CN115483394B - Negative electrode material of sodium ion battery and preparation method thereof - Google Patents
Negative electrode material of sodium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN115483394B CN115483394B CN202211068874.1A CN202211068874A CN115483394B CN 115483394 B CN115483394 B CN 115483394B CN 202211068874 A CN202211068874 A CN 202211068874A CN 115483394 B CN115483394 B CN 115483394B
- Authority
- CN
- China
- Prior art keywords
- nano
- cuboid
- ion battery
- sodium ion
- ncs
- 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.)
- Active
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007773 negative electrode material Substances 0.000 title claims description 6
- UGTGQPFWMZNLBE-UHFFFAOYSA-L cobalt(2+);2-hydroxyacetate Chemical compound [Co+2].OCC([O-])=O.OCC([O-])=O UGTGQPFWMZNLBE-UHFFFAOYSA-L 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000005341 cation exchange Methods 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 11
- 239000010406 cathode material Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 102
- 239000011669 selenium Substances 0.000 claims description 38
- 235000019441 ethanol Nutrition 0.000 claims description 28
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 27
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000012467 final product Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 abstract description 22
- 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 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GAIMSHOTKWOMOB-UHFFFAOYSA-N [Se]=[Co]=[Se] Chemical compound [Se]=[Co]=[Se] GAIMSHOTKWOMOB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910009529 yH2 O Inorganic materials 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002078 nanoshell Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000011144 upstream manufacturing 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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/36—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a sodium ion battery cathode material and a preparation method thereof, wherein Fe is introduced into a system cobalt glycolate nano cuboid NCs by utilizing a cation exchange method, and is converted into a Co 0.85Se-Fe7Se8 sodium ion battery cathode material with a hollow shell nano cuboid structure through solvothermal selenizing reaction. According to the method, a simple two-step diffusion control method is adopted to synthesize cobalt glycolate Nano Cuboid (NCs), fe is introduced into a system by utilizing a cation exchange method, and finally, the cobalt glycolate nano cuboid is converted into a Co 0.85Se-Fe7Se8 material with a hollow shell nano cuboid structure through solvothermal selenization reaction. The material is in a hollow shell nano cuboid structure, which is not only beneficial to shortening the diffusion path of sodium ions, but also can effectively buffer the volume change of the material in the charge and discharge process. Secondly, the existence of the Co 0.85Se-Fe7Se8 heterojunction, the synergistic effect among the multicomponent metal ions helps to accelerate the oxidation-reduction reaction in the process of electrochemical reaction. The prepared Co 0.85Se-Fe7Se8 material shows excellent electrochemical performance as a sodium storage anode material.
Description
Technical Field
The invention belongs to the technical field of sodium batteries, and relates to a sodium ion battery anode material and a preparation method thereof, in particular to a preparation method of a sodium ion battery anode material Co 0.85Se-Fe7Se8 composite material.
Background
The lithium ion battery has been greatly successful in recent years in the energy storage fields of electronic products, vehicles and the like due to high energy density and good cycle performance. However, the growing application market tends to exacerbate the problem of lithium resource shortage, and the development of other low-cost and high-performance energy storage systems has a certain perspective. The sodium ion battery has the characteristics of rich resources, low price and environmental friendliness, and in a wide temperature range, sodium ions are high in conductivity and lower in charge transfer impedance and electrochemical polarization effect. Therefore, in the application fields of large-scale and high-power energy storage, the sodium ion battery has more obvious application potential. In the process of promoting the industrialization of the sodium ion battery, the development of a low-cost and high-efficiency sodium storage anode system is an important link and is a key for determining the performance of the sodium ion battery.
