CN116779832B - Intercalation sodium ion battery layered oxide positive electrode material, preparation and application thereof - Google Patents
Intercalation sodium ion battery layered oxide positive electrode material, preparation and application thereof Download PDFInfo
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 42
- 238000009830 intercalation Methods 0.000 title claims abstract description 40
- 230000002687 intercalation Effects 0.000 title claims abstract description 39
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 150000001768 cations Chemical class 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 52
- 229920001940 conductive polymer Polymers 0.000 abstract description 27
- 239000011229 interlayer Substances 0.000 abstract description 11
- 239000010406 cathode material Substances 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 30
- 239000011572 manganese Substances 0.000 description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- -1 sodium hexafluorophosphate Chemical compound 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/485—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
- 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
- H01M4/52—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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- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/604—Polymers containing aliphatic main chain polymers
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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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
- 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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Abstract
The invention belongs to the technical field of batteries, and particularly relates to an intercalation sodium ion battery layered oxide positive electrode material, and preparation and application thereof. The preparation method of the positive electrode material comprises the following steps of preparing layered oxide Na x Ni i Fe j Mn k M m O 2 Wherein M ions are large-radius cations with the radius of 0.07-0.12 nm; and (3) carrying out ultrasonic treatment on the mixed solution of the layered oxide and the 3, 4-ethylenedioxythiophene, adding an oxidant, continuing ultrasonic treatment, separating and drying to obtain the layered oxide cathode material of the intercalation sodium-ion battery. According to the invention, EDOT is oxidized and self-polymerized by large-size cation doping to be inserted into the layered oxide, so that the PEDOT-NFM-TM layered oxide of the conductive polymer intercalation is generated, the interlayer structure of the NFM is stabilized, the interlayer spacing is enlarged, the cut-off voltage of the material in the charge and discharge process is improved, and the gram capacity of the material is improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to an intercalation sodium ion battery layered oxide positive electrode material, and preparation and application thereof.
Background
In recent years, sodium ion batteries have been widely focused on energy markets because of the advantages of abundant reserves, low cost, safety and stability, energy density equivalent to that of lithium iron phosphate, and the like, and have wide application prospects in the fields of low-cost transportation power electricity utilization, large-scale energy storage technology, and the like. The positive electrode material is closely related to the performance and cost of the sodium ion battery, and is one of the core components of the sodium ion battery. Among known cathode materials, layered transition metal oxides exhibit advantages of high specific capacity, adjustable structure, mature synthesis method, and the like, and have extremely strong competitive advantages in commercial applications.
For O3 phase manganese-based layered oxides, high voltage regions (> 4V vs. Na) + Na) complex phase transition of O3-O '3-P3-P'3-O3'', evolution of long-term and local structures of lattice oxygen precipitation. These irreversible structural evolutions will cause anisotropic lattice strain and huge unit cell volume changes in the material, which in turn leads to rapid decay of cell performance. Therefore, how to solve the problem of mutual restriction between capacity and structural stability, breaking through the constraint, namely realizing high capacity and high stability at the same time, is a great challenge in the research of the positive electrode material of the sodium ion battery.
Disclosure of Invention
The invention aims to solve the problems, and provides an intercalation sodium ion battery layered oxide positive electrode material, a preparation method and an application thereof, wherein the interlayer spacing of the material is improved, the layered oxide structure is stabilized, and the phase change of the material in a high voltage (more than 4V) range is inhibited to cause structural change, so that capacity attenuation is caused.
According to the technical proposal of the invention, the preparation method of the intercalation sodium ion battery layered oxide cathode material comprises the following steps,
s1: ni is added with i Fe j Mn k M m (OH) 2 Mixing the precursor with a sodium source, and sintering to obtain layered oxide Na x Ni i Fe j Mn k M m O 2 Wherein x is more than 0.6 and less than or equal to 1, i is more than 0 and less than 1, j is more than 0 and less than 1, k is more than 0 and less than 1, m is more than 0 and less than 0.3, i+j+k+m=1, and M ions are large-radius cations with the radius of 0.07-0.12 nm;
s2: the layered oxide Na x Ni i Fe j Mn k M m O 2 Dissolving in an organic solvent, then adding 3, 4-ethylenedioxythiophene, and performing ultrasonic treatment to obtain a mixed solution;
s3: under the ultrasonic condition, adding an oxidant into the mixed solution, continuing ultrasonic treatment, separating and drying to obtain the intercalation sodium-ion battery layered oxide anode material.
