CN115924993B - Nickel-iron-manganese hydroxide and preparation method thereof - Google Patents
Nickel-iron-manganese hydroxide and preparation method thereof Download PDFInfo
- Publication number
- CN115924993B CN115924993B CN202211678926.7A CN202211678926A CN115924993B CN 115924993 B CN115924993 B CN 115924993B CN 202211678926 A CN202211678926 A CN 202211678926A CN 115924993 B CN115924993 B CN 115924993B
- Authority
- CN
- China
- Prior art keywords
- solution
- reaction kettle
- nickel
- iron
- reaction
- 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
- IREHHCMIJCTSKK-UHFFFAOYSA-H [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] IREHHCMIJCTSKK-UHFFFAOYSA-H 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 71
- 239000011163 secondary particle Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 159
- 239000000243 solution Substances 0.000 claims description 130
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 117
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 69
- 239000007788 liquid Substances 0.000 claims description 67
- 229910021645 metal ion Inorganic materials 0.000 claims description 61
- 230000000536 complexating effect Effects 0.000 claims description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 41
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 41
- 230000006911 nucleation Effects 0.000 claims description 40
- 238000010899 nucleation Methods 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 40
- 229910021529 ammonia Inorganic materials 0.000 claims description 34
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000011572 manganese Chemical class 0.000 claims description 27
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 26
- 239000012266 salt solution Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 229910052748 manganese Chemical class 0.000 claims description 23
- 229910052742 iron Inorganic materials 0.000 claims description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 19
- 239000008139 complexing agent Substances 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 235000006708 antioxidants Nutrition 0.000 claims description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 4
- 235000010350 erythorbic acid Nutrition 0.000 claims description 4
- 229940026239 isoascorbic acid Drugs 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 3
- 229960005055 sodium ascorbate Drugs 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 235000010352 sodium erythorbate Nutrition 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 18
- 239000007774 positive electrode material Substances 0.000 abstract description 14
- 238000005245 sintering Methods 0.000 abstract description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 5
- 241001391944 Commicarpus scandens Species 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 17
- 230000001276 controlling effect Effects 0.000 description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- 229940083542 sodium Drugs 0.000 description 12
- 235000015424 sodium Nutrition 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000002243 precursor Substances 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 7
- 238000000975 co-precipitation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000012716 precipitator Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000863 Ferronickel Inorganic materials 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides nickel-iron-manganese hydroxide and a preparation method thereof, and relates to the technical field of preparation of sodium ion battery anode materials. The nickel-iron-manganese hydroxide prepared by the invention is a spheroid secondary particle assembled by primary crystal grains, the primary crystal grains are tightly connected, the nickel-iron-manganese hydroxide has a layered structure, the inside is a disordered stack of lamellar crystal grains, the outside is a thick-plate crystal grain and extends outwards, and the defect that the spheroid particles are easy to break in the back-stage sintering process can be effectively relieved, so that the prepared positive electrode material has higher structural stability, energy density and cycle performance.
Description
Technical Field
The invention relates to the technical field of preparation of a sodium ion battery anode material, in particular to a nickel-iron-manganese hydroxide and a preparation method thereof.
Background
In the field of power grid energy storage, the sodium ion battery is considered to be one of ideal power supplies which are hopeful to replace lithium ion batteries by virtue of the advantages of abundant raw material resources, low cost, environmental friendliness and the like. The positive electrode material which is an important component of the sodium ion battery determines the key performances of battery energy density, cycle performance, multiplying power performance and the like, and the development of the positive electrode material which has stable structure and rapid sodium ion diffusion performance becomes the focus of market attention. The sodium-containing ternary nickel-iron-manganese layered oxide anode material has higher energy density and stable crystal structure, and is a sodium-ion battery anode material with very good application prospect.
The properties of the sodium-containing ternary nickel-iron-manganese layered oxide depend largely on the properties of the precursor in terms of material synthesis. When the nickel-iron-manganese hydroxide precursor is synthesized by adopting the coprecipitation method, different sizes, shapes, structures and the like have great influence on the processing of the subsequent process, and the electrochemical performance of the final material is influenced. At present, the common particle morphology of hydroxide precursors in the market is spheroid secondary particles formed by stacking nanoscale primary grains, and the primary grains have microsphere shapes, needle shapes, plate shapes, strip shapes, sheet shapes and the like. From the structural point of view, most of agglomeration is the result of surface energy interaction such as electric charge, moisture, van der Waals force among primary crystal grains, connection among crystal grains is weak, more gaps exist, secondary spherical particle fragmentation easily occurs in the subsequent sintering process, and the defects of low tap density, poor consistency and the like of materials are caused, so that the performance of the sodium ion battery is seriously influenced.