Transition metal sulfur/selenide is of great interest because of its good electron conductivity, higher theoretical capacity and lower cost, making it the most competitive alkali metal ion electrochemical storage candidate. Document CHEMICAL ENGINEERING Journal 328 (2017) pp.546-555 discloses a method for preparing a carbon-coated cobalt diselenide (CoSe 2 @C) composite material. Co (NO 3)2·6H2 O is used as a cobalt source and hexadecyl trimethyl ammonium bromide is dissolved in 2-methylimidazole, stirring is carried out, after the mixture is maintained for 30 minutes at room temperature, ultrapure water and ethanol are centrifugally cleaned and naturally dried to obtain a cobalt-containing metal-organic framework compound (ZIF-67), then an intermediate product is placed in a tube furnace containing (5%H 2/Ar) mixed atmosphere, the mixture is burned at 550 ℃ for 3 hours to obtain a carbon-coated cobalt (Co@C) composite material, finally the Co@C composite material and selenium powder are placed in the tube furnace, the mixture is burned at 300 ℃ for 6 hours to obtain a final product of the carbon-coated cobalt diselenide (CoSe 2 @C) composite material.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a negative electrode material of a sodium ion battery and a preparation method thereof, and overcomes the defect of insufficient circulation stability of CoSe 2 prepared by the prior method.
Technical proposal
A sodium ion battery cathode material is characterized in that Fe is introduced into a system cobalt glycolate nano cuboid NCs by a cation exchange method, and is converted into a Co 0.85Se-Fe7Se8 sodium ion battery cathode material with a hollow shell nano cuboid structure through solvothermal selenization reaction.
The preparation method of the sodium ion battery anode material is characterized by comprising the following steps:
Step 1: adding Co (Ac) 4·4H2 O and polyvinylpyrrolidone PVP into ethanol, and performing ultrasonic dispersion until the mixture is uniform;
Step 2: transferring the mixture into a water bath kettle, continuously magnetically stirring, heating to 70-100 ℃, and reacting in a reflux state for 3-8 h;
step 3: naturally cooling the solution, centrifugally washing with absolute ethyl alcohol to obtain pink precipitate, transferring the precipitate into a culture dish, and drying in a baking oven at 60-100 ℃ to obtain Co-containing cobalt glycolate nano cuboid NCs;
Step 4: dispersing Co-containing cobalt glycolate nano cuboid NCs and K 3[Fe(CN)6 in a mixed solvent of ethanol and water at room temperature, continuously stirring to perform cation exchange reaction, and washing a reaction product by absolute ethanol to obtain a hollow nano cuboid containing Fe and Co at the same time;
Step 5: dissolving the hollow nano cubes containing Fe and Co, selenium powder and sodium borohydride in ethanol, ultrasonically dispersing until the mixture is uniform, transferring the obtained mixed solution into an autoclave with a polytetrafluoroethylene lining, and reacting at 140-200 ℃ to obtain the final product Co 0.85Se-Fe7Se8 hollow shell nano cuboid.
The molecular weight of the polyvinylpyrrolidone PVP is 8000-300000.
The mass ratio of the cobalt glycolate nanometer cuboid NCs containing Co to the K 3[Fe(CN)6 is 1:1.
The mass ratio of Co (Ac) 4·4H2 O to polyvinylpyrrolidone PVP is 1:1-1:3.
The continuous stirring time of the step 4 is 10-15 mins.
And the mass ratio of the hollow nano cubes containing Fe and Co, the selenium powder and the sodium borohydride in the step 5 is 1:1:1.
The reaction is carried out for 10 to 24 hours at the temperature of 5140 to 200 ℃.
Advantageous effects
According to the sodium ion battery anode material and the preparation method, a simple two-step diffusion control method is adopted to synthesize the cobalt glycolate Nano Cuboid (NCs), then Fe is introduced into a system by utilizing a cation exchange method, and finally the cobalt glycolate nano cuboid is converted into the Co 0.85Se-Fe7Se8 material with a hollow shell nano cuboid structure through solvothermal selenizing reaction. Firstly, the material is in a hollow shell layer nano cuboid structure, which is not only beneficial to shortening the diffusion path of sodium ions, but also can effectively buffer the volume change of the material in the charge and discharge process. Secondly, the existence of the Co 0.85Se-Fe7Se8 heterojunction, the synergistic effect among the multicomponent metal ions helps to accelerate the oxidation-reduction reaction in the process of electrochemical reaction. The prepared Co 0.85Se-Fe7Se8 material shows excellent electrochemical performance as a sodium storage anode material.
