CN116885121A - Nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material, and preparation method and application thereof - Google Patents
Nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN116885121A CN116885121A CN202310789074.7A CN202310789074A CN116885121A CN 116885121 A CN116885121 A CN 116885121A CN 202310789074 A CN202310789074 A CN 202310789074A CN 116885121 A CN116885121 A CN 116885121A
- Authority
- CN
- China
- Prior art keywords
- nickel
- sodium
- vanadium
- sodium alginate
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 title claims abstract description 45
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 45
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 45
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 22
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 15
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 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 abstract description 12
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims abstract description 11
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000007547 defect Effects 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 6
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 6
- 210000003278 egg shell Anatomy 0.000 claims abstract description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 5
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
- 238000000498 ball milling Methods 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- 239000011324 bead Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000011231 conductive filler Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 208000035475 disorder Diseases 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000001364 causal effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000012002 vanadium phosphate Substances 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
- H01M4/04—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
- H01M4/58—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
-
- 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
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
Abstract
The application belongs to the technical field of sodium ion battery positive electrode materials, and provides a nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material, a preparation method and application thereof, and aims to solve the problems of poor intrinsic conductivity and low energy density of the existing sodium vanadium phosphate. Nickel acetate tetrahydrate, vanadium pentoxide and sodium carbonate are used as raw materials, sodium alginate is used as a partial sodium source and a reducing agent, the solid phase method is used for preparing the nickel-doped vanadium site, a redox couple is introduced into the nickel-doped vanadium site to generate a vanadium tetravalent and vanadium pentavalent redox couple, three high-discharge platforms are constructed, nickel-crosslinked sodium alginate, nickel ions and G blocks in the sodium alginate structure are subjected to ion exchange and integrated to form an egg-shell structure, and a nickel-doped carbon coating layer with a large number of defects and a gauze-shaped carbon interconnection network are formed after sintering; and obtaining the nickel-crosslinked sodium vanadium phosphate composite anode material induced by the nickel-crosslinked sodium alginate, which is composed of the sodium vanadium phosphate nickel-doped carbon coating layer. The device has stable multi-section high-voltage platform, high energy density and remarkable practical value.
Description
Technical Field
The application belongs to the technical field of sodium ion battery anode materials, and particularly relates to a nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite anode material, and a preparation method and application thereof.
Background
Lithium ion batteries have been widely used as the most advanced energy storage secondary batteries. However, the battery resources required upstream are difficult to cope with the large scale of downstream applications, exposing to lithium resource shortages and being susceptible to both the causal and oligopolistic pain issues. The sodium element and the lithium element are the same main group element and have similar chemical properties. And the structure and packaging process of the sodium ion battery are highly similar to those of a lithium battery, and a factory for producing the lithium battery can directly produce the sodium battery without great modification. Therefore, sodium ion batteries are considered as the main stream batteries of the new generation, and are the most preferred alternative to lithium batteries.
The hexagonal sodium vanadium phosphate has a higher voltage platform (3.4 V.s.Na) and a high theoretical specific capacity (117.6 mAh/g), is a potential sodium ion battery polyanion type positive electrode material, and has the advantages of sodium super ion conductor (NASICON) structure, good chemical stability, long service life, high natural abundance and the like. However, the larger atomic radius and mass of sodium ions compared to lithium ions lead to the fact that it suffers from low energy density in practical applications, which makes sodium ion batteries difficult to apply in the field of power batteries. Therefore, increasing the energy density of the sodium vanadium phosphate cathode material becomes a key to its practical application. At the same time, the strong bond and action of the v—o bond results in a low electronic conductivity of the vanadium sodium phosphate material, which limits its further development.
Since the content of active sodium ions of the sodium vanadium phosphate determines the discharge capacity, the energy density can only be improved by a method for improving a discharge platform. The discharge platform corresponds to a redox couple, but a common redox couple is difficult to realize a high discharge platform, and the energy density of the vanadium sodium phosphate electrode material is limited to be improved. In addition, the improvement in the electron conductivity of the battery is generally achieved by a carbon-coated approach. However, the ordering of the carbon layer may hinder the diffusion process of sodium ions, negatively affecting the discharge process.