Disclosure of Invention
The invention aims to provide the nickel-iron-manganese hydroxide and the preparation method thereof, and the nickel-iron-manganese hydroxide prepared by the method is spheroid secondary particles, continuously grows from the center to the outside, is tightly connected with the inside, and is integrated with the outside and the inside crystal grains, so that the defect that the particles are easy to break in the later sintering process can be effectively relieved, and the prepared positive electrode material has higher structural stability, energy density and cycle performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of nickel-iron-manganese hydroxide, which comprises the following steps:
dissolving divalent salts of nickel, iron and manganese in water to obtain a mixed salt solution; mixing the mixed salt solution with an organic complexing agent to carry out a complexing reaction to obtain a metal ion complexing solution;
dissolving an antioxidant, sodium hydroxide and ammonia water in water to obtain a reaction kettle bottom solution; the pH value of the bottom solution of the reaction kettle is 11.0-13.0, and the ammonia concentration is 0.2-0.8 mol/L;
heating the reaction kettle bottom liquid to 30-70 ℃, introducing nitrogen into the reaction kettle bottom liquid to maintain the oxygen content in the reaction kettle bottom liquid to be lower than 0.5%, and simultaneously introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution into the reaction kettle bottom liquid under the stirring condition of 800-1000 rpm, maintaining the pH value of the reaction kettle bottom liquid to be 11.0-13.0, the ammonia concentration to be 0.2-0.8 mol/L, and carrying out nucleation reaction at the temperature of 30-70 ℃, wherein the nucleation reaction time is 30-100 min; the flow rate of the metal ion complexing solution is 2-6% of the volume of the reaction kettle per hour;
after the nucleation reaction is finished, continuously and circularly introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution under the stirring condition of 600-800 rpm, and entering a uniform-speed growth stage; the temperature of the reaction kettle liquid in the uniform growth stage is 30-70 ℃, the pH value of the reaction kettle liquid is maintained to be 10.5-11.0 by controlling the feeding quantity, the ammonia concentration is 0.2-0.5 mol/L, and when the D50 of the precipitated particles reaches a preset value, the uniform growth stage is finished; the flow rate of the metal ion complexing solution in the uniform growth stage is 1-2 times of the flow rate in the nucleation reaction stage;
continuously and circularly introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution under the stirring condition of 400-600 rpm, and entering a rapid growth stage; the temperature of the reaction kettle liquid in the rapid growth stage is 30-70 ℃, the pH value of the reaction kettle liquid is maintained to be 10.0-10.5 by controlling the feeding quantity, the ammonia concentration is 0.2-0.4 mol/L, until the D50 of the precipitated particles reaches the target value, and the feeding is stopped; the flow rate of the metal ion complexing solution in the rapid growth stage is 1-4 times of the flow rate in the nucleation reaction stage;
after the rapid growth stage is finished, aging the obtained precipitate particles in reaction kettle liquid, wherein the pH value, ammonia concentration and stirring rotation speed of the reaction kettle liquid are maintained unchanged in the aging process, and nitrogen is continuously introduced;
and (3) carrying out solid-liquid separation and drying on the aged precipitate particles to obtain the nickel-iron-manganese hydroxide.
Preferably, the total concentration of nickel, iron and manganese in the mixed salt solution is 1.0-4.0 mol/L.
Preferably, the organic complexing agent is one or more of ethylenediamine tetraacetic acid, citric acid, oxalic acid, acetic acid, polyacrylic acid, tartaric acid and sodium salts thereof; the ratio of the total molar weight of the organic complexing agent to the total molar weight of nickel, iron and manganese in the mixed salt solution is 0.01-0.2:1.
Preferably, the antioxidant comprises one or more of ascorbic acid, sodium ascorbate, isoascorbic acid and sodium isoascorbate; the concentration of the antioxidant in the bottom solution of the reaction kettle is 0.01-0.1 mol/L.
Preferably, the concentration of the sodium hydroxide solution is 2-8 mol/L.
Preferably, the concentration of the ammonia water is 4-10 mol/L.
Preferably, the solid content of the precipitated particles in the nucleation stage is 0.5-2.0%; the D50 of the precipitated particles is less than 1.5 μm.
Preferably, the D50 set value of the precipitation particles in the uniform growth stage is more than 2 mu m and less than or equal to 4 mu m.
Preferably, the D50 target value of the rapid growth stage precipitation particles is set to be greater than 4 μm and less than 10 μm.
The invention provides nickel-iron-manganese hydroxide prepared by the preparation method, which is a spheroid secondary particle, wherein the secondary particle is formed by assembling flaky primary grains; the primary grains at the center of the secondary particles are arranged in a disordered manner; the primary grains of the outer layer are arranged to extend outwards.
According to the invention, the complexing agent is adopted to pre-complex metal ions before coprecipitation reaction, and compared with a reaction system which uses ammonia as the complexing agent alone, the pre-complexing mode can enable part of metal ions to be slowly released on the surface of crystal grains, so that the growth rate of primary crystal grains is slowed down, the crystal grains are enabled to continuously grow from the center to the outside along the radial direction, and the risk of cracking of spherical particles in the sintering process is solved; on the other hand, the organic complexing agent has high solubility in water, can be completely removed by calcination, and has no influence on the whole processing.
In addition, the coprecipitation reaction comprises three stages, and the morphology and arrangement mode of the precursor are controlled by regulating and controlling the pH, the concentration of ammonia water, the flow rate of metal ion complexing solution and the stirring rotation speed of different stages. The direction of the coprecipitation reaction, the size, the shape and the growth rate of primary grains can be controlled by adjusting the pH value, the ammonia concentration and the flow rate of the metal ion complexing solution; the agglomeration of crystal grains can be improved by adjusting the stirring rotation speed, so that an ordered growth mode is obtained, and a specific appearance of outwards extending arrangement is formed.
Drawings
FIG. 1 is an SEM image of nickel iron manganese hydroxide particles prepared according to example 1;
FIG. 2 is a cross-sectional SEM image of nickel iron manganese hydroxide particles prepared according to example 1;
fig. 3 is an SEM image of the positive electrode material particles prepared in example 1;
FIG. 4 is an SEM image of nickel iron manganese hydroxide particles prepared according to comparative example 1;
FIG. 5 is an SEM image of nickel iron manganese hydroxide particles prepared according to comparative example 2;
FIG. 6 is an XRD pattern of the precursor prepared in example 1;
FIG. 7 is an XRD pattern of a sodium-containing ternary nickel-iron-manganese layered oxide positive electrode material obtained by sodium mixing and sintering in example 1;
FIG. 8 is a graph showing the initial charge and discharge at 0.1C of the positive electrode material prepared in example 1;
fig. 9 is an SEM image of particles of the positive electrode material prepared in example 1 after 100 cycles.
Detailed Description
The invention provides a preparation method of nickel-iron-manganese hydroxide, which comprises the following steps:
dissolving divalent salts of nickel, iron and manganese in water to obtain a mixed salt solution; mixing the mixed salt solution with an organic complexing agent to carry out a complexing reaction to obtain a metal ion complexing solution;
dissolving an antioxidant, sodium hydroxide and ammonia water in water to obtain a reaction kettle bottom solution; the pH value of the bottom solution of the reaction kettle is 11.0-13.0, and the concentration of ammonia water is 0.2-0.8 mol/L;
heating the reaction kettle bottom liquid to 30-70 ℃, introducing nitrogen into the reaction kettle bottom liquid to maintain the oxygen content in the reaction kettle bottom liquid to be lower than 0.5%, and simultaneously introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution into the reaction kettle bottom liquid under the stirring condition of 800-1000 rpm, maintaining the pH value of the reaction kettle bottom liquid to be 11.0-13.0, the ammonia concentration to be 0.2-0.8 mol/L, and carrying out nucleation reaction at the temperature of 30-70 ℃, wherein the nucleation reaction time is 30-100 min; the flow rate of the metal ion complexing solution is 2-6% of the volume of the reaction kettle per hour;
after the nucleation reaction is finished, continuously and circularly introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution under the stirring condition of 600-800 rpm, and entering a uniform-speed growth stage; the temperature of the reaction kettle liquid in the uniform growth stage is 30-70 ℃, the pH value of the reaction kettle liquid is maintained to be 10.5-11.0 by controlling the feeding quantity, the ammonia concentration is 0.2-0.5 mol/L, and when the D50 of the precipitated particles reaches a preset value, the uniform growth stage is finished; the flow rate of the metal ion complexing solution in the uniform growth stage is 1-2 times of the flow rate in the nucleation reaction stage;
continuously and circularly introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution under the stirring condition of 400-600 rpm, and entering a rapid growth stage; the temperature of the reaction kettle liquid in the rapid growth stage is 30-70 ℃, the pH value of the reaction kettle liquid is maintained to be 10.0-10.5 by controlling the feeding quantity, the ammonia concentration is 0.2-0.4 mol/L, until the D50 of the precipitated particles reaches the target value, and the feeding is stopped; the flow rate of the metal ion complexing solution in the rapid growth stage is 1-4 times of the flow rate in the nucleation reaction stage;
after the rapid growth stage is finished, aging the obtained precipitate particles in reaction kettle liquid, wherein the pH value, ammonia concentration and stirring rotation speed of the reaction kettle liquid are maintained unchanged in the aging process, and nitrogen is continuously introduced;
and (3) carrying out solid-liquid separation and drying on the aged precipitate particles to obtain the nickel-iron-manganese hydroxide.
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
The invention dissolves the divalent salt of nickel, iron and manganese in water to obtain mixed salt solution.
The invention has no special requirement on the divalent salt of nickel, iron and manganese, and the divalent salt which is well known in the field and can be dissolved in water can be selected from nickel sulfate, ferrous sulfate and manganese sulfate. In the present invention, the total concentration of nickel, iron and manganese in the mixed solution is preferably 1.0 to 4.0mol/L, more preferably 1.5 to 3.5mol/L, and still more preferably 2mol/L. The invention has no special requirement on the proportion of the nickel, the iron and the manganese, and is set by a person skilled in the art according to actual requirements.
After the mixed salt solution is obtained, the mixed salt solution is mixed with an organic complexing agent for complex reaction, and then the metal ion complex solution is obtained.
In the present invention, the organic complexing agent is preferably one or more of ethylenediamine tetraacetic acid, citric acid, oxalic acid, acetic acid, polyacrylic acid, tartaric acid and their respective sodium salts; the ratio of the total molar amount of the organic complexing agent to the nickel, iron and manganese in the mixed salt solution is preferably 0.01-0.2:1, more preferably 0.05-0.15: 1, more preferably 0.07 to 0.12:1.
The invention dissolves the antioxidant, sodium hydroxide and ammonia water in water to obtain the bottom solution of the reaction kettle; the pH value of the bottom solution of the reaction kettle is 11.0-13.0, and the concentration of ammonia water is 0.2-0.8 mol/L.
In the present invention, the antioxidant preferably includes one or more of ascorbic acid, sodium ascorbate, isoascorbic acid and sodium isoascorbic acid; the concentration of the antioxidant in the reaction kettle bottom liquid is preferably 0.01-0.1 mol/L, more preferably 0.03-0.07 mol/L. In the invention, the antioxidant has the function of removing trace oxidation free radicals in water and preventing metal ions from being oxidized before coprecipitation reaction; the sodium hydroxide is used as a precipitant; the ammonia water is used as a complexing agent.
In the present invention, the volume of the reaction vessel base liquid is preferably 1/3 to 2/3, more preferably 1/2 of the volume of the reaction vessel.
After the metal ion complexing solution, the sodium hydroxide solution, the ammonia water solution and the reaction kettle bottom solution are obtained, the reaction kettle bottom solution is heated to 30-70 ℃, nitrogen is introduced into the reaction kettle bottom solution to maintain the oxygen content in the reaction kettle bottom solution to be lower than 0.5%, the metal ion complexing solution, the sodium hydroxide solution and the ammonia water solution are concurrently introduced into the reaction kettle bottom solution under the stirring condition of 800-1000 rpm, the pH value of the reaction kettle bottom solution is maintained to be 11.0-13.0, the ammonia concentration is 0.2-0.8 mol/L, and the temperature is 30-70 ℃, so that the nucleation reaction is carried out.
In the present invention, the sodium hydroxide solution is preferably obtained by dissolving sodium hydroxide in water, and the concentration of the sodium hydroxide solution is preferably 2 to 8mol/L, more preferably 3 to 7mol/L, and still more preferably 4mol/L.
In the present invention, the concentration of the aqueous ammonia is preferably 4 to 10mol/L, more preferably 5 to 9mol/L, and still more preferably 8mol/L.
In the invention, in the nucleation reaction stage, the pH value of the reaction kettle liquid is preferably 11.5-12.5, the concentration of ammonia water is preferably 0.4-0.6 mol/L, and the temperature is preferably 40-60 ℃; the flow rate of the metal ion complexing solution is 2-6%, preferably 3-5% of the volume of the reaction kettle per hour.
In the present invention, the time for the nucleation reaction is 30 to 100 minutes, preferably 40 to 90 minutes, more preferably 50 to 80 minutes. In the present invention, the stirring speed in the nucleation stage is preferably 850 to 950rpm; the solid content of the precipitated particles is preferably 0.5 to 2.0%, more preferably 1.0 to 1.5%; the D50 of the precipitated particles is less than 1.5 μm.
After the nucleation reaction is finished, continuously and circularly introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia solution under the stirring condition of 600-800 rpm, and entering a constant-speed growth stage; the temperature of the reaction kettle liquid in the uniform growth stage is 30-70 ℃, the pH value of the reaction kettle liquid is maintained to be 10.5-11.0 by controlling the feeding quantity, the ammonia concentration is 0.2-0.5 mol/L, and when the D50 of the precipitated particles reaches a preset value, the uniform growth stage is finished; the flow rate of the metal ion complexing solution in the uniform growth stage is 1-2 times of the flow rate in the nucleation reaction stage.