The invention has the following effective effects:
Most hollow structural shells are composed of single-phase components and exhibit ordinary electrochemical properties. Therefore, a hollow nano-shell structure composed of multiple components is attracting attention because it has more excellent electrochemical properties than a conventional hollow structure. In the work, a Co precursor is used as a template to prepare the novel Co 0.85Se-Fe7Se8 sodium storage anode material with a hollow shell nano cuboid structure. In the rapid ion exchange process, the Co precursor reacts with K 3[Fe(CN)6 in water/ethanol solution to release Co 2+ and [ Fe (CN) 6]3- ] to react rapidly to generate Co 2Fe(CN)6 particles, and the Co particles are deposited on the outer surface of the Co precursor to form a hollow shell layer. Various experimental results show that the material has a unique multicomponent hollow cavity structure, so that the material has larger specific surface area, higher electronic and sodium ion conductivity and more excellent electrochemical performance, and the volume stress in the process of removing and embedding sodium ions is relieved; in addition, due to the existence of the Co 0.85Se-Fe7Se8 heterojunction, the synergistic effect among the multicomponent metal ions helps to accelerate the oxidation-reduction reaction in the process of electrochemical reaction. In the aspect of the synthesis process, compared with high-temperature selenization, the solvothermal selenization has the advantages of low temperature, capability of reducing component volatilization in a closed space, capability of producing a nano composite material with good crystallization and uniform morphology, and the like. Therefore, the multi-metal selenide structure can effectively improve the volume expansion effect of the material in the charge and discharge process and improve the electrochemical performance of the material.
Drawings
FIG. 1 is a graph of the previous two charge and discharge curves of the product of example 1 at a current density of 100mA g -1 (0.01-3.0V);
By comparing the first two charge-discharge curves of Co 0.85 Se and Co 0.85Se-Fe7Se8 under the current density of 100mA g -1, the first circle coulomb efficiency of the hollow nano cuboid with the hollow shell of Co 0.85Se-Fe7Se8 can reach 79.4% under the effect of heterojunction, and the Co 0.85 Se is only 68.5% lower than the former.
FIG. 2 is a graph of the cycle performance of the product of example 1 at a current density of 100mA g -1 (0.01-3.0V);
By comparing the cycle diagrams of Co 0.85 Se and Co 0.85Se-Fe7Se8 under the current density of 100mA g -1, co 0.85Se-Fe7Se8 shows more excellent electrochemical performance, the capacity is still stable at 332.3mAh g -1 after 200 charge and discharge cycles, the capacity of Co 0.85 Se is continuously attenuated in the first 30 circles, and the capacity is only 161.3mAh g -1 after 200 circles.
FIG. 3 is an SEM image of hollow nanocubes of cobalt glycolate Nanocubes (NCs) and Co 0.85Se-Fe7Se8 of example 1;
The work is based on cobalt glycolate nanometer cuboid and utilizes a rapid ion exchange method to prepare the hollow Co 0.85Se-Fe7Se8 heterojunction cuboid sodium storage anode material. When the Co-containing precursor reacts with K 3[Fe(CN)6 in aqueous solution, the released Co 2+ and [ Fe (CN) 6] 3- react rapidly to generate Co 2Fe(CN)6 particles, and the Co 2Fe(CN)6 particles are deposited on the outer surface of the cuboid to form a shell layer. Notably, coO and Co/Fe-PBA exhibit distinct morphologies after solvothermal selenization. Co 0.85Se-Fe7Se8 has a complete hollow cuboid structure, while Co 0.85 Se material powder has no longer exist in a severe cuboid shape, which indicates that the introduction of Fe element and the formation of heterostructures obviously enhance the structural stability of Co 0.85Se-Fe7Se8.
FIG. 4 is an XRD pattern of hollow nanocubes in Co 0.85Se-Fe7Se8 in example 1;
The XRD results can clearly see the existence of characteristic peaks of two products of Co 0.85 Se and Fe 7Se8, and the successful synthesis of the Co 0.85Se-Fe7Se8 heterostructure can be further proved by combining the characterization results of TEM, XPS and the like.
