CN111200124B - Sodium-nickel battery positive electrode material and preparation method thereof - Google Patents
Sodium-nickel battery positive electrode material and preparation method thereof Download PDFInfo
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- CN111200124B CN111200124B CN201910935170.1A CN201910935170A CN111200124B CN 111200124 B CN111200124 B CN 111200124B CN 201910935170 A CN201910935170 A CN 201910935170A CN 111200124 B CN111200124 B CN 111200124B
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- FPBMTPLRBAEUMV-UHFFFAOYSA-N nickel sodium Chemical compound [Na][Ni] FPBMTPLRBAEUMV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 102
- 239000011780 sodium chloride Substances 0.000 claims abstract description 51
- 239000011573 trace mineral Substances 0.000 claims abstract description 23
- 235000013619 trace mineral Nutrition 0.000 claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010406 cathode material Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 105
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 51
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 33
- 238000012216 screening Methods 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 24
- 239000008187 granular material Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000011775 sodium fluoride Substances 0.000 claims description 17
- 235000013024 sodium fluoride Nutrition 0.000 claims description 17
- 235000009518 sodium iodide Nutrition 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 229940095991 ferrous disulfide Drugs 0.000 claims description 9
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000013339 cereals Nutrition 0.000 description 20
- 235000020985 whole grains Nutrition 0.000 description 20
- 238000005469 granulation Methods 0.000 description 16
- 230000003179 granulation Effects 0.000 description 16
- 239000003921 oil Substances 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- TWLBWHPWXLPSNU-UHFFFAOYSA-L [Na].[Cl-].[Cl-].[Ni++] Chemical compound [Na].[Cl-].[Cl-].[Ni++] TWLBWHPWXLPSNU-UHFFFAOYSA-L 0.000 description 2
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M10/30—Nickel 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/582—Halogenides
-
- 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
- H01M2004/028—Positive 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
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a positive electrode material for a sodium-nickel battery, which consists of nickel powder, sodium chloride and trace elements, wherein the mass ratio of the nickel powder to the sodium chloride to the trace elements is X: y: 1-x-y; the invention also provides a preparation method of the sodium-nickel battery positive electrode material, wherein x is 0.4-0.6, y is 0.4-0.6, and 1-x-y is 0-0.2. The cathode material has better conductivity and higher tap density.
Description
Technical Field
The invention relates to the field of sodium-nickel batteries, in particular to a positive electrode material for a sodium-nickel battery.
Background
The sodium-nickel battery, also called sodium salt battery or sodium-nickel chloride battery, is one kind of high-temperature sodium battery, its positive pole is solid NiCl2, negative pole is liquid Na, electrolyte is solid beta' -Al2O3 ceramic, sodium ion drifts between positive and negative poles through the ceramic electrolyte during charging and discharging. The environment-friendly composite material is a green product which has strong stability, high safety, long service life, wide application range, easily obtained and nontoxic raw materials, simple recovery process and no pollution.
The sodium nickel battery has the following four main application fields: peak clipping and valley adjusting, wind and light energy storage, a backup power supply and a new energy automobile.
Because of the excellent safety of the sodium-nickel battery, the sodium-nickel battery has good application prospect in pure electric vehicles and hybrid electric vehicles. Currently, over 1 million sodium nickel battery electric vehicles are in operation in europe and the united states, and the electric vehicles comprise mini cars, trucks, buses and buses, and one sodium-nickel chloride battery electric vehicle of the company AEG Anglo Batteries GmbH, germany, runs more than 69000 miles (1 mile-1609.3 m, corresponding to 1200 normal cycles) in a real road test for more than 3 years without any maintenance. Sodium nickel batteries using liquid cooling technology have been assembled in the Renault Twingo, ciio, OpelAstra, gallo and bmw series 3 automobiles. The sodium nickel battery has highlighted its powerful advantages as a new generation of automotive high-energy battery.
Only Ningxia green energy-gathering source limited company is used for researching the sodium-nickel battery in China, and the company and northern national university develop the research and development cooperation of the obstetrics and the studies, and are researched and manufactured for two and a half years,
some progress is made on key technologies such as sintering of the positive electrode material of the sodium-nickel battery, preparation of ceramic electrolyte and the like, and the core technology and process of the positive electrode material of the sodium-nickel battery are not mastered.
The domestic sodium salt battery industry is just started, the anode material is used as a core key part of the sodium salt battery, the mass continuous production and manufacturing process of the anode material is a problem which is bound to face, and the situation is very urgent.
