CN116230842B - Preparation method of lithium supplementing agent - Google Patents
Preparation method of lithium supplementing agent Download PDFInfo
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- CN116230842B CN116230842B CN202211587905.4A CN202211587905A CN116230842B CN 116230842 B CN116230842 B CN 116230842B CN 202211587905 A CN202211587905 A CN 202211587905A CN 116230842 B CN116230842 B CN 116230842B
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- lithium
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- ferrite
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- supplementing agent
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 67
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000001354 calcination Methods 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 23
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 61
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 15
- 238000010298 pulverizing process Methods 0.000 claims description 14
- 238000001694 spray drying Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 229960001645 ferrous gluconate Drugs 0.000 claims description 10
- 235000013924 ferrous gluconate Nutrition 0.000 claims description 10
- 239000004222 ferrous gluconate Substances 0.000 claims description 10
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 claims description 10
- 229910002096 lithium permanganate Inorganic materials 0.000 claims description 10
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical group O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 9
- 229940009827 aluminum acetate Drugs 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000009461 vacuum packaging Methods 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 6
- 159000000002 lithium salts Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 238000005507 spraying Methods 0.000 abstract description 5
- 230000002950 deficient Effects 0.000 abstract description 4
- 239000011164 primary particle Substances 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 3
- 239000013589 supplement Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000005056 compaction Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical class O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 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
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention relates to a preparation method of a lithium supplementing agent, which comprises the steps of preparing amorphous doped lithium ferrite by a hydrothermal method, adding soluble aluminum salt, spraying to coat aluminum, and calcining at high temperature in an oxygen-deficient nitrogen atmosphere to obtain high-crystallinity lithium ferrite. The invention avoids the agglomeration of the lithium salt remained in the calcination process after melting and cooling, and simultaneously, a small amount of residual alkali reacts with the coated aluminum in the calcination process, thereby greatly reducing the existence of the residual alkali, greatly improving the stability of the product, contributing to a certain capacity, and having small primary particle size, large BET, high activity and high primary charging capacity of the obtained lithium ferrite.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and relates to a preparation method of a lithium supplementing agent, which can avoid melting and cooling agglomeration of residual lithium salt in the calcining process and reduce the existence of residual alkali so as to ensure that the product has high stability, small primary particle size, large BET (BET) and high activity and primary charging capacity.
Background
The first time negative electrode efficiency of lithium batteries is low, consuming lithium from the positive electrode, and generally improving the first time coulombic efficiency of the negative electrode by adding a lithium replenishing agent. The first effect loss of the silicon negative electrode is more serious, so the lithium supplementing agent discharge amount is generally similar to that of the silicon negative electrode, but the lithium supplementing agent can not be added into the graphite negative electrode, and BYD blade batteries are also adopted.
The lithium supplementing mode comprises negative electrode lithium supplementing and positive electrode lithium supplementing. The negative electrode generally adopts simple substance lithium, but because the process is complex, the flow is not well controlled, the danger is easy to occur, and the simple substance lithium is more expensive. The positive electrode is generally made of lithium-rich oxide (lithium nickelate/lithium ferrite), the capacity of the lithium nickelate is 450-500mAh/g, and the capacity of the lithium ferrite (Li 5FeO 4) is 750-800mAh/g.
In 2020, the price of lithium nickelate is 22 ten thousand yuan/ton, and in 21, 41 ten thousand yuan/ton, and the price of nickel and lithium is greatly improved. Lithium ferrite has low price, and the main iron metal has low price. The addition amount of lithium nickelate is 3-4%, the energy density is improved by 1-3%, the addition amount of lithium ferrite is 1-2%, and the energy density is improved by 4-6%. The advantages of lithium ferrite are very pronounced.