Disclosure of Invention
The application provides a nickel-crosslinked sodium alginate-induced vanadium phosphate composite anode material, a preparation method and application thereof, and aims to solve the problems of poor intrinsic conductivity and low energy density of the existing sodium vanadium phosphate. By doping vanadium sites with nickel, a new redox couple is introduced, and the formation of a tetravalent vanadium redox couple and a pentavalent vanadium redox couple is promoted, so that the construction of three high-discharge platforms is realized, and the energy density of the material is greatly improved. Meanwhile, the nickel-crosslinked sodium alginate forms a nickel-doped carbon coating layer with a large number of defects and a gauze-like carbon interconnection network in the sintering process, so that the ionic conductivity and the electronic conductivity of the material are improved, and the material shows excellent electrochemical performance. The electrode material is loaded on 2025 button cells, shows excellent cycle stability and high-rate long cycle performance, and can be regarded as a sodium ion battery positive electrode material with great prospect.
The application is realized by the following technical scheme: the composite positive electrode material is prepared by taking nickel acetate tetrahydrate, vanadium pentoxide and sodium carbonate as raw materials and sodium alginate as partial sodium sources and reducing agents through a solid phase method, wherein nickel is doped with vanadium sites, redox electric pairs are introduced, and the generation of vanadium tetravalent and vanadium pentavalent redox electric pairs is promoted, so that three high-discharge platforms are constructed, meanwhile, nickel crosslinked sodium alginate, nickel ions and G blocks in the sodium alginate structure are subjected to ion exchange and integrated to form an egg-shell structure, and a nickel doped carbon coating layer with a large number of defects and a gauze-like carbon interconnection network are formed after sintering; and obtaining the nickel-crosslinked sodium vanadium phosphate composite anode material induced by the nickel-crosslinked sodium alginate, which is composed of the sodium vanadium phosphate nickel-doped carbon coating layer.
The method for preparing the nickel crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material comprises the following specific steps:
(1) Sodium alginate, vanadium pentoxide, sodium carbonate, monoammonium phosphate and nickel acetate tetrahydrate are taken and placed in a planetary ball milling tank; wherein the mass ratio of the sodium alginate to the vanadium pentoxide to the sodium carbonate to the ammonium dihydrogen phosphate to the nickel acetate tetrahydrate is 0.5:2.3935:1.0461:2.2707:0.0143 to 0.0257;
(2) Adding 25mL of absolute ethyl alcohol into a planetary ball milling tank, and putting into ball milling beads; wherein the mass ratio of the raw materials to the beads is 1:60, ball milling frequency is 40Hz, ball milling time is 8h, and the ball milling time is respectively rotated for 4h in the positive and negative directions to obtain a precursor;
(3) Placing the precursor in a blast oven, and drying at 80 ℃ for 12 hours;
(4) The obtained precursor is presintered and finally burned in the atmosphere of nitrogen to obtain a final product; wherein, the presintering process is to heat up to 450 ℃ from room temperature at a heating rate of 2 ℃/min, and cool naturally after heat preservation for 4 hours; the final firing process is to heat up to 700 ℃ from room temperature at a heating rate of 2 ℃/min, and cool naturally after heat preservation for 6 hours.
The application also provides application of the nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material as a positive electrode material in a sodium ion battery.
The specific method comprises the following steps:
(1) Preparing a positive electrode plate: according to 7:2:1, mixing 0.21g of nickel crosslinked sodium alginate-induced vanadium sodium phosphate composite anode material, 0.06g of acetylene black conductive filler and 0.03g of polyvinylidene fluoride binder in 1.6 mLN-methyl pyrrolidone organic solvent; placing the mixture into a ball milling tank, performing unidirectional ball milling for 4 hours to obtain slurry, and coating the slurry on aluminum foil coated with carbon on one side; then drying the aluminum foil coated with the slurry at 40 ℃ for 4 hours, then drying the aluminum foil in vacuum at 120 ℃ for 6 hours, and cutting the aluminum foil into round pole pieces of 16 mm;
(2) Preparation of button cell: taking the round pole piece obtained in the step (1) as an anode, taking metal sodium as a cathode, taking a ceramic Celgard diaphragm as a diaphragm, and assembling the round pole piece into a 2025 type button cell in a vacuum glove box; wherein, 1M sodium perchlorate as electrolyte is dissolved in a vinyl carbonate/diethyl carbonate system with the volume ratio of 1:1, and 5 weight percent of fluoroethylene carbonate is added at the same time based on sodium perchlorate.