In the invention, the temperature of the reaction kettle liquid in the constant-speed growth stage is preferably 40-60 ℃. In the invention, the stirring rotation speed in the uniform growth stage is preferably 650-750 rpm; the D50 set point of the precipitated particles is preferably > 2 μm and < 4. Mu.m.
After the uniform growth stage is finished, continuously introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia solution into the reactor under the stirring condition of 400-600 rpm, and entering a rapid growth stage; the temperature of the reaction kettle liquid in the rapid growth stage is 30-70 ℃, the pH value of the reaction kettle liquid is maintained to be 10.0-10.5 by controlling the feeding quantity, the ammonia concentration is 0.2-0.4 mol/L, until the D50 of the precipitated particles reaches the target value, and the feeding is stopped; the flow rate of the metal ion complexing solution in the rapid growth stage is 1-4 times of the flow rate in the nucleation reaction stage.
In the invention, the temperature of the reaction kettle liquid in the rapid growth stage is preferably 40-60 ℃. In the invention, the stirring rotation speed of the rapid growth stage is preferably 450-550 rpm; the D50 target value of the precipitated particles is preferably set to > 4 μm and < 10 μm.
The coprecipitation reaction comprises three stages, and the morphology and arrangement mode of the precursor are controlled by regulating and controlling the pH, ammonia concentration, metal ion complexing solution flow and stirring rotation speed of different stages. The direction of the coprecipitation reaction, the size, the shape and the growth rate of primary grains can be controlled by adjusting the pH value, the ammonia concentration and the flow rate of the metal ion complexing solution; the agglomeration of crystal grains can be improved by adjusting the stirring rotation speed, so that an ordered growth mode is obtained, and a special appearance of outwards extending arrangement is formed.
After the rapid growth stage is finished, the obtained precipitate particles are aged in the reaction kettle liquid, the pH value, the ammonia concentration and the stirring rotation speed of the reaction kettle liquid are maintained unchanged in the aging process, and nitrogen is continuously introduced.
In the present invention, the aging time is preferably 4 to 8 hours, more preferably 5 to 7 hours. The invention utilizes aging to dissolve the tiny grains and convert the small grains into large grains.
After the aging is finished, the aged precipitate particles are subjected to solid-liquid separation and drying to obtain the nickel-iron-manganese hydroxide.
The solid-liquid separation mode is not particularly required, and can be any solid-liquid separation mode known in the art, such as filtration. After solid-liquid separation, the present invention preferably further comprises washing the obtained solid particles, followed by drying. The drying conditions are not particularly limited in the present invention, and drying processes well known in the art may be employed.
The invention provides nickel-iron-manganese hydroxide prepared by the preparation method, which is a spheroid secondary particle, wherein the secondary particle is formed by assembling flaky primary grains; the primary grains at the center of the secondary particles are arranged in a disordered manner; the primary grains of the outer layer are arranged to extend outwards.
In the present invention, the thickness of the primary crystal grains in the center of the secondary particles is preferably 10 to 100nm; the thickness of the primary grains of the outer layer is preferably 100 to 500nm.
The nickel-iron-manganese hydroxide particles are tightly connected with the inside, and the outside and the inside crystal grains are integrated, so that the defect that spheroid particles are easy to break in the later sintering process can be effectively relieved, and the prepared anode material has higher structural stability, energy density and cycle performance.
The nickel iron manganese hydroxide and the preparation method thereof provided by the present invention are described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The chemical formula for preparing the nickel-iron-manganese hydroxide is Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 The preparation method comprises the following steps:
nickel sulfate, ferrous sulfate and manganese sulfate are selected as reaction raw materials, the content of nickel, iron and manganese in a precursor is designed according to the mole ratio of Ni, fe and Mn of 1:1:1, the nickel, iron and manganese and pure water are prepared into a mixed salt solution with the total metal ion concentration of 2.0mol/L, citric acid is added into the mixed salt solution, and the concentration of the citric acid in the mixed salt solution is 0.1mol/L, so that a metal ion complexing solution is obtained; sodium hydroxide solution with the molar concentration of 4mol/L is taken as a precipitator; ammonia water with the molar concentration of 8mol/L is used as a complexing agent;
mixing ascorbic acid, sodium hydroxide solution and ammonia water to obtain reaction kettle bottom solution; the molar concentration of the ascorbic acid in the bottom solution of the reaction kettle is 0.1mol/L, the molar concentration of the sodium hydroxide is 0.1mol/L, and the concentration of the ammonia is 0.5mol/L; placing the bottom solution of the reaction kettle in the reaction kettle to the position of 1/2 of the liquid level of the reaction kettle, starting stirring at 900rpm, heating to 60 ℃, introducing nitrogen, and controlling the oxygen content of the bottom solution of the reaction kettle to be lower than 0.5%;
introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle in parallel, maintaining the pH value of the kettle liquid of the reaction kettle to be 11.5, the ammonia concentration to be 0.5mol/L, the temperature to be 60 ℃, and the stirring speed to be 900rpm, and carrying out a nucleation reaction, wherein the flow rate of the metal ion complexing solution is 5% of the volume of the reaction kettle per hour, the reaction time is 60min, and the nucleation reaction stage is finished; the method comprises the steps of entering a uniform growth stage, adjusting the pH value of kettle liquid of a reaction kettle to be 10.8, the concentration of ammonia water to be 0.5mol/L, the temperature to be 60 ℃, the stirring rotation speed to be 700rpm, the flow rate of a metal ion complexing solution to be 2 times that of a nucleation reaction stage, and ending the uniform growth stage when the D50 of precipitated particles reaches 4 mu m; the rapid growth stage is carried out, the pH value of the kettle liquid of the reaction kettle is regulated to 10.3, the ammonia concentration is regulated to 0.3mol/L, the temperature is regulated to 60 ℃, the stirring rotation speed is regulated to 500rpm, the flow rate of the metal ion complexing solution is 3 times that of the nucleation stage, until the D50 of the precipitated particles reaches 6 mu m, and the feeding is stopped;
and aging the obtained precipitate particles in a reaction kettle for 6 hours, and filtering, washing and drying the precipitate particles to obtain a target product.