However, the conventional calcination process has a great problem of melting and agglomerating materials. The lithium is melted under the condition that a large amount of lithium exists and lithium ferrite is not completely generated, the melted lithium is connected together after being cooled at the back, so that the purity of the lithium ferrite is influenced, the lithium ferrite is sintered into a block, the later use is influenced, and meanwhile, most of containers made of materials including silicon oxides, aluminum oxides and the like are corroded due to the fact that the lithium is strong alkali salt, and the caking materials cannot be buckled from the containers.
For example, patent 202010903556.7 proposes to prepare lithium ferrite by an aqueous solution method, namely, to use water-soluble ferric salt and lithium salt, and to obtain lithium ferrite by drying and calcining, wherein nitrate is the main component, but the process has the biggest problem that a large amount of waste gas containing nitrogen oxide compounds is generated, which causes great environmental protection treatment difficulty.
The 201810436559.7 patent discloses Mn-doped lithium ferrate, lithium supplementing anode material, preparation and application thereof, and relates to a preparation method of lithium ferrate.
The 201910328272.7 invention discloses a preparation method of nano lithium ferrite, which comprises the steps of preparing a ferrous solution and a lithium bicarbonate solution; adding a base solution into a reaction kettle, adding a ferrous solution, a lithium bicarbonate solution and an acid-base modifier pair into the reaction kettle, and reacting to obtain slurry; transferring the slurry into a high-pressure reaction kettle, stirring and reacting for 3-5 hours at 220-250 ℃ and 0.6-0.9 MPa, cooling and decompressing, taking out the material, and filtering and washing to obtain a precipitate; placing the precipitate into a roller kiln, calcining for 5-8h at 400-500 ℃, introducing air in the calcining process, maintaining the air flow rate in the calcining kiln to be 2-3m/S, cooling the calcined material, performing jet milling, classifying by a classifying wheel, and screening to remove iron to obtain nano lithium ferrite. The method has the advantages of simple process and low cost, and the obtained nano lithium ferrite has large specific surface area and uniform particle size distribution. However, in the process, because ferrous precipitate is added, amorphous lithium ferrite is obtained after lithium salt is added, and because iron in the lithium ferrite is in a divalent state and other materials are not coated on the surface, the problem of excessive residual alkali still exists; meanwhile, when ferrous iron is converted into ferric iron, a part of alkali may also leak out and melt mutually, and after cooling, the part of alkali still can be agglomerated; meanwhile, because the lithium iron ratio in the lithium ferrite is 5:1, a large amount of residual alkali exists and can react with water vapor and carbon dioxide in the air, so that lithium carbonate and lithium hydroxide are obtained, and the capacity of the lithium ferrite is attenuated.
Therefore, how to prevent the lithium supplement from melting and agglomerating due to the high lithium content and from capacity fading due to residual alkali on the surface of the lithium supplement becomes a key for preparing the high-performance lithium supplement.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a method for producing a lithium-supplementing agent which can prevent the residual lithium salt from being melted and agglomerated after cooling during calcination, and can reduce the residual alkali so as to improve the stability of the product, and which has a small primary particle size, a large BET, and a high activity and initial charge capacity.
The invention is realized by the following technical scheme:
the preparation method of the lithium supplementing agent comprises the steps of preparing amorphous doped lithium ferrite by a hydrothermal method, adding soluble aluminum salt, spraying to coat aluminum, and calcining at high temperature in an oxygen-deficient nitrogen atmosphere to obtain the lithium ferrite with high crystallinity.
The preparation method of the lithium supplementing agent comprises the steps of adding lithium permanganate, ferrous gluconate, ammonia water, lithium hydroxide and pure water into a high-pressure reaction kettle together according to a molar ratio of 1:3.5-4.5:1-1.5:23-26:200-400, and preparing amorphous doped lithium ferrite slurry by a hydrothermal method; adding soluble aluminum salt into the slurry, spray drying, calcining, crushing, screening and removing iron to obtain lithium ferrite.
