GB2619658A - Sodium-ion battery positive electrode material, and preparation method therefor and use thereof - Google Patents
Sodium-ion battery positive electrode material, and preparation method therefor and use thereof Download PDFInfo
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- GB2619658A GB2619658A GB2314639.2A GB202314639A GB2619658A GB 2619658 A GB2619658 A GB 2619658A GB 202314639 A GB202314639 A GB 202314639A GB 2619658 A GB2619658 A GB 2619658A
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- sodium
- positive electrode
- electrode material
- salt solution
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 54
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 44
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000012266 salt solution Substances 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- XXSPKSHUSWQAIZ-UHFFFAOYSA-L 36026-88-7 Chemical compound [Ni+2].[O-]P=O.[O-]P=O XXSPKSHUSWQAIZ-UHFFFAOYSA-L 0.000 claims description 8
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229960002413 ferric citrate Drugs 0.000 claims description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 3
- 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 3
- 239000002904 solvent Substances 0.000 claims description 3
- MVNQJLFBHVHULX-UHFFFAOYSA-L cobalt(2+);2-hydroxybutanedioate Chemical compound [Co+2].[O-]C(=O)C(O)CC([O-])=O MVNQJLFBHVHULX-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229940049920 malate Drugs 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 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 abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052708 sodium Inorganic materials 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 150000001768 cations Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000011229 interlayer Substances 0.000 abstract 1
- 239000012298 atmosphere Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000001632 sodium acetate Substances 0.000 description 5
- 235000017281 sodium acetate Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910020939 NaC104 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 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
- H01M4/48—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
- H01M4/362—Composites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/36—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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The present invention belongs to the technical field of sodium-ion batteries, and discloses a sodium-ion battery positive electrode material, and a preparation method therefor and the use thereof. The general formula of the sodium-ion positive electrode material is NaaMbNicPdO2, wherein M is at least one of cobalt, iron and manganese; and 0<a<1, 0<b<1, 0<c<1, and 1-b-c<d<1. In the sodium-ion positive electrode material of the present invention, part of nickel and phosphorus enter the crystal lattices of a sodium-rich material to occupy sodium sites, such that not only is the mixed arrangement of cations reduced, but the interlayer spacing of crystals is also increased, and the specific capacity and cycle performance of the positive electrode material are improved; and the surface thereof is further coated with a metal oxide, such that the cycling stability and safety are improved, and not only is an increase in the total impedance effectively prevented and a transfer impedance during charging in a desodiation state reduced, but a side reaction of an electrolyte and the positive electrode material is also prevented.
Description
SODIUM-ION BATTERY POSITIVE ELECTRODE MATERIAL, AND PREPARATION
METHOD THEREFOR AND USE THEREOF
FIELD
100011 The present disclosure belongs to the technical field of sodium-ion batteries, and specifically relates to a positive electrode material for sodium-ion battery and a preparation method and application thereof.
BACKGROUND
[0002] Sodium-ion batteries have been widely used in the field of energy storage. Sodium-ion batteries have the advantages of abundant resources, low price, and environmental friendliness, and sodium element will not undergo an alloying reaction with the aluminum current collector, so that the negative electrode can also use cheap aluminum instead of copper as the current collector, which further reduces the system cost However, the large ionic radius and slow kinetic rate of sodium ions have become the main factors restricting the development of sodium storage materials. The specific capacity of positive electrode materials (80-150 mAh-g-1) is still far lower than that of negative electrode materials (carbon material: not less than 250 mAh-g--1; alloy material: 400-600 mAlrg-1). Therefore, the development of high-performance sodium-intercalating positive electrode materials is the key to improving the specific energy of sodium-ion batteries and advancing their applications.
[0003] At present, there are still many problems in the performance of positive electrode materials for sodium-ion batteries that need to be improved. When the sodium ions in the positive electrode material are deintercalated, it is susceptible to the collapse of the structure and the change of the volume. The electrolyte reacts with the positive active material, resulting in a decrease in specific capacity, thereby affecting the performance of the battery. Insufficiency of oxygen vacancies in the positive electrode material leads to the deintercalati on of oxygen from the lattice, thereby affecting the crystal structure.
