CN114835174B - Low-cobalt positive electrode active material, method for producing same, electrochemical device, and electronic device - Google Patents
Low-cobalt positive electrode active material, method for producing same, electrochemical device, and electronic device Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 142
- 239000010941 cobalt Substances 0.000 title claims abstract description 142
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 150000001868 cobalt Chemical class 0.000 claims abstract description 29
- 150000002696 manganese Chemical class 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000975 co-precipitation Methods 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910013716 LiNi Inorganic materials 0.000 claims description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- 230000003247 decreasing effect Effects 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 30
- 230000014759 maintenance of location Effects 0.000 abstract description 9
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- 239000002245 particle Substances 0.000 description 12
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 229920000515 polycarbonate Polymers 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
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- 239000011267 electrode slurry Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
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- 230000008569 process Effects 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
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- 238000010884 ion-beam technique Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
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- 235000011121 sodium hydroxide Nutrition 0.000 description 2
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- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding 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
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a low-cobalt positive electrode active material, a preparation method thereof, an electrochemical device and electronic equipment, wherein the preparation method comprises the following steps: (1) Mixing nickel salt, cobalt salt, manganese salt, a complexing agent and a precipitator, and performing coprecipitation reaction to obtain a precursor inner core; (2) Increasing the molar concentration of the cobalt salt, reducing the molar concentration of the manganese salt, and performing coprecipitation reaction to obtain a low cobalt precursor; (3) Mixing the low-cobalt precursor with lithium salt, and sintering to obtain the low-cobalt positive electrode active material; the molar concentration ratio of the nickel salt, the cobalt salt and the manganese salt in the step (1) is x, wherein x is more than or equal to 0.55 and less than or equal to 0.60,0.05, and y is more than or equal to 0.15. The invention solves the defects of low capacity and poor storage caused by fire sintering of the coated cobalt, improves the crystallinity, interface stability and dynamic performance of the material, and further improves the gram capacity, coulomb efficiency and capacity retention rate of the electrochemical device.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a low-cobalt positive electrode active material, a preparation method thereof, an electrochemical device and electronic equipment.
Background
The ternary material has higher theoretical specific capacity and voltage platform, but the cost of cobalt in the ternary material is higher, and the product cost can be saved by reducing the cobalt content; however, the reduction of the cobalt content in the ternary material can affect the overall conductivity of the material and improve the diffusion barrier of lithium ions in the crystal lattice, so that the reaction kinetics of the material is retarded, and the capacity exertion of the material is finally affected.
At present, when the low-cobalt ternary material is sintered by a fire method, the surface of the low-cobalt ternary material is coated with cobalt, so that the kinetic problem of the material can be solved, but only when the temperature of secondary sintering is between 700 and 800 ℃, cobalt can be effectively coated, but other coating elements at the temperature can migrate and permeate into the interior of material particles, so that the coating effect is influenced, and the high-temperature storage performance of the material is deteriorated; therefore, the preparation method of the low-cobalt ternary material with excellent dynamic performance is provided, and has important significance for reducing production cost and improving the performance of the low-cobalt ternary material.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a low-cobalt positive electrode active material, a preparation method thereof, an electrochemical device and electronic equipment. The invention carries out two-step coprecipitation reaction by controlling the concentration of metal salt to obtain the low-cobalt anode active material with low cobalt inside and rich cobalt on the surface, solves the defects of low capacity and poor storage caused by sintering coated cobalt by a fire method, and the prepared material has uniform particles, good sphericity, narrow particle size distribution, higher crystallinity and interface stability, excellent dynamic performance, and higher gram capacity, coulombic efficiency and capacity retention rate when applied to an electrochemical device.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a low cobalt positive electrode active material, the method comprising the steps of:
(1) Mixing nickel salt, cobalt salt, manganese salt, a complexing agent and a precipitator, and performing coprecipitation reaction to obtain a precursor inner core;
(2) Increasing the molar concentration of the cobalt salt, reducing the molar concentration of the manganese salt, and performing coprecipitation reaction to obtain a low cobalt precursor;
(3) Mixing the low-cobalt precursor with lithium salt, and sintering to obtain the low-cobalt positive electrode active material;
the molar concentration ratio of the nickel salt, the cobalt salt and the manganese salt in the step (1) is x, wherein x is more than or equal to 0.55 and less than or equal to 0.60,0.05, and y is more than or equal to 0.15.