Chinese patent CN106033825A proposes a positive electrode supported type sodium-nickel battery, in which the positive electrode is used as the strength support of the sodium-nickel battery, the positive electrode adopts a support body with a multi-gap structure, the electrolyte is a thin film layer located at one side of the support body, the positive electrode active material Ni, NaCl particles and molten NaAlCl4 are distributed and filled in the gaps, and the gaps form channels communicated to the electrolyte layer. The whole process of preparing the anode described in the patent must be carried out under the protection of inert gas, and the molten NaAlCl4 has extremely high requirements on equipment and is extremely expensive to realize.
Disclosure of Invention
In order to solve the technical problems, the invention provides a positive electrode material for a sodium-nickel battery, which consists of nickel powder, sodium chloride and trace elements, wherein the mass ratio of the nickel powder to the sodium chloride to the trace elements is X: y: 1-x-y; wherein x is 0.4-0.6, y is 0.4-0.6, and 1-x-y is 0-0.2.
Further, the nickel powder is one or more of T123, T210, T255 and T287;
further, the purity of the sodium chloride is more than 99.0%, the particle size is less than 75 μm, and the water content is less than 0.2%.
Further, 0.2-0.8% of an anticaking agent is added into the sodium chloride, the anticaking agent is silicon dioxide, and the specific surface area is 45-90 m 2/g.
Further, the trace elements are one or a combination of several of iron powder, aluminum powder, ferrous sulfide, sulfur, sodium fluoride, tungsten carbide, titanium dioxide, ferrous disulfide and sodium iodide.
Further, the purity of the iron powder is more than 99.0%, the particle size is less than 125 microns, and the apparent density is 2.6-3.0 g/cc; the purity of the aluminum powder is more than 99.0%, and the particle size is less than 125 microns; the particle size of the ferrous sulfide is less than 125 μm; the purity of the sulfur is more than 99.5 percent, and the particle size is less than 125 mu m; the purity of the sodium fluoride is more than 98.0%, and the particle size is less than 125 μm; the purity of the tungsten carbide is more than 99.5%, and the particle size is 1-20 mu m; the purity of the titanium dioxide is more than 99.0%, and the particle size of the titanium dioxide is less than 125 mu m; the purity of the ferrous disulfide is more than 99.5%, and the particle size is less than 125 μm; the purity of the sodium iodide is more than 99.0%, and the particle size is less than 125 μm.
Furthermore, the positive electrode material is positive electrode material particles, the particle size of the positive electrode material is distributed between 0.3mm and 1.7mm, the tap density is within the range of 1.90g/cc to 2.20g/cc, and the water content is less than 750 ppm.
The invention also provides a preparation method of the sodium-nickel battery anode material.
The positive electrode material is applied to the sodium-nickel battery, and in order to meet the requirements of high discharge rate and high specific energy of the battery, the positive electrode material is required to have better conductivity, reasonable particle size and particle size distribution and higher tap density. In order to fill the cell with as much active material as possible, the tap density of the positive electrode pellets needs to be above 1.90 g/cc.
The invention discloses a process for manufacturing a positive electrode material for a sodium-nickel battery, which comprises the following steps: the drying of sodium chloride, the premixing of trace elements, the total mixing of ingredients, the granulation and the screening can be continuously realized in batches.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a picture of the appearance of the positive electrode particles of the Na-Ni battery of the present invention;
fig. 3 is a typical particle size distribution of acceptable positive electrode particles of the present invention.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
The positive electrode material of the sodium-nickel battery consists of nickel powder, sodium chloride and trace elements, wherein the mass ratio of the nickel powder to the sodium chloride to the trace elements is x: y: 1-x-y; wherein x is 0.4-0.6, y is 0.4-0.6, and 1-x-y is 0-0.2. The nickel powder is one or more of T123, T210, T255 and T287; the purity of sodium chloride is more than 99.0%, the particle size is less than 75 microns, the water content is less than 0.2%, 0.2-0.8% of an anticaking agent is added, the anticaking agent is silicon dioxide, and the specific surface area is 45-90 m 2/g; the microelements are one or more of iron powder, aluminum powder, ferrous sulfide, sulfur, sodium fluoride, tungsten carbide, titanium dioxide, ferrous disulfide and sodium iodide; wherein the purity of the iron powder is more than 99.0 percent, the particle size is less than 125 mu m, and the apparent density is 2.6-3.0 g/cc; aluminum powder with purity more than 99.0% and particle size less than 125 μm; ferrous sulfide with particle size less than 125 μm; sulfur with purity more than 99.5% and particle size less than 125 μm; sodium fluoride, the purity is greater than 98.0%, the particle size is smaller than 125 μm; tungsten carbide with the purity of more than 99.5 percent and the particle size of 1-20 mu m; titanium dioxide with purity of more than 99.0% and particle size of less than 125 μm; ferrous disulfide with purity more than 99.5% and particle size less than 125 μm; sodium iodide with purity higher than 99.0% and particle size smaller than 125 μm. The positive electrode material has a particle size distribution of 0.3 to 1.7mm, a tap density of 1.90 to 2.20g/cc, and a water content of less than 750 ppm.