According to the application, sodium alginate is used as a carbon source, nickel acetate tetrahydrate is added as a carbon layer, doping hetero atoms of a sodium vanadium phosphate crystal and an additional redox couple are added, and the sodium vanadium phosphate with multiple discharge platforms is synthesized in one step through a solid phase method, so that the energy density of the material is greatly improved. The nickel ions can be ion exchanged with the G block in the sodium alginate structure and integrate to form the characteristic of an 'egg-shell' structure. After sintering, a nickel doped highly conductive carbon coating and carbon tissue network is formed. The nickel doped highly conductive carbon coating has a number of defects which allow for rapid transport of electrons and sodium ions. The carbon tissue conductive network promotes electron transfer among all the vanadium sodium phosphate particles, so that the intrinsic conductivity and the ionic conductivity are improved simultaneously.
Compared with the prior art, the application has the following advantages and beneficial effects:
according to the application, sodium alginate is used as a part of sodium source and also used as a carbon source, and nickel heteroatom doping is introduced into a carbon layer and vanadium sodium phosphate crystals to prepare the high-energy-density positive electrode material with a triple discharge platform, so that the preparation steps are simple, and the raw materials are low in cost.
The nickel ions and the G block in the sodium alginate structure are subjected to ion exchange and integrated to form an egg-shell structure, and a carbon coating layer with a large number of defects is formed after sintering, so that rapid transmission of electrons and ions is realized.
The nickel ions replace vanadium sites, are doped into the sodium vanadium phosphate crystal, bring about additional redox pairs, and promote corresponding high discharge platforms, namely V 3+/4+ -3.4 V, Ni 2+/3+ -3.7 V, V 4+/5+ -3.9, V. The material prepared by the application has stable multi-section high-voltage platform, high energy density and remarkable practical value.
Drawings
FIG. 1 is a photograph of a nickel-crosslinked sodium alginate-induced sodium vanadium phosphate composite positive electrode material prepared in example 1;
fig. 2 is a Raman spectrum of a nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material prepared in example 1, wherein a nickel-doped carbon coating layer formed after carbonization of the nickel-crosslinked sodium alginate has a higher disorder degree;
FIG. 3 is a fine XPS spectrum of nickel element of the nickel crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material prepared in example 1, wherein nickel ions are successfully doped into vanadium sodium phosphate crystals;
fig. 4 is a graph showing the measured constant current charge and discharge curve when the nickel crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material prepared in example 1 is assembled into 2025 type button cell, and the current density is 0.1C;
FIG. 5 is a graph showing the constant current charge and discharge at multiple current densities when the nickel crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material prepared in example 1 was assembled into 2025-type coin cells;
fig. 6 is a graph of measured constant current intermittent titration curves when the nickel crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material prepared in example 1 is assembled into 2025 type button cells.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments; all other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs, the disclosure of which is incorporated herein by reference as is commonly understood by reference.
Those skilled in the art will recognize that equivalents of the specific embodiments described, as well as those known by routine experimentation, are intended to be encompassed within the present application.
The experimental methods in the following examples are conventional methods unless otherwise specified. The instruments used in the following examples are laboratory conventional instruments unless otherwise specified; the experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
Example 1: preparation of nickel crosslinked sodium alginate-induced vanadium sodium phosphate composite anode material:
0.5g of sodium alginate, 2.3935g of vanadium pentoxide, 1.0461g of sodium carbonate, 2.2707g of monoammonium phosphate and 0.0257g of nickel acetate tetrahydrate are taken into a planetary ball milling tank, and absolute ethanol 25mL is added. Then the mass ratio of the raw materials to the ball-milling beads is 1:60 ball-milling beads were added. Forward and reverse rotation was performed on 40Hz for 4 hours each. Taking out, and drying in a blast oven at 80 ℃ for 12 hours; the obtained precursor is presintered for four hours at 450 ℃ in nitrogen atmosphere, then pressed into tablets, and finally sintered for six hours at 700 ℃ and then ground for one hour to obtain the final product.
The photo of the prepared nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite anode material is shown in fig. 1, and it can be seen from the graph that the particle size of the material is low and the dispersion is uniform, and the nickel-doped carbon coating layer and the gauze-like conductive network are formed after the sodium alginate is carbonized in situ, and are connected with each other between the particles, so that the electron conduction between the particles is improved.
The Raman spectrum is shown in fig. 2, and it can be seen from fig. 2 that the nickel-doped carbon coating formed after carbonization of the nickel-crosslinked sodium alginate has higher disorder degree.
