide in the step A2 is 1g:2.2g:15mL, the dosage of the p-toluenesulfonic acid is 1% of that of 4-aminobenzaldehyde, and the dosage ratio of the precursor 2 to the dimethyl sulfoxide to the dilute sulfuric acid is 1g:10mL:2.5mL of dilute sulfuric acid with a concentration of 40%, the dosage ratio of precursor 3, 1, 6-hexamethylenediamine, absolute ethanol and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide being 1g:0.95g:15mL:1g, the dosage of the precursor 1 is 200g, the dosage of the precursor 2 is 180g, and the dosage of the precursor 3 is 160g.
The additive 2 is prepared by the following steps:
step B1: uniformly mixing 3,3 '-diamino-4, 4' -dihydroxybiphenyl, pyridine and trifluoroacetic anhydride, reacting for 3 hours at the speed of 100rpm and the temperature of 40 ℃ to obtain an intermediate 2, uniformly mixing the intermediate 2, 3-fluoropropionic acid, dimethyl sulfoxide and sodium hydroxide, reacting for 50 minutes at the temperature of 30 ℃, heating to 80 ℃, reacting for 2 hours at the speed of 150rpm to obtain an intermediate 3, uniformly mixing the intermediate 3, (S) -3-amino-1, 2-propanediol, concentrated sulfuric acid and dimethylformamide, and reacting for 5 hours at the speed of 110rpm and the temperature of 60 ℃ to obtain the intermediate 4.
Step B2: uniformly mixing the intermediate 4, urea, zinc oxide and dimethylformamide, reacting for 4 hours at the speed of 100rpm and the temperature of 155 ℃ to obtain an intermediate 5, dissolving the intermediate 5 in methanol, continuously introducing ammonia gas at the speed of 120rpm and the temperature of 80 ℃ to react for 5 hours to obtain an intermediate 6, uniformly mixing the intermediate 6, 2-cyanoacrylate, ethanol and p-toluenesulfonic acid, and reacting for 3 hours at the speed of 120rpm and the temperature of 80 ℃ to obtain the additive 2.
The dosage ratio of the 3,3 '-diamino-4, 4' -dihydroxybiphenyl to the trifluoroacetic anhydride in the step B1 is 1g:10mL of pyridine is 1.5% of 3,3 '-diamino-4, 4' -dihydroxybiphenyl mass, and the dosage ratio of the intermediate 2, 3-fluoropropionic acid, dimethyl sulfoxide and sodium hydroxide is 1g:5mL:15mL:10mL of sodium hydroxide solution with a concentration of 1mol/L, and the dosage ratio of the intermediate 3, (S) -3-amino-1, 2-propanediol, concentrated sulfuric acid and dimethylformamide is 1g:2.2g:0.2g:12mL, 70% by mass of concentrated sulfuric acid, 200g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 180g of intermediate 2 and 160g of intermediate 3.
The dosage ratio of the intermediate 4, urea and dimethylformamide in the step B2 is 1g:1.5g:10mL of zinc oxide was used in an amount of 2% by mass of intermediate 4, and the ratio of intermediate 5 to methanol was 1g:10mL, the dosage ratio of intermediate 6, 2-cyanoacrylate and ethanol is 1g:5mL:10mL, intermediate 4 in an amount of 180g, intermediate 5 in an amount of 160g, and intermediate 6 in an amount of 150g.
Example 2
The preparation method of the low-temperature electrolyte specifically comprises the following steps:
in glove box (O) 2 ，H 2 O<0.1 ppm), propylene carbonate is subjected to water removal treatment by using a molecular sieve of A3+A4, lithium hexafluorophosphate is added, and the mixture is left for 10 hours to prepare a basic electrolyte, and an additive 1 and an additive 2 are added to prepare a low-temperature electrolyte.
The concentration of lithium hexafluorophosphate in the electrolyte was 1mol/L.
The additive 1 is prepared by the following steps:
step A1: dissolving 4-aminobenzaldehyde in methanol, adding manganese dioxide, reacting for 1h at the rotation speed of 100rpm and the temperature of 40 ℃ to obtain an intermediate 1, dispersing nano alumina in ethanol, adding deionized water and KH560 at the rotation speed of 80rpm and the temperature of 20 ℃, stirring for 30min, filtering to remove filtrate, dispersing a filter cake in ethanol, adding the intermediate 1, and reacting for 10h at the rotation speed of 100rpm and the temperature of 40 ℃ to obtain the precursor 1.
