CN115490277A - 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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- 239000000463 material Substances 0.000 title claims abstract description 53
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 32
- 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 28
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 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
- 238000000034 method Methods 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
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 10
- 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
- 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
- 238000004804 winding Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 230000008092 positive effect Effects 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 229910017226 Ni0.8Co0.1Mn0.1CO3 Inorganic materials 0.000 description 5
- 241000080590 Niso Species 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion 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
- 230000005540 biological transmission Effects 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
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process 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
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 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
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- 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
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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
- H01M4/362—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
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- 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
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Abstract
The invention discloses a magnetic field modified ternary material for a lithium ion battery and a preparation method thereof, and the specific method comprises the steps of mixing a nickel source, a cobalt source, a manganese source and water, and stirring to form a uniform ionic solution; dissolving sodium carbonate in water, adding a complexing agent to control the pH value of the solution to be 11-12, then adding sodium dodecyl benzene sulfonate, uniformly mixing, then mixing with an ionic solution, heating for reaction, simultaneously applying a magnetic field, washing a product after the reaction is finished, drying 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 for the lithium ion battery. By matching the external magnetic field with the hydrothermal reaction and fully utilizing the positive effect of the magnetic field on the hydrothermal reaction, the prepared ternary material has the advantages of uniform appearance, similar size, good conductivity and electrochemical performance, better rate capability and cycle stability, and wide application prospect in the fields of lithium ion battery electrode material preparation 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 major progress of society does not leave improvement and replacement of energy technology. However, due to the large consumption of fossil fuels in industrial society, there are serious problems such as environmental pollution, greenhouse effect, and resource exhaustion. In order to realize long-term sustainable development and protect natural resources and environment on which human beings depend, the development and application of new clean energy is a major challenge facing the present society. In the lithium ion battery, the anode material is the most critical component, and in order to improve the performance of the lithium ion battery, the anode 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 and electron transmission, low specific surface area, good compatibility with electrolyte, rich reserves, low price and the like. Through a lot of attempts, the current research on the anode materials mainly focuses on the transition metal lithium intercalation compounds, including cobalt-based, nickel-based, manganese-based materials, and the like. NCM 811 Are considered to be the most promising high specific energy positive electrode materials. Wherein nickel is used as the main oxidation-reduction active element and benefits from Ni 2+ /Ni 4+ The double electron transfer process can provide high capacity, but the improvement of the nickel content in the material can cause the reduction of the structural stability, the aggravation of electrode/electrolyte interface side reaction and the violent change of the insertion and extraction crystal lattice along with lithium ions, so that the poor cycle stability and rate capability are caused, and the large-scale commercial process of the material is severely restricted.
NCM 811 Different synthetic methods have important influence on the structure, composition and morphology of the material. The magnetic field can be used to control chemical reaction, which has great influence on the conductivity, crystal form and shape of product, and the invention combines hydrothermal reaction and magnetic fieldThe optimization design of the material and the development of new functional materials have great significance.
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 ternary material of a magnetic field modified lithium ion battery and a preparation method thereof, and the prepared ternary material has uniform appearance, similar size, good conductivity and electrochemical performance and can inhibit Ni to a certain extent 3+ To Ni 2+ Reducing cation miscarrying, stabilizing the layered structure and increasing Li + Diffusion rate and rate capability in the crystal lattice.
The invention is realized by the following technical scheme:
a preparation method of a magnetic field modified ternary material of a lithium ion battery comprises the following steps:
(1) Mixing a nickel source, a cobalt source, a manganese source and water, and stirring to form a uniform ionic 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, washing a product after the reaction is finished, and drying to obtain a precursor material;
(4) And (4) mixing the precursor material in the step (3) with a lithium source, and calcining and grinding to obtain the magnetic field modified ternary material for 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.
Further, the molar ratio of the sodium carbonate to metal cations in the ionic solution in the step (2) is 1 to 1.5, and the addition amount of the sodium dodecyl benzene sulfonate is 0.5 to 5 percent 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 intensity is 3-15mT; the heating reaction and the magnetic field applying time are 8 to 15h.
