CN116979051A - Manganese series lithium supplementing additive, preparation method and application thereof - Google Patents
Manganese series lithium supplementing additive, preparation method and application thereof Download PDFInfo
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- CN116979051A CN116979051A CN202311229200.XA CN202311229200A CN116979051A CN 116979051 A CN116979051 A CN 116979051A CN 202311229200 A CN202311229200 A CN 202311229200A CN 116979051 A CN116979051 A CN 116979051A
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- lithium
- positive electrode
- polyethylene glycol
- manganese
- additive
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- 239000000654 additive Substances 0.000 title claims abstract description 61
- 230000000996 additive effect Effects 0.000 title claims abstract description 61
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 150000002696 manganese Chemical class 0.000 title claims description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 58
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 58
- 239000007774 positive electrode material Substances 0.000 claims abstract description 36
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011247 coating layer Substances 0.000 claims abstract description 30
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000010410 layer Substances 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 239000006258 conductive agent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims abstract description 4
- 239000013589 supplement Substances 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 22
- 239000012046 mixed solvent Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- KKLSEIIDJBCSRK-UHFFFAOYSA-N 1-(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC=CC=C1C=C KKLSEIIDJBCSRK-UHFFFAOYSA-N 0.000 claims description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000012312 sodium hydride Substances 0.000 claims description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 11
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910010699 Li5FeO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910018688 LixC6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application belongs to the technical field of lithium ion battery anode materials, and particularly relates to a manganese lithium supplementing additive, a preparation method and application thereof. The lithium supplementing additive provided by the application comprises lithium manganate and a coating layer; the coating layer is coated on the surface of the lithium manganate; the coating layer is modified polyethylene glycol; the application also provides a positive plate which comprises a positive current collector and a positive material layer; wherein the positive electrode material layer comprises a positive electrode active material, a modified composite binder, a conductive agent and a manganese lithium supplementing additive; the manganese lithium-supplementing additive prepared by the method has good stability, can provide rich lithium ions, is used for supplementing irreversible lithium ions consumed by forming an SEI film on a negative electrode, thereby keeping abundant lithium ions in a battery system, improving the first coulombic efficiency and the overall electrochemical performance of the battery, and being beneficial to prolonging the service life of the battery.
Description
Technical Field
The application belongs to the technical field of lithium ion battery anode materials, and particularly relates to a manganese lithium supplementing additive, a preparation method and application thereof.
Background
The lithium ion battery is widely applied in the fields of digital fields, electric tools, two-wheelers, electric automobiles and the like, and various performances of the lithium ion battery are continuously improved along with the improvement of the energy density requirements of the lithium ion battery in various application fields. However, in the first charge and discharge process, lithium at the positive electrode end of the lithium ion battery is extracted and migrates towards the negative electrode direction, and lithium ions are not completely inserted into the negative electrode after reaching the negative electrode, and a part of lithium ions are consumed by providing a lithium source for the formation of an SEI film on the surface of the negative electrode, so that the energy density of the lithium ion battery is reduced, the lithium ions are tried to be added into the positive electrode end to make up for the lost lithium, and a large amount of Li+ is extracted from the lithium-supplementing agent in the charge process, so that the reversible capacity loss of the first charge and discharge of the battery is compensated.
The Chinese patent with publication number CN111769288B and publication day 2022, 05 and 03 discloses an in-situ lithium supplementing method for a positive electrode material of a lithium ion battery, wherein a carbon layer and Li5FeO4 formed in situ avoid the problem of non-uniformity caused by physical mixing and the problem that the accumulation of inorganic matters influences the cycle performance and the multiplying power performance of the battery after discharging, can effectively reduce interface resistance and improve the first coulomb efficiency and the cycle performance of the lithium battery, but the preparation method is complex and has higher cost; the patent with the application number of 202210278685.0 discloses a carbon-coated lithium ferrite material and a preparation method thereof, and the carbon-coated lithium ferrite material is prepared by a vapor deposition method, and although the carbon coating layer can relieve contact between lithium ferrite and water in air and improve the stability of the material, the carbon coating layer is difficult to thoroughly isolate contact with water in air all the time, so that the material is deteriorated and fails.