The preparation method of the cathode material comprises the following steps:
(1) feeding sodium chloride in vacuum to a heating ribbon mixer, and heating at the temperature of 200-300 ℃;
(2) discharging the sodium chloride in the step (1) to a jacket water-cooling ribbon mixer, and cooling to 30-50 ℃;
(3) weighing iron powder, aluminum powder, sodium iodide, sodium fluoride and ferrous sulfide, and mixing;
(4) mixing nickel powder, sodium chloride in the step (2) and trace elements in the step (3);
(5) lifting the mixed powder in the step (4) to a storage bin of a dry granulating machine by using a pipe chain conveyor;
(6) extruding and granulating by a dry granulating machine;
(7) screening the mixture in the step (6) by using a rotary vibration screen;
(8) independently extruding and granulating the granules with unqualified particle sizes obtained in the step (7);
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7);
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer;
(12) and (3) sealing and storing the particles in the step (11) under an argon atmosphere.
As shown in figures 1-3
Example 1
(1) Feeding sodium chloride in vacuum to a heating ribbon mixer, and heating for 90min at 250 ℃;
(2) discharging the sodium chloride in the step (1) to a jacket water-cooling ribbon mixer, and cooling to 50 ℃;
(3) weighing 16.0kg of iron powder, 2.0kg of aluminum powder, 1.2kg of sodium iodide, 4.5kg of sodium fluoride and 5.0kg of ferrous sulfide, and mixing for 30min by using a V-shaped mixer;
(4) 155kg of weight-reducing charging material, 115kg of sodium chloride in the step (2), and trace elements in the step (3) are mixed for 4 hours by a ribbon mixer;
(5) lifting the mixed powder in the step (4) to a storage bin of a dry granulating machine by using a pipe chain conveyor;
(6) the dry granulator uses the following parameters: feeding screw rotation speed S is 38rpm, pinch roller rotation speed R is 4rpm, pinch roller gap delta is 1.5mm, oil pump pressure P is 13MPa, coarse and whole grain rotation speed R1 is 30rpm, finishing grain rotation speed R2 is 35rpm, coarse and whole grain sieve mesh diameter phi 1 is 3mm, finishing grain sieve mesh diameter phi 2 is 1.4mm, and extruding granulation is carried out;
(7) screening the mixture in the step (6) by using a rotary vibration screen, wherein the aperture of the upper screen of the rotary vibration screen is phi 3-1.5 mm, and the aperture of the bottom screen is phi 4-0.3 mm, so as to obtain particles with the required particle size range;
(8) independently extruding and granulating the granules with unqualified particle sizes obtained in the step (7);
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7) to obtain particles with the required particle size range;
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer for 15 min;
(12) and (3) sealing and storing the particles in the step (11) under an argon atmosphere.