In the invention, the low cobalt positive electrode active material refers to a material with a chemical formula of LiNi x Co y Mn 1-x-y O 2 In the positive electrode active material of (2), y is less than or equal to 0.15.
In the invention, the molar concentration ratio of the nickel salt, the cobalt salt and the manganese salt in the step (1) is x:y (1-x-y), wherein x is more than or equal to 0.55 and less than or equal to 0.60, such as 0.55, 0.56, 0.57, 0.58, 0.59 or 0.6, and y is more than or equal to 0.05 and less than or equal to 0.15, such as 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14 or 0.15, and the like. In the element proportion range, the safety of the finished battery can be improved, and the use of rare element cobalt can be reduced.
In the method, nickel salt, cobalt salt, manganese salt, complexing agent and precipitant with certain concentration are mixed for coprecipitation reaction, after a precursor inner core is generated, the concentration of cobalt salt and manganese salt in a container for coprecipitation reaction is changed for coprecipitation again, a cobalt-rich coating layer is formed on the surface of the precursor inner core by increasing the concentration of cobalt salt and reducing the concentration of manganese salt, a low-cobalt precursor is obtained, and finally lithium salt is added for sintering, so that the low-cobalt positive electrode active material with low cobalt inside and rich cobalt on the surface is obtained.
According to the preparation method, the fire sintering cladding is not needed, the concentration of metal salt is controlled only in a wet process stage, materials with different internal and external cobalt contents are generated through two coprecipitation reactions, the prepared low-cobalt precursor particles are uniform, the sphericity is good, the particle size distribution is narrow, the low-cobalt positive electrode active material is obtained through sintering of the low-cobalt precursor and lithium salt, the crystallinity and the interface stability of the low-cobalt positive electrode active material are controlled within the optimal range, the polarization of an electrochemical device is reduced, the dynamic performance of the electrochemical device is improved, and therefore the electrochemical device with excellent capacity, circulation, storage and other performances is obtained.
In the present invention, the mode of increasing the molar concentration of the cobalt salt and decreasing the molar concentration of the manganese salt is not particularly limited, and the coprecipitation reaction in the step (1) and the step (2) is performed in two reaction kettles, respectively, the precursor core in the step (1) is taken out from the reaction kettle, placed in another reaction kettle, and mixed with the nickel salt, the manganese salt, the cobalt salt, the complexing agent and the precipitant, wherein the molar concentration of the added cobalt salt is higher than that in the step (1), and the molar concentration of the added manganese salt is lower than that in the step (1), and then the coprecipitation reaction is performed to obtain the low cobalt precursor.
Preferably, the volume ratio of the precursor inner core to the low cobalt precursor is 1 (1.5 to 2.5), which may be, for example, 1:1.5, 1:1.8, 1:2, 1:2.2, or 1:2.5, etc.
According to the preparation method, the concentration of the metal salt is preferably changed when the volume of the precursor inner core grows to about half of the volume of the low-cobalt precursor, different reaction stages are set according to different particle sizes, and when the volume of the precursor inner core is larger, the cobalt content is higher, so that the preparation cost of the material is further increased; when the volume of the precursor is smaller, the capacity, dynamics and cycle performance of the material are affected.
In the invention, the low-cobalt precursor and the precursor core have high sphericity, the shape of the precursor core is spherical or spheroid, and when the volume ratio of the precursor core to the low-cobalt precursor is 1:2 by taking the spherical shape as an example, namely, the radius of the precursor core is (1/2) of the radius of the low-cobalt precursor 1/3 。
Preferably, the nickel salt of step (1) comprises nickel sulphate.
Preferably, the manganese salt of step (1) comprises manganese sulphate.
Preferably, the cobalt salt of step (1) comprises cobalt sulphate.
Preferably, the complexing agent of step (1) comprises aqueous ammonia.
Preferably, the precipitant of step (1) comprises sodium hydroxide.
In the present invention, the molar concentration of the complexing agent and the precipitant is not particularly limited, and the content thereof may satisfy the precipitation requirement, and the molar concentration of the complexing agent may be, for example, 1mol/L to 3mol/L, and the molar concentration of the precipitant may be 6mol/L to 12mol/L.
Preferably, step (2) increases the molar concentration of the cobalt salt, and after decreasing the molar concentration of the manganese salt, the ratio of the molar concentrations of the nickel salt, cobalt salt, and manganese salt is x:z (1-x-z), wherein 0.05.ltoreq.y < z.ltoreq.0.15, and z may be, for example, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, or the like.