Further, the magnetic field in the step (3) is formed by winding an enameled wire into an electromagnetic coil and then externally connecting a direct current power supply to form the magnetic field.
Further, the molar ratio of the precursor material in the step (4) to the cation in the lithium source is 1.05 to 1.1.
Further, the calcination in the step (4) is two-stage calcination, the calcination is carried out at the temperature of 450 to 550 ℃ for 3 to 8 hours, the calcination is carried out at the temperature of 800 to 900 ℃ for 8 to 12 hours, and the heating rate is 3 to 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.
According to the invention, the magnetic field modified ternary material for the lithium ion battery prepared by the preparation method has better rate capability and cycle stability, and has wide application prospects in the fields of preparation of electrode materials of the lithium ion battery and the like.
Advantageous effects
According to the invention, the external magnetic field is matched with the hydrothermal reaction, the positive effect of the magnetic field on the hydrothermal reaction is fully utilized, the prepared ternary material has the advantages of uniform appearance, similar size, good conductivity and electrochemical performance, and Ni can be inhibited to a certain extent 3+ To Ni 2+ Reducing cation miscarrying, stabilizing the layered structure and increasing Li + The diffusion rate and rate performance in crystal lattices are better, the rate performance and the cycle stability performance are better, and the application prospect in the fields of lithium ion battery electrode material preparation and the like is wide.
Drawings
FIG. 1 is an SEM image of the ternary magnetic field modified lithium ion battery material prepared in example 1;
FIG. 2 is a magnification diagram of the ternary material of the magnetic field modified lithium ion battery prepared in example 1;
fig. 3 is a cycle diagram of the magnetic field modified ternary lithium ion battery material prepared in example 1.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope 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 to dissolve to form a 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 the mixture into an oil bath pot, heating the mixture to 180 ℃, simultaneously applying a magnetic field with the external magnetic field intensity of 15mT, reacting for 10 hours, washing a product until the pH value of a washing liquid is neutral after the reaction is finished, and then placing the product 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 with lithium carbonate, wherein the molar ratio of lithium ions to the precursor is 1.05 2 Two-stage sintering is carried out under the atmosphere, the temperature is kept for 5h at 500 ℃, and the precursor is fully 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 And (3) fully reacting, wherein the heating rate is 5 ℃/min, crushing the sintered product, and sieving the crushed sintered product with a 350-mesh sieve to obtain the magnetic field modified ternary material for the lithium ion battery, wherein an SEM picture of the ternary material is shown in figure 1 and is of a uniform spherical structure.
The ternary material of the magnetic field modified lithium ion battery prepared in example 1 is used as a positive electrode material of a lithium ion battery, and electrochemical performance is tested, wherein a multiplying power performance diagram is shown in fig. 2, and a charge-discharge cycle diagram is shown in fig. 3. The 0.1C initial discharge specific capacity of the ternary material of the magnetic field modified lithium ion battery prepared in the embodiment 1 is 195.5 mAh/g, and the charge-discharge efficiency is 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 dissolving to form a uniform ionic solution;
(2) Weighing 0.3g of sodium carbonate powder, dissolving the sodium carbonate powder in 100mL of distilled water, adding 25% ammonia water to control the pH value of the solution to be 11, then adding 0.3g of sodium dodecyl benzene sulfonate, and uniformly mixing;
(3) Mixing the mixed solution obtained in the step (2) with the ionic solution obtained in the step (1), transferring the mixed solution into an oil bath pan, heating the mixed solution 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 value of the washing solution is neutral after the reaction is finished, and then placing the product 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 with lithium carbonate, wherein the molar ratio of lithium ions to the precursor is 1.1 2 And (3) performing two-stage sintering in the atmosphere, keeping the temperature at 500 ℃ for 5h, continuously heating to 850 ℃ and keeping the temperature 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 for the lithium ion battery.
