CN115710021A - Method for reducing content of magnetic substances in lithium battery positive electrode material - Google Patents
Method for reducing content of magnetic substances in lithium battery positive electrode material Download PDFInfo
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- CN115710021A CN115710021A CN202211446826.1A CN202211446826A CN115710021A CN 115710021 A CN115710021 A CN 115710021A CN 202211446826 A CN202211446826 A CN 202211446826A CN 115710021 A CN115710021 A CN 115710021A
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- lithium battery
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 97
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 87
- 239000000126 substance Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 27
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 20
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 39
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 16
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 16
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 12
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 13
- 230000005347 demagnetization Effects 0.000 abstract description 10
- 230000002411 adverse Effects 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 239000000696 magnetic material Substances 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 10
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 5
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000010146 3D printing Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 4
- 238000007885 magnetic separation Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 3
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003571 electronic cigarette Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for reducing the content of a magnetic substance in a lithium battery positive electrode material, which comprises the following steps: (1) Uniformly mixing a first lithium battery positive electrode material and a lithium salt to obtain a positive electrode mixed material; (2) Sintering the positive electrode mixed material obtained in the step (1) to obtain a second lithium battery positive electrode material; compared with the positive electrode material of the first lithium battery, the content of the magnetic substance in the positive electrode material of the second lithium battery is reduced by more than or equal to 50%; or the content of the magnetic substance in the positive electrode material of the second lithium battery is less than or equal to 100ppb. The method provided by the invention is particularly directed at weak magnetic substances, so that the adverse effect of the weak magnetic substances on the performance of the battery is avoided, the demagnetization efficiency is improved while the demagnetization effect is improved, and the safety risk and the process cost are reduced.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, relates to a lithium battery positive electrode material, and particularly relates to a method for reducing the content of magnetic substances in the lithium battery positive electrode material.
Background
With the rapid development of the lithium ion battery industry, the lithium ion battery has been widely applied to various fields such as mobile phones, digital cameras, notebook computers, electronic cigarettes, unmanned aerial vehicles and new energy vehicles by virtue of its higher energy density and rate capability and longer service life.
As is well known, the positive electrode material is a key component of the lithium ion battery, and the performance of the positive electrode material directly affects a plurality of important indexes of the lithium ion battery. When magnetic substances such as iron, chromium, nickel, zinc and the like exist in the positive electrode material, after the voltage of the battery in the formation stage reaches the oxidation-reduction potential of the magnetic foreign metal elements, the magnetic foreign metal elements are firstly oxidized and dissolved in the positive electrode, and then migrate to the negative electrode to be reduced into metal simple substances. When the metal elementary substance at the negative electrode is accumulated to a certain degree, metal dendrite can be formed to pierce the diaphragm, so that the self-discharge failure of the battery is caused, and even the combustion explosion of the lithium ion battery can be caused under severe conditions. Therefore, it is important to remove the magnetic substances in the material as much as possible during the production of the positive electrode material.
For the lithium battery anode material, a physical method is generally adopted by technicians in the field when the content of magnetic substances in the lithium battery anode material is reduced, namely, in the production process of the lithium battery anode material, a magnetic bar, a deironing machine and other equipment are designed through a production line to remove trace magnetic substances in the product. Although this method can remove magnetic substances, it has a problem of poor demagnetization effect, and particularly weak magnetic substances cannot be completely removed by the magnet, so that adverse effects of the magnetic substances on the battery performance cannot be effectively avoided.
Moreover, since the ternary material itself has weak magnetism and the stronger magnetic field intensity easily blocks the pipeline, the iron remover generally needs to be adjusted to the lower magnetic field intensity for demagnetizing, so that the demagnetizing effect of the ternary positive electrode material is remarkably reduced, and the magnetic substance of the ternary positive electrode material is difficult to remove once the ternary positive electrode material is polluted, so that the content of the magnetic substance is higher, the safety risk is easily caused, and particularly, the weak magnetic substance is difficult to remove.
In addition, some high-magnetism substances are often generated in the production process of the lithium battery, and the conventional method for reducing the content of the magnetic foreign matters is mainly screening to remove iron, namely, passing the materials through a high-strength Gaussian flux magnetic core to adsorb the magnetic substances. However, due to the interference of weak magnetic substances, the method needs to be repeated for many times, the demagnetizing effect is not ideal, and particularly, the method has poor adsorption capacity for the weak magnetic substances in the materials and has no effect on products detected by using a weak magnetic method.