Detailed Description
The invention will now be further described with reference to examples, figures:
Embodiment one:
(1) Adding Co (Ac) 4·4H2 O and polyvinylpyrrolidone (PVP, molecular weight 58000) (mass ratio of 1:1) into a round-bottom flask (volume 250 mL) containing 80-120 mL of ethanol, and performing ultrasonic dispersion until the materials are uniform;
(2) Transferring the round-bottom flask into a water bath kettle, continuously magnetically stirring, heating to 70-100 ℃, and reacting for 3-8 h in a reflux state;
(3) Naturally cooling the solution, centrifugally washing with absolute ethyl alcohol to obtain pink precipitate, transferring the precipitate into a culture dish, and drying in a baking oven at 60-100 ℃ to obtain cobalt glycolate nano-cuboids (NCs);
(4) Dispersing cobalt glycolate Nano Cuboid (NCs) containing Co and K 3[Fe(CN)6 (the ratio is 1:1) obtained in the step (3) in a mixed solvent of ethanol and water at room temperature, continuously stirring for 10-15 mins, performing cation exchange reaction, and washing a reaction product by absolute ethanol to obtain a hollow nano cuboid containing Fe and Co at the same time;
(5) And (3) dissolving the hollow nano-cubes containing Fe and Co, selenium powder and sodium borohydride obtained in the step (4) in ethanol according to a ratio of 1:1:1, ultrasonically dispersing until the mixture is uniform, transferring the obtained mixed solution into an autoclave with a polytetrafluoroethylene lining, and reacting for 10-24 hours at 140-200 ℃ to obtain a final product Co 0.85Se-Fe7Se8 hollow shell nano-cuboid.
The product of example 1 was assembled into a CR2016 button cell, using a sodium sheet (Φ=16 purity > 99.9%) as a counter electrode, a glass fiber membrane (Φ=18) as a separator, and a 1mol/L mixed solution of NaClO 4 Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (VEC: VDMC =1:1) as an electrolyte, and the CR2016 cell was completed in a glove box filled with argon. The electrode is formed by casting a faradaic film, the slurry used is formed by mixing 80% (mass percent) of active material, 10% of PVDF solution, 10% of acetylene black and 1-methyl-2-pyrrolidone (NMP), and the substrate of the electrode film is copper foil. And (3) carrying out a charge-discharge performance test under the condition of 100mA g -1, wherein the charge-discharge voltage range is 0.01-3.0V. The first charge-discharge curve is shown in fig. 1, and the cycle performance is shown in fig. 2. The first discharge capacity of the product can reach 714.38mAh g -1, the first charge capacity is 323.25mAh g -1, and the discharge capacity is kept to 320.3mAh g -1 after 100 cycles.
The XRD spectrum of the product is shown in figure 3, and the characteristic peaks of the composite material mainly correspond to Co 0.85 Se orthorhombic crystal forms (standard cards PDF#52-1008) and Fe 7Se8 cubic crystal forms (standard cards PDF#33-0676) as can be seen from the XRD spectrum. The morphology structure of the product is shown in figure 4, and as can be seen from an SEM image, after high-temperature selenium thermal reaction, the Co 0.85Se-Fe7Se8 material is in a hollow shell hollow nano cuboid structure, and the unique structure can effectively improve the sodium storage capacity of the material.
Embodiment two: (Co (Ac) 4·4H2 O was replaced with Co (NO 3)2·6H2 O)
(1) Co (NO 3)2·6H2 O and polyvinylpyrrolidone (PVP, molecular weight 58000) (mass ratio 1:1) are added into a round bottom flask (volume 250 mL) containing 80-120 mL of ethanol, and ultrasonic dispersion is carried out until uniformity;
(2) Transferring the round-bottom flask into a water bath kettle, continuously magnetically stirring, heating to 70-100 ℃, and reacting for 3-8 h in a reflux state;
(3) Naturally cooling the solution, centrifugally washing with absolute ethyl alcohol to obtain pink precipitate, transferring the precipitate into a culture dish, and drying in a baking oven at 60-100 ℃ to obtain cobalt glycolate nano-cuboids (NCs);
(4) Dispersing cobalt glycolate Nano Cuboid (NCs) containing Co and K 3[Fe(CN)6 (the ratio is 1:1) obtained in the step (3) in a mixed solvent of ethanol and water at room temperature, continuously stirring for 10-15 mins, performing cation exchange reaction, and washing a reaction product by absolute ethanol to obtain a hollow nano cuboid containing Fe and Co at the same time;
(5) And (3) dissolving the hollow nano-cubes containing Fe and Co, selenium powder and sodium borohydride obtained in the step (4) in ethanol according to a ratio of 1:1:1, ultrasonically dispersing until the mixture is uniform, transferring the obtained mixed solution into an autoclave with a polytetrafluoroethylene lining, and reacting for 10-24 hours at 140-200 ℃ to obtain a final product Co 0.85Se-Fe7Se8 hollow shell nano-cuboid.
