CN115490277B - Magnetic field modified ternary material for lithium ion battery and preparation method thereof - Google Patents
Magnetic field modified ternary material for lithium ion battery and preparation method thereof Download PDFInfo
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- CN115490277B CN115490277B CN202211210754.0A CN202211210754A CN115490277B CN 115490277 B CN115490277 B CN 115490277B CN 202211210754 A CN202211210754 A CN 202211210754A CN 115490277 B CN115490277 B CN 115490277B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 32
- 150000001768 cations Chemical class 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 230000008092 positive effect Effects 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 229910017226 Ni0.8Co0.1Mn0.1CO3 Inorganic materials 0.000 description 5
- 241000080590 Niso Species 0.000 description 5
- 238000005056 compaction Methods 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000003028 elevating effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- -1 cobalt-based Chemical class 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a magnetic field modified ternary material for a lithium ion battery and a preparation method thereof, and the specific method is that a nickel source, a cobalt source, a manganese source and water are mixed and stirred to form a uniform ion solution; dissolving sodium carbonate in water, adding a complexing agent to control the pH of the solution to be 11-12, adding sodium dodecyl benzene sulfonate, uniformly mixing, then mixing with an ion solution, heating for reaction, applying a magnetic field at the same time, washing and drying a product after the reaction is finished to obtain a precursor material, mixing the precursor material with a lithium source, and calcining and grinding to obtain the magnetic field modified ternary material of the lithium ion battery. By matching the external magnetic field with the hydrothermal reaction, the positive effect of the magnetic field on the hydrothermal reaction is fully utilized, and the prepared ternary material has the advantages of uniform appearance, similar size, good conductivity and electrochemical performance, better multiplying power performance and cycling stability, and wide application prospect in the fields of preparation of electrode materials of lithium ion batteries and the like.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a magnetic field modified ternary material for a lithium ion battery and a preparation method thereof.
Background
Energy is an important foundation for promoting the development of human civilization, and every great progress of society is not separated from the improvement and replacement of energy technology. However, the great consumption of fossil fuels in the industrial society causes the problems of environmental pollution, greenhouse effect, and resource exhaustion, which are increasingly serious at present. In order to realize long-term sustainable development and protect natural resources and environments for human survival, development and application of novel clean energy are important challenges facing the society today. In a lithium ion battery, a positive electrode material is the most critical component, and in order to improve the performance of the lithium ion battery, the positive electrode material is required to have high specific capacity, high electrode potential, good charge-discharge reversibility, stable structure, small charge-discharge lattice change and Li + Fast insertion and extraction, low specific surface area, good compatibility with electrolyte, rich reserves, low price and the like. Through a great deal of attempts, the current research on cathode materials is mainly focused on transition metal lithium intercalation compounds, including cobalt-based, nickel-based, manganese-based and other materials. NCM (NCM) 811 Is considered to be the most promising high specific energy cathode material. Wherein nickel is used as the elementThe main redox active element benefits from Ni 2+ /Ni 4+ The double electron transfer process of (2) can provide high capacity, but the improvement of nickel content in the material can cause the reduction of structural stability, the aggravation of electrode/electrolyte interface side reaction and the severe change of intercalation and deintercalation crystal lattice along with lithium ions, so that poor cycle stability and rate capability seriously limit the large-scale commercial process.
NCM 811 Different synthetic methods have important effects on the structure, composition and morphology of the material. The magnetic field can be used for controlling chemical reaction under the same conditions as temperature and pressure in the traditional preparation, and has great influence on the conductivity, crystal form and morphology of the product.
Disclosure of Invention
Aiming at the problems of poor cycle stability and rate capability of a nickel-cobalt-manganese lithium battery in the prior art, the invention provides a magnetic field modified ternary material for a lithium ion battery and a preparation method thereof, and the prepared ternary material has uniform morphology, similar size, good conductivity and electrochemical performance and inhibits Ni to a certain extent 3+ To Ni 2+ Reducing cation mixing, stabilizing lamellar structure and elevating Li + Diffusion rate and rate capability in the lattice.
