CN118231644A - Ternary material, preparation method thereof, positive plate, lithium ion battery and electric equipment - Google Patents

Ternary material, preparation method thereof, positive plate, lithium ion battery and electric equipment Download PDF

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Publication number
CN118231644A
CN118231644A CN202311863040.4A CN202311863040A CN118231644A CN 118231644 A CN118231644 A CN 118231644A CN 202311863040 A CN202311863040 A CN 202311863040A CN 118231644 A CN118231644 A CN 118231644A
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ternary material
diffraction peak
sintering
lithium
diffraction
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Inventor
余旭阳
葛立萍
张梦霞
田业成
何科峰
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Chuzhou Fudi Battery Co ltd
BYD Co Ltd
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Chuzhou Fudi Battery Co ltd
BYD Co Ltd
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Priority to CN202311863040.4A priority Critical patent/CN118231644A/en
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

In order to overcome the technical problems in the existing ternary materials of the lithium ion battery, the present disclosure provides a ternary material, wherein the chemical formula of the ternary material is LiNi 1‑x‑yCoxMnyMaO2, x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.3, a is more than 0 and less than or equal to 0.05, and M is one or more selected from Zr, ti, zn, mg, ta, V, W, al and B; the ternary material comprises single crystal particles; in the X-ray diffraction spectrum of the ternary material, a (108) diffraction peak with a diffraction angle 2 theta at 64+/-0.5 DEG and a (110) diffraction peak with a diffraction angle 2 theta at 65+/-0.5 DEG are provided, and the following relation is satisfied: The ternary material provided by the disclosure has good crystallinity and lamellar structure stability, so that the prepared lithium ion battery has higher cycle life, rate capability and energy density.

Description

Ternary material, preparation method thereof, positive plate, lithium ion battery and electric equipment
Technical Field
The invention belongs to the technical field of energy storage, and particularly relates to a ternary material, a preparation method thereof, a positive plate, a lithium ion battery and electric equipment.
Background
The positive electrode material of the lithium ion battery is taken as an important component of the lithium ion battery and is also one of key factors influencing the performance of the lithium ion battery. The nickel cobalt lithium manganate (ternary material) integrates the advantages of lithium manganate, lithium cobaltate and lithium nickelate, has high specific capacity and good discharge multiplying power, and is the main positive electrode material of the lithium ion battery at present.
The main development trend of the ternary material is single crystallization, and the single crystal particles can reduce the crystal boundary cracking in the cycling process of the ternary material and improve the cycle life of the ternary material. However, the preparation of the single crystal material requires higher sintering temperature, lithium and nickel are easily mixed at high temperature, and the higher the nickel content is, the more serious the mixed phenomenon is, thereby affecting the structural order of the ternary material and leading to poor cycle performance of the ternary lithium battery.
Disclosure of Invention
In view of this, a first aspect of the present disclosure provides a ternary material having the chemical formula LiNi 1-x- yCoxMnyMaO2, wherein 0 < x.ltoreq.0.1, 0 < y.ltoreq.0.3, 0 < a.ltoreq.0.05, m being selected from one or more of Zr, ti, zn, mg, ta, V, al, Y, W and B; the ternary material comprises single crystal particles; in the X-ray diffraction spectrum of the ternary material, a (108) diffraction peak with a diffraction angle 2 theta at (64+/-0.5) DEG and a (110) diffraction peak with a diffraction angle 2 theta at (65+/-0.5) DEG are provided; the (108) diffraction peak and the (110) diffraction peak satisfy the following relationship: Wherein FWHM (108) is the half-peak width of the (108) diffraction peak; FWHM (110) is the half-peak width of the (110) diffraction peak.
The ternary material provided by the present disclosure has the following effects because of containing the crystal structure characteristics required by the present disclosure: firstly, ensuring that the ternary material has a stable layered structure and a reasonable atomic arrangement mode in the charge and discharge process, so that the ternary material has higher energy density and longer cycle life; secondly, the contact area between the ternary material and the electrolyte can be reduced, the occurrence of side reaction in the circulation process is effectively inhibited, the structural stability of the ternary material is enhanced, and the cycle life of the battery is further prolonged.
In a second aspect, the present disclosure provides a method of preparing a ternary material, comprising the steps of: 1) Mixing a first lithium source with a transition metal precursor to obtain a first mixture, and adding a gelling agent and a first doping agent into the first mixture to obtain gel particles; wherein the transition metal precursor comprises nickel, cobalt and manganese elements; the molar ratio of the nickel, cobalt and manganese elements is (1-x-y): x: y, x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.3; the molar ratio of the lithium element in the first lithium source to the total of nickel, cobalt and manganese elements in the precursor is (0.3-0.9): 1; 2) Mixing the gel particles with a second lithium source to obtain a second mixture, and performing primary sintering on the second mixture in an oxygen-containing atmosphere to obtain a primary sintering product; wherein the molar ratio of the lithium element in the second lithium source to the total of nickel, cobalt and manganese elements in the precursor is (0.15-0.75): 1; the first lithium source and the second lithium source may be the same or different; 3) Mixing the primary sintering product with an optional second doping agent, and performing secondary sintering in an oxygen-containing atmosphere to obtain the ternary material; wherein the first dopant and the second dopant comprise M elements, M being selected from one or more of Zr, ti, zn, mg, ta, V, al, Y, W and B; the ratio of the sum of the molar amounts of M elements in the first doping agent and the second doping agent to the sum of the molar amounts of nickel, cobalt and manganese elements in the precursor is a 1, and a is more than 0 and less than or equal to 0.05.
