CN113540431A - Alkaline iron-nickel secondary battery negative electrode active material and preparation method thereof - Google Patents
Alkaline iron-nickel secondary battery negative electrode active material and preparation method thereof Download PDFInfo
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- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000006182 cathode active material Substances 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000011240 wet gel Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 6
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011149 active material Substances 0.000 abstract description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01M10/24—Alkaline accumulators
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a negative active material of an alkaline iron-nickel secondary battery and a preparation method thereof, wherein the negative active material of the iron-nickel secondary battery is a negative active material of carbon-coated tin doped iron; the preparation method comprises the following steps: (1) dissolving soluble ferric salt and tin salt, adding an organic reducing agent, drying and grinding the wet gel after reaction to obtain a precursor of the cathode active material of the iron-nickel secondary battery; (2) and calcining the precursor of the cathode active material of the iron-nickel battery under the protection of inert atmosphere to obtain the cathode active material of the iron-nickel secondary battery. Compared with the conventional iron-nickel battery which singly uses ferroferric oxide or ferric oxide as the negative active material, the negative active material prepared by the method can effectively improve the discharge specific capacity of the battery, reduce the hydrogen evolution amount, and further reduce the active material falling off due to electrode expansion, thereby prolonging the cycle number of the battery and prolonging the service life.
Description
Technical Field
The invention belongs to the technical field of cathode active materials of iron-nickel batteries, and particularly relates to a cathode active material of an alkaline iron-nickel secondary battery and a preparation method thereof.
Background
At present, batteries on the market are various, and among them, common commercial secondary batteries include lithium ion batteries, lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries, and the like. However, the range of applications of these batteries is greatly limited due to some limitations of the batteries themselves. The lithium ion battery is the most widely used battery in the current market, but the electrolyte contained in the lithium ion battery is an organic solution, so that the lithium ion battery is easy to burn after being punctured, and the waste battery is difficult to recover and is easy to pollute the environment, so that the lithium ion battery has a great promotion space as a green and safe power battery. Lead-acid batteries and nickel-chromium batteries occupy certain markets, but the batteries have low specific energy of discharge and contain heavy metals of lead and chromium which seriously pollute the environment, and the batteries are not the direction of sustainable development of the batteries in the future. The nickel-metal hydride battery has short cycle life, and the possibility of being used as a large power supply is limited due to the high cost of a large amount of rare earth added into the nickel-metal hydride battery.
The iron-nickel battery is developed by edison in the beginning of the 20 th century. In recent years, due to the advantages of long cycle life, good safety performance, environmental friendliness, low cost, high theoretical power (267Wh/kg) and the like, the solar energy and wind energy storage device has attracted wide attention in terms of large-scale energy storage, and is considered to be one of solutions for solving the problems of modern energy. In addition, the iron-nickel battery has good durability, and can perform more than 3000 cycles even under unfavorable operating conditions; and can produce a service life of approximately 20 years. However, the actual specific capacity of the iron electrode is far from the theoretical specific capacity (962mAh/g), mainly due to the severe hydrogen evolution reaction on the iron electrode and due to the Fe (OH) produced during the discharge cycle2Resulting in passivation. Now, Fe is used as a negative electrode material for preparing iron-nickel batteries3O4The adopted method mainly comprises a chemical coprecipitation method and a precipitation oxidation method, the crystallinity of the powder synthesized by the chemical coprecipitation method is poor, and sulfate ions are difficult to wash away by the precipitation oxidation method, so that the discharge performance is influenced.
Therefore, how to increase the specific discharge capacity of the iron-nickel battery cathode active material battery is a problem to be solved urgently.
Disclosure of Invention
The technical task of the invention is to provide a preparation process of the cathode material of the iron-nickel battery, which can reduce the volume of an iron electrode, improve the hydrogen evolution overpotential and improve the discharge specific capacity of the battery, wherein tin contained in the cathode material prepared by the process can effectively reduce the hydrogen evolution overpotential of the battery and reduce the generation amount of hydrogen on the cathode, thereby reducing the phenomenon that the cathode active material falls off due to electrode expansion and improving the cycle performance and the charging efficiency of the battery. The carbon left in the negative electrode material due to decomposition of organic reducing agents such as citric acid and glucose is coated on the surface of the negative electrode material to achieve the effect of electric conduction, and no additional conductive agent is needed to be added, so that the volume of the iron electrode can be obviously reduced, and more monomer electrodes can be filled in the same volume.
