CN116706234A - Layered ternary cathode material-adapted electrolyte, ternary lithium ion battery and preparation method thereof - Google Patents
Layered ternary cathode material-adapted electrolyte, ternary lithium ion battery and preparation method thereof Download PDFInfo
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- CN116706234A CN116706234A CN202310771212.9A CN202310771212A CN116706234A CN 116706234 A CN116706234 A CN 116706234A CN 202310771212 A CN202310771212 A CN 202310771212A CN 116706234 A CN116706234 A CN 116706234A
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- naphthalene
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 60
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 30
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- 239000010406 cathode material Substances 0.000 claims abstract description 7
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 41
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 36
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical group [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims 1
- 230000006978 adaptation Effects 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 239000010439 graphite Substances 0.000 abstract description 15
- 229910002804 graphite Inorganic materials 0.000 abstract description 15
- 239000007774 positive electrode material Substances 0.000 abstract description 7
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 5
- 239000010452 phosphate Substances 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- ZZPDMMIMRUGHBQ-UHFFFAOYSA-N 1-prop-1-enylnaphthalene Chemical compound C1=CC=C2C(C=CC)=CC=CC2=C1 ZZPDMMIMRUGHBQ-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KIXIRVPOOYJMDA-UHFFFAOYSA-N trimethyl(naphthalen-1-yl)silane Chemical compound C1=CC=C2C([Si](C)(C)C)=CC=CC2=C1 KIXIRVPOOYJMDA-UHFFFAOYSA-N 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 150000003014 phosphoric acid esters Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 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
- 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)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the field of lithium ion batteries, and particularly relates to electrolyte for adapting a layered ternary cathode material, a ternary lithium ion battery and a preparation method thereof. The electrolyte provided by the invention uses the additive, so that the electrolyte has excellent flame retardance and overcharge resistance, and also has better oxidation resistance; the composite material has good compatibility with a graphite negative electrode, and solves the problem of limited use of the graphite negative electrode caused by use of a phosphate additive; the electrolyte provided by the invention has a simple preparation method, can greatly improve the safety performance of the ternary lithium ion battery using the layered ternary positive electrode material, and provides the ternary lithium ion battery using the layered ternary positive electrode material with good electrochemical performance under the high-temperature condition (40-50 ℃), and the capacity retention rate can reach 86% after 400 cycles.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and in particular relates to electrolyte for adapting a layered ternary cathode material, a ternary lithium ion battery and a preparation method thereof.
Background
In lithium ion batteries, the layered ternary positive electrode material provides a higher practical specific capacity than the olivine structured positive electrode. The ternary positive electrode, such as NCM811, is often assembled with a graphite negative electrode and electrolyte to provide a ternary lithium ion battery. Graphite has high conductivity, stability, wear resistance and wide temperature range, is widely applied as a negative electrode in the field of lithium ion batteries, but has the defects of low cycle life and easiness in reaction with electrolyte.
In addition, carbonate organic solvents are often used in lithium ion battery electrolyte, and the electrolyte has the advantages of high solubility to lithium salt and good oxidation resistance, and is difficult to replace as the electrolyte solvent at present. However, due to the use of the carbonate-based organic solvent in the electrolyte, when the temperature is increased, oxygen radicals are released from the layered ternary cathode material represented by NCM811, and at this time, some of the H-containing carbonate-based organic solvent undergoes a chain reaction with the oxygen radicals to release a large amount of heat, so that the electrolyte is heated to an excessively high temperature, and further the electrolyte is ignited and burned.
In order to solve the inflammable problem of the electrolyte, phosphate additives are usually added into the electrolyte, and the P/F free radical is introduced to interrupt the chain reaction of combustion, so that the purpose of protecting the electrolyte and the battery is achieved, and better effects are achieved, such as Chinese patent applications CN108987808A and CN 115312858A. However, these phosphate additives are not compatible with graphite anodes, resulting in Li + The graphite cathode is peeled off during intercalation, so that the graphite cathode of the ternary lithium ion battery taking the layered ternary cathode material as a cathode is limited in use.
Disclosure of Invention
In order to solve the problems, the invention provides the electrolyte for adapting the layered ternary anode material, and the electrolyte has the functions of overcharge prevention, flame retardance, oxidation resistance and the like at the same time by adding the specific additive, so that the electrolyte can also provide better electrochemical performance of the ternary lithium ion battery. The specific technical scheme of the invention is as follows:
an electrolyte for adapting a layered ternary anode material comprises lithium salt, an ester organic solvent and an additive;
the additive has the structure shown in the following formula (I):
wherein R1, R2 and R3 are selected from propenyl, nitrile group and trimethylsilyl group, and R1, R2 and R3 are different from each other.
