CN114937766B - Preparation method of transition metal doped poly (m-phenylenediamine) coated positive electrode material - Google Patents
Preparation method of transition metal doped poly (m-phenylenediamine) coated positive electrode material Download PDFInfo
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- CN114937766B CN114937766B CN202210604727.5A CN202210604727A CN114937766B CN 114937766 B CN114937766 B CN 114937766B CN 202210604727 A CN202210604727 A CN 202210604727A CN 114937766 B CN114937766 B CN 114937766B
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- positive electrode
- electrode material
- phenylenediamine
- copper
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 33
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 32
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229940018564 m-phenylenediamine Drugs 0.000 title claims abstract description 31
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- -1 transition metal salt Chemical class 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000010405 anode material Substances 0.000 claims abstract description 6
- 150000004985 diamines Chemical class 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000005119 centrifugation Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- MGIOWAASSQPWAP-UHFFFAOYSA-N dialuminum dioxido(dioxo)manganese Chemical compound [Mn](=O)(=O)([O-])[O-].[Al+3].[Mn](=O)(=O)([O-])[O-].[Mn](=O)(=O)([O-])[O-].[Al+3] MGIOWAASSQPWAP-UHFFFAOYSA-N 0.000 claims 1
- 229960002413 ferric citrate Drugs 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011247 coating layer Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 230000002411 adverse Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 abstract description 3
- 239000002103 nanocoating Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007772 electrode material Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000004151 quinonyl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 1
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 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
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- 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
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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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
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Abstract
The invention discloses a preparation method of a transition metal doped poly (m-phenylenediamine) coated positive electrode material, and belongs to the technical field of secondary battery positive electrode materials. The technical scheme is that the method comprises the following steps: 1) Dispersing the anode material particles into an organic solvent, then adding m-phenylenediamine monomers, uniformly mixing, and stirring to obtain a mixed system; 2) Adding transition metal salt into the mixed system to react; 3) And separating the solid and the liquid of the mixed system by centrifugation or filtration, washing the solid by ethanol, and drying to obtain the transition metal doped polymetaphenylene diamine coated positive electrode material. The preparation method is carried out in an organic solvent, so that the adverse effect of the existing water system treatment method is completely avoided, the operation process is simple, the cost is low, the nano-scale coating layer is directly constructed in one step, and the thickness of the coating layer is adjustable.
Description
Technical Field
The invention relates to the technical field of preparation of secondary battery anode materials, in particular to a preparation method of a transition metal doped poly (m-phenylenediamine) -coated anode material.
Background
Electric vehicles using lithium ion batteries as energy sources are developed to facilitate carbon neutralization in the early days. The problem that the endurance mileage of the electric automobile decreases with the increase of the use times exists. The problem can be solved by improving the cycling stability of the lithium ion battery, and the popularization and the use of the electric automobile are promoted.
One of the important causes of the decrease in cycling stability of lithium ion batteries is the decay of the electrode material. The positive electrode material is used as a main component of the lithium ion battery, and is corroded by electrolyte in the charging and discharging process, so that side reaction is caused, transition metal is dissolved out, the material structure is attenuated, and the discharging specific capacity of the lithium ion battery is reduced along with the increase of the charging and discharging times. For example, a high nickel ternary positive electrode material (LiNixCoyMn 1-x-yO2 (x is more than or equal to 60%) is corroded by trace HF in electrolyte in charge-discharge cycles, transition metals such as Ni, co, mn and the like in the electrode material are dissolved into the electrolyte, irreversible phase transformation occurs on the surface lamellar structure, and the cycling stability of the lithium ion battery is reduced.