In a third aspect, the present disclosure provides a positive electrode sheet comprising the ternary material described above, or a ternary material obtained by the preparation method described above.
In a fourth aspect, the present disclosure provides a positive electrode sheet, the positive electrode sheet comprising a ternary material having a chemical formula LiNi 1-x-yCoxMnyMaO2, wherein 0 < x is equal to or less than 0.1,0 < y is equal to or less than 0.3,0 < a is equal to or less than 0.05, and m is one or more selected from Zr, ti, zn, mg, ta, V, al, Y, W and B; the ternary material comprises single crystal particles; in the X-ray diffraction spectrum of the positive electrode sheet, there are a (108) diffraction peak at a diffraction angle 2 theta of (64 + -0.5) ° and a (110) diffraction peak at a diffraction angle 2 theta of (65 + -0.5) °; the (108) diffraction peak and the (110) diffraction peak satisfy the following relationship: Wherein FWHM (108) is the half-peak width of the (108) diffraction peak; FWHM (110) is the half-peak width of the (110) diffraction peak.
The lithium ion battery positive plate provided by the disclosure has the excellent effects of the ternary material, higher compaction density and excellent electrode processing performance.
In a fifth aspect, the present disclosure provides a lithium ion battery comprising the positive electrode sheet described above.
In a sixth aspect, the present disclosure provides an electrical device, including the above lithium ion battery.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure.
Fig. 1 is an SEM image of a transition metal precursor magnified 10000 times in example 1 of the present disclosure;
FIG. 2 is an SEM image at 50000 magnification of transition metal precursor of example 1 of the disclosure;
fig. 3 is an SEM image of the ternary material prepared in example 1 of the present disclosure at 10000 x magnification.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The nickel cobalt lithium manganate (ternary material) integrates the advantages of lithium manganate, lithium cobaltate and lithium nickelate, and is widely applied to ternary materials in lithium ion batteries. In the crystal structure of the ternary material, transition metal ions and lithium ions respectively occupy octahedral gaps alternately and are arranged in a layered mode, and the atomic arrangement form enables the ternary material to have excellent electrochemical performance. Single crystallization is one of the main directions of the development of the current ternary material, and single crystal particles can reduce the grain boundary cracking in the material circulation process and improve the circulation life of the ternary material. However, higher sintering temperatures are required to produce single crystals, and the high temperatures tend to cause mixing of lithium and nickel, thereby deteriorating the specific capacity and cycle life of the material.
The first embodiment of the invention provides a ternary material, which has a chemical formula of LiNi 1-x- yCoxMnyMaO2, wherein x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.3, a is more than 0 and less than or equal to 0.05, and M is one or more than one of Zr, ti, zn, mg, ta, V, al, Y, W and B; the ternary material comprises single crystal particles; in the X-ray diffraction spectrum of the ternary material, a (108) diffraction peak with a diffraction angle 2 theta at (64+/-0.5) DEG and a (110) diffraction peak with a diffraction angle 2 theta at (65+/-0.5) DEG are provided; the (108) diffraction peak and the (110) diffraction peak satisfy the following relationship: Wherein FWHM (108) is the half-peak width of the (108) diffraction peak; FWHM (110) is the half-peak width of the (110) diffraction peak.
The ternary material belongs to a hexagonal system, wherein a (110) crystal face is related to an a-axis and a b-axis, and a (108) crystal face is related to a c-axis; further, the combination of the (110) crystal plane and the (108) crystal plane can reflect the characteristics of the ternary material in the three directions of the a, b and c axes in the unit cell, and can be used for evaluating the crystal structure of the ternary material. The order of the layered structure of the ternary material can be roughly determined, and the rationality of the atomic arrangement between layers can be evaluated. The two diffraction peaks of the (108) crystal face and the (110) crystal face in the XRD pattern of the ternary material show obvious cracking peaks, which are marks that the crystal structure in the ternary material reaches a proper interval range, and at the moment, a regular lamellar structure formed by alternation of transition metal and lithium is formed in the ternary material.
The present inventors have found through a great deal of experimental study that, when in the X-ray diffraction spectrum of a single crystal ternary material, there are a (108) diffraction peak at a diffraction angle 2θ of (64±0.5) ° and a (110) diffraction peak at a diffraction angle 2θ of (65±0.5) °, and the (108) diffraction peak and the (110) diffraction peak satisfy the relation: When the ternary material is used, transition metals and lithium are alternately arranged more regularly, the lithium and nickel are less in mixed arrangement, and the specific capacity is higher; and the layer structure formed by the transition metal and lithium alternately is more stable, so that the ternary material can be ensured to have higher cycle life.
In the present application, single crystal grains are relative to polycrystalline grains; wherein, the single crystal particles are single dispersed or quasi-single dispersed particles from the appearance; the polycrystalline particles are secondary particles formed by agglomeration of a plurality of primary particles.