In the application process of the positive electrode lithium supplementing agent, an oily binder polyvinylidene fluoride (PVDF) is usually used, and the PVDF has the defects of poor electronic conductivity, poor ionic conductivity, poor binding power and the like, has higher swelling degree in electrolyte, has exothermic reaction with metallic lithium and LixC6 at higher temperature, and has larger potential safety hazard; and the organic solvent N-methyl pyrrolidone used together with PVDF has the characteristics of volatility, flammability, explosiveness, high toxicity, high recovery cost and the like. The use of aqueous binders instead of oily binders has been a recent trend in terms of environmental protection and performance.
In order to solve the problems of unstable air, reduced reversible capacity and the like of the battery of the existing positive electrode lithium supplementing agent, a positive electrode lithium supplementing agent with good stability needs to be searched; meanwhile, a binder with better performance needs to be developed, so that the application of the lithium supplementing agent is facilitated, the reversible capacity loss of the battery is supplemented, and the battery with higher energy density and cycle stability is obtained.
Disclosure of Invention
The application aims at overcoming the defects of the prior art and providing a manganese lithium supplementing additive and a preparation method and application thereof; the manganese series lithium supplementing additive has good stability, can be used as a lithium source for high-efficiency lithium removal in the first-cycle charging process, provides rich lithium ions and is used for supplementing irreversible lithium ions consumed by forming an SEI film on a negative electrode, so that the abundance of lithium ions in a battery system is maintained, the first coulomb efficiency and the overall electrochemical performance of the battery are improved, and the service life of the battery is prolonged.
The technical scheme adopted by the application for achieving the purpose is as follows:
a manganese series lithium supplementing additive comprises lithium manganate and a coating layer; the coating layer is coated on the surface of the lithium manganate; the coating layer is modified polyethylene glycol;
the preparation method of the modified polyethylene glycol comprises the following steps: adding polyethylene glycol and sodium hydride into anhydrous tetrahydrofuran, heating to 30-40 ℃ under the protection of nitrogen, reacting for 2-3h, adding chloromethyl vinyl benzene into the reaction solution, and continuing to react for 2-3h to obtain the modified polyethylene glycol.
Further, the molar ratio of the polyethylene glycol to the sodium hydride to the chloromethyl vinyl benzene is 1:8-10:8-10.
Further, the synthesis reaction formula of the modified polyethylene glycol is as follows:
。
the application provides a preparation method of a manganese series lithium supplementing additive, which comprises the steps of sequentially adding modified polyethylene glycol and lithium manganate into a mixed solvent, carrying out ultrasonic treatment for 40-60min, centrifuging, removing supernatant, and drying to obtain the manganese series lithium supplementing additive.
Further, the mass ratio of the modified polyethylene glycol to the lithium manganate is 1-2:100; the mixed solvent is acetonitrile and ethanol with the volume ratio of 1:1-1.5.
The application provides application of the manganese lithium supplement additive, namely the manganese lithium supplement additive is used for preparing a positive plate, and the positive plate comprises a positive current collector and a positive material layer; the positive electrode material layer comprises a positive electrode active material, a modified composite binder, a conductive agent and a manganese lithium supplementing additive.
Further, the positive electrode active material is lithium cobaltate; the conductive agent is carbon black; the mass of the manganese series lithium supplementing additive is 2-4% of the mass of the positive electrode material layer.