The invention adopts large-size cation doping to match 3, 4-ethylenedioxythiophene (C) 6 H6O 2 S, EDOT) oxidation self-polymerization intercalation into Na x Ni i Fe j Mn k M m O 2 In the layered oxide of (NFM-TM), PEDOT-NFM-TM layered oxide of conductive polymer intercalation is generated, the interlayer structure of the NFM is stabilized, the interlayer spacing is enlarged, the cut-off voltage of the material in the charge and discharge process is improved, and the gram capacity of the material is improved.
Specifically, i, j, k and m are the molar ratios of the corresponding elements respectively; when x is more than 0.6 and less than or equal to 0.8, the layered oxide is a layered oxide of P2 phase; when x is more than 0.8 and less than or equal to 1, the layered oxide is the layered oxide of O3 phase.
Further, the M ion is selected from Ca 2+ 、Ti 4+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Sn 4+ 、La 3+ 、Sr 2+ 、In 3+ 、Sm 3+ 、Nd 3 + 、Zr 4+ One or more of the following.
Further, in the step S1, high-temperature solid-phase sintering is performed for 4-20 hours at the temperature of 750-1100 ℃ (the heating rate is 1-10 ℃/min) to obtain a layered oxide Na x Ni i Fe j Mn k M m O 2 。
Further, the sodium source is selected from one or more of sodium carbonate, sodium hydroxide, sodium acetate, sodium oxalate, sodium nitrate, and sodium oxide.
Specifically, ni i Fe j Mn k M m (OH) 2 The precursor and the sodium source are mixed by ball milling,the ball milling rotating speed is 300-800 r/min, and the time is 0.5-5 h; during the mixing process, the sodium source is in excess of 3-5% by weight.
Further, the organic solvent is selected from one or more of methanol, ethanol, isopropanol, tetrahydrofuran and acetonitrile.
Specifically, the addition amount of the organic solvent and the layered oxide Na x Ni i Fe j Mn k M m O 2 The mass ratio of (2) is 10-15:1.
Further, in the step S2, the mass ratio of the layered oxide to the 3, 4-ethylenedioxythiophene is 1:0.08-0.15, for example, may be 1:0.08, 1:0.09, 1:0.1, 1:0.11, 1:0.12, 1:0.13, 1:0.14, 1:0.15, or any two ratio values.
Further, in the step S2, the time of the ultrasonic treatment is 0.5 to 2 hours.
Further, the oxidant is selected from one or more of ammonium persulfate, sodium persulfate, ferric sulfate and ferric chloride.
Further, in the steps S2 and S3, the molar ratio of the added 3, 4-ethylenedioxythiophene to the oxidant is 1:0.5-1, for example, may be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, or any two ratio values. Because the 3, 4-ethylenedioxythiophene has stronger reducibility than the layered oxide, and the 3, 4-ethylenedioxythiophene is oxidized firstly after the oxidant is added, the addition amount of the 3, 4-ethylenedioxythiophene is generally excessive, and the content of PEDOT is controlled by regulating and controlling the content of the oxidant. If the addition amount of the oxidant is too small, part of 3, 4-ethylene dioxythiophene is oxidized from the polymerization intercalation sodium ion battery layered oxide positive electrode material, and the rest part of unreacted 3, 4-ethylene dioxythiophene can be removed by absolute ethyl alcohol filtration; if the addition amount of the oxidant is too large, the more PEDOT is generated by the oxidation self-polymerization reaction of the 3, 4-ethylenedioxythiophene, and when the use amount of the 3, 4-ethylenedioxythiophene is too large, part of the polymer is difficult to be inserted between the layered oxide layers of the sodium ion battery and becomes impurities, so that the performance of the layered oxide anode material is affected.
Further, in the step S3, the time for continuing the ultrasonic treatment is 8 to 15 hours.
In the step S3, an organic solvent (such as absolute ethanol) is used for filtering, and the filtering times are 3-5 times; the drying is carried out under the vacuum condition, the drying temperature is 100-130 ℃, and the drying time is 5-12 h.
Further, the steps S1-S3 are carried out under the condition that the ambient humidity is less than or equal to 5 percent.
The second aspect of the invention provides the intercalation sodium-ion battery layered oxide positive electrode material prepared by the preparation method.