The lithium salt comprises one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis-fluoro-methylsulfonimide or lithium bis-trifluoro-methylsulfonimide.
The concentration of the lithium salt is 0.5-3M, and the volume ratio of the ester organic solvent to the additive is 80-98: 2 to 20.
The ester organic solvent is selected from one or more of methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate or ethylene carbonate.
The preparation method of the additive comprises the following steps:
adding a catalyst into a hydroxyl-containing naphthalene compound, adding phosphorus oxychloride for substitution reaction, and then carrying out reduced pressure distillation, separation and purification to obtain the additive.
The temperature of the substitution reaction is 70-130 ℃ and the reaction time is 6-9 h;
the addition amount of the catalyst is 1-3 wt% of the addition amount of phosphorus oxychloride;
the hydroxyl-containing naphthalene compound is a combination of 1-hydroxy-5-propenyl naphthalene, 1-hydroxy-5-nitrile naphthalene and 1-hydroxy-5-trimethylsilyl naphthalene, and the molar ratio of the 1-hydroxy-5-propenyl naphthalene to the 1-hydroxy-5-nitrile naphthalene to the 1-hydroxy-5-trimethylsilyl naphthalene to the phosphorus oxychloride is 1:1:1:1;
the preparation method of the 1-hydroxy-5-propenyl naphthalene, 1-hydroxy-5-nitrile naphthalene and 1-hydroxy-5-trimethylsilyl naphthalene comprises the following steps:
step 1, respectively carrying out substitution reaction on 1-propenyl naphthalene, 1-nitrile naphthalene, 1-trimethylsilyl naphthalene and bromine simple substance to respectively obtain 1-bromo-5-propenyl naphthalene, 1-bromo-5-nitrile naphthalene and 1-bromo-5-trimethylsilyl naphthalene;
step 2, respectively reacting the 1-bromo-5-propenyl naphthalene, 1-bromo-5-nitrile naphthalene and 1-bromo-5-trimethylsilyl naphthalene obtained in step 1 with NaOH to obtain 1-hydroxy-5-propenyl naphthalene, 1-hydroxy-5-nitrile naphthalene and 1-hydroxy-5-trimethylsilyl naphthalene.
In the step 1, the molar ratio of 1-propenyl naphthalene, 1-nitrile naphthalene and 1-trimethylsilyl naphthalene to bromine simple substance is 1: (1.2-1.5);
the temperature of the substitution reaction in the step 1 is 60-80 ℃;
in the step 2, the molar weight ratio of 1-bromo-5-propenyl naphthalene, 1-bromo-5-nitrile naphthalene and 1-bromo-5-trimethylsilyl naphthalene to NaOH is 1 (1-1.8);
the reaction temperature in the step 2 is 50-90 ℃;
the catalyst is a calcium-magnesium catalyst, and the preparation steps of the calcium-magnesium catalyst are as follows:
(1) Mixing HZSM-5 molecular sieve, calcium nitrate, magnesium chloride and water to obtain a mixed solution;
(2) Heating the mixed solution in the step (1) to react under the stirring condition to obtain a reactant;
(3) Filtering and washing the reactant obtained in the step (2) to obtain a product;
(4) And (3) drying, grinding, sieving and roasting the product obtained in the step (3) to obtain the calcium-magnesium catalyst.
The content of HZSM-5 molecular sieve, calcium sulfate and magnesium chloride in the mixed solution in the step (1) is 25 to 45 weight percent, 3 to 8 weight percent and 5 to 12 weight percent respectively;
in the step (2), the mixed solution is heated to 95-105 ℃ for 3-5 hours;
the step (3) reactant is washed by water;
the drying temperature in the step (4) is 100-130 ℃ and the drying time is 8-12 h;
grinding and sieving in the step (4), namely grinding the dried product into small particles, and sieving the particles with the particle size less than or equal to 150 meshes;
and (3) roasting in the step (4) at the temperature of 400-450 ℃ for 16-20 h.
A method of preparing the electrolyte of any one of the preceding claims, comprising: and (3) taking lithium salt, additives and ester organic solvents according to a proportion, and uniformly mixing to obtain the electrolyte.