The invention is realized by the following technical scheme:
a preparation method of a magnetic field modified lithium ion battery ternary material comprises the following steps:
(1) Mixing a nickel source, a cobalt source, a manganese source and water, and stirring to form a uniform ion solution;
(2) Dissolving sodium carbonate in water, adding a complexing agent to control the pH of the solution to be 11-12, then adding sodium dodecyl benzene sulfonate, and uniformly mixing;
(3) Mixing the mixed solution in the step (2) with the ionic solution in the step (1), heating for reaction, applying a magnetic field at the same time, washing a product after the reaction is finished, and drying to obtain a precursor material;
(4) And (3) mixing the precursor material in the step (3) with a lithium source, and calcining and grinding to obtain the magnetic field modified ternary material of the lithium ion battery.
Further, in the step (1), the molar ratio of metal cations in the nickel source, the cobalt source and the manganese source is 8:1:1.
Further, the molar ratio of the sodium carbonate in the step (2) to the metal cations in the ion solution is 1-1.5:1, and the adding amount of the sodium dodecyl benzene sulfonate is 0.5-5% of the mass of the sodium carbonate.
Further, the complexing agent in the step (2) is ammonia water.
Further, the heating reaction in the step (3) is oil bath heating, the heating temperature is 120-180 ℃, and the magnetic field strength is 3-15mT; the heating reaction and the time of applying the magnetic field are 8-15 h.
Further, the magnetic field in the step (3) is formed by winding an enameled wire into an electromagnetic coil and then externally connecting a magnetic field formed by a direct current power supply.
Further, the molar ratio of the precursor material in the step (4) to the cations in the lithium source is 1:1.05-1.1.
Further, the calcination in the step (4) is two-stage calcination, wherein the calcination is performed for 3-8 hours at 450-550 ℃, the calcination is performed for 8-12 hours at 800-900 ℃, and the temperature rising rate is 3-8 ℃/min.
Further, the nickel source is more than one of nickel nitrate, nickel sulfate and nickel chloride; the cobalt source is more than one of cobalt nitrate, cobalt sulfate and cobalt chloride; the manganese source is more than one of manganese nitrate, manganese sulfate and manganese chloride; the lithium source is lithium carbonate.
In the invention, the magnetic field modified ternary material of the lithium ion battery prepared by the preparation method has better multiplying power performance and cycle stability, and has wide application prospect in the fields of preparation of electrode materials of the lithium ion battery and the like.
Advantageous effects
The invention combines the external magnetic field and the hydrothermal reaction, fully utilizes the positive effect of the magnetic field on the hydrothermal reaction, and prepares the ternary material with uniform morphology and dimension phaseNear, the conductivity and the electrochemical performance are good, and Ni is inhibited to a certain extent 3+ To Ni 2+ Reducing cation mixing, stabilizing lamellar structure and elevating Li + The diffusion rate and the multiplying power performance in the crystal lattice are better, and the multiplying power performance and the circulation stability performance are better, and the application prospect in the fields of preparation of lithium ion battery electrode materials and the like is wide.
