Nothing Special   »   [go: up one dir, main page]

WO2020134774A1 - 一种抗压的正极活性材料及电化学储能装置 - Google Patents

一种抗压的正极活性材料及电化学储能装置 Download PDF

Info

Publication number
WO2020134774A1
WO2020134774A1 PCT/CN2019/120511 CN2019120511W WO2020134774A1 WO 2020134774 A1 WO2020134774 A1 WO 2020134774A1 CN 2019120511 W CN2019120511 W CN 2019120511W WO 2020134774 A1 WO2020134774 A1 WO 2020134774A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
active material
electrode active
particles
primary particles
Prior art date
Application number
PCT/CN2019/120511
Other languages
English (en)
French (fr)
Inventor
杜锐
刘勇超
赵德宇
王嗣慧
沈重亨
柳娜
Original Assignee
宁德时代新能源科技股份有限公司
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
Priority claimed from CN201811637371.5A external-priority patent/CN111384371B/zh
Application filed by 宁德时代新能源科技股份有限公司 filed Critical 宁德时代新能源科技股份有限公司
Priority to US17/416,122 priority Critical patent/US20220045324A1/en
Priority to EP19903072.7A priority patent/EP3790083A4/en
Publication of WO2020134774A1 publication Critical patent/WO2020134774A1/zh

Links

Images

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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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

