CN112758893A - Spray pyrolysis preparation method and device of ternary cathode material - Google Patents
Spray pyrolysis preparation method and device of ternary cathode material Download PDFInfo
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- CN112758893A CN112758893A CN201911000212.9A CN201911000212A CN112758893A CN 112758893 A CN112758893 A CN 112758893A CN 201911000212 A CN201911000212 A CN 201911000212A CN 112758893 A CN112758893 A CN 112758893A
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- spray pyrolysis
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- chloride
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- 238000005118 spray pyrolysis Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000010406 cathode material Substances 0.000 title claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000003860 storage Methods 0.000 claims abstract description 48
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 239000006227 byproduct Substances 0.000 claims abstract description 22
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 15
- 238000004064 recycling Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229940099607 manganese chloride Drugs 0.000 claims description 7
- 235000002867 manganese chloride Nutrition 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 40
- 239000007789 gas Substances 0.000 abstract description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 150000003841 chloride salts Chemical class 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000007774 positive electrode material Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 38
- 238000005282 brightening Methods 0.000 description 29
- 239000000243 solution Substances 0.000 description 20
- 239000008399 tap water Substances 0.000 description 12
- 235000020679 tap water Nutrition 0.000 description 12
- 230000007246 mechanism Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000002737 fuel gas Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000035622 drinking Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000004851 dishwashing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 241000190070 Sarracenia purpurea Species 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 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
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
- C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种三元正极材料的喷雾热解制备方法及装置，本发明仅通过喷雾热解法就制备出了三元正极材料，反应流程简单，反应过程不需要酸或碱的消耗且没有废渣、废水的排放，经济效益显著，有利于工业大规模生产；本发明选用金属的氯化物盐作为原料，副产仅有氯化氢气体和水蒸气，冷凝后作为盐酸回收再利用，整个生产过程实现了物料的循环利用，经济环保；本发明使用钛合金材料制备盐酸储罐，解决了盐酸回收过程因腐蚀而导致的品质差的问题。
The invention discloses a spray pyrolysis preparation method and device for a ternary positive electrode material. The invention only prepares a ternary positive electrode material through the spray pyrolysis method, the reaction process is simple, and the reaction process does not require the consumption of acid or alkali and There is no discharge of waste residue and waste water, the economic benefit is remarkable, and it is beneficial to industrial large-scale production; the present invention selects metal chloride salts as raw materials, and the by-products only have hydrogen chloride gas and water vapor, which are recovered and reused as hydrochloric acid after condensation, and the whole production process The recycling of materials is realized, which is economical and environmentally friendly; the invention uses titanium alloy materials to prepare the hydrochloric acid storage tank, and solves the problem of poor quality caused by corrosion in the hydrochloric acid recovery process.
Description
Technical Field
The invention belongs to the technical field of lithium battery materials, and particularly relates to a spray pyrolysis preparation method and device of a ternary cathode material.
Background
Compared with a liquid-phase precipitation method for preparing the precursor of the ternary cathode material, the spray pyrolysis method has the advantages of short flow, strong adaptability to raw materials, simple working procedures, high productivity, high production efficiency and the like, and is favorable for industrial production; the product has the advantages of spherical shape, controllable particle size, uniform distribution, large specific surface area, uniform product components and the like. The spray pyrolysis method is widely used for preparing lithium ion battery cathode materials with different crystal forms. At present, the research on the preparation of the lithium ion anode material by adopting metal chloride as a raw material through spray pyrolysis is less, because the decomposition temperature of the chloride is higher than that of nitrate, and hydrogen chloride in tail gas corrodes equipment. And at present, there is no report of preparing the ternary cathode material only by a spray pyrolysis method, because the physical and chemical properties such as solubility, supersaturation, melting point, thermal decomposition temperature and the like of different salts are greatly different, when the mixed metal salt is directly subjected to spray pyrolysis, atomized liquid drops affect the morphology, granularity and surface structure of the formed solid oxide particles due to different mechanisms for forming the solid oxide particles, thereby affecting the electrochemical performance of the finally formed ternary cathode material.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a sink bowl washer with a dish brightening agent feeding mechanism, which solves the problems that the dish brightening agent of the existing sink bowl washer is directly added into the sink of the bowl washer, the operation process is troublesome, and the dish brightening agent and water are not uniformly mixed, so that the washing is not thorough.
In order to achieve the purpose, the technical scheme of the invention is realized as follows: the utility model provides a basin dish washer with bright dish agent input mechanism, includes bright dish agent input mechanism, bowl washing groove, first water pipe, second water pipe, bright dish agent input mechanism sets firmly the back in bowl washing groove, bright dish agent input mechanism communicates with water source and bowl washing groove respectively through first water pipe and second water pipe.
Preferably, the brightening agent feeding mechanism comprises a brightening agent storage box, a brightening agent storage cover and an electromagnetic valve, wherein the brightening agent storage box and the brightening agent storage cover are hermetically connected to form a brightening agent storage chamber and a tap water flowing chamber, and the tap water flowing chamber is positioned below the brightening agent storage chamber; the electromagnetic valve is arranged between the brightening agent storage chamber and the tap water flowing chamber and is used for controlling the brightening agent in the brightening agent storage chamber to flow out.
Preferably, the bottom of the brightening saucer agent storage chamber is provided with a brightening saucer agent outlet, and the brightening saucer agent outlet is communicated with the tap water flowing chamber.
Preferably, the top of bright dish agent locker room is provided with bright dish agent and adds the mouth, the bowl washing groove on with bright dish agent adds the mouth corresponding position department be provided with bright dish agent adds the mouth matched with through-hole.
Preferably, the bottom of the tap water flowing chamber is provided with a tap water inlet and a brightening agent solution outlet, the tap water inlet is connected with the first water pipe, and the brightening agent solution outlet is connected with the second water pipe.
Preferably, the tap water inlet is provided with a water inlet joint extending into the tap water flowing chamber, and the height of the top of the water inlet joint extending into the tap water flowing chamber is higher than the height of the bottom of the tap water flowing chamber.
Preferably, a brightening saucer agent solution outflow joint is arranged at the brightening saucer agent solution outflow opening, and the height of the top of the brightening saucer agent solution outflow joint is equal to the height of the bottom of the tap water flowing chamber.
Preferably, the dish brightening agent feeding mechanism further comprises a floater, and the floater is arranged in the dish brightening agent storage chamber and used for prompting whether dish brightening agent needs to be added into the dish brightening agent storage chamber again.
Preferably, the sink dish-washing machine further comprises a third water pipe and a dish-washing machine drain valve, wherein one end of the third water pipe is connected with the water softener, and the other end of the third water pipe is connected with a water source; the dishwasher drain valve is arranged at the bottom of the dishwasher and communicated with the dishwasher; a water inlet valve of a dish washing machine is arranged on the third water pipe.
Preferably, this basin dish washer still includes drinking cup, water softener, drinking cup and water softener all set firmly the bottom in bowl washing groove, bright dish agent input mechanism is through first water pipe, second water pipe respectively with water softener and drinking cup intercommunication, drinking cup and bowl washing groove intercommunication.
Preferably, the water-saving device further comprises a control unit, and the electromagnetic valve, the drain valve and the water inlet valve are electrically connected with the control unit.
Compared with the prior art, the dish brightening agent feeding mechanism, the water cup and the water softener are arranged on the bowl washing tank, so that the process of manually feeding the dish brightening agent into the bowl washing tank is avoided, the manpower is effectively reduced, the operation steps are simplified, the dish brightening agent and the water are uniformly mixed firstly, and then the mixed liquid of the dish brightening agent and the water is fed into the bowl washing tank through the water cup, so that the tableware is washed cleanly and brightly without traces.
The invention aims to provide a method and a device for preparing a ternary cathode material by using mixed metal chloride salt as a raw material through spray pyrolysis.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a spray pyrolysis preparation method of a ternary cathode material comprises the following steps:
respectively preparing aqueous solutions of lithium chloride, nickel chloride, cobalt chloride and manganese chloride with certain concentrations;
mixing the chloride aqueous solutions of the metal salts according to a certain stoichiometric ratio to obtain a mixed solution;
carrying out spray pyrolysis on the mixed solution in a spray pyrolysis furnace to obtain a ternary cathode material;
condensing the by-products in the spray pyrolysis furnace, and recycling.
Preferably, the total metal ion concentration of the mixed solution is 0.5-5.0M, wherein the metal ion concentration ratio satisfies the following condition: (nickel + cobalt + manganese) ═ 1.0 to 1.1: 1.
preferably, the concentration ratio of nickel, cobalt and manganese is 6: 2: 2 or 5: 2: 3 or 8: 1: 1.
preferably, the mixed solution is mixed under stirring at 40 ℃ to 80 ℃.
Preferably, the temperature of the spray pyrolysis furnace is 800-1100 ℃, and the reaction is carried out in an oxygen-rich atmosphere. The ratio of oxygen to fuel gas is 1: 1-3, and the oxygen flow is as follows: 1 to 10m3/h。
Preferably, the recovery of the by-product is recovered in a titanium alloy storage tank.
The invention also provides a spray pyrolysis preparation device of the ternary cathode material, which comprises the following components: the device comprises a plurality of raw material liquid storage tanks, a plurality of high-precision flow meters, a mixing tank with a stirring device, a delivery pump, a spray pyrolysis furnace, an aggregate hopper and a hydrochloric acid storage tank; the high-precision flow meter is used for controlling the feeding amount of the raw material liquid storage tank to the mixing tank, the aggregate bin is used for collecting prepared ternary cathode materials, and the hydrochloric acid storage tank is used for recovering byproducts.
Preferably, a heating device is arranged outside the mixing tank, and the temperature in the mixing tank is 40-80 ℃.
Preferably, the hydrochloric acid storage tank is made of a titanium alloy material.
Preferably, a condenser is further arranged in the hydrochloric acid storage tank.
Compared with the prior art, the invention has the following technical effects: the ternary cathode material is prepared only by a spray pyrolysis method, the reaction flow is simple, the consumption of acid or alkali is not needed in the reaction process, and no waste residue or waste water is discharged, so that the economic benefit is remarkable, and the industrial large-scale production is facilitated; according to the invention, metal chloride salt is selected as a raw material, only hydrogen chloride gas and water vapor are obtained as byproducts, and the byproduct is condensed and then recycled as hydrochloric acid, so that the whole production process realizes the recycling of materials, and is economic and environment-friendly.
The spray pyrolysis preparation device for the ternary cathode material is additionally provided with the heating device outside the raw material mixing tank, so that spray pyrolysis raw material liquid can enter the spray pyrolysis furnace at a higher feeding concentration, the quality of the product is ensured, and the energy consumption is reduced; meanwhile, the titanium alloy material is used for preparing the hydrochloric acid storage tank, so that the problem of poor quality caused by corrosion in the hydrochloric acid recovery process is solved.
Drawings
Fig. 1 is a schematic structural diagram of a spray pyrolysis preparation apparatus for a ternary cathode material provided in embodiment 4 of the present invention.
Fig. 2 is an SEM image of the ternary cathode material obtained in example 1 of the present invention.
FIG. 3 is a graph showing the cycle performance test results of the ternary cathode material of example 1 of the present invention as a battery material.
FIG. 4 is a graph showing the results of measuring the capacity performance of the ternary cathode material of example 1 of the present invention as a battery material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a spray pyrolysis preparation method of a ternary cathode material, which comprises the following steps:
step 1, respectively preparing aqueous solutions of lithium chloride, nickel chloride, cobalt chloride and manganese chloride with certain concentrations;
and 4, condensing the byproduct hydrogen chloride gas and water vapor in the spray pyrolysis furnace in the step 3, and recycling.
The ternary cathode material is prepared only by a spray pyrolysis method, the reaction process is simple, acid or alkali consumption is not needed in the reaction process, waste residues and waste water are not discharged, the economic benefit is obvious, and the industrial large-scale production is facilitated; according to the invention, metal chloride salt is selected as a raw material, only hydrogen chloride gas and water vapor are obtained as byproducts, and the byproduct is condensed and then recycled as hydrochloric acid, so that the whole production process realizes the recycling of materials, and is economic and environment-friendly.
In the invention, the concentration of the chloride solution of each metal salt in the mixing tank has a great influence on the prepared ternary cathode material, if the preparation concentration is too dilute, the production energy consumption is too large, and if the preparation concentration is too large, the quality of the ternary cathode material generated in the spray pyrolysis process can be influenced. Preferably, the total metal ion concentration of the aqueous solution of lithium chloride, nickel chloride, cobalt chloride and manganese chloride in the step 2 is 0.5-5.0M, wherein the metal ion concentration ratio satisfies the following condition: (nickel + cobalt + manganese) ═ 1.0 to 1.1: 1.
more preferably, the metal ion concentration in step 2 is nickel: cobalt: manganese 6: 2: 2 or 5: 2: 3 or 8: 1: 1.
in order to increase the solubility of each metal chloride salt in water and prepare a raw material solution having a high concentration, it is necessary to heat the mixed raw material solution in the mixing tank. Preferably, the mixing in the step 2 is carried out under stirring at 40 ℃ to 80 ℃.
The decomposition temperature of chloride salts is high, and a high furnace temperature needs to be maintained in order to effectively decompose chloride salts of each metal in the spray pyrolysis furnace. Meanwhile, the oxygen-rich atmosphere is beneficial to maintaining high electrochemical performance of the prepared ternary cathode material, but if the oxygen amount is too high, excessive heat can be taken away, so that the energy consumption of the whole production is high, and therefore, the control of the proper proportion of oxygen and fuel gas is crucial to the economy of the whole production process.
Further, the temperature of the spray pyrolysis furnace in the step 3 is 800-1100 ℃, and the reaction is carried out in an oxygen-rich atmosphere; the proportion of oxygen to fuel gas is: 1: 1-3, the oxygen flow is as follows: 1 to 10m 3/h.
Further, the by-product in the step 4 is recovered in a titanium alloy storage tank. The titanium alloy has good corrosion resistance, and the quality of the recovered hydrochloric acid can be improved by using the titanium alloy to prepare the hydrochloric acid storage tank, so that the titanium alloy can be subsequently recycled.
The following is a further description with reference to specific examples.
Example 1:
the embodiment provides a spray pyrolysis preparation method of a ternary cathode material, which comprises the following steps:
step 1, according to the molar ratio of metal ions to lithium: (nickel + cobalt + manganese) ═ 1.05: 1, nickel: cobalt: manganese 6: 2: 2, respectively preparing aqueous solutions of lithium chloride, nickel chloride, cobalt chloride and manganese chloride with certain concentrations with the total metal ion concentration of 5.0M, and respectively storing the aqueous solutions in each raw material solution storage tank;
and 3, conveying the chloride solution of each metal salt mixed in the mixing tank in the step 2 to a spray pyrolysis furnace by adopting a centrifugal pump for spray pyrolysis, controlling the furnace temperature at 1000 ℃, and enabling the volume ratio of oxygen to LNG fuel gas to be as follows in an oxygen-rich atmosphere: 1.5: 1, oxygen flow rate is 1m3Collecting the prepared ternary positive electrode material in a collecting hopper at the lower part of the spray pyrolysis furnace;
and 4, conveying the byproduct hydrogen chloride gas and the water vapor in the spray pyrolysis furnace in the step 3 to a hydrochloric acid storage tank for titanium alloy preparation for recycling, wherein a condenser is arranged at the upper part of the hydrochloric acid storage tank to cool the recovered byproduct.
1) Performing electron microscope Scanning (SEM) detection on the ternary cathode material prepared in the third step, wherein the detection result is shown in fig. 2: as can be seen from fig. 2: the positive electrode material obtained by the invention is spherical and is distributed more uniformly;
2) selecting the ternary cathode material prepared in the third step as a battery material and assembling the ternary cathode material into a battery, and detecting the cycle performance of the assembled battery, wherein the detection result is shown in figure 3:
as can be seen from fig. 3: the battery made of the anode material obtained by the invention has better cycle performance;
3) selecting the ternary cathode material prepared in the third step as a battery material and assembling the ternary cathode material into a battery, and detecting the capacity performance of the assembled battery, wherein the detection result is shown in fig. 4:
as can be seen from fig. 4: the battery made of the anode material obtained by the invention has high capacity.
Example 2:
the embodiment provides a spray pyrolysis preparation method of a ternary cathode material, which comprises the following steps:
step 1, according to the molar ratio of metal ions to lithium: (nickel + cobalt + manganese) ═ 1.08: 1, nickel: cobalt: 5 of manganese: 2: 3, respectively preparing aqueous solutions of lithium chloride, nickel chloride, cobalt chloride and manganese chloride with certain concentrations, wherein the total metal ion concentration is 3.0M, and respectively storing the aqueous solutions in each raw material solution storage tank;
and 3, conveying the chloride solution of each metal salt mixed in the mixing tank in the step 2 to a spray pyrolysis furnace by adopting a centrifugal pump for spray pyrolysis, controlling the furnace temperature at 950 ℃, and enabling the volume ratio of oxygen to LNG fuel gas to be as follows under the oxygen-enriched atmosphere: 2.0: 1, oxygen flow rate is 1m3Collecting the prepared ternary positive electrode material in a collecting hopper at the lower part of the spray pyrolysis furnace;
and 4, conveying the byproduct hydrogen chloride gas and the water vapor in the spray pyrolysis furnace in the step 3 to a hydrochloric acid storage tank for titanium alloy preparation for recycling, wherein a condenser is arranged at the upper part of the hydrochloric acid storage tank to cool the recovered byproduct.
Example 3:
the embodiment provides a spray pyrolysis preparation method of a ternary cathode material, which comprises the following steps:
step 1, according to the molar ratio of metal ions to lithium: (nickel + cobalt + manganese) ═ 1.02: 1, nickel: cobalt: manganese 8: 1:1, respectively preparing aqueous solutions of lithium chloride, nickel chloride, cobalt chloride and manganese chloride with certain concentrations with the total metal ion concentration of 1.0M, and respectively storing the aqueous solutions in various raw material solution storage tanks;
And 3, conveying the chloride solution of each metal salt mixed in the mixing tank in the step 2 to a spray pyrolysis furnace by adopting a centrifugal pump for spray pyrolysis, controlling the furnace temperature at 1100 ℃, and enabling the volume ratio of oxygen to LNG fuel gas to be as follows in an oxygen-rich atmosphere: 1.2: 1, collecting the prepared ternary cathode material in a collecting hopper at the lower part of a spray pyrolysis furnace, wherein the oxygen flow is 1m 3/h;
and 4, conveying the byproduct hydrogen chloride gas and the water vapor in the spray pyrolysis furnace in the step 3 to a hydrochloric acid storage tank for titanium alloy preparation for recycling, wherein a condenser is arranged at the upper part of the hydrochloric acid storage tank to cool the recovered byproduct.
Example 4:
the embodiment provides a preparation device of a ternary cathode material, which comprises a plurality of raw material liquid storage tanks 1, a plurality of high-precision flow meters 2, a mixing tank 3 with a stirring device, a delivery pump 4, a spray pyrolysis furnace 5, a collecting hopper 6 and a hydrochloric acid storage tank 7; the high-precision flowmeter 2 is used for controlling the feeding amount of the raw material liquid storage tank 1 to the mixing tank 3, the aggregate bin 6 is used for collecting prepared ternary anode materials, and the hydrochloric acid storage tank 7 is used for recovering byproducts.
Chloride salts of metals prepared in a raw material liquid storage tank 1 are conveyed into a mixing tank 3 through a high-precision flowmeter 2 according to a certain stoichiometric ratio, uniformly mixed under stirring, and then conveyed into a spray pyrolysis furnace 5 through a conveying pump 4, the prepared ternary anode material is collected in a collecting hopper 6, and by-products, namely hydrogen chloride gas and water vapor, enter a hydrochloric acid storage tank 7 for recycling.
The spray pyrolysis preparation device for the ternary cathode material is provided with a plurality of raw material liquid storage tanks 1 and a plurality of high-precision flow meters 2 which are connected in parallel, and different feeding types and feeding amounts can be respectively controlled according to requirements, so that materials with different types and performances can be prepared.
Furthermore, in order to improve the solubility of each metal chloride in water and ensure higher feeding concentration of the spray pyrolysis raw material liquid, a jacketed water bath heating device 31 is arranged outside the mixing tank 3, and the temperature in the mixing tank 3 is controlled to be 40-80 ℃.
Further, in order to ensure the quality of hydrochloric acid recovery and prevent the quality of hydrochloric acid from being degraded by corrosion, the hydrochloric acid storage tank 7 is made of an anticorrosive titanium alloy material.
Further, in order to rapidly lower the temperature of the by-product hydrogen chloride gas and water vapor, a condenser 71 is provided in the hydrochloric acid storage tank 7.
According to the spray pyrolysis preparation device for the ternary cathode material, the heating device 31 is additionally arranged outside the raw material mixing tank 3, so that spray pyrolysis raw material liquid can enter the spray pyrolysis furnace 5 at a high feeding concentration, the product quality is guaranteed, and the energy consumption is reduced; meanwhile, the titanium alloy material is used for preparing the hydrochloric acid storage tank 7, so that the problem of poor quality caused by corrosion in the hydrochloric acid recovery process is solved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A spray pyrolysis preparation method of a ternary cathode material is characterized by comprising the following steps: the method comprises the following steps:
respectively preparing aqueous solutions of lithium chloride, nickel chloride, cobalt chloride and manganese chloride with certain concentrations;
mixing the chloride aqueous solutions of the metal salts according to a certain stoichiometric ratio to obtain a mixed solution;
carrying out spray pyrolysis on the mixed solution in a spray pyrolysis furnace to obtain a ternary cathode material;
condensing the by-products in the spray pyrolysis furnace, and recycling.
2. The spray pyrolysis preparation method of a ternary cathode material according to claim 1, characterized in that: the total metal ion concentration of the mixed solution is 0.5-5.0M, wherein the metal ion concentration ratio satisfies the following conditions: (nickel + cobalt + manganese) ═ 1.0 to 1.1: 1.
3. the spray pyrolysis preparation method of a ternary cathode material according to claim 2, characterized in that: the concentration ratio of nickel to cobalt to manganese is 6: 2: 2 or 5: 2: 3 or 8: 1: 1.
4. the spray pyrolysis preparation method of a ternary cathode material according to claim 1, characterized in that: the mixed solution is stirred and mixed at the temperature of 40-80 ℃.
5. The spray pyrolysis preparation method of a ternary cathode material according to claim 1, characterized in that: the temperature of the spray pyrolysis furnace is 800-1100 ℃, and the reaction is carried out in an oxygen-rich atmosphere.
6. The spray pyrolysis preparation method of a ternary cathode material according to claim 1, characterized in that: and recovering the by-product in a titanium alloy storage tank.
7. The spray pyrolysis preparation device of the ternary cathode material is characterized by comprising the following components: the device comprises a plurality of raw material liquid storage tanks, a plurality of high-precision flow meters, a mixing tank with a stirring device, a delivery pump, a spray pyrolysis furnace, a collecting hopper and a hydrochloric acid storage tank; the high-precision flow meter is used for controlling the feeding amount of the raw material liquid storage tank to the mixing tank, the aggregate bin is used for collecting prepared ternary cathode materials, and the hydrochloric acid storage tank is used for recovering byproducts.
8. The apparatus according to claim 7, wherein a heating device is further provided outside the mixing tank, and the temperature in the mixing tank is 40 ℃ to 80 ℃.
9. The apparatus according to claim 7, wherein the hydrochloric acid storage tank is made of a titanium alloy material.
10. The apparatus for spray pyrolysis preparation of a ternary cathode material according to claim 7, wherein a condenser is further disposed in the hydrochloric acid storage tank.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115991505A (en) * | 2022-12-13 | 2023-04-21 | 材料科学姑苏实验室 | A modified ternary cathode material and its preparation method and application |
| CN116747757A (en) * | 2023-08-17 | 2023-09-15 | 新乡市弘力电源科技有限公司 | Pretreatment equipment for monocrystal high-nickel ternary material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101369651A (en) * | 2008-09-27 | 2009-02-18 | 浙江华友钴业股份有限公司 | Novel method for preparing lithium ion battery anode ternary material LiCoxNiyMn2O2 |
| CN105932269A (en) * | 2016-05-24 | 2016-09-07 | 浙江美达瑞新材料科技有限公司 | Method for preparing positive electrode material for lithium ion cell by spraying, combusting and pyrolyzing |
| CN106587172A (en) * | 2015-10-14 | 2017-04-26 | 金昌鑫盛源金属材料有限公司 | Production process and production device of power battery cathode ternary oxide |
| CN109539792A (en) * | 2018-11-27 | 2019-03-29 | 横店集团东磁股份有限公司 | A kind of spray pyrolysis unit preparing tertiary cathode presoma and its application method |
| CN109647310A (en) * | 2018-12-17 | 2019-04-19 | 横店集团东磁股份有限公司 | A method of the spray pyrolysis unit with microwave heating and ternary precursor is prepared with it |
-
2019
- 2019-10-21 CN CN201911000212.9A patent/CN112758893A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101369651A (en) * | 2008-09-27 | 2009-02-18 | 浙江华友钴业股份有限公司 | Novel method for preparing lithium ion battery anode ternary material LiCoxNiyMn2O2 |
| CN106587172A (en) * | 2015-10-14 | 2017-04-26 | 金昌鑫盛源金属材料有限公司 | Production process and production device of power battery cathode ternary oxide |
| CN105932269A (en) * | 2016-05-24 | 2016-09-07 | 浙江美达瑞新材料科技有限公司 | Method for preparing positive electrode material for lithium ion cell by spraying, combusting and pyrolyzing |
| CN109539792A (en) * | 2018-11-27 | 2019-03-29 | 横店集团东磁股份有限公司 | A kind of spray pyrolysis unit preparing tertiary cathode presoma and its application method |
| CN109647310A (en) * | 2018-12-17 | 2019-04-19 | 横店集团东磁股份有限公司 | A method of the spray pyrolysis unit with microwave heating and ternary precursor is prepared with it |
Non-Patent Citations (1)
| Title |
|---|
| 冯光华: "《绿色发展与绿色评估》", 30 June 2016, 中国金融出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115991505A (en) * | 2022-12-13 | 2023-04-21 | 材料科学姑苏实验室 | A modified ternary cathode material and its preparation method and application |
| CN116747757A (en) * | 2023-08-17 | 2023-09-15 | 新乡市弘力电源科技有限公司 | Pretreatment equipment for monocrystal high-nickel ternary material |
| CN116747757B (en) * | 2023-08-17 | 2023-11-14 | 新乡市弘力电源科技有限公司 | Pretreatment equipment for monocrystal high-nickel ternary material |
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