Example 2
The chemical formula for preparing the nickel-iron-manganese hydroxide is Ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 The preparation method comprises the following steps:
nickel sulfate, ferrous sulfate and manganese sulfate are selected as reaction raw materials, the content of nickel, iron and manganese in a precursor is designed according to the mole ratio of Ni, fe and Mn of 1:1:1, the nickel, iron and manganese and pure water are prepared into a mixed salt solution with the total metal ion concentration of 2.0mol/L, citric acid is added into the mixed salt solution, and the concentration of the citric acid in the mixed salt solution is 0.2mol/L, so that a metal ion complexing solution is obtained; sodium hydroxide solution with the molar concentration of 4mol/L is taken as a precipitator; ammonia water with the molar concentration of 8mol/L is used as a complexing agent;
mixing ascorbic acid, sodium hydroxide solution and ammonia water to obtain reaction kettle bottom solution; the molar concentration of the ascorbic acid in the bottom solution of the reaction kettle is 0.1mol/L, the molar concentration of the sodium hydroxide is 0.05mol/L, and the concentration of the ammonia water is 0.4mol/L; placing the bottom solution of the reaction kettle in the reaction kettle to the position of 1/2 of the liquid level of the reaction kettle, starting stirring at 900rpm, heating to 60 ℃, introducing nitrogen, and controlling the oxygen content of the bottom solution of the reaction kettle to be lower than 0.5%;
introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle in parallel, maintaining the pH value of the kettle liquid of the reaction kettle to be 11.0, the ammonia concentration to be 0.4mol/L, the temperature to be 60 ℃, and the stirring speed to be 900rpm, and carrying out a nucleation reaction, wherein the flow rate of the metal ion complexing solution is 3% of the volume of the reaction kettle per hour, the reaction time is 60min, and the nucleation reaction stage is finished; the reactor enters a uniform growth stage, the pH value of the reactor kettle liquid is regulated to 10.5, the ammonia concentration is regulated to 0.4mol/L, the temperature is regulated to 60 ℃, the stirring rotation speed is regulated to 700rpm, the flow rate of the metal ion complexing solution is 1.5 times that of the nucleation reaction stage, the D50 of the particles to be precipitated reaches 4 mu m, and the uniform growth stage is finished; the rapid growth stage is carried out, the pH value of the kettle liquid of the reaction kettle is regulated to 10.0, the ammonia concentration is regulated to 0.25mol/L, the temperature is regulated to 60 ℃, the stirring rotation speed is regulated to 500rpm, the flow rate of the metal ion complexing solution is 2 times that of the nucleation stage, until the D50 of the precipitated particles reaches 6 mu m, and the feeding is stopped;
and aging the obtained precipitate particles in a reaction kettle for 6 hours, and filtering, washing and drying the precipitate particles to obtain a target product.
Example 3
The chemical formula for preparing the nickel-iron-manganese hydroxide is Ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 The preparation method comprises the following steps:
nickel sulfate, ferrous sulfate and manganese sulfate are selected as reaction raw materials, the content of nickel, iron and manganese in a precursor is designed according to the molar ratio of Ni, fe and Mn of 4:2:4, the nickel, iron and manganese and pure water are prepared into a mixed salt solution with the total metal ion concentration of 2.0mol/L, citric acid is added into the mixed salt solution, and the concentration of the citric acid in the mixed salt solution is 0.1mol/L, so that a metal ion complexing solution is obtained; sodium hydroxide solution with the molar concentration of 4mol/L is taken as a precipitator; ammonia water with the molar concentration of 8mol/L is used as a complexing agent;
mixing ascorbic acid, sodium hydroxide solution and ammonia water to obtain reaction kettle bottom solution; the molar concentration of the ascorbic acid in the bottom solution of the reaction kettle is 0.05mol/L, the molar concentration of the sodium hydroxide is 0.1mol/L, and the concentration of the ammonia water is 0.8mol/L; placing the bottom solution of the reaction kettle in the reaction kettle to the position of 1/2 of the liquid level of the reaction kettle, starting stirring at 900rpm, heating to 60 ℃, introducing nitrogen, and controlling the oxygen content of the bottom solution of the reaction kettle to be lower than 0.5%;
introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle in parallel, maintaining the pH value of the kettle liquid of the reaction kettle to be 12.0, the ammonia concentration to be 0.7mol/L, the temperature to be 60 ℃, and the stirring speed to be 900rpm, and carrying out a nucleation reaction, wherein the flow rate of the metal ion complexing solution per hour is 3% of the volume of the reaction kettle, the reaction time is 60min, and the nucleation reaction stage is finished; the method comprises the steps of entering a uniform growth stage, adjusting the pH value of the kettle liquid of a reaction kettle to 11.0, the ammonia concentration to 0.5mol/L, the temperature to 60 ℃, the stirring rotation speed to 700rpm, and the flow rate of a metal ion complexing solution to be 2 times that of a nucleation reaction stage, wherein the D50 of the particles to be precipitated reaches 4 mu m, and ending the uniform growth stage; the rapid growth stage is carried out, the pH value of the kettle liquid of the reaction kettle is regulated to 10.5, the ammonia concentration is regulated to 0.4mol/L, the temperature is regulated to 60 ℃, the stirring rotation speed is regulated to 500rpm, the flow rate of the metal ion complexing solution is 3 times that of the nucleation stage, until the D50 of the precipitated particles reaches 6 mu m, and the feeding is stopped;
and aging the obtained precipitate particles in a reaction kettle for 6 hours, and filtering, washing and drying the precipitate particles to obtain a target product.