Embodiment III: (PVP molecular weight Change)
(1) Adding Co (Ac) 4·4H2 O and polyvinylpyrrolidone (PVP, molecular weight 10000) (mass ratio is 1:1) into a round-bottom flask (volume 250 mL) containing 80-120 mL of ethanol, and performing ultrasonic dispersion until the materials are uniform;
(2) Transferring the round-bottom flask into a water bath kettle, continuously magnetically stirring, heating to 70-100 ℃, and reacting for 3-8 h in a reflux state;
(3) Naturally cooling the solution, centrifugally washing with absolute ethyl alcohol to obtain pink precipitate, transferring the precipitate into a culture dish, and drying in a baking oven at 60-100 ℃ to obtain cobalt glycolate nano-cuboids (NCs);
(4) Dispersing cobalt glycolate Nano Cuboid (NCs) containing Co and K 3[Fe(CN)6 (the ratio is 1:1) obtained in the step (3) in a mixed solvent of ethanol and water at room temperature, continuously stirring for 10-15 mins, performing cation exchange reaction, and washing a reaction product by absolute ethanol to obtain a hollow nano cuboid containing Fe and Co at the same time;
(5) And (3) dissolving the hollow nano-cubes containing Fe and Co, selenium powder and sodium borohydride obtained in the step (4) in ethanol according to a ratio of 1:1:1, ultrasonically dispersing until the mixture is uniform, transferring the obtained mixed solution into an autoclave with a polytetrafluoroethylene lining, and reacting for 10-24 hours at 140-200 ℃ to obtain a final product Co 0.85Se-Fe7Se8 hollow shell nano-cuboid.
Embodiment four: (solvothermal selenizing method is changed into tubular furnace calcining selenizing method)
(1) Adding Co (Ac) 4·4H2 O and polyvinylpyrrolidone (PVP, molecular weight 58000) (mass ratio of 1:1) into a round-bottom flask (volume 250 mL) containing 80-120 mL of ethanol, and performing ultrasonic dispersion until the materials are uniform;
(2) Transferring the round-bottom flask into a water bath kettle, continuously magnetically stirring, heating to 70-100 ℃, and reacting for 3-8 h in a reflux state;
(3) Naturally cooling the solution, centrifugally washing with absolute ethyl alcohol to obtain pink precipitate, transferring the precipitate into a culture dish, and drying in a baking oven at 60-100 ℃ to obtain cobalt glycolate nano-cuboids (NCs);
(4) Dispersing cobalt glycolate Nano Cuboid (NCs) containing Co and K 3[Fe(CN)6 (the ratio is 1:1) obtained in the step (3) in a mixed solvent of ethanol and water at room temperature, continuously stirring for 10-15 mins, performing cation exchange reaction, and washing a reaction product by absolute ethanol to obtain a hollow nano cuboid containing Fe and Co at the same time;
(5) And (3) respectively placing 30mg of the hollow nano cubic block containing Fe and Co and 60mg of selenium powder obtained in the step (4) into two independent quartz boats, wherein the quartz boat containing the selenium powder is positioned at the upstream position (the downstream position) of a 1200 ℃ tubular furnace, heating the furnace to 550 ℃ at 3 ℃/min under Ar atmosphere, preserving heat for 2 hours, and cooling to room temperature under Ar atmosphere to obtain the Co 0.85Se-Fe7Se8 hollow shell nano cuboid.