The technical scheme adopted by the invention for solving the technical problems is as follows: the negative active material of the alkaline iron-nickel secondary battery is a negative active material of carbon-coated tin doped iron.
The preparation method of the alkaline iron-nickel secondary battery negative electrode active material comprises the following steps:
(1) dissolving soluble ferric salt and tin salt, adding an organic reducing agent, drying and grinding the wet gel after reaction to obtain a precursor of the cathode active material of the iron-nickel secondary battery;
(2) and calcining the precursor of the cathode active material of the iron-nickel battery under the protection of inert atmosphere to obtain the cathode active material of the iron-nickel secondary battery.
Further, the soluble ferric salt is one or more of ferrous sulfate and ferrous nitrate; the soluble tin salt is one or more of stannous sulfate or stannous chloride, and the organic reducing agent is citric acid or glucose.
Further, Fe in the step (1)2+:Sn2+The molar ratio of (a) to (b) is 1:0.05 to 0.5, and the molar ratio of the organic reducing agent to the total metal ions is (1.5 to 3): 1.
further, the solvent for dissolving the soluble iron salt and the soluble tin salt in the step (1) is water or ethylene glycol, and the organic reducing agent adopts the same solvent to form an organic reducing agent solution.
Further, when the solvent in the step (1) is water, the drying temperature is 80-100 ℃; when the solvent is ethylene glycol, the drying temperature is 150-170 ℃.
Further, the step (1) is specifically: dissolving iron salt and tin salt in water or ethylene glycol at 70-90 ℃ to form a solution with the total metal ion concentration of 0.18-0.3 mol/L, stirring for 0.5-2 h, adding an organic reducing agent solution, heating in a water bath to maintain the reaction temperature at 70-90 ℃, and taking out the rotor until the stirring rotor does not rotate any more to obtain wet gel.
Further, the concentration of the organic reducing agent solution is 0.27-0.9 mol/L, and the organic reducing agent solution needs to be stirred for 0.5-1 h in advance before adding.
Further, the calcining temperature in the step (2) is 500-900 ℃, and the calcining time is 2-6 h.
Further, during the calcination in the step (2), the temperature rise rate is 5-20 ℃/min.
Further, the inert atmosphere in the step (2) is one or more of nitrogen or argon.
Compared with the prior art, the invention has the following beneficial effects:
(1) the cathode active material of the iron-nickel secondary battery is a loose porous material containing iron, tin and carbon, in the preparation process, the carbon left after decomposition of organic reducing agents such as citric acid, glucose and the like is coated on the surface of the cathode material, compared with the graphene which is additionally added as a conductive agent, the volume of an iron electrode is reduced, more iron electrodes can be loaded in the battery with the same volume, and the micro-discharge phenomenon on the surface of the iron electrode is reduced. The added tin improves the hydrogen evolution overpotential of the cathode material, reduces the precipitation of hydrogen, ensures that the passivation degree is smaller in the charging and discharging process, reduces the internal resistance of the battery, and further improves the specific discharge capacity of the iron-nickel battery.
(2) Compared with the conventional iron-nickel battery which singly uses ferroferric oxide or ferric oxide as the negative active material, the negative active material prepared by the method can effectively improve the discharge specific capacity of the battery, reduce the hydrogen evolution amount, and further reduce the active material falling off due to electrode expansion, thereby prolonging the cycle number of the battery and prolonging the service life.
Drawings
Fig. 1 is a graph comparing specific discharge capacity of a negative active material prepared in example 1 with that of a general iron negative material;
FIG. 2 is a comparison of the XRD pattern of the negative active material prepared in example 1 with PDF card No.99-0073 of a standard card;
fig. 3 is a cyclic voltammetry comparison curve of the negative active material prepared in example 1 and a general iron negative material.
Detailed Description
The above-mentioned contents of the present invention are further described in detail by examples below, but it should not be understood that the scope of the above-mentioned subject matter of the present invention is limited to the following examples, and any technologies realized based on the above-mentioned contents of the present invention are within the scope of the present invention.