The magnetic field modified ternary material of the lithium ion battery prepared in the embodiment 2 is used as a positive electrode material of the lithium ion battery, and the electrochemical performance is tested, wherein the initial discharge specific capacity at 0.1C is 192.3mAh/g mAh/g, and the charge-discharge efficiency is 84%; after current cycling at 0.5C for 200 times, 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 Dissolved in 250mL of distilled water to form a uniform solutionAn ionic solution;
(2) Weighing 12.7g of sodium carbonate powder, dissolving the sodium carbonate powder in 100mL of distilled water, adding 25% ammonia water to control the pH value of the solution to be 11, 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 the mixture into an oil bath pot, heating the mixture to 180 ℃, simultaneously applying a magnetic field with the external magnetic field intensity of 9mT, reacting for 10 hours, washing a product until the pH value of a washing liquid is neutral after the reaction is finished, and then placing the product 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 with lithium carbonate, wherein the molar ratio of lithium ions to the precursor is 1.05 2 And (3) performing two-stage sintering in the atmosphere, keeping the temperature at 500 ℃ for 5h, continuously heating to 850 ℃ and keeping the temperature for 10h, wherein the heating rate is 5 ℃/min, crushing the sintered product, and sieving the crushed sintered product with a 350-mesh sieve to obtain the magnetic field modified ternary material for the lithium ion battery.
The magnetic field modified ternary material for the lithium ion battery prepared in the embodiment 3 is used as a positive electrode material of the lithium ion battery, and the electrochemical performance of the ternary material is tested, so that the initial discharge specific capacity at 0.1C is 197.6mAh/g, the charge-discharge efficiency is 88%, and the capacity retention rate is 89% after the ternary material is subjected to current circulation at 0.5C for 200 times.
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 dissolving to form a uniform ionic solution;
(2) Weighing 12.7g of sodium carbonate powder, dissolving the sodium carbonate powder 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 the mixture into an oil bath pot, heating the mixture to 160 ℃, simultaneously applying a magnetic field with the external magnetic field intensity of 12mT, reacting for 12 hours, after the reaction is finished,washing the product until the pH value of the washing liquid is neutral, and then placing the product 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 with lithium carbonate, wherein the molar ratio of lithium ions to the precursor is 1.05 2 And (3) performing two-stage sintering in the atmosphere, keeping the temperature at 500 ℃ for 5h, continuously heating to 850 ℃ and keeping the temperature for 10h, wherein the heating rate is 5 ℃/min, crushing the sintered product, and sieving the crushed sintered product with a 350-mesh sieve to obtain the magnetic field modified ternary material for the lithium ion battery.
The ternary material of the magnetic field modified lithium ion battery prepared in the embodiment 4 is used as the anode material of the lithium ion battery, and the electrochemical performance is tested, wherein the initial discharge specific capacity at 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 dissolving to form a uniform ionic solution;
(2) Weighing 12.7g of sodium carbonate powder, dissolving the sodium carbonate powder in 100mL of distilled water, adding 25% ammonia water to control the pH value of the solution to be 12, then adding 0.2g of sodium dodecyl benzene sulfonate, and uniformly mixing;
(3) Mixing the mixed solution obtained in the step (2) with the ionic solution obtained in the step (1), transferring the mixed solution into an oil bath pan, heating and reacting for 10 hours, washing a product until the pH value of a washing solution is neutral after the reaction is finished, and then placing the product 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 with lithium carbonate, wherein the molar ratio of lithium ions to the precursor is 1.05 2 Two-stage sintering at 500 deg.C for 5 hr, and performing heat preservationAnd continuously heating to 850 ℃ and preserving the heat for 10 hours, wherein the heating rate is 5 ℃/min, and crushing the sintered product and sieving the crushed sintered product with a 350-mesh sieve to obtain the ternary material of the lithium ion battery.