The preparation method of the lithium supplementing agent comprises the following specific steps:
firstly, adding lithium permanganate, ferrous gluconate, ammonia water, lithium hydroxide and pure water into a high-pressure reaction kettle together according to the molar ratio of 1:3.5-4.5:1-1.5:23-26:200-400, heating to 180-230 ℃ under the stirring state, reacting for 12-20h under the condition of 1-2.8MPa, decompressing and cooling, and taking out the slurry to obtain amorphous doped lithium ferrite slurry;
secondly, adding soluble aluminum salt into the slurry, and then spray-drying to obtain a spray-dried material;
thirdly, placing the spray-dried material into a roller kiln for calcination, and calcining for 2-4 hours at 800-900 ℃;
and fourthly, crushing, screening and removing iron to obtain lithium ferrite.
The preparation method of the lithium supplementing agent comprises the following steps: in the first step, the stirring speed is 100-250r/min.
The preparation method of the lithium supplementing agent comprises the following steps: in the second step, the mole number of the added soluble aluminum salt is 1.1-1.5 times of the lithium content in the supernatant liquid in the slurry. The soluble aluminum salt is preferably aluminum acetate.
The preparation method of the lithium supplementing agent comprises the following steps: in the second step, the air inlet temperature of spray drying is 200-250 ℃, the discharging temperature is 90-100 ℃, and the spray particle size is 3-8 mu m.
The preparation method of the lithium supplementing agent comprises the following steps: in the third step, a stainless steel sagger is adopted for calcination, nitrogen is simultaneously introduced for protection, the introduced nitrogen enables the volume concentration of oxygen in the roller hearth furnace to be 1-5%, and the calcination is carried out for 2-5 hours at the temperature of 750-900 ℃.
The preparation method of the lithium supplementing agent comprises the following steps: in the fourth step, cooling to the material temperature of less than or equal to 150 ℃, discharging, conveying the material into a pulverizer through positive pressure of nitrogen with the humidity of 1-5%, and pulverizing the material into particles with the particle size of 1-2 mu m by adopting nitrogen with the humidity of 1-5% and the temperature of 100-150 ℃.
The preparation method of the lithium supplementing agent comprises the following steps: in the fourth step, screening, deironing and vacuum packaging are carried out in a constant temperature and constant humidity room with humidity less than or equal to 10% and temperature of 15-25 ℃.
The beneficial effects are that:
the invention provides a preparation process, which comprises the steps of preparing amorphous lithium ferrite, introducing an aluminum source for coating, and calcining at high temperature to obtain high-crystallinity lithium ferrite, wherein the lithium ferrite is obtained before calcining, so that the agglomeration of the lithium salt remained in the calcining process after melting and cooling is avoided, and meanwhile, a small amount of residual alkali reacts with the coated aluminum in the calcining process, so that the existence of the residual alkali is greatly reduced, the stability of the product is greatly improved, a certain capacity is contributed, and meanwhile, the obtained lithium ferrite has small primary particle size, large BET (lithium ion battery) activity and high first charging capacity.
1) The process of hydrothermal method-spray coating-calcination solidification is adopted, the doped lithium ferrite with low crystallinity can be formed by the hydrothermal method, then aluminum coating is carried out by spraying, and then calcination is carried out, thus forming a complete coating layer (lithium aluminate), and simultaneously improving the crystallinity of the doped lithium ferrite, reducing the BET and improving the capacity of the doped lithium ferrite
2) Compared with the traditional solid-phase calcination, the invention needs lithium oxide to prevent caking, can use conventional lithium hydroxide salt, greatly reduces the cost, and greatly reduces the calcination time in the calcination process.
3) After the hydrothermal reaction, the soluble aluminum salt is added, and then spraying and calcining are carried out, so that aluminum coating is realized, the residual alkali of the doped lithium ferrite can be reduced, the capacity of the doped lithium ferrite can be increased, and the performance of the doped lithium ferrite can be improved.
4) The invention adopts oxygen-deficient nitrogen gas during calcination, can effectively eliminate anions on ferric salt, simultaneously greatly reduces the calcination temperature and calcination time in the calcination stage, avoids the influence of too coarse particles on capacity, and greatly improves the crystallinity of materials after calcination.
Drawings
FIG. 1 is a charge-discharge curve of a battery prepared with the lithium-compensating agent prepared in example 1 of the present invention;
fig. 2 is an SEM image of a battery prepared with the lithium-compensating agent prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of a battery prepared with the lithium supplement prepared in example 1 of the present invention;
fig. 4 is a charge-discharge curve of a battery prepared with the lithium supplement agent prepared in example 2 of the present invention.
Detailed Description
The preparation method of the lithium supplementing agent comprises the steps of preparing amorphous doped lithium ferrite by adopting a hydrothermal method, adding soluble aluminum salt, spraying to coat aluminum, and calcining at high temperature in an oxygen-deficient nitrogen atmosphere to obtain the lithium ferrite with high crystallinity. Further, the method comprises the steps of adding lithium permanganate, ferrous gluconate, ammonia water, lithium hydroxide and pure water together in proportion, putting the mixture into a high-pressure reaction kettle, and preparing amorphous doped lithium ferrite slurry by adopting a hydrothermal method; adding soluble aluminum salt into the slurry, spray drying
The preparation method of the lithium supplementing agent comprises the following specific steps:
1) Adding lithium permanganate, ferrous gluconate, ammonia water, lithium hydroxide and pure water into a high-pressure reaction kettle together according to the molar ratio of 1:3.5-4.5:1-1.5:23-26:200-400, heating to 180-230 ℃ under the stirring state, reacting for 12-20h under the condition, decompressing and cooling, and taking out the slurry to obtain amorphous doped lithium ferrite slurry;
2) Adding soluble aluminum salt into the slurry, and then spray-drying to obtain a spray-dried material;
3) Calcining the spray-dried material in a roller kiln at 750-900 ℃ for 2-5h;
4) Cooling to material temperature less than or equal to 150deg.C, discharging, conveying to pulverizer by nitrogen positive pressure with humidity of 1-5%, pulverizing with nitrogen with humidity of 1-5% at 100-150deg.C, and pulverizing to particle size of 1-2 μm. And then screening, removing iron and vacuum packaging in a constant temperature and humidity room to obtain lithium ferrite.
In the step 1), the stirring speed is 100-250r/min.
In the step 2), the soluble aluminum salt is preferably aluminum acetate, and the mole number of the added aluminum acetate is 1.1-1.5 times of the lithium content in the supernatant liquid in the slurry;
the air inlet temperature of spray drying is 200-250 ℃, the discharging temperature is 90-100 ℃, and the spray particle diameter is 3-8 mu m.
The humidity of the constant temperature and humidity room is less than or equal to 10 percent, and the temperature is 15-25 ℃.
Example 1
Adding lithium permanganate, ferrous gluconate, ammonia water, lithium hydroxide and pure water together according to the molar ratio of 1:4:1.2:25.5:300 into a high-pressure reaction kettle, heating to 200 ℃ under the stirring condition of the stirring speed of 180r/min, reacting for 18 hours under the condition, decompressing and cooling, taking out the slurry, adding aluminum acetate into the supernatant of the slurry in a molar number which is 1.3 times that of lithium, and spray-drying under the conditions that the air inlet temperature is 230 ℃, the discharging temperature is 95 ℃ and the spray particle size is 5.7 mu m to obtain a spray-dried material;
calcining the spray-dried material in a roller way furnace by adopting a stainless steel sagger, simultaneously introducing nitrogen for protection, introducing nitrogen to enable the oxygen volume concentration in the roller way furnace to be 3%, calcining for 5 hours at the temperature of 750 ℃, cooling to 125 ℃, discharging, conveying the material into a pulverizer by positive pressure of nitrogen with the humidity of 3.2%, pulverizing by adopting nitrogen with the humidity of 3.2% at 140 ℃, wherein the dew point of the nitrogen is-30 ℃, pulverizing to the grain size of 1.5 mu m, sieving and deironing in a constant temperature and constant humidity room with the humidity of 8% at 20.7 ℃, and vacuum packaging to obtain lithium ferrite.