Drawings
FIG. 1 is an SEM image of a magnetic field modified ternary lithium ion battery material prepared in example 1;
FIG. 2 is a magnification view of the ternary material of the magnetic field modified lithium ion battery prepared in example 1;
fig. 3 is a cycle chart of the magnetic field modified lithium ion battery ternary material prepared in example 1.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
(1) Weighing 0.8mol of NiSO 4 ·6H 2 O、0.1molCoSO 4 ·7H 2 O and 0.1mol MnSO 4 Adding distilled 250mL of water for dissolution to form uniform ionic solution;
(2) Weighing 12.7g of sodium carbonate powder, dissolving in 100mL of distilled water, adding 25% ammonia water to control the pH of the solution to be 12, then adding 0.2g of sodium dodecyl benzene sulfonate, and uniformly mixing;
(3) Mixing the mixed solution in the step (2) with the ionic solution in the step (1), transferring into an oil bath, heating to 180 ℃, simultaneously applying a magnetic field with the external magnetic field strength of 15mT, reacting for 10 hours, washing the product until the pH of the washing solution is neutral after the reaction is finished, and then placing in a vacuum drying oven for drying to obtain Ni 0.8 Co 0.1 Mn 0.1 CO 3 A precursor;
(4) Ni in step (3) 0.8 Co 0.1 Mn 0.1 CO 3 The precursor is fully mixed with lithium carbonate, lithiumThe molar ratio of the ions to the precursor is 1.05:1, the mixture is transferred into a corundum sagger for compaction, and the sagger is transferred into a sintering furnace for O 2 Two-stage sintering is carried out under the atmosphere, the temperature is kept for 5 hours at 500 ℃ to ensure that the precursor is dehydrated and decomposed into oxide and Li 2 CO 3 Fully melting, continuously heating to 850 ℃ and preserving heat for 10h to ensure that the precursor and Li 2 CO 3 Fully reacting, wherein the heating rate is 5 ℃/min, crushing the sintered product, and sieving the crushed product with a 350-mesh sieve to obtain the magnetic field modified ternary material of the lithium ion battery, and the SEM (scanning electron microscope) graph of the ternary material is shown in figure 1 and is of a uniform spherical structure.
The magnetic field modified ternary material of the lithium ion battery prepared in example 1 is used as a positive electrode material of the lithium ion battery, the electrochemical performance is tested, the rate performance diagram is shown in fig. 2, and the charge-discharge cycle diagram is shown in fig. 3. The magnetic field modified lithium ion battery ternary material prepared in example 1 has a 0.1C initial discharge specific capacity of 195.5 mAh/g and a charge-discharge efficiency of 86%; after 200 cycles of current at 0.5C, the capacity retention was 88.1%.
Example 2
(1) Weighing 0.8mol of NiSO 4 ·6H 2 O、0.1molCoSO 4 ·7H 2 O and 0.1mol MnSO 4 Adding 250mL of distilled water for dissolution to form uniform ion solution;
(2) Weighing 0.3g of sodium carbonate powder, dissolving in 100mL of distilled water, adding 25% ammonia water to control the pH of the solution to be 11, then adding 0.3g of sodium dodecyl benzene sulfonate, and uniformly mixing;
(3) Mixing the mixed solution in the step (2) with the ionic solution in the step (1), transferring into an oil bath, heating to 150 ℃, simultaneously applying a magnetic field with the external magnetic field strength of 6mT, reacting for 15 hours, washing the product until the pH of the washing solution is neutral after the reaction is finished, and then placing in a vacuum drying oven for drying to obtain Ni 0.8 Co 0.1 Mn 0.1 CO 3 A precursor;
(4) Ni in step (3) 0.8 Co 0.1 Mn 0.1 CO 3 The precursor and lithium carbonate are fully mixed, the molar ratio of lithium ions to the precursor is 1.1:1, and the mixture is transferred into a corundum sagger for compaction, and the mixture is in a box shapeTransferring the pot to a sintering furnace in O 2 And (3) performing two-stage sintering under the atmosphere, preserving heat for 5 hours at 500 ℃, continuously heating to 850 ℃ and preserving heat for 10h, wherein the heating rate is 5 ℃/min, crushing the sintered product, and sieving with a 350-mesh sieve to obtain the magnetic field modified ternary material of the lithium ion battery.
The magnetic field modified lithium ion battery ternary material prepared in the embodiment 2 is used as a positive electrode material of a lithium ion battery, the electrochemical performance is tested, the initial discharge specific capacity of 0.1C is 192.3mAh/g mAh/g, and the charge-discharge efficiency is 84%; after 200 cycles of current at 0.5C, the capacity retention was 85%.