Definitions

  • the invention relates to the technical field of batteries, in particular to a pressure-resistant positive active material and an electrochemical energy storage device.
  • Lithium ion batteries have the advantages of high specific energy, wide application temperature range, low self-discharge rate, long cycle life, good safety performance, and no pollution. They have been used in various fields. Lithium-ion batteries have been gradually tried to replace traditional diesel locomotives as the energy system of automobiles. However, currently commonly used lithium iron phosphate (LiFePO 4 ), low nickel ternary (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ), etc., due to the limitations of the nature of the material itself, can not fully meet the lithium ion of power batteries The energy density of the positive electrode active material of the battery.
  • the high-nickel ternary cathode material is one of the main research objects of power batteries.
  • the direct side reaction between the positive electrode active material and the electrolyte is also significantly intensified, and the cycle performance is significantly deteriorated, which is one of the bottlenecks in the commercialization of mass production.
  • the main means to solve the cycle performance is to optimize the content of the main elements, increase the doping and coating modification technology. These three methods can improve the cycle performance to a certain extent, but there is still a gap with the market demand.
  • the polycrystalline high-nickel ternary material has a high nickel content and a strong surface activity, and is prone to side reactions with the electrolyte, resulting in a significant deterioration of the cell cycle performance. It is one of the main difficulties in the current market application. Through research, it is found that the ternary cathode material will have particle cracking during the cycling process, and cell failure analysis has found that particle cracking is the main reason for the deterioration of the cell's cycling performance. Therefore, how to improve the problem of particle crushing in the circulation process is particularly important for improving the circulation performance.
  • the object of the present invention is to provide a positive electrode active material with a compact structure and good compression resistance, and an electrochemical energy storage device using the positive electrode active material.
  • the positive electrode active material with better ionic performance can improve the cycle service life of the battery, control the volume expansion rate of the cycle process, and improve the dynamic performance of the battery.
  • the positive electrode active material includes secondary particles composed of primary particles, the number of primary particles per unit area in the SEM image of the secondary particles ⁇ 5 pieces/ ⁇ m 2 ⁇ 30 pieces/ ⁇ m 2 , the single particle compressive strength of the positive electrode active material is 60MPa ⁇ 300MPa, the molecular formula of the positive electrode active material is Li x Ni y Co z M k Me p O r A m , 0.95 ⁇ x ⁇ 1.05, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ k ⁇ 1, 0 ⁇ p ⁇ 0.1, 1 ⁇ r ⁇ 2, 0 ⁇ m ⁇ 2, m+r ⁇ 2, M is selected from Mn And/or Al, Me is selected from one or more of Zr, Zn, Cu, Cr, Mg, Fe, V, Ti, Sr, Sb, Y, W, Nb, and A is selected from N, F, One or more combinations of S and Cl.
  • Another aspect of the present invention provides a positive electrode material including the positive electrode active material of the present invention, an outer coating layer is provided on the surface of the positive electrode active material, the outer coating layer includes a coating element, and the outer coating layer
  • the covering element is selected from one or more of Al, Ba, Zn, Ti, Co, W, Y, Si, Sn, B, P.
  • Another aspect of the present invention provides a method for determining the number of primary particles per unit sphere surface area of secondary particles in the cathode active material or cathode material of the present invention, including the following steps:
  • the number ⁇ of primary particles per unit surface area of the positive electrode active material is calculated by the following formula:
  • x1 represents the number of primary particles in the transverse direction of the lower edge of the picture in the SEM image of 10K multiples of secondary particles
  • x2 represents the number of primary particles in the transverse direction of the upper edge of the picture in the SEM image of 10K multiples of secondary particles
  • y1 represents the number of primary particles in the longitudinal direction of the left edge of the picture in the SEM image of 10K multiples of secondary particles
  • y2 represents the number of primary particles in the longitudinal direction of the right edge of the picture in the SEM image of 10K multiples of secondary particles
  • A represents the actual measured length in the transverse direction of the SEM image of the 10K multiple of the secondary particles in mm;
  • B represents the actual measured length in the longitudinal direction of the SEM image of 10K multiples of the secondary particles in mm;
  • C represents the actual measured length corresponding to the 10K multiple of the secondary particles in the SEM picture, when the scale is 1 ⁇ m, the unit is mm/ ⁇ m;
  • Another aspect of the present invention provides an electrochemical energy storage device including the cathode active material or cathode material of the present invention.
  • the positive electrode active material of the present invention includes secondary particles composed of primary particles.
  • the secondary particles have a compact structure, high compressive strength, and a moderate ion transmission distance, which can effectively improve the problem of particle cracking in the circulation process and avoid particles due to particles.
  • the gas generation problem caused by crushing and the excellent ion-conducting performance, therefore, the lithium ion battery using the cathode active material of the present invention has good cycle performance, low volume expansion rate and good kinetic performance.
  • Figure 1 is a graph of the compressive strength of particles of Example 4 of the present invention.
  • Figure 2 is a graph of the compressive strength of particles of Comparative Example 3 of the present invention.
  • Fig. 3 is a diagram of a compressive strength testing device of the present invention.
  • FIG. 4 is an SEM image of particles of Example 1 of the present invention at 10K times.
  • the cathode active material, the cathode material according to the present invention, and the electrochemical energy storage device using the cathode active material or the cathode material according to the present invention will be described in detail below.
  • a first aspect of the present invention provides a positive electrode active material
  • the positive electrode active material includes secondary particles composed of primary particles, and the number of primary particles per unit surface area of the SEM image of the secondary particles is 5 / ⁇ m 2 to 30 pieces/ ⁇ m 2 , the single particle compressive strength of the secondary particles is 60 MPa to 300 MPa, the molecular formula of the positive electrode active material is Li x Ni y Co z M k Me p O r A m , 0.95 ⁇ x ⁇ 1.05, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ k ⁇ 1, 0 ⁇ p ⁇ 0.1, 1 ⁇ r ⁇ 2, 0 ⁇ m ⁇ 2, m+r ⁇ 2, M is selected from Mn and/or Al, Me is selected from one or more of Zr, Zn, Cu, Cr, Mg, Fe, V, Ti, Sr, Sb, Y, W, Nb, A is selected from N, F , S, Cl one or more combinations.
  • the positive electrode active material of lithium metal transition oxide is secondary particles composed of primary particles. Compared with single crystal particles, the polarization of secondary particles is smaller, which can effectively reduce the internal resistance of lithium ion batteries; There is a certain gap between the primary particles and different synthesis processes lead to significant differences in the binding force between the primary particles. By controlling the number of primary particles per unit surface area of the surface layer of the secondary particles, the surface structure of the secondary particles can be improved. Solidity.
  • the positive electrode active material of the present invention has high surface structure compactness, excellent single particle compressive strength, and moderate ion transmission distance, which can improve the problem of particle cracking during cycling, and at the same time ensure that the positive electrode active material has good ion conductivity, thereby It is ensured that the lithium ion battery using the positive electrode active material of the present invention has good cycle performance, low volume expansion rate and good dynamic performance.
  • the cathode active material is a lithium transition metal oxide, and due to the segregation of a certain element content during the preparation process, the lithium element in the molecular formula of the cathode active material may be to a certain extent
  • the relative content of lithium element in the range of 0.95 ⁇ x ⁇ 1.05 has little effect on the capacity of the positive electrode active material, optionally, the relative content of lithium element is 0.95 ⁇ x ⁇ 1. 1 ⁇ x ⁇ 1.05.
  • the positive electrode active material is a ternary lithium transition metal oxide containing at least one element of Ni, Co, and Mn or Al, and the molecular formula of the positive electrode active material Medium: 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ k ⁇ 1, 0 ⁇ p ⁇ 0.1, 1 ⁇ r ⁇ 2, 0 ⁇ m ⁇ 2, m+r ⁇ 2.
  • the positive electrode active material is a high nickel positive electrode active material, and in the molecular formula of the positive electrode active material, 0.50 ⁇ y ⁇ 0.95, 0.05 ⁇ z ⁇ 0.2, 0.05 ⁇ k ⁇ 0.4, 0 ⁇ p ⁇ 0.05.
  • the positive electrode active material may be LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.5 Co 0.25 Mn 0.25 O 2 , LiNi 0.55 Co 0.15 Mn 0.3 O 2 , LiNi 0.55 Co 0.1 Mn 0.35 O 2 , LiNi 0.55 Co 0.05 Mn 0.4 O 2 , LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.75 Co 0.1 Mn 0.15 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNi 0.85 Co 0.05 Mn 0.1 O 2 , LiNi 0.88 Co 0.05 Mn 0.07 O 2 , LiNi 0.9 Co 0.05 Mn 0.05 O 2 , LiNi 0.72 Co 0.18 Al 0.1 O 2 , LiNi 0.81 Co 0.045 Mn 0.045 Al 0.1 O 2 Me and/or A pair of active materials after partial substitution modification, where Me is selected from one of Z
  • a positive electrode active material with a high nickel content is selected from the positive electrode active materials. Since the higher the relative content of the Ni element and the higher the theoretical gram capacity of the material, the volume energy density of the battery can be effectively improved, but the high nickel positive electrode active material The amount of residual lithium on the surface is higher, and the particles are more likely to break. By controlling the surface compactness of the secondary particles of the high-nickel positive electrode active material and the compressive strength of the single particles, it can effectively solve the gas generation problem of the high-capacity battery during the cycling process , Improve the energy density and service life of the battery.
  • the single particle compressive strength of the secondary particles refers to "the particle size fluctuates by 10% in the range of the average particle diameter D v 50, and a single secondary particle is used as a single particle. Under the action of external force, the minimum pressure during crushing".
  • the single particle compressive strength of the secondary particles in the present invention is selected from 60 MPa to 300 MPa, 60 MPa to 80 MPa, 80 MPa to 100 MPa, 100 MPa to 120 MPa, 120 MPa to 150 MPa, 150 MPa to 180 MPa, 180 MPa to 200 MPa, 200 MPa to 220 MPa, 220 MPa to 240 MPa, 240MPa ⁇ 260MPa, 260MPa ⁇ 280MPa, 280MPa ⁇ 300MPa.
  • the powder density of the positive electrode active material is not less than 3.3 g/cm 3 .
  • the positive electrode active material of the present invention has good compression resistance and high powder compaction density, so it can withstand large pressure without breaking during the production of the pole piece, which is beneficial to increase the compaction density of the positive pole piece To increase the volumetric energy density of the battery.
  • Dv 10 of the secondary particles is 2 ⁇ m to 8 ⁇ m
  • D v 50 is 5 ⁇ m to 18 ⁇ m
  • D v 90 is 10 ⁇ m to 30 ⁇ m.
  • D v 10 is 2 ⁇ m to 3 ⁇ m, 3 ⁇ m to 4 ⁇ m, 4 ⁇ m to 5 ⁇ m, 5 ⁇ m to 6 ⁇ m, 6 ⁇ m to 7 ⁇ m, 7 ⁇ m to 8 ⁇ m
  • D v 50 is 5 ⁇ m to 18 ⁇ m, 5 ⁇ m to 8 ⁇ m, 8 ⁇ m to 10 ⁇ m, 10 ⁇ m to 12 ⁇ m, 12 ⁇ m to 15 ⁇ m, 15 ⁇ m to 18 ⁇ m
  • D v 90 is 10 ⁇ m to 30 ⁇ m, 10 ⁇ m to 15 ⁇ m, 15 ⁇ m to 20 ⁇ m, 20 ⁇ m to 25 ⁇ m, 25 ⁇ m to 30 ⁇ m.
  • the secondary particles are obtained by stacking primary particles in the extending direction of the primary particles, the primary particles are rod-shaped, cone-shaped, or needle-shaped, and the primary particles are extended and stacked in the radial direction Secondary particles are formed.
  • the length of the primary particles is 100 nm to 1000 nm, and the cross-sectional width is 50 nm to 400 nm.
  • the length of the primary particles is 100 nm to 1000 nm, 100 nm to 200 nm, 200 nm to 300 nm, 300 nm to 400 nm, 400 nm to 500 nm, 500 nm to 600 nm, 600 nm to 700 nm, 700 nm to 800 nm, 800 nm to 900 nm, 900 nm to 1000 nm;
  • the cross-sectional width is 50 nm to 400 nm, 50 nm to 100 nm, 100 nm to 150 nm, 150 nm to 200 nm, 200 nm to 300 nm, 300 nm to 350 nm, and 350 nm to 400 nm.
  • the ratio of the length of the primary particles to the radial cross-sectional width is 2-20, 2-5, 5-8, 8-10, 10-12, 12-15, 15-18 , 18-20.
  • the positive electrode active material of the present invention is provided, the BET of secondary particles is 0.3m 2 /g ⁇ 0.8m 2 /g,0.3m 2 /g ⁇ 0.4m 2 /g,0.4m 2 /g ⁇ 0.5m 2 /g,0.5m 2 /g ⁇ 0.6m 2 /g,0.6m 2 /g ⁇ 0.7m 2 /g,0.7m 2 /g ⁇ 0.8m 2 / g.