A ternary lithium ion battery comprising the electrolyte of any one of the above.
A preparation method of a ternary lithium ion battery is obtained by assembling a ternary positive electrode, a graphite negative electrode, a glass fiber diaphragm and any electrolyte.
The preparation method of the ternary positive electrode comprises the steps of homogenizing 80-90 parts of layered ternary positive electrode material, 5-10 parts of conductive agent and 5-10 parts of binder, and then coating the mixture on a current collector aluminum foil to form the ternary positive electrode, wherein the coating thickness is 17-150 um.
The layered ternary anode material is selected from one of nickel cobalt manganese and nickel cobalt aluminum.
The action mechanism of the additive in the electrolyte is as follows:
first, in the additive used in the electrolyte of the present invention, naphthalene groups are oxidized and polymerized at high potential to form high polymers so that the battery is powered off to avoid overcharging, -PO 3 The P in the catalyst is used for effectively blocking the chain reaction of oxygen free radicals and hydrogen free radicals, playing a role in flame retardance, and simultaneously further increasing the flame retardance of the additive due to the existence of the azonitrile group, so that the combustion of the electrolyte is restrained from two aspects; at the same time, alkyl groups directly attached to the phosphate esters lead to Li + The graphite cathode is peeled off during intercalation, and the naphthyl in the additive is directly connected with the phosphate, so that Li can be improved + The problem of graphite cathode flaking during intercalation can be avoided, and the rapid attenuation of battery capacity can be further avoided;
in addition, of the additives used in the electrolyte of the present invention, CH 2 CH＝CH 2 SEI film formed on the negative electrode by preferential reductive decomposition to make Li + The graphite negative electrode is inserted/removed smoothly, the negative electrode compatibility characteristic of electrolyte and graphite is greatly improved, meanwhile, the structural stability of the SEI film can be enhanced by N atoms in-CN, the SEI film is prevented from being heated and decomposed, and the heat-resistant stability of the negative electrode is enhanced;
finally, the electrolyte of the invention is usedAdditive of-CH 2 CH＝CH 2 and-Si (CH) 3 ) 3 The surface of the ternary positive electrode is crosslinked to form a stable crosslinked CEI structure, and the structure can prevent transition metal ions in the ternary positive electrode material from being dissolved due to structural collapse under high potential, and further enhance the structural stability of the SEI film.
Compared with the prior art, the invention has the following beneficial effects:
(1) The electrolyte provided by the invention uses a new additive, so that the electrolyte provided by the invention has excellent flame retardance, stability, better overcharge resistance and oxidation resistance; the electrolyte has better compatibility with the graphite cathode, and solves the problem of limited use of the graphite cathode caused by use of the phosphate additive;
(2) The electrolyte provided by the invention has a simple preparation method, can greatly improve the safety performance of the ternary lithium ion battery using the layered ternary positive electrode material, and finally enables the ternary lithium ion battery using the layered ternary positive electrode material to have better electrochemical performance, and the capacity retention rate can reach 86% after 400 cycles of circulation at a high temperature (40-50 ℃).
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The method for measuring the self-extinguishing time of the electrolyte combustion comprises the following steps:
1mL of the electrolyte is taken and is dripped on 50mg of round medical cotton, the round medical cotton is ignited by a lighter in the air, and the time from the start of burning to the natural extinction of the medical cotton, which is abbreviated as the burning self-extinguishing time, is recorded by a stopwatch.
The preparation method of the ternary lithium ion battery, the constant current charge and discharge test and the overcharge prevention test method comprise the following steps:
and respectively placing the graphite negative electrode, the glass fiber diaphragm, the NCM811 ternary positive electrode and electrolyte in a CR2032 button cell, standing for 6 hours, and then performing constant current charge and discharge test and overcharge prevention test.
The constant current charge and discharge test conditions are as follows: current Density (100 mA g) -1 ) The voltage range (2.7-4.3V) is 400 circles at 40-50 ℃.
The overcharge-preventing test conditions were: current density (100 mAg) -1 ) Voltage interval (2.7-5V).