Example 4
The chemical formula for preparing the nickel-iron-manganese hydroxide is Ni 0.25 Fe 0.5 Mn 0.25 (OH) 2 The preparation method comprises the following steps:
nickel sulfate, ferrous sulfate and manganese sulfate are selected as reaction raw materials, the content of nickel, iron and manganese in a precursor is designed according to the mole ratio of Ni, fe and Mn of 1:2:1, the nickel, iron and manganese and pure water are prepared into a mixed salt solution with the total metal ion concentration of 2.0mol/L, citric acid is added into the mixed salt solution, and the concentration of the citric acid in the mixed salt solution is 0.2mol/L, so that a metal ion complexing solution is obtained; sodium hydroxide solution with the molar concentration of 4mol/L is taken as a precipitator; ammonia water with the molar concentration of 8mol/L is used as a complexing agent;
mixing ascorbic acid, sodium hydroxide solution and ammonia water to obtain reaction kettle bottom solution; the molar concentration of the ascorbic acid in the bottom solution of the reaction kettle is 0.2mol/L, the molar concentration of the sodium hydroxide is 0.1mol/L, and the concentration of the ammonia water is 0.4mol/L; placing the bottom solution of the reaction kettle in the reaction kettle to the position of 1/2 of the liquid level of the reaction kettle, starting stirring at 900rpm, heating to 50 ℃, introducing nitrogen, and controlling the oxygen content of the bottom solution of the reaction kettle to be lower than 0.5%;
introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle in parallel, maintaining the pH value of the kettle liquid of the reaction kettle to be 11.5, the ammonia concentration to be 0.4mol/L, and the temperature to be 50 ℃, and stirring at 900rpm to perform a nucleation reaction, wherein the flow rate of the metal ion complexing solution per hour is 3% of the volume of the reaction kettle, the reaction time is 60min, and the nucleation reaction stage is finished; the method comprises the steps of entering a uniform growth stage, adjusting the pH value of the kettle liquid of a reaction kettle to be 10.8, the ammonia concentration to be 0.3mol/L, the temperature to be 50 ℃, the stirring rotation speed to be 700rpm, and the flow rate of a metal ion complexing solution to be 2 times that of a nucleation reaction stage, wherein the D50 of the particles to be precipitated reaches 4 mu m, and ending the uniform growth stage; the rapid growth stage is carried out, the pH value of the kettle liquid of the reaction kettle is regulated to 10.3, the ammonia concentration is regulated to 0.2mol/L, the temperature is regulated to 50 ℃, the stirring rotation speed is regulated to 500rpm, the flow rate of the metal ion complexing solution is 3 times that of the nucleation stage, until the D50 of the precipitated particles reaches 6 mu m, and the feeding is stopped;
and aging the obtained precipitate particles in a reaction kettle for 6 hours, and filtering, washing and drying the precipitate particles to obtain a target product.
Comparative example 1
Nickel iron manganese hydroxide was prepared as in example 1 except that the flow of the metal ion complexing solution was maintained constant at 5% of the reactor volume per hour.
Comparative example 2
Nickel iron manganese hydroxide was prepared as in example 1, except that the stirring speed used in the constant growth stage and the rapid growth stage was maintained at 900rpm at all times.
Comparative example 3
Nickel iron manganese hydroxide was prepared as in example 1, except that the particle D50 was stopped at 2 μm during the constant growth stage and then entered the rapid growth stage.
Comparative example 4
Nickel iron manganese hydroxide was prepared as in example 1, except that the reaction was stopped after the fast growth stage particles D50 was 10 μm.
Structure and performance characterization:
the nickel-iron-manganese hydroxide and lithium carbonate prepared in the examples and the comparative examples are metered and mixed uniformly according to the mass ratio of 1:1.05, then are spread into a corundum sagger, are put into a muffle furnace, are introduced with air, are heated to 500 ℃ at 3 ℃/min for 4 hours, are heated to 870 ℃ at 2 ℃/min for sintering for 10 hours, are naturally cooled to room temperature, and are finally screened and separated to obtain the sodium-containing ternary nickel-iron-manganese layered oxide anode material.
The ferronickel manganese hydroxide obtained in example 1 and the calcined sodium-containing ternary ferronickel manganese layered oxide and the ferronickel manganese hydroxides obtained in comparative examples 1 and 2 were examined by means of a field emission Scanning Electron Microscope (SEM) (JSM-7800F), as shown in fig. 1 to 5. Wherein FIG. 1 is an SEM image of nickel iron manganese hydroxide particles prepared in example 1, FIG. 2 is a cross-sectional SEM image of nickel iron manganese hydroxide particles prepared in example 1, FIG. 3 is an SEM image of positive electrode material particles prepared in example 1, FIG. 4 is an SEM image of nickel iron manganese hydroxide particles prepared in comparative example 1, and FIG. 5 is an SEM image of nickel iron manganese hydroxide particles prepared in comparative example 2.
It can be seen from fig. 1 and 2 that the nickel iron manganese hydroxide particles prepared in example 1 are spheroid secondary particles assembled by primary grains, have an obvious layered structure, have lamellar grains randomly stacked in the interior and have thick lamellar grains extending outwards in the exterior. The morphology of the particles of comparative example 1 and comparative example 2 was the same as that of the spheroid secondary particles, but the morphology of the primary grains constituting the particles was greatly different from that of example 1. Fig. 3 shows that the sodium-containing ternary nickel-iron-manganese layered oxide cathode material obtained by sintering in example 1 has a polycrystalline structure, and primary particles on the surface are coarse.
The XRD diffractometer (Panalycal X' PERT PRO MPD) is adopted to detect the phase structure of the nickel-iron-manganese hydroxide prepared in the example 1 and the sodium-containing ternary nickel-iron-manganese layered oxide positive electrode material obtained by sodium mixing and sintering, and the results are shown in figures 6 and 7, and have higher crystallinity and are consistent with the crystal form of the target product.
The materials obtained by mixing sodium and sintering the nickel-iron-manganese ternary precursors prepared in examples 1-4 and comparative examples 1-4 are used as sodium ion battery anode materials, and are respectively mixed with SP and PVDF in a mass ratio of 8:1:1 in a drying room with humidity less than 10%Homogenizing in NMP, controlling solid content at 45%, coating on aluminum foil current collector, vacuum baking at 100-110 deg.C for 4-8 hr, rolling and punching to obtain sodium ion battery positive plate. The button half cell is assembled in a glove box filled with argon, a counter electrode is a metal sodium sheet, a used diaphragm is a PE diaphragm, and an electrolyte is NaPF of 1mol/L 6 EC/DMC (volume ratio 1:1). The button cell is subjected to charge and discharge test, the 0.1C capacity test flow is 0.1C CC4.0V,4.0V CV0.05C,0.1C DC 2V, the first charge and discharge curve of the material is measured, the 1C cycle test flow is 1C CC4.0V,4.0V CV 0.1C,1C DC 2V, and the cycle life curve is obtained by 100 times of cycle.