The fine XPS spectrum of nickel element of the nickel crosslinked sodium alginate-induced vanadium sodium phosphate composite anode material is shown in figure 3, and figure 3 shows that nickel ions are successfully doped into vanadium sodium phosphate crystals.
A slurry was prepared using the positive electrode material prepared in this example as an active material. According to 7:2:1 a positive electrode material (0.21 g), acetylene black (conductive filler) (0.06 g) and polyvinylidene fluoride (binder) (0.03 g) were mixed in a ratio of 1.6 ml of ln-methylpyrrolidone (organic solvent). Placing the mixture into a ball milling tank, performing unidirectional ball milling for four hours to obtain slurry, and coating the slurry on aluminum foil coated with carbon on one side. The slurry coated aluminum foil was then dried at 40 ℃ for four hours, then dried at 120 ℃ under vacuum for six hours, and cut into 16 mm round pole pieces. Taking the metal sodium as a positive electrode and the metal sodium as a negative electrode, taking a ceramic Celgard diaphragm as a diaphragm, and assembling the ceramic Celgard diaphragm into the 2025 type button cell in a vacuum glove box. Wherein, the electrolyte is prepared by dissolving 1M sodium perchlorate in a system of ethylene carbonate/diethyl carbonate with the volume ratio of 1:1 and simultaneously adding 5 percent wt percent of fluoroethylene carbonate.
And carrying out constant current charge and discharge test on the assembled button cell at room temperature within the voltage range of 2.3-4.1 and V. Specifically, the first-turn charge-discharge curve is shown in fig. 4, and the charge-discharge curves under different multiplying powers are shown in fig. 5.
Electrochemical tests show that the specific discharge capacity of the material under 0.1C can reach 111.3mAh g -1 . In addition, it also exhibited three stable charge and discharge platforms, 3.4V, 3.7V and 3.9V, respectively. At different current densities, three platforms all exist and remain stable.
The assembled button cell was subjected to constant current intermittent titration test at room temperature in the voltage range of 2.3-4.1V. The results are shown in fig. 6, which shows that: at all three plateaus of 3.4V, 3.7V and 3.9V, there was a significant drop in sodium diffusion coefficient, indicating that phase transfer occurred at all three voltage plateaus.
The above examples illustrate: the application uses a simple solid phase method and rapidly synthesizes the nickel-crosslinked sodium alginate-induced multi-discharge platform sodium vanadium phosphate anode material through a planetary ball mill. The positive electrode material has three stable high voltage platforms at 3.4V, 3.7V and 3.9V. This can be attributed to the Ni that promotes the production after the nickel doping into the sodium vanadium phosphate crystals 2+/3+ And V 4+5+ Is a redox couple of (a) and (b). In addition, nickel ions can exchange with G blocks in the sodium alginate structure to further form an egg-shell structure, and after sintering, a nickel-doped high-conductivity carbon coating layer and a carbon tissue network are formed, so that the nickel-doped high-conductivity carbon coating layer has more defects and can allow ions and electrons to move rapidly, and the intrinsic conductivity and the ionic conductivity of the material are improved. The electrode material of the application has three stable high voltage levels through test characterizationThe stage has excellent electrochemical properties, especially high energy density. Meanwhile, the material has simple preparation flow and low cost, and is expected to be popularized in industry.
Example 2: the mass ratio of the sodium alginate, the vanadium pentoxide, the sodium carbonate, the ammonium dihydrogen phosphate and the nickel acetate tetrahydrate is 0.5:2.3935:1.0461:2.2707:0.0143; the remainder of the procedure was as described in example 1.
Example 3: the mass ratio of the sodium alginate, the vanadium pentoxide, the sodium carbonate, the ammonium dihydrogen phosphate and the nickel acetate tetrahydrate is 0.5:2.3935:1.0461:2.2707:0.0200; the remainder of the procedure was as described in example 1.
Comparative example 1: preparation of a common sodium vanadium phosphate anode material:
2.3935g of vanadium pentoxide, 1.0461g of sodium carbonate and 2.2707g of ammonium dihydrogen phosphate are taken into a planetary ball milling tank, and absolute ethanol 25mL is added. Then the mass ratio of the raw materials to the ball-milling beads is 1:60 ball-milling beads were added. Forward and reverse rotation was performed on 40Hz for 4 hours each. Taking out, and drying in a blast oven at 80 ℃ for 12 hours; the obtained precursor is presintered for four hours at 450 ℃ in nitrogen atmosphere, then pressed into tablets, and finally sintered for six hours at 700 ℃ and then ground for one hour to obtain the final product.