The final product test data are shown in Table 1:
table 1 test data for lithium supplement prepared in example 1
| Index (I) | Li | Fe | Mn |
| Data | 23.1% | 27.8% | 7.1% |
| Li/(Fe+Mn) | Al | C | D10 |
| 5.29 | 1.89% | 0.75% | 0.3μm |
| D50 | D90 | 0.1C first charge capacity | 0.1C first discharge capacity |
| 1.5μm | 10.7μm | 723.9mAh/g | 0.9mAh/g |
| BET | Density of compaction | Tap density | Residual alkali (calculated as LiOH) |
| 4.7m2/g | 3.1g/mL | 1.4g/mL | 0.41% |
| Mg | Na | Ni | Cr |
| 57.4ppm | 75.9ppm | 10.5ppm | 4.6ppm |
| Zn | Cu | Ca | KF moisture |
| 25.4ppm | 0.2ppm | 67.9ppm | 235ppm |
Adding lithium ferrite, SP and PVDF into NMP according to the mass ratio of 80:12:8, uniformly coating on an aluminum foil, using a lithium sheet as a negative electrode, assembling to form a buckling electricity, wherein the whole assembling process needs to be assembled in an environment with humidity below 10%, the voltage range during measurement is 2.5-4.3V, the current is 0.05C, the measurement charge-discharge curve is shown in figure 1, the SEM of the product is shown in figure 2, and the XRD of the product is shown in figure 3.
Example 2
Adding lithium permanganate, ferrous gluconate, ammonia water, lithium hydroxide and pure water together in a molar ratio of 1:4.5:1.5:26:400 into a high-pressure reaction kettle, heating to 230 ℃ under the stirring state at the speed of 250r/min, reacting for 18 hours under the condition, decompressing and cooling, taking out the slurry, adding aluminum acetate with the molar number being 1.5 times of the lithium content in the supernatant liquid in the slurry, and spray-drying under the condition that the air inlet temperature is 250 ℃, the discharging temperature is 90 ℃ and the spray particle size is 8 mu m to obtain a spray-dried material;
calcining the spray-dried material in a roller way furnace, introducing nitrogen to enable the volume concentration of oxygen in the roller way furnace to be 5%, calcining for 3 hours at the temperature of 830 ℃, cooling to the material temperature of 120 ℃, discharging, conveying the material into a pulverizer by positive pressure of nitrogen with the humidity of 3%, pulverizing by adopting nitrogen with the humidity of 1% at 150 ℃, pulverizing to the particle size of 1.9 mu m at the dew point of-40 ℃, sieving to remove iron in a constant temperature and humidity room with the humidity of 5% and the temperature of 25 ℃, and vacuum packaging to obtain lithium ferrite.
The final product test data are shown in Table 2:
table 2 lithium supplement test data prepared in example 2
| Index (I) | Li | Fe | Mn |
| Data | 23.7% | 29.4% | 5.2% |
| Li/(Fe+Mn) | Al | C | D10 |
| 5.49 | 2.15% | 0.57% | 0.3μm |
| D50 | D90 | 0.1C first charge capacity | 0.1C first discharge capacity |
| 1.9μm | 12.1μm | 720.4mAh/g | 1.3 mAh/g |
| BET | Density of compaction | Tap density | Residual alkali (calculated as LiOH) |
| 4.1m2/g | 3.5g/mL | 1.5g/mL | 0.38% |
| Mg | Na | Ni | Cr |
| 52.4ppm | 79.8ppm | 7.5ppm | 4.1ppm |
| Zn | Cu | Ca | KF moisture |
| 30.4ppm | 0.2ppm | 87.5ppm | 201ppm |
Adding lithium ferrite, SP and PVDF into NMP according to the mass ratio of 80:12:8, uniformly coating on an aluminum foil, using a lithium sheet as a negative electrode, and assembling to form a buckling electricity, wherein the whole assembling process needs to be assembled in an environment with humidity of less than 10%, the voltage range during measurement is 2.5-4.3V, and the current is 0.05C. The charge-discharge curve was measured as shown in fig. 4.
Example 3
Adding lithium permanganate, ferrous gluconate, ammonia water, lithium hydroxide and pure water together according to the molar ratio of 1:3.5:1:24:350 into a high-pressure reaction kettle, heating to 180 ℃ under the stirring condition of the stirring speed of 200r/min, reacting for 20 hours under the condition, decompressing and cooling, taking out the slurry, adding aluminum acetate into the slurry according to the molar ratio of 1.2 times of the lithium content in the supernatant, and spray-drying under the condition that the air inlet temperature is 210 ℃, the discharging temperature is 100 ℃ and the spray particle size is 4 mu m to obtain a spray-dried material;
calcining the spray-dried material in a roller way furnace by adopting a stainless steel sagger, simultaneously introducing nitrogen for protection, introducing nitrogen to enable the oxygen volume concentration in the roller way furnace to be 2%, calcining for 4 hours at the temperature of 850 ℃, cooling to the material temperature of 135 ℃, discharging, conveying the material to a pulverizer by positive pressure of nitrogen with the humidity of 5%, pulverizing by adopting nitrogen with the humidity of 2% at the temperature of 120 ℃, pulverizing to the dew point of-20 ℃ to the grain diameter of 2 mu m, sieving and removing iron in a constant temperature and constant humidity room with the humidity of 9% at the temperature of 17 ℃, and vacuum packaging to obtain lithium ferrite.
The final product test data are shown in Table 3:
TABLE 3 lithium supplement detection data prepared in example 3
| Index (I) | Li | Fe | Mn |
| Data | 24.9% | 24.8% | 7.5% |
| Li/(Fe+Mn) | Al | C | D10 |
| 6.186 | 1.97% | 0.65% | 0.4μm |
| D50 | D90 | 0.1C first charge capacity | 0.1C first discharge capacity |
| 2.0μm | 14.7μm | 727.9mAh/g | 1.1 mAh/g |
| BET | Density of compaction | Tap density | Residual alkali (calculated as LiOH) |
| 5.7m2/g | 3.1g/mL | 1.6g/mL | 0.44% |
| Mg | Na | Ni | Cr |
| 51.8ppm | 80.8ppm | 7.1ppm | 4.4ppm |
| Zn | Cu | Ca | KF moisture |
| 37.9ppm | 0.1ppm | 80.9ppm | 276ppm |
Example 4
Adding lithium permanganate, ferrous gluconate, ammonia water, lithium hydroxide and pure water together according to the molar ratio of 1:3.8:1.4:23:200 into a high-pressure reaction kettle, heating to 210 ℃ under the stirring condition of the stirring speed of 100r/min, reacting for 15 hours under the condition, decompressing and cooling, taking out the slurry, adding aluminum acetate into the slurry according to the molar ratio of 1.1 times of the lithium content in the supernatant, and spray-drying under the condition that the air inlet temperature is 200 ℃, the discharge temperature is 93 ℃ and the spray particle size is 7 mu m to obtain a spray-dried material;
calcining the spray-dried material in a roller way furnace by adopting a stainless steel sagger, simultaneously introducing nitrogen for protection, introducing nitrogen to enable the volume concentration of oxygen in the roller way furnace to be 1%, calcining for 2 hours at the temperature of 900 ℃, cooling to 145 ℃, discharging, conveying the material into a pulverizer by positive pressure of nitrogen with the humidity of 2%, pulverizing by adopting nitrogen with the humidity of 4% at the temperature of 100 ℃, pulverizing to obtain the particle size of 1 mu m at the dew point of-28 ℃, sieving, removing iron and vacuum packaging in a constant temperature and humidity room with the humidity of 7% at the temperature of 15 ℃, and obtaining lithium ferrite.
The final product test data are shown in Table 4:
TABLE 4 lithium supplement test data prepared in example 4
| Index (I) | Li | Fe | Mn |
| Data | 21.9% | 26.9% | 5.9% |
| Li/(Fe+Mn) | Al | C | D10 |
| 5.32 | 1.96% | 0.51% | 0.2μm |
| D50 | D90 | 0.1C first charge capacity | 0.1C first discharge capacity |
| 1.0μm | 10.5μm | 716.8mAh/g | 1.1 mAh/g |
| BET | Density of compaction | Tap density | Residual alkali (calculated as LiOH) |
| 3.89m2/g | 3.4g/mL | 1.6g/mL | 0.39% |
| Mg | Na | Ni | Cr |
| 50.8ppm | 73.8ppm | 9.9ppm | 2.8ppm |
| Zn | Cu | Ca | KF moisture |
| 10.4ppm | 0.1ppm | 67.5ppm | 198ppm |
Example 5
Adding lithium permanganate, ferrous gluconate, ammonia water, lithium hydroxide and pure water together according to the molar ratio of 1:4.2:1.3:25:260 into a high-pressure reaction kettle, heating to 190 ℃ under the stirring condition of the stirring speed of 150r/min, reacting for 12 hours under the condition, decompressing and cooling, taking out the slurry, adding aluminum acetate into the supernatant of the slurry in a molar number which is 1.4 times that of lithium, and spray-drying under the condition that the air inlet temperature is 250 ℃, the discharging temperature is 98 ℃ and the spray particle size is 3 mu m to obtain a spray-dried material;
calcining the spray-dried material in a roller way furnace by adopting a stainless steel sagger, simultaneously introducing nitrogen for protection, introducing nitrogen to enable the volume concentration of oxygen in the roller way furnace to be 4%, calcining for 3 hours at the temperature of 800 ℃, cooling to the material temperature of 150 ℃, discharging, conveying the material into a pulverizer by adopting positive pressure of nitrogen with the humidity of 1%, pulverizing by adopting nitrogen with the humidity of 5% at the temperature of 125 ℃, pulverizing to the dew point of-35 ℃ to the grain size of 1.7 mu m, sieving and removing iron in a constant temperature and constant humidity room with the humidity of 10% at the temperature of 22 ℃, and vacuum packaging to obtain lithium ferrite.
The final product test data are shown in Table 5:
TABLE 5 lithium supplement test data prepared in example 5
| Index (I) | Li | Fe | Mn |
| Data | 22.1% | 25.9% | 6.9% |
| Li/(Fe+Mn) | Al | C | D10 |
| 5.41 | 2.57% | 0.51% | 0.3μm |
| D50 | D90 | 0.1C first charge capacity | 0.1C first discharge capacity |
| 1.7μm | 15.8μm | 724.8mAh/g | 1.2mAh/g |
| BET | Density of compaction | Tap density | Residual alkali (calculated as LiOH) |
| 5.3m2/g | 3.1g/mL | 1.4g/mL | 0.29% |
| Mg | Na | Ni | Cr |
| 52.1ppm | 72.7ppm | 7.1ppm | 4.5ppm |
| Zn | Cu | Ca | KF moisture |
| 31.7ppm | 0.1ppm | 82.8ppm | 197ppm |
Claims (7)
1. The preparation method of the lithium supplementing agent comprises the following specific steps:
firstly, adding lithium permanganate, ferrous gluconate, ammonia water, lithium hydroxide and pure water into a high-pressure reaction kettle together according to the molar ratio of 1:3.5-4.5:1-1.5:23-26:200-400, heating to 180-230 ℃ under the stirring state, reacting for 12-20h under the condition of 1-2.8MPa, decompressing and cooling, and taking out the slurry to obtain amorphous doped lithium ferrite slurry;
secondly, adding soluble aluminum salt into the slurry, and then spray-drying to obtain a spray-dried material, wherein the mole number of the added soluble aluminum salt is 1.1-1.5 times of the lithium content in the supernatant of the slurry;
thirdly, placing the spray drying material into a roller kiln for calcination, wherein the calcination is performed by adopting a stainless steel sagger, and simultaneously, introducing nitrogen for protection, wherein the introduced nitrogen ensures that the oxygen volume concentration in the roller kiln is 1-5%, and the calcination is performed for 2-5 hours at the temperature of 750-900 ℃;
and fourthly, crushing, screening and removing iron to obtain lithium ferrite.
2. The method for preparing the lithium supplementing agent according to claim 1, wherein: in the first step, the stirring speed is 100-250r/min.
3. The method for preparing the lithium supplementing agent according to claim 1, wherein: the soluble aluminum salt is aluminum acetate.
4. The method for preparing the lithium supplementing agent according to claim 1, wherein: in the second step, the air inlet temperature of spray drying is 200-250 ℃, the discharging temperature is 90-100 ℃, and the spray particle size is 3-8 mu m.
5. The method for preparing the lithium supplementing agent according to claim 1, wherein: in the third step, calcining is carried out for 2-4 hours at the temperature of 800-900 ℃.
6. The method for preparing the lithium supplementing agent according to claim 1, wherein: in the fourth step, cooling to the material temperature of less than or equal to 150 ℃, discharging, conveying the material into a pulverizer through positive pressure of nitrogen with the humidity of 1-5%, and pulverizing the material into particles with the particle size of 1-2 mu m by adopting nitrogen with the humidity of 1-5% and the temperature of 100-150 ℃.
7. The method for preparing the lithium supplementing agent according to claim 1, wherein: in the fourth step, screening, removing iron and vacuum packaging are carried out in a constant temperature and humidity room with humidity less than or equal to 10% and temperature of 15-25 ℃ to obtain lithium ferrite.
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| JP2013212959A (en) * | 2012-04-03 | 2013-10-17 | National Institute Of Advanced Industrial Science & Technology | Lithium manganese-based composite oxide and method for producing the same |
| CN111533184A (en) * | 2020-05-11 | 2020-08-14 | 蒋达金 | Preparation method of phosphorus-doped lithium nickel cobalt ferrite |
| CN114709391A (en) * | 2022-04-01 | 2022-07-05 | 湖北亿纬动力有限公司 | Positive electrode lithium supplement material, preparation method thereof and lithium ion battery |
| CN115249792A (en) * | 2022-07-11 | 2022-10-28 | 浙江锂威能源科技有限公司 | Positive electrode lithium supplement material, preparation method thereof, positive plate and secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013212959A (en) * | 2012-04-03 | 2013-10-17 | National Institute Of Advanced Industrial Science & Technology | Lithium manganese-based composite oxide and method for producing the same |
| CN111533184A (en) * | 2020-05-11 | 2020-08-14 | 蒋达金 | Preparation method of phosphorus-doped lithium nickel cobalt ferrite |
| CN114709391A (en) * | 2022-04-01 | 2022-07-05 | 湖北亿纬动力有限公司 | Positive electrode lithium supplement material, preparation method thereof and lithium ion battery |
| CN115249792A (en) * | 2022-07-11 | 2022-10-28 | 浙江锂威能源科技有限公司 | Positive electrode lithium supplement material, preparation method thereof, positive plate and secondary battery |
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