Example 3
(1) Weighing 0.8mol of NiSO 4 ·6H 2 O、0.1molCoSO 4 ·7H 2 O and 0.1mol MnSO 4 Adding 250mL of distilled water for dissolution to form uniform ion solution;
(2) 12.7g of sodium carbonate powder is weighed and dissolved in 100mL of distilled water, 25% ammonia water is added to control the pH of the solution to 11, then 0.2g of sodium dodecyl benzene sulfonate is added to the solution, and the solution is uniformly mixed;
(3) Mixing the mixed solution in the step (2) with the ionic solution in the step (1), transferring into an oil bath, heating to 180 ℃, simultaneously applying a magnetic field with the external magnetic field strength of 9mT, reacting for 10 hours, washing the product until the pH of the washing solution is neutral after the reaction is finished, and then placing in a vacuum drying oven for drying to obtain Ni 0.8 Co 0.1 Mn 0.1 CO 3 A precursor;
(4) Ni in step (3) 0.8 Co 0.1 Mn 0.1 CO 3 Fully mixing the precursor and lithium carbonate, wherein the molar ratio of lithium ions to the precursor is 1.05:1, transferring the mixture into a corundum sagger for compaction, transferring the sagger into a sintering furnace, and placing the sagger into O 2 And (3) performing two-stage sintering under the atmosphere, preserving heat for 5 hours at 500 ℃, continuously heating to 850 ℃ and preserving heat for 10h, wherein the heating rate is 5 ℃/min, crushing the sintered product, and sieving with a 350-mesh sieve to obtain the magnetic field modified ternary material of the lithium ion battery.
The magnetic field modified lithium ion battery ternary material prepared in example 3 is used as a positive electrode material of a lithium ion battery, electrochemical performance is tested, the initial discharge specific capacity of 0.1C is 197.6mAh/g, the charge and discharge efficiency is 88%, and after 200 times of current circulation of 0.5C, the capacity retention rate is 89%.
Example 4
(1) Weighing 0.8mol of NiSO 4 ·6H 2 O、0.1molCoSO 4 ·7H 2 O and 0.1mol MnSO 4 Adding 250mL of distilled water for dissolution to form uniform ion solution;
(2) Weighing 12.7g of sodium carbonate powder, dissolving in 100mL of distilled water, adding 25% ammonia water to control the pH of the solution to be 11-12, then adding 0.4g of sodium dodecyl benzene sulfonate, and uniformly mixing;
(3) Mixing the mixed solution in the step (2) with the ionic solution in the step (1), transferring to an oil bath kettle, heating to 160 ℃, simultaneously applying a magnetic field with the external magnetic field strength of 12mT, reacting for 12 hours, washing the product until the pH of the washing solution is neutral after the reaction is finished, and then placing in a vacuum drying oven for drying to obtain Ni 0.8 Co 0.1 Mn 0.1 CO 3 A precursor;
(4) Ni in step (3) 0.8 Co 0.1 Mn 0.1 CO 3 Fully mixing the precursor and lithium carbonate, wherein the molar ratio of lithium ions to the precursor is 1.05:1, transferring the mixture into a corundum sagger for compaction, transferring the sagger into a sintering furnace, and placing the sagger into O 2 And (3) performing two-stage sintering under the atmosphere, preserving heat for 5 hours at 500 ℃, continuously heating to 850 ℃ and preserving heat for 10h, wherein the heating rate is 5 ℃/min, crushing the sintered product, and sieving with a 350-mesh sieve to obtain the magnetic field modified ternary material of the lithium ion battery.
The magnetic field modified lithium ion battery ternary material prepared in the embodiment 4 is used as a positive electrode material of a lithium ion battery, and the electrochemical performance is tested, wherein the initial discharge specific capacity of 0.1C is 188.9mAh/g, and the charge-discharge efficiency is 86%; after 200 cycles of current at 0.5C, the capacity retention was 87%.