[0004] Therefore, it is urgent to study a new joint modified positive electrode material and a preparation method thereof, so as to improve the inadequate performance, such as specific capacity and cycle performance, of the positive electrode material.
SUMMARY
[0005] The present disclosure aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, the present disclosure proposes a positive electrode material for sodium-ion battery and a preparation method and application thereof, and the sodium-ion positive electrode material has excellent specific capacity and cycle performance.
[0006] To achieve the above object, the present disclosure adopts the following technical solutions [0007] A sodium-ion positive electrode material with a general formula of NaaMbNi0Pd02; wherein M is at least one of cobalt, iron and manganese; and 0<a<1, 0<b<1, 0<c<1, 1-b-c<d<1.
[0008] Preferably, the sodium-ion positive electrode material has a general formula of NarM,Nic.Pd02; wherein M is at least one of cobalt, iron, and manganese; and 0. 5<a<1, 0<b<0. 8, 0<c<1, 1 -b-c<d< I. [0009] Preferably, the sodium-ion positive electrode material is one of Na0.4MnNi0.05P0.0402, Na0.35CoNi0.09130.0602, Na0.6FeNi0.12P0.0802 and Na0.7MnNi0.17P0.1302.
[0010] A preparation method of a sodium-ion positive electrode material, comprising steps of: [0011] (1) mixing an M salt solution and a sodium salt solution, adding a chelating agent, reacting, and calcining to obtain NaaMb02; and 100121 (2) mixing the NaaM,02 with a solvent, adding nickel hypophosphite, reacting, and calcining to obtain the sodium-ion positive electrode material; wherein the M salt solution is at least one of a manganese salt solution, a cobalt salt solution, and an iron salt solution.
[0013] Preferably, the manganese salt solution is at least one of manganese malate, manganese oxalate and manganese acetate.
[0014] Preferably, the cobalt salt solution is at least one of cobalt acetate, cobalt malate, and cobalt oxalate.
100151 Preferably, the iron salt solution is at least one of ferric citrate, ferric acetate, and ferric oxalate [0016] Preferably, in step (1), before adding the chelating agent, it further comprises mixing the M salt solution and the sodium salt solution and adding the mixture into a dispersing agent for dispersion; and the dispersing agent is at least one of ethanol, propanol and formaldehyde resin.
100171 Preferably, in step (1), the chelating agent is at least one of ethanedioic acid, oxalic acid and citric acid [0018] Preferably, in step (1), a temperature of the reaction is 40-60°C, and a duration of the reaction is I 2-24 h. [0019] Preferably, in step (1), the calcining comprises first calcination and second calcination, a temperature of the first calcination is 300-500°C and a duration of the first calcination is 2-4 h; a temperature of the second calcination is 800-1000°C, and a duration of the second calcination is 12-AS h. 100201 Preferably, in step (2), the solvent is ethanol.
[0021] Preferably, in step (2), a temperature of the reaction is 40-60°C, and a duration of the reaction is 4-8 h. [0022] Preferably, in step (2), a temperature of the calcination is 500-600°C, and a duration of the calcination is 6-12 h. [0023] The reaction equation in step (2) is: Ni(H2P02)2 -N HP0.1+ P1-131; 2NiHPO4 = Ni2P207 + H20, Ni2P207 NaaMb02 -Naa-x-vMbNixPy 02 ± N12-xNaxP2-y 07, where 0<x<I,0<y< I. [0024] A battery, comprising the sodium-ion positive electrode material.
100251 Compared with the prior art, the present disclosure has the following beneficial effects: [0026] 1. In the sodium-ion positive electrode material NaMI,NT.Pd02 of the present disclosure, part of nickel element and phosphorus element enter the crystal lattice of the sodium-rich material to occupy sodium positions, which not only reduces cation mixing, but also increases the crystal layer spacing and improves the specific capacity and cycle performance of the positive -3 -electrode material with a specific capacity up to174 mAh/g. In addition, the surface is coated with metal oxide to improve cycle stability and safety, which not only effectively prevents the increase of total impedance and reduces the charge transfer impedance in the state of sodium deintercalation, but also prevents side reactions between the electrolyte and the positive electrode material.