Further, the intercalation sodium ion battery layered oxide positive electrode material comprises layered oxide and intercalation; the layered oxide is Na x Ni i Fe j Mn k M m O 2 Wherein x is more than 0.6 and less than or equal to 1, i is more than 0 and less than 1, j is more than 0 and less than 1, k is more than 0 and less than 1, m is more than 0 and less than 0.3, i+j+k+m=1, and M ions are large-radius cations with the radius of 0.07-0.12 nm; the intercalation is PEDOT (polymer of EDOT).
The third aspect of the invention provides a sodium ion positive plate, comprising the intercalation sodium ion battery layered oxide positive electrode material.
A fourth aspect of the present invention provides a sodium ion battery comprising the sodium ion positive electrode sheet described above.
Compared with the prior art, the technical scheme of the invention has the following advantages: the invention discloses a method for intercalating a layered oxide positive electrode material of a sodium ion battery by large-size cation doping and matching 3, 4-ethylenedioxythiophene oxidation self-polymerization reaction. The large-radius cation doping and the intercalation of the conductive polymer expand the interlayer spacing, which is beneficial to the high-rate charge and discharge performance of the material; the intercalation of the conductive polymer stabilizes the layered oxide structure, improves the electrochemical performance of the material under high voltage, and improves the gram capacity of the material.
Drawings
FIG. 1 is a scanning electron microscope image of the material obtained in example 1.
FIG. 2 is an X-ray diffraction pattern of the material obtained in example 1.
FIG. 3 is a high power transmission electron micrograph of example 1, comparative examples 1-5, wherein (a) is a high power transmission electron micrograph of example 1, (b) is a high power transmission electron micrograph of comparative example 1, (c) is a high power transmission electron micrograph of comparative example 2, (d) is a high power transmission electron micrograph of comparative example 3, (e) is a high power transmission electron micrograph of comparative example 4, and (f) is a high power transmission electron micrograph of comparative example 5.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The invention provides a preparation method of an intercalation sodium ion battery layered oxide positive electrode material, which comprises the following steps:
A. ni is added with i Fe j Mn k M m (OH) 2 Placing the precursor and a sodium source (the excess is 3-5%) in a ball milling tank, and ball milling for 0.5-5 h at the rotating speed of 300-800 r/min to fully mix the precursor and the sodium source; placing the mixed powder into a muffle furnace, performing high-temperature solid-phase sintering at 750-1100 ℃ (the heating rate is 1-10 ℃/min) for 4-20 h, and naturally cooling and grinding to obtain a layered oxide material Na x Ni i Fe j Mn k M m O 2 (NFM-TM, TM represents a doping element) black powder.
Wherein M ions are large-radius cations, the radius r ranges from 0.07nm to 0.12nm and is selected from Ca 2+ 、Ti 4+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Sn 4+ 、La 3+ 、Sr 2+ 、In 3+ 、Sm 3+ 、Nd 3+ 、Zr 4+ One or more of the following; i, j, k and m are molar ratios of corresponding elements respectively, and satisfy 0 < i < 1,0 < j < 1,0 < k < 1,0 < m < 0.3, i+j+k+m=1; 0.6 <x is less than or equal to 1, when x is more than 0.6 and less than or equal to 0.8, the layered oxide is a layered oxide of P2 phase, and when x is more than 0.8 and less than or equal to 1, the layered oxide is a layered oxide of O3 phase.
B. To layered oxide material Na x Ni i Fe j Mn k M m O 2 The black powder of (2) is dissolved in an organic solvent, then 3, 4-ethylenedioxythiophene is added, and ultrasonic treatment is carried out for 0.5-2 h to obtain a mixed solution. And then, slowly adding a certain amount of oxidant into the mixed solution under the condition of continuous ultrasonic treatment, and continuing ultrasonic treatment for 8-15 hours. And filtering the obtained product with absolute ethyl alcohol for 3-5 times, and drying in a vacuum oven at 100-130 ℃ for 5-12 hours. Finally obtaining the PEDOT-NFM-TM material of the conductive polymer PEDOT intercalation.
Wherein the organic solvent is selected from one or more of methanol, ethanol, isopropanol, tetrahydrofuran and acetonitrile, and the mass ratio of the using amount of the organic solvent to the layered oxide powder is 10-15:1;
the mass ratio of the addition amount of the 3, 4-ethylenedioxythiophene to the layered oxide powder is 0.08-0.15:1;
the oxidant is one or more of ammonium persulfate, sodium persulfate, ferric sulfate and ferric chloride, and the molar ratio of the addition amount of the oxidant to the 3, 4-ethylenedioxythiophene is 0.5-1:1.