CN 112125347A discloses a low-energy-consumption fast preparation method and system of lithium cobaltate, the method includes the following steps: (1) preparing a 3D printing mixture: uniformly mixing the raw materials to obtain a 3D printing mixture; (2) Adopting a 3D printing technology to manufacture the 3D printing mixture into a uniform and solid mixture; (3) Sintering the uniform and compact mixture to obtain a blocky solid material; (4) crushing treatment: crushing the massive solid material to obtain a primary lithium cobaltate material; (5) Screening out large particles in the primary lithium cobaltate product through screening treatment, and removing or reducing magnetic foreign matters such as iron, chromium, nickel, zinc and the like in the primary lithium cobaltate product through magnetic separation treatment to obtain the lithium cobaltate product. However, the magnetic separation treatment adopted by the invention cannot completely remove weak magnetic substances in the lithium cobaltate product, and needs to be repeated for many times, so that the magnetic separation efficiency is low and the magnetic separation effect needs to be further improved.
Therefore, how to provide a method for reducing the content of magnetic substances in the lithium battery positive electrode material, especially aiming at weak magnetic substances, the method avoids the adverse effect of the weak magnetic substances on the battery performance, improves the demagnetization efficiency while improving the demagnetization effect, reduces the safety risk and the process cost, and becomes a problem which needs to be solved urgently by technical personnel in the field at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for reducing the content of magnetic substances in a lithium battery positive electrode material, which is especially for weak magnetic substances, avoids the adverse effect of the weak magnetic substances on the battery performance, improves the demagnetization effect, improves the demagnetization efficiency, and reduces the safety risk and the process cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for reducing the content of a magnetic substance in a lithium battery positive electrode material, which comprises the following steps:
(1) Uniformly mixing a first lithium battery positive electrode material and a lithium salt to obtain a positive electrode mixed material;
(2) And (3) sintering the positive electrode mixed material obtained in the step (1) to obtain a second lithium battery positive electrode material.
The content of the magnetic substance in the second lithium battery positive electrode material is reduced by 50% or more, for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% as compared with the first lithium battery positive electrode material, but the content is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Alternatively, the content of the magnetic substance in the positive electrode material for the second lithium battery is 100ppb or less, and may be, for example, 10ppb, 20ppb, 30ppb, 40ppb, 50ppb, 60ppb, 70ppb, 80ppb, 90ppb or 100ppb, but is not limited to the recited values, and other values not recited within the range of the values are also applicable.
The invention mixes the lithium battery anode material and lithium salt evenly and carries out sintering treatment, and utilizes the lithium salt and weak magnetic substances in the anode material, such as Fe and Fe 2 O 3 Etc. react to form nonmagnetic Li z Fe x Co y O 2 Etc. to thereby realize reduction in the content of the lithium battery positive electrode materialThe content of the magnetic substance is reduced by more than 50 percent or the content of the magnetic substance is reduced to less than 100ppb, the battery performance and the safety performance are not adversely affected, the process flow is simple, the cost is low, and the large-scale popularization and application are facilitated.
Preferably, the first lithium battery positive electrode material in the step (1) includes a lithium battery positive electrode material having a magnetic material content of 100ppb or more, and may be, for example, 100ppb, 200ppb, 300ppb, 400ppb, 500ppb, 600ppb, 700ppb, 800ppb, or 900ppb, but is not limited to the recited values, and other values not recited within the range of the recited values are also applicable.
Preferably, the first lithium battery positive electrode material in step (1) includes any one or a combination of at least two of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel manganese oxide, lithium cobalt oxide, or lithium manganese oxide, and typical but non-limiting combinations include a combination of lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate, a combination of lithium nickel cobalt aluminate and lithium nickel manganese oxide, a combination of lithium cobalt oxide and lithium manganese oxide, a combination of lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium nickel manganese oxide, a combination of lithium nickel cobalt aluminate, lithium nickel manganese oxide and lithium cobalt oxide, or a combination of lithium nickel manganese oxide, lithium cobalt oxide and lithium manganese oxide.
Preferably, the lithium salt in step (1) comprises any one of lithium carbonate, lithium hydroxide or lithium oxide or a combination of at least two thereof, and typical but non-limiting combinations include a combination of lithium carbonate and lithium hydroxide, a combination of lithium hydroxide and lithium oxide, a combination of lithium carbonate and lithium oxide, or a combination of lithium carbonate, lithium hydroxide and lithium oxide.