Constructing the surface coating layer is an effective method for improving the cycling stability of the cathode material. By introducing the protective layer on the surface of the positive electrode material, the surface side reaction can be effectively inhibited, and the cycle stability of the battery can be improved. The existing methods for constructing surface coatings are mainly mechanical mixing and liquid phase coating. Among them, the liquid phase method has the characteristics of uniform coating and wide application range, and is widely concerned. However, the existing liquid phase coating means are almost all carried out in water systems, which causes damage to some lithium ion battery cathode materials. For example, high nickel ternary positive electrode materials are susceptible to li+/h+ ion exchange reactions and transition metal dissolution in water, degrading electrochemical performance; the high-nickel ternary positive electrode material treated by water is poor in thermal stability, and is easy to cause thermal runaway, so that safety accidents are caused. The well-known lithium ion battery scientist Jaephil Cho was written: the treatment of high nickel ternary cathode materials in water is not a good method and we have sought other solutions to replace it (Junhyeok Kim et al. A method for preparing a metal a-doped poly-m-phenylenediamine coated cathode materials (Adv Energy mate 2018, 8, 1702028).
CN201410755934.6 reports a scheme for synthesizing copper doped poly (m-phenylenediamine) nanoparticles in a water system by copper catalysis, but the scheme is performed in the water system, only copper doped poly (m-phenylenediamine) nanoparticles are produced by using the introduced air as an oxidant, and the construction of a poly (m-phenylenediamine) coating is not realized; CN201410616618.0 reports on the use of persulfate catalysis in aqueous systemsMethod for constructing a coating of polymetaphenylene diamine, which is carried out in water using persulfate-catalyzed polymerization, and Jeff Dahn's recent study (J. Electrochem. Soc. 2020, 167, 130521) for electrode material systems shows that water causes high nickel ternary electrode materials to undergo Li + /H + Ion exchange and transition metal dissolution, thereby reducing the electrochemical performance of the material.
Disclosure of Invention
The invention aims to solve the technical problems that: the preparation method of the positive electrode material coated by the transition metal doped poly (m-phenylenediamine) has the advantages that the preparation method overcomes the defects of the prior art, the thickness of a coating layer can be effectively controlled by controlling the growth rate of a polymer in an organic solvent, adverse effects on the structure of an electrode material are avoided, side reactions on the surface of the electrode material can be effectively reduced, the dissolution of transition metal is inhibited, and the cycling stability of the positive electrode material is improved.
The technical scheme of the invention is as follows:
a preparation method of a transition metal doped poly (m-phenylenediamine) coated positive electrode material comprises the following steps:
1) Dispersing the anode material particles into an organic solvent, then adding m-phenylenediamine monomers, uniformly mixing, and stirring to obtain a mixed system;
2) Adding transition metal salt into the mixed system to react;
3) And separating the solid and the liquid of the mixed system by centrifugation or filtration, washing the solid by ethanol, and drying to obtain the transition metal doped polymetaphenylene diamine coated positive electrode material.
Preferably, the positive electrode material in step 1) is selected from one or more of lithium cobaltate, lithium manganate, lithium nickelate and lithium-rich lithium manganate.
Preferably, the organic solvent in step 1) comprises one or more of methanol, ethanol, propanol, butanol, acetonitrile, acetone, ethylene glycol, cyclohexanone, methylcyclohexanone, and N-methylpyrrolidone.
Preferably a mixed solution of ethanol and ethylene glycol.
Preferably, the mass ratio of the m-phenylenediamine monomer to the positive electrode material in the step 1) is 10:1-1:25.
Preferably, in the step 2), the mass ratio of the transition metal salt to the m-phenylenediamine monomer is 8:1-1:8.
Preferably, the transition metal salt in step 2) is a transition metal salt containing copper ions or iron ions, including one or more of copper chloride, copper nitrate, copper acetate, copper citrate, iron nitrate, iron chloride, iron citrate.
Preferably, the reaction time in the step 2) is 0.5-36 h, and the reaction temperature is 10-100 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method is carried out in an organic solvent, so that the adverse effect of the existing water system treatment method is completely avoided, the operation process is simple, the cost is low, the nano-scale coating layer is directly constructed in one step, and the thickness of the coating layer is adjusted by controlling the amount of the added reactant.
2. The transition metal doped poly (m-phenylenediamine) nano layer constructed by the invention is uniformly coated on the surface of the positive electrode material, so that the electrolyte and the positive electrode material are separated, side reactions of the electrolyte on the surface of the material in the charge and discharge process are reduced, the dissolution of the transition metal is inhibited, and the circulation stability of the positive electrode material is improved.
Drawings
FIG. 1 is an SEM image of 622@Cu-PmPD prepared in example 1 and 622 prepared in comparative example 1.
FIG. 2 is a TEM image of 622@Cu-PmPD prepared in example 1 and 622 prepared in comparative example 1.
FIG. 3 XRD spectra of 622@Cu-PmPD prepared in example 1 and 622 prepared in comparative example 1.
FIG. 4 is a TEM image of 622@Fe-PmPD prepared in example 4.
FIG. 5 is a Fourier transform infrared spectrum of Cu-PmPD obtained in example 2.
Fig. 6 is a plot of the first charge and discharge at 0.2C rate for the 622@cu-PmPD cell and 622 cell of example 3.
Fig. 7 is a graph of cycle performance at 0.2C for 622@cu-PmPD cells and 622 cells in example 3.
FIG. 8 is an SEM image of 622@Cu-PmPD prepared in example 5.
Detailed Description
The positive electrode material is selected from one or more of lithium cobalt oxide, lithium manganate, lithium nickelate, lithium nickel manganate, lithium nickel cobalt aluminum lithium and lithium-rich lithium manganate, and is hereinafter denoted by LiNi 0.6 Co 0.2 Mn 0.2 O 2 (622) The invention is further illustrated by way of example with other positive electrode materials being similar. The kind of transition metal and the solvent can be adjusted according to actual conditions, so that the construction of the coating layers under different anode materials and different solvents is realized. The invention is not limited to these examples of implementation.
Example 1
This example provides a copper-doped poly (m-phenylenediamine) (Cu-PmPD) -coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 The preparation method of the (622@Cu-PmPD) positive electrode material comprises the following steps:
first prepared 622 by conventional co-precipitation: will be 0.788g NiSO 4 .H 2 O,0.26g CoSO 4 . H 2 O,0.253g MnSO 4 . H 2 Adding O into 30 ml water to obtain a metal sulfate solution; adding appropriate amount of sodium hydroxide solution, adjusting pH to 11, stirring vigorously at 40deg.C for 4 hr, centrifuging, taking out precipitate, washing with clear water, and drying. The Ni obtained 0.6 Co 0.2 Mn 0.2 O 2 Mixed with 0.13g LiOH and calcined at 850℃for 10h to give 622 material.
And then coating 622: 0.5 g 622 material was dispersed in an organic solvent containing 15 ml ethanol and 15 ml ethylene glycol, 0.15 g m-phenylenediamine was added, stirred for 0.5 h, then 0.07 g copper chloride was added, and stirred for 3 h. The mixture was placed in a centrifuge tube, centrifuged at 10000r/min for 1 min, and washed with ethanol three times to obtain a solid substance. And drying to obtain 622@Cu-PmPD.
Comparative example 1
Will be 0.788g NiSO 4 .H 2 O,0.26g CoSO 4 . H 2 O,0.253g MnSO 4 . H 2 Adding O into 30 ml water to obtain a metal sulfate solution; adding appropriate amount of sodium hydroxide solution, adjusting pH to 11, stirring vigorously at 40deg.C for 4 hr, centrifuging, taking out precipitate, washing with clear water, and drying. The Ni obtained 0.6 Co 0.2 Mn 0.2 O 2 Mixed with 0.13g LiOH and calcined at 850℃for 10h to give 622 material.
Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) images of 622@cu-PmPD prepared in example 1 and 622 material prepared in comparative example 1, respectively, are shown in fig. 1 and 2 (a is 622 and b is 622@cu-PmPD in fig. 1 and 2), respectively, and X-ray diffraction analysis (XRD) was performed on 622@cu-PmPD prepared in example 1 and 622 material prepared in comparative example 1, respectively, and the results are shown in fig. 3.
As can be seen from fig. 1, no significant difference was observed between the SEM images of 622@cu-PmPD prepared in example 1 and 622 material of comparative example 1, indicating that the copper-doped polymetaphenylene diamine formed was entirely coated on 622 without phase separation. TEM images confirm this (FIG. 2). The 622 surface prepared in comparative example 1 is smooth, and the 622@Cu-PmPD surface coated in example 1 has a 5 nm thick coating layer, so that the effectiveness of the coating method is proved. Fig. 3 shows that the XRD spectrum of 622@cu-PmPD electrode material prepared in example 1 is unchanged from that of 622 prepared in comparative example, indicating that the structure of the electrode material is not affected by the coating treatment.
Example 2
Example 2 is a characterization of Cu-PmPD of a copper-doped poly (m-phenylenediamine) coating, and the specific method is as follows:
dispersing 0.2. 0.2 g m-phenylenediamine into a mixed solvent containing 15 ml ethanol and 15 ml ethylene glycol, stirring for 1 h, adding 0.1 g copper nitrate, and stirring for 2 h. Putting the mixture into a centrifuge tube, centrifuging at 10000r/min for 1 min, and washing with ethanol for three times to obtain solid Cu-PmPD. Obtaining the copper doped poly (m-phenylenediamine) Cu-PmPD. To prove the structure of the coating layer, the effect of the positive electrode material in the coating layer on the measurement result was eliminated, and the junction of the coating layer Cu-PmPD was measuredThe characterization of the structure by fourier transform infrared spectrum is shown in fig. 5. It is at 3500 cm -1 And 3000 cm -1 The broad absorption peak between them is the telescopic vibration peak of-NH-, which is in 1620 cm -1 The nearby peak is the telescopic vibration absorption peak of the quinone ring, namely 1520-1520 cm -1 Is the stretching vibration peak of benzene ring. 1322 cm -1 And 1260 cm -1 The peaks at the positions are C-N stretching vibration peaks on the quinone ring and the benzene ring respectively, which shows that the synthetic substance is truly copper-doped poly-m-phenylenediamine.
Example 3
Example 3 is a graph of the electrochemical performance characterization of 622@cu-PmPD prepared in example 1 and 622 prepared in comparative example 1, specifically as follows,
622@Cu-PmPD prepared in example 1 and 622 prepared in comparative example 1 were used as electrode materials, respectively, according to the following electrode materials: carbon black: pvdf=8:1:1, the slurry was formulated and coated on top of aluminum foil. Drying and slicing; lithium metal is used as a negative electrode; the electrolyte is 1M LiPF6 electrolyte, and the solvent is EC: DEC: DMC (1:1:1). Button cells were assembled in a glove box, 622@Cu-PmPD cell and 622 cell, respectively. Multiplying power is 0.2C (theoretical specific capacity is 200 mAhg) in voltage range of 3-4.5V -1 ) Is a test of electrochemical cycling. The test temperature was 25 ℃. The first charge and discharge curves of 622@Cu-PmPD cells and 622 cells at 0.2C rate are shown in FIG. 6, and the cycle performance images of 622@Cu-PmPD cells and 622 cells at 0.2C rate are shown in FIG. 7.
As shown in fig. 6, the first-turn charge-discharge curve of the 622@cu-PmPD battery is not significantly different from that of the uncoated 622 battery, indicating that the coating has no effect on the lithium ion intercalation/deintercalation process. As can be seen from fig. 7, after 100 cycles, the capacity retention of the 622@cu-PmPD cell was 74.45%, which is much higher than the untreated 622 capacity retention (54.2%), fully illustrating the role of the coating layer in improving the cycling stability of the electrode material. The battery after 100 circles of circulation is disassembled, the electrolyte is characterized by an inductively coupled plasma spectrometer, and the content of transition metal dissolved in the electrolyte is tested. The results are shown in Table 1, and the Cu-PmPD coating significantly inhibited the transition metal elution.
TABLE 1
Example 4
The embodiment provides a preparation method of 622 material (622@Fe-PmPD for short) coated by iron-doped poly (m-phenylenediamine) (Fe-PmPD), which comprises the following steps:
2 g 622 material was dispersed in a mixed solvent containing 15 ml ethanol and 15 ml ethylene glycol, 0.2 g m-phenylenediamine was added, stirred for 1 h, then 0.15 g ferric chloride was added, and stirred for 2 h. The mixture was placed in a centrifuge tube, centrifuged at 10000r/min for 1 min, and washed with ethanol three times to obtain a solid substance. And drying to obtain 622@Fe-PmPD. TEM image of 622@Fe-PmPD is shown in FIG. 4.
As can be seen from fig. 4, the resultant iron-doped polymetaphenylene diamine is entirely coated on 622.
Example 5
0.1 g 622 material was dispersed in an organic solvent containing 15 ml ethanol and 15 ml ethylene glycol, 0.3 g m-phenylenediamine was added, stirred for 0.5 h, then 0.07 g copper chloride was added, and stirred for 3 h. The mixture was placed in a centrifuge tube, centrifuged at 10000r/min for 1 min, and washed with ethanol three times to obtain a solid substance. Drying gave a thicker coating of 622@Cu-PmPD as shown in FIG. 8, thus demonstrating our ability to adjust the coating thickness.
The preparation method is carried out in an organic solvent, so that the adverse effect of the existing water system treatment method is completely avoided, the operation process is simple, the cost is low, the nano-scale coating layer is directly constructed in one step, and the thickness of the coating layer is adjustable; the transition metal doped poly (m-phenylenediamine) nano layer constructed by the invention is uniformly coated on the surface of the positive electrode material, so that the electrolyte and the positive electrode material are separated, side reactions of the electrolyte on the surface of the material in the charge and discharge process are reduced, the dissolution of the transition metal is inhibited, and the circulation stability of the positive electrode material is improved.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (3)
1. The preparation method of the transition metal doped poly (m-phenylenediamine) coated positive electrode material is characterized by comprising the following steps of:
1) Dispersing the anode material particles into an organic solvent, then adding m-phenylenediamine monomers, uniformly mixing, and stirring to obtain a mixed system;
2) Adding transition metal salt into the mixed system to react;
3) Separating the solid and the liquid of the mixed system through centrifugation or filtration, washing the solid with ethanol, and drying to obtain the transition metal doped polymetaphenylene diamine coated positive electrode material;
the mass ratio of the m-phenylenediamine monomer to the positive electrode material in the step 1) is 10:1-1:25;
the mass ratio of the transition metal salt to the m-phenylenediamine monomer in the step 2) is 8:1-1:8;
the transition metal salt in the step 2) is copper ion-containing or iron ion-containing transition metal salt, and comprises one or more of copper chloride, copper nitrate, copper acetate, copper citrate, ferric nitrate, ferric chloride and ferric citrate;
the reaction time in the step 2) is 0.5-36 h, and the reaction temperature is 10-100 ℃;
the organic solvent in the step 1) is a mixed solution of ethanol and glycol.
2. The method for preparing a transition metal doped poly (m-phenylenediamine) -coated positive electrode material according to claim 1, wherein the method comprises the following steps: the positive electrode material in the step 1) is selected from one or more of lithium cobaltate, lithium manganate, lithium nickelate aluminum manganate and lithium-rich lithium manganate.
3. The method for preparing a transition metal doped poly (m-phenylenediamine) -coated positive electrode material according to claim 1, wherein the method comprises the following steps: the organic solvent in step 1) comprises one or more of methanol, ethanol, propanol, butanol, acetonitrile, acetone, ethylene glycol, cyclohexanone, methylcyclohexanone, and N-methylpyrrolidone.
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