The lithium ion battery ternary material prepared in the comparative example 1 is used as a positive electrode material of a lithium ion battery, and the electrochemical performance is tested, wherein the first discharge specific capacity of 0.1C is 180.6mAh/g, and the charge-discharge efficiency is 81%; after current cycling at 0.5C for 200 times, the capacity retention was 82%.
Claims (10)
1. A preparation method of a magnetic field modified ternary material for a lithium ion battery is characterized by comprising the following steps:
(1) Mixing a nickel source, a cobalt source, a manganese source and water, and stirring to form a uniform ionic solution;
(2) Dissolving sodium carbonate in water, adding a complexing agent to control the pH of the solution to be 11 to 12, then adding sodium dodecyl benzene sulfonate, and uniformly mixing;
(3) Mixing the mixed solution obtained in the step (2) with the ionic solution obtained in the step (1), heating for reaction, applying a magnetic field, washing a product after the reaction is finished, and drying to obtain a precursor material;
(4) And (4) mixing the precursor material in the step (3) with a lithium source, and calcining and grinding to obtain the magnetic field modified ternary material for the lithium ion battery.
2. The method for preparing the magnetic field modified ternary material for the lithium ion battery according to claim 1, wherein the molar ratio of metal cations in the nickel source, the cobalt source and the manganese source in the step (1) is 8.
3. 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 sodium carbonate to the metal cations in the ionic solution in the step (2) is 1 to 1.5, and the addition amount of the sodium dodecyl benzene sulfonate is 0.5 to 5 percent of the mass of the sodium carbonate.
4. The method for preparing the ternary material of the magnetic field modified lithium ion battery according to claim 1, wherein the complexing agent in the step (2) is ammonia water.
5. The method for preparing the ternary material of the magnetic field modified lithium ion battery according to claim 1, wherein 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 magnetic field application time are 8 to 15h.
6. The method for preparing the ternary material of the magnetic field modified 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 connecting the electromagnetic coil with a direct current power supply to form the magnetic field.
7. 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 the cations in the lithium source is 1.05 to 1.1.
8. The method for preparing the magnetic field modified ternary material for the lithium ion battery as claimed in claim 1, wherein the calcination in the step (4) is two-stage calcination, the calcination is performed at 450 to 550 ℃ for 3 to 8 hours, the calcination is performed at 800 to 900 ℃ for 8 to 12 hours, and the heating rate is 3 to 8 ℃/min.
9. The method for preparing the ternary material of the magnetic field modified lithium ion battery according to claim 1, wherein the nickel source is one or more 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.
10. The ternary material of the magnetic field modified lithium ion battery prepared by the preparation method of any one of claims 1 to 9.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103746110A (en) * | 2014-01-26 | 2014-04-23 | 中国科学院长春应用化学研究所 | Preparation method of nickel-cobalt-manganese ternary material and anode material for lithium ion battery |
| JP2014091657A (en) * | 2012-11-06 | 2014-05-19 | Taiheiyo Cement Corp | Method for producing secondary battery cathode-active material precursor |
| US20160016815A1 (en) * | 2013-03-11 | 2016-01-21 | Guangdong Brunp Recycling Technology Co., Ltd | Method for preparing nickel-cobalt-manganese hydroxide |
| CN105322155A (en) * | 2014-06-06 | 2016-02-10 | 安泰科技股份有限公司 | Lithium-rich manganese-based layered composite oxide cathode material, preparation method and application thereof |