Example 2 (FIG. 1)
(1) Conveying the sodium chloride to a rake dryer by a screw, and heating for 120min at 200 ℃;
(2) discharging the sodium chloride in the step (1) to a jacket oil-cooled ribbon mixer, and cooling to 40 ℃;
(3) weighing 30.0kg of iron powder, 2.5kg of aluminum powder, 3.5kg of sodium iodide, 7.0kg of sodium fluoride and 4.5kg of ferrous disulfide, and mixing for 40min by using a V-shaped mixer;
(4) reducing weight, adding 140kg of nickel powder, adding 120kg of sodium chloride in the step (2), and mixing with trace elements in the step (3) for 3 hours by using a double-cone mixer;
(5) lifting the mixed powder in the step (4) to a dry method granulator bin by using a screw conveyer;
(6) the dry granulator uses the following parameters: feeding screw rotation speed S is 51rpm, pinch roller rotation speed R is 5rpm, pinch roller gap delta is 1.8mm, oil pump pressure P is 12MPa, coarse and whole grain rotation speed R1 is 35rpm, finishing grain rotation speed R2 is 40rpm, coarse and whole grain sieve mesh diameter phi 1 is 5mm, finishing grain sieve mesh diameter phi 2 is 1.5mm, and extruding granulation is carried out;
(7) screening the mixture in the step (6) by using a rotary vibration screen, wherein the aperture of the upper screen of the rotary vibration screen is phi 3-1.4 mm, and the aperture of the bottom screen is phi 4-0.355 mm, so as to obtain particles with the required particle size range;
(8) independently extruding and granulating the granules with unqualified particle sizes obtained in the step (7);
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7) to obtain particles with the required particle size range;
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer for 30 min;
(12) and (3) hermetically storing the particles in the step (11) in a nitrogen atmosphere.
Example 3 (FIG. 1)
(1) Conveying the sodium chloride pipe chain to a heating vacuum three-dimensional mixer, and heating for 60min at 270 ℃;
(2) discharging the sodium chloride in the step (1) to a hollow spiral cooler, and cooling to 30 ℃;
(3) weighing 20.0kg of iron powder, 1.8kg of aluminum powder, 3.0kg of sodium iodide, 5.0kg of sodium fluoride and 7.0kg of ferrous sulfide, and mixing for 10min by using a V-shaped mixer;
(4) reducing weight, adding 170kg of nickel powder, adding 110kg of sodium chloride in the step (2), and mixing with trace elements in the step (3) for 2 hours by using a three-dimensional mixer;
(5) lifting the mixed powder in the step (4) to a storage bin of a dry granulating machine by a bucket elevator;
(6) the dry granulator uses the following parameters: feeding screw rotation speed S is 56rpm, pinch roller rotation speed R is 6rpm, pinch roller gap delta is 2.0mm, oil pump pressure P is 15MPa, coarse and whole grain rotation speed R1 is 40rpm, finishing grain rotation speed R2 is 45rpm, coarse and whole grain sieve mesh diameter phi 1 is 5mm, finishing grain sieve mesh diameter phi 2 is 1.8mm, and extruding granulation is carried out;
(7) screening the mixture in the step (6) by using a rotary vibration screen, wherein the aperture of the upper screen of the rotary vibration screen is phi 3-1.6 mm, and the aperture of the bottom screen is phi 4-0.4 mm, so as to obtain particles with the required particle size range;
(8) independently extruding and granulating the granules with unqualified particle sizes obtained in the step (7);
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7) to obtain particles with the required particle size range;
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer for 45 min;
(12) and (3) hermetically storing the particles in the step (11) in a nitrogen atmosphere.
Example 4 (FIG. 1)
(1) Vacuum feeding sodium chloride to a heating ribbon mixer, and heating at 300 deg.C for 45 min;
(2) discharging the sodium chloride in the step (1) to a jacket water-cooling ribbon mixer, and cooling to 50 ℃;
(3) weighing 16kg of iron powder, 2kg of aluminum powder, 1.2kg of sodium iodide, 4.5kg of sodium fluoride and 5kg of sulfur, and mixing for 15min by using a V-shaped mixer;
(4) reducing weight, adding 156kg of nickel powder, 115.68kg of sodium chloride in the (2), and mixing with trace elements in the (3) for 2.5 hours by using a ribbon mixer;
(5) lifting the mixed powder in the step (4) to a storage bin of a dry granulating machine by using a pipe chain conveyor;
(6) the dry granulator uses the following parameters: feeding screw rotation speed S is 63rpm, pinch roller rotation speed R is 7rpm, pinch roller gap delta is 1.5mm, oil pump pressure P is 18MPa, coarse whole grain rotation speed R1 is 45rpm, finishing grain rotation speed R2 is 50rpm, coarse whole grain sieve mesh diameter L1 xL 2 is 5 x5 mm, finishing grain sieve mesh diameter phi 2 is 1.5mm, and extruding granulation is carried out;
(7) screening the mixture in the step (6) by using a rotary vibration screen, wherein the aperture of the upper screen of the rotary vibration screen is phi 3-1.7 mm, and the aperture of the bottom screen is phi 4-0.45 mm, so as to obtain particles with the required particle size range;
(8) feeding the granules with unqualified particle size obtained in the step (7) to a granulator bin in vacuum for extrusion granulation;
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7) to obtain particles with the required particle size range;
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer for 20 min;
(12) and (3) hermetically storing the particles in the step (11) in a nitrogen atmosphere.