Specifically, 2θ (110) in the relational expression refers to a specific position at the diffraction peak of (110) in an X-ray diffraction spectrum actually obtained when XRD test is performed on the ternary material. Similarly, 2θ (108) refers to a specific position at the diffraction peak of (108) in an X-ray diffraction spectrum actually obtained when XRD test is performed on powder of the ternary material.
In some preferred embodiments of the present disclosure, the ternary material has the chemical formula LiNi 1-x-yCoxMnyMaO2, where 0 < x.ltoreq.0.1, 0 < y.ltoreq.0.1, and 0 < a.ltoreq.0.02.
Along with the high content of Ni element in the ternary material, the specific capacity of the ternary material can be obviously increased; however, as the content of Ni element is high, the risk of occurrence of lithium-nickel mixed discharge increases, resulting in a decrease in cycle life thereof. Therefore, under the condition of meeting the relational expression, the stability of the high-nickel ternary material layer structure and the arrangement order of the interlayer transition metal elements and lithium can be ensured, so that the ternary material has higher specific capacity and simultaneously has high cycle life.
In some preferred embodiments of the present disclosure, the (108) diffraction peak and the (110) diffraction peak satisfy the following relationship:
in some preferred embodiments of the present disclosure, the (108) diffraction peak and the (110) diffraction peak satisfy the following relationship: In the preferred range, the relationship formula is higher in order of the layered structure of the ternary material, and higher in atom arrangement stability among transition metal layers, so that the ternary material has higher specific capacity and simultaneously has high cycle life.
In some preferred embodiments of the present disclosure, the half-peak width FWHM (108) of the (108) diffraction peak in the X-ray diffraction spectrum of the ternary material is in the range of 0.1 to 0.15.
Specifically, the half-width FWHM (108) of the diffraction peak of (108) means a value of the peak width of the diffraction peak of (108) at the half-peak height position of the diffraction peak of (108) in parallel to the diffraction angle 2θ axis in the X-ray diffraction spectrum. FWHM (108) ranges from 0.1 to 0.15, and the prepared ternary material does not contain quasicrystal, has good monocrystal property, smooth lithium ion deintercalation channel and good multiplying power performance.
In some preferred embodiments of the present disclosure, in the X-ray diffraction spectrum of the ternary material, the half-peak width FWHM (110) of the (110) diffraction peak at the diffraction angle 2θ of (65±0.5) ° ranges from 0.1 to 0.15. Specifically, the half-width FWHM (110) of the (110) diffraction peak refers to a value parallel to the diffraction angle 2θ axis in the X-ray diffraction spectrum and is the peak width of the (110) diffraction peak at the half-peak height position of the (110) diffraction peak. FWHM (110) ranges from 0.1 to 0.15, and the prepared ternary material does not contain quasicrystal, has good monocrystal property, smooth lithium ion deintercalation channel and good multiplying power performance.
In some preferred embodiments of the present disclosure, the ternary material has an alpha-NaFeO 2 layered structure.
It is understood that the X-ray diffraction spectrum of the ternary material in this disclosure can be obtained by scanning a copper target X-ray generator at a scan rate of 2 to 5 °/min at 3 ° to 90 °.
In some preferred embodiments of the present disclosure, the ternary material has a particle size (D50) of 2 μm to 6 μm. The grain diameter is in the range, so that the ternary material can be ensured to have better mechanical strength and compaction density.
In a second aspect of the present disclosure, a method for preparing a ternary material is provided, comprising the steps of: 1) Mixing a first lithium source with a transition metal precursor to obtain a first mixture, and adding a gelling agent and a first doping agent into the first mixture to obtain gel particles; wherein the transition metal precursor comprises nickel, cobalt and manganese elements; the molar ratio of the nickel, cobalt and manganese elements is (1-x-y): x: y, x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.3; the molar ratio of the lithium element in the first lithium source to the total of nickel, cobalt and manganese elements in the precursor is (0.3-0.9): 1; 2) Mixing the gel particles with a second lithium source to obtain a second mixture, and performing primary sintering on the second mixture in an oxygen-containing atmosphere to obtain a primary sintering product; wherein the molar ratio of the lithium element in the second lithium source to the total of nickel, cobalt and manganese elements in the precursor is (0.15-0.75): 1; the first lithium source and the second lithium source may be the same or different; 3) Mixing the primary sintering product with an optional second doping agent, and performing secondary sintering in an oxygen-containing atmosphere to obtain the ternary material; wherein the first dopant and the second dopant comprise M elements, M being selected from one or more of Zr, ti, zn, mg, ta, V, al, Y, W and B; the ratio of the sum of the molar amounts of M elements in the first doping agent and the second doping agent to the sum of the molar amounts of nickel, cobalt and manganese elements in the precursor is a 1, and a is more than 0 and less than or equal to 0.05.
Compared with the prior art, the preparation method of the ternary material has the following effects: firstly, a gel pretreatment process is adopted, so that lithium elements are close to lithium sites after sintering in advance, van der Waals force is formed, the fact that lithium and nickel cobalt manganese are combined in crystal lattices in the subsequent sintering process is guaranteed to be more regular, the crystal lattice crystallinity is higher, the crystal form is more complete, internal stress is small, and internal lattice dislocation is not easy to generate; secondly, lithium ions and/or doping elements are mixed uniformly with the transition metal precursor by a step-by-step lithium mixing and/or doping process, and the lithium ions and/or doping elements are arranged orderly after being embedded into the crystal lattice of the ternary material, so that the crystallinity of the inner part and the outer part of the ternary material is consistent, and the generation of single crystal materials is facilitated; thirdly, the sintering temperature can be adjusted for multiple times by the step sintering process, and the negative influence of continuous high temperature on lithium nickel mixed discharge of the single crystal material is balanced.