As a preferable technical scheme of the preparation method, y is more than or equal to 0.05 and less than or equal to 0.1,0.1 and z is more than or equal to 0.15, and further preferable is that y is more than or equal to 0.09 and less than or equal to 0.1,0.14 and z is more than or equal to 0.15.
According to the invention, the content of cobalt in the core and the shell is further optimized, so that the cost of the NCM ternary material can be reduced, the capacity exertion can be ensured while the cost is reduced, and the dynamics and the cycle performance are improved; unlike fire sintering coating, the coating of cobalt in proper content on the precursor end can improve the defect of low fire capacity.
Preferably, after the coprecipitation reaction in step (2) and before the sintering in step (3), the low cobalt precursor is further subjected to washing, drying, batch mixing, sieving, demagnetizing and packaging.
Preferably, the molar ratio of the low cobalt precursor and lithium salt of step (3) is 1 (1.04 to 1.06), which may be, for example, 1:1.04, 1:1.045, 1:1.05, 1:1.055, 1:1.06, or the like.
Preferably, the sintering temperature in step (3) is 900 ℃ to 1000 ℃, and may be 900 ℃, 920 ℃, 940 ℃, 960 ℃, 980 ℃, 1000 ℃, or the like.
Preferably, the sintering time in step (3) is 10h to 20h, for example, 10h, 12h, 14h, 16h, 18h, 20h, or the like.
In a second aspect, the invention provides a low-cobalt positive electrode active material, which is prepared by adopting the preparation method according to the first aspect, wherein the low-cobalt positive electrode active material comprises a low-cobalt positive electrode active material inner core and a low-cobalt positive electrode active material outer shell coated on the surface of the low-cobalt positive electrode active material inner core;
the low-cobalt positive electrode active material inner core comprises LiNi x Co y Mn 1-x-y O 2 The low cobalt positive electrode active material shell comprises LiNi x Co z Mn 1-x-z O 2 Wherein x is more than or equal to 0.55 and less than or equal to 0.60,0.05 and y is more than or equal to 0.55 and less than or equal to 0.60,0.05<z≤0.15。
In the invention, the low-cobalt positive electrode active material is in a core-shell structure, the inner core is a low-cobalt component, the outer shell is a cobalt-rich component, the lithium ion diffusion rate of the single-component low-cobalt material is improved, the polarization and the internal resistance of the material are greatly reduced, and the gram capacity, the coulomb efficiency and the cycle performance of the material are improved.
Preferably, the total molar amount of cobalt in the low-cobalt positive electrode active material is 5% to 15%, for example, may be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, etc., based on the total molar amount of nickel, cobalt and manganese in the low-cobalt positive electrode active material being 100%. On the one hand, compared with the surface cobalt-rich positive electrode active material with the cobalt content increasing in a linear gradient manner from the inner core to the outer shell, on the other hand, the cobalt-rich region of the low-cobalt positive electrode active material is thicker, the polarization is lower during lithium removal, and the positive electrode active material is higher due to the fact that the cobalt content is increasing in a linear manner and the cobalt-rich region is thinner; on the other hand, from the viewpoint of a preparation method, the low-cobalt positive electrode active material disclosed by the invention is strong in operability and easy to adjust the size and morphology of a target product only by changing the concentration of the metal salt once, and if the cobalt content of the positive electrode active material is linearly increased or decreased, the concentration of the cobalt salt is gradually changed, so that the target product is easily achieved when the target product is not produced, or the target product cannot be produced when the target product is achieved, the production of the low-cobalt positive electrode active material with proper size and morphology is further influenced, and the electrochemical performance of the material is reduced.
Preferably, the surface of the low-cobalt positive electrode active material includes free lithium, and the content of lithium element in the free lithium is 150ppm to 1000ppm, for example, 150ppm, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1000ppm, or the like, based on the mass of the low-cobalt positive electrode active material.
In a third aspect, the present invention provides an electrochemical device comprising the low cobalt positive electrode active material according to the second aspect in a positive electrode of the electrochemical device.
The low-cobalt positive electrode active material has high crystallinity, stable low-cobalt interface structure, small polarization, small internal resistance and good dynamic performance, and an electrochemical device prepared by adopting the low-cobalt positive electrode active material has higher gram capacity, coulombic efficiency and cycle capacity retention rate.
In an alternative embodiment, the instant invention provides a method for detecting whether an electrochemical device comprises a low cobalt positive electrode active material according to the instant invention, comprising:
splitting the electrochemical device sample to obtain a positive electrode, washing the positive electrode by using a solvent, drying, scraping the surface of the positive electrode to obtain active material powder, performing an Inductively Coupled Plasma (ICP) test on the active material powder or cutting the particle section of the active material powder by using a focused ion beam, and matching with an EDS line scanning or surface scanning test to obtain the distribution condition and the content of each element;
when the test result shows that the particles in the active material powder are divided into an inner core and a coating layer, wherein the inner core and the coating layer both contain Ni, co and Mn, and the cobalt content in the inner core and the cobalt content in the outer part of the particles are obvious boundary lines, and the cobalt content in the inner core is lower than the cobalt content in the coating layer, so that the positive electrode of the electrochemical device sample can be confirmed to contain the low-cobalt positive electrode active material.
In an alternative embodiment, the present invention provides a method for preparing the positive electrode, including:
and mixing the low-cobalt positive electrode active material, the conductive agent and the binder with a solvent to obtain positive electrode slurry, coating the positive electrode slurry on an aluminum foil, and rolling to obtain the positive electrode.
Preferably, the conductive agent includes conductive carbon black (SP) and/or Carbon Nanotubes (CNT).
Preferably, the binder comprises polyvinylidene fluoride (PVDF).
Preferably, the mass ratio of the low cobalt positive electrode active material, SP, CNT, and PVDF is (90 to 99): 1:0.5:1, for example, may be 90:1:0.5:1, 92:1:0.5:1, 94:1:0.5:1, 96:1:0.5:1, 98:1:0.5:1, 99:1:0.5:1, or the like.
In an alternative embodiment, the electrochemical device is a lithium ion battery.
In an alternative embodiment, the negative electrode of the electrochemical device comprises graphite, SP, carboxymethylcellulose (CMC), and Styrene Butadiene Rubber (SBR), the mass ratio of graphite, SP, CMC, and SBR being (90 to 99): 1.5:2, for example, may be 90:1:1.5:2, 92:1:1.5:2, 94:1:1.5:2, 96:1:1.5:2, 98:1:1.5:2, or 99:1:1.5:2, etc.
In an alternative embodiment, the electrolyte of the electrochemical device includes a lithium salt and a solvent.
In an alternative embodiment, the lithium salt comprises LiPF 6 。
In an alternative embodiment, the lithium salt is present in an amount of 4wt% to 24wt%, such as 4wt%, 8wt%, 10wt%, 15wt%, 20wt%, 24wt%, etc., based on 100wt% of the electrolyte.
In an alternative embodiment, the solvent includes at least one or a combination of any two of Ethylene Carbonate (EC), ethylmethyl carbonate (EMC), dimethyl carbonate (DMC) and Polycarbonate (PC), for example, a combination of EC and EMC, a combination of DMC and PC, a combination of EC, EMC and DMC, or a combination of EC, EMC, DMC and PC, etc.
In an alternative embodiment, the mass ratio of EC, EMC, DMC to PC in the solvent is (2 to 4): 3 to 5): 2 to 4): 0 to 1, the selection range of EC (2 to 4) may be, for example, 2, 2.5, 3, 3.5 or 4, etc., the selection range of EMC (3 to 5) may be, for example, 3, 3.5, 4, 4.5 or 5, etc., the selection range of DMC (2 to 4) may be, for example, 2, 2.5, 3, 3.5 or 4, etc., the selection range of PC (0 to 1) may be, for example, 0, 0.1, 0.2, 0.3, 0.5, 0.7 or 1, etc., and when PC is 0, it means that PC is not contained in the solvent.
In an alternative embodiment, the separator of the electrochemical device has a thickness of 9 μm to 18 μm, for example, 9 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, or the like.
In an alternative embodiment, the separator of the electrochemical device has an air permeability of 180s/100mL to 380s/100mL, and may be, for example, 180s/100mL, 200s/100mL, 240s/100mL, 250s/100mL, 280s/100mL, 300s/100mL, 250s/100mL, 380s/100mL, or the like.
In an alternative embodiment, the porosity of the separator of the electrochemical device is 30% to 50%, for example, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48% or 50%, etc.
In the present invention, the method of assembling an electrochemical device using the positive electrode, the negative electrode and the separator is the prior art, and those skilled in the art can assemble the electrochemical device by referring to the methods disclosed in the prior art. Taking a lithium ion battery as an example, sequentially winding or stacking a positive electrode, a diaphragm and a negative electrode to form a battery core, filling the battery core into a battery shell, injecting electrolyte, forming, and packaging to obtain the electrochemical device.
The membrane with proper parameters is matched with the positive electrode and the negative electrode to prepare the electrochemical device, so that the capacity and the cycling stability of the electrochemical device are improved.
In a fourth aspect, the present invention provides an electronic device comprising the electrochemical apparatus according to the third aspect.
The electronic device according to the invention may be, for example, a mobile computer, a cellular phone, a memory card, a liquid crystal television, an automobile, a motorcycle, a motor, a timepiece, a camera, etc.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method, the fire sintering cladding is not needed, the concentration of metal salt is controlled only in a wet process stage, materials with different internal and external cobalt contents are generated through two coprecipitation reactions, the prepared low-cobalt precursor particles are uniform, the sphericity is good, the particle size distribution is narrow, the low-cobalt positive electrode active material is obtained through sintering of the low-cobalt precursor and lithium salt, the crystallinity and the interface stability of the low-cobalt positive electrode active material are controlled within the optimal range, the polarization of an electrochemical device is reduced, the dynamic performance of the electrochemical device is improved, and therefore the electrochemical device with excellent capacity, circulation, storage and other performances is obtained.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
Example 1
The embodiment provides a preparation method of a low-cobalt positive electrode active material, which comprises the following steps:
(1) Adding nickel sulfate, cobalt sulfate, manganese sulfate, ammonia water and sodium hydroxide into a reaction kettle, performing coprecipitation reaction, and stopping the reaction when the volume of the product of the coprecipitation reaction is half of the volume of the target product to obtain the precursor inner core Ni 58 Co 10 Mn 32 (OH) 2 ；
(2) Taking out the precursor core in the step (1), mixing with nickel sulfate, cobalt sulfate, manganese sulfate, ammonia water and sodium hydroxide in another reaction kettle, and performing coprecipitation reaction again to obtain Ni 58 Co 10 Mn 32 (OH) 2 Surface generation Ni 58 Co 12 Mn 30 (OH) 2 Obtaining a low-cobalt precursor, wherein the volume of the low-cobalt precursor is 2 times of the volume of the precursor core;
(3) Mixing the low-cobalt precursor in the step (2) and lithium hydroxide according to a molar ratio of 1:1.05, and sintering for 17 hours at 950 ℃ to obtain a low-cobalt positive electrode active material;
wherein the molar concentration ratio of nickel sulfate, cobalt sulfate and manganese sulfate in the reaction kettle in the step (1) is 0.58:0.1:0.32, and the molar concentration ratio of nickel sulfate, cobalt sulfate and manganese sulfate in the reaction kettle in the step (2) is 0.58:0.12:0.3.
The low-cobalt positive electrode active material prepared in the embodiment comprises a low-cobalt positive electrode active material core LiNi 0.58 Co 0.1 Mn 0.32 O 2 And a low-cobalt positive electrode active material shell LiNi coated on the surface of the low-cobalt positive electrode active material inner core 0.58 Co 0.12 Mn 0.3 O 2 The surface of the low-cobalt positive electrode active material also comprises free lithium, and the content of lithium element in the free lithium is 338ppm based on the mass of the low-cobalt positive electrode active material.
1. Assembly of lithium ion batteries
(1) Preparation of positive electrode: mixing the low-cobalt positive electrode active materials, SP, CNT and PVDF prepared in the examples and the comparative examples according to the mass ratio of 97.5:1:0.5:1 with Nitrogen Methyl Pyrrolidone (NMP) to prepare positive electrode slurry, coating the positive electrode slurry on aluminum foil, and rolling to obtain a positive electrode;
(2) Preparation of the negative electrode: mixing graphite, SP, CMC and SBR according to the mass ratio of 95.5:1:1.5:2 to prepare slurry, coating the slurry on copper foil, and rolling to obtain a negative electrode;
(3) Preparation of a lithium ion battery: the positive electrode lug made of aluminum is stuck on the positive electrode,a copper negative electrode lug is adhered to a negative electrode, a diaphragm with the thickness of 10 mu m, the air permeability of 200s/100mL and the porosity of 40% is selected, a positive electrode, the diaphragm and the negative electrode are sequentially and tightly stacked together, and a solute of 5wt% LiPF is injected at two sides of the diaphragm 6 And the solvent is EC, EMC, DMC and PC electrolyte with the mass ratio of 3:4:3:0.5 to obtain a battery cell, and the battery cell is stacked to the required layer number to obtain the lithium ion battery.
2. Performance testing
(1) Test of low cobalt positive electrode active material:
the method for testing the cobalt element in the low-cobalt positive electrode active material comprises the following steps: the powder particles were cut by a focused ion beam method, and then the distribution of cobalt element was tested by a time-of-flight secondary ion mass spectrometer.
Testing the free lithium content of the surface of the low-cobalt positive electrode active material: placing 1g of low-cobalt positive electrode active material powder into deionized water, stirring for 5 minutes by a glass rod, standing for 4 hours, taking supernatant, and testing LiOH and Li by using a potentiometric titrator 2 CO 3 The content of lithium element is the content of free lithium coated on the surface.
(2) Testing of lithium ion batteries:
performing a first discharge gram capacity test and an 800-cycle capacity retention test by using a Cheng Hong electric appliance stock electric company battery performance test system (equipment model: BTS05/10C 8D-HP);
the first discharge gram capacity test method comprises the following steps: charging and discharging for one week in a charging and discharging mode of 0.063A/g at 25 ℃ with a voltage interval of 2.8V to 4.35V, and dividing the obtained charge and discharge capacity by the positive electrode usage amount to obtain the first charge/discharge gram capacity; the first discharge capacity divided by the first charge capacity is the first coulombic efficiency.
The cyclic capacity retention test method: at 25 ℃, the cycle is carried out in a charge-discharge system of 0.19A/g (calculated by the mass of the positive electrode material), and the voltage interval is 2.8V to 4.35V. After cycling to 800 weeks, dividing the discharge capacity of the battery at the moment by the discharge capacity of the first cycle, namely the 800-cycle capacity retention rate of the battery.
Examples 2 to 7 and comparative examples 1 to 2 were subjected to parameter modification based on the procedure of example 1, and the specifically modified parameters and test results are shown in tables 1 to 4.
TABLE 1
TABLE 2
As can be seen from the comparison of the examples 1 and 4 to 5 in Table 2, when the volume ratio of the precursor inner core to the low cobalt precursor is 1 (1.5 to 2.5), the prepared material can be low in cost and has the best electrochemical performance; in the embodiment 4, the precursor has larger core, the prepared low-cobalt positive electrode active material has larger core than the shell, the preparation cost of the product is increased, and the capacity and the cycle performance of the material are not obviously improved; in example 5, the precursor core is smaller, the prepared low-cobalt positive electrode active material core is smaller, and the prepared low-cobalt positive electrode active material core is more outer shell, so that the capacity, the dynamic performance and the cycle performance of the material are affected, therefore, in example 1, the initial discharge gram capacity, the coulombic efficiency and the 800-cycle capacity retention rate of the prepared low-cobalt positive electrode active material are best by adopting the proper precursor core and low-cobalt precursor volume ratio.
TABLE 3 Table 3
As is apparent from a comparison of example 1 and examples 6 to 7 in Table 3, the metal salt concentration in the co-precipitation of the step (1) and the step (2) is adjusted in the present invention, so that the outer shell and the inner core in the low cobalt positive electrode active material have a specific cobalt content, and the inner core and the outer shell are matched, so that the gram capacity, the coulombic efficiency and the capacity retention rate of the material are further improved. The low cobalt positive electrode active material prepared in example 1 has a cobalt content of both the outer shell and the inner core within an optimal range, and thus, the capacity and the cycle stability of example 1 are higher than those of examples 6 to 7.
Comparative example 1
Eliminating the operation of the step (2), and after sintering in the step (3), mixing the sintered product with LiNi 58 Co 12 Mn 30 O 2 The mixture was sintered at 650℃for 6 hours, and the rest was the same as in example 1.
Comparative example 2
The procedure of example 1 was repeated except that the step (2) was not performed.