The calcium-magnesium catalysts used in the embodiments of the invention are prepared by the following methods:
(1) Mixing 0.3g of HZSM-5 molecular sieve, 0.05g of calcium nitrate, 0.1g of magnesium chloride and 0.55g of water to obtain a mixed solution;
(2) Heating the mixed solution in the step (1) to 100 ℃ under stirring for reacting for 4 hours to obtain a reactant;
(3) Filtering the reactant obtained in the step (2) and washing the reactant with water for 2 times to obtain a product;
(4) Drying the product obtained in the step (3) at 130 ℃ for 12 hours, grinding, sieving, taking the product which is less than or equal to 150 meshes, and roasting at 450 ℃ for 20 hours to obtain the calcium-magnesium catalyst.
The additives in the embodiment of the invention are prepared by the following methods:
step 1, respectively carrying out substitution reaction on 0.1mol of 1-propenyl naphthalene, 0.1mol of 1-nitrile naphthalene, 0.1mol of 1-trimethylsilyl naphthalene and 0.1mol of bromine simple substance at 70 ℃ to respectively obtain 1-bromo-5-propenyl naphthalene, 1-bromo-5-nitrile naphthalene and 1-bromo-5-trimethylsilyl naphthalene;
step 2, respectively adding 0.1mol of NaOH into the 1-bromo-5-propenyl naphthalene, the 1-bromo-5-nitrile naphthalene and the 1-bromo-5-trimethylsilyl naphthalene obtained in the step 1 to react to obtain 1-hydroxy-5-propenyl naphthalene, 1-hydroxy-5-nitrile naphthalene and 1-hydroxy-5-trimethylsilyl naphthalene;
step 3, mixing the 1-hydroxy-5-propenyl naphthalene, 1-hydroxy-5-nitrile naphthalene and 1-hydroxy-5-trimethylsilyl naphthalene prepared in the step 2, adding 0.3g of catalyst and 0.1mol of phosphorus oxychloride for substitution reaction, and then carrying out reduced pressure distillation, separation and purification to obtain the additive.
Example 1
15.2g of lithium hexafluorophosphate (concentration 1M), 90ml of ester organic solvent (volume ratio of methyl ethyl carbonate to ethylene carbonate is 7:3) and 10ml of additive in the step (1) are taken and uniformly mixed, and the electrolyte of the embodiment is obtained.
Example 2
15.2g of lithium hexafluorophosphate (concentration 1M), 95ml of ester organic solvent (volume ratio of methyl ethyl carbonate to ethylene carbonate is 7:3) and 5ml of the additive in the step (1) are taken and uniformly mixed, and the electrolyte of the embodiment is obtained.
Example 3
15.2g of lithium hexafluorophosphate (concentration 1M), 92ml of ester organic solvent (volume ratio of methyl ethyl carbonate to ethylene carbonate is 7:3) and 8ml of the additive in the step (1) are taken and uniformly mixed, and the electrolyte of the embodiment is obtained.
Comparative example 1
15.2g of lithium hexafluorophosphate (concentration 1M), 90ml of ester organic solvent (volume ratio of methyl ethyl carbonate to ethylene carbonate is 7:3), 1ml of trimethyl phosphate, 3ml of 1-hydroxy-5-propenyl naphthalene, 3ml of 1-hydroxy-5-nitrile naphthalene and 3ml of 1-hydroxy-5-trimethylsilyl naphthalene are uniformly mixed, and the electrolyte of the embodiment is obtained.
Test results:
the electrolyte according to the present invention was added to the electrolyte according to the present invention, and the electrolyte according to comparative example 1 was prepared using the prior art, and the same organic reagent as the main group according to the present invention was added thereto, and then the electrolytes obtained in examples and comparative examples were tested using the above-described method.
From the test results, the additive provided by the invention is used in the electrolyte, so that the prepared electrolyte has excellent flame retardance, oxidation resistance and overcharge resistance, and the electrolyte can be applied to a ternary lithium ion battery to enable the battery to have electrochemical performance.
Claims (10)
1. The electrolyte for adapting the layered ternary anode material is characterized by comprising lithium salt, an ester organic solvent and an additive; the additive has the structure shown in the following formula:
wherein R1, R2 and R3 are selected from propenyl, nitrile and trimethylsilyl, and R1, R2 and R3 are different from each other.
2. The layered ternary cathode material-adapted electrolyte of claim 1, wherein the lithium salt comprises one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis-fluoromethanesulfonimide, or lithium bis-trifluoromethanesulfonyl imide.
3. The layered ternary cathode material-adapted electrolyte of claim 1, wherein the ester-based organic solvent is selected from one or more of methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, or ethylene carbonate.