Specifically, in step 1), the order of adding the gelling agent and the dopant is not limited; the gelling agent may be added first and mixed with the first mixture before adding the dopant; or adding the gel after mixing the doping agent and the first mixture; and also to mix with the first product with simultaneous addition of gelling agent and dopant.
In particular, the transition metal precursor is suitable for preparing ternary single crystal particles.
In some preferred embodiments of the present disclosure, the D50 of the transition metal precursor is between about 2 μm and about 6 μm, the morphology is small agglomerates with a nearly circular shape, the primary particles are coarser, the agglomerates are broken up after subsequent sintering, so that the appearance morphology of the single crystal precursor is not inherited by the ternary single crystal particles. Among them, the pulverizing method is preferably jet milling.
In some preferred embodiments of the present disclosure, the nickel cobalt manganese precursor comprises at least one of a hydroxide precursor or a carbonate precursor.
In some preferred embodiments of the present disclosure, the first lithium source and the second lithium source are each independently a lithium-containing compound. Preferably, the lithium-containing compound comprises one or more of lithium hydroxide, lithium nitrate, lithium carbonate, lithium acetate, lithium chloride, lithium fluoride, lithium iodide.
In some preferred embodiments of the present disclosure, the first dopant and the second dopant may be the same or different. The above dopant is a compound containing a doping element. The doping element comprises M element, M is selected from one or more of Zr, ti, zn, mg, ta, V, al, Y, W and B. Optionally, the doping element-containing compound includes at least one of zinc hydroxide, magnesium hydroxide, molybdenum hydroxide, vanadium hydroxide, germanium hydroxide, aluminum hydroxide, titanium dioxide powder, zirconium oxide powder, tantalum pentoxide, yttrium oxide, boric acid, and tungstic acid. The doping elements have the radius similar to that of transition metal ions and have stronger binding energy with oxygen, so that the crystal structure of the ternary material is more stable, and the ion diffusion resistance of the single-crystal ternary material is reduced.
In some preferred embodiments of the present disclosure, the molar ratio of the lithium element in the lithium compound to the M element in the dopant is 1: (0.001-0.05); wherein the dopants include a first dopant and a second dopant. The method has the advantages that the effectiveness of element doping can be improved by controlling the molar ratio of lithium to doping elements within the range, the nickel ion mixing degree of the material can be reduced by proper element doping, the stability of the crystal surface structure is improved, the lattice distortion generated in the charge-discharge process of the ternary material is effectively inhibited, the number of times that lithium ions pass through a grain boundary in the deintercalation process is reduced, and the deintercalation of the lithium ions in the circulation process is faster, so that the structural stability and the multiplying power performance of the material are improved.
In some preferred embodiments of the present disclosure, the gelling agent comprises a solvent, a complexing agent, and a polymer monomer; wherein the mass percentage of the solvent in the gel is 10-50 wt%; the solvent includes at least one of absolute ethanol or deionized water. The mass percentage of the solvent in the gel is in the range, so that a lithium source can be effectively dispersed, lithium ions can be uniformly dispersed on the surface of the transition metal precursor, and lithiation is facilitated.
In some preferred embodiments of the present disclosure, the complexing agent is present in the gelling agent in an amount of 0.2wt% to 2wt%; the complexing agent comprises Sodium Dodecyl Sulfate (SDS). The complexing agent is favorable for combining the gel and the lithium source, and the mass percent of the complexing agent is in the range, so that the lithium source is favorable for being dispersed in the gel, and a more stable ternary material is formed.
In some preferred embodiments of the present disclosure, the volume ratio of the polymer monomer to the solvent is (0.1-0.4): 1; the polymer monomer comprises at least one of methyl methacrylate, styrene or acrylonitrile; methyl methacrylate is preferred. The polymer monomer is a precursor for forming gel, and the volume ratio of the polymer monomer to the solvent is controlled within the range, so that the gel with better coating performance is formed, and the crystallinity is improved after lithiation. Wherein, the methyl methacrylate is synthesized by converging in the mixing process, the dispersibility to the lithium source is higher, and the surface binding property with the metal precursor is better. Meanwhile, the carbon residue of the finished product after polymethyl methacrylate sintering is in the range of 0.1-3%wt. The carbon residue ratio in this range is favorable for further improvement of the rate capability.
In some preferred embodiments of the present disclosure, during the addition of the gelling agent and optional dopant to the first mixture to obtain the gelled particles, a suitable heat treatment may be performed at a temperature ranging from 40 ℃ to 80 ℃ to facilitate the polymerization reaction.
In some preferred embodiments of the present disclosure, the first sintering comprises: the first sintering temperature is 600-950 ℃, the first sintering time is 8-24 hours, and the first cooling is carried out after the first sintering is finished.