Example 1
Ferrous sulfate and stannous sulfate are mixed according to the mol ratio of Fe2+:Sn2+Dissolving the mixture in deionized water at the temperature of 80 ℃ in a ratio of 1:0.25, wherein the concentration of total metal ions is 0.2mol/L, stirring for 0.5h, and then adding 0.3mol/L of 0.5h stirred aqueous citric acid, wherein the molar ratio of citric acid to the total metal ions in the aqueous citric acid is 1.5: 1, heating in a water bath to maintain the reaction temperature at 80 ℃ until the rotor does not rotate any more, taking out the rotor, drying the reacted wet gel at 80 ℃, and grinding to obtain a dry gel precursor of the cathode active material of the iron-nickel secondary battery; and (3) heating the prepared precursor to 800 ℃ at a heating rate of 10 ℃/min and calcining for 2h under the condition of introducing argon for protection, thus obtaining the cathode active material of the iron-nickel secondary battery.
Fig. 1 is a comparison curve of specific discharge capacity of the negative electrode active material prepared in example 1 and a general iron negative electrode material (conventional material, ferroferric oxide); FIG. 2 is a comparison of the XRD pattern of the negative active material prepared in example 1 with PDF card No.99-0073 of a standard card; fig. 3 is a cyclic voltammetry comparison curve of the negative active material prepared in example 1 and a general iron negative material; through comparison of a discharge specific capacity curve and a cyclic voltammetry curve, the iron-nickel battery cathode material prepared by the method can effectively improve the discharge specific capacity of a battery, reduce the precipitation amount of hydrogen and further reduce active materials falling off due to electrode expansion compared with the conventional material ferroferric oxide, so that the cycle frequency of the battery is prolonged, and the service life is prolonged.
Example 2
Ferrous sulfate and stannous sulfate are mixed according to the mol ratio of Fe2+:Sn2+Dissolving the mixture in deionized water at 90 ℃ in a ratio of 1:0.5, wherein the concentration of total metal ions is 0.3mol/L, stirring for 1h, and then adding 0.9mol/L glucose aqueous solution which is stirred for 1h, wherein the molar ratio of glucose to the total metal ions in the glucose aqueous solution is 3: 1, heating in a water bath to maintain the reaction temperature at 90 ℃ until the rotor does not rotate any more, taking out the rotor, drying the reacted wet gel at 90 ℃, and grinding to obtain a dry gel precursor of the cathode active material of the iron-nickel secondary battery; and (3) heating the prepared precursor to 900 ℃ at the heating rate of 20 ℃/min and calcining for 6h under the condition of introducing argon for protection, thus obtaining the cathode active material of the iron-nickel secondary battery.
Example 3
Ferrous sulfate and stannous sulfate are mixed according to the mol ratio of Fe2+:Sn2+Dissolving the mixture in ethylene glycol at 70 ℃ in a ratio of 1:0.05, wherein the concentration of total metal ions is 0.19mol/L, stirring for 2h, and then adding 0.27mol/L citric acid glycol solution which is stirred for 2h, wherein the molar ratio of citric acid to the total metal ions in the citric acid glycol solution is 1.5: 1, heating in a water bath to maintain the reaction temperature at 70 ℃ until the rotor does not rotate any more, taking out the rotor, drying the reacted wet gel at 170 ℃, and grinding to obtain a dry gel precursor of the cathode active material of the iron-nickel secondary battery; and (3) heating the prepared precursor to 700 ℃ at the heating rate of 20 ℃/min and calcining for 4h under the condition of introducing argon for protection, thus obtaining the cathode active material of the iron-nickel secondary battery.
Example 4
Ferrous sulfate and stannous sulfate are mixed according to the mol ratio of Fe2+:Sn2+Dissolving the mixture in deionized water at the temperature of 80 ℃ in a ratio of 1:0.3, wherein the concentration of total metal ions is 0.24mol/L, stirring for 1h, and then adding 0.48mol/L of citric acid aqueous solution which is stirred for 1h, wherein the molar ratio of citric acid to the total metal ions in the citric acid aqueous solution is 2: 1, heating in water bath to maintain the reaction temperature at 80 ℃ until a rotorTaking out the rotor after no rotation, drying the reacted wet gel at 100 ℃, and grinding to obtain a dry gel precursor of the cathode active material of the iron-nickel secondary battery; and (3) heating the prepared precursor to 600 ℃ at the heating rate of 5 ℃/min and calcining for 6h under the condition of introducing argon for protection, thus obtaining the cathode active material of the iron-nickel secondary battery.