The obtained PEDOT-NFM-TM material with the conductive polymer PEDOT intercalated can be used for preparing sodium ion positive plates and sodium ion batteries.
Example 1:
1.1 Ni 0.2 Fe 0.3 Mn 0.45 Zr 0.05 (OH) 2 Placing the precursor and sodium acetate in a ball milling tank with the rotating speed of 300r/min according to the molar ratio of 1:1.03, and ball milling for 2 hours to fully mix the precursor and the sodium acetate; placing the mixed powder into a muffle furnace, carrying out high-temperature solid-phase sintering at 800 ℃ for 10h at a heating rate of 5 ℃/min, and naturally cooling and grinding to obtain a layered oxide material NaNi 0.2 Fe 0.3 Mn 0.45 Zr 0.05 O 2 (NFM-Zr) black powder.
1.2 layering oxide Material Na x Ni i Fe j Mn k M m O 2 The black powder of (2) is dissolved in an organic solvent (the organic solvent is ethanol, the mass ratio of the layered oxide to the organic solvent is 1:10), then 3, 4-ethylenedioxythiophene (the mass ratio of the layered oxide to the 3, 4-ethylenedioxythiophene is 1:0.15) is added, and the mixed solution is obtained by ultrasonic treatment for 1 h. Then, under the condition of continuous ultrasonic treatment, a certain content of sodium persulfate is slowly added into the mixed solution (the molar ratio of 3, 4-ethylenedioxythiophene to sodium persulfate is 1:0.7), and ultrasonic treatment is continued for 8 hours. And filtering the obtained product with absolute ethyl alcohol for 5 times, and drying in a vacuum oven at 100-130 ℃ for 5-12 h. Finally obtaining the PEDOT-NFM-Zr material of the conductive polymer PEDOT intercalation.
The scanning electron microscope image of the obtained material is shown in fig. 1, the X-ray diffraction image is shown in fig. 2, and the high-power transmission electron microscope image is shown in fig. 3 (a).
Example 2:
this example was prepared exactly as in example 1, except that: preparation of sodium ion Battery layered oxide cathode Material NaNi 0.3 Fe 0.25 Mn 0.4 La 0.05 O 2 Finally obtaining the PEDOT-NFM-La material of the conductive polymer intercalation.
Example 3:
this example was prepared exactly as in example 1, except that: preparation of sodium ion Battery layered oxide cathode Material NaNi 0.25 Fe 0.25 Mn 0.4 Zn 0.1 O 2 Finally obtaining the PEDOT-NFM-Zn material of the conductive polymer intercalation.
Example 4:
this example was prepared exactly as in example 1, except that: preparation of sodium ion Battery layered oxide cathode Material NaNi 0.25 Fe 0.25 Mn 0.45 Cu 0.05 O 2 Finally obtaining the PEDOT-NFM-Cu material of the conductive polymer intercalation.
Example 5:
this example was prepared exactly as in example 1, except that: the molar ratio of 3, 4-ethylenedioxythiophene to sodium persulfate is 1:1, finally obtaining the PEDOT-NFM-Zr material of the conductive polymer intercalation.
Comparative example 1:
this comparative example was prepared exactly according to the protocol of example 1, except that: preparation of non-conductive polymer intercalation sodium ion battery layered oxide positive electrode material NaNi 0.33 Fe 0.33 Mn 0.34 O 2 。
The high power transmission electron microscope image of the obtained material is shown in fig. 3 (b).
Comparative example 2:
this comparative example was prepared exactly according to the protocol of example 1, except that: preparation of non-conductive polymer intercalation sodium ion battery layered oxide positive electrode material NaNi 0.33 Fe 0.33 Mn 0.34 O 2 Finally obtaining the PEDOT-NFM material of the conductive polymer intercalation.
The high power transmission electron microscope image of the obtained material is shown in fig. 3 (c).
Comparative example 3:
this comparative example was prepared exactly according to the protocol of example 1, except that: preparation of NaN, a layered oxide cathode material of sodium ion battery without conductive polymer intercalation 0.2 Fe 0.3 Mn 0.45 Zr 0.05 O 2 。
The high power transmission electron microscope image of the obtained material is shown in fig. 3 (d).