The slurry was prepared using the positive electrode material prepared in this example as an active material in the same manner as described in example 1. And carrying out constant current charge and discharge test on the assembled button cell at room temperature within the voltage range of 2.3-4.1 and V. Specifically, the first-turn charge-discharge curve is shown in fig. 4. The specific discharge capacity of the material under 0.1C is only 74.3mAh g -1 And only one charge-discharge plateau at 3.4V, which corresponds to V 3+/4+ Is a redox couple of (a) and (b).
It is obvious from the comparison example that the specific discharge capacity of the nickel crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material prepared by the application under 0.1C can reach 111.3mAh g -1 The intrinsic conductivity and the ionic conductivity of the material are improved far higher than those of the comparative example. Through the test meterThe electrode material of the application can show three stable charge and discharge platforms, which are respectively positioned at 3.4V, 3.7V and 3.9V. At different current densities, three platforms all exist and remain stable. Has excellent electrochemical properties, especially high energy density. Meanwhile, the material has simple preparation flow and low cost, and is expected to be popularized in industry.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (4)
1. A nickel crosslinked sodium alginate induced vanadium sodium phosphate composite positive electrode material is characterized in that: the composite positive electrode material is prepared by taking nickel acetate tetrahydrate, vanadium pentoxide and sodium carbonate as raw materials, sodium alginate as partial sodium sources and reducing agents through a solid phase method, wherein a nickel doped vanadium site is introduced, redox electric pairs are promoted to be generated, three high-discharge platforms are constructed, nickel crosslinked sodium alginate is simultaneously formed, nickel ions and G blocks in the sodium alginate structure are subjected to ion exchange and integrated to form an egg-shell structure, and a nickel doped carbon coating layer with a large number of defects and a gauze-like carbon interconnection network are formed after sintering; and obtaining the nickel-crosslinked sodium vanadium phosphate composite anode material induced by the nickel-crosslinked sodium alginate, which is composed of the sodium vanadium phosphate nickel-doped carbon coating layer.
2. The method for preparing the nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material according to claim 1, which is characterized by comprising the following steps: the method comprises the following specific steps:
(1) Sodium alginate, vanadium pentoxide, sodium carbonate, monoammonium phosphate and nickel acetate tetrahydrate are taken and placed in a planetary ball milling tank; wherein the mass ratio of the sodium alginate to the vanadium pentoxide to the sodium carbonate to the ammonium dihydrogen phosphate to the nickel acetate tetrahydrate is 0.5:2.3935:1.0461:2.2707:0.0143 to 0.0257;
(2) Adding 25mL of absolute ethyl alcohol into a planetary ball milling tank, and putting into ball milling beads; wherein the mass ratio of the raw materials to the beads is 1:60, ball milling frequency is 40Hz, ball milling time is 8h, and the ball milling time is respectively rotated for 4h in the positive and negative directions to obtain a precursor;
(3) Placing the precursor in a blast oven, and drying at 80 ℃ for 12 hours;
(4) The obtained precursor is presintered and finally burned in the atmosphere of nitrogen to obtain a final product; wherein, the presintering process is to heat up to 450 ℃ from room temperature at a heating rate of 2 ℃/min, and cool naturally after heat preservation for 4 hours; the final firing process is to heat up to 700 ℃ from room temperature at a heating rate of 2 ℃/min, and cool naturally after heat preservation for 6 hours.
3. The application of the nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material in a sodium ion battery, which is characterized in that: the nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material is used as a positive electrode material to be applied to a sodium ion battery.