  • the volume particle size distribution of the secondary particles when the volume particle size distribution of the secondary particles is within the above range, it is possible to ensure that the specific surface area of the positive electrode active material is low and the ion transmission distance is moderate.
  • the particle size of the secondary particles is within the above range, the length, width, and ratio of the length to the radial cross-sectional width of the primary particles are further controlled within the above range, which can ensure that the surface and internal structure of the formed secondary particles have a high Density, the transmission distance of lithium ions between primary particles is moderate, and it is also conducive to improving the mechanical strength of secondary particles.
  • the inner coating layer includes a coating element, the inner The coating element of the coating layer is selected from one or more combinations of Al, Ba, Zn, Ti, Co, W, Y, Si, Sn, B, and P.
  • the coating elements of the inner coating layer are not reflected in the positive electrode active material molecular formula Li x Ni y Co z M k Me p O r A m . Generally, the coating elements of the inner coating layer do not enter the crystal lattice.
  • the coating element of the inner coating layer is at least two or more selected from Al, Ba, Zn, Ti, Co, W, Y, Si, Sn, B, and P.
  • the inner coating layer on the surface of the primary particles contains oxides of at least two or more of the above elements, which can improve the stability of the adhesion of the inner coating layer on the surface of the primary particles, so that the inner coating layer has both Certain ion conductivity and conductivity, reduce the impact of the inner coating layer on the polarization problem of the positive electrode active material, thereby effectively avoiding direct contact between the positive electrode active material and the electrolyte, reducing side reactions with the electrolyte, and avoiding the circulation process A large amount of gas, while ensuring the battery's low impedance, excellent cycle and rate performance.
  • a second aspect of the present invention provides a positive electrode material, including the positive electrode active material of the first aspect of the present invention, an outer coating layer is provided on the surface of the positive electrode active material, and the coating element of the outer coating layer is selected from Al, Ba, Zn , Ti, Co, W, Y, Si, Sn, B, P one or more combinations.
  • the outer coating layer is provided on the surface of the positive electrode material, at least a portion of the primary particles on the surface of the non-outermost layer of the secondary particles are provided with an inner coating layer. Further preferably, the coating material of the outer coating layer and the inner coating layer are the same.
  • the coating element of the outer coating layer is at least two or more selected from Al, Ba, Zn, Ti, Co, W, Y, Si, Sn, B, and P.
  • the outer coating layer on the surface of the positive electrode active material contains oxides of at least two or more of the above elements, which can improve the stability of the adhesion of the outer coating layer on the surface of the positive electrode active material, so that the outer coating layer It has certain ion conductivity and conductivity, reducing the impact of the outer coating layer on the polarization problem of the positive electrode active material, thereby effectively avoiding direct contact between the positive electrode active material and the electrolyte, reducing side reactions with the electrolyte, and avoiding A large amount of gas during the cycle, while ensuring that the battery has a low impedance and excellent cycle and rate performance.
  • the outer coating layer is a continuous and/or discontinuous layered coating layer; preferably, the outer coating layer is a continuous first coating layer and a non-continuous layer In the composite form of the continuous second coating layer, more preferably, the substance forming the discontinuous coating layer is different from the substance of the continuous coating layer.
  • the element forming the discontinuous coating layer is selected from one or more combinations of Al, Ba, Zn, Ti, Co, and the element forming the continuous coating layer is selected from W, Y, Si, B, A combination of one or more of P and Sn.
  • the discontinuous layered coating layer may be a discrete island-shaped outer coating layer, and the discontinuous coating layer may act like a "nano nail" on the surface of the cathode active material Not only can it be firmly combined with the positive electrode active material, which effectively reduces the probability of the positive electrode active material particles breaking during the cycle, but the discontinuous layered coating can also enhance the primary particles and primary particles of the positive electrode active material.
  • the binding force between them makes the overall mechanical strength of the positive electrode active material (especially in the form of secondary particles formed by agglomeration of primary particles) increase and is not easily broken.
  • a continuous coating layer is also formed on the surface of the positive electrode active material, which can effectively reduce the roughness of the surface of the positive electrode material, reduce the specific surface area of the positive electrode material, thereby reducing the effective contact area of the positive electrode material surface and the electrolyte, and reducing the positive electrode material surface and
  • the side reaction of the electrolyte avoids the side reaction of the positive electrode material and the electrolyte to generate a large amount of gas.
  • a third aspect of the present invention provides a method for determining the number of primary particles per unit sphere surface area of secondary particles in the positive electrode active material of the first aspect of the present invention or the positive electrode material of the second aspect, including the following steps:
  • step (1) the number of primary particles per unit area in the positive electrode active material ⁇ (pieces/ ⁇ m 2 ) is calculated by the following formula:
  • x1 represents the number of primary particles in the transverse direction of the lower edge of the picture in the SEM image of 10K multiples of secondary particles
  • x2 represents the number of primary particles in the transverse direction of the upper edge of the picture in the SEM image of 10K multiples of secondary particles
  • y1 represents the number of primary particles in the longitudinal direction of the left edge of the picture in the SEM image of 10K multiples of secondary particles
  • y2 represents the number of primary particles in the longitudinal direction of the right edge of the picture in the SEM image of 10K multiples of secondary particles
  • A represents the actual measured length in the transverse direction of the SEM image of the 10K multiple of the secondary particles in mm;
  • B represents the actual measured length in the longitudinal direction of the SEM image of 10K multiples of the secondary particles in mm;
  • C represents the actual measured length corresponding to the 10K multiple of the secondary particles in the SEM picture, when the scale is 1 ⁇ m, the unit is mm/ ⁇ m;
  • the above method can be used to intuitively characterize the number ⁇ of primary particles per unit surface area of the sphere, which truly reflects the size and distribution of primary particles on the surface of the secondary particles.
  • the method of calculating the number of primary particles in the SEM picture at 10K times of secondary particles is an effective way to objectively characterize the compactness of the secondary particle sphere structure composed of primary particles.
  • the fourth aspect of the present invention provides the preparation method of the positive electrode active material of the first aspect of the present invention
  • the method of the positive electrode active material should be known to those skilled in the art, for example, it may include: According to the element composition of the positive electrode active material, select the appropriate raw material and ratio of the positive electrode active material.
  • the raw material of the positive electrode active material may include a ternary material precursor of nickel, cobalt, manganese, and/or aluminum, a lithium source, a Me source, an A source, etc.
  • the ratio between the raw materials generally refers to the elements in the positive electrode active material Proportioning.
  • the ternary material precursor may include, but not limited to, Ni 1/3 Co 1/3 Mn 1/3 (OH) 2 , Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 , Ni 0.5 Co 0.25 Mn 0.25 (OH) 2 , Ni 0.55 Co 0.15 Mn 0.3 (OH) 2 , Ni 0.55 Co 0.1 Mn 0.35 (OH) 2 , Ni 0.55 Co 0.05 Mn 0.4 (OH) 2 , Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 , Ni 0.75 Co 0.1 Mn 0.15 (OH) 2 , Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 , Ni 0.88 Co 0.05 Mn 0.07 (OH) 2 , 0.9Ni 0.8 Co 0.2 (OH) 2 ⁇ 0.1Al(OH) 3 , 0.9Ni 0.9 Co 0.05 Mn 0.05 (OH) 2 ⁇ 0.1Al(OH) 3 , the lithium source may be a lithium-containing compound, and the lithium-containing compound may include but not limited to LiOH ⁇ H 2
  • the method for preparing the positive electrode active material may further include providing an inner coating layer on the surface of the primary particles at least part of the secondary particles in the non-outermost layer, and forming the inner coating layer on the surface of the primary particles It should be known to those skilled in the art, for example, it may include: sintering the primary particles in the presence of a compound containing a coating element to form an inner coating layer on the surface of the primary particles.
  • the inner coating technology and the outer coating technology can be combined into a one-step process, and the coating can pass through the surface of the secondary particles and the internal pores, The outer surface of the secondary particles and at least part of the inner primary particles are simultaneously coated.
  • the compound containing the coating element may be an oxide, nitrate, phosphoric acid containing one or more elements of Al, Ba, Zn, Ti, Co, W, Y, Si, Sn, B, P Salts, carbonates, etc.
  • the amount of the compound containing the coating element may be 0.01% to 0.5%.
  • the sintering conditions may be high-temperature sintering at 200°C to 700°C.
  • a fifth aspect of the present invention provides a method for preparing a positive electrode material of the second aspect of the present invention, comprising: forming an outer coating layer on the surface of the positive electrode active material of the first aspect of the present invention.
  • the method of forming an outer coating layer on the surface of the positive electrode active material should be known to those skilled in the art, for example, it may include: sintering the positive electrode active material in the presence of a compound containing a coating element to An outer coating layer is formed on the surface of the active material.
  • a person skilled in the art may select a suitable type, compounding ratio, and sintering conditions of the compound containing the coating element according to parameters such as the composition of the outer coating layer, the powder compressive strength of the positive electrode active material, and the resistivity powder resistivity.
  • the compound containing the coating element may be an oxide, nitrate, phosphoric acid containing one or more elements of Al, Ba, Zn, Ti, Co, W, Y, Si, Sn, B, P Salts, carbonates, etc.
  • the amount of the compound containing the coating element may be 0.01% to 0.5%.
  • the sintering conditions may be high-temperature sintering at 200°C to 700°C.
  • a sixth aspect of the present invention provides an electrochemical energy storage device including the positive electrode active material of the first aspect of the present invention or the positive electrode material of the second aspect of the present invention.
  • the electrochemical energy storage device may be a supercapacitor, a lithium ion battery, a lithium metal battery, or a sodium ion battery.
  • the electrochemical energy storage device is a lithium ion battery are shown, but the present invention is not limited thereto.
  • a lithium-ion battery in a lithium-ion battery, it includes a positive pole piece, a negative pole piece, a separator that is spaced between the positive pole piece and the negative pole piece, and an electrolyte, wherein the positive pole piece includes the positive electrode active material of the first aspect of the invention Or the positive electrode material of the second aspect of the invention.
  • the method for preparing the lithium-ion battery should be known to those skilled in the art.
  • the positive pole piece, the separator, and the negative pole piece can each be a layered body, so that they can be cut to the target size in turn Stacked, it can also be wound to the target size for the formation of batteries, and can be further combined with the electrolyte to form a lithium-ion battery.
  • the positive electrode tab includes a positive electrode current collector and a positive electrode material layer on the positive electrode current collector, the positive electrode material layer including the positive electrode active material of the first aspect of the invention or the second aspect of the invention Positive electrode material, binder, conductive agent.
  • a person skilled in the art may select a suitable method to prepare the positive electrode sheet.
  • the method may include the steps of: mixing a positive electrode active material or a positive electrode material, a binder, and a conductive agent to form a slurry, and then coating the positive electrode current collector .