Further, the preparation method of the modified composite binder comprises the following steps:
s1, adding acrylic acid and lithium hydroxide into water, and reacting for 1-2 hours at room temperature to obtain lithium acrylate; the molar ratio of the acrylic acid to the lithium hydroxide is 1:1; the reaction process is as follows:
；
s2, adding lithium acrylate and modified polyethylene glycol into a mixed solvent to obtain a mixed solution, heating to 90-100 ℃, dropwise adding an ammonium persulfate aqueous solution with the mass fraction of 40-50%, and continuing to react for 4-6 hours after the dropwise addition to obtain a modified composite binder; the mass ratio of the lithium acrylate to the modified polyethylene glycol is 1:0.5-1.0; the mass fraction of lithium acrylate in the mixed solution is 40-60%; the dosage of ammonium persulfate is 8-10% of the mass of lithium acrylate; the mixed solvent is ethanol and water with the volume ratio of 1:1-2.
The application also provides a secondary battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte.
The application has the following beneficial effects:
in order to improve the stability of the lithium supplementing material, polyethylene glycol with stronger film forming property is used as a raw material, hydrophobic modification is carried out on the polyethylene glycol, and hydrophobic groups methyl vinyl benzene are used for replacing hydroxyl groups at two ends of the polyethylene glycol to obtain hydrophobic modified polyethylene glycol; according to the application, the modified polyethylene glycol and lithium acrylate are polymerized to form the network copolymer modified composite adhesive, and ester groups contained in molecules of the network copolymer modified composite adhesive can form more intermolecular hydrogen bonds with other components, so that the binding force among the components is increased, the adhesion is tighter, and the peeling strength between the positive electrode material layer in the positive electrode plate and the aluminum foil is improved; the modified composite binder and the coating modified polyethylene glycol of the lithium supplementing additive also have better compatibility, so that the components are fused more fully, the binding force between the positive electrode active layer and the positive electrode current collector is enhanced, and the cycle performance of the battery is improved; the modified composite adhesive prepared by the application has better bonding effect and is more environment-friendly.
The manganese lithium-supplementing additive prepared by the method has good stability, can be used as a lithium source for high-efficiency lithium removal in the first-cycle charging process, provides rich lithium ions and is used for supplementing irreversible lithium ions consumed by forming an SEI film on a negative electrode, so that the abundance of lithium ions in a battery system is maintained, the first coulomb efficiency and the overall electrochemical performance of the battery are improved, and the service life of the battery is prolonged.
Drawings
Fig. 1 is a graph of the cycle at 0.5C for 100 weeks for different cells.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Polyethylene glycol 2K CAS number 25322-68-3; sodium hydride CAS number 7646-69-7; chloromethyl vinyl benzene CAS No. 30030-25-2; acrylic CAS number 79-10-7; lithium hydroxide CAS number 1310-65-2; ammonium persulfate CAS number 7727-54-0; anhydrous tetrahydrofuran CAS number 109-99-9; ethanol CAS number 64-17-5; acetonitrile CAS number 75-05-8; all chemical reagents are commercially available.
Example 1
A manganese series lithium supplementing additive comprises lithium manganate and a coating layer; wherein the coating layer is coated on the surface of lithium manganate, and the coating layer is modified polyethylene glycol.
A preparation method of a manganese series lithium supplement additive comprises the steps of sequentially adding modified polyethylene glycol and lithium manganate into a mixed solvent, carrying out ultrasonic treatment for 60min, centrifuging, removing supernatant fluid, and drying to obtain the manganese series lithium supplement additive; wherein the mass ratio of the modified polyethylene glycol to the lithium manganate is 2:100; the mixed solvent is acetonitrile and ethanol with the volume ratio of 1:1.5; the use amount of the mixed solvent is the same as the mass of the lithium manganate.