Preferably, the mixed mass of the lithium salt in the step (1) accounts for 0 to 5% of the mass of the first lithium battery positive electrode material, but does not include 0, and may be, for example, 0.01%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%, but is not limited to the enumerated values, and other non-enumerated values within the numerical range are also applicable.
Preferably, the mixing in step (1) is accompanied by stirring at a rate of 100-500rpm, such as 100rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm or 500rpm, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the sintering process of step (2) is performed in a sagger, and the sagger is placed in a kiln.
Preferably, the temperature increase rate of the sintering treatment in step (2) is 0.1 to 5 ℃/min, for example, 0.1 ℃/min, 0.5 ℃/min, 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, or 5 ℃/min, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the sintering treatment of step (2) is carried out at a target temperature of 300 to 950 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or 950 ℃, but not limited to the recited values, and other unrecited values within the range of values are also applicable.
In the invention, the target temperature of the sintering treatment needs to be controlled within a reasonable range. When the target temperature is lower than 300 ℃, the lithium salt and the weak magnetic substance in the positive electrode material do not completely react, so that the demagnetization efficiency is reduced, and the demagnetization effect is not ideal; when the target temperature is higher than 950 ℃, it causes an unnecessary increase in the processing cost.
Preferably, the heat preservation time of the sintering treatment in the step (2) is 12-30h, for example, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h or 30h, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) Uniformly mixing a first lithium battery positive electrode material and lithium salt, and stirring at a speed of 100-500rpm to obtain a positive electrode mixed material; the first lithium battery positive electrode material comprises a lithium battery positive electrode material with the magnetic substance content of more than or equal to 100ppb, and the first lithium battery positive electrode material comprises any one or the combination of at least two of nickel cobalt lithium manganate, nickel cobalt lithium aluminate, nickel lithium manganate, lithium cobaltate or lithium manganate; the lithium salt comprises any one or the combination of at least two of lithium carbonate, lithium hydroxide or lithium oxide, and the mixed mass of the lithium salt accounts for 0-5% of the mass of the positive electrode material of the first lithium battery, but does not comprise 0;
(2) Transferring the positive electrode mixed material obtained in the step (1) into a sagger, placing the sagger into a kiln for sintering treatment, wherein the heating rate of the sintering treatment is 0.1-5 ℃/min, the target temperature is 300-950 ℃, and the heat preservation time is 12-30h, so as to finally obtain a second lithium battery positive electrode material; compared with the positive electrode material of the first lithium battery, the content of the magnetic substance in the positive electrode material of the second lithium battery is reduced by more than or equal to 50%; or the content of the magnetic substance in the second lithium battery positive electrode material is less than or equal to 100ppb.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
the lithium battery positive electrode material and the lithium salt are uniformly mixed and sintered, and the lithium salt and weak magnetic substances in the positive electrode material, such as Fe and Fe, are utilized 2 O 3 Etc. react to form nonmagnetic Li z Fe x Co y O 2 And the content of the magnetic substance is reduced by more than 50 percent or the content of the magnetic substance is reduced to less than 100ppb, the performance and the safety performance of the battery are not adversely affected, the process flow is simple, the cost is low, and the method is convenient for large-scale popularization and application.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a method for reducing the content of a magnetic substance in a positive electrode material of a lithium battery, which comprises the following steps:
(1) Uniformly mixing lithium cobaltate and lithium carbonate, wherein the mixing mass of the lithium carbonate accounts for 0.1% of the mass of the lithium cobaltate, and stirring at the speed of 200rpm to obtain a positive electrode mixed material;
(2) And (2) transferring the positive electrode mixed material obtained in the step (1) into a sagger, placing the sagger into a kiln for sintering treatment, wherein the heating rate of the sintering treatment is 1 ℃/min, the target temperature is 600 ℃, and the heat preservation time is 18h, so that the lithium cobaltate positive electrode material with the magnetic substance content of 30ppb is finally obtained.