  • the binder generally includes a fluorine-containing polyolefin-based binder.
  • the fluorine-containing polyolefin-based binder Compared with the fluorine-containing polyolefin-based binder, water is usually a good solvent, that is, the fluorine-containing polyolefin-based binder is usually in It has good solubility in water.
  • the fluorine-containing polyolefin binder may include, but not limited to, polyvinylidene fluoride (PVDF), vinylidene fluoride copolymer, etc. or their modification (for example, carboxylic acid, Modified derivatives such as acrylic acid and acrylonitrile.
  • the conductive agent may be various conductive agents suitable for lithium ion (secondary) batteries in the art, for example, may include but not limited to acetylene black, conductive carbon black, carbon fiber (VGCF), carbon nanotube (CNT), One or more combinations of Ketjen Black, etc.
  • the positive electrode current collector may generally be a layered body, the positive electrode current collector is usually a structure or part that can collect current, and the positive electrode current collector may be various materials suitable for use as a positive electrode current collector of a lithium ion battery in the art, for example
  • the positive electrode current collector may include but is not limited to metal foil, etc., and more specifically may include but not limited to copper foil, aluminum foil, etc.
  • the negative electrode tab usually includes a negative electrode current collector and a negative electrode active material layer on the surface of the negative electrode current collector, and the negative electrode active material layer usually includes a negative electrode active material.
  • the negative electrode active material may be various materials suitable for negative electrode active materials of lithium ion batteries in the art, for example, may include but not limited to graphite, soft carbon, hard carbon, carbon fiber, mesophase carbon microspheres, silicon-based materials , Tin-based materials, lithium titanate or other metals that can be alloyed with lithium, etc., in one or more combinations.
  • the graphite may be selected from one or more of artificial graphite, natural graphite and modified graphite;
  • the silicon-based material may be selected from elemental silicon, silicon oxide compound, silicon carbon composite, silicon alloy One or more combinations of the above;
  • the tin-based material may be selected from one or more combinations of elemental tin, tin oxide compounds, and tin alloys.
  • the negative electrode current collector is usually a structure or part that collects current.
  • the negative electrode current collector may be various materials suitable for use as a negative electrode current collector of a lithium ion battery in the art.
  • the negative electrode current collector may include but is not limited to The metal foil and the like may more specifically include but not limited to copper foil and the like.
  • the separator may be various materials suitable for the separator of the lithium ion battery in the art, for example, may include but not limited to polyethylene, polypropylene, polyvinylidene fluoride, aramid, and poly One or more combinations of ethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester and natural fiber.
  • the electrolyte may be various electrolytes suitable for lithium ion batteries in the art, for example, the electrolyte generally includes an electrolyte and a solvent, and the electrolyte may generally include a lithium salt and the like, more specifically
  • the lithium salt may be an inorganic lithium salt and/or an organic lithium salt, etc., and may specifically include but not limited to, the lithium salt may be selected from LiPF 6 , LiBF 4 , LiN(SO 2 F) 2 (abbreviated as LiFSI ), LiN(CF 3 SO 2 ) 2 (abbreviated as LiTFSI), LiClO 4 , LiAsF 6 , LiB(C 2 O 4 ) 2 (abbreviated as LiBOB), LiBF 2 C 2 O 4 (abbreviated as LiDFOB) One or more combinations.
  • the concentration of the electrolyte may be between 0.8 mol/L and 1.5 mol/L.
  • the solvent may be any solvent suitable for an electrolyte of a lithium ion battery in the art.
  • the solvent of the electrolyte is usually a non-aqueous solvent, preferably an organic solvent, and may specifically include but not limited to ethylene carbonate, carbonic acid Propylene ester, butylene carbonate, pentenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, etc. or a combination of one or more of their halogenated derivatives.
  • one or more of the method steps mentioned in the present invention does not exclude that there may be other method steps before or after the combination step or that other method steps may be inserted between these explicitly mentioned steps unless otherwise Explained; It should also be understood that the combined connection relationship between one or more devices/devices mentioned in the present invention does not exclude that there may be other devices/devices or those mentioned explicitly in these before and after the combined device/device Other devices/apparatuses can also be inserted between the two devices/apparatuses unless otherwise stated.
  • each method step is only a convenient tool to identify each method step, not to limit the order of each method step or to limit the scope of the present invention, the change or adjustment of its relative relationship, in If the technical content is not substantially changed, it should be regarded as the scope of the invention.
  • Ni 0.8 Co is prepared by using the hydroxide co-precipitation technology 0.1 Mn 0.1 (OH) 2 .
  • the initial pH during co-precipitation was controlled to be 9.5
  • the ammonia concentration was 0.4M
  • the aging time after reaction was 5h.
  • Step 1 Mix the prepared positive electrode material, binder polyvinylidene fluoride, and conductive agent acetylene black according to a mass ratio of 98:1:1, add N ⁇ methylpyrrolidone (NMP), and stir evenly under the action of a vacuum mixer Obtain the positive electrode slurry; evenly coat the positive electrode slurry on an aluminum foil with a thickness of 12 ⁇ m;
  • NMP N ⁇ methylpyrrolidone
  • Step 2 The coated pole pieces are dried in an oven at 100°C ⁇ 130°C;
  • Step 3 After cold pressing and slitting, a positive pole piece is obtained.
  • the organic solvent is mixed with ethylene carbonate (EC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC) in a volume ratio of 20:20:60 in an argon atmosphere glove box with a water content of ⁇ 10ppm , Dissolve the fully dried lithium salt at a concentration of 1 mol/L in an organic solvent, mix well, and obtain an electrolyte.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • the positive pole piece, the separator and the negative pole piece in order, so that the separator is between the positive and negative pole pieces to play the role of isolation, and then wound into a square bare cell, and put into an aluminum plastic film. After baking and removing water at 80°C, the corresponding non-aqueous electrolyte is injected and sealed, and after standing, hot and cold pressing, formation, jigs, and volume separation, the finished battery is obtained.
  • Example 2 It is basically the same as Example 1 except for the preparation method of the cathode material: during the preparation of the precursor, the pH value during the co-precipitation is adjusted to 10.5, the ammonia concentration is 0.3M, and the aging time after the reaction is 3h.
  • Example 2 It is basically the same as Example 1 except for the preparation method of the cathode material: during the preparation of the precursor, the pH value during the co-precipitation is adjusted to 11, the ammonia concentration is 0.2 M, and the aging time after the reaction is 5 hours.
  • Example 2 It is basically the same as Example 1 except for the preparation method of the cathode material: during the preparation of the precursor, the pH value during co-precipitation is adjusted to 10, the ammonia concentration is 0.4 M, and the aging time after the reaction is 2 h.
  • Example 2 It is basically the same as Example 1 except for the preparation method of the cathode material: during the preparation of the precursor, the pH value during the coprecipitation is adjusted to 11.5, the ammonia concentration is 0.3M, and the aging time after the reaction is 2h.
  • Example 2 It is basically the same as Example 1 except for the preparation method of the positive electrode material: during the preparation of the precursor, the pH during co-precipitation is adjusted to 9.8, the ammonia concentration is 0.3 M, and the aging time after the reaction is 4 h.
  • Example 2 It is basically the same as Example 1 except for the preparation method of the cathode material: the relative content of Ni, Co and Mn elements in the precursor is 0.75:0.1:0.15, and the pH value during the coprecipitation is adjusted during the preparation of the precursor 10.2.
  • the ammonia concentration is 0.5M and the aging time after the reaction is 6h.
  • Example 2 It is basically the same as Example 1 except for the preparation method of the cathode material: the relative content of Ni, Co, and Mn elements in the precursor is 0.6:0.2:0.2, and the pH value during coprecipitation is adjusted during the preparation of the precursor 11.5. The ammonia concentration is 0.6M, and the aging time after the reaction is 3h.
  • Example 2 It is basically the same as Example 1, except that the preparation method of the cathode material is: the relative content of Ni, Co, and Mn elements in the precursor is 0.55:0.15:0.3, and the pH value during the coprecipitation is adjusted during the preparation of the precursor 11.2.
  • the ammonia concentration is 0.3M, and the aging time after the reaction is 2h.
  • Example 2 It is basically the same as Example 1 except for the preparation method of the cathode material: the relative content of Ni, Co and Mn elements in the precursor is 0.33:0.33:0.33, and the pH value during the coprecipitation is adjusted during the preparation of the precursor 10.9.
  • the ammonia concentration is 0.4M and the aging time after the reaction is 3h.
  • the preparation method of Comparative Example 1 refers to the preparation method of Example 1 as described above, except that the preparation method of the positive electrode material is: during the preparation of the precursor, the pH value during the coprecipitation is adjusted to 11, the ammonia concentration is 0.5M, and the reaction The aging time after is 6h.
  • the preparation method of Comparative Example 2 refers to the preparation method of Example 1 as described above, except that the preparation method of the cathode material is: during the preparation of the precursor, the pH value during the coprecipitation is adjusted to 12, the ammonia concentration is 0.6M, and the reaction The aging time after is 7h.
  • the preparation method of Comparative Example 3 refers to the preparation method of Example 1 as described above, except that the preparation method of the cathode material is: during the preparation of the precursor, the pH value during the coprecipitation is adjusted to 10.5, the ammonia concentration is 0.1M, and the reaction The aging time after is 6h.
  • the positive electrode materials prepared in Examples 1 to 10 and Comparative Examples 1 to 3 were used to test the compressive strength of single particles per unit sphere area of secondary particles, the number of primary particles ⁇ , compacted density and BET. The test results are shown in Table 2.
  • the BET test is carried out using the national standard method gas adsorption BET method to determine the specific surface area of solid materials GB/T 19587-2004 test method.
  • the compaction density test is carried out using the GB/T 24533-2009 test method for graphite-based anode materials for lithium-ion batteries on the national standard, and the test pressure is 5 tons.
  • the volume expansion rate (%) of the battery (volume after standing for 30 days/initial volume-1) ⁇ 100%.
  • Lithium-ion battery was allowed to stand for 2h at a constant temperature of 25°C, then charged to 4.2V according to 1/3C under 2.8V ⁇ 4.2V, then charged at 4.2V with constant voltage to current ⁇ 0.05mA, and left for 5min Then, discharge to 2.8V according to 1C, and record the capacity of the lithium-ion battery; divide the capacity test value by the mass of the cathode material in the lithium-ion battery, which is 1/3C capacity of the cathode material.
  • the test results are shown in Table 3.
  • the number of primary particles per unit sphere area of the positive electrode material in Comparative Example 1 is moderate, and the compressive strength of the single particles is low, indicating that the binding force between the primary particles in the secondary particles is weak, so the prepared positive pole piece
  • the secondary particles are easy to break during the cold pressing of the pole piece and the cycle, resulting in a large number of fresh surfaces in the positive electrode material directly contacting the electrolyte, so the gas production is serious and the cycle performance is poor.
  • the relative contents of Ni, Co, and Mn elements in the lithium transition metal oxide in the cathode material are different.
  • the number of primary particles per unit sphere area of the cathode material and the compressive strength of the single particles are In a specific range, as the Ni content decreases, the discharge capacity of the lithium-ion battery decreases slightly, but the cycle performance and gas production issues are significantly optimized.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明涉及电池技术领域，特别是涉及一种抗压的正极活性材料及电化学储能装置。所述正极活性材料包括由一次颗粒组成的二次颗粒，所述二次颗粒的SEM图谱中单位球面积内一次颗粒的个数σ为5个/μm2～30个/μm2，所述二次颗粒的单颗粒抗压强度为60MPa～300MPa，所述正极活性材料的分子式为LixNiyCozMkMepOrAm，0.95≤x≤1.05，0≤y≤1，0≤z≤1，0≤k≤1，0≤p≤0.1，1≤r≤2，0≤m≤2，m+r≤2，M选自Mn和/或Al，Me选自Zr、Zn、Cu、Cr、Mg、Fe、V、Ti、Sr、Sb、Y、W、Nb中的一种或多种的组合，A选自N、F、S、Cl中的一种或多种的组合。本发明的正极活性材料的颗粒结构紧实、具有较高的单颗粒抗压强度，使用本发明所述正极活性材料的锂离子电池具有良好的循环性能、较低的体积膨胀率以及良好的动力学性能。