[0027] 2. In the preparation method of the present disclosure, nickel hypophosphite will generate PH3 under high temperature conditions. PH3 has strong reducibility, can cause the release of active oxygen from the positive electrode material of the battery and generate more oxygen vacancies. The oxygen vacancies are beneficial to buffering the migration of 02. during the charge-discharge process, inhibiting the irreversible loss of lattice oxygen, and providing favorable conditions for the next step of generating Ni213207.
BRIEF DESCRIPTION OF DRAWINGS
[0028] FIG 1 is an SEM image of the positive electrode material in Example I of the present
disclosure;
[0029] FIG. 2 is XRD patterns of the positive electrode materials in Example 1 and Comparative Example 1 of the present disclosure.
DETAILED DESCRIPTION
[0030] The concept of the present disclosure and the technical effects produced thereby will be clearly and completely described below in conj unction with the examples, so as to fully understand the purpose, characteristics and effects of the present disclosure. Obviously, the described examples are only a part of the embodiments of the present disclosure, rather than all the embodiments. Based on the embodiments of the present disclosure, other embodiments obtained by those skilled in the art without creative efforts are all within the scope of protection
of the present disclosure.
Example 1
[0031] The sodium-ion positive electrode material of this example has a formula of Na() 4MnNio 06P0 0402.
[0032] The preparation method of the sodium-ion positive electrode material of this example comprises the following specific steps: [0033] (1) 0.5 mol of sodium acetate solution and 1 mol of manganese acetate solution were dissolved in 100 nth of ethanol, and added with 1 mol of ethanedioic acid under mixing. The mixture was reacted in an environment of 40°C for 12 h, and then calcined under an air atmosphere at 300°C for 2 h. After cooling to room temperature, an intermediate of Na0.5Mn02 was synthesized and calcined under an air atmosphere at 800°C for 12 h. After cooling to room temperature naturally, the final product Na0.5Mn02 was obtained [0034] (2) 4 mol Nao.5Mn02 was added to 50 mL of ethanol, and then I mol of nickel hypophosphite was added. The mixture was reacted at 40°C for 4 h until all the ethanol was evaporated. The obtained substance was ground, and calcined under Ar atmosphere at 500°C for 6 h to synthesize the positive electrode material for sodium-ion battery, Na0.4.N4nNio.06P0.0402.
Example 2
[0035] The sodium-ion positive electrode material of this example has a formula of Na035CONi0.09P0.0602.
[0036] The preparation method of the sodium-ion positive electrode material of this example comprises the following specific steps: [0037] ( I) 0.5 mol of sodium acetate solution and I mol of cobalt acetate solution were dissolved in 100 inL of ethanol, and added with 1.2 mol of ethanedioic acid under mixing. The mixture was reacted in an environment of 45°C for 15 h, and then calcined under an air atmosphere at 350°C for 2.5 h. After cooling to room temperature, an intermediate of Na0.5Co02 was synthesized and calcined under an air atmosphere at 800°C for 12 h. After cooling to room temperature naturally, the final product Nao.5Co02 was obtained.
[0038] (2) 3 mol Na0.5C002. was added to 50 mL of ethanol, and then 1 mol of nickel hypophosphite was added. The mixture was reacted at 40°C for 4 h until all the ethanol was evaporated. The obtained substance was ground, and calcined under Ar atmosphere at 500°C for 6 h to synthesize the positive electrode material for sodium-ion battery, Na0.35CoNio.09P0.0602. -5 -
Example 3
[0039] The sodium-ion positive electrode material of this example has a formula of Na0.6FeNio.i2Po.0502.