Fifth embodiment: (K 3[Fe(CN)6 ] is replaced by Fe (NO 3)3·9H2 O)
(1) Adding Co (Ac) 4·4H2 O and polyvinylpyrrolidone (PVP, molecular weight 58000) (mass ratio of 1:1) into a round-bottom flask (volume 250 mL) containing 80-120 mL of ethanol, and performing ultrasonic dispersion until the materials are uniform;
(2) Transferring the round-bottom flask into a water bath kettle, continuously magnetically stirring, heating to 70-100 ℃, and reacting for 3-8 h in a reflux state;
(3) Naturally cooling the solution, centrifugally washing with absolute ethyl alcohol to obtain pink precipitate, transferring the precipitate into a culture dish, and drying in a baking oven at 60-100 ℃ to obtain cobalt glycolate nano-cuboids (NCs);
(4) Dispersing cobalt glycolate Nano Cuboid (NCs) containing Co and Fe (NO 3)3·9H2 O (the ratio is 1:1) obtained in the step (3) in a mixed solvent of ethanol and water at room temperature, continuously stirring for 10-15 mins, performing cation exchange reaction, and washing a reaction product by absolute ethanol to obtain hollow nano cuboid containing Fe and Co at the same time;
(5) And (3) dissolving the hollow nano-cubes containing Fe and Co, selenium powder and sodium borohydride obtained in the step (4) in ethanol according to a ratio of 1:1:1, ultrasonically dispersing until the mixture is uniform, transferring the obtained mixed solution into an autoclave with a polytetrafluoroethylene lining, and reacting for 10-24 hours at 140-200 ℃ to obtain a final product Co 0.85Se-Fe7Se8 hollow shell nano-cuboid.
Example six: (K 3[Fe(CN)6 ] replaced with K 4[Fe(CN)6)
(1) Adding Co (Ac) 4·4H2 O and polyvinylpyrrolidone (PVP, molecular weight 58000) (mass ratio of 1:1) into a round-bottom flask (volume 250 mL) containing 80-120 mL of ethanol, and performing ultrasonic dispersion until the materials are uniform;
(2) Transferring the round-bottom flask into a water bath kettle, continuously magnetically stirring, heating to 70-100 ℃, and reacting for 3-8 h in a reflux state;
(3) Naturally cooling the solution, centrifugally washing with absolute ethyl alcohol to obtain pink precipitate, transferring the precipitate into a culture dish, and drying in a baking oven at 60-100 ℃ to obtain cobalt glycolate nano-cuboids (NCs);
(4) Dispersing cobalt glycolate Nano Cuboid (NCs) containing Co and K 4[Fe(CN)6 (the ratio is 1:1) obtained in the step (3) in a mixed solvent of ethanol and water at room temperature, continuously stirring for 10-15 mins, performing cation exchange reaction, and washing a reaction product by absolute ethanol to obtain a hollow nano cuboid containing Fe and Co at the same time;
(5) And (3) dissolving the hollow nano-cubes containing Fe and Co, selenium powder and sodium borohydride obtained in the step (4) in ethanol according to a ratio of 1:1:1, ultrasonically dispersing until the mixture is uniform, transferring the obtained mixed solution into an autoclave with a polytetrafluoroethylene lining, and reacting for 10-24 hours at 140-200 ℃ to obtain a final product Co 0.85Se-Fe7Se8 hollow shell nano-cuboid.
Embodiment seven: (K 3[Fe(CN)6 ] replaced with xFeCl 3·yH2 O)
(1) Adding Co (Ac) 4·4H2 O and polyvinylpyrrolidone (PVP, molecular weight 58000) (mass ratio of 1:1) into a round-bottom flask (volume 250 mL) containing 80-120 mL of ethanol, and performing ultrasonic dispersion until the materials are uniform;
(2) Transferring the round-bottom flask into a water bath kettle, continuously magnetically stirring, heating to 70-100 ℃, and reacting for 3-8 h in a reflux state;
(3) Naturally cooling the solution, centrifugally washing with absolute ethyl alcohol to obtain pink precipitate, transferring the precipitate into a culture dish, and drying in a baking oven at 60-100 ℃ to obtain cobalt glycolate nano-cuboids (NCs);
(4) Dispersing cobalt glycolate Nano Cuboid (NCs) containing Co and xFeCl 3·yH2 O (the ratio is 1:1) obtained in the step (3) in a mixed solvent of ethanol and water at room temperature, continuously stirring for 10-15 mins, performing cation exchange reaction, and washing a reaction product by absolute ethanol to obtain a hollow nano cuboid containing Fe and Co at the same time;
(5) And (3) dissolving the hollow nano-cubes containing Fe and Co, selenium powder and sodium borohydride obtained in the step (4) in ethanol according to a ratio of 1:1:1, ultrasonically dispersing until the mixture is uniform, transferring the obtained mixed solution into an autoclave with a polytetrafluoroethylene lining, and reacting for 10-24 hours at 140-200 ℃ to obtain a final product Co 0.85Se-Fe7Se8 hollow shell nano-cuboid.