Step A2: uniformly mixing a precursor 1, pentafluorobenzoic acid, p-toluenesulfonic acid and dimethylformamide, reacting for 3 hours at the speed of 80rpm and the temperature of 80 ℃ to obtain a precursor 2, dissolving the precursor 2 in dimethyl sulfoxide, adding dilute sulfuric acid, reacting for 2 hours at the speed of 100rpm and the temperature of 50 ℃ to obtain a precursor 3, dissolving the precursor 3 and 1, 6-hexamethylenediamine in absolute ethyl alcohol, reacting for 2 hours at the speed of 80rpm and the temperature of 80 ℃ under the protection of nitrogen, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and reacting for 3 hours at the speed of 80rpm and the temperature of 80 ℃ to obtain the additive 1.
The dosage ratio of the nano 4-aminobenzaldehyde to the methanol in the step A1 is 1g:20mL, 2.5% of manganese dioxide, 1g of nano aluminum oxide, ethanol, deionized water and KH 560: 50mL:50mL:10mL, cake, ethanol and intermediate 1 in an amount ratio of 1g:10mL: the dosage ratio of 2.3g of 4-aminobenzaldehyde is 200g, the dosage of nano alumina is 20g, and the dosage of intermediate 1 is 180g.
Further, the ratio of the amount of the precursor 1, pentafluorobenzoic acid and dimethylformamide in the step A2 is 1g:2.2g:15mL, the dosage of the p-toluenesulfonic acid is 1% of that of 4-aminobenzaldehyde, and the dosage ratio of the precursor 2 to the dimethyl sulfoxide to the dilute sulfuric acid is 1g:10mL:2.5mL of dilute sulfuric acid with a concentration of 40%, the dosage ratio of precursor 3, 1, 6-hexamethylenediamine, absolute ethanol and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide being 1g:0.95g:15mL:1g, the dosage of the precursor 1 is 200g, the dosage of the precursor 2 is 180g, and the dosage of the precursor 3 is 160g.
The additive 2 is prepared by the following steps:
step B1: uniformly mixing 3,3 '-diamino-4, 4' -dihydroxybiphenyl, pyridine and trifluoroacetic anhydride, reacting for 2 hours at the temperature of 30 ℃ at the speed of 80rpm to obtain an intermediate 2, uniformly mixing the intermediate 2, 3-fluoropropionic acid, dimethyl sulfoxide and sodium hydroxide, reacting for 30 minutes at the temperature of 25 ℃, heating to 70 ℃, reacting for 1 hour at the speed of 120rpm to obtain an intermediate 3, uniformly mixing the intermediate 3, (S) -3-amino-1, 2-propanediol, concentrated sulfuric acid and dimethylformamide, and reacting for 3 hours at the temperature of 50 ℃ at the speed of 90rpm to obtain an intermediate 4.
Step B2: uniformly mixing the intermediate 4, urea, zinc oxide and dimethylformamide, reacting for 3 hours at the speed of 80rpm and the temperature of 145 ℃ to obtain an intermediate 5, dissolving the intermediate 5 in methanol, continuously introducing ammonia gas at the speed of 110rpm and the temperature of 60 ℃ to react for 3 hours to obtain an intermediate 6, uniformly mixing the intermediate 6, 2-cyanoacrylate, ethanol and p-toluenesulfonic acid, and reacting for 2 hours at the speed of 100rpm and the temperature of 70 ℃ to obtain the additive 2.
The dosage ratio of the 3,3 '-diamino-4, 4' -dihydroxybiphenyl to the trifluoroacetic anhydride in the step B1 is 1g:10mL of pyridine is 1.5% of 3,3 '-diamino-4, 4' -dihydroxybiphenyl mass, and the dosage ratio of the intermediate 2, 3-fluoropropionic acid, dimethyl sulfoxide and sodium hydroxide is 1g:5mL:15mL:10mL of sodium hydroxide solution with a concentration of 1mol/L, and the dosage ratio of the intermediate 3, (S) -3-amino-1, 2-propanediol, concentrated sulfuric acid and dimethylformamide is 1g:2.2g:0.2g:12mL, 70% by mass of concentrated sulfuric acid, 200g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 180g of intermediate 2 and 160g of intermediate 3.
The dosage ratio of the intermediate 4, urea and dimethylformamide in the step B2 is 1g:1.5g:10mL of zinc oxide was used in an amount of 2% by mass of intermediate 4, and the ratio of intermediate 5 to methanol was 1g:10mL, the dosage ratio of intermediate 6, 2-cyanoacrylate and ethanol is 1g:5mL:10mL, intermediate 4 in an amount of 180g, intermediate 5 in an amount of 160g, and intermediate 6 in an amount of 150g.