The test equipment of the button cell was a commercial LAND cell test system of blue electric electronics Co., ltd. In Wuhan, at a test temperature of 25℃to obtain the results shown in Table 1, and the first charge-discharge curve of the positive electrode material obtained in example 1 is shown in FIG. 8.
Table 1 electrical properties of examples and comparative examples
Comparing the electrical property data of example 1 and comparative examples 1 to 4, the specific capacity, the first coulombic efficiency and the cycle performance of the positive electrode materials prepared in example 1 are all superior to those of comparative examples 1 to 4. Further, the capacity retention rate was highest after 100 cycles of example 1, compared to examples 2 to 4.
The morphology of the particles of the positive electrode material prepared in example 1 after 1C cycle for 100 times was detected by using a field emission Scanning Electron Microscope (SEM) (JSM-7800F), as shown in fig. 9, compared with fig. 3, the particles can be seen to maintain a more complete initial morphology, no particle cracks were detected, and good structural stability was achieved.
As can be seen from the above examples and comparative examples, the nickel iron manganese hydroxide particles prepared by the method have compact internal connection, layered structure, disordered stacking of lamellar crystal grains in the internal and thick lamellar crystal grains in the external and outward extending arrangement, and can effectively relieve the defect that spheroid particles are easy to break in the subsequent sintering process, so that the prepared positive electrode material has higher structural stability, energy density and cycle performance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The preparation method of the nickel-iron-manganese hydroxide is characterized by comprising the following steps of:
dissolving divalent salts of nickel, iron and manganese in water to obtain a mixed salt solution; mixing the mixed salt solution with an organic complexing agent to carry out a complexing reaction to obtain a metal ion complexing solution; the organic complexing agent is one or more of ethylenediamine tetraacetic acid, citric acid, oxalic acid, acetic acid, polyacrylic acid, tartaric acid and sodium salts thereof; the ratio of the total molar weight of the organic complexing agent to the total molar weight of nickel, iron and manganese in the mixed salt solution is 0.01-0.2:1;
dissolving an antioxidant, sodium hydroxide and ammonia water in water to obtain a reaction kettle bottom solution; the pH value of the bottom solution of the reaction kettle is 11.0-13.0, and the ammonia concentration is 0.2-0.8 mol/L;
heating the reaction kettle bottom liquid to 30-70 ℃, introducing nitrogen into the reaction kettle bottom liquid to maintain the oxygen content in the reaction kettle bottom liquid to be lower than 0.5%, and simultaneously introducing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution into the reaction kettle bottom liquid under the stirring condition of 800-1000 rpm, maintaining the pH value of the reaction kettle bottom liquid to be 11.0-13.0, the ammonia concentration to be 0.2-0.8 mol/L, and the temperature to be 30-70 ℃, and carrying out nucleation reaction, wherein the nucleation reaction time is 30-100 min; the flow rate of the metal ion complexing solution is 2-6% of the volume of the reaction kettle per hour; the solid content of the precipitated particles in the nucleation reaction stage is 0.5-2.0%; the D50 of the precipitated particles is less than 1.5 μm;
after the nucleation reaction is finished, continuously flowing a metal ion complexing solution, a sodium hydroxide solution and an ammonia solution in parallel under the stirring condition of 650-750 rpm, and entering a uniform-speed growth stage; the temperature of the reaction kettle liquid in the uniform growth stage is 30-70 ℃, the pH value of the reaction kettle liquid is maintained to be 10.5-11.0 by controlling the feeding amount, the ammonia concentration is 0.2-0.5 mol/L, and when the D50 of the precipitated particles reaches a preset value, the uniform growth stage is finished; the flow rate of the metal ion complexing solution in the uniform growth stage is 1.5-2 times of the flow rate in the nucleation reaction stage; the D50 set value of the sediment particles at the constant speed growth stage is more than 2 mu m and less than or equal to 4 mu m;
continuously flowing a metal ion complexing solution, a sodium hydroxide solution and an ammonia water solution under the stirring condition of 400-600 rpm, and entering a rapid growth stage; the temperature of the reaction kettle liquid in the rapid growth stage is 30-70 ℃, the pH value of the reaction kettle liquid is maintained to be 10.0-10.5 by controlling the feeding quantity, the ammonia concentration is 0.2-0.4 mol/L, until the D50 of the precipitated particles reaches a target value, and the feeding is stopped; the flow rate of the metal ion complexing solution in the rapid growth stage is 3-4 times of the flow rate in the nucleation reaction stage; the D50 target value of the rapid growth stage precipitation particles is set to be greater than 4 μm and less than 10 μm;
after the rapid growth stage is finished, aging the obtained precipitate particles in reaction kettle liquid, maintaining the pH value, ammonia concentration and stirring rotation speed of the reaction kettle liquid unchanged during the aging process, and continuously introducing nitrogen;
and (3) carrying out solid-liquid separation and drying on the aged precipitate particles to obtain the nickel-iron-manganese hydroxide.
2. The preparation method according to claim 1, wherein the total concentration of nickel, iron and manganese in the mixed salt solution is 1.0-4.0 mol/L.
3. The method of claim 1, wherein the antioxidant comprises one or more of ascorbic acid, sodium ascorbate, isoascorbic acid, and sodium isoascorbate; the concentration of the antioxidant in the bottom solution of the reaction kettle is 0.01-0.1 mol/L.