Description

一种抗压的正极活性材料及电化学储能装置 技术领域
本发明涉及电池技术领域，特别是涉及一种抗压的正极活性材料及电化学储能装置。
背景技术
随着能源危机以及环境问题的不断升级，开发新型绿色能源已迫在眉睫。锂离子电池具有比能量高、应用温度范围宽、自放电率低、循环寿命长、安全性能好、无污染等优点，现已被应用于各个领域中。锂离子电池作为汽车的能源系统取代传统内燃机车已在世界各地逐步尝试。然而目前常用的磷酸铁锂(LiFePO 4)、低镍三元(LiNi 1/3Co 1/3Mn 1/3O 2)等，由于受到材料本身的性质局限，不能完全满足动力电池对锂离子电池正极活性材料能量密度的需求。提高高镍三元正极材料的镍含量可以提升电池的能量密度，因此，高镍三元正极材料是目前动力电池的主要研究对象之一。但是，随着镍含量的增加，正极活性材料与电解液直接的副反应也明显加剧，循环性能明显恶化，是目前量产商业化的瓶颈之一。
目前在材料层面，解决循环性能主要手段为主元素含量优化、增加掺杂及包覆改性技术。这三种手段均能一定程度的提高循环性能，但仍与市场需求存在差距。多晶的高镍三元材料的由于镍含量高，表面活性强，容易与电解液发生副反应，导致电芯循环性能恶化明显，是目前市场化应用的主要难点之一。通过研究发现，三元正极材料在循环过程中，会存在颗粒开裂的现象，而电芯失效分析发现颗粒开裂是电芯循环性能恶化的主要原因。因此，如何改善循环过程中的颗粒破碎问题对循环性能的提升尤为重要。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种结构紧密、抗压性能较好的正极活性材料以及使用该正极活性材料的电化学储能装置，通过使用力学强度优良、导离子性能较好的正极活性材料，提升电池的循环使用寿命、控制循环过程的体积膨胀率、提升电池的动力学性能。
为实现上述目的及其他相关目的，本发明的一方面提供一种正极活性材料，正极活性材料包括由一次颗粒组成的二次颗粒，二次颗粒的SEM图谱中单位面积内一次颗粒的个数σ为5个/μm 2～30个/μm 2，正极活性材料的单颗粒抗压强度为60MPa～300MPa，正极活性材料的分子式为Li xNi yCo zM kMe pO rA m，0.95≤x≤1.05，0≤y≤1，0≤z≤1，0≤k≤1，0≤p≤0.1，1≤r≤2，0≤m≤2，m+r≤2，M选自Mn和/或Al，Me选自Zr、Zn、Cu、Cr、Mg、Fe、V、Ti、Sr、Sb、Y、W、 Nb中的一种或多种的组合，A选自N、F、S、Cl中的一种或多种的组合。
本发明的另一方面提供一种正极材料，包括本发明的正极活性材料，正极活性材料表面设置有外包覆层，所述外包覆层包括包覆元素，所述外包覆层的包覆元素选自Al、Ba、Zn、Ti、Co、W、Y、Si、Sn、B、P中的一种或多种的组合。
本发明的另一方面提供一种测定本发明的正极活性材料或正极材料中二次颗粒的单位球表面积内一次颗粒的个数的方法，包括以下步骤：
(1)选取粒径为所述二次颗粒平均粒径D v50±20％的正极活性材料样品，对样品进行SEM检测，得到10K倍数下的SEM图谱；
(2)根据步骤(1)得到的SEM图谱，通过以下公式计算正极活性材料中单位球表面积内一次颗粒的个数σ：
σ＝(x1+x2)/2*(y1+y2)/2/(A/C*B/C)
其中，
x1表示在二次颗粒10K倍数的SEM图中，图片下边缘横向上的一次颗粒的个数；
x2表示在二次颗粒10K倍数的SEM图中，图片上边缘横向上的一次颗粒的个数；
y1表示在二次颗粒10K倍数的SEM图中，图片左边缘纵向上的一次颗粒的个数；
y2表示在二次颗粒10K倍数的SEM图中，图片右边缘纵向上的一次颗粒的个数；
A表示二次颗粒10K倍数的SEM图的横向实际测量长度，单位为mm；
B表示二次颗粒10K倍数的SEM图的纵向实际测量长度，单位为mm；
C表示在二次颗粒10K倍数的SEM图中，标尺为1μm时对应的实际测量长度，单位为mm/μm；
在计算二次颗粒10K倍数的SEM图中的一次颗粒的个数时，只要出现了一次颗粒的一部分，就算作一个一次颗粒。
本发明的另一方面提供一种电化学储能装置，包括本发明的正极活性材料或正极材料。
相对于现有技术，本发明的有益效果为：
本发明的正极活性材料包括由一次颗粒组成的二次颗粒，所述二次颗粒的结构紧实、抗压强度高、离子传输距离适中，能够有效改善循环过程中的颗粒开裂问题，避免因颗粒破碎而引起的产气问题，并且导离子性能优良，因此使用本发明所述正极活性材料的锂离子电池具有良好的循环性能、较低的体积膨胀率以及良好的动力学性能。
附图说明
图1是本发明实施例4颗粒抗压强度曲线图。
图2是本发明对比例3颗粒抗压强度曲线图。
图3是本发明抗压强度测试装置图。
图4是本发明实施例1颗粒10K倍下的SEM图。
具体实施方式
下面详细说明根据本发明的正极活性材料、正极材料以及使用本发明正极活性材料或正极材料的电化学储能装置。
本发明的第一方面提供一种正极活性材料，所述正极活性材料包括由一次颗粒组成的二次颗粒，所述二次颗粒的SEM图谱中单位球表面积内一次颗粒的个数σ为5个/μm 2～30个/μm 2，所述二次颗粒的单颗粒抗压强度为60MPa～300MPa，所述正极活性材料的分子式为Li xNi yCo zM kMe pO rA m，0.95≤x≤1.05，0≤y≤1，0≤z≤1，0≤k≤1，0≤p≤0.1，1≤r≤2，0≤m≤2，m+r≤2，M选自Mn和/或Al，Me选自Zr、Zn、Cu、Cr、Mg、Fe、V、Ti、Sr、Sb、Y、W、Nb中的一种或多种的组合，A选自N、F、S、Cl中的一种或多种的组合。锂金属过渡氧化物的正极活性材料为一次颗粒组成的二次颗粒，相比于单晶颗粒，二次颗粒的极化较小，能够有效降低锂离子电池的内阻；但是由于二次颗粒内部的一次颗粒之间存在一定间隙且不同的合成工艺导致一次颗粒间的结合力有明显差异，通过控制二次颗粒表层单位球表面积内一次颗粒的个数，能够提高二次颗粒的表面结构的紧实度。本发明中的正极活性材料的表面结构紧实度较高、单颗粒抗压强度优良、离子传输距离适中，能够改善循环过程中的颗粒开裂问题，同时保证正极活性材料的导离子性能良好，从而保证使用本发明所述正极活性材料的锂离子电池具有良好的循环性能、较低的体积膨胀率以及良好的动力学性能。
本发明所提供的正极活性材料中，所述正极活性材料为锂过渡金属氧化物，由于在制备过程中存在一定的元素含量偏析，因此所述正极活性材料的分子式中锂元素可能在一定程度上存在贫锂或者富锂的情况，锂元素的相对含量范围在0.95≤x≤1.05时，对所述正极活性材料的容量发挥影响不大，可选的，锂元素的相对含量为0.95≤x≤1、1≤x≤1.05。
本发明所提供的正极活性材料中，优选的，所述正极活性材料为同时含有Ni、Co，以及Mn或Al中至少一种元素的三元锂过渡金属氧化物，所述正极活性材料的分子式中：0<y<1，0<z<1，0<k<1，0≤p≤0.1，1≤r≤2，0≤m≤2，m+r≤2。
作为本发明的进一步优选方式，所述正极活性材料为高镍正极活性材料，在所述正极活性材料的分子式中，0.50<y≤0.95，0.05≤z≤0.2，0.05≤k≤0.4，0≤p≤0.05。具体的，所述正极活性材料可以为LiNi 1/3Co 1/3Mn 1/3O 2、LiNi 0.5Co 0.2Mn 0.3O 2、LiNi 0.5Co 0.25Mn 0.25O 2、LiNi 0.55Co 0.15Mn 0.3O 2、LiNi 0.55Co 0.1Mn 0.35O 2、LiNi 0.55Co 0.05Mn 0.4O 2、LiNi 0.6Co 0.2Mn 0.2O 2、LiNi 0.75Co 0.1Mn 0.15O 2、LiNi 0.8Co 0.1Mn 0.1O 2、LiNi 0.85Co 0.05Mn 0.1O 2、LiNi 0.88Co 0.05Mn 0.07O 2、LiNi 0.9Co 0.05Mn 0.05O 2、LiNi 0.72Co 0.18Al 0.1O 2、LiNi 0.81Co 0.045Mn 0.045Al 0.1O 2，也可以为上述物质经过Me和/或A对进行部分取代改性后的活性材料，其中，Me选自Zr、Zn、Cu、Cr、Mg、Fe、V、Ti、Sr、Sb、Y、W、Nb中的一种或多种的组合，A选自N、F、S、Cl中的一种或多种的组合。
更为优选的，在所述正极活性材料的分子式中，0.70≤y≤0.95，0≤z≤0.2，0≤k≤0.2，0≤p≤0.05。
本发明中正极活性材料中选择镍含量较高的正极活性材料，由于Ni元素的相对含量越高、该材料的理论克容量越高，能够有效提高电池的体积能量密度，但是高镍正极活性材料的表面残锂量较高、颗粒更加容易发生破碎，通过控制高镍正极活性材料的二次颗粒表面紧实度、单颗粒的抗压强度，能够有效解决高容量电池在循环过程的产气问题，提高电池的能量密度和使用寿命。
本发明所提供的正极活性材料中，所述二次颗粒的单颗粒抗压强度，是指“粒径在平均粒径D v50上下波动10％范围、单独的一个二次颗粒作为单颗粒，在外力作用下，压碎时的最小压强”。本发明中二次颗粒的单颗粒抗压强度选自60MPa～300MPa、60MPa～80MPa、80MPa～100MPa、100MPa～120MPa、120MPa～150MPa、150MPa～180MPa、180MPa～200MPa、200MPa～220Mpa、220MPa～240Mpa、240MPa～260MPa、260MPa～280MPa、280MPa～300MPa。
本发明所提供的正极活性材料中，所述正极活性材料的粉体压实密度不低于3.3g/cm 3。本发明所述的正极活性材料的抗压性能良好、粉体压实密度高，因此在极片制作过程中，能够承受较大的压力而不发生破碎，有利于提高正极极片的压实密度，提高电池的体积能量密度。
本发明所提供的正极活性材料中，所述二次颗粒的D v10为2μm～8μm，D v50为5μm～18μm，D v90为10μm～30μm。可选的，D v10为2μm～3μm、3μm～4μm、4μm～5μm、5μm～6μm、6μm～7μm、7μm～8μm，D v50为5μm～18μm、5μm～8μm、8μm～10μm、10μm～12μm、12μm～15μm、15μm～18μm，D v90为10μm～30μm、10μm～15μm、15μm～20μm、20μm～25μm、25μm～30μm。
本发明所提供的正极活性材料中，所述二次颗粒为一次颗粒按一次颗粒的延伸方向堆积获得，所述一次颗粒为棒状、锥状、或针状，一次颗粒沿其径向方向延伸堆积形成二次颗粒。 所述一次颗粒的长度为100nm～1000nm，截面宽度为50nm～400nm。可选的，所述一次颗粒长度为100nm～1000nm、100nm～200nm、200nm～300nm、300nm～400nm、400nm～500nm、500nm～600nm、600nm～700nm、700nm～800nm、800nm～900nm、900nm～1000nm；截面宽度为50nm～400nm、50nm～100nm、100nm～150nm、150nm～200nm、200nm～300nm、300nm～350nm、350nm～400nm。
作为本发明的一种优选方式，所述一次颗粒的长度与径向截面宽度的比值为2～20、2～5、5～8、8～10、10～12、12～15、15～18、18～20。
本发明所提供的正极活性材料中，所述二次颗粒的BET为0.3m 2/g～0.8m 2/g、0.3m 2/g～0.4m 2/g、0.4m 2/g～0.5m 2/g、0.5m 2/g～0.6m 2/g、0.6m 2/g～0.7m 2/g、0.7m 2/g～0.8m 2/g。
本发明中所提供的正极活性材料中，二次颗粒的体积粒径分布在上述范围内时，能够保证正极活性材料的比表面积较低、同时离子传输距离适中。当二次颗粒的粒径在上述范围内时，进一步控制一次颗粒的长度、宽度以及长度与径向截面宽度的比值在上述范围，能够保证形成的二次颗粒的表面以及内部结构具有较高的致密度，锂离子在一次颗粒之间的传输距离适中，还有利于提升二次颗粒的力学强度。
本发明所提供的正极活性材料中，所述二次颗粒中，至少部分的非最外层位置的一次颗粒表面设置有内包覆层，所述内包覆层包括包覆元素，所述内包覆层的包覆元素选自Al、Ba、Zn、Ti、Co、W、Y、Si、Sn、B、P中的一种或多种的组合。内包覆层的包覆元素不体现在正极活性材料分子式Li xNi yCo zM kMe pO rA m中，通常情况下内包覆层的包覆元素并不进入晶格中。
作为本发明的一种优选方式，所述内包覆层的包覆元素至少选自Al、Ba、Zn、Ti、Co、W、Y、Si、Sn、B、P中的两种或以上。本发明中，在一次颗粒表面的内包覆层中含有至少两种及以上的上述元素形成的氧化物，可以提高内包覆层在一次颗粒表面附着的稳定性，使内包覆层兼具一定的导离子性和导电子性，减少内包覆层对正极活性材料极化问题的影响，从而有效地避免正极活性材料与电解液的直接接触，降低与电解液的副反应，避免循环过程中大量气体，同时保证电池的阻抗较低、循环和倍率性能优良。
本发明第二方面提供一种正极材料，包括本发明第一方面的正极活性材料，所述正极活性材料表面设置有外包覆层，外包覆层的包覆元素选自Al、Ba、Zn、Ti、Co、W、Y、Si、Sn、B、P中的一种或多种的组合。
作为本发明的一种优选方式，在所述正极材料表面设置有外包覆层的同时，所述二次颗 粒中至少部分的非最外层位置的一次颗粒表面设置有内包覆层。进一步优选地，所述外包覆层与所述内包覆层的包覆物质相同。
作为本发明的一种优选方式，所述外包覆层的包覆元素至少选自Al、Ba、Zn、Ti、Co、W、Y、Si、Sn、B、P中的两种或以上。本发明中，在正极活性材料表面的外包覆层中含有至少两种及以上的上述元素形成的氧化物，可以提高外包覆层在正极活性材料表面附着的稳定性，使外包覆层兼具一定的导离子性和导电子性，减少外包覆层对正极活性材料极化问题的影响，从而有效地避免正极活性材料与电解液的直接接触，降低与电解液的副反应，避免循环过程中大量气体，同时保证电池的阻抗较低、循环和倍率性能优良。
本发明所提供的正极材料中，所述外包覆层为连续的和/或非连续的层状包覆层；优选地，所述外包覆层为连续状的第一包覆层与非连续状的第二包覆层的复合形态，更优选地，形成所述非连续的包覆层的物质与所述连续状包覆层的物质不同。其中，形成非连续状包覆层的元素选自Al、Ba、Zn、Ti、Co中的一种或多种的组合，形成连续状包覆层的元素选自W、Y、Si、B、P、Sn中一种或多种的组合。
本发明所提供的正极材料中，非连续的层状包覆层可以是离散的岛状形态的外包覆层，非连续的包覆层可在正极活性材料的表面起到类似“纳米钉”的作用，这样不仅可与正极活性材料牢固地结合，有效地降低循环过程中正极活性材料颗粒破碎的概率，同时非连续的层状包覆层还能增强正极活性材料的一次颗粒与一次颗粒之间的结合力，使得正极活性材料(尤其是一次颗粒团聚形成的二次颗粒形式)整体的机械强度增加，不容易破碎。同时，还在正极活性材料表面形成连续状包覆层，能有效降低正极材料表面的粗糙度，降低正极材料的比表面积，进而减少正极材料表面与电解液的有效接触面积，降低正极材料表面与电解液的副反应，避免正极材料表面与电解液发生副反应而产生大量气体。
本发明第三方面提供一种测定本发明第一方面的正极活性材料或第二方面的正极材料中二次颗粒的单位球表面积内一次颗粒的个数的方法，包括以下步骤：
(1)选取粒径为所述二次颗粒平均粒径D v50±20％的正极活性材料样品，对样品进行SEM检测，得到10K倍数下的SEM图谱；
(2)根据步骤(1)得到的SEM图谱，通过以下公式计算正极活性材料中单位面积内一次颗粒的个数σ(个/μm 2)：
σ＝(x1+x2)/2*(y1+y2)/2/(A/C*B/C)
其中，
x1表示在二次颗粒10K倍数的SEM图中，图片下边缘横向上的一次颗粒的个数；
x2表示在二次颗粒10K倍数的SEM图中，图片上边缘横向上的一次颗粒的个数；
y1表示在二次颗粒10K倍数的SEM图中，图片左边缘纵向上的一次颗粒的个数；
y2表示在二次颗粒10K倍数的SEM图中，图片右边缘纵向上的一次颗粒的个数；
A表示二次颗粒10K倍数的SEM图的横向实际测量长度，单位为mm；
B表示二次颗粒10K倍数的SEM图的纵向实际测量长度，单位为mm；
C表示在二次颗粒10K倍数的SEM图中，标尺为1μm时对应的实际测量长度，单位为mm/μm；
在计算二次颗粒10K倍数的SEM图中的一次颗粒的个数时，只要出现了一次颗粒的一部分，就算作一个一次颗粒。
本发明中通过上述方法可以直观的表征单位球表面积内一次颗粒的个数σ，真实的反映出二次颗粒表面一次颗粒的大小及分布情况，相比于仅表征一次颗粒以及二次颗粒的晶粒尺寸，计算二次颗粒10K倍下SEM图中一次颗粒个数的方法，是客观表征由一次颗粒组成的二次颗粒球体结构的紧实程度的一种有效途径。
本发明的第四方面提供本发明第一方面的正极活性材料的制备方法，所述正极活性材料的方法对于本领域技术人员来说应该是已知的，例如，可以包括：本领域技术人员可根据正极活性材料的元素组成，选择合适的正极活性材料的原料和配比。例如，所述正极活性材料的原料可以包括镍钴锰和/或铝的三元材料前驱体、锂源、Me源、A源等，各原料之间的比例通常参照正极活性材料中各元素的比例进行配比。更具体的，所述三元材料前驱体可以是包括但不限于Ni 1/3Co 1/3Mn 1/3(OH) 2、Ni 0.5Co 0.2Mn 0.3(OH) 2、Ni 0.5Co 0.25Mn 0.25(OH) 2、Ni 0.55Co 0.15Mn 0.3(OH) 2、Ni 0.55Co 0.1Mn 0.35(OH) 2、Ni 0.55Co 0.05Mn 0.4(OH) 2、Ni 0.6Co 0.2Mn 0.2(OH) 2、Ni 0.75Co 0.1Mn 0.15(OH) 2、Ni 0.8Co 0.1Mn 0.1(OH) 2、Ni 0.88Co 0.05Mn 0.07(OH) 2、0.9Ni 0.8Co 0.2(OH) 2·0.1Al(OH) 3、0.9Ni 0.9Co 0.05Mn 0.05(OH) 2·0.1Al(OH) 3，所述锂源可以是含锂的化合物，所述含锂化合物可以是包括但不限于LiOH·H 2O、LiOH、Li 2CO 3、Li 2O等中的一种或多种的组合，所述Me源通常可以是含Me元素的化合物，所述含Me元素的化合物可以是含有Zr、Zn、Cu、Cr、Mg、Fe、V、Ti、Sr、Sb、Y、W、Nb中至少一种元素的氧化物、硝酸盐、碳酸盐中的一种或几种，所述A源可以是含A元素的化合物，所述含A元素的化合物可以是包括但不限于LiF、NaCl、Na 2S、Li 3N等中的一种或多种的组合。再例如，所述烧结的条件可以是800℃、氧气浓度≥20％。
所述正极活性材料的制备方法中还可以包括在所述二次颗粒中至少部分的非最外层位置的一次颗粒表面设置有内包覆层，在一次颗粒表面形成内包覆层的方法对于本领域技术人员来说应该是已知的，例如，可以包括：将一次颗粒在含包覆元素的化合物存在的条件下烧结，以在一次颗粒表面形成内包覆层。再例如，当内层包覆物质与外层包覆物质相同时，内层包覆工艺与外层包覆工艺可以合并为一步工艺，包覆物可以穿过二次颗粒表面及内部的孔隙，对二次颗粒的外表面及至少部分的内部一次颗粒进行同时包覆。本领域技术人员可根据内包覆层的组成、正极活性材料的粉末抗压强度、电阻率粉体电阻率等参数，选择合适的含包覆元素的化合物的种类、配比和烧结条件等。例如，所述含包覆元素的化合物可以是含有Al、Ba、Zn、Ti、Co、W、Y、Si、Sn、B、P中的一种或多种元素的氧化物、硝酸盐、磷酸盐、碳酸盐等，再例如，所述含包覆元素的化合物的使用量可以是0.01％～0.5％，再例如，所述烧结的条件可以是200℃～700℃高温烧结。
本发明的第五方面提供本发明第二方面的正极材料的制备方法，包括：在本发明第一方面的正极活性材料表面形成外包覆层。
在正极活性材料表面形成外包覆层的方法对于本领域技术人员来说应该是已知的，例如，可以包括：将正极活性材料在含包覆元素的化合物存在的条件下烧结，以在正极活性材料表面形成外包覆层。本领域技术人员可根据外包覆层的组成、正极活性材料的粉末抗压强度、电阻率粉体电阻率等参数，选择合适的含包覆元素的化合物的种类、配比和烧结条件等。例如，所述含包覆元素的化合物可以是含有Al、Ba、Zn、Ti、Co、W、Y、Si、Sn、B、P中的一种或多种元素的氧化物、硝酸盐、磷酸盐、碳酸盐等，再例如，所述含包覆元素的化合物的使用量可以是0.01％～0.5％，再例如，所述烧结的条件可以是200℃～700℃高温烧结。
本发明的第六方面提供一种电化学储能装置，包括本发明第一方面的正极活性材料或本发明第二方面的正极材料。
在本发明第六方面所述的电化学储能装置中，需要说明的是，所述电化学储能装置可为超级电容器、锂离子电池、锂金属电池或钠离子电池。在本发明的实施例中，仅示出电化学储能装置为锂离子电池的实施例，但本发明不限于此。
在锂离子电池中，包括正极极片、负极极片、间隔于正极极片和负极极片之间的隔离膜、电解液，其中，所述正极极片包括本发明第一方面的正极活性材料或本发明第二方面的正极材料。制备所述锂离子电池的方法对于本领域技术人员来说应该是已知的，例如，所述正极极片、隔离膜和负极极片各自都可以是层体，从而可以裁剪成目标尺寸后依次叠放，还可以 卷绕至目标尺寸，以用于形成电芯，并可以进一步与电解液结合以形成锂离子电池。
在锂离子电池中，所述正极极片包含正极集流体和位于所述正极集流体上的正极材料层，所述正极材料层包括本发明第一方面的正极活性材料或本发明第二方面的正极材料、粘结剂、导电剂。本领域技术人员可选择合适的方法制备所述正极极片，例如，可以包括如下步骤：将正极活性材料或正极材料、粘结剂、导电剂混合形成浆料后，涂布于正极集流体上。所述粘结剂通常包括含氟聚烯烃类粘结剂，相对于所述含氟聚烯烃类粘结剂来说，水通常是良溶剂，即所述含氟聚烯烃类粘结剂通常在水中具有良好的溶解性，例如，所述含氟聚烯烃类粘结剂可以是包括但不限于聚偏氟乙烯(PVDF)、偏氟乙烯共聚物等或它们的改性(例如，羧酸、丙烯酸、丙烯腈等改性)衍生物等。所述导电剂可以是本领域各种适用于锂离子(二次)电池的导电剂，例如，可以是包括但不限于乙炔黑、导电炭黑、碳纤维(VGCF)、碳纳米管(CNT)、科琴黑等中的一种或多种的组合。所述正极集流体通常可以为层体，所述正极集流体通常是可以汇集电流的结构或零件，所述正极集流体可以是本领域各种适用于作为锂离子电池正极集流体的材料，例如，所述正极集流体可以是包括但不限于金属箔等，更具体可以是包括但不限于铜箔、铝箔等。
在锂离子电池中，所述负极极片通常包括负极集流体和位于负极集流体表面的负极活性物质层，所述负极活性物质层通常包括负极活性物质。所述负极活性物质可以是本领域各种适用于锂离子电池的负极活性物质的材料，例如，可以是包括但不限于石墨、软碳、硬碳、碳纤维、中间相碳微球、硅基材料、锡基材料、钛酸锂或其他能与锂形成合金的金属等中的一种或多种的组合。其中，所述石墨可选自人造石墨、天然石墨以及改性石墨中的一种或多种的组合；所述硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅合金中的一种或多种的组合；所述锡基材料可选自单质锡、锡氧化合物、锡合金中的一种或多种的组合。所述负极集流体通常是汇集电流的结构或零件，所述负极集流体可以是本领域各种适用于作为锂离子电池负极集流体的材料，例如，所述负极集流体可以是包括但不限于金属箔等，更具体可以是包括但不限于铜箔等。
在锂离子电池中，所述隔离膜可以是本领域各种适用于锂离子电池隔离膜的材料，例如，可以是包括但不限于聚乙烯、聚丙烯、聚偏氟乙烯、芳纶、聚对苯二甲酸乙二醇酯、聚四氟乙烯、聚丙烯腈、聚酰亚胺，聚酰胺、聚酯和天然纤维等中的一种或多种的组合。