Example 3
The preparation method of the low-temperature electrolyte specifically comprises the following steps:
in glove box (O) 2 ，H 2 O<0.1 ppm), propylene carbonate is subjected to water removal treatment by using a molecular sieve of A3+A4, lithium hexafluorophosphate is added, and the mixture is left for 11 hours to prepare a basic electrolyte, and an additive 1 and an additive 2 are added to prepare a low-temperature electrolyte.
The concentration of lithium hexafluorophosphate in the electrolyte was 1mol/L.
The additive 1 is prepared by the following steps:
step A1: dissolving 4-aminobenzaldehyde in methanol, adding manganese dioxide, reacting for 1.5h at the rotation speed of 110rpm and the temperature of 45 ℃ to obtain an intermediate 1, dispersing nano alumina in ethanol, adding deionized water and KH560 at the rotation speed of 90rpm and the temperature of 22 ℃, stirring for 35min, filtering to remove filtrate, dispersing a filter cake in ethanol, adding the intermediate 1, and reacting for 11h at the rotation speed of 110rpm and the temperature of 45 ℃ to obtain the precursor 1.
Step A2: uniformly mixing a precursor 1, pentafluorobenzoic acid, p-toluenesulfonic acid and dimethylformamide, reacting for 4 hours at the speed of 100rpm and the temperature of 90 ℃ to obtain a precursor 2, dissolving the precursor 2 in dimethyl sulfoxide, adding dilute sulfuric acid, reacting for 2.5 hours at the speed of 110rpm and the temperature of 55 ℃ to obtain a precursor 3, dissolving the precursor 3 and 1, 6-hexamethylenediamine in absolute ethyl alcohol, reacting for 2.5 hours at the speed of 100rpm and the temperature of 85 ℃ under the protection of nitrogen, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and reacting for 4 hours at the speed of 100rpm and the temperature of 85 ℃ to obtain the additive 1.
The dosage ratio of the nano 4-aminobenzaldehyde to the methanol in the step A1 is 1g:20mL, 2.5% of manganese dioxide, 1g of nano aluminum oxide, ethanol, deionized water and KH 560: 50mL:50mL:10mL, cake, ethanol and intermediate 1 in an amount ratio of 1g:10mL: the dosage ratio of 2.3g of 4-aminobenzaldehyde is 200g, the dosage of nano alumina is 20g, and the dosage of intermediate 1 is 180g.
The dosage ratio of the precursor 1, the pentafluorobenzoic acid and the dimethylformamide in the step A2 is 1g:2.2g:15mL, the dosage of the p-toluenesulfonic acid is 1% of that of 4-aminobenzaldehyde, and the dosage ratio of the precursor 2 to the dimethyl sulfoxide to the dilute sulfuric acid is 1g:10mL:2.5mL of dilute sulfuric acid with a concentration of 40%, the dosage ratio of precursor 3, 1, 6-hexamethylenediamine, absolute ethanol and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide being 1g:0.95g:15mL:1g, the dosage of the precursor 1 is 200g, the dosage of the precursor 2 is 180g, and the dosage of the precursor 3 is 160g.
The additive 2 is prepared by the following steps:
step B1: uniformly mixing 3,3 '-diamino-4, 4' -dihydroxybiphenyl, pyridine and trifluoroacetic anhydride, reacting for 2.5 hours at the rotation speed of 90rpm and the temperature of 35 ℃ to obtain an intermediate 2, uniformly mixing the intermediate 2, 3-fluoropropionic acid, dimethyl sulfoxide and sodium hydroxide, reacting for 40 minutes at the temperature of 28 ℃, heating to 75 ℃, reacting for 1.5 hours at the rotation speed of 135rpm to obtain an intermediate 3, uniformly mixing the intermediate 3, (S) -3-amino-1, 2-propanediol, concentrated sulfuric acid and dimethylformamide, and reacting for 4 hours at the rotation speed of 100rpm and the temperature of 55 ℃ to obtain the intermediate 4.