Example 5 (FIG. 1)
(1) Feeding sodium chloride in vacuum to a heating ribbon mixer, and heating for 1.5h at 280 ℃;
(2) discharging the sodium chloride in the step (1) to a jacket water-cooling ribbon mixer, and cooling to 40 ℃;
(3) weighing 16.32kg of iron powder, 1.56kg of aluminum powder, 1.2kg of sodium iodide, 4.44kg of sodium fluoride and 4.8kg of ferrous disulfide, and mixing for 45min by using a V-shaped mixer;
(4) 155kg of weight-reducing charging material, 115kg of sodium chloride in the step (2), and trace elements in the step (3) are mixed for 3 hours by a ribbon mixer;
(5) lifting the mixed powder in the step (4) to a storage bin of a dry granulating machine by using a pipe chain conveyor;
(6) the dry granulator uses the following parameters: feeding screw rotation speed S is 75rpm, pinch roller rotation speed R is 8rpm, pinch roller gap delta is 2.0mm, oil pump pressure P is 15MPa, coarse and whole grain rotation speed R1 is 55rpm, finishing grain rotation speed R2 is 60rpm, coarse and whole grain sieve mesh diameter phi 1 is 5mm, finishing grain sieve mesh diameter phi 2 is 1.8mm, and extruding granulation is carried out;
(7) screening the mixture in the step (6) by using a rotary vibration screen, wherein the aperture of an upper screen of the rotary vibration screen is phi 3-1.4 mm, and the aperture of a bottom screen is phi 4-0.335 mm, so as to obtain particles with the required particle size range;
(8) independently extruding and granulating the granules with unqualified particle sizes obtained in the step (7);
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7) to obtain particles with the required particle size range;
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer for 45 min;
(12) and (3) hermetically storing the particles in the step (11) in a nitrogen atmosphere.
Example 6 (FIG. 1)
(1) Feeding sodium chloride in vacuum to a heating ribbon mixer, and heating for 1.5h at 250 ℃;
(2) discharging the sodium chloride in the step (1) to a jacket water-cooling ribbon mixer, and cooling to 50 ℃;
(3) weighing 30.3kg of iron powder, 2.04kg of aluminum powder, 3.51kg of sodium iodide, 6.63kg of sodium fluoride and 4.47kg of ferrous sulfide, and mixing for 45min by using a V-shaped mixer;
(4) carrying out weight reduction charging on 138.72kg of nickel powder, 114.33kg of sodium chloride in the (2) and trace elements in the (3), and mixing for 3h by using a ribbon mixer;
(5) lifting the mixed powder in the step (4) to a storage bin of a dry granulating machine by using a pipe chain conveyor;
(6) the dry granulator uses the following parameters: feeding screw rotation speed S is 80rpm, pinch roller rotation speed R is 7rpm, pinch roller gap delta is 2.0mm, oil pump pressure P is 15MPa, coarse whole grain rotation speed R1 is 50rpm, finishing grain rotation speed R2 is 55rpm, coarse whole grain sieve mesh diameter L1 xL 2 is 5 x5 mm, finishing grain sieve mesh diameter phi 2 is 1.8mm, and extruding granulation is carried out;
(7) screening the mixture in the step (6) by using a rotary vibration screen, wherein the aperture of an upper screen of the rotary vibration screen is phi 3-1.4 mm, and the aperture of a bottom screen is phi 4-0.335 mm, so as to obtain particles with the required particle size range;
(8) independently extruding and granulating the granules with unqualified particle sizes obtained in the step (7);
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7) to obtain particles with the required particle size range;
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer for 45 min;
(12) and (3) hermetically storing the particles in the step (11) in a nitrogen atmosphere.