In some preferred embodiments of the present disclosure, the second sintering comprises: after the first cooling is finished, performing secondary sintering in a pure oxygen atmosphere environment, wherein the secondary sintering temperature is 300-750 ℃, the secondary sintering time is 3-24 hours, and after the secondary sintering is finished, performing secondary cooling. The ternary material has high crystallinity by adopting twice sintering, and the grain size of the intermediate product is controlled by adopting twice cooling mode, so that the grains of the ternary material are quickly stabilized in a proper size range, the compaction density of the ternary material is improved, other impurities can be avoided, and the ordering of the ternary material layered structure is improved. The twice sintering cooling mode saves the cooling time of sintering equipment, shortens the process time, is beneficial to obtaining the ternary material with a highly ordered layered structure, and ensures that the ternary material has higher specific capacity.
In some embodiments, the first sintering further comprises: the temperature rising rate in the primary sintering is 1 ℃/min-8 ℃/min, the primary sintering time (or primary sintering time) is 8 h-24 h under the condition of the primary sintering temperature of 600 ℃ to 950 ℃, the primary cooling is carried out after the primary sintering is finished, the primary cooling temperature is 20 ℃ to 30 ℃, the cooling mode adopts quenching, and the primary sintering product after the sintering is directly transferred to the room temperature.
The transition metal precursor is subjected to the first sintering operation, so that a ternary material with better crystallinity is formed, the polymer coating layer of the transition metal precursor is carbonized, the true density of the material is improved, and the specific surface of the material is adjusted. After the first sintering is finished, the first cooling operation is performed, and the purpose of the first cooling operation is to control the grain size of the intermediate product, so that the grains of the material are quickly stabilized at a fixed size, the quick crystallization of the ternary material can be ensured, other miscellaneous items are avoided, and the ordering of the layered structure of the ternary material is improved.
In some embodiments, the second sintering comprises: the temperature rising rate in the second sintering is 1 ℃/min-8 ℃/min, the second sintering temperature is 300 ℃ to 750 ℃, the second sintering time is 3h to 24h, the second cooling is carried out after the second sintering is finished, the second cooling temperature is 20 ℃ to 30 ℃, the cooling mode adopts quenching, and the second sintering product after the sintering is directly transferred to the room temperature.
Specifically, the pure oxygen atmosphere environment refers to a space filled with pure oxygen, the second sintering is performed in the space filled with pure oxygen, and the effects of the first sintering and the second sintering are the same, so that the ternary material with better crystallinity is formed, and the compactness of the ternary material is improved. The effect of the first cooling and the second cooling is the same, and the purpose of the method is to control the grain size of the intermediate product, enable the grains of the ternary material to be quickly stabilized at a fixed size, increase the compaction density of the ternary material when the ternary material is used for preparing pole pieces, simultaneously ensure the quick crystallization of the ternary material, avoid generating other miscellaneous items and improve the ordering of the layered structure of the ternary material. It is understood that the equipment selected for the first sintering and the second sintering comprises one of a tube furnace, a box furnace, a fluidized bed, a rotary kiln, a microwave oven and a tunnel furnace.
In some preferred embodiments of the present disclosure, the method further comprises performing a third sintering after the second sintering and cooling, wherein the third sintering is performed at a temperature of 300-500 ℃ for 3-8 hours. At the third sintering, a lithium source and/or dopant is optionally added. The third sintering is mainly used for forming a ternary material with higher stability and higher crystallinity.
In a third aspect of the disclosure, a positive electrode sheet is provided, which includes the ternary material provided in the first aspect, or the ternary material prepared by the preparation method of the ternary material provided in the second aspect.
The positive plate provided by the disclosure contains the ternary material and has higher specific capacity and cycle life.
The ternary material is used for preparing the positive plate, and the positive plate is applied to a battery, so that the battery has higher energy density and longer cycle life.
In some preferred embodiments of the present disclosure, the positive electrode sheet has a compacted density of 3.2g/cm 3～3.5g/cm3.
The positive plate prepared from the ternary material prepared by the method has the advantages of complete material layered structure and high compaction density, and can be applied to batteries to improve the energy density and the cycle life of the batteries.
In a fourth aspect of the present disclosure, there is provided a positive electrode sheet, including a ternary material having a chemical formula LiNi 1-x-yCoxMnyMaO2, wherein x is 0 < 0.1, y is 0 < 0.3, a is 0 < 0.05, and m is one or more selected from Zr, ti, zn, mg, ta, V, al, Y, W and B; the ternary material comprises single crystal particles; in the X-ray diffraction spectrum of the positive electrode sheet, there are a (108) diffraction peak at a diffraction angle 2 theta of (64 + -0.5) ° and a (110) diffraction peak at a diffraction angle 2 theta of (65 + -0.5) °; the (108) diffraction peak and the (110) diffraction peak satisfy the following relationship: Wherein FWHM (108) is the half-peak width of the (108) diffraction peak; FWHM (110) is the half-peak width of the (110) diffraction peak.
In a fifth aspect of the present disclosure, a lithium ion battery is provided, including the positive electrode sheet described above. The lithium ion battery using the present disclosure has higher energy density and cycle life.
The lithium ion battery also comprises a negative plate, a diaphragm and electrolyte. The negative electrode sheet comprises a current collector and a negative electrode active material layer coated on at least one surface of the current collector; the anode active material layer includes an anode active material, a conductive agent, and a binder.
The anode active material includes a carbon-based material; the carbon-based material includes one or more of artificial graphite, natural graphite, hard carbon material, or soft carbon material.
The negative electrode active material further includes one or more of a silicon-based material, a tin-based material, and a lithium titanate material. The silicon-based material can be one or a combination of a plurality of simple substance silicon, silicon oxide (SiO x, 0 < x < 2) and silicon alloy. The tin-based material can be one or a combination of a plurality of simple substance tin, tin oxide (SnO x, x is more than 0 and less than or equal to 2) and tin alloy. The lithium titanate material may be Li 4Ti5O12 or the like.
The binder may be a combination of one or more of styrene-butadiene rubber (Styrene Butadiene Rubber, SBR), sodium carboxymethylcellulose (Carboxymethyl Cellulose, CMC), polyacrylic Acid (PAA), polyethylene acrylic Acid (Polyacrylic ETHYLENE ACRYLIC ACID, PEAA), sodium alginate, carboxymethyl chitosan, polyacrylonitrile (PAN), and polyvinyl alcohol (Polyvinyl alcohol, PVA).
The current collector may be any one of copper foil, carbon coated copper foil, polymer coated copper foil, carbon cloth, carbon nanotube film, or carbon paper.
The separator may be a composite film of one or more of polyethylene, polypropylene, polyvinylidene fluoride.
The electrolyte is an organic solvent in which carrier ions are dissolved. The electrolyte is not limited, and can be automatically prepared according to actual conditions.
In a sixth aspect of the disclosure, an electrical device is provided, including the above lithium ion battery.
The electric equipment prepared by using the lithium ion battery disclosed by the disclosure can have higher market competitiveness.
In some embodiments of the present disclosure, the electrical equipment includes, but is not limited to, wearable electronic devices such as mobile phones, notebook computers, tablet computers, smart watches, etc., electronic cigarettes, new energy automobiles, electric power assisted vehicles, etc.
The present invention will be described in further detail with reference to examples.
Example 1
The embodiment is used for explaining the ternary material disclosed by the invention and the preparation method thereof, and comprises the following steps:
1) The hydroxide precursor of Ni 0.92Co0.06Mn0.02 is used, a lithium source is used as LiOH, and the following steps are firstly carried out according to the following steps: adding lithium hydroxide in a proportion of transition metal element=0.4 and mixing to obtain a first mixture; continuously adding titanium dioxide powder (1250 ppm calculated based on the molar content of titanium element), zirconium oxide powder (2500 ppm calculated based on the molar content of zirconium element), tantalum pentoxide (1000 ppm calculated based on the molar content of tantalum element) and yttrium oxide powder (1000 ppm complementary content calculated based on the molar content of yttrium element) into the first mixture, and carrying out high-speed mixing for 8 hours; pouring into a ball mill, ball-milling and mixing for 8 hours by using absolute ethyl alcohol, adding 0.4wt% of sodium dodecyl sulfate, 30wt% of H 2 O and methyl methacrylate with the water volume ratio of 0.25 into the mixture, stirring for 1 hour to obtain a mixture of gel-like coated precursor, lithium salt and doping agent, heating the mixture to 80 ℃, preserving heat for 1 hour, and collecting gel particles;
2) The gel particles were then again mixed with LiOH according to lithium: mixing transition metal element=0.63 at high speed, sintering for the first time in oxygen atmosphere at a heating rate of 5 ℃/min and a sintering temperature of 800 ℃ for 18 hours, and crushing and sieving to obtain a first sintered product;
3) Mixing the first sintering product with aluminum oxide (1500 ppm calculated based on the molar content of aluminum element) powder, performing secondary sintering at a heating rate of 5 ℃/min for 10 hours at a sintering temperature of 700 ℃ in an oxygen atmosphere, and crushing and sieving to obtain a second sintering product;
4) And mixing the second sintering product with boric acid (1000 ppm calculated based on the molar content of boron element) and tungstic acid powder (1000 ppm calculated based on the molar content of tungsten element), sintering for 5 hours in an oxygen atmosphere at 300 ℃, and pulverizing to obtain the final ternary material.
Wherein the hydroxide precursor D50 of Ni 0.92Co0.06Mn0.02 is 4 μm, the SEMs of which are different magnifications are shown in fig. 1 and 2, and the hydroxide precursor of Ni 0.92Co0.06Mn0.02 in the low-magnification SEM (fig. 1) is a secondary sphere particle packed from primary particles; primary particles were coarser in high-magnification SEM (fig. 2). The resulting ternary material finished product (LiNi 0.90Co0.05Mn0.05O2) had a D50 of 4 μm and its SEM was as in fig. 3, liNi 0.92Co0.06Mn0.02MO2 did not inherit the hydroxide precursor morphology of Ni 0.92Co0.06Mn0.02, but formed irregular primary particles.
XRD testing was performed on the finished ternary material using a copper target X-ray generator, scanning was performed at a 3/min scan rate at 10-80.
Example 2
Example 2 differs from example 1 in that no titanium dioxide or tantalum pentoxide is added during the sintering of step 1).
Example 3
Example 3 differs from example 1 in that no alumina is added in step 2).
Example 4
Example 4 differs from example 1 in that no tungstic acid was added in step 4).
Example 5
Example 5 differs from example 1 in that tantalum pentoxide and yttrium oxide powders are not added during the sintering of step 1); alumina is not added in the step 2); step 4) is not performed.
Example 6
Example 6 differs from example 1 in that a precursor of Ni 0.89Co0.06Mn0.06 proportion was used, the first sintering temperature being 770 ℃,16h; the second sintering temperature is 620 ℃ and 8 hours.
Example 7
Example 7 differs from example 1 in that in step 1), according to lithium: transition metal element=0.9; in step 2), according to lithium: transition metal element=0.15.
Example 8
Example 8 differs from example 1 in that in step 1) 2% by weight of Sodium Dodecyl Sulfate (SDS), 50% by weight of H 2 O and a water volume ratio of Methyl Methacrylate (MMA) of 0.4 are added to the mixture.
Example 9
Example 9 differs from example 1 in that in step 1) 0.2% by weight of Sodium Dodecyl Sulfate (SDS), 10% by weight of H 2 O, methyl Methacrylate (MMA) in a water ratio of 0.1 are added to the mixture.
Example 10
Example 10 differs from example 1 in that in step 1) 0.8% by weight of Sodium Dodecyl Sulfate (SDS), 40% by weight of H 2 O, methyl Methacrylate (MMA) in a water volume ratio of 0.5 are added to the mixture.
Comparative example 1
Comparative example 1 differs from example 1 in that the gel coating treatment in example 1 was not performed.
Comparative example 2
Comparative example 2 differs from example 1 in that the element doping, gel coating treatment, and no lithium source addition of example 1 were not performed, and in the first mixing process, the following lithium: transition metal element=1.05.
Comparative example 3
Comparative example 3 differs from example 6 in that the gel coating treatment in example 6 was not performed and lithium was added in portions; according to lithium: transition metal element=1.05.
Comparative example 4
Comparative example 4 differs from example 1 in that a precursor of Ni 0.74Mn0.26 proportion was used, the first sintering temperature was 820 ℃,14h; the second sintering temperature is 600 ℃ and 8 hours; the lithium addition and doping treatments in example 1 were not performed in portions; according to lithium: transition metal element=1.05.
Specific data of FWHM (108), FWHM (110), 2 theta (108) and 2 theta (110) in XRD spectra obtained after XRD test of the ternary materials prepared in the above examples 1 to 10 and comparative examples 1 to 4 are recorded in the table 1, and XRD half-peak width and peak position data are obtained from a processing software MDIJade for analyzing XRD original test files, and the specific data are shown in the table 1.
Table 1 ternary materials part data tables for examples 1-10 and comparative examples 1-4
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The positive electrode sheet S containing the ternary materials of examples 1, 7 and comparative examples 1, 4 was selected, specific data of FWHM (108), FWHM (110), 2θ (108) and 2θ (110) in the XRD spectrum obtained by XRD test of the positive electrode sheet is recorded in table 2, and the XRD half-peak width and peak position data are obtained from processing software MDIJade for analysis of XRD original test files, and the specific data are shown in table 2.
TABLE 2 Positive plate partial data sheet
Performance test:
positive electrode sheets, batteries were prepared from the ternary materials prepared in examples 1 to 10 and comparative examples 1 to 4 described above, and the following tests were performed.
Specific capacity test: taking the ternary material, PVDF and SP according to a proportion of 96:3:1, NMP is used as a solvent to be mixed for 2 hours to form stable and uniform anode slurry. The positive electrode slurry was coated on an aluminum foil using a coater, dried, cold-pressed to obtain a positive electrode sheet having a compacted density of 3.40g/cm 3, and dried at 120℃for 24 hours. The lithium sheet is used as a negative electrode, the cellgard2300 porous membrane is used as a diaphragm, a mixed electrolyte of 1mol/LLiPF 6 +DMC (volume ratio of 1:1) is used as an electrolyte, the button cell 2032 is assembled for testing, the charge and discharge test is carried out at a rate of 0.2C, and the specific capacity of the third discharge test is taken as the specific capacity of the ternary material.
Preparation of a battery: and preparing the prepared positive plate, the prepared negative plate and the prepared isolating film into a bare cell according to a conventional preparation process, drying the bare cell, injecting electrolyte, and packaging to finally prepare the battery.
Wherein, the negative electrode active material artificial graphite, conductive carbon black, thickener (CMC) and binder (SBR) are mixed according to the proportion of 96:1:1:2, and the powder and deionized water are stirred into negative electrode slurry by a refiner and uniformly coated on the copper foil, thus obtaining the negative electrode plate.
And (3) testing normal temperature cycle performance: and (3) carrying out a normal-temperature 25 ℃ cycle test on the battery core obtained after the formation, carrying out a charge and discharge test at 0.5C/0.5C, and recording the discharge capacity retention of the battery after 500 cycles.
Direct Current Internal Resistance (DCIR) test: and (3) carrying out a high-temperature 45 ℃ cycle test on the battery core obtained after the formation, carrying out a charge and discharge test at 1C/1C, and recording DCIR (direct current ir) retention of the battery for 500 times.
Table 2 table of performance data for examples 1-10 and comparative examples 1-4
As can be seen from the data in table 3, the ternary materials provided in the examples of the present disclosure satisfy the crystal structure characteristics required in the present disclosure, and the discharge capacity, cycle performance, and DCIR of the battery are improved relative to the comparative examples.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (13)

1. A ternary material, wherein the chemical formula of the ternary material is LiNi 1-x-yCoxMnyMaO2, wherein x is more than 0and less than or equal to 0.1, y is more than 0and less than or equal to 0.3, a is more than 0and less than or equal to 0.05, and M is one or more than one of Zr, ti, zn, mg, ta, V, al, Y, W and B;
the ternary material comprises single crystal particles;
in the X-ray diffraction spectrum of the ternary material, a (108) diffraction peak with a diffraction angle 2 theta at (64+/-0.5) DEG and a (110) diffraction peak with a diffraction angle 2 theta at (65+/-0.5) DEG are provided;
The (108) diffraction peak and the (110) diffraction peak satisfy the following relationship:
Wherein FWHM (108) is the half-peak width of the (108) diffraction peak; FWHM (110) is the half-peak width of the (110) diffraction peak.
2. The ternary material of claim 1, wherein 0 < x.ltoreq.0.1, 0 < y.ltoreq.0.1, 0 < a.ltoreq.0.02.
3. The ternary material of claim 1, wherein the (108) diffraction peak and the (110) diffraction peak further satisfy:
4. The ternary material of claim 1, wherein the (108) diffraction peak and the (110) diffraction peak further satisfy:
5. The ternary material of claim 1, wherein in an X-ray diffraction spectrum of the ternary material, the half-peak width FWHM (108) of the (108) diffraction peak is in the range of 0.1-0.15; and/or
The half-width FWHM (110) of the diffraction peak of the (110) is in the range of 0.1 to 0.15.
6. The preparation method of the ternary material comprises the following steps:
1) Mixing a first lithium source with a transition metal precursor to obtain a first mixture, and adding a gelling agent and a first doping agent into the first mixture to obtain gel particles; wherein the transition metal precursor comprises nickel, cobalt and manganese elements; the molar ratio of the nickel, cobalt and manganese elements is (1-x-y): x: y, x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.3; the molar ratio of the lithium element in the first lithium source to the total of nickel, cobalt and manganese elements in the precursor is (0.3-0.9): 1;
2) Mixing the gel particles with a second lithium source to obtain a second mixture, and performing primary sintering on the second mixture in an oxygen-containing atmosphere to obtain a primary sintering product; wherein the molar ratio of the lithium element in the second lithium source to the total of nickel, cobalt and manganese elements in the precursor is (0.15-0.75): 1; the first lithium source and the second lithium source may be the same or different;
3) Mixing the primary sintering product with an optional second doping agent, and performing secondary sintering in an oxygen-containing atmosphere to obtain the ternary material;
Wherein the first dopant and the second dopant comprise M elements, M being selected from one or more of Zr, ti, zn, mg, ta, V, al, Y, W and B; the ratio of the sum of the molar amounts of M elements in the first doping agent and the second doping agent to the sum of the molar amounts of nickel, cobalt and manganese elements in the precursor is a1, and a is more than 0 and less than or equal to 0.05.
7. The method of preparing a ternary material of claim 6, wherein the gelling agent comprises a solvent, a complexing agent, and a polymer monomer;
Wherein, the mass percent of the solvent is 10 to 50 percent by weight based on the total mass of the gel; the mass percentage of the complexing agent is 0.2-2 wt%; the volume ratio of the polymer monomer to the solvent is (0.1-0.4): 1.
8. The method of preparing a ternary material of claim 7, wherein the solvent comprises at least one of absolute ethanol or deionized water; and/or
The complexing agent comprises sodium dodecyl sulfate; and/or
The polymer monomer comprises at least one of methyl methacrylate, styrene or acrylonitrile; methyl methacrylate is preferred.
9. The method for preparing ternary material according to claim 8, wherein,
The first sintering comprises: the first sintering temperature is 600-950 ℃, the first sintering time is 8-24 hours, and the first cooling is carried out after the first sintering is finished; and/or
And the second sintering comprises the steps of performing the second sintering in pure oxygen atmosphere after the first cooling is finished, wherein the second sintering temperature is 300-750 ℃, the second sintering time is 3-24 h, and performing the second cooling after the second sintering is finished.
10. A positive electrode sheet comprising the ternary material according to any one of claims 1 to 5 or the ternary material obtained by the method for producing a ternary material according to any one of claims 6 to 9.
11. A positive plate comprises ternary materials,
The chemical formula of the ternary material is LiNi 1-x-yCoxMnyMaO2, wherein x is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.3, a is more than 0 and less than or equal to 0.05, and M is one or more than one of Zr, ti, zn, mg, ta, V, al, Y, W and B;
the ternary material comprises single crystal particles;
in the X-ray diffraction spectrum of the positive electrode sheet, there are a (108) diffraction peak at a diffraction angle 2 theta of (64 + -0.5) ° and a (110) diffraction peak at a diffraction angle 2 theta of (65 + -0.5) °;
The (108) diffraction peak and the (110) diffraction peak satisfy the following relationship:
Wherein FWHM (108) is the half-peak width of the (108) diffraction peak;
FWHM (110) is the half-peak width of the (110) diffraction peak.
12. A lithium ion battery comprising the positive electrode sheet according to claim 10 or the positive electrode sheet according to claim 11.
13. A powered device comprising the lithium-ion battery of claim 12.
CN202311863040.4A 2023-12-29 2023-12-29 Ternary material, preparation method thereof, positive plate, lithium ion battery and electric equipment Pending CN118231644A (en)

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