Comparative example 4:
this comparative example was prepared exactly according to the protocol of example 1, except that: preparation of non-conductive polymer intercalation sodium ion battery layered oxide positive electrode material NaNi 0.2 Fe 0.3 Mn 0.45 Co 0.05 O 2 。
The high power transmission electron microscope image of the obtained material is shown in fig. 3 (e).
Comparative example 5:
this comparative example was prepared exactly according to the protocol of example 1, except that: preparation of sodium ion Battery layered oxide cathode Material NaNi 0.2 Fe 0.3 Mn 0.45 Co 0.05 O 2 Finally, the conductive polymer insert is obtainedThe PEDOT-NFM-Co material of the layer.
The high power transmission electron microscope image of the obtained material is shown in fig. 3 (f).
Analysis of results:
sodium ion batteries were prepared using the materials obtained in examples 1 to 5 and comparative examples 1 to 5, and subjected to electrochemical tests.
The preparation method of the sodium ion battery comprises the following steps:
grinding the obtained material, conductive agent Super P and binder PVDF uniformly according to the mass ratio of 9:0.5:0.5, adding a proper amount of NMP to prepare slurry, uniformly coating the slurry on the pretreated aluminum foil, drying the aluminum foil in a blast drying oven at 80 ℃ for 1h, and drying the aluminum foil in a vacuum drying oven at 120 ℃ for 12h; then cutting into 14mm round positive plates by a cutting machine. Sodium metal sheet with the diameter of 14mm and the thickness of 0.2mm is used as a negative electrode, 0.1mol/L sodium hexafluorophosphate/ethylene carbonate/dimethyl carbonate solution is used as electrolyte, whatman GF/F glass fiber with the diameter of 16mm is used as a diaphragm, and the CR2032 button cell is assembled in a glove box filled with high-purity argon.
The electrochemical test method comprises the following steps:
the charge and discharge test was performed at a current density of 0.1C using a constant current charge and discharge mode. The test items include: the material has 0.1C first-turn charge-discharge capacity, rate capability (1C, 2C, 5C and 10C discharge capacity) and capacity retention rate of 200 turns of 1C charge-discharge in sodium ion batteries. The test results are shown in table 1 under the condition that the discharge cut-off voltage is 2.0V and the charge cut-off voltage is 4.12V.
TABLE 1
| Group of | Material | 0.1C first circle Discharge capacity mAh/g | 1C discharge capacity mAh/g | 2C discharge vessel Amount mAh/g | 5C discharge vessel Amount mAh/g | 10C discharge Capacity mAh/g | 1C 200 circle Capacity retention Rate% |
| Example 1 | PEDOT-NFM-Zr | 137.6 | 134.3 | 128.1 | 116.3 | 101.5 | 83.4 |
| Example 2 | PEDOT-NFM-La | 145.2 | 142.2 | 136.6 | 124.3 | 109.3 | 82.1 |
| Example 3 | PEDOT-NFM-Zn | 142.5 | 139.5 | 133.7 | 121.1 | 106.4 | 82.5 |
| Example 4 | PEDOT-NFM-Cu | 141.6 | 139.9 | 133.8 | 121.7 | 106.9 | 83.1 |
| Example 5 | PEDOT-NFM-Zr | 134.6 | 131.1 | 124.1 | 112.4 | 95.5 | 80.2 |
| Comparative example 1 | NFM | 148.9 | 142.3 | 134.5 | 104.3 | 54.6 | 56.1 |
| Comparative example 2 | PEDOT-NFM | 147.2 | 141.7 | 133.5 | 103.6 | 52.3 | 57.5 |
| Comparative example 3 | NFM-Zr | 137.8 | 133.5 | 125.1 | 109.1 | 69.3 | 66.5 |
| Comparative example 4 | NFM-Co | 141.8 | 136.4 | 129.1 | 113.5 | 73.1 | 65.4 |
| Comparative example 5 | PEDOT-NFM-Co | 139.2 | 134.1 | 124.3 | 108.4 | 68.1 | 65.1 |
As can be seen from table 1, in the case that the main materials of examples 1 to 5 and comparative examples 1 to 5 are layered oxide cathode materials, the materials prepared by the method of doping large-size cations and matching with the intercalation of conductive polymer according to the present invention in examples 1 to 5 have excellent cycle and rate performance under a high voltage test of 4.12V; example 5 is compared to example 14, the higher the proportion of the oxidant is, the more PEDOT is generated by the oxidation self-polymerization reaction of 3, 4-ethylenedioxythiophene, the more PEDOT polymer possibly exists, and part of the PEDOT polymer is difficult to insert between layers of layered oxides to become impurities in the positive electrode material, so that the gram capacity exertion and capacity retention rate of the embodiment 5 are weaker than those of the embodiments 1-4. Comparative example 1 is an undoped matrix material NFM, which is inferior in cycle and rate compared to examples 1-5. Comparative example 2 conducting polymer intercalation was carried