4. A use according to claim 3, characterized in that: the specific method comprises the following steps:
(1) Preparing a positive electrode plate: according to 7:2:1, mixing 0.21g of nickel crosslinked sodium alginate-induced vanadium sodium phosphate composite anode material, 0.06g of acetylene black conductive filler and 0.03g of polyvinylidene fluoride binder in 1.6 mLN-methyl pyrrolidone organic solvent; placing the mixture into a ball milling tank, performing unidirectional ball milling for 4 hours to obtain slurry, and coating the slurry on aluminum foil coated with carbon on one side; then drying the aluminum foil coated with the slurry at 40 ℃ for 4 hours, then drying the aluminum foil in vacuum at 120 ℃ for 6 hours, and cutting the aluminum foil into round pole pieces of 16 mm;
(2) Preparation of button cell: taking the round pole piece obtained in the step (1) as an anode, taking metal sodium as a cathode, taking a ceramic Celgard diaphragm as a diaphragm, and assembling the round pole piece into a 2025 type button cell in a vacuum glove box; wherein, 1M sodium perchlorate as electrolyte is dissolved in a vinyl carbonate/diethyl carbonate system with the volume ratio of 1:1, and 5 weight percent of fluoroethylene carbonate is added at the same time based on sodium perchlorate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310789074.7A CN116885121A (en) | 2023-06-30 | 2023-06-30 | Nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310789074.7A CN116885121A (en) | 2023-06-30 | 2023-06-30 | Nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116885121A true CN116885121A (en) | 2023-10-13 |
Family
ID=88265458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310789074.7A Pending CN116885121A (en) | 2023-06-30 | 2023-06-30 | Nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116885121A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117317223A (en) * | 2023-11-28 | 2023-12-29 | 烟台康司坦新材料科技有限公司 | Preparation method and application of active porous carbon |
-
2023
- 2023-06-30 CN CN202310789074.7A patent/CN116885121A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117317223A (en) * | 2023-11-28 | 2023-12-29 | 烟台康司坦新材料科技有限公司 | Preparation method and application of active porous carbon |
| CN117317223B (en) * | 2023-11-28 | 2024-02-02 | 烟台康司坦新材料科技有限公司 | Preparation method and application of active porous carbon |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110642247B (en) | Artificial graphite negative electrode material, preparation method thereof and lithium ion battery | |
| CN109192953B (en) | High-rate spherical lithium iron phosphate carbon composite cathode material and preparation method thereof | |
| CN109119592B (en) | Lithium titanate negative electrode piece, preparation method and lithium titanate battery | |
| CN112133896B (en) | High-capacity graphite-silicon oxide composite material and preparation method and application thereof | |
| CN106602067B (en) | Graphite-based composite material, preparation method thereof and lithium ion battery containing composite material | |
| CN110931781A (en) | Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material | |
| CN111342018B (en) | Carbon-coated lithium-containing transition metal phosphate positive electrode material and preparation method thereof | |
| CN110957483A (en) | Preparation method and application of sulfur composite cathode material | |
| CN113479860B (en) | SbPO (styrene-ethylene-propylene-diene monomer) 4 Preparation method of nitrogen-doped carbon composite material | |
| CN108899499B (en) | Sb/Sn phosphate-based negative electrode material, preparation method thereof and application thereof in sodium ion battery | |
| CN111009659A (en) | Preparation method and application of biomass carbon/poly-sodium manganese fluorophosphate composite material | |
| CN111559741B (en) | Preparation method of polyanion composite material | |
| CN114572956B (en) | Nanoscale olivine type sodium iron phosphate and preparation method and application thereof | |
| CN116169260A (en) | β”-Al 2 O 3 And N-doped C composite coated Na 3 V 2 (PO 4 ) 2 F 3 Electrode material | |
| CN116885121A (en) | Nickel-crosslinked sodium alginate-induced vanadium sodium phosphate composite positive electrode material, and preparation method and application thereof | |
| CN111755665B (en) | Lithium ion battery negative electrode material, battery negative electrode and application thereof | |
| CN116741972A (en) | Carbon-compounded mixed polyanion compound for sodium ion battery anode material and preparation method thereof | |
| CN109390572B (en) | Phosphorus-sulfur/carbon composite material and preparation and application thereof | |
| CN114937758B (en) | Negative electrode active material, negative electrode plate containing same and battery | |
| CN107492656B (en) | Self-supporting NaVPO4F/C sodium ion composite anode and preparation method thereof | |
| CN114583137B (en) | Method for modifying carbon surface by sulfur doped phosphorus and application thereof | |
| JPH10233207A (en) | Negative electrode for lithium secondary cell | |
| CN115036486B (en) | Polyvinylpyrrolidone-induced vanadium sodium phosphate composite positive electrode material, and preparation method and application thereof | |
| CN116190660B (en) | Adhesive, preparation method and application thereof, silicon-based negative electrode and preparation method thereof | |
| CN108682798B (en) | Preparation method of cubic carbon-coated vanadium-based positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |