CN113471423B - Lithium ion battery anode material and preparation method thereof - Google Patents

Lithium ion battery anode material and preparation method thereof Download PDF

Info

Publication number
CN113471423B
CN113471423B CN202110619765.3A CN202110619765A CN113471423B CN 113471423 B CN113471423 B CN 113471423B CN 202110619765 A CN202110619765 A CN 202110619765A CN 113471423 B CN113471423 B CN 113471423B
Authority
CN
China
Prior art keywords
lithium ion
ion battery
battery anode
anode material
ball milling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110619765.3A
Other languages
Chinese (zh)
Other versions
CN113471423A (en
Inventor
胡朴
张占辉
赵周桥
潘冰冰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Institute of Technology
Original Assignee
Wuhan Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Institute of Technology filed Critical Wuhan Institute of Technology
Priority to CN202110619765.3A priority Critical patent/CN113471423B/en
Publication of CN113471423A publication Critical patent/CN113471423A/en
Application granted granted Critical
Publication of CN113471423B publication Critical patent/CN113471423B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a lithium ion battery anode material, which has the chemical formula: li (Li) 1‑x M x/a Ni 1/3 Co 1/3 Mn 1/3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0 and less than or equal to 0.1, and a is the valence state of M element; m=na, K, mg or Ca; the ball milling and drying process is carried out by taking cobalt trioxide, nickel oxide, manganese dioxide, lithium hydroxide and alkali metal carbonate as raw materials, and sintering. The invention uses M (M=Na, K, mg or Ca) to carry out the reaction of LiNi 1/3 Co 1/ 3 Mn 1/3 O 2 Doping modification and preparation of single crystal Li with good lamellar structure and electrochemical property by using one-step method 1‑x M x/a Ni 1/ 3 Co 1/3 Mn 1/3 O 2 The electrochemical performance of the catalyst can be effectively improved; the preparation method is simple, convenient to operate and suitable for popularization and application.

Description

Lithium ion battery anode material and preparation method thereof
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a lithium ion battery anode material and a preparation method thereof.
Background
LiNi 1/3 Co 1/3 Mn 1/3 O 2 Spatial structure and LiCoO of (C) 2 The structure is similar, belonging to the lamellar structure. LiNi 1/3 Co 1/3 Mn 1/ 3 O 2 The positive electrode material is synthesized by Ohzuku for the first time in 2001, so that the ternary positive electrode material formally enters the market of lithium ion batteries. However, the material still has the defects of insufficient specific discharge capacity, insufficient rate capability and the like at present, and the defects prevent the further development of the material.
Currently, alkali metal cation doping is accomplished by maintaining LiNi 1/3 Co 1/3 Mn 1/3 O 2 The simplest and most efficient way to improve performance is by the structure and thermal stability of the material. The ionic radius of the alkali metal cations is larger than that of the lithium ions, M + 、M 2+ (m= Na, K, mg, ca) into LiNi 1/3 Co 1/3 Mn 1/3 O 2 After the lithium ion interlayer, the interlayer spacing of the material is increased, which is favorable for the deintercalation behavior of lithium ions in the charge and discharge process and enlarges the diffusion coefficient of lithium ions, so that a small amount of alkali metal cations are doped into the layered LiNi 1/3 Co 1/3 Mn 1/3 O 2 The structural stability of the material can be enhanced in the positive electrode material, and the interlayer spacing is enlarged, so that the purposes of improving the cycle stability and the multiplying power performance of the material are achieved. The doping method commonly used at present is a coprecipitation method, the method has a plurality of steps, the reaction condition is complex, the structural stability of the obtained product is poor, and industrial production is difficult to realize.
Disclosure of Invention
The main purpose of the invention is to solve the defects existing in the prior art, and utilize M (M=Na, K, mg, ca) to carry out the preparation of the LiNi 1/3 Co 1/3 Mn 1/3 O 2 Doping modification and preparation of single crystal Li with good lamellar structure and electrochemical property by using one-step method 1-x M x Ni 1/3 Co 1/3 Mn 1/3 O 2 。
In order to achieve the above purpose, the invention adopts the following technical scheme:
a lithium ion battery positive electrode material has a stoichiometric formula: li (Li) 1-x M x/a Ni 1/3 Co 1/3 Mn 1/3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0 and less than or equal to 0.1, and a is the valence state of M element; m=na, K, mg or Ca.
In the scheme, the lithium ion battery anode material is prepared by ball milling, drying and sintering cobalt sesquioxide, nickel oxide, manganese dioxide, lithium hydroxide and alkali metal carbonate serving as raw materials.
The preparation method of the lithium ion battery anode material comprises the following steps:
1) Weighing raw materials according to a stoichiometric ratio;
2) Adding the weighed raw materials into a ball milling tank for mixing, ball milling and drying;
3) And sintering the dried material to obtain the lithium ion battery anode material.
In the above scheme, the cobalt source is cobaltous oxide; the nickel source is nickel oxide; manganese source is manganese dioxide; the lithium source is lithium hydroxide; the alkali metal source is an alkali metal carbonate.
In the above scheme, the alkali metal is one of Na, K, mg, ca.
In the scheme, ethanol is added in the ball milling step, and the mass-volume ratio of the ethanol to the solid-liquid adopted by the mixed raw materials is 0.4-0.6g/mL.
In the scheme, the ball milling speed is 180-250r/min, and the time is 1.5-2.5h.
In the scheme, the drying temperature is 80-100 ℃ and the drying time is 2-3h.
In the scheme, the sintering temperature is 950-1000 ℃ and the reaction time is 9-11h.
The invention takes cobalt oxide, nickel oxide, manganese dioxide, lithium hydroxide hydrate and alkali metal carbonate as raw materials, and prepares Li by adopting a high-temperature solid phase method 1-x M x/a Ni 1/3 Co 1/3 Mn 1/3 O 2 (x is more than or equal to 0 and less than or equal to 0.1, a is the valence state of M element; M=Na, K, mg, ca), li during the charging process of the lithium ion battery + Is separated from the interlayer of the ternary layered positive electrode material and enters into electrolyte, li + Is formed with a large number of Li vacancies between layers of the positive electrode material, ni in the transition metal layer 2+ Due to the exclusion of oxygen from the adjacent oxygen layer, it enters between the lithium ion layers and occupies lithium vacancies, which results in Li + /Ni 2+ The mixed discharge phenomenon occurs, and the lithium ion hysteresis existing in the charging process can aggravate the mixed discharge degree, li + /Ni 2+ The increase of the mixed discharge degree is beneficial to the generation of rock salt phase, so that the layered structure of the material starts to find rock salt phase change, and a NiO-like phase with low electronic conductivity appears; meanwhile, during charging, ni 2+ Will be oxidized to Ni 3+ Or Ni 4+ Migration to the lithium ion layer, which causes local collapse between the cell layers, which increases Li + The diffusion resistance of the material is increased, and the cycle performance of the material is reduced; the invention is realized by incorporating M + 、M 2+ (m=na, K, mg, ca) can enter between lithium ion layers, occupy lithium ion vacancies formed by lithium ion deintercalation during charge and discharge, which can lower Ni in the transition metal layer 3+ The probability of entering the layers can also enhance the structural stability of the material, thereby enhancing the electrochemical performance of the material.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention fully uses the characteristic of similar chemical properties of alkali metal ions and adopts a one-step method to make M + ，M 2+ (m=na, K, mg, ca) successful incorporation into LiNi 1/3 Co 1/3 Mn 1/3 O 2 Is occupied by Li + Sites, meanwhile, the interlayer spacing of lithium ions is increased, the electrochemical performance of the material is improved, and meanwhile, li is promoted 1-x M x/a Ni 1/3 Co 1/3 Mn 1/3 O 2 Forming a single crystal structure; the related preparation method is simple, short in time consumption, less in reaction loss, free of waste liquid and waste gas, small in environmental pollution and suitable for large-scale industrial production;
2) Single crystal Li obtained by the present invention 1-x M x/a Ni 1/3 Co 1/3 Mn 1/3 O 2 The structure still can maintain a good layered structure, and meanwhile, the structure has high stability and excellent performance, and is suitable for the energy fields of new energy automobiles, electric tools, intelligent electronic equipment and the like;
3) The invention is realized by the method of preparing LiNi 1/3 Co 1/3 Mn 1/3 O 2 The doping modification is carried out, so that the specific charge and discharge capacity and the multiplying power performance can be effectively improved, and the method has a good application prospect.
Drawings
FIG. 1 is Li obtained in example 1 of the present invention 0.94 Na 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 Is a XRD pattern of (C).
FIG. 2 is Li obtained in example 1 of the present invention 0.94 Na 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 SEM images of (a).
FIG. 3 is Li obtained in example 1 of the present invention 0.94 Na 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 Constant current cycle pattern of (2).
FIG. 4 is Li obtained in example 2 of the present invention 0.94 K 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 Is a XRD pattern of (C).
FIG. 5 is Li obtained in example 2 of the present invention 0.94 K 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 SEM images of (a).
FIG. 6 is Li obtained in example 2 of the present invention 0.94 K 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 Constant current cycle pattern of (2).
FIG. 7 is Li obtained in example 3 of the present invention 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 Is a XRD pattern of (C).
FIG. 8 is Li obtained in example 3 of the present invention 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 SEM images of (a).
FIG. 9 is Li obtained in example 3 of the present invention 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 Constant current cycle pattern of (2).
FIG. 10 shows the LiNi obtained in comparative example 1 1/3 Co 1/3 Mn 1/3 O 2 Constant current cycle pattern of (2).
FIG. 11 is Li obtained in comparative example 2 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 Is a XRD pattern of (C).
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. 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.
Example 1
A lithium ion battery anode material with a stoichiometric formula of Li 0.94 Na 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 The specific preparation method comprises the following steps:
1) Putting 0.5705g of weighed cobalt oxide, 0.5131g of nickel oxide, 0.6080g of manganese dioxide, 0.8690g of lithium hydroxide hydrate and 0.0654g of sodium carbonate into a ball mill, putting 5mL of ethanol, and ball milling for 2 hours at a speed of 180 r/min;
2) Drying the material obtained in the step 1) for 2 hours at 80 ℃ in a blast drier, and then sintering in a muffle furnace at 1000 ℃ for 10 hours; after sintering is completed, li is obtained 0.94 Na 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 。
FIG. 1 shows Li obtained in this example 0.94 Na 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 An XRD pattern of (a); as can be seen from the figure, each diffraction peak in the XRD spectrum of the sample is narrow and sharp, and the positions and the relative intensities of each diffraction peak are in one-to-one correspondence with the standard card, which shows that the sample has good crystallinity and completely accords with alpha-NaFeO 2 (space type, R3 m) structure, no other impurity crystal phase appeared in each sample, while a low angular shift appeared in the (003) peak of each doped sample relative to the (003) peak of the undoped sample, indicating Na + Is successfully doped with Li + Site, at the same time Na + Is not to change Li 1 Ni 1/3 Co 1/3 Mn 1/3 O 2 Other impurities are not generated due to the original crystal structure. Simultaneous sample I (003)/(104) = 1.6313, indicating that the cation mix of the sample is very low. The c/a value of the sample was 4.98965, indicating that the sample had good structural stability.
FIG. 2 shows Li obtained in this example 0.94 Na 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 SEM images of (a). From the graph, the crystallinity of the obtained product is good, and the particle size distribution of the particles is uniform; the primary particles in the obtained product were hexagonal long particles (Li 0.94 Na 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 Single crystal), the primary particles are further stacked to form ellipsoidal particles.
FIG. 3 is Li obtained in the example 0.94 Na 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 Is a constant current cycle chart of (2); the result shows that the initial discharge specific capacity of the obtained product is 167.5mAh/g, the discharge specific capacity of the sample after 50 times of recycling is 157.3mAh/g, and the capacity retention rate is 93.9%, so that the sample has high discharge specific capacity and good cycle stability.
Example 2
A lithium ion battery anode material with a stoichiometric formula of Li 0.94 K 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 The preparation method comprises the following steps ofThe steps are as follows:
1) Putting 0.5649g of weighed cobalt oxide, 0.5081g of nickel oxide, 0.6020g of manganese dioxide, 0.9154g of lithium hydroxide hydrate and 0.0844g of potassium carbonate into a ball mill, adding a proper amount of ethanol 5mL, and ball milling for 2 hours at a speed of 180 r/min;
2) Drying the material obtained in the step 1) for 2 hours at 80 ℃ in a blast drier, and then sintering in a muffle furnace at 1000 ℃ for 10 hours; after sintering is completed, li is obtained 0.94 K 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 。
FIG. 4 shows Li obtained in this example 0.94 K 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 An XRD pattern of (a); as can be seen, each diffraction peak in the XRD spectrum of the obtained sample is narrow and sharp, and the positions and the relative intensities of each diffraction peak are all in one-to-one correspondence with the standard card, which shows that the sample has good crystallinity and completely accords with alpha-NaFeO 2 (space type, R3 m) structure, no other impurity crystal phase appeared in each sample, while a low angular shift appeared in the (003) peak of each doped sample relative to the (003) peak of the undoped sample, indicating K + Is successfully doped with Li + Site, at the same time K + Is not to change Li 1 Ni 1/3 Co 1/3 Mn 1/3 O 2 Other impurities are not generated due to the original crystal structure. Simultaneous sample I (003)/(104) = 1.6181, indicating that the cation mix of the sample is very low. The c/a value of the sample was 4.98392, indicating that the sample had good structural stability.
FIG. 5 shows Li obtained in this example 0.94 K 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 SEM images of (a). As can be seen from the figure, the crystallinity of the sample is good, and the particle size distribution is uniform. The primary particles in the obtained product were hexagonal long particles (Li 0.94 K 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 Single crystal), the primary particles are further stacked to form ellipsoidal particles.
FIG. 6 shows Li obtained in this example 0.94 K 0.06 Ni 1/3 Co 1/3 Mn 1/3 O 2 As shown in the graph, the first discharge specific capacity of the sample is 162.8mAh/g, the discharge specific capacity of the sample after 50 times of recycling is 149.4mAh/g, and the capacity retention rate is 91.8%, which indicates that the sample has high discharge specific capacity and good cycle stability.
Example 3
A lithium ion battery anode material with a stoichiometric formula of Li 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 The specific preparation method comprises the following steps:
1) Weighing 0.572g of cobalt oxide, 0.5146g of nickel oxide, 0.6096g of manganese dioxide and 0.8899g of lithium hydroxide hydrate, putting 0.0801g of basic magnesium carbonate into a ball mill, putting 5mL of ethanol, and ball milling for 2 hours at the speed of 200 r/min;
2) Drying the material obtained in the step 1) for 2 hours at 80 ℃ in a blast drier, and then sintering in a muffle furnace at 1000 ℃ for 10 hours; after sintering is completed, li is obtained 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 。
FIG. 7 is Li obtained in this example 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 An XRD pattern of (a); as can be seen, each diffraction peak in the XRD spectrum of the obtained sample is narrow and sharp, and the positions and the relative intensities of each diffraction peak are all in one-to-one correspondence with the standard card, which shows that the sample has good crystallinity and completely accords with alpha-NaFeO 2 (Structure of space type, R3 m), no other impurity crystal phase appeared in each sample, indicating Mg 2+ Is not to change Li 1 Ni 1/3 Co 1/3 Mn 1/3 O 2 Other impurities are not generated due to the original crystal structure. Simultaneous sample I (003)/(104) = 1.5988, indicating that the cation mix of the sample is very low. The c/a value of the sample was 4.97683, indicating that the sample had good structural stability.
FIG. 8 is Li obtained in this example 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 SEM images of (a). As can be seen from the figure, the crystallinity of the sample is good, and the particle size distribution is uniform. The primary particles in the obtained product were hexagonal long particles (Li 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 ) The primary particles are further packed to form ellipsoidal particles.
FIG. 9 is Li obtained in this example 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 As shown in the graph, the first discharge specific capacity of the sample is 163.9mAh/g, the discharge specific capacity of the sample after 50 times of recycling is 150.7mAh/g, and the capacity retention rate is 91.9%, which indicates that the sample has high discharge specific capacity and good cycle stability.
Comparative example 1
LiNi 1/3 Co 1/3 Mn 1/3 O 2 The battery positive electrode material was prepared in the same manner as in example 1, except that the alkali metal carbonate was not used for doping modification.
LiNi obtained in this comparative example 1/3 Co 1/3 Mn 1/3 O 2 The constant current cycle chart of (2) is shown in FIG. 10, the initial discharge specific capacity is 144.3mAh/g, the discharge specific capacity of the sample after 50 times of recirculation is 126.9mAh/g, and the capacity retention rate is 87.9%.
Comparative example 2
A lithium ion battery anode material with a stoichiometric formula of Li 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 The specific preparation method comprises the following steps:
1) Weighing 0.572g of cobalt oxide, 0.5146g of nickel oxide, 0.6096g of manganese dioxide and 0.8899g of lithium hydroxide hydrate, putting 0.0801g of basic magnesium carbonate into a ball mill, putting 5mL of ethanol, and ball milling for 2 hours at the speed of 200 r/min;
2) Drying the material obtained in the step 1) for 2 hours at 80 ℃ in a blast drier, and then sintering in a muffle furnace at 900 ℃ for 10 hoursh, performing H; after sintering is completed, li is obtained 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 。
FIG. 11 shows Li obtained in this example 0.92 Mg 0.04 Ni 1/3 Co 1/3 Mn 1/3 XRD pattern of O; as can be seen, impurity peaks appear on the right side of the (104) peak and the (018) peak in the XRD pattern of the obtained sample, and the impurity peaks are diffraction peaks of NiO, indicating NiO impurities appear in the sample, ni of the transition metal layer 2+ A large amount of lithium ions enter between the layers.
The above examples are presented for clarity of illustration only and are not limiting of the embodiments. Other variations and modifications of the above description will be apparent to those of ordinary skill in the art, and it is not necessary or exhaustive of all embodiments, and thus all obvious variations or modifications that come within the scope of the invention are desired to be protected.

Claims (3)

1. The preparation method of the lithium ion battery anode material is characterized by comprising the following steps:
1) Weighing raw materials according to a stoichiometric ratio; the stoichiometric formula of the lithium ion battery anode material is as follows: li (Li) 1-x M x/a Ni 1/3 Co 1/ 3 Mn 1/3 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein 0 is<x is less than or equal to 0.1, a is the valence state of M element; m=na, K, mg or Ca; the lithium ion battery anode material takes cobalt oxide, nickel oxide, manganese dioxide, lithium hydroxide and M metal carbonate as raw materials;
2) Adding the weighed raw materials into a ball milling tank for mixing, ball milling and drying; the ball milling speed is 180-250r/min, and the time is 1.5-2.5h; the drying temperature is 80-100deg.C, and the drying time is 2-3h
3) Sintering the dried material to obtain the lithium ion battery anode material;
the sintering temperature is 950-1000 ℃ and the reaction time is 9-11h;
the primary particles in the obtained product are hexagonal long particles, and the primary particles enterForming elliptic spherical particles by one-step stacking; is Li 1-x M x/a Ni 1/3 Co 1/3 Mn 1/3 O 2 And (3) single crystals.
2. The method of claim 1, wherein the M metal is one of Na, K, mg, ca.
3. The method according to claim 1, wherein the ball milling step is performed by adding ethanol, and the mass-to-volume ratio of the ethanol to the solid-liquid mass-to-volume ratio adopted by the mixed raw materials is 0.4-0.6g/mL.
CN202110619765.3A 2021-06-03 2021-06-03 Lithium ion battery anode material and preparation method thereof Active CN113471423B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110619765.3A CN113471423B (en) 2021-06-03 2021-06-03 Lithium ion battery anode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110619765.3A CN113471423B (en) 2021-06-03 2021-06-03 Lithium ion battery anode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113471423A CN113471423A (en) 2021-10-01
CN113471423B true CN113471423B (en) 2023-09-26

Family

ID=77872089

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110619765.3A Active CN113471423B (en) 2021-06-03 2021-06-03 Lithium ion battery anode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113471423B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101764210A (en) * 2010-01-14 2010-06-30 镇江科捷锂电池有限公司 Anode material of lithium battery in Al2O3 wrapping manganese-base layered crystal structure
CN103855384A (en) * 2014-03-25 2014-06-11 海宁美达瑞新材料科技有限公司 Rare-earth doping modified lithium ion battery ternary positive electrode material and preparation method thereof
CN109473657A (en) * 2018-12-03 2019-03-15 林奈（中国）新能源有限公司 A kind of nickel cobalt aluminium manganese quaternary lithium-ion battery positive electrode material being mixed with, Preparation method and use

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101764210A (en) * 2010-01-14 2010-06-30 镇江科捷锂电池有限公司 Anode material of lithium battery in Al2O3 wrapping manganese-base layered crystal structure
CN103855384A (en) * 2014-03-25 2014-06-11 海宁美达瑞新材料科技有限公司 Rare-earth doping modified lithium ion battery ternary positive electrode material and preparation method thereof
CN109473657A (en) * 2018-12-03 2019-03-15 林奈（中国）新能源有限公司 A kind of nickel cobalt aluminium manganese quaternary lithium-ion battery positive electrode material being mixed with, Preparation method and use

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
High rate charge–discharge properties of LiNi1/3Co1/3Mn1/3O2 synthesized via a low temperature solid-state method;Long Tan, Haowen Liu等;《Solid State Ionics》;20101031;第181卷;正文第1530页右边栏第3-4段 *
Long Tan, Haowen Liu等.High rate charge–discharge properties of LiNi1/3Co1/3Mn1/3O2 synthesized via a low temperature solid-state method.《Solid State Ionics》.2010,第181卷P1530-1533. *
Syntheses and electrochemical properties of layered Li0.95Na0.05Ni1/3Co1/3Mn1/3O2 and LiNi1/3Co1/3Mn1/3O2;Chunxia Gong, Weixin Lv, Limin Qu等;《Journal of Power Sources》;20130831;第247卷;摘要 *
球磨辅助高温固相法制备Li1.0Na0.2Ni0.13Co0.13Mn0.54O2正极材料及其性能;王力臻、易祖良、张林森、方华、王诗文;《无机化学学报》;20160630;第32卷(第6期);正文第1009页右边栏第3段 *
超细球磨技术用于制备LiNi1/3Co1/3Mn1/3O2;杜柯、赵军峰、胡国荣、彭忠东;《电池》;20110630;第41卷(第3期);正文第141页右边栏第2段 *

Also Published As

Publication number Publication date
CN113471423A (en) 2021-10-01

Similar Documents

Publication Publication Date Title
Liu et al. Comparison of structure and electrochemistry of Al-and Fe-doped LiNi1/3Co1/3Mn1/3O2
CN112820861B (en) Positive electrode material, preparation method thereof and lithium ion battery
CN102891309B (en) Preparation method of spherical lithium-enriched anode material with gradient concentration
CN108767216B (en) Lithium ion battery anode material with variable slope and full concentration gradient and synthesis method thereof
CN102983326B (en) Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method
CN108483516B (en) Lithium ion battery anode material with superlattice ordered structure and synthesis method thereof
CN105336941A (en) High-voltage LiNixCoyMnzM(1-x-y-z)O2 cathode material, preparation method thereof, cathode and battery
CN108493435B (en) Lithium ion battery anode material Li (Ni)0.8Co0.1Mn0.1)1-xYxO2And preparation method
CN103794773A (en) Method for producing high-capacity 523-type ternary positive material
CN108232182A (en) A kind of modified nickel-cobalt lithium manganate cathode material and preparation method thereof
CN111403729A (en) Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery
CN113889617B (en) Composite structure high manganese-based material and preparation method and application thereof
CN103794782A (en) Lithium-rich manganese-based material, preparation method thereof and lithium-ion battery
CN115207340A (en) Sodium ion battery layered oxide positive electrode material and preparation method and application thereof
CN113517424A (en) Cobalt-free positive electrode material of high-voltage lithium ion battery and preparation method thereof
CN111952562A (en) LiZr2(PO4)3Method for preparing coated lithium-rich material
CN111342008A (en) Potassium fluoride doped lithium-rich manganese-based material and preparation method and application thereof
KR20240011822A (en) Surface coated cathode material and manufacturing method thereof, lithium ion battery
CN116093303A (en) Sodium-lanthanum co-doped modified lithium-rich manganese-based positive electrode material and preparation method thereof
CN109755530B (en) Surface coating method for titanium barium bimetallic oxide of high-pressure lithium cobalt oxide positive electrode material
CN111710843A (en) Method for manufacturing nickel cobalt lithium manganate serving as high-compaction lithium battery cathode material
CN115611319B (en) Copper-iron-manganese-based positive electrode material of sodium ion battery and preparation method thereof
CN116706017A (en) Sodium ion battery positive electrode material and preparation method thereof
CN113471423B (en) Lithium ion battery anode material and preparation method thereof
CN115881913A (en) High-nickel positive electrode material, preparation method, positive plate, battery and electric device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant