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CN116281926B - Magnetic core active material and preparation method and application thereof - Google Patents

Magnetic core active material and preparation method and application thereof Download PDF

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Publication number
CN116281926B
CN116281926B CN202310148725.4A CN202310148725A CN116281926B CN 116281926 B CN116281926 B CN 116281926B CN 202310148725 A CN202310148725 A CN 202310148725A CN 116281926 B CN116281926 B CN 116281926B
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lithium
active material
magnetic
magnetic core
core active
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CN116281926A (en
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李爱霞
谢英豪
余海军
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202310148725.4A priority Critical patent/CN116281926B/en
Priority to PCT/CN2023/083937 priority patent/WO2024174329A1/en
Priority to ARP230101533A priority patent/AR129624A1/en
Priority to CL2023001776A priority patent/CL2023001776A1/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
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    • C01G49/00—Compounds of iron
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    • C01G49/08—Ferroso-ferric oxide [Fe3O4]
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/42—Magnetic properties
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Abstract

The invention discloses a magnetic core active material, a preparation method and application thereof, and belongs to the technical field of materials. The product has the advantages that due to the composite design of the structure and the specificity of the formula raw materials, particles are uniformly dispersed after the preparation is finished, the product has excellent lithium extraction activity, and meanwhile, the product mainly contains magnetic substance components, so that the subsequent process implementation can be carried out through a process without binder introduction when the lithium extraction pole piece is prepared, and the lithium extraction efficiency of the obtained lithium extraction pole piece is effectively improved.

Description

Magnetic core active material and preparation method and application thereof
Technical Field
The invention relates to the technical field of materials, in particular to a magnetic core active material, and a preparation method and application thereof.
Background
Lithium metal is considered as "21 st century energy metal", and is widely applied to the fields of aerospace, glass, lithium batteries and the like, however, traditional lithium metal is prepared by lithium mining smelting, and the process condition is mature, but the energy consumption is high and the pollution is heavy. In recent years, the traditional lithium extraction method of lithium ores is gradually replaced by a method for extracting lithium from non-mineral lithium sources such as salt lake brine, low-cost brine, seawater and the like.
The specific implementation method for extracting lithium from brine comprises a precipitation method, a solvent extraction method, an adsorption method, a membrane separation method, an electrochemical method and the like, and the electrochemical method has more prospects due to the advantages of good selectivity, environmental friendliness and the like. In the electrochemical method, the performance of the lithium extraction electrode determines the effect of the whole lithium extraction process, however, when the lithium extraction electrode is prepared, the active substance is coated and fixed on the surface of the current collector by a polymer binder such as PVDF. However, since the binder covers the surface of the active material, the lithium extraction efficiency is inevitably reduced, and meanwhile, since the binder is mostly a hydrophobic material, the mass transfer effect is further reduced, and the lithium extraction effect falls into the bottleneck.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide the magnetic core active material, and the product has the advantages that due to the composite design of the structure and the specificity of the formula raw materials, particles are uniformly dispersed after the preparation is finished, the product has excellent lithium extraction activity, and meanwhile, the product mainly contains magnetic substance components, so that the subsequent process of preparing the lithium extraction pole piece can be implemented through a process without introducing a binder, and the lithium extraction efficiency of the obtained lithium extraction pole piece is effectively improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A magnetic core active material comprises a core and a carbon shell layer coated on the surface of the lithium iron phosphate core; the core comprises lithium iron phosphate and a magnetic iron compound, and the mass ratio of the lithium iron phosphate to the magnetic iron compound is (9:1) - (4:1).
Preferably, the magnetic iron compound is at least one of Fe 3O4、LiFe5O8.
More preferably, the preparation raw materials of the inner core comprise a magnetic iron source, a lithium source, a phosphorus source and a reducing agent, wherein the magnetic iron source is at least one of Fe 3O4、LiFe5O8, and the reducing agent is at least one of Fe powder and carbon powder.
More preferably, the magnetic iron source is Fe 3O4, and when the reducing agent is Fe powder, the molar ratio of Fe 3O4 to Fe powder is (1.2 to 1.5): 1, a step of;
The magnetic iron source is Fe 3O4, and when the reducing agent is carbon powder, the molar ratio of Fe 3O4 to the carbon powder is (2.4-3): 1, a step of;
When the magnetic iron source is LiFe 5O8 and the reducing agent is Fe powder, the molar ratio of LiFe 5O8 to Fe powder is (2.6-3.5): 5, a step of;
When the magnetic iron source is LiFe 5O8 and the reducing agent is carbon powder, the molar ratio of LiFe 5O8 to carbon powder is (4.8-5.9): 5.
In the magnetic core active material, a magnetic iron source is introduced into the core as a raw material during preparation, and the magnetic iron source is arranged in a specific proportion with a reducing agent, so that the reduction degree of the magnetic iron source is incomplete in the reduction process, and part of unreacted magnetic iron compounds still remain, and the part of substances can guide the whole magnetic core active material to regularly gather under the action of a magnetic field during preparation of a lithium extraction pole piece, and the gathering degree is controlled through the regulation and control of the magnetic field intensity, so that the lithium extraction efficiency and the mass transfer effect are improved under the condition that a binder is not introduced, and the tight connection among particles of the magnetic core active material can be ensured, and loose falling can not occur. Meanwhile, the introduction amount of the reducing agent is critical, if too much reducing agent is introduced, the magnetic acting force is too small to effectively and uniformly gather when the prepared magnetic core active material is prepared by the subsequent lithium extraction pole piece, and if too little reducing agent is introduced, the purity of lithium iron phosphate in the magnetic core active material is influenced, the activity of lithium extraction is weakened, meanwhile, when the lithium extraction pole piece is prepared, the gathering degree among particles is too high due to too strong magnetic force effect, the porosity is too small, and the lithium extraction efficiency is adversely affected, so that the proportion of the reducing agent and the magnetic iron source in the preparation raw materials needs to be regulated, and the mass ratio of the lithium iron phosphate to the magnetic iron compound in the core of the product is controlled within the range of (9:1) - (8:2).
Preferably, the lithium source is at least one of lithium carbonate, lithium hydroxide, lithium chloride, lithium phosphate and lithium sulfate.
Preferably, the phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid and ammonium phosphate.
More preferably, the molar ratio of the lithium element in the lithium source, the iron element in the magnetic iron source, the total iron element in the reduced iron powder and the phosphorus element in the phosphorus source is (1-2): (1-1.5): (1-1.5).
Another object of the present invention is to provide a method for preparing a magnetic core active material, comprising the steps of:
(1) Uniformly mixing the preparation raw materials of each inner core, and heating and preserving heat under a protective atmosphere to obtain the inner cores;
(2) Heating the core obtained in the step (1) in a mixed atmosphere of nitrogen and acetylene, performing vapor deposition treatment, and cooling to obtain the magnetic core active material.
According to the preparation method of the magnetic core active material, the surface of the core to be magnetized is coated with the carbon shell layer by the vapor deposition method, so that the stability of the core particles after the core particles are subsequently prepared into the lithium-extracted pole piece is higher, the higher porosity can be effectively reserved, the mass transfer effect of the lithium-extracted pole piece is excellent, and the thickness uniformity of the carbon shell layer obtained by vapor deposition is higher.
Preferably, the heating and heat-preserving treatment in the step (1) comprises a first-stage heating and heat-preserving treatment and a second-stage heating and heat-preserving treatment, wherein the temperature of the first-stage heating and heat-preserving treatment is 400-500 ℃ and the time is 3-5 h, and the temperature of the second-stage heating and heat-preserving treatment is 650-750 ℃ and the time is 5-10 h.
More preferably, the heating rate in the heating and heat-preserving treatment is 4-6 ℃/min.
More preferably, the protective atmosphere in the step (1) is at least one of nitrogen and argon, and the flow is 0.01-0.05L/min.
Preferably, the temperature in the vapor deposition treatment in the step (2) is 600-800 ℃ and the time is 0.5-2 h.
More preferably, the flow rate of the mixed atmosphere in the step (2) is 0.01-0.05L/min, and the volume ratio of nitrogen to acetylene in the mixed atmosphere is (1:1) - (1:5).
The invention also aims to provide a lithium-extracting pole piece which comprises a magnetic conductive current collector and the magnetic core active material.
The invention also aims to provide a preparation method of the lithium extraction pole piece, which comprises the following steps:
(1) Connecting a magnetically permeable current collector with an electromagnet and setting the magnetic field of the electromagnet to be 0.3-0.9T;
(2) And (3) adsorbing the magnetic core active material by using a magnetic conductivity current collector, and obtaining the lithium extraction pole piece after the magnetic core active material is completely adsorbed.
When the lithium extraction pole piece is prepared, because of the special magnetic activity of the magnetic core active material, the magnetic core active material can be adsorbed on a current collector by magnetic force combination under the condition that a conventional binder is not introduced, and naturally, secondary pore forming is not needed to be carried out on the active material by further introducing a pore-forming agent (the original pore of the active material after the binder is conventionally used can be filled by the binder, the porosity is low, and thus the pore forming is additionally needed to be carried out to avoid low mass transfer effect), the operation is convenient and quick, and if the lithium extraction pole piece is polluted or the lithium extraction degree is complete in working, the magnetic field can be directly eliminated to demagnetize the current collector, and the adsorbed magnetic core active material can completely fall off, so that the purification and the cleaning are convenient; after the magnetic core active material is purified or reactivated, the lithium extraction pole piece can be reconstructed by adopting the same method, so that the directional circulation integrated process of the product is realized.
Preferably, in the step (2), the adsorption of the magnetic core active material is performed by inserting a magnetically permeable current collector into the magnetic core active material.
Preferably, in the step (2), the adsorption of the magnetic core active material is performed by coating the magnetic core active material on the surface of the magnetically permeable current collector.
Preferably, in the step (2), the adsorption of the magnetic core active material is performed by spraying the magnetic core active material on the surface of the magnetically permeable current collector.
Preferably, in the lithium extraction pole piece, the density of the magnetic core active material after being adsorbed is 1.5-2.5 kg/m 2.
Preferably, the magnetically permeable current collector is at least one of a nickel-based magnetically permeable current collector, a cobalt-based magnetically permeable current collector and an iron-based magnetically permeable current collector.
The invention also aims to provide the application of the lithium extraction pole piece in electrochemical lithium extraction, and when the adsorption ratio of the magnetic core active material in the lithium extraction pole piece is less than or equal to 60%, the magnetic field is controlled to be more than or equal to 0.5T; when the adsorption ratio of the magnetic core active material is more than 80%, controlling the magnetic field to be less than 0.5T; the adsorption ratio of the magnetic core active material is the ratio of the actual adsorption capacity to the limit capacity (adsorption end point) which can be achieved by the actual adsorption.
Preferably, when the adsorption ratio of the magnetic core active material is less than or equal to 60%, the porosity of the magnetic core active material is 2-10%; when the adsorption ratio of the magnetic core active material is more than 80%, the porosity of the magnetic core active material is 10-15%.
According to the invention, in the electrochemical lithium extraction process, the lithium extraction efficiency of each stage in the whole lithium extraction process can be adjusted directly through magnetic field intensity control according to the real-time change of the lithium extraction saturation degree of the lithium extraction pole piece: in the early stage of lithium extraction, as the adsorption of the magnetic core active material is lower, the magnetic field strength is maintained higher, so that the magnetic core active material is tightly connected, and the stability of the early stage of lithium extraction can be maintained; in the middle and later stages of lithium extraction, the adsorption of the magnetic core active material is relatively low and is close to saturation, so that the lithium extraction efficiency is reduced, the magnetic field strength is reduced, the arrangement of the magnetic core active material is loosened, the overall porosity is increased, the contact area and the mass transfer effect of the magnetic core active material are improved, and the lithium extraction rate is dynamically maintained. The use method has real-time performance for maintaining the lithium extraction efficiency, does not need to additionally regulate and control the particle size or component content of the active material as described in the prior art, does not need to chemically modify the active material, and has simple operation steps and high economic benefit.
The invention has the beneficial effects that the invention provides the magnetic core active material, the product has excellent lithium extraction activity due to the composite design of the structure and the specificity of the formula raw materials, and meanwhile, the product mainly contains magnetic substance components, so that the subsequent process of preparing the lithium extraction pole piece can be implemented through a process without introducing a binder, and the lithium extraction efficiency and the lithium extraction stability of the lithium extraction pole piece can be ensured in real time by virtue of magnetic field regulation and control in the use process.
Drawings
Fig. 1 is an XRD spectrum of the magnetic core active material prepared in example 1 of the present invention.
Fig. 2 is a graph showing the relationship between the lithium concentration of the anolyte and the electrolysis time when the lithium extraction pole piece obtained in example 1 and comparative example 1 of the present invention is subjected to the electrolysis to extract lithium.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present invention, and the object of the present invention is to be understood in detail, not to limit the present invention. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments involved in the practice of the present invention are common reagents and instruments unless otherwise specified.
Example 1
The invention relates to a magnetic core active material, a preparation method and an application embodiment thereof:
The preparation method of the magnetic core active material comprises the following steps:
(1) Uniformly mixing magnetic iron source Fe 3O4, lithium source lithium carbonate, phosphorus source monoammonium phosphate and reducing agent Fe powder, heating to 450 ℃ at a speed of 5 ℃/min under a nitrogen atmosphere (0.02L/min) for one-stage heat preservation treatment for 3 hours, and then continuously heating to 750 ℃ for two-stage heat preservation treatment for 8 hours to obtain a core; the molar ratio of Fe 3O4 to Fe powder is 1.3:1, a step of; the molar ratio of the lithium element in the lithium source, the total iron element in the magnetic iron source to the iron element in the reduced iron powder and the phosphorus element in the phosphorus source is 1.1:1.1:1.05;
(2) Heating the core obtained in the step (1) to 750 ℃ in a mixed atmosphere (0.02L/min) of nitrogen and acetylene mixed according to a volume ratio of 1:5, performing vapor deposition treatment for 2 hours, and cooling to obtain the magnetic core active material, wherein the magnetic core active material comprises a core and a carbon shell layer coated on the surface of a lithium iron phosphate core; the core comprises lithium iron phosphate and a magnetic iron compound Fe 3O4, wherein the mass ratio of the lithium iron phosphate to the magnetic iron compound Fe 3O4 is about 5.7 after ICP test analysis: 1. XRD testing of the product, as shown in FIG. 1, shows that a portion of Fe 3O4 remains in the product, and particularly in the core, which portion of the magnetic iron compound will impart magnetic properties to the overall product.
The magnetic core active material is applied to the preparation of the lithium extraction pole piece:
(1) Connecting a commercial nickel-based magnetically permeable current collector with an electromagnet and setting the magnetic field of the electromagnet to be 0.5T;
(2) And inserting the magnetic conduction current collector into the magnetic core active material and adsorbing the magnetic core active material, slowly extracting after the magnetic core active material is completely adsorbed, and obtaining the lithium extraction pole piece, wherein the density of the adsorbed magnetic core active material is about 2kg/m 2.
The lithium-extracted electrode is taken as an anode, commercial foam nickel is taken as a cathode and placed in NaCl solution with the concentration of 20g/L, 1.0V voltage is applied to two ends of the electrode until the current density is lower than 0.5A/m 2, the under-lithium electrode is manufactured, a commercial anion membrane is adopted to divide an electrolysis device into a cathode chamber and an anode chamber, and the commercial lithium-enriched electrode and the manufactured under-lithium electrode are respectively placed in the anode chamber and the cathode chamber. Injecting 24L of brine to be treated into the cathode chamber respectively, wherein the components of the simulated brine are shown in the following table 1; the anode was injected with 4L of 5g/L NaCl solution as a supporting electrolyte. A voltage of 0.3V was applied to the cathode and anode, and the electrolyte was processed at 25 ℃. And when the lithium pole piece is electrolyzed for 2 hours, the adsorption ratio of the magnetic core active material in the lithium pole piece reaches 65%, and the magnetic field strength is reduced to 0.3T. After 4 hours of electrolysis, the concentration of lithium in the anode lithium-rich liquid rises to 3.453g/L, the extraction amount of lithium ions is 34.53mg/g, and the capacity retention rate after 50 times of circulation is 98.51%.
TABLE 1
Example 2
The invention relates to a magnetic core active material, a preparation method and an application embodiment thereof:
The preparation method of the magnetic core active material comprises the following steps:
(1) Uniformly mixing magnetic iron source LiFe 5O8, lithium source lithium carbonate, phosphorus source monoammonium phosphate and reducing agent carbon powder, heating to 400 ℃ at a speed of 5 ℃/min under a nitrogen atmosphere (0.02L/min) for one-stage heat preservation treatment for 5 hours, and then continuously heating to 700 ℃ for two-stage heat preservation treatment for 7 hours to obtain a core; the molar ratio of LiFe 5O8 to carbon powder is 5.2:5; the molar ratio of the lithium element in the lithium source, the iron element in the magnetic iron source and the phosphorus element in the phosphorus source is 1.1:1.1:1.05;
(2) Heating the core obtained in the step (1) to 750 ℃ in a mixed atmosphere (0.02L/min) of nitrogen and acetylene mixed according to a volume ratio of 1:5, performing vapor deposition treatment for 2 hours, and cooling to obtain the magnetic core active material, wherein the magnetic core active material comprises a core and a carbon shell layer coated on the surface of a lithium iron phosphate core; the core comprises lithium iron phosphate and a magnetic iron compound LiFe 5O8, and the mass ratio of the lithium iron phosphate to the magnetic iron compound LiFe 5O8 is about 6.4:1 through ICP test analysis.
The magnetic core active material is applied to the preparation of the lithium extraction pole piece:
(1) Connecting a commercial nickel-based magnetically permeable current collector with an electromagnet and setting the magnetic field of the electromagnet to be 0.5T;
(2) And inserting the magnetic conduction current collector into the magnetic core active material and adsorbing the magnetic core active material, slowly extracting after the magnetic core active material is completely adsorbed, and obtaining the lithium extraction pole piece, wherein the density of the adsorbed magnetic core active material is about 2kg/m 2.
The lithium-extracted electrode is taken as an anode, commercial foam nickel is taken as a cathode and placed in NaCl solution with the concentration of 20g/L, 1.0V voltage is applied to two ends of the electrode until the current density is lower than 0.5A/m 2, the under-lithium electrode is manufactured, a commercial anion membrane is adopted to divide an electrolysis device into a cathode chamber and an anode chamber, and the commercial lithium-enriched electrode and the manufactured under-lithium electrode are respectively placed in the anode chamber and the cathode chamber. Respectively injecting brine 24L to be treated into the cathode chamber, wherein the components of the brine are shown in table 1; the anode was injected with 4L of 5g/L NaCl solution as a supporting electrolyte. A voltage of 0.3V was applied to the cathode and anode, and the electrolyte was processed at 25 ℃. And when the lithium pole piece is electrolyzed for 2 hours, the adsorption ratio of the magnetic core active material in the lithium pole piece reaches 70%, and the magnetic field strength is reduced to 0.3T. After 4 hours of electrolysis, the concentration of lithium in the anode lithium-rich liquid rises to 3.442g/L, the extraction amount of lithium ions is 34.42mg/g, and the capacity retention rate after 50 times of circulation is 98.47%.
Example 3
The invention relates to a magnetic core active material, a preparation method and an application embodiment thereof:
The preparation method of the magnetic core active material comprises the following steps:
(1) Uniformly mixing magnetic iron source Fe 3O4, lithium source lithium carbonate, phosphorus source monoammonium phosphate and reducing agent carbon powder, heating to 500 ℃ at a speed of 5 ℃/min under a nitrogen atmosphere (0.02L/min) for one-stage heat preservation treatment for 3 hours, and then continuously heating to 650 ℃ for two-stage heat preservation treatment for 10 hours to obtain a core; the molar ratio of Fe 3O4 to carbon powder is 2.5:1, a step of; the molar ratio of the lithium element in the lithium source, the iron element in the magnetic iron source and the phosphorus element in the phosphorus source is 1.1:1.1:1.05;
(2) Heating the core obtained in the step (1) to 750 ℃ in a mixed atmosphere (0.02L/min) of nitrogen and acetylene mixed according to a volume ratio of 1:5, performing vapor deposition treatment for 2 hours, and cooling to obtain the magnetic core active material, wherein the magnetic core active material comprises a core and a carbon shell layer coated on the surface of a lithium iron phosphate core; the core comprises lithium iron phosphate and a magnetic iron compound Fe 3O4, wherein the mass ratio of the lithium iron phosphate to the magnetic iron compound Fe 3O4 is about 8.2:1 through ICP test analysis.
The magnetic core active material is applied to the preparation of the lithium extraction pole piece:
(1) Connecting a commercial nickel-based magnetically permeable current collector with an electromagnet and setting the magnetic field of the electromagnet to be 0.5T;
(2) And inserting the magnetic conduction current collector into the magnetic core active material and adsorbing the magnetic core active material, slowly extracting after the magnetic core active material is completely adsorbed, and obtaining the lithium extraction pole piece, wherein the density of the adsorbed magnetic core active material is about 2kg/m 2.
The lithium-extracted electrode is taken as an anode, commercial foam nickel is taken as a cathode and placed in NaCl solution with the concentration of 20g/L, 1.0V voltage is applied to two ends of the electrode until the current density is lower than 0.5A/m 2, the under-lithium electrode is manufactured, a commercial anion membrane is adopted to divide an electrolysis device into a cathode chamber and an anode chamber, and the commercial lithium-enriched electrode and the manufactured under-lithium electrode are respectively placed in the anode chamber and the cathode chamber. Respectively injecting brine 24L to be treated into the cathode chamber, wherein the components of the brine are shown in table 1; the anode was injected with 4L of 5g/L NaCl solution as a supporting electrolyte. A voltage of 0.3V was applied to the cathode and anode, and the electrolyte was processed at 25 ℃. And when the lithium pole piece is electrolyzed for 2 hours, the adsorption ratio of the magnetic core active material in the lithium pole piece reaches 65%, and the magnetic field strength is reduced to 0.3T. After 4 hours of electrolysis, the concentration of lithium in the anode lithium-rich liquid rises to 3.448g/L, the extraction amount of lithium ions is 34.48mg/g, and the capacity retention rate after 50 times of circulation is 98.49%.
Example 4
The invention relates to a magnetic core active material, a preparation method and an application embodiment thereof:
The preparation method of the magnetic core active material comprises the following steps:
(1) Uniformly mixing magnetic iron source Fe 3O4, lithium source lithium carbonate, phosphorus source monoammonium phosphate and reducing agent Fe powder, heating to 450 ℃ at a speed of 5 ℃/min under a nitrogen atmosphere (0.02L/min) for one-stage heat preservation treatment for 3 hours, and then continuously heating to 750 ℃ for two-stage heat preservation treatment for 8 hours to obtain a core; the molar ratio of Fe 3O4 to Fe powder is 1.3:1, a step of; the molar ratio of the lithium element in the lithium source, the total iron element in the magnetic iron source to the iron element in the reduced iron powder and the phosphorus element in the phosphorus source is 1.1:1.1:1.05;
(2) Heating the core obtained in the step (1) to 750 ℃ in a mixed atmosphere (0.05L/min) of nitrogen and acetylene mixed according to a volume ratio of 1:2, performing vapor deposition treatment for 2 hours, and cooling to obtain the magnetic core active material, wherein the magnetic core active material comprises a core and a carbon shell layer coated on the surface of a lithium iron phosphate core; the core comprises lithium iron phosphate and a magnetic iron compound Fe 3O4, wherein the mass ratio of the lithium iron phosphate to the magnetic iron compound Fe 3O4 is about 5.8:1 through ICP test analysis.
The magnetic core active material is applied to the preparation of the lithium extraction pole piece:
(1) Connecting a commercial nickel-based magnetically permeable current collector with an electromagnet and setting the magnetic field of the electromagnet to be 0.5T;
(2) And inserting the magnetic conduction current collector into the magnetic core active material and adsorbing the magnetic core active material, slowly extracting after the magnetic core active material is completely adsorbed, and obtaining the lithium extraction pole piece, wherein the density of the adsorbed magnetic core active material is about 2kg/m 2.
The lithium-extracted electrode is taken as an anode, commercial foam nickel is taken as a cathode and placed in NaCl solution with the concentration of 20g/L, 1.0V voltage is applied to two ends of the electrode until the current density is lower than 0.5A/m 2, the under-lithium electrode is manufactured, a commercial anion membrane is adopted to divide an electrolysis device into a cathode chamber and an anode chamber, and the commercial lithium-enriched electrode and the manufactured under-lithium electrode are respectively placed in the anode chamber and the cathode chamber. Respectively injecting brine 24L to be treated into the cathode chamber, wherein the components of the brine are shown in table 1; the anode was injected with 4L of 5g/L NaCl solution as a supporting electrolyte. A voltage of 0.3V was applied to the cathode and anode, and the electrolyte was processed at 25 ℃. And when the lithium pole piece is electrolyzed for 2 hours, the adsorption ratio of the magnetic core active material in the lithium pole piece reaches 65%, and the magnetic field strength is reduced to 0.3T. After 4 hours of electrolysis, the concentration of lithium in the anode lithium-rich liquid rises to 3.443g/L, the extraction amount of lithium ions is 34.43mg/g, and the capacity retention rate after 50 times of circulation is 98.43%.
Comparative example 1
The difference between the magnetic core active material and the preparation method and application thereof is that the magnetic field intensity is not regulated all the time until 4 hours during electrolysis, the lithium concentration in the anode lithium-rich liquid rises to 3.1g/L after 4 hours of electrolysis, the extraction amount of lithium ions is 31.0mg/g, the capacity retention rate after 50 cycles is 98.2%, and the change of the lithium concentration of the anode liquid in the example 1 and the comparative example 1 in the electrolysis process is counted, as shown in the result of fig. 2, it can be seen that the lithium extraction rate is obviously slowed down when the magnetic field intensity is not regulated in the product of the comparative example 1 for 2 hours along with the electrolysis time, and the effect of the product of the example 1 can still be achieved after 5 hours, but the lithium extraction efficiency is obviously lower than that of the product of the example 1.
Comparative example 2
The preparation method of the core active material comprises the following steps:
(1) Uniformly mixing magnetic iron source Fe 3O4, lithium source lithium carbonate, phosphorus source monoammonium phosphate and reducing agent Fe powder, heating to 450 ℃ at a speed of 5 ℃/min under a nitrogen atmosphere (0.02L/min) for one-stage heat preservation treatment for 3 hours, and then continuously heating to 750 ℃ for two-stage heat preservation treatment for 8 hours to obtain a core; the molar ratio of Fe 3O4 to Fe powder is 1:2.05; the molar ratio of the lithium element in the lithium source, the total iron element in the magnetic iron source to the iron element in the reduced iron powder and the phosphorus element in the phosphorus source is 1.1:1.1:1.05;
(2) Heating the core obtained in the step (1) to 750 ℃ in a mixed atmosphere (0.02L/min) of nitrogen and acetylene mixed according to a volume ratio of 1:5, performing vapor deposition treatment for 2 hours, and cooling to obtain the core active material.
The core active material is applied to the preparation of the lithium extraction pole piece: the core active material, binder PVDF, commercial acetylene black, ammonium bicarbonate and N-methylpyrrolidone were mixed in a mass ratio of 100:1:0.5:10:200 and stirred under vacuum to slurry and coat on aluminum foil with a coating density of about 2kg/m 2. And then drying for 3 hours at 60 ℃ and drying for 8 hours at 120 ℃ to obtain the lithium-extracted pole piece.
The lithium-extracted electrode is taken as an anode, commercial foam nickel is taken as a cathode and placed in NaCl solution with the concentration of 20g/L, 1.0V voltage is applied to two ends of the electrode until the current density is lower than 0.5A/m 2, the under-lithium electrode is manufactured, a commercial anion membrane is adopted to divide an electrolysis device into a cathode chamber and an anode chamber, and the commercial lithium-enriched electrode and the manufactured under-lithium electrode are respectively placed in the anode chamber and the cathode chamber. Respectively injecting brine 24L to be treated into the cathode chamber, wherein the components of the brine are shown in table 1; the anode was injected with 4L of 5g/L NaCl solution as a supporting electrolyte. A voltage of 0.3V was applied to the cathode and anode, and the electrolyte was processed at 25 ℃. After 4 hours of electrolysis, the concentration of lithium in the anode lithium-rich solution is increased to 3.12g/L, the extraction amount of lithium ions is 30.12mg/g, and the capacity retention rate after 50 times of circulation is 96.2%. Obviously, the lithium extraction pole piece prepared by adopting the conventional active material and the binder cannot realize the same lithium extraction efficiency of the product of the embodiment of the invention because the binder is obvious.
Comparative example 3
The difference between the magnetic core active material and the preparation method and application thereof is that the adsorption ratio of the magnetic core active material in the lithium-ion-extracting pole piece reaches 65% when the lithium-ion-extracting pole piece is electrolyzed for 2h, and the magnetic field strength is reduced to 0.1T. After 4 hours of electrolysis, the lithium concentration in the anode lithium-rich solution increased to 3.42g/L, the extraction amount of lithium ions was 34.2mg/g, and the capacity retention rate after 50 cycles was 82.5%. It can be seen that if the magnitude of the decrease in the magnetic field strength is too large when a certain degree of adsorption saturation is reached, the porosity of the magnetic core active material is too large, and although the influence on the amount of lithium extraction is not large, it has a significant impairment of the cycle stability.
Comparative example 4
The difference between the magnetic core active material and the preparation method and application thereof and the embodiment 1 is that the adsorption ratio of the magnetic core active material in the lithium-ion-extracting pole piece reaches 65% when the lithium-ion-extracting pole piece is electrolyzed for 2 hours, and the magnetic field strength is increased to 2T. After 4 hours of electrolysis, the concentration of lithium in the anode lithium-rich liquid rises to 3.06g/L, the extraction amount of lithium ions is 30.6mg/g, and the capacity retention rate after 50 times of circulation is 98.3 percent. It can be seen that if the magnetic field strength is increased when a certain adsorption saturation level is reached, the lithium extraction rate of the product is seriously reduced.
Comparative example 5
The difference between the magnetic core active material and the preparation method and application thereof and the embodiment 1 is that the molar ratio of Fe 3O4 to Fe powder is 2 when the core is prepared: 1.
Lithium extraction was performed under the same lithium extraction conditions as in example 1, and after 4 hours of electrolysis, the lithium concentration in the anode lithium-rich solution was increased to 2.97g/L, the extraction amount of lithium ions was 29.7mg/g, and the capacity retention rate after 50 cycles was 98.2%. It can be seen that, if the magnetic core active material is prepared with too much magnetic iron compound, the relative content of lithium iron phosphate becomes smaller, and the lithium extraction activity of the product is inevitably reduced, and the lithium extraction efficiency per unit time is inevitably reduced.
Comparative example 6
The difference between the magnetic core active material and the preparation method and application thereof and the embodiment 1 is that the molar ratio of Fe 3O4 to Fe powder is 1.05 when the core is prepared: 1.
Lithium extraction was performed under the same lithium extraction conditions as in example 1, and after 4 hours of electrolysis, the lithium concentration in the anode lithium-rich solution was increased to 3.43g/L, the extraction amount of lithium ions was 34.3mg/g, and the capacity retention rate after 50 cycles was 93.1%. It can be seen that if the magnetic core active material is prepared with too little magnetic iron compound, the lithium extraction activity of the product is not greatly affected but the cycle stability is significantly reduced.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (9)

1. The magnetic core active material is characterized by comprising a core and a carbon shell layer coated on the surface of the lithium iron phosphate core; the inner core comprises lithium iron phosphate and a magnetic iron compound, and the mass ratio of the lithium iron phosphate to the magnetic iron compound is (9:1) - (4:1); the magnetic iron compound is at least one of Fe 3O4、LiFe5O8;
The preparation raw materials of the inner core comprise a magnetic iron source, a lithium source, a phosphorus source and a reducing agent, wherein the magnetic iron source is at least one of Fe 3O4、LiFe5O8, and the reducing agent is at least one of Fe powder and carbon powder;
The magnetic iron source is Fe 3O4, and when the reducing agent is Fe powder, the molar ratio of Fe 3O4 to Fe powder is (1.2-1.5): 1, a step of;
The magnetic iron source is Fe 3O4, and when the reducing agent is carbon powder, the molar ratio of Fe 3O4 to the carbon powder is (2.4-3): 1, a step of;
When the magnetic iron source is LiFe 5O8 and the reducing agent is Fe powder, the molar ratio of LiFe 5O8 to Fe powder is (2.6-3.5): 5, a step of;
When the magnetic iron source is LiFe 5O8 and the reducing agent is carbon powder, the molar ratio of LiFe 5O8 to carbon powder is (4.8-5.9): 5.
2. The magnetic core active material of claim 1, wherein the lithium source is at least one of lithium carbonate, lithium hydroxide, lithium chloride, lithium phosphate, lithium sulfate; the phosphorus source is at least one of monoammonium phosphate, diammonium phosphate, phosphoric acid and ammonium phosphate; the molar ratio of the lithium element in the lithium source, the total iron element in the magnetic iron source to the iron element in the reduced iron powder and the phosphorus element in the phosphorus source is (1-2): (1-1.5): (1-1.5).
3. The method for preparing a magnetic core active material according to any one of claims 1 to 2, comprising the steps of:
(1) Uniformly mixing the preparation raw materials of each inner core, and heating and preserving heat under a protective atmosphere to obtain the inner cores;
(2) Heating the core obtained in the step (1) in a mixed atmosphere of nitrogen and acetylene, performing vapor deposition treatment, and cooling to obtain the magnetic core active material.
4. The method of preparing a magnetic core active material according to claim 3, comprising at least one of the following (a) - (e):
(a) The heating and heat-preserving treatment in the step (1) comprises a first-stage heating and heat-preserving treatment and a second-stage heating and heat-preserving treatment, wherein the temperature of the first-stage heating and heat-preserving treatment is 400-500 ℃ and the time is 3-5 h, and the temperature of the second-stage heating and heat-preserving treatment is 650-750 ℃ and the time is 5-10 h;
(b) The heating rate in the heating and heat preservation treatment is 4-6 ℃/min;
(c) The protective atmosphere in the step (1) is at least one of nitrogen and argon, and the flow is 0.01-0.05L/min;
(d) The temperature in the vapor deposition treatment in the step (2) is 600-800 ℃ and the time is 0.5-2 h;
(e) The flow rate of the mixed atmosphere in the step (2) is 0.01-0.05L/min, and the volume ratio of nitrogen to acetylene in the mixed atmosphere is (1:1) - (1:5).
5. A lithium extraction pole piece characterized by comprising a magnetically permeable current collector and the magnetic core active material of any one of claims 1-2.
6. The method for preparing the lithium-extracted pole piece according to claim 5, comprising the steps of:
(1) Connecting a magnetically permeable current collector with an electromagnet and setting the magnetic field of the electromagnet to be 0.3-0.9T;
(2) And (3) adsorbing the magnetic core active material by using a magnetic conductivity current collector, and obtaining the lithium extraction pole piece after the magnetic core active material is completely adsorbed.
7. The method for preparing a lithium-extracted pole piece according to claim 6, wherein the density of the magnetic core active material of the lithium-extracted pole piece after being adsorbed is 1.5-2.5 kg/m 2.
8. The method of claim 6, wherein in the step (2), the magnetically permeable current collector is inserted into the magnetically permeable active material to adsorb the magnetically permeable active material, or the magnetically permeable current collector is coated with the magnetically permeable active material to adsorb the magnetically permeable active material, or the magnetically permeable current collector is sprayed with the magnetically permeable current collector to adsorb the magnetically permeable active material.
9. The use of the lithium-extracting pole piece according to claim 5 in electrochemical lithium extraction, wherein when the adsorption ratio of the magnetic core active material in the lithium-extracting pole piece is less than or equal to 60%, the magnetic field is controlled to be more than or equal to 0.5T; when the adsorption ratio of the magnetic core active material is more than 80%, controlling the magnetic field to be less than 0.5T; the adsorption ratio of the magnetic core active material is the ratio of the actual adsorption capacity of the magnetic core active material to the limit capacity which can be achieved by the actual adsorption.
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