在锂离子电池中，所述电解液可以是本领域各种适用于锂离子电池的电解液，例如，所述电解液通常包括电解质和溶剂，所述电解质通常可以包括锂盐等，更具体的，所述锂盐可 以是无机锂盐和/或有机锂盐等，具体可以是包括但不限于，所述锂盐可选自LiPF 6、LiBF 4、LiN(SO 2F) 2(简写为LiFSI)、LiN(CF 3SO 2) 2(简写为LiTFSI)、LiClO 4、LiAsF 6、LiB(C 2O 4) 2(简写为LiBOB)、LiBF 2C 2O 4(简写为LiDFOB)中的一种或多种的组合。再例如，所述电解质的浓度可以为0.8mol/L～1.5mol/L之间。所述溶剂可以是本领域各种适用于锂离子电池的电解液的溶剂，所述电解液的溶剂通常为非水溶剂，优选可以为有机溶剂，具体可以是包括但不限于碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸戊烯酯、碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲乙酯等或它们的卤代衍生物中的一种或多种的组合。
以下结合实施例进一步说明本发明的有益效果。
为了使本发明的发明目的、技术方案和有益技术效果更加清晰，以下结合实施例进一步详细描述本发明。但是，应当理解的是，本发明的实施例仅仅是为了解释本发明，并非为了限制本发明，且本发明的实施例并不局限于说明书中给出的实施例。实施例中未注明具体实验条件或操作条件的按常规条件制作，或按材料供应商推荐的条件制作。
此外应理解，本发明中提到的一个或多个方法步骤并不排斥在所述组合步骤前后还可以存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤，除非另有说明；还应理解，本发明中提到的一个或多个设备/装置之间的组合连接关系并不排斥在所述组合设备/装置前后还可以存在其他设备/装置或在这些明确提到的两个设备/装置之间还可以插入其他设备/装置，除非另有说明。而且，除非另有说明，各方法步骤的编号仅为鉴别各方法步骤的便利工具，而非为限制各方法步骤的排列次序或限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容的情况下，当亦视为本发明可实施的范畴。
在下述实施例中，所使用到的试剂、材料以及仪器如没有特殊的说明，均可商购获得。
一、电池的制备
实施例1
1、正极材料的制备
1)将硫酸镍、硫酸锰、硫酸钴按摩尔比8:1:1配置成浓度为1mol/L的溶液，利用氢氧化物共沉淀技术，制备得到镍钴锰三元材料前驱体Ni 0.8Co 0.1Mn 0.1(OH) 2。制备前躯体的过程中，控制共沉淀时的起始pH值为9.5、氨浓度为0.4M、反应后陈化时间5h。
2)将上述镍钴锰三元材料前驱体Ni 0.8Co 0.1Mn 0.1(OH) 2、含Li化合物LiOH·H 2O按摩尔比1:1.05置于混料设备中进行混料，然后置于气氛炉中800℃进行烧结，冷却后通过机械研磨即为正极活性材料基体；将上述正极活性材料基体与添加剂Al 2O 3按质量比100:0.3置于混料设 备中进行混料，然后置于气氛炉中进行烧结450℃，形成经Al 2O 3包覆处理的正极材料。
2、正极极片的制备
步骤1：将制备得到的正极材料、粘接剂聚偏氟乙烯、导电剂乙炔黑按照质量比98:1:1进行混合，加入N～甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌均匀获得正极浆料；将正极浆料均匀涂覆于厚度为12μm的铝箔上；
步骤2：将涂覆后的极片经过100℃～130℃烘箱干燥；
步骤3：经过冷压、分切得到正极极片。
3、负极极片制备
将负极活性材料石墨、增稠剂羧甲基纤维素钠、粘接剂丁苯橡胶、导电剂乙炔黑按照质量比97:1:1:1进行混合，加入去离子水，在真空搅拌机作用下获得负极浆料；将负极浆料均匀涂覆在厚度为8μm的铜箔上；将铜箔在室温晾干后转移至120℃烘箱干燥1h，然后经过冷压、分切得到负极极片。
4、电解液制备
有机溶剂为含有碳酸亚乙酯(EC)、碳酸甲乙酯(EMC)和碳酸二乙酯(DEC)按体积比为20:20:60混合，在含水量<10ppm的氩气气氛手套箱中，将充分干燥的浓度为1mol/L锂盐溶解于有机溶剂中，混合均匀，获得电解液。
5、隔离膜的制备
选用12μm厚的聚丙烯隔离膜。
6、电池的制备
将正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正、负极极片之间起到隔离的作用，再卷绕成方形的裸电芯后，装入铝塑膜，然后在80℃下烘烤除水后，注入相应的非水电解液、封口，经静置、热冷压、化成、夹具、分容等工序后，得到成品电池。
实施例2
与实施例1基本相同，不同之处在于的正极材料的制备方法：前驱体制备过程中调节共沉淀时的pH值为10.5、氨浓度为0.3M，以及反应后的陈化时间为3h。
实施例3
与实施例1基本相同，不同之处在于正极材料的制备方法：前驱体制备过程中调节共沉淀时的pH值为11、氨浓度为0.2M，以及反应后的陈化时间为5h。
实施例4
与实施例1基本相同，不同之处在于正极材料的制备方法：前驱体制备过程中调节共沉淀时的pH值为10、氨浓度为0.4M，以及反应后的陈化时间为2h。
实施例5
与实施例1基本相同，不同之处在于正极材料的制备方法：前驱体制备过程中调节共沉淀时的pH值为11.5、氨浓度为0.3M，以及反应后的陈化时间2h。
实施例6
与实施例1基本相同，不同之处在于正极材料的制备方法：前驱体制备过程中调节共沉淀时的pH值为9.8、氨浓度为0.3M，以及反应后的陈化时间为4h。
实施例7
与实施例1基本相同，不同之处在于正极材料的制备方法：前驱体中Ni、Co、Mn元素的相对含量为0.75:0.1:0.15，在前驱体制备过程中调节共沉淀时的pH值为10.2、氨浓度为0.5M以及反应后的陈化时间为6h。
实施例8
与实施例1基本相同，不同之处在于正极材料的制备方法：前驱体中Ni、Co、Mn元素的相对含量为0.6:0.2:0.2，在前驱体制备过程中调节共沉淀时的pH值为11.5、氨浓度为0.6M，以及反应后的陈化时间为3h。
实施例9
与实施例1基本相同，不同之处在于正极材料的制备方法：前驱体中Ni、Co、Mn元素的相对含量为0.55:0.15:0.3，在前驱体制备过程中调节共沉淀时的pH值为11.2、氨浓度为0.3M，以及反应后的陈化时间为2h。
实施例10
与实施例1基本相同，不同之处在于正极材料的制备方法：前驱体中Ni、Co、Mn元素的相对含量为0.33:0.33:0.33，在前驱体制备过程中调节共沉淀时的pH值为10.9、氨浓度为0.4M以及反应后的陈化时间为3h。
对比例1
对比例1的制备方法参照如上所述的实施例1制备方法，不同之处在于正极材料的制备方法：前驱体制备过程中调节共沉淀时的pH值为11、氨浓度为0.5M，以及反应后的陈化时间为6h。
对比例2
对比例2的制备方法参照如上所述的实施例1制备方法，不同之处在于正极材料的制备方法：前驱体制备过程中调节共沉淀时的pH值为12、氨浓度为0.6M，以及反应后的陈化时间为7h。
对比例3
对比例3的制备方法参照如上所述的实施例1制备方法，不同之处在于正极材料的制备方法：前驱体制备过程中调节共沉淀时的pH值为10.5、氨浓度为0.1M，以及反应后的陈化时间为6h。
二、性能测试
取实施例1～10及对比例1～3制备的正极材料，测试其二次颗粒单位球体面积内单颗粒抗压强度、一次颗粒个数σ、压实密度及BET。测试结果见表2。
1、抗压强度的测试方法
(1)将样品放置于载物台上；
(2)将压头以0.1μm/min的速度向下靠近样品，直至与样品可以接触；
(3)接触的瞬间开始记录压头的压强和位移；
(4)持续以恒定速度向下挤压颗粒，直至颗粒碎裂；
2、BET测试方法
BET的测试采用国标方法气体吸附BET法测定固态物质比表面积GB/T 19587-2004测试方法进行。
3、压实密度测试方法
压实密度的测试采用国标上的锂离子电池石墨类负极材料GB/T 24533-2009测试方法进行，测试压力为5吨。
4、一次颗粒个数的测定方法
用于测试二次颗粒中单位面积中一次颗粒个数，并且在实施例1中制备的样品的10K倍数的SEM图如图4所示，产品一次颗粒计算如下。
根据公式σ＝(x1+x2)/2*(y1+y2)/2/(A/C*B/C)计算在1μm×1μm的单位面积内的一次颗粒的个数，计算结果见表1中。
σ 1＝(32+32)/2*(22+23)/2/(112/10*75/10)＝8.5个/μm 2。
其他实施例及对比例的计算方法相同，计算结果参见表2。
表1 实施例1的单位球表面积内一次颗粒个数
Figure PCTCN2019120511-appb-000001
5、电池的循环性能测试方法
在45℃的恒温环境下，在2.8V～4.2V下，按照1C充电至4.2V，然后在4.2V下恒压充电至电流≤0.05mA，静置5min，然后按照1C放电至2.8V，容量记为Dn(n＝0,1,2……)，重复前面过程，直至容量衰减到初始容量的80％，记录该锂离子电池的循环圈数。实施例1～10和对比例1～3结果如表3所示。
6、电池的高温产气测试方法
将电池以1C满充电至4.2V后，于70℃恒温箱中静置30天。并通过排水法测定电池的初始体积与静置30天后的体积，得到电池的体积膨胀率。
电池的体积膨胀率(％)＝(静置30天后的体积/初始体积-1)×100％。
测试结果见表3。
7、1/3C容量测试方法
将锂离子电池在25℃的恒温环境下静置2h，然后在2.8V～4.2V下，按照1/3C充电至4.2V，然后在4.2V下恒压充电至电流≤0.05mA，静置5min，然后按照1C放电至2.8V，记录该锂离子电池的容量；将该容量测试值除以锂离子电池中正极材料的质量，即为该正极材料的1/3C容量。测试结果见表3。
表2 实施例1～10与对比例1～3正极活性材料粉末表征
Figure PCTCN2019120511-appb-000002
Figure PCTCN2019120511-appb-000003
表3 实施例1～10与对比例1～3电池电化学性能测试结果
Figure PCTCN2019120511-appb-000004
从表2和表3中可以发现：实施例1～6与对比例1～3的正极材料中Ni、Co、Mn元素的相对含量相同，由于实施例1～6中正极材料的单位球体面积中一次颗粒的个数以及单颗粒的抗压强度在特定范围，因此实施例1～6中正极材料的颗粒微观结构较紧实且粉体材料的力学强度较高、容量发挥较好，颗粒在极片制备或循环过程中不易发生破裂。实施例1～6中正极材料制备的锂离子电池的循环性能明显的高于对比例1～3，循环过程中的体积膨胀率明显下降。其中，对比例1中正极材料的单位球体面积中一次颗粒的个数适中、单颗粒的抗压强度较低，表明该二次颗粒内一次颗粒间的结合力较弱，因此制备的正极极片的压密较难提高； 同时，二次颗粒容易在极片冷压以及循环过程中发生破裂，导致正极材料中大量的新鲜表面与电解液直接接触，因此产气较严重、循环性能较差。而在对比例2中，正极材料的单颗粒的单位球体面积中一次颗粒的个数偏低、单颗粒的抗压强度过高，表明此时二次颗粒内部一次颗粒的尺寸过大且相邻一次颗粒间的孔隙较少，导致正极材料的极化较高、离子传输率降低，因此电池的内阻偏高，劣化电池的循环性能。在对比例3中，正极材料的单位球体面积中一次颗粒的个数过高、单颗粒的抗压强度适中，表明该正极材料的二次颗粒中一次颗粒尺寸偏低、BET较高，因此形成的锂离子电池的产气量仍较大、循环性能较差。
而在实施例7～10中，正极材料中锂过渡金属氧化物中的Ni、Co、Mn元素的相对含量不同，正极材料的单位球体面积中一次颗粒的个数以及单颗粒的抗压强度在特定范围，随Ni含量的降低，锂离子电池的放电容量略有降低，但循环性能和产气问题有明显优化。
以上所述，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。凡熟悉本专业的技术人员，在不脱离本发明的精神和范围的情况下，当可利用以上所揭示的技术内容而做出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对上述实施例所作的任何等同变化的更动、修饰与演变，均仍属于本发明的技术方案的范围内。