Example 7 (FIG. 1)
(1) Feeding sodium chloride in vacuum to a heating ribbon mixer, and heating for 1.5h at 280 ℃;
(2) discharging the sodium chloride in the step (1) to a jacket water-cooling ribbon mixer, and cooling to 40 ℃;
(3) weighing 16.32kg of iron powder, 1.56kg of aluminum powder, 1.0kg of tungsten carbide, 1.2kg of sodium iodide, 4.44kg of sodium fluoride and 4.8kg of ferrous sulfide, and mixing for 45min by using a V-shaped mixer;
(4) 155kg of weight-reducing charging material, 115kg of sodium chloride in the step (2), and trace elements in the step (3) are mixed for 3 hours by a ribbon mixer;
(5) lifting the mixed powder in the step (4) to a storage bin of a dry granulating machine by using a pipe chain conveyor;
(6) the dry granulator uses the following parameters: feeding screw rotation speed S is 51rpm, pinch roller rotation speed R is 5rpm, pinch roller gap delta is 2.0mm, oil pump pressure P is 12MPa, coarse whole grain rotation speed R1 is 40rpm, finishing grain rotation speed R2 is 40rpm, coarse whole grain sieve mesh diameter phi 1 is 5mm, finishing grain sieve mesh diameter phi 2 is 1.5mm, and extruding granulation is carried out;
(7) screening the mixture in the step (6) by using a rotary vibration screen, wherein the aperture of the upper screen of the rotary vibration screen is phi 3-1.4 mm, and the aperture of the bottom screen is phi 4-0.4 mm, so as to obtain particles with the required particle size range;
(8) feeding the granules with unqualified particle size obtained in the step (7) to a granulator bin in vacuum for extrusion granulation;
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7) to obtain particles with the required particle size range;
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer for 30 min;
(12) and (3) hermetically storing the particles in the step (11) in a nitrogen atmosphere.
Example 8 (FIG. 1)
(1) Feeding sodium chloride in vacuum to a heating ribbon mixer, and heating for 2h at 250 ℃;
(2) discharging the sodium chloride in the step (1) to a jacket water-cooling ribbon mixer, and cooling to 30 ℃;
(3) weighing 30.3kg of iron powder, 2.0kg of aluminum powder, 0.5kg of titanium dioxide, 3.5kg of sodium iodide, 6.6kg of sodium fluoride and 4.8kg of ferrous sulfide, and mixing for 40min by using a V-shaped mixer;
(4) reducing weight, adding 138kg of nickel powder, adding 114kg of sodium chloride in the step (2), and mixing with trace elements in the step (3) for 3 hours by using a ribbon mixer;
(5) lifting the mixed powder in the step (4) to a storage bin of a dry granulating machine by using a pipe chain conveyor;
(6) the dry granulator uses the following parameters: feeding screw rotation speed S is 49rpm, pinch roller rotation speed R is 4rpm, pinch roller gap delta is 2.0mm, oil pump pressure P is 12MPa, coarse whole grain rotation speed R1 is 40rpm, finishing grain rotation speed R2 is 45rpm, coarse whole grain sieve mesh diameter phi 1 is 4mm, finishing grain sieve mesh diameter phi 2 is 1.5mm, and extruding granulation is carried out;
(7) screening the mixture in the step (6) by using a rotary vibration screen, wherein the aperture of the upper screen of the rotary vibration screen is phi 3-1.4 mm, and the aperture of the bottom screen is phi 4-0.355 mm, so as to obtain particles with the required particle size range;
(8) feeding the granules with unqualified particle size obtained in the step (7) to a granulator bin in vacuum for extrusion granulation;
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7) to obtain particles with the required particle size range;
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer for 40 min;
(12) and (3) sealing and storing the particles in the step (11) under an argon atmosphere.
Example 9 (FIG. 1)
(1) Feeding sodium chloride in vacuum to a heating ribbon mixer, and heating for 1.5h at 280 ℃;
(2) discharging the sodium chloride in the step (1) to a jacket water-cooling ribbon mixer, and cooling to 40 ℃;
(3) weighing 20kg of iron powder, 1.0kg of titanium dioxide, 5.0kg of sodium fluoride and 5.0kg of ferrous disulfide, and mixing for 30min by using a three-dimensional mixer;
(4) 160kg of weight-reduced feeding nickel powder, 120kg of sodium chloride in the step (2), and trace elements in the step (3) are mixed for 2 hours by a ribbon mixer;
(5) lifting the mixed powder in the step (4) to a storage bin of a dry granulating machine by a bucket elevator;
(6) the dry granulator uses the following parameters: feeding screw rotation speed S is 80rpm, pinch roller rotation speed R is 7rpm, pinch roller gap delta is 2.0mm, oil pump pressure P is 14MPa, coarse whole grain rotation speed R1 is 50rpm, finishing grain rotation speed R2 is 55rpm, coarse whole grain sieve mesh diameter L1 xL 2 is 3 x3 mm, finishing grain sieve mesh diameter phi 2 is 1.8mm, and extruding granulation is carried out;
(7) screening the mixture in the step (6) by using a rotary vibration screen, wherein the aperture of the upper screen of the rotary vibration screen is phi 3-1.7 mm, and the aperture of the bottom screen is phi 4-0.5 mm, so as to obtain particles with the required particle size range;
(8) feeding the granules with unqualified particle size obtained in the step (7) to a granulator bin in vacuum for extrusion granulation;
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7) to obtain particles with the required particle size range;
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer for 20 min;
(12) and (3) hermetically storing the particles in the step (11) in a nitrogen atmosphere.