Claims (7)
1. A sodium ion battery cathode material is characterized in that Fe is introduced into a system cobalt glycolate nano cuboid NCs by a cation exchange method, and is converted into a Co 0.85Se-Fe7Se8 sodium ion battery cathode material with a hollow shell nano cuboid structure through solvothermal selenization reaction; the preparation method comprises the following steps:
Step 1: adding Co (Ac) 4·4H2 O and polyvinylpyrrolidone PVP into ethanol, and performing ultrasonic dispersion until the mixture is uniform;
step 2: transferring the mixture into a water bath kettle, continuously magnetically stirring, heating to 70-100 ℃, and reacting in a reflux state for 3-8 hours;
Step 3: naturally cooling the solution, centrifugally washing with absolute ethyl alcohol to obtain pink precipitate, transferring the precipitate to a culture dish, and drying in a baking oven at 60-100 ℃ to obtain Co-containing cobalt glycolate nano cuboid NCs;
Step 4: dispersing Co-containing cobalt glycolate nano cuboid NCs and K 3[Fe(CN)6 in a mixed solvent of ethanol and water at room temperature, continuously stirring to perform cation exchange reaction, and washing a reaction product by absolute ethanol to obtain a hollow nano cuboid containing Fe and Co at the same time;
Step 5: dissolving the hollow nano cubes containing Fe and Co, selenium powder and sodium borohydride in ethanol, ultrasonically dispersing until the mixture is uniform, transferring the obtained mixed solution into an autoclave with a polytetrafluoroethylene lining, and reacting at 140-200 ℃ to obtain the final product Co 0.85Se-Fe7Se8 hollow shell nano cuboid.
2. The sodium ion battery anode material of claim 1, wherein: the molecular weight of polyvinylpyrrolidone PVP is 8000-300000.
3. The sodium ion battery anode material of claim 1, wherein: the mass ratio of the cobalt glycolate nanometer cuboid NCs containing Co to the K 3[Fe(CN)6 is 1:1.
4. The sodium ion battery anode material of claim 1, wherein: the mass ratio of Co (Ac) 4·4H2 O to polyvinylpyrrolidone PVP is 1:1-1:3.
5. The method for preparing the negative electrode material of the sodium ion battery according to claim 1, wherein the method comprises the following steps: and (3) continuously stirring for 10-15 mins in the step (4).
6. The method for preparing the negative electrode material of the sodium ion battery according to claim 1, wherein the method comprises the following steps: and the mass ratio of the hollow nano cubes containing Fe and Co, the selenium powder and the sodium borohydride in the step 5 is 1:1:1.