| CN106784782A (en) * | 2016-12-27 | 2017-05-31 | 国联汽车动力电池研究院有限责任公司 | A kind of preparation method of the polynary presoma of low impurity |
| CN107959022A (en) * | 2017-10-31 | 2018-04-24 | 华南理工大学 | A kind of solvent-thermal method prepares tertiary cathode material and preparation method thereof |
| CN108264098A (en) * | 2018-02-26 | 2018-07-10 | 重庆大学 | The preparation method of two-dimensional sheet lithium nickel cobalt manganese oxygen |
| WO2020019920A1 (en) * | 2018-07-24 | 2020-01-30 | 眉山顺应动力电池材料有限公司 | Method for preparing ternary cathode material from laterite nickel ore nitric acid leaching solution |
| CN111072075A (en) * | 2019-12-29 | 2020-04-28 | 桂林理工大学 | Preparation method of lithium ion battery anode material |
| CN111640936A (en) * | 2020-04-18 | 2020-09-08 | 浙江金鹰新能源技术开发有限公司 | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery |
| CN112960703A (en) * | 2021-02-02 | 2021-06-15 | 天津巴莫科技有限责任公司 | Preparation method of lithium ion battery anode core-shell material with concentration gradient |
| CN113582248A (en) * | 2021-07-22 | 2021-11-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nickel-cobalt-manganese ternary cathode material |
| CN115172721A (en) * | 2022-08-02 | 2022-10-11 | 天津巴莫科技有限责任公司 | Hollow high-conductivity lithium cathode material and preparation method thereof |
| CN115784189A (en) * | 2022-10-21 | 2023-03-14 | 山东精工电子科技股份有限公司 | Method for preparing lithium iron phosphate electrode material under hydrothermal magnetic field synergistic effect |
-
2022
- 2022-09-30 CN CN202211210754.0A patent/CN115490277B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014091657A (en) * | 2012-11-06 | 2014-05-19 | Taiheiyo Cement Corp | Method for producing secondary battery cathode-active material precursor |
| US20160016815A1 (en) * | 2013-03-11 | 2016-01-21 | Guangdong Brunp Recycling Technology Co., Ltd | Method for preparing nickel-cobalt-manganese hydroxide |
| CN103746110A (en) * | 2014-01-26 | 2014-04-23 | 中国科学院长春应用化学研究所 | Preparation method of nickel-cobalt-manganese ternary material and anode material for lithium ion battery |
| CN105322155A (en) * | 2014-06-06 | 2016-02-10 | 安泰科技股份有限公司 | Lithium-rich manganese-based layered composite oxide cathode material, preparation method and application thereof |
| CN106784782A (en) * | 2016-12-27 | 2017-05-31 | 国联汽车动力电池研究院有限责任公司 | A kind of preparation method of the polynary presoma of low impurity |
| CN107959022A (en) * | 2017-10-31 | 2018-04-24 | 华南理工大学 | A kind of solvent-thermal method prepares tertiary cathode material and preparation method thereof |
| CN108264098A (en) * | 2018-02-26 | 2018-07-10 | 重庆大学 | The preparation method of two-dimensional sheet lithium nickel cobalt manganese oxygen |
| WO2020019920A1 (en) * | 2018-07-24 | 2020-01-30 | 眉山顺应动力电池材料有限公司 | Method for preparing ternary cathode material from laterite nickel ore nitric acid leaching solution |
| CN111072075A (en) * | 2019-12-29 | 2020-04-28 | 桂林理工大学 | Preparation method of lithium ion battery anode material |
| CN111640936A (en) * | 2020-04-18 | 2020-09-08 | 浙江金鹰新能源技术开发有限公司 | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery |
| CN112960703A (en) * | 2021-02-02 | 2021-06-15 | 天津巴莫科技有限责任公司 | Preparation method of lithium ion battery anode core-shell material with concentration gradient |
| CN113582248A (en) * | 2021-07-22 | 2021-11-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nickel-cobalt-manganese ternary cathode material |
| CN115172721A (en) * | 2022-08-02 | 2022-10-11 | 天津巴莫科技有限责任公司 | Hollow high-conductivity lithium cathode material and preparation method thereof |
| CN115784189A (en) * | 2022-10-21 | 2023-03-14 | 山东精工电子科技股份有限公司 | Method for preparing lithium iron phosphate electrode material under hydrothermal magnetic field synergistic effect |
Non-Patent Citations (7)
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|---|---|
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