Example 10 (FIG. 1)
(1) Feeding sodium chloride in vacuum to a heating ribbon mixer, and heating for 2h at 200 ℃;
(2) discharging the sodium chloride in the step (1) to a jacket water-cooling ribbon mixer, and cooling to 40 ℃;
(3) weighing 25kg of iron powder, 2.0kg of tungsten carbide, 1.2kg of sodium iodide and 2.0kg of ferrous sulfide, and mixing for 15min by using a three-dimensional mixer;
(4) reducing weight, adding 170kg of nickel powder, adding 130kg of sodium chloride in the step (2), and mixing with trace elements in the step (3) for 2 hours by using a three-dimensional mixer;
(5) lifting the mixed powder in the step (4) to a storage bin of a dry granulating machine by a bucket elevator;
(6) the dry granulator uses the following parameters: feeding screw rotation speed S is 75rpm, pinch roller rotation speed R is 8rpm, pinch roller gap delta is 1.8mm, oil pump pressure P is 14MPa, coarse whole grain rotation speed R1 is 40rpm, finishing grain rotation speed R2 is 45rpm, coarse whole grain sieve mesh diameter L1 xL 2 is 5 x 5mm, finishing grain sieve mesh diameter phi 2 is 1.5mm, and extruding granulation is carried out;
(7) screening the mixture in the step (6) by using a rotary vibration screen, wherein the aperture of an upper screen of the rotary vibration screen is phi 3-1.4 mm, and the aperture of a bottom screen is phi 4-0.335 mm, so as to obtain particles with the required particle size range;
(8) feeding the granules with unqualified particle size obtained in the step (7) to a granulator bin in vacuum for extrusion granulation;
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7) to obtain particles with the required particle size range;
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer for 40 min;
(12) and (3) hermetically storing the particles in the step (11) in a nitrogen atmosphere.
Claims (10)
1. The preparation method of the positive electrode material of the sodium-nickel battery is characterized by comprising the following steps of:
(1) feeding sodium chloride in vacuum to a heating ribbon mixer, and heating;
(2) discharging the sodium chloride in the step (1) to a jacket water-cooling ribbon mixer for cooling;
(3) weighing iron powder, aluminum powder, sodium iodide, sodium fluoride and ferrous sulfide, and mixing;
(4) mixing nickel powder, sodium chloride in the step (2) and trace elements in the step (3);
(5) lifting the mixed powder in the step (4) to a storage bin of a dry granulating machine by using a pipe chain conveyor;
(6) extruding and granulating by a dry granulating machine;
(7) and (4) screening the mixture in the step (6) by using a rotary vibration screen.
2. The method for preparing the positive electrode material of the sodium-nickel battery according to claim 1, further comprising the following steps after the step (7):
(8) independently extruding and granulating the granules with unqualified particle sizes obtained in the step (7);
(9) screening the mixture in the step (8) by using a medium-sized rotary vibration screen in the step (7);
(10) repeating (8) and (9);
(11) mixing the qualified granules in the steps (7), (9) and (10) by using a three-dimensional mixer;
(12) and (3) sealing and storing the particles in the step (11) under an argon atmosphere.
3. The method for preparing the positive electrode material of the sodium-nickel battery as claimed in claim 2, wherein the heating temperature in the step (1) is 200 ℃ to 300 ℃, and the cooling temperature in the step (2) is 30 ℃ to 50 ℃.
4. The method for producing the positive electrode material for a sodium-nickel battery according to any one of claims 1 to 3, wherein the positive electrode material for a sodium-nickel battery comprises nickel powder, sodium chloride and trace elements, and the mass ratio of the nickel powder to the sodium chloride to the trace elements is x: y: 1-x-y; wherein x is 0.4-0.6, y is 0.4-0.6, and 1-x-y is 0-0.2.
5. The method for preparing the positive electrode material of the sodium-nickel battery according to claim 4, wherein the nickel powder is composed of one or more of T123, T210, T255 and T287.
6. The method for preparing the positive electrode material of the sodium-nickel battery as claimed in claim 4, wherein the purity of the sodium chloride is more than 99.0%, the particle size is less than 75 μm, and the water content is less than 0.2%.
7. The method for preparing the positive electrode material of the sodium-nickel battery as claimed in claim 6, wherein 0.2-0.8% of an anticaking agent is added to the sodium chloride, the anticaking agent component is silicon dioxide, and the specific surface area is 45-90 m 2/g.
8. The method for preparing the positive electrode material of the sodium-nickel battery as claimed in claim 4, wherein the trace element is one or more of iron powder, aluminum powder, ferrous sulfide, sulfur, sodium fluoride, tungsten carbide, titanium dioxide, ferrous disulfide and sodium iodide.
9. The method for preparing the positive electrode material for the sodium-nickel battery according to claim 8, wherein the iron powder has a purity of more than 99.0%, a particle size of less than 125 μm, and a bulk density of 2.6 to 3.0 g/cc; the purity of the aluminum powder is more than 99.0%, and the particle size is less than 125 microns; the particle size of the ferrous sulfide is less than 125 μm; the purity of the sulfur is more than 99.5 percent, and the particle size is less than 125 mu m; the purity of the sodium fluoride is more than 98.0%, and the particle size is less than 125 μm; the purity of the tungsten carbide is more than 99.5%, and the particle size is 1-20 mu m; the purity of the titanium dioxide is more than 99.0%, and the particle size of the titanium dioxide is less than 125 mu m; the purity of the ferrous disulfide is more than 99.5%, and the particle size is less than 125 μm; the purity of the sodium iodide is more than 99.0%, and the particle size is less than 125 μm.
10. The method for preparing the cathode material of the sodium-nickel battery according to claim 4, wherein the cathode material is cathode material particles, the cathode material particle size distribution is 0.3-1.7 mm, the tap density is within a range of 1.90-2.20 g/cc, and the water content is less than 750 ppm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102239587A (en) * | 2008-12-24 | 2011-11-09 | 日本碍子株式会社 | Plate-shaped particles for positive electrode active material of lithium secondary batteries, lithium secondary battery positive electrode active material films, manufacturing method therefor, lithium secondary battery positive electrode active mater |
| CN102856554A (en) * | 2011-06-28 | 2013-01-02 | 通用电气公司 | Cathode for sodium-metal halide battery, battery comprising the same, and its preparation method and use |
| CN103078118A (en) * | 2013-01-17 | 2013-05-01 | 宁夏天宇光电太阳能科技有限公司 | Preparation method of sodium-nickel battery cathode material |
| CN106033825A (en) * | 2015-03-17 | 2016-10-19 | 中国科学院宁波材料技术与工程研究所 | Positive electrode support type sodium nickel battery and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9537179B2 (en) * | 2013-09-25 | 2017-01-03 | Ceramatec, Inc. | Intermediate temperature sodium-metal halide battery |
-
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- 2019-09-29 CN CN201910935170.1A patent/CN111200124B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102239587A (en) * | 2008-12-24 | 2011-11-09 | 日本碍子株式会社 | Plate-shaped particles for positive electrode active material of lithium secondary batteries, lithium secondary battery positive electrode active material films, manufacturing method therefor, lithium secondary battery positive electrode active mater |
| CN102856554A (en) * | 2011-06-28 | 2013-01-02 | 通用电气公司 | Cathode for sodium-metal halide battery, battery comprising the same, and its preparation method and use |
| CN103078118A (en) * | 2013-01-17 | 2013-05-01 | 宁夏天宇光电太阳能科技有限公司 | Preparation method of sodium-nickel battery cathode material |
| CN106033825A (en) * | 2015-03-17 | 2016-10-19 | 中国科学院宁波材料技术与工程研究所 | Positive electrode support type sodium nickel battery and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 单质硫对钠-氯化镍电池循环性能影响的机理分析;敖昕等;《储能科学与技术》;20160501;第349-354页 * |
| 工作温度对钠氯化镍电池正极结构及电化学性能的影响;敖昕等;《无机材料学报》;20171129;第1243-1249页 * |
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