While the basic principles, principal process flow and advantages of the invention have been shown and described, various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The negative active material of the alkaline iron-nickel secondary battery is characterized in that the negative active material of the iron-nickel secondary battery is a negative active material of carbon-coated tin doped iron.
2. The method for preparing the negative active material of the alkaline iron-nickel secondary battery based on the claim 1 is characterized by comprising the following steps:
(1) dissolving soluble ferric salt and tin salt, adding an organic reducing agent, drying and grinding the wet gel after reaction to obtain a precursor of the cathode active material of the iron-nickel secondary battery;
(2) and calcining the precursor of the cathode active material of the iron-nickel battery in the protection of inert or reducing atmosphere to obtain the cathode active material of the iron-nickel secondary battery.
3. The method of claim 2, wherein: the soluble ferric salt is one or more of ferrous nitrate or ferrous sulfate; the soluble tin salt is one or more of stannous sulfate or stannous chloride, and the organic reducing agent is citric acid or glucose.
4. The method of claim 2, wherein: fe in the step (1)2+:Sn2+The molar ratio of (a) to (b) is 1:0.05 to 0.5, and the molar ratio of the organic reducing agent to the total metal ions is (1.5 to 3): 1.
5. the preparation method according to claim 2, wherein the solvent for dissolving the soluble iron salt and tin salt in step (1) is water or ethylene glycol, and the organic reducing agent is the same solvent to form an organic reducing agent solution.
6. The preparation method according to claim 5, wherein when the solvent in the step (1) is water, the drying temperature is 80-100 ℃; when the solvent is ethylene glycol, the drying temperature is 150-170 ℃.
7. The preparation method according to claim 2, wherein the step (1) is specifically: dissolving iron salt and tin salt in water or ethylene glycol at 70-90 ℃ to form a solution with the total metal ion concentration of 0.18-0.3 mol/L, stirring for 0.5-2 h, adding an organic reducing agent solution, heating in a water bath to maintain the reaction temperature at 70-90 ℃, and taking out the rotor until the stirring rotor does not rotate any more to obtain wet gel.
8. The preparation method according to claim 2, wherein the concentration of the organic reducing agent solution is 0.27-0.9 mol/L, and the organic reducing agent solution needs to be stirred for 0.5-2 hours before being added.
9. The preparation method according to claim 2, wherein the calcination temperature in the step (2) is 500 to 900 ℃ and the calcination time is 2 to 6 hours.
10. The method for preparing the iron negative electrode material of the iron-nickel battery according to claim 2, characterized in that: and (3) during calcination in the step (2), the heating rate is 5-20 ℃/min, and the inert atmosphere is one or more of nitrogen or argon.
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| CN202110779638.XA CN113540431A (en) | 2021-07-09 | 2021-07-09 | Alkaline iron-nickel secondary battery negative electrode active material and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106848256A (en) * | 2017-03-24 | 2017-06-13 | 中南大学 | A kind of nickel iron cell core duplex shell structure negative pole nano material and its preparation method and application |
| CN110112395A (en) * | 2019-05-21 | 2019-08-09 | 东北大学 | A method of iron-based negative electrode material is prepared based on sol-gal process |
| CN111029563A (en) * | 2019-12-10 | 2020-04-17 | 河南创力新能源科技股份有限公司 | Preparation method of alkaline secondary battery iron negative electrode material |
| CN111029564A (en) * | 2019-12-10 | 2020-04-17 | 河南创力新能源科技股份有限公司 | Preparation method of iron negative electrode material of iron-nickel secondary battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106848256A (en) * | 2017-03-24 | 2017-06-13 | 中南大学 | A kind of nickel iron cell core duplex shell structure negative pole nano material and its preparation method and application |
| CN110112395A (en) * | 2019-05-21 | 2019-08-09 | 东北大学 | A method of iron-based negative electrode material is prepared based on sol-gal process |
| CN111029563A (en) * | 2019-12-10 | 2020-04-17 | 河南创力新能源科技股份有限公司 | Preparation method of alkaline secondary battery iron negative electrode material |
| CN111029564A (en) * | 2019-12-10 | 2020-04-17 | 河南创力新能源科技股份有限公司 | Preparation method of iron negative electrode material of iron-nickel secondary battery |
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