[0040] The preparation method of the sodium-ion positive electrode material of this example comprises the following specific steps: [0041] (1) 0.8 mol of sodium acetate solution and 1 mol of ferric citrate solution were dissolved in 100 mL of ethanol, and added with 1.5 mol of ethanedioic acid under mixing. The mixture was reacted in an environment of 50°C for 18 h, and then calcined under an air atmosphere at 300°C for 2 h. After cooling to room temperature, an intermediate of Nao.gFe02 was synthesized and calcined under an air atmosphere at 800°C for 16 h. After cooling to room temperature naturally, the final product NaD.8Fe02 was obtained.
[0042] (2) 2 mol Na0.8Fe02 was added to 50 mL of ethanol, and then 1 mol of nickel hypophosphite was added. The mixture was reacted at 50°C for 6 h until all the ethanol was evaporated. The obtained substance was ground, and calcined under Ar atmosphere at 560°C for 10 h to synthesize the positive electrode material for sodium-ion battery, Na0.6FeNift12P0.0802.
Example 4
[0043] The sodium-ion positive electrode material of this example has a formula of Na0.7MnNi0.171"0.1302.
[0044] The preparation method of the sodium-ion positive electrode material of this example comprises the following specific steps: [0045] (1) 1 mol of sodium acetate solution and 1 mol of manganese acetate solution were dissolved in 100 mL of ethanol, and added with 2 mol of ethanedioic acid under mixing. The mixture was reacted in an environment of 50°C for 18 h, and then calcined under an air atmosphere at 300°C for 2 h. After cooling to room temperature, an intermediate of NaMn02 was synthesized and calcined under an air atmosphere at 1000°C for 18 h. After cooling to room temperature naturally, the final product NaMn02 was obtained.
[0046] (2) 1 mol NaMn02 was added to 50 mL of ethanol, and then 1 mol of nickel hypophosphite was added. The mixture was reacted at 60°C for 8 h until all the ethanol was
- -
evaporated. The obtained substance was ground, and calcined under Ar atmosphere at 600°C for 12 h to synthesize the positive electrode material for sodium-ion battery, Na0.7MnNi0.17E0.1302.
Comparative Example 1 [0047] The sodium-ion positive electrode material of this comparative example has a formula of Na0.51V1n02.
[0048] The preparation method of the sodium-ion positive electrode material of this comparative example comprises the following specific steps: [0049] (1) 0.5 mol of sodium acetate solution and 1 mol of manganese acetate solution were dissolved in 100 mL of ethanol, and added with 1 mol of ethanedioic acid under mixing. The mixture was reacted in an environment of 40°C for 12 h, and then calcined under an air atmosphere at 300°C for 2 h. After cooling to room temperature, an intermediate of Na0.5Mn02 was synthesized and calcined under an air atmosphere at 800°C for 12 h. After cooling to room temperature naturally, the final product NaD.5Mn02 was obtained.
Analysis of Examples 1-4 and Comparative Example 1: [0050] The sodium-ion positive electrode material, carbon black conductive agent, and polytetrafluoroethylene were mixed and dissolved in deionized water in a mass ratio of 80:10:10 to prepare a slurry, which was then coated on aluminum foil to form electrode sheet. The electrode sheet was placed in a drying box to dry at 80°C for 12 h, and stamped into a disc with a die. The disc was cut into a counter electrode sheet with a diameter of 10 mm. 1.0 mol/L NaC104 was added to carbonate as an electrolyte, Celgard2400 was used as separator, and the battery was assembled in a vacuum glove box under argon atmosphere. The cycle performance was tested with an electrochemical workstation, and the test was performed at a current density of 150 mA*g-1 and a rate of 2C.