The preparation method of the modified polyethylene glycol comprises the following steps: adding polyethylene glycol and sodium hydride into anhydrous tetrahydrofuran, protecting with nitrogen, heating to 40 ℃, reacting for 3 hours, adding chloromethyl vinyl benzene into the reaction solution, continuing to react for 3 hours, filtering, removing insoluble substances, concentrating the filtrate under reduced pressure, adding into n-hexane, stirring for 20-30 minutes, standing, filtering, washing filter residues, and drying to obtain modified polyethylene glycol; the prepared modified polyethylene glycol has fluorescence absorption under an ultraviolet lamp (256 nm); the substitution number of the hydrophobic end group is 2, which indicates that most of the hydroxyl groups at the two ends of the polyethylene glycol are substituted by hydrophobic groups methyl vinyl benzene; wherein the mol ratio of polyethylene glycol, sodium hydride and chloromethyl vinyl benzene is 1:10:10; the dosage of anhydrous tetrahydrofuran is 10 times of the mass of polyethylene glycol; the dosage of the n-hexane is one third of the anhydrous tetrahydrofuran; the synthesis reaction formula of the modified polyethylene glycol is as follows:
。
the application provides application of the manganese lithium supplement additive, namely, the manganese lithium supplement additive is used for preparing a positive plate, wherein the positive plate comprises a positive current collector and a positive material layer; the positive electrode material layer comprises a positive electrode active material, a modified composite binder, a conductive agent and a manganese lithium supplementing additive; wherein the positive electrode active material is lithium cobaltate; the conductive agent is carbon black; the mass of the manganese series lithium supplementing additive is 4% of the mass of the positive electrode material layer.
The preparation method of the modified composite adhesive comprises the following steps:
s1, adding acrylic acid and lithium hydroxide into water, reacting for 2 hours at room temperature, adjusting pH to be neutral after the reaction is completed, and removing water to obtain lithium acrylate; wherein the molar ratio of the acrylic acid to the lithium hydroxide is 1:1; the reaction process of the lithium acrylate comprises the following steps:
；
s2, adding lithium acrylate and modified polyethylene glycol into a mixed solvent to obtain a mixed solution, heating to 90 ℃, dropwise adding an ammonium persulfate aqueous solution with the mass fraction of 50%, continuously reacting for 6 hours after the completion of the dripping, naturally cooling to room temperature, filtering, and drying filter residues to obtain a modified composite binder; the prepared modified composite adhesive has fluorescence absorption under an ultraviolet lamp (256 nm); wherein the mass ratio of the lithium acrylate to the modified polyethylene glycol is 1:0.5; the mass fraction of lithium acrylate in the mixed solution is 50%; the dosage of the ammonium persulfate is 10% of the mass of the lithium acrylate; the mixed solvent is ethanol and water with the volume ratio of 1:2.
The preparation method of the positive plate comprises the following steps: adding positive active material lithium cobaltate, conductive agent carbon black, modified composite binder and manganese lithium supplementing additive into a container according to the mass ratio of 90:2:4:4, adding deionized water and N, N-dimethylformamide according to the volume ratio of 2:1, stirring until the mixture is uniform to obtain slurry, controlling the solid content of the slurry to be 50%, uniformly coating the slurry on a positive current collector aluminum foil, drying, rolling, cutting, and placing in a vacuum drying box for 12h at 120 ℃, and removing trace water to obtain the positive plate.
Example 2
A manganese series lithium supplementing additive comprises lithium manganate and a coating layer; wherein the coating layer is coated on the surface of lithium manganate, and the coating layer is modified polyethylene glycol.
A preparation method of a manganese series lithium supplement additive comprises the steps of sequentially adding modified polyethylene glycol and lithium manganate into a mixed solvent, carrying out ultrasonic treatment for 50min, centrifuging, removing supernatant, and drying to obtain the manganese series lithium supplement additive; wherein the mass ratio of the modified polyethylene glycol to the lithium manganate is 1:100; the mixed solvent is acetonitrile and ethanol with the volume ratio of 1:1; the use amount of the mixed solvent is the same as the mass of the lithium manganate.
The application provides application of the manganese lithium supplement additive, namely, the manganese lithium supplement additive is used for preparing a positive plate, wherein the positive plate comprises a positive current collector and a positive material layer; the positive electrode material layer comprises a positive electrode active material, a modified composite binder, a conductive agent and a manganese lithium supplementing additive; wherein the positive electrode active material is lithium cobaltate; the conductive agent is carbon black; the mass of the manganese series lithium supplementing additive is 3% of the mass of the positive electrode material layer.
The preparation method of the modified polyethylene glycol and the modified composite binder is the same as that of the example 1.
The preparation method of the positive plate comprises the following steps: adding positive active material lithium cobaltate, conductive agent carbon black, modified composite binder and manganese lithium supplementing additive into a container according to the mass ratio of 90:2:5:3, adding deionized water and N, N-dimethylformamide according to the volume ratio of 2:1, stirring until the mixture is uniform to obtain slurry, controlling the solid content of the slurry to be 50%, uniformly coating the slurry on a positive current collector aluminum foil, drying, rolling, cutting, and placing in a vacuum drying box for 12h at 120 ℃, and removing trace water to obtain the positive plate.
Example 3
A manganese series lithium supplementing additive comprises lithium manganate and a coating layer; wherein the coating layer is coated on the surface of lithium manganate, and the coating layer is modified polyethylene glycol.
A preparation method of a manganese series lithium supplement additive comprises the steps of sequentially adding modified polyethylene glycol and lithium manganate into a mixed solvent, carrying out ultrasonic treatment for 40min, centrifuging, removing supernatant, and drying to obtain the manganese series lithium supplement additive; wherein the mass ratio of the modified polyethylene glycol to the lithium manganate is 1.5:100; the mixed solvent is acetonitrile and ethanol with the volume ratio of 1:1.3; the use amount of the mixed solvent is the same as the mass of the lithium manganate.
The application provides application of the manganese lithium supplement additive, namely, the manganese lithium supplement additive is used for preparing a positive plate, wherein the positive plate comprises a positive current collector and a positive material layer; the positive electrode material layer comprises a positive electrode active material, a modified composite binder, a conductive agent and a manganese lithium supplementing additive; wherein the positive electrode active material is lithium cobaltate; the conductive agent is carbon black; the mass of the manganese series lithium supplementing additive is 2% of the mass of the positive electrode material layer.
The preparation method of the modified polyethylene glycol and the modified composite binder is the same as that of the example 1.
The preparation method of the positive plate comprises the following steps: adding positive active material lithium cobaltate, conductive agent carbon black, modified composite binder and manganese lithium supplementing additive into a container according to the mass ratio of 90:2:6:2, adding deionized water and N, N-dimethylformamide according to the volume ratio of 2:1, stirring until the mixture is uniform to obtain slurry, controlling the solid content of the slurry to be 50%, uniformly coating the slurry on a positive current collector aluminum foil, drying, rolling, cutting, and placing in a vacuum drying box for 12h at 120 ℃, and removing trace water to obtain the positive plate.
Comparative example 1
In comparison with example 1, the coating layer was different.
A manganese series lithium supplementing additive comprises lithium manganate and a coating layer; wherein the coating layer is coated on the surface of lithium manganate, and the coating layer is polyethylene glycol.
A preparation method of a manganese series lithium supplement additive comprises the steps of sequentially adding polyethylene glycol and lithium manganate into a mixed solvent, carrying out ultrasonic treatment for 50min, centrifuging, removing supernatant, and drying to obtain the manganese series lithium supplement additive; wherein the mass ratio of polyethylene glycol to lithium manganate is 1:100; the mixed solvent is acetonitrile and ethanol with the volume ratio of 1:1; the use amount of the mixed solvent is the same as the mass of the lithium manganate.
The application provides application of the manganese lithium supplement additive, namely, the manganese lithium supplement additive is used for preparing a positive plate, wherein the positive plate and the preparation method thereof are the same as those of the embodiment 1.
Comparative example 2
In which the binder in the positive electrode material layer is different as compared with example 1.
A manganese-based lithium supplement additive and a preparation method thereof are the same as in example 1.
The application provides application of the manganese lithium supplement additive, namely, the manganese lithium supplement additive is used for preparing a positive plate, wherein the positive plate comprises a positive current collector and a positive material layer; the positive electrode material layer comprises a positive electrode active material, a PVDF binder, a conductive agent and a manganese lithium supplementing additive; wherein the positive electrode active material is lithium cobaltate; the conductive agent is carbon black; the mass of the positive electrode lithium supplementing agent is 4% of the mass of the positive electrode material layer.
The preparation method of the positive plate comprises the following steps: adding a positive electrode active material lithium cobaltate, a conductive agent carbon black, a PVDF binder and deionized water and N, N-dimethylformamide in a volume ratio of 2:1 into a container according to a mass ratio of the positive electrode active material lithium cobaltate, the conductive agent carbon black to the PVDF binder to the 90:2:4, stirring until the deionized water and the N, N-dimethylformamide are mixed uniformly to obtain slurry, controlling the solid content of the slurry to be 50%, uniformly coating the slurry on a positive electrode current collector aluminum foil, drying, rolling, cutting into pieces, and placing into a vacuum drying oven for drying at 120 ℃ for 12 hours to remove trace water to obtain the positive electrode sheet.
Correlation testing
1. Peel strength test of positive plate
The positive electrode sheets prepared in examples 1 to 3 and comparative examples 1 to 2 were cut into 20cm×2.5cm strips, the current collector side was bonded to a steel plate having a thickness of 1mm with double-sided tape, a transparent adhesive tape was attached to the coating layer side, the coating layer was peeled off in the 180 ° direction at a speed of 100mm/min with a tensile tester, and the peel stress was measured, and the test results are shown in table 1.
Table 1 results of peel strength test of positive electrode sheet
As shown in Table 1, the modified composite adhesive used in example 1 is a network copolymer of lithium acrylate and modified polyethylene glycol, has stronger adhesive force, and ester groups contained in the molecule can form more intermolecular hydrogen bonds with other components, so that the adhesive force between the components is increased, the adhesive force is tighter, and the adhesive force is improved, compared with comparative example 2 (PVDF adhesive), the adhesive strength of the positive electrode material layer in the positive electrode sheet and the aluminum foil is improved.
2. Electrochemical performance test
The positive electrode sheets prepared in examples 1-3 and comparative examples 1-2 were assembled into lithium ion batteries, respectively, wherein the batteries include a positive electrode sheet, a negative electrode sheet, a separator, and an electrolyte; the negative plate is a lithium metal plate; the diaphragm is a polypropylene microporous diaphragm; the electrolyte is 1mol/L LiPF6 solution, and the solvent consists of EC (ethylene carbonate) and DEC (diethyl carbonate) according to the volume ratio of 1:1; and (3) assembling a lithium ion battery: assembling the lithium ion battery in an inert atmosphere glove box according to the assembling sequence of the lithium metal sheet, the diaphragm, the electrolyte and the positive electrode sheet; the test voltage range is 3.0-4.5V, the first charge and discharge specific capacity, the first coulombic efficiency, the multiplying power and the cycle data are shown in Table 1; the 100-week cycle curve at 0.5C is shown in FIG. 1.
TABLE 2 electrochemical Performance test results
As can be seen from the results in Table 2, the battery prepared from the positive electrode sheets of examples 1-3 has higher initial coulombic efficiency, specific capacity after 100 weeks discharge and discharge capacity retention rate, which are far superior to those of comparative examples 1-2, and FIG. 1 also shows that the battery prepared from the positive electrode sheets of examples 1-3 has much higher specific capacity after 100 weeks discharge than those of comparative examples 1-2, which indicates that the battery prepared from the application has better electrochemical performance; compared with comparative example 1 (the coating layer is polyethylene glycol), the coating layer used in example 1 is modified polyethylene glycol, hydrophobic groups methyl vinyl benzene at two ends of molecules of the modified polyethylene glycol can play a better role in protecting lithium manganate in the lithium supplementing additive, and the modified polyethylene glycol can be prevented from being in contact with water, carbon dioxide and the like in the air to react and deteriorate, so that the performance of a battery is influenced, and the stability of the lithium supplementing additive is improved due to the presence of the coating layer; compared with comparative example 2 (PVDF binder is adopted), the modified composite binder used in example 1 is a reticular copolymer of lithium acrylate and modified polyethylene glycol, has better compatibility with the modified polyethylene glycol of the coating layer of the lithium supplementing additive, has good bonding effect, enhances the bonding force between the positive electrode active layer and the positive electrode current collector, and improves the cycle performance of the battery.
It should be noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus; although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The manganese lithium supplementing additive is characterized by comprising lithium manganate and a coating layer; the coating layer is coated on the surface of the lithium manganate; the coating layer is modified polyethylene glycol;
the preparation method of the modified polyethylene glycol comprises the following steps: adding polyethylene glycol and sodium hydride into anhydrous tetrahydrofuran, heating to 30-40 ℃ under the protection of nitrogen, reacting for 2-3h, adding chloromethyl vinyl benzene into the reaction solution, and continuing to react for 2-3h to obtain the modified polyethylene glycol.
2. The manganese lithium supplement additive according to claim 1, wherein the molar ratio of polyethylene glycol, sodium hydride and chloromethyl vinyl benzene is 1:8-10:8-10.
3. The method for preparing the manganese series lithium supplement additive according to any one of claims 1 to 2, wherein modified polyethylene glycol and lithium manganate are sequentially added into a mixed solvent, ultrasonic treatment is carried out for 40 to 60 minutes, centrifugation is carried out, supernatant fluid is removed, and the manganese series lithium supplement additive is obtained after drying.
4. The method for preparing the manganese lithium supplement additive according to claim 3, wherein the mass ratio of the modified polyethylene glycol to the lithium manganate is 1-2:100; the mixed solvent is acetonitrile and ethanol with the volume ratio of 1:1-1.5.
5. A positive electrode sheet, characterized in that the positive electrode sheet comprises a positive electrode current collector and a positive electrode material layer; the positive electrode material layer comprises a positive electrode active material, a modified composite binder, a conductive agent and the manganese-based lithium supplementing additive according to any one of claims 1 to 4.
6. The positive electrode sheet according to claim 5, wherein the modified composite binder is prepared by the following steps:
s1, adding acrylic acid and lithium hydroxide into water, and reacting for 1-2 hours at room temperature to obtain lithium acrylate;
s2, adding lithium acrylate and modified polyethylene glycol into the mixed solvent to obtain a mixed solution, heating to 90-100 ℃, dropwise adding an ammonium persulfate aqueous solution with the mass fraction of 40-50%, and continuing to react for 4-6 hours after the completion of the dropwise addition to obtain the modified composite binder.
7. The positive electrode sheet according to claim 6, wherein the molar ratio of the acrylic acid to the lithium hydroxide in the step S1 is 1:1; the mass ratio of the lithium acrylate to the modified polyethylene glycol in the step S2 is 1:0.5-1.0; the mass fraction of lithium acrylate in the mixed solution is 40-60%; the dosage of ammonium persulfate is 8-10% of the mass of lithium acrylate; the mixed solvent is ethanol and water with the volume ratio of 1:1-2.
8. The positive electrode sheet according to claim 5, wherein the positive electrode active material is lithium cobaltate; the conductive agent is carbon black; the mass of the manganese series lithium supplementing additive is 2-4% of the mass of the positive electrode material layer.
9. A secondary battery comprising the positive electrode sheet, the negative electrode sheet, the separator and the electrolyte according to any one of claims 5 to 8.
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