Step B2: uniformly mixing the intermediate 4, urea, zinc oxide and dimethylformamide, reacting for 3.5 hours at the speed of 80-100rpm and the temperature of 150 ℃ to obtain an intermediate 5, dissolving the intermediate 5 in methanol, continuously introducing ammonia gas at the speed of 115rpm and the temperature of 70 ℃ to react for 4 hours to obtain an intermediate 6, uniformly mixing the intermediate 6, 2-cyanoacrylate, ethanol and p-toluenesulfonic acid, and reacting for 2.5 hours at the speed of 110rpm and the temperature of 75 ℃ to obtain the additive 2.
The dosage ratio of the 3,3 '-diamino-4, 4' -dihydroxybiphenyl to the trifluoroacetic anhydride in the step B1 is 1g:10mL of pyridine is 1.5% of 3,3 '-diamino-4, 4' -dihydroxybiphenyl mass, and the dosage ratio of the intermediate 2, 3-fluoropropionic acid, dimethyl sulfoxide and sodium hydroxide is 1g:5mL:15mL:10mL of sodium hydroxide solution with a concentration of 1mol/L, and the dosage ratio of the intermediate 3, (S) -3-amino-1, 2-propanediol, concentrated sulfuric acid and dimethylformamide is 1g:2.2g:0.2g:12mL, 70% by mass of concentrated sulfuric acid, 200g of 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 180g of intermediate 2 and 160g of intermediate 3.
The dosage ratio of the intermediate 4, urea and dimethylformamide in the step B2 is 1g:1.5g:10mL of zinc oxide was used in an amount of 2% by mass of intermediate 4, and the ratio of intermediate 5 to methanol was 1g:10mL, the dosage ratio of intermediate 6, 2-cyanoacrylate and ethanol is 1g:5mL:10mL, intermediate 4 in an amount of 180g, intermediate 5 in an amount of 160g, and intermediate 6 in an amount of 150g.
Comparative example 1
The procedure is otherwise identical for this comparative example as compared to example 1 without the addition of pentafluorobenzoic acid.
Comparative example 2
The comparative example was carried out in the same manner as in example 1 except that 2-cyanoacrylate was not added.
Comparative example 3
Additive 1 was not used in this comparative example, and the rest of the procedure was the same.
Comparative example 4
Additive 2 was not used in this comparative example, and the rest of the procedure was the same.
Comparative example 5
This comparative example is the electrolyte prepared in example 1 of chinese patent CN105811003 a.
The electrolytes prepared in examples 1 to 3 and comparative examples 1 to 5 were applied to CR2025 type coin cells (active materials are Li) 4 Ti 5 O 12 The conductive agent is carbon black, the binder is polyvinylidene fluoride, the mass ratio of active substances to the conductive agent to the binder is 8:1:1, the positive electrode material is NCM 622), and the LAND battery test system is adopted to conduct constant current charge and discharge tests of different multiplying power on the prepared battery, and the discharge capacity at 25 ℃ for 10 weeks and 20 weeks and the discharge capacity retention rate at 40 ℃, 0 ℃ and-20 ℃ are tested.
As is clear from the above table, the electrolyte solutions prepared in examples 1 to 3 had relatively close capacities of the cells discharged at 25℃for 10 weeks and 20 weeks, and the discharge capacity retention rate at 0℃and-20℃was slightly better than that of comparative example 3, and much stronger than that of comparative examples 1 to 4, as compared with comparative examples 1 to 5. Comparative example 2 since pentafluorobenzoic acid was not added, the degree of wetting of the electrolyte and the positive electrode was reduced, li + The movement of ions is limited, and the temperature is reduced to increase the viscosity of the electrolyte, further limiting Li + The movement of ions causes a decrease in the discharge capacity retention rate. Comparative example 2 since 2-cyanoacrylate was not added, the electrochemical window of the electrolyte was narrowed, the reduction stability was deteriorated, and the discharge capacity retention rate was lowered. Comparative example 3 lacks additive 1, both F - Wetting of anions and absence of benzene rings for electrodesProtection, resulting in a decrease in discharge capacity retention rate. Comparative example 4 lacks additive 2, lacks biphenyl structure, and has a carbonate group structure for protecting electrode, and has a higher conductivity of nitrile group, resulting in a decrease in discharge capacity retention rate. Therefore, the electrolyte prepared by the invention can still maintain excellent performance at low temperature.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (10)
1. A preparation method of low-temperature electrolyte is characterized in that: the method specifically comprises the following steps:
in a glove box, propylene carbonate is subjected to water removal treatment by using a molecular sieve of A3+A4, lithium hexafluorophosphate is added, the mixture is stood to prepare a basic electrolyte, and an additive 1 and an additive 2 are added to prepare a low-temperature electrolyte.