Example 2
The embodiment provides a method for reducing the content of a magnetic substance in a lithium battery positive electrode material, which comprises the following steps:
(1) Uniformly mixing lithium cobaltate with the magnetic substance content of 500ppb and lithium carbonate, wherein the mixing mass of the lithium carbonate accounts for 0.2% of the mass of the lithium cobaltate, and stirring at the speed of 100rpm to obtain a positive electrode mixed material;
(2) And (2) transferring the positive electrode mixed material obtained in the step (1) into a sagger, placing the sagger into a kiln for sintering treatment, wherein the temperature rise rate of the sintering treatment is 1 ℃/min, the target temperature is 300 ℃, and the heat preservation time is 24h, so that the lithium cobaltate positive electrode material with the magnetic substance content of 11ppb is finally obtained, and the reduction amplitude of the magnetic substance content reaches 97.8%.
Example 3
The embodiment provides a method for reducing the content of a magnetic substance in a lithium battery positive electrode material, which comprises the following steps:
(1) Uniformly mixing lithium cobaltate and lithium hydroxide, wherein the mixing mass of the lithium hydroxide accounts for 0.01% of the mass of the lithium cobaltate, and stirring at the speed of 300rpm to obtain a positive electrode mixed material;
(2) And (2) transferring the positive electrode mixed material obtained in the step (1) into a sagger, placing the sagger into a kiln for sintering treatment, wherein the heating rate of the sintering treatment is 2 ℃/min, the target temperature is 900 ℃, and the heat preservation time is 12h, so that the lithium cobaltate positive electrode material with the magnetic substance content of 50ppb is finally obtained.
Example 4
The embodiment provides a method for reducing the content of a magnetic substance in a positive electrode material of a lithium battery, which comprises the following steps:
(1) Uniformly mixing the lithium nickel cobalt manganese oxide with the magnetic substance content of 600ppb and lithium hydroxide, wherein the mixing mass of the lithium hydroxide accounts for 2.5% of the mass of the lithium nickel cobalt manganese oxide, and stirring at the speed of 250rpm to obtain a positive electrode mixed material;
(2) And (2) transferring the positive electrode mixed material obtained in the step (1) into a sagger, placing the sagger into a kiln for sintering treatment, wherein the temperature rise rate of the sintering treatment is 5 ℃/min, the target temperature is 900 ℃, the heat preservation time is 12h, and finally the nickel cobalt lithium manganate positive electrode material with the magnetic material content of 15ppb is obtained, and the reduction range of the magnetic material content reaches 97.5%.
Example 5
The embodiment provides a method for reducing the content of a magnetic substance in a lithium battery positive electrode material, which comprises the following steps:
(1) Uniformly mixing nickel cobalt lithium aluminate and lithium oxide, wherein the mixing mass of the lithium oxide accounts for 4% of the mass of the nickel cobalt lithium aluminate, and stirring at a speed of 200rpm to obtain a positive electrode mixed material;
(2) And (2) transferring the positive electrode mixed material obtained in the step (1) into a sagger, placing the sagger into a kiln for sintering treatment, wherein the heating rate of the sintering treatment is 3 ℃/min, the target temperature is 600 ℃, and the heat preservation time is 20h, so that the nickel-cobalt lithium aluminate positive electrode material with the magnetic substance content of 40ppb is finally obtained.
Example 6
The embodiment provides a method for reducing the content of a magnetic substance in a lithium battery positive electrode material, which comprises the following steps:
(1) Uniformly mixing 650ppb of lithium nickel manganese oxide and lithium oxide, wherein the mixed mass of the lithium oxide accounts for 5% of the mass of the lithium nickel manganese oxide, and stirring at the speed of 200rpm to obtain a positive electrode mixed material;
(2) And (2) transferring the positive electrode mixed material obtained in the step (1) into a sagger, placing the sagger into a kiln for sintering treatment, wherein the temperature rise rate of the sintering treatment is 3 ℃/min, the target temperature is 600 ℃, and the heat preservation time is 20h, so that the lithium nickel manganese oxide positive electrode material with the magnetic substance content of 80ppb is finally obtained, and the reduction amplitude of the magnetic substance content reaches 87.7%.
Example 7
This example provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery, except that the lithium carbonate in step (1) is changed to a mixture of lithium carbonate and lithium hydroxide of equal mass, and the other steps and conditions are the same as those in example 1, and therefore are not described herein again.
The magnetic material content of the lithium positive electrode material of the lithium battery obtained in the embodiment is 28ppb.