TABLE 4 Table 4
As can be seen from a comparison of example 1 and comparative examples 1 to 2 in table 4, the first discharge capacity, the coulombic efficiency and the cycle capacity retention rate were all affected by the firing process to produce a low cobalt positive electrode active material having a cobalt-rich surface, or by the single-step coprecipitation process alone. In comparative example 1, a layer of cobalt-rich material was directly sintered on the surface of the precursor core obtained by precipitation, and in comparative example 2, no secondary co-precipitation was performed, and no surface cobalt-rich structure was provided, and the electrochemical properties were significantly different from those of example 1.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (9)
1. A method for preparing a low-cobalt positive electrode active material, which is characterized by comprising the following steps:
(1) Mixing nickel salt, cobalt salt, manganese salt, a complexing agent and a precipitator, and performing coprecipitation reaction to obtain a precursor inner core;
(2) Increasing the molar concentration of the cobalt salt, reducing the molar concentration of the manganese salt, and performing coprecipitation reaction to obtain a low cobalt precursor;
(3) Mixing the low-cobalt precursor with lithium salt, and sintering to obtain the low-cobalt positive electrode active material;
the molar concentration ratio of the nickel salt, the cobalt salt and the manganese salt in the step (1) is x, wherein x is more than or equal to 0.55 and less than or equal to 0.60,0.05, and y is more than or equal to 0.15;
step (2) increasing the molar concentration of the cobalt salt, and reducing the molar concentration of the manganese salt, wherein the ratio of the molar concentrations of the nickel salt, the cobalt salt and the manganese salt is x to z (1-x-z), wherein y is more than or equal to 0.05 and less than or equal to 0.15;
the volume ratio of the precursor inner core to the low-cobalt precursor is 1 (1.5 to 2.5);
the molar concentration of the cobalt salt in the step (2) is increased in a non-gradient manner, and the molar concentration of the manganese salt is reduced in a non-gradient manner.
2. The production method according to claim 1, wherein the nickel salt, manganese salt, cobalt salt, complexing agent and precipitant of step (1) satisfy any one of the following conditions (a) to (e):
(a) The nickel salt comprises nickel sulfate;
(b) The manganese salt comprises manganese sulfate;
(c) The cobalt salt comprises cobalt sulfate;
(d) The complexing agent comprises ammonia water;
(e) The precipitant includes sodium hydroxide.
3. The production method according to claim 1, wherein step (2) increases the molar concentration of the cobalt salt, and after decreasing the molar concentration of the manganese salt, the cobalt salt and the manganese salt satisfy: y is more than or equal to 0.05 and less than or equal to 0.1,0.1, and z is more than or equal to 0.15.
4. The method according to claim 3, wherein step (2) increases the molar concentration of the cobalt salt, and after decreasing the molar concentration of the manganese salt, the cobalt salt and the manganese salt satisfy: y is more than or equal to 0.09 and less than or equal to 0.1,0.14, and z is more than or equal to 0.15.
5. The production method according to claim 1, wherein step (3) satisfies any one of the following conditions (h) to (i):
(h) The molar ratio of the low cobalt precursor to the lithium salt is 1 (1.04 to 1.06);
(i) The sintering temperature is 900-1000 ℃;
(j) The sintering time is 10 to 20 hours.
6. A low-cobalt positive electrode active material, characterized in that the low-cobalt positive electrode active material is prepared by the preparation method according to any one of claims 1 to 5, and the low-cobalt positive electrode active material comprises a low-cobalt positive electrode active material inner core and a low-cobalt positive electrode active material outer shell coated on the surface of the low-cobalt positive electrode active material inner core;
the low-cobalt positive electrode active material inner core comprises LiNi x Co y Mn 1-x-y O 2 The low cobalt positive electrode active material shell comprises LiNi x Co z Mn 1-x-z O 2 Wherein x is more than or equal to 0.55 and less than or equal to 0.60,0.05 and y is more than or equal to 0.55 and less than or equal to 0.60,0.05<z≤0.15。
7. The low-cobalt positive electrode active material according to claim 6, wherein the surface of the low-cobalt positive electrode active material comprises free lithium, and the content of lithium element in the free lithium is 150ppm to 1000ppm based on the mass of the low-cobalt positive electrode active material.
8. An electrochemical device characterized in that the low-cobalt positive electrode active material according to claim 6 or 7 is included in a positive electrode of the electrochemical device.
9. An electronic device, characterized in that the electrochemical device according to claim 8 is included in the electronic device.
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