Claims (11)

  1. 一种正极活性材料，所述正极活性材料包括由一次颗粒组成的二次颗粒，所述二次颗粒的SEM图谱中单位球表面积内一次颗粒的个数σ为5个/μm 2～30个/μm 2，所述二次颗粒的单颗粒抗压强度为60MPa～300MPa，
    所述正极活性材料的分子式为Li xNi yCo zM kMe pO rA m，0.95≤x≤1.05，0≤y≤1，0≤z≤1，0≤k≤1，0≤p≤0.1，1≤r≤2，0≤m≤2，m+r≤2，M选自Mn和/或Al，Me选自Zr、Zn、Cu、Cr、Mg、Fe、V、Ti、Sr、Sb、Y、W、Nb中的一种或多种的组合，A选自N、F、S、Cl中的一种或多种的组合。
  2. 如权利要求1所述的正极活性材料，其特征在于，在所述正极活性材料的分子式中，0.70≤y≤0.95，0≤z≤0.2，0≤k≤0.2，0≤p≤0.05。
  3. 如权利要求1所述的正极活性材料，其特征在于，所述正极活性材料的粉体压实密度不低于3.3g/cm 3。
  4. 如权利要求1所述的正极活性材料，其特征在于，所述二次颗粒的D v10为2μm～8μm，D v50为5μm～18μm，D v90为10μm～30μm。
  5. 如权利要求4所述的正极活性材料，其特征在于，所述二次颗粒为一次颗粒按一次颗粒的延伸方向堆积获得，所述一次颗粒为棒状、锥状、或针状，所述一次颗粒为长度为100nm～1000nm，所述一次颗粒的径向截面宽度为50nm～400nm，优选地，所述一次颗粒的长度与径向截面宽度的比值为2～10。
  6. 如权利要求1所述的正极活性材料，其特征在于，所述二次颗粒的BET为0.3m 2/g～0.8m 2/g。
  7. 如权利要求1所述的正极活性材料，其特征在于，所述二次颗粒中，至少部分的非最外层位置的一次颗粒表面设置有内包覆层，所述内包覆层包括包覆元素，所述内包覆层的包覆元素选自Al、Ba、Zn、Ti、Co、W、Y、Si、Sn、B、P中的一种或多种的组合。
  8. 一种正极材料，包括如权利要求1～7任一项所述的正极活性材料，所述正极活性材料表面设置有外包覆层，所述外包覆层包括包覆元素，所述外包覆层的包覆元素选自Al、Ba、Zn、Ti、Co、W、Y、Si、Sn、B、P中的一种或多种的组合。
  9. 如权利要求8所述的正极材料，其特征在于，所述外包覆层为连续状和/或非连续状的包覆层；优选地，所述外包覆层为连续状的第一包覆层与非连续状的第二包覆层的复合形态；更优选地，所述非连续状包覆层的物质与所述连续状包覆层的物质不同。
  10. 一种测定如权利要求1～7任一项所述的正极活性材料或如权利要求8～9任一项所述的正极材料中所述二次颗粒的单位球表面积内一次颗粒的个数的方法，包括以下步骤：
    (1)选取粒径为所述二次颗粒平均粒径D v50±20％的正极活性材料样品，对样品进行SEM检测，得到10K倍数下的SEM图谱；
    (2)根据步骤(1)得到的SEM图谱，通过以下公式计算正极活性材料中单位球表面积内一次颗粒的个数σ：
    σ＝(x1+x2)/2*(y1+y2)/2/(A/C*B/C)
    其中，
    x1表示在二次颗粒10K倍数的SEM图中，图片下边缘横向上的一次颗粒的个数；
    x2表示在二次颗粒10K倍数的SEM图中，图片上边缘横向上的一次颗粒的个数；
    y1表示在二次颗粒10K倍数的SEM图中，图片左边缘纵向上的一次颗粒的个数；
    y2表示在二次颗粒10K倍数的SEM图中，图片右边缘纵向上的一次颗粒的个数；
    A表示二次颗粒10K倍数的SEM图的横向实际测量长度，单位为mm；
    B表示二次颗粒10K倍数的SEM图的纵向实际测量长度，单位为mm；
    C表示在二次颗粒10K倍数的SEM图中，标尺为1μm时对应的实际测量长度，单位为mm/μm；
    在计算二次颗粒10K倍数的SEM图中的一次颗粒的个数时，只要出现了一次颗粒的一部分，就算作一个一次颗粒。
  11. 一种电化学储能装置，包括如权利要求1～7任一项所述的正极活性材料或如权利要求8～9任一项所述的正极材料。
PCT/CN2019/120511 2018-12-27 2019-11-25 一种抗压的正极活性材料及电化学储能装置 WO2020134774A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US17/416,122 US20220045324A1 (en) 2018-12-27 2019-11-25 Pressure-resistant positive active material and electrochemical energy storage apparatus
EP19903072.7A EP3790083A4 (en) 2018-12-27 2019-11-25 ANTI-COMPRESSION POSITIVE ELECTRODE ACTIVE MATERIAL AND ELECTROCHEMICAL ENERGY STORAGE DEVICE

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201811611482.9 2018-12-27
CN201811611482 2018-12-27
CN201811637371.5A CN111384371B (zh) 2018-12-29 2018-12-29 一种抗压的正极活性材料及电化学储能装置
CN201811637371.5 2018-12-29

Publications (1)

Publication Number Publication Date
WO2020134774A1 true WO2020134774A1 (zh) 2020-07-02

Family

ID=71127495

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/120511 WO2020134774A1 (zh) 2018-12-27 2019-11-25 一种抗压的正极活性材料及电化学储能装置

Country Status (3)

Country Link
US (1) US20220045324A1 (zh)
EP (1) EP3790083A4 (zh)
WO (1) WO2020134774A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4199152A4 (en) * 2020-12-23 2024-04-10 Lg Chem, Ltd. POSITIVE ELECTRODE ACTIVE MATERIAL, METHOD OF PRODUCING THE SAME, POSITIVE ELECTRODE MATERIAL THEREOF, POSITIVE ELECTRODE AND LITHIUM SECONDARY BATTERY

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6323117B2 (ja) * 2014-03-28 2018-05-16 住友金属鉱山株式会社 非水電解質二次電池用正極活物質の前駆体の製造方法、及び非水電解質二次電池用正極活物質の製造方法
WO2018155121A1 (ja) * 2017-02-21 2018-08-30 パナソニック株式会社 非水電解質二次電池用正極活物質、及び非水電解質二次電池

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006049098B4 (de) * 2006-10-13 2023-11-09 Toda Kogyo Corp. Pulverförmige Verbindungen, Verfahren zu deren Herstellung sowie deren Verwendung in Lithium-Sekundärbatterien
CN101707252B (zh) * 2009-11-09 2012-01-25 深圳市振华新材料股份有限公司 多晶钴镍锰三元正极材料及其制备方法、二次锂离子电池
KR102272265B1 (ko) * 2014-11-21 2021-07-05 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
CN108780889B (zh) * 2016-03-30 2021-08-06 松下知识产权经营株式会社 非水电解质二次电池用正极活性物质和非水电解质二次电池

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6323117B2 (ja) * 2014-03-28 2018-05-16 住友金属鉱山株式会社 非水電解質二次電池用正極活物質の前駆体の製造方法、及び非水電解質二次電池用正極活物質の製造方法
WO2018155121A1 (ja) * 2017-02-21 2018-08-30 パナソニック株式会社 非水電解質二次電池用正極活物質、及び非水電解質二次電池

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4199152A4 (en) * 2020-12-23 2024-04-10 Lg Chem, Ltd. POSITIVE ELECTRODE ACTIVE MATERIAL, METHOD OF PRODUCING THE SAME, POSITIVE ELECTRODE MATERIAL THEREOF, POSITIVE ELECTRODE AND LITHIUM SECONDARY BATTERY

Also Published As

Publication number Publication date
EP3790083A4 (en) 2021-10-06
US20220045324A1 (en) 2022-02-10
EP3790083A1 (en) 2021-03-10

Similar Documents

Publication Publication Date Title
WO2020134781A1 (zh) 一种高压实密度正极材料及电化学储能装置
CN110660961B (zh) 正极片及锂离子电池
US11289691B2 (en) Spherical or spherical-like cathode material for a lithium battery, a battery and preparation method and application thereof
WO2020134780A1 (zh) 一种正极材料及其制备方法和用途
EP4057390A1 (en) Carbon-coated lithium-rich oxide composite material and preparation method therefor
WO2020135766A1 (zh) 正极活性材料、正极极片、电化学储能装置及装置
WO2020135767A1 (zh) 正极活性材料、正极极片、电化学储能装置及装置
CN111384371B (zh) 一种抗压的正极活性材料及电化学储能装置
WO2021108945A1 (zh) 一种用于二次电池的正极极片、二次电池、电池模块、电池包和装置
WO2020258996A1 (zh) 一种低产气高容量的三元正极材料
WO2020063740A1 (zh) 一种正极极片、使用该正极极片的锂离子电池、电池模块、电池包及装置
WO2020258997A1 (zh) 一种正极材料及其制备方法和用途
CN117038880A (zh) 用于锂二次电池的正极活性材料及包括其的锂二次电池
WO2010106768A1 (ja) 非水電解質二次電池用正極、それを用いた非水電解質二次電池、およびその製造方法
CN110890525B (zh) 用于锂二次电池的正极活性材料及包括其的锂二次电池
CN102201572A (zh) 锂离子电池正极材料锰铝酸锂固溶体
JP2017520892A (ja) リチウム電池用正極
WO2021108994A1 (zh) 二次电池及含有该二次电池的装置
JP2021157925A (ja) リチウムイオン二次電池
WO2023070268A1 (zh) 一种电化学装置及包含该电化学装置的用电装置
JP7565281B2 (ja) 負極材料、負極片、電気化学装置及び電子装置
WO2024007142A1 (zh) 负极极片、二次电池、电池模块、电池包及用电装置
KR20230154276A (ko) 스피넬형 리튬-니켈-망간 산화물 재료 및 이의 제조 방법
JP6984202B2 (ja) 非水電解質二次電池の制御装置および制御方法、当該制御装置を有する非水電解質二次電池システム、並びに非水電解質二次電池の製造方法
CN109860587A (zh) 锂离子电池的正极材料及其制备方法、锂离子电池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19903072

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019903072

Country of ref document: EP

Effective date: 20201202

NENP Non-entry into the national phase

Ref country code: DE