4. The electrolyte for the adaptation of the layered ternary cathode material according to claim 1, wherein the lithium salt concentration is 0.5-3M, and the volume ratio of the ester organic solvent to the additive is 80-98: 2 to 20.
5. The layered ternary cathode material-adapted electrolyte of claim 1, wherein the additive is prepared by the steps of:
adding a catalyst into a hydroxyl-containing naphthalene compound, adding phosphorus oxychloride for substitution reaction, and then carrying out reduced pressure distillation, separation and purification to obtain the additive.
6. The electrolyte for adapting a layered ternary cathode material according to claim 5, wherein the hydroxyl-containing naphthalene compound is a combination of 1-hydroxy-5-propenyl naphthalene, 1-hydroxy-5-nitril naphthalene and 1-hydroxy-5-trimethylsilyl naphthalene.
7. The electrolyte for adapting the layered ternary cathode material according to claim 5, wherein the temperature of the substitution reaction is 70-130 ℃ and the reaction time is 6-9 h.
8. The layered ternary cathode material-adapted electrolyte of claim 5, wherein the catalyst is a calcium magnesium catalyst.
9. A method for producing the electrolytic solution according to any one of claims 1 to 8, comprising: and (3) taking lithium salt, additives and ester organic solvents according to a proportion, and uniformly mixing to obtain the overcharge-preventing flame-retardant electrolyte.
10. A ternary lithium ion battery comprising the electrolyte of any one of claims 1-8.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160233546A1 (en) * | 2015-02-06 | 2016-08-11 | Ningde Amperex Technology Limited | Electrolyte solution and lithium ion batteries using the same |
| CN106898827A (en) * | 2015-12-18 | 2017-06-27 | 丰田自动车株式会社 | lithium solid state battery |
| CN107069090A (en) * | 2017-01-23 | 2017-08-18 | 合肥国轩高科动力能源有限公司 | Ternary cathode material lithium ion battery electrolyte |
| WO2017152624A1 (en) * | 2016-03-09 | 2017-09-14 | 中国科学院宁波材料技术与工程研究所 | Electrolyte and lithium ion battery |
| CN108448170A (en) * | 2018-01-26 | 2018-08-24 | 合肥国轩高科动力能源有限公司 | Electrolyte for high-voltage lithium ion battery |
| CN108987808A (en) * | 2018-07-30 | 2018-12-11 | 桑顿新能源科技有限公司 | A kind of high-voltage lithium ion batteries nonaqueous electrolytic solution and lithium ion battery |
| CN110148774A (en) * | 2019-04-24 | 2019-08-20 | 东莞东阳光科研发有限公司 | Nickelic tertiary cathode material system battery electrolytic solution and lithium ion battery |
| CN113506914A (en) * | 2021-07-14 | 2021-10-15 | 国家纳米科学中心 | Ternary lithium ion battery electrolyte and lithium ion battery containing same |
-
2023
- 2023-06-28 CN CN202310771212.9A patent/CN116706234B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160233546A1 (en) * | 2015-02-06 | 2016-08-11 | Ningde Amperex Technology Limited | Electrolyte solution and lithium ion batteries using the same |
| CN106898827A (en) * | 2015-12-18 | 2017-06-27 | 丰田自动车株式会社 | lithium solid state battery |
| WO2017152624A1 (en) * | 2016-03-09 | 2017-09-14 | 中国科学院宁波材料技术与工程研究所 | Electrolyte and lithium ion battery |
| CN107069090A (en) * | 2017-01-23 | 2017-08-18 | 合肥国轩高科动力能源有限公司 | Ternary cathode material lithium ion battery electrolyte |
| CN108448170A (en) * | 2018-01-26 | 2018-08-24 | 合肥国轩高科动力能源有限公司 | Electrolyte for high-voltage lithium ion battery |
| CN108987808A (en) * | 2018-07-30 | 2018-12-11 | 桑顿新能源科技有限公司 | A kind of high-voltage lithium ion batteries nonaqueous electrolytic solution and lithium ion battery |
| CN110148774A (en) * | 2019-04-24 | 2019-08-20 | 东莞东阳光科研发有限公司 | Nickelic tertiary cathode material system battery electrolytic solution and lithium ion battery |
| CN113506914A (en) * | 2021-07-14 | 2021-10-15 | 国家纳米科学中心 | Ternary lithium ion battery electrolyte and lithium ion battery containing same |
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