out on undoped matrix material NFM, and as seen from the transmission electron microscopy pictures, the interlayer spacing of the material did not change significantly, and the surface conducting polymer did not intercalate between layers of the material, affecting the interlayer spacing. Comparative example 3 and example 1 have the same matrix material NFM-Zr, except that comparative example 3 has no conductive polymer intercalation, and as can be seen from the transmission electron microscope picture, the interlayer spacing of the conductive polymer intercalation example 1 material is significantly increased, and the rate performance and cycle performance of example 1 are significantly improved compared with comparative example 3 at high voltage. Comparative example 4 and comparative example 5 have the same base materials of small ion radius doped NFM-Co material and conductive polymer intercalated NFM-Co material, respectively, as seen from transmission electron microscopy pictures, the interlayer spacing of the small ion radius doped NFM material is not significantly changed compared to the NFM material, and thus the conductive polymer is not intercalated between the layers; there is no significant change in the interlayer spacing of the NFM-Co material of the conductive polymer intercalation. The reason why the magnification and the cycle performance of the NFM-Co material and the NFM-Co material intercalated by the conductive polymer are superior to those of the NFM material of the substrate material at high voltage is that Co is introduced 3+ Doping stabilizes the structure of the material, but its rate and cycle performance are also somewhat different from examples 1-5.
In conclusion, the method for doping large-size cations and matching with the intercalation of the conductive polymer greatly improves the multiplying power and the cycle performance of the material under high pressure.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the intercalation sodium ion battery layered oxide positive electrode material is characterized by comprising the following steps of,
s1: ni is added with i Fe j Mn k M m (OH) 2 Mixing the precursor with a sodium source, and sintering to obtain layered oxide Na x Ni i Fe j Mn k M m O 2 Wherein x is more than 0.6 and less than or equal to 1, i is more than 0 and less than 1, j is more than 0 and less than 1, k is more than 0 and less than 1, m is more than 0 and less than 0.3, i+j+k+m=1, and M ions are large-radius cations with the radius of 0.07-0.12 nm;
s2: the layered oxide Na x Ni i Fe j Mn k M m O 2 Dissolving in an organic solvent, then adding 3, 4-ethylenedioxythiophene, and performing ultrasonic treatment to obtain a mixed solution;
s3: under the ultrasonic condition, adding an oxidant into the mixed solution, continuing ultrasonic treatment, separating and drying to obtain the intercalation sodium-ion battery layered oxide anode material.
2. The method according to claim 1, wherein in the step S1, the sintering temperature is 750-1100 ℃ and the sintering time is 4-20 hours.
3. The method of claim 1, wherein the M ion is selected from the group consisting of Ca 2+ 、Ti 4+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Sn 4+ 、La 3+ 、Sr 2+ 、In 3+ 、Sm 3+ 、Nd 3+ 、Zr 4+ One or more of the following.
4. The process according to claim 1, wherein in step S2, 3, 4-ethylenedioxythiophene is added in the form of layered oxide Na x Ni i Fe j Mn k M m O 2 8% -15% of the weight.
5. The method of claim 1, wherein the oxidizing agent is selected from one or more of ammonium persulfate, sodium persulfate, ferric sulfate, and ferric chloride.
6. The method according to claim 1 or 5, wherein in the steps S2 and S3, the molar ratio of the 3, 4-ethylenedioxythiophene to the oxidizing agent is 1:0.5-1.
7. The method according to claim 1, wherein in the step S3, the ultrasonic treatment is continued for 8 to 15 hours.
8. An intercalated sodium ion battery layered oxide positive electrode material prepared by the preparation method of any one of claims 1-7.
9. A sodium ion positive electrode sheet comprising the intercalated sodium ion battery layered oxide positive electrode material of claim 8.
10. A sodium ion battery comprising the sodium ion positive electrode sheet of claim 9.
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| CN115642237A (en) * | 2022-10-28 | 2023-01-24 | 无锡零一未来新材料技术研究院有限公司 | Sodium ion composite cathode material and preparation method and application thereof |
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