Example 8
This example provides a method for reducing the content of magnetic substances in the positive electrode material of a lithium battery, except that the lithium carbonate in step (1) is changed to a mixture of lithium hydroxide and lithium oxide with equal mass, and the other steps and conditions are the same as those in example 1, and therefore, the description thereof is omitted here.
The magnetic material content of the lithium battery positive electrode material obtained in this example was 26ppb.
Example 9
This example provides a method for reducing the content of magnetic material in the positive electrode material of a lithium battery, except that the ratio of the mixed mass of lithium carbonate in step (1) to the mass of lithium cobaltate is changed to 0.005%, and the other steps and conditions are the same as those in example 1, and therefore are not described herein again.
The magnetic material content of the lithium cobaltate positive electrode material obtained in this example was 50ppb.
Example 10
This example provides a method for reducing the content of magnetic substances in a positive electrode material of a lithium battery, except that the ratio of the mixed mass of lithium carbonate in step (1) to the mass of lithium cobaltate is changed to 5.5%, and the remaining steps and conditions are the same as those in example 1, and therefore, details are not repeated here.
The magnetic material content of the lithium battery positive electrode material obtained in this example was 22ppb.
Example 11
This embodiment provides a method for reducing the content of magnetic material in the positive electrode material of a lithium battery, except that the target temperature of the sintering process in step (2) is changed to 250 ℃, and the other steps and conditions are the same as those in embodiment 1, and therefore, the description thereof is omitted.
The magnetic material content of the lithium battery positive electrode material obtained in this example was 48ppb.
Example 12
This embodiment provides a method for reducing the content of magnetic material in the positive electrode material of a lithium battery, except that the target temperature of the sintering process in step (2) is changed to 1000 ℃, and the other steps and conditions are the same as those in embodiment 1, and therefore, the description thereof is omitted.
The magnetic material content of the lithium battery positive electrode material obtained in the embodiment is 26ppb.
Comparative example 1
The comparison example provides a method for reducing the content of magnetic substances in a lithium battery positive electrode material, and the method is characterized in that a demagnetizing bar and a deironing machine are additionally arranged on a production line so as to remove trace magnetic substances in the positive electrode material.
Compared with example 1, in this comparative example, although the magnetic material can be removed, the weak magnetic material cannot be completely removed, and repeated demagnetization is required, so that the process is complicated, and the equipment cost is high.
Therefore, the invention utilizes the lithium salt and weak magnetic substances in the positive electrode material, such as Fe and Fe, to mix uniformly with the lithium salt and sinter the mixture 2 O 3 Etc. react to form nonmagnetic Li z Fe x Co y O 2 And the content of the magnetic substance is reduced by more than 50 percent or the content of the magnetic substance is reduced to less than 100ppb, the performance and the safety performance of the battery are not adversely affected, the process flow is simple, the cost is low, and the method is convenient for large-scale popularization and application.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for reducing the content of magnetic substances in a positive electrode material of a lithium battery is characterized by comprising the following steps:
(1) Uniformly mixing a first lithium battery positive electrode material and a lithium salt to obtain a positive electrode mixed material;
(2) Sintering the positive electrode mixed material obtained in the step (1) to obtain a second lithium battery positive electrode material;
compared with the positive electrode material of the first lithium battery, the content of the magnetic substance in the positive electrode material of the second lithium battery is reduced by more than or equal to 50%;
or the content of the magnetic substance in the positive electrode material of the second lithium battery is less than or equal to 100ppb.
2. The method according to claim 1, wherein the first lithium battery positive electrode material in step (1) comprises a lithium battery positive electrode material with a magnetic content of 100ppb or more;
preferably, the first lithium battery positive electrode material in the step (1) includes any one of nickel cobalt lithium manganate, nickel cobalt lithium aluminate, nickel lithium manganate, lithium cobaltate or lithium manganate or a combination of at least two of the two.
3. The method of claim 1 or 2, wherein the lithium salt of step (1) comprises any one of lithium carbonate, lithium hydroxide or lithium oxide or a combination of at least two thereof.
4. The method according to any one of claims 1 to 3, wherein the mixed mass of the lithium salt in the step (1) is 0 to 5% of the mass of the positive electrode material for the first lithium battery, excluding 0.
5. The method according to any one of claims 1 to 4, wherein the mixing in step (1) is accompanied by stirring at a rate of 100 to 500rpm.
6. The method according to any one of claims 1 to 5, wherein the sintering treatment of step (2) is carried out in a sagger, and the sagger is placed in a kiln.