7. The method for preparing the negative electrode material of the sodium ion battery according to claim 1, wherein the method comprises the following steps: and (3) in the step5, reacting for 10-24 hours at the temperature of 140-200 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211068874.1A CN115483394B (en) | 2022-08-29 | 2022-08-29 | Negative electrode material of sodium ion battery and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211068874.1A CN115483394B (en) | 2022-08-29 | 2022-08-29 | Negative electrode material of sodium ion battery and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115483394A CN115483394A (en) | 2022-12-16 |
CN115483394B true CN115483394B (en) | 2024-05-28 |
Family
ID=84421790
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211068874.1A Active CN115483394B (en) | 2022-08-29 | 2022-08-29 | Negative electrode material of sodium ion battery and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115483394B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004196604A (en) * | 2002-12-19 | 2004-07-15 | Nippon Chem Ind Co Ltd | Lithium cobaltate complex compound, its preparation method and non-aqueous electrolyte secondary battery |
CN107934923A (en) * | 2017-11-07 | 2018-04-20 | 陕西科技大学 | A kind of nanometer sheet self assembly flower ball-shaped Sb2Se3The preparation method of anode material of lithium-ion battery |
CN108615864A (en) * | 2018-04-25 | 2018-10-02 | 中南大学 | Sodium-ion battery anode material ferrous selenide/graphene and preparation method thereof |
-
2022
- 2022-08-29 CN CN202211068874.1A patent/CN115483394B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004196604A (en) * | 2002-12-19 | 2004-07-15 | Nippon Chem Ind Co Ltd | Lithium cobaltate complex compound, its preparation method and non-aqueous electrolyte secondary battery |
CN107934923A (en) * | 2017-11-07 | 2018-04-20 | 陕西科技大学 | A kind of nanometer sheet self assembly flower ball-shaped Sb2Se3The preparation method of anode material of lithium-ion battery |
CN108615864A (en) * | 2018-04-25 | 2018-10-02 | 中南大学 | Sodium-ion battery anode material ferrous selenide/graphene and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
二次碱性电池负极材料Co-B合金制备和性能研究;吕东生;李伟善;谭春林;;广州化工;20090415(第02期);全文 * |
Also Published As
Publication number | Publication date |
---|---|
CN115483394A (en) | 2022-12-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108550821B (en) | Preparation method of core-shell structure nickel phosphide/carbon microspheres based on Ni-MOF | |
CN113410440B (en) | Cobalt diselenide @ porous nitrogen-doped carbon nanocomposite, potassium ion battery and preparation method of cobalt diselenide @ porous nitrogen-doped carbon nanocomposite | |
CN108232142B (en) | Zinc sulfide/graphene composite material, and preparation method and application thereof | |
CN110600695B (en) | Yolk-eggshell structure tin@hollow mesoporous carbon sphere material and preparation method thereof | |
CN109659540B (en) | Preparation method of porous carbon-coated antimony telluride nanosheet and application of porous carbon-coated antimony telluride nanosheet as negative electrode material of metal ion battery | |
CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
CN109742398A (en) | The synthesis and application method of a kind of lithium ion battery with manganese systems Prussian blue analogue material | |
CN110571416B (en) | Transition metal selenium-sulfur compound and preparation method thereof | |
CN112174167A (en) | Prussian blue material with core-shell structure and preparation method and application thereof | |
CN112599743B (en) | Carbon-coated nickel cobaltate multi-dimensional assembled microsphere negative electrode material and preparation method thereof | |
CN110615480A (en) | Method for preparing layered lithium manganate material by dynamic hydrothermal method | |
CN107311119B (en) | Hollow nanometer prism material of nickel cobalt diselenide, preparation method and application thereof | |
CN114188502B (en) | Prussian white composite material and preparation method and application thereof | |
CN114314673B (en) | Preparation method of flaky FeOCl nano material | |
CN103400980A (en) | Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof | |
CN109279663B (en) | Borate sodium-ion battery negative electrode material and preparation and application thereof | |
CN114735660A (en) | Copper selenide-molybdenum selenide heterojunction nano material and preparation method and application thereof | |
CN107959024B (en) | Flaky Sb for sodium ion battery cathode2Se3Method for preparing nanocrystalline | |
CN113161527A (en) | Preparation method and application of MOFs-derived cobalt sulfide particle composite carbon material | |
CN111463406B (en) | Preparation method of cobalt-doped zinc-based metal selenide composite electrode for lithium ion battery | |
CN110416508B (en) | Electrostatic self-assembly three-dimensional flower-like cobalt disulfide/MXene composite material and preparation method and application thereof | |
CN115483394B (en) | Negative electrode material of sodium ion battery and preparation method thereof | |
CN114094063B (en) | Method for preparing battery anode material by combining cavity precursor and ZIF derivative | |
CN110600710A (en) | Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery | |
CN113690422B (en) | Hollow nanocube multi-element metal compound composite material with layered structure, preparation method and application in lithium ion battery |
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 | ||
GR01 | Patent grant |