Table I: Effect data of Examples 1-4 and Comparative Example I Sample type Specific capacity Capacity retention Capacity retention rate at the first rate after 100 after 200 cycles of charge-discharge cycles of battery battery charged at 1C mAh/g charged at 1 C (%) (%) Nao5Mn02, 142 90.5 80.4 Example 1 158 96.2 90.2 Example 2 162 95.8 90.3 Example 3 182 95.3 89.7 Example 4 174 95.6 91.8 [0051] Referring to FIGs. 1-2, FIG. 1 is an SEM image of the positive electrode material in Example 1 of the present disclosure; it can be seen from FIG. 1 that the prepared battery positive electrode material was in a block shape; FIG. 2 is XRD patterns of the positive electrode materials prepared in Example 1 and Comparative Example 1 of the present disclosure; it can be seen from FIG. 2 that nickel element and phosphorus element were doped into the battery positive electrode material.
[0052] The embodiments of the present disclosure have been described in detail above in conjunction with the drawings. However, the present disclosure is not limited to the above-mentioned embodiments, and various modifications can be made without departing from the purpose of the present disclosure within the scope of knowledge possessed by those of ordinary skill in the art. In addition, in the case of no conflict, the embodiments of the present disclosure and the features in the embodiments may be combined with each other.
Claims (10)
- CLAIMSI. A sodium-ion positive electrode material with a general formula of Na"MbNicl3d02; wherein M is at least one of cobalt, iron and manganese; and 0<a< I, 0<b<I, 0<c<I, I -b-c<d<I.
- 2. The sodium-ion positive electrode material according to claim 1, wherein the sodium-ion positive electrode material is one of Na0.4MnNi0.06P0.0402, Na0.35CoNi0.09P0.0602, Na0.6FeNio.i2Po.0802 and Na0.7MnNi0.17P0.1302.
- 3. A preparation method of the sodium-ion positive electrode material according to any one of claims 1-2, comprising steps of: (1) mixing an M salt solution and a sodium salt solution, adding a chelating agent, reacting, and calcining to obtain NaaMb02, and (2) mixing the NaaM1,02 with a solvent, adding nickel hypophosphite, reacting, and calcining to obtain the sodium-ion positive electrode material; wherein the M salt solution is at least one of a manganese salt solution, a cobalt salt solution, and an iron salt solution.
- 4. The preparation method according to claim 3, wherein the manganese salt solution is at least one of manganese malate, manganese oxalate and manganese acetate; and the cobalt salt solution is at least one of cobalt acetate, cobalt malate and cobalt oxalate.
- 5. The preparation method according to claim 3, wherein the iron salt solution is at least one of ferric citrate, ferric acetate and ferric oxalate.
- 6. The preparation method according to claim 3, wherein in step (1), before adding the chelating agent, it further comprises mixing the M salt solution and the sodium salt solution and adding the mixture into a dispersing agent for dispersion; and the dispersing agent is at least one of ethanol, propanol and formaldehyde resin.
- 7. The preparation method according to claim 3, wherein in step ( I), the chelating agent is at least one of ethanedioic acid, oxalic acid and citric acid.
- 8. The preparation method according to claim 3, wherein in step (1), the calcining comprises first calcination and second calcination, a temperature of the first calcination is 300-500°C and a duration of the first calcination is 2-4 h; a temperature of the second calcination is 800-1000°C, and a duration of the second calcination is 12-18 h.
- 9. The preparation method according to claim 3, wherein in step (2), a molar ratio of Na.1\41302 to nickel hypophosphite is (1-4): 1
- 10. A battery, comprising the sodium-ion positive electrode material according to any one of claims 1-2.-10 -
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| CN114256451A (en) * | 2021-11-29 | 2022-03-29 | 广东邦普循环科技有限公司 | Sodium-ion battery positive electrode material and preparation method and application thereof |
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| JPH0714579A (en) * | 1993-06-25 | 1995-01-17 | Fuji Photo Film Co Ltd | Nonaqueous electrolyte secondary battery |
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| CN113130877B (en) * | 2021-06-18 | 2021-09-24 | 长沙理工大学 | Polycrystalline positive electrode material synchronously modified by doping and dip coating, and solid-phase preparation method and application thereof |
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| JPH0714579Y2 (en) * | 1990-10-23 | 1995-04-10 | 株式会社アルファ | Light guide member for keyhole illumination |
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