7. The method according to any one of claims 1 to 6, wherein the temperature increase rate of the sintering treatment in step (2) is 0.1 to 5 ℃/min.
8. The method according to any one of claims 1 to 7, wherein the target temperature of the sintering process of step (2) is 300 to 950 ℃.
9. The method according to any one of claims 1 to 8, wherein the sintering treatment of step (2) is carried out for a holding time of 12 to 30 hours.
10. Method according to any of claims 1-9, characterized in that the method comprises the steps of:
(1) Uniformly mixing a first lithium battery positive electrode material and lithium salt, and stirring at a speed of 100-500rpm to obtain a positive electrode mixed material; the first lithium battery positive electrode material comprises a lithium battery positive electrode material with the magnetic substance content of more than or equal to 100ppb, and the first lithium battery positive electrode material comprises any one or the combination of at least two of nickel cobalt lithium manganate, nickel cobalt lithium aluminate, nickel lithium manganate, lithium cobaltate or lithium manganate; the lithium salt comprises any one or the combination of at least two of lithium carbonate, lithium hydroxide or lithium oxide, and the mixed mass of the lithium salt accounts for 0-5% of the mass of the positive electrode material of the first lithium battery, but does not comprise 0;
(2) Transferring the positive electrode mixed material obtained in the step (1) into a sagger, placing the sagger into a kiln for sintering treatment, wherein the temperature rise rate of the sintering treatment is 0.1-5 ℃/min, the target temperature is 300-950 ℃, and the heat preservation time is 12-30h, so as to finally obtain a second lithium battery positive electrode material; compared with the positive electrode material of the first lithium battery, the content of the magnetic substance in the positive electrode material of the second lithium battery is reduced by more than or equal to 50%; or the content of the magnetic substance in the positive electrode material of the second lithium battery is less than or equal to 100ppb.
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| CN202211446826.1A CN115710021A (en) | 2022-11-18 | 2022-11-18 | Method for reducing content of magnetic substances in lithium battery positive electrode material |
| PCT/CN2023/086978 WO2024103614A1 (en) | 2022-11-18 | 2023-04-07 | Method for reducing content of magnetic substances in lithium battery positive electrode material |
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| WO2024103614A1 (en) * | 2022-11-18 | 2024-05-23 | 格林美（无锡）能源材料有限公司 | Method for reducing content of magnetic substances in lithium battery positive electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105244493A (en) * | 2015-08-27 | 2016-01-13 | 青岛新正锂业有限公司 | Method for removing magnetic substance from lithium ion battery positive electrode material |
| CN109728262A (en) * | 2018-11-30 | 2019-05-07 | 高点(深圳)科技有限公司 | Anode material for lithium-ion batteries and its preparation method and application |
| CN113113578A (en) * | 2021-03-10 | 2021-07-13 | 欣旺达电动汽车电池有限公司 | Cathode material, preparation method thereof and lithium ion battery |
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| JP5596790B2 (en) * | 2010-12-28 | 2014-09-24 | 三井金属鉱業株式会社 | Method for producing positive electrode active material for lithium secondary battery |
| JP2015060755A (en) * | 2013-09-19 | 2015-03-30 | 日揮触媒化成株式会社 | Method of producing lithium ion secondary battery positive electrode active material |
| JP7403946B2 (en) * | 2018-08-20 | 2023-12-25 | 株式会社田中化学研究所 | Method for producing purified lithium compound and method for producing lithium transition metal composite oxide |
| CN115710021A (en) * | 2022-11-18 | 2023-02-24 | 格林美（无锡）能源材料有限公司 | Method for reducing content of magnetic substances in lithium battery positive electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105244493A (en) * | 2015-08-27 | 2016-01-13 | 青岛新正锂业有限公司 | Method for removing magnetic substance from lithium ion battery positive electrode material |
| CN109728262A (en) * | 2018-11-30 | 2019-05-07 | 高点(深圳)科技有限公司 | Anode material for lithium-ion batteries and its preparation method and application |
| CN113113578A (en) * | 2021-03-10 | 2021-07-13 | 欣旺达电动汽车电池有限公司 | Cathode material, preparation method thereof and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2024103614A1 (en) * | 2022-11-18 | 2024-05-23 | 格林美（无锡）能源材料有限公司 | Method for reducing content of magnetic substances in lithium battery positive electrode material |
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