2. The method for preparing a low-temperature electrolyte according to claim 1, wherein: the concentration of the lithium hexafluorophosphate in the electrolyte is 1mol/L.
3. The method for preparing a low-temperature electrolyte according to claim 1, wherein: the additive 1 is prepared by the following steps:
step A1: dissolving 4-aminobenzaldehyde in methanol, adding manganese dioxide, reacting to obtain an intermediate 1, dispersing nano alumina in ethanol, adding deionized water and KH560, stirring and filtering to remove filtrate, dispersing a filter cake in ethanol, adding the intermediate 1, and reacting to obtain a precursor 1;
step A2: uniformly mixing a precursor 1, pentafluorobenzoic acid, p-toluenesulfonic acid and dimethylformamide, reacting to obtain a precursor 2, dissolving the precursor 2 in dimethyl sulfoxide, adding dilute sulfuric acid, reacting to obtain a precursor 3, dissolving the precursor 3 and 1, 6-hexamethylenediamine in absolute ethyl alcohol, reacting, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and reacting to obtain the additive 1.
4. A method for preparing a low-temperature electrolyte according to claim 3, wherein:
the dosage ratio of the nano 4-aminobenzaldehyde to the methanol in the step A1 is 1g:20mL, 2.5% of manganese dioxide, 1g of nano aluminum oxide, ethanol, deionized water and KH 560: 50mL:50mL:10mL, cake, ethanol and intermediate 1 in an amount ratio of 1g:10mL:2.3g.
5. A method for preparing a low-temperature electrolyte according to claim 3, wherein:
the dosage ratio of the precursor 1, the pentafluorobenzoic acid and the dimethylformamide in the step A2 is 1g:2.2g:15mL, the dosage of the p-toluenesulfonic acid is 1% of that of 4-aminobenzaldehyde, and the dosage ratio of the precursor 2 to the dimethyl sulfoxide to the dilute sulfuric acid is 1g:10mL:2.5mL of precursor 3, 1, 6-hexamethylenediamine, anhydrous ethanol and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in a dosage ratio of 1g:0.95g:15mL:1g.
6. The method for preparing a low-temperature electrolyte according to claim 1, wherein: the additive 2 is prepared by the following steps:
step B1: uniformly mixing 3,3 '-diamino-4, 4' -dihydroxybiphenyl, pyridine and trifluoroacetic anhydride, reacting to obtain an intermediate 2, uniformly mixing the intermediate 2, 3-fluoropropionic acid, dimethyl sulfoxide and sodium hydroxide, reacting, heating to react for 1-2h to obtain an intermediate 3, uniformly mixing the intermediate 3, (S) -3-amino-1, 2-propanediol, concentrated sulfuric acid and dimethylformamide, and reacting to obtain an intermediate 4;
step B2: the intermediate 4, urea, zinc oxide and dimethylformamide are uniformly mixed and reacted to prepare an intermediate 5, the intermediate 5 is dissolved in methanol, ammonia gas is continuously introduced to react to prepare an intermediate 6, and the intermediate 6, 2-cyanoacrylate, ethanol and p-toluenesulfonic acid are uniformly mixed and reacted to prepare the additive 2.
7. The method for preparing a low-temperature electrolyte according to claim 6, wherein:
the dosage ratio of the 3,3 '-diamino-4, 4' -dihydroxybiphenyl to the trifluoroacetic anhydride in the step B1 is 1g:10mL of pyridine is 1.5% of 3,3 '-diamino-4, 4' -dihydroxybiphenyl mass, and the dosage ratio of the intermediate 2, 3-fluoropropionic acid, dimethyl sulfoxide and sodium hydroxide is 1g:5mL:15mL:10mL of intermediate 3, (S) -3-amino-1, 2-propanediol, concentrated sulfuric acid and dimethylformamide in a 1g ratio: 2.2g:0.2g:12mL.
8. The method for preparing a low-temperature electrolyte according to claim 6, wherein:
the dosage ratio of the intermediate 4, urea and dimethylformamide in the step B2 is 1g:1.5g:10mL of zinc oxide was used in an amount of 2% by mass of intermediate 4, and the ratio of intermediate 5 to methanol was 1g:10mL, the dosage ratio of intermediate 6, 2-cyanoacrylate and ethanol is 1g:5mL:10mL.
9. A low temperature electrolyte, characterized by: the preparation method according to any one of claims 1-8.
10. A lithium battery, characterized in that: the lithium battery comprising the electrolyte of any one of claims 1-9.
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