Comparative example 1
(1) Weighing 0.8mol of NiSO 4 ·6H 2 O、0.1molCoSO 4 ·7H 2 O and 0.1mol MnSO 4 Adding 250mL of distilled water for dissolution to form uniform ion solution;
(2) Weighing 12.7g of sodium carbonate powder, dissolving in 100mL of distilled water, adding 25% ammonia water to control the pH of the solution to be 12, then adding 0.2g of sodium dodecyl benzene sulfonate, and uniformly mixing;
(3) Mixing the mixed solution in the step (2) with the ionic solution in the step (1), transferring into an oil bath, heating and reacting for 10 hours, washing the product until the pH value of the washing solution is neutral after the reaction is finished, and then placing the washing solution into a vacuum drying oven for drying to obtain Ni 0.8 Co 0.1 Mn 0.1 CO 3 A precursor;
(4) Ni in step (3) 0.8 Co 0.1 Mn 0.1 CO 3 Fully mixing the precursor and lithium carbonate, wherein the molar ratio of lithium ions to the precursor is 1.05:1, transferring the mixture into a corundum sagger for compaction, transferring the sagger into a sintering furnace, and placing the sagger into O 2 And (3) performing two-stage sintering under the atmosphere, preserving heat for 5 hours at 500 ℃, continuously heating to 850 ℃ and preserving heat for 10h, wherein the heating rate is 5 ℃/min, crushing the sintered product, and sieving with a 350-mesh sieve to obtain the ternary material of the lithium ion battery.
The ternary material of the lithium ion battery prepared in the comparative example 1 is used as a positive electrode material of the lithium ion battery, and the electrochemical performance is tested, wherein the initial discharge specific capacity of 0.1C is 180.6mAh/g, and the charge-discharge efficiency is 81%; after 200 cycles of current at 0.5C, the capacity retention was 82%.
Claims (8)
1. The preparation method of the magnetic field modified lithium ion battery ternary material is characterized by comprising the following steps of:
(1) Mixing a nickel source, a cobalt source, a manganese source and water, and stirring to form a uniform ion solution;
(2) Dissolving sodium carbonate in water, adding a complexing agent to control the pH of the solution to be 11-12, then adding sodium dodecyl benzene sulfonate, and uniformly mixing;
(3) Mixing the mixed solution in the step (2) with the ionic solution in the step (1), heating for reaction, applying a magnetic field at the same time, washing a product after the reaction is finished, and drying to obtain a precursor material;
(4) Mixing the precursor material in the step (3) with a lithium source, and calcining and grinding to obtain a magnetic field modified ternary material of the lithium ion battery;
the molar ratio of the sodium carbonate to the metal cations in the ion solution in the step (2) is 1-1.5:1, and the addition amount of the sodium dodecyl benzene sulfonate is 0.5-5% of the mass of the sodium carbonate;
the heating reaction in the step (3) is oil bath heating, the heating temperature is 120-180 ℃, and the magnetic field strength is 3-15mT; the heating reaction and the time of applying the magnetic field are 8-15 h.
2. The method for preparing the magnetic field modified ternary material for the lithium ion battery, according to claim 1, wherein in the step (1), the molar ratio of metal cations in a nickel source, a cobalt source and a manganese source is 8:1:1.
3. The method for preparing the magnetic field modified ternary material for the lithium ion battery according to claim 1, wherein the complexing agent in the step (2) is ammonia water.
4. The method for preparing the magnetic field modified ternary material for the lithium ion battery according to claim 1, wherein the magnetic field in the step (3) is formed by winding an enameled wire into an electromagnetic coil and then externally connecting a magnetic field formed by a direct current power supply.
5. The method for preparing the magnetic field modified ternary material for the lithium ion battery according to claim 1, wherein the molar ratio of the precursor material in the step (4) to cations in the lithium source is 1:1.05-1.1.
6. The preparation method of the magnetic field modified lithium ion battery ternary material according to claim 1, wherein the calcination in the step (4) is two-stage calcination, wherein the calcination is performed at 450-550 ℃ for 3-8 hours, the calcination is performed at 800-900 ℃ for 8-12 hours, and the heating rate is 3-8 ℃/min.
7. The method for preparing the magnetic field modified lithium ion battery ternary material according to claim 1, wherein the nickel source is more than one of nickel nitrate, nickel sulfate and nickel chloride; the cobalt source is more than one of cobalt nitrate, cobalt sulfate and cobalt chloride; the manganese source is more than one of manganese nitrate, manganese sulfate and manganese chloride; the lithium source is lithium carbonate.
8. A magnetic field modified lithium ion battery ternary material prepared by the preparation method of any one of claims 1-7.
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