4. The preparation method according to claim 1, wherein the concentration of the sodium hydroxide solution is 2-8 mol/L.
5. The preparation method of claim 1, wherein the concentration of the ammonia water is 4-10 mol/L.
6. The nickel-iron-manganese hydroxide prepared by the preparation method according to any one of claims 1-5 is spheroid secondary particles, and the secondary particles are formed by assembling flaky primary grains; the primary grains at the center of the secondary particles are arranged in a disordered manner; the primary grains of the outer layer are arranged to extend outwards.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211678926.7A CN115924993B (en) | 2022-12-27 | 2022-12-27 | Nickel-iron-manganese hydroxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211678926.7A CN115924993B (en) | 2022-12-27 | 2022-12-27 | Nickel-iron-manganese hydroxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115924993A CN115924993A (en) | 2023-04-07 |
| CN115924993B true CN115924993B (en) | 2024-03-26 |
Family
ID=86652378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211678926.7A Active CN115924993B (en) | 2022-12-27 | 2022-12-27 | Nickel-iron-manganese hydroxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115924993B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116462238A (en) * | 2023-04-10 | 2023-07-21 | 宁夏中色金辉新能源有限公司 | Application of alcohol as precursor antioxidant and precursor preparation method |
| CN116375111B (en) * | 2023-06-06 | 2023-09-01 | 宜宾锂宝新材料有限公司 | Sodium ion battery, positive electrode material and precursor thereof and preparation method |
| CN116835668A (en) * | 2023-07-17 | 2023-10-03 | 新乡天力锂能股份有限公司 | Ultra-high nickel quaternary positive electrode material precursor with uniform particle size and no cracks and preparation method thereof |
| CN116621234B (en) * | 2023-07-20 | 2023-11-07 | 宜宾光原锂电材料有限公司 | Sodium ion positive electrode material precursor, preparation method and positive electrode material |
| CN116854152B (en) * | 2023-08-14 | 2024-06-14 | 金驰能源材料有限公司 | Sodium ion battery positive electrode material precursor, preparation method thereof, positive electrode material and sodium ion battery |
| CN117342630B (en) * | 2023-12-04 | 2024-02-23 | 宜宾锂宝新材料有限公司 | Sodium ion positive electrode material, preparation method thereof, positive electrode plate and sodium battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106395754A (en) * | 2016-11-16 | 2017-02-15 | 天津巴莫科技股份有限公司 | Preparation method of mono-/multi-metal coprecipitation hydroxide or carbonate |
| CN114408988A (en) * | 2022-03-31 | 2022-04-29 | 金驰能源材料有限公司 | Ternary positive electrode material precursor and preparation method thereof |
| CN115196691A (en) * | 2022-07-18 | 2022-10-18 | 宿迁市翔鹰新能源科技有限公司 | Nickel-iron-manganese ternary precursor for sodium ion battery and preparation method and application thereof |
| CN115504522A (en) * | 2022-09-28 | 2022-12-23 | 中伟新材料股份有限公司 | Sodium-ion battery positive electrode material precursor and preparation method thereof, sodium-ion battery positive electrode material, sodium-ion battery and electric equipment |
-
2022
- 2022-12-27 CN CN202211678926.7A patent/CN115924993B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106395754A (en) * | 2016-11-16 | 2017-02-15 | 天津巴莫科技股份有限公司 | Preparation method of mono-/multi-metal coprecipitation hydroxide or carbonate |
| CN114408988A (en) * | 2022-03-31 | 2022-04-29 | 金驰能源材料有限公司 | Ternary positive electrode material precursor and preparation method thereof |
| CN115196691A (en) * | 2022-07-18 | 2022-10-18 | 宿迁市翔鹰新能源科技有限公司 | Nickel-iron-manganese ternary precursor for sodium ion battery and preparation method and application thereof |
| CN115504522A (en) * | 2022-09-28 | 2022-12-23 | 中伟新材料股份有限公司 | Sodium-ion battery positive electrode material precursor and preparation method thereof, sodium-ion battery positive electrode material, sodium-ion battery and electric equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115924993A (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115924993B (en) | Nickel-iron-manganese hydroxide and preparation method thereof | |
| CN112750999B (en) | Cathode material, preparation method thereof and lithium ion battery | |
| CN109244436A (en) | A kind of nickelic positive electrode and preparation method thereof and a kind of lithium ion battery | |
| WO2021175233A1 (en) | Lithium-manganese-rich material, preparation method for same, and applications thereof | |
| JP2008258160A (en) | Active material for nonaqueous electrolyte secondary battery, and its manufacturing method | |
| CN112928253B (en) | Nickel-manganese-titanium composite material and preparation method and application thereof | |
| WO2015039490A1 (en) | Lithium-rich anode material and preparation method thereof | |
| CN112047382B (en) | Positive electrode material and preparation method and application thereof | |
| CN112751006B (en) | Cobalt-free lithium ion battery layered positive electrode material and preparation method and application thereof | |
| CN113839040B (en) | High-nickel ternary cathode material, preparation method thereof and lithium ion battery | |
| WO2024066892A1 (en) | Manganese-rich oxide precursor, preparation method therefor, and use thereof | |
| KR20160083638A (en) | Cathode active material for lithium secondary and lithium secondary batteries comprising the same | |
| CN106910887A (en) | A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode | |
| CN114843469B (en) | MgFe 2 O 4 Modified P2/O3 type nickel-based layered sodium ion battery positive electrode material and preparation method thereof | |
| CN114583141B (en) | Precursor material with three-layer structure, preparation method thereof and anode material | |
| CN115000383B (en) | Hollow ternary positive electrode material and preparation method thereof | |
| CN115818737A (en) | Nickel-iron-manganese ternary precursor and preparation method and application thereof | |
| CN112952056B (en) | Lithium-rich manganese-based composite cathode material and preparation method and application thereof | |
| CN116375111B (en) | Sodium ion battery, positive electrode material and precursor thereof and preparation method | |
| KR100668051B1 (en) | Manganese Oxides by co-precipitation method, Spinel type cathode active material for lithium secondary batteries using thereby and Preparation of the same | |
| CN108807971B (en) | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof | |
| CN114455647A (en) | Preparation method of surface confinement treatment full-concentration gradient quaternary high-nickel NCMA positive electrode material | |
| KR101458505B1 (en) | The maufacturing method of Lithium-Nickel-Cobalt-Manganese complex oxide by using thermal degradation of oxalate anion | |
| CN114284472B (en) | Monocrystalline lithium-rich material with superconductive modification layer, and preparation method and application thereof | |
| CN114649522A (en) | Mo-doped Fe2O3Coated lithium-rich manganese-based positive electrode material and preparation method thereof |
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 | ||
| GR01 | Patent grant |