CN116190632B - Composite layered oxide positive electrode material and sodium ion battery - Google Patents

Composite layered oxide positive electrode material and sodium ion battery Download PDF

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CN116190632B
CN116190632B CN202310483350.7A CN202310483350A CN116190632B CN 116190632 B CN116190632 B CN 116190632B CN 202310483350 A CN202310483350 A CN 202310483350A CN 116190632 B CN116190632 B CN 116190632B
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positive electrode
electrode material
layered oxide
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CN116190632A (en
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程斯琪
王建鑫
王伟刚
李树军
唐堃
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Liyang Zhongke Haina Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

Abstract

The invention relates to a composite layered oxide positive electrode material and a sodium ion battery, belongs to the technical field of sodium ion batteries, and solves the problems that in the prior art, the coating of the sodium ion positive electrode material affects the electrochemical performance of the positive electrode material, so that the capacity of the sodium ion battery is reduced, the multiplying power performance is reduced and the like. The positive electrode material comprises a matrix material and a coating material, wherein the coating material contains three elements of Al-Ti-Zr at the same time. According to the invention, the coating material is selected to contain three elements of Al, ti and Zr, so that the coating material can play roles of protecting an interface, inhibiting electrolyte decomposition and certain high-temperature flame retardance on the surface of the positive electrode material, the consumption of residual alkali on the surface can be realized, the stability of the positive electrode material is further improved, and the capacity and other electrical properties of the battery are further improved.

Description

Composite layered oxide positive electrode material and sodium ion battery
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a composite layered oxide positive electrode material and a sodium ion battery.
Background
The energy density of the sodium ion battery is relatively low, although the layered oxide cathode material has higher theoretical capacity, as sodium metal is active alkali metal, sodium carbonate, sodium oxide and sodium hydroxide all have the characteristics of strong alkalinity, easy water absorption, easy deterioration and the like, and the layered oxide cathode material of the sodium ion battery is not exceptional and is particularly easy to harden, high in alkalinity, unstable in thermodynamics and the like, so that the material has poor flowability, the cell manufacturing process is difficult, and the metal dissolution catalytic electrolyte is easy to decompose and the like in the electrochemical process.
The existing fluidity modification method mainly aims at the morphology, the particle size, the water content, the stacking condition and the like of the material, but the improvement of the morphology and the particle size of the material is limited by the preparation process, the equipment requirement is high, the requirement of the water content and the stacking condition on the environmental control is high, and the process is difficult to change.
At present, three methods of water washing, doping of other elements and coating of compounds are basically adopted for improvement, but the water washing process is difficult to control, the process is complex, the process of doping other elements is difficult to operate, and satisfactory effects are difficult to achieve. In addition, the coating compound is divided into an active coating and an inactive coating, and the sintering conditions of the active coating agent and the layered oxide positive electrode material in the sodium ion battery system are not compatible; although the non-active coating can effectively improve the cycle performance, the increase of the coating amount affects the electrochemical performance of the cathode material, and is mainly represented by capacity reduction, rate performance reduction and the like.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a composite layered oxide positive electrode material and a sodium ion battery, which are used for solving the problems that the coating of the existing sodium ion positive electrode material affects the electrochemical performance of the positive electrode material, so that the capacity of the sodium ion battery is reduced, the rate performance is reduced, the material consistency is poor, and the like.
In one aspect, the invention provides a composite layered oxide cathode material, which comprises a matrix material and a coating material, wherein the coating material comprises three elements of Al, ti and Zr.
Further, when the positive electrode material is prepared, three elements of Al, ti and Zr are added in the form of one or more of metal oxides, carbonates or hydroxides.
Further, the general formula of the positive electrode material is as follows:
Na x1 Cu y1 Mn z1 Li s1 Ni t1 Fe u1 O 2+nδ /α(Na a1 Al b1 Ti c1 Zr d1 O 2 ) Wherein x1 is more than 0.9 and less than or equal to 0.95, y1 is more than or equal to 0.05 and less than or equal to 0.20,0.33, z1 is more than or equal to 0.40,0.01, s1 is more than or equal to 0.07,0.08, t1 is more than or equal to 0.22,0.33, u1 is more than or equal to 0.40,0 and n is more than or equal to 0.05, delta is more than or equal to 1 and less than or equal to 3, alpha is more than or equal to 0.1, a1 is more than or equal to 0.3 and less than or equal to 0.5,0.3 and less than or equal to 0.6, c1 is more than or equal to 0.1 and less than or equal to 0.2,0.2 and less than or equal to d1 is less than or equal to 0.5, a1+3b1+4c1+4d1=4,b1+c1+d1=1，x1+2y1+3z1+3u1+s1+2t1＜4＜x1+2y1+4z1+3u1+s1+3t1，y1+z1+s1+t1 +u1=1。
further, the particle size distribution of the positive electrode material is as follows: d10 is more than or equal to 4 mu m and less than or equal to 6 mu m, D50 is more than or equal to 9 mu m and less than or equal to 20 mu m, D90 is more than or equal to 16 mu m and less than or equal to 30 mu m, and D50/(D90-D10) is more than or equal to 0.5 and less than or equal to 1.
Further, the positive electrode material is O3 type layered oxide.
Further, the average peak height ratio of (003)/(104) of the positive electrode material satisfies that HI is more than or equal to 0.01 and less than or equal to 5.5, and the average peak area ratio is more than or equal to 0.05 and less than or equal to 4.5.
Further, the repose angle psi of the positive electrode material is less than or equal to 40 degrees.
Further, the repose angle psi of the positive electrode material is less than or equal to 30 degrees.
Further, the pH value of the positive electrode material is 11.40-12.05.
In another aspect, the invention provides a sodium ion battery comprising the positive electrode material.
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) The coating material of the composite layered oxide anode material comprises three elements of Al, ti and Zr, can play roles of protecting an interface, inhibiting electrolyte decomposition and certain high-temperature flame retardance on the surface of the anode material, can realize consumption of residual alkali on the surface, and further improves the stability of the anode material;
(2) According to the invention, the average peak height ratio of the material in (003)/(104) is enabled to meet the requirement that HI is more than or equal to 0.01 and less than or equal to 5.5, and the average peak area ratio is more than or equal to 0.05 and less than or equal to 4.5 through controlling the particle size distribution of the positive electrode material particles, so that morphology control is carried out from two scales of micro and macro, and the consistency of the material is better;
(3) The invention forms a high ion layer conducting coating layer composed of inactive metal oxide and residual alkali on the surface of the material on the basis of controlling the appearance of the positive electrode material, so that the material is easy to harden, high in alkalinity, unstable in thermodynamics and the like are improved;
(4) The metal elements of the positive electrode material adopt a specific proportion, and even if the molar ratio of the coating material is 0.1, the battery prepared from the positive electrode material can still keep capacity and rate performance from being reduced, and more coating materials can reduce contact between the material and electrolyte and side reaction, so that the cycle life of the battery is prolonged.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to designate like parts throughout the drawings;
FIG. 1 is an SEM image of the positive electrode material prepared in comparative example 1;
FIG. 2 is an SEM image of the positive electrode material prepared in comparative example 2;
FIG. 3 is an SEM image of the positive electrode material prepared in comparative example 3;
fig. 4 is an SEM image of the positive electrode material prepared in example 1;
fig. 5 is an SEM image of the positive electrode material prepared in example 2;
FIG. 6 is an XRD pattern of the positive electrode materials prepared in example 1, example 2, and comparative examples 1 to 3;
fig. 7 is a schematic view of the shape of the positive electrode material prepared according to the present invention.
Wherein, 1-cladding material, 2-matrix material.
Detailed Description
The following detailed description of preferred embodiments of the invention is made in connection with the accompanying drawings, which form a part hereof, and together with the description of the embodiments of the invention, are used to explain the principles of the invention and are not intended to limit the scope of the invention.
The invention discloses a composite layered oxide anode material, which comprises a matrix material and a coating material, wherein the coating material comprises three elements of Al, ti and Zr.
Specifically, when the positive electrode material is prepared, three elements of Al, ti and Zr are added in the form of one or more of metal oxides, carbonates or hydroxides.
Compared with the prior art, the coating material of the positive electrode material comprises three elements of Al, ti and Zr, can play roles of protecting an interface, inhibiting electrolyte decomposition and certain high-temperature flame retardance on the surface of the positive electrode material, can realize consumption of residual alkali on the surface, and further improves the stability of the positive electrode material.
Specifically, the general formula of the positive electrode material is shown as follows:
Na x1 Cu y1 Mn z1 Li s1 Ni t1 Fe u1 O 2+nδ /α(Na a1 Al b1 Ti c1 Zr d1 O 2 ) Wherein 0.9 < x1 < 0.95,0.05 < y1 < 0.20,0.33 < z1 < 0.40,0.01 > s1 < 0.07,0.08 < t1 < 0.22,0.33 < u1 < 0.40,0 < n < 0.05, -1 < delta < 3,0 < alpha < 0.1,0.3 < a1 < 0.5,0.3 < b1 < 0.6,0.1 < c1 < 0.2,0.2 < d1 < 0.5, a1+3b1+4c1+4d1=4, b1+c1+d1=1, x1+2y1+3z1+3u1+s1+2t1 < 4 < x1+2y1+4z1+3u1+s1+3t1+z1+y1+y1+t1+t1+t1+t1+t1, the above-mentioned inequality is to ensure that the change of the valence can achieve the conservation of charges.
In the present invention, na a1 Al b1 Ti c1 Zr d1 O 2 As coating material, na x1 Cu y1 Mn z1 Li s1 Ni t1 Fe u1 O 2+nδ Is a matrix material, alpha is Na a1 Al b1 Ti c1 Zr d1 O 2 The molar ratio of the addition of the coating material.
Specifically, the particle size distribution of the positive electrode material is as follows: d10 is more than or equal to 4 mu m and less than or equal to 6 mu m, D50 is more than or equal to 9 mu m and less than or equal to 20 mu m, D90 is more than or equal to 16 mu m and less than or equal to 30 mu m, and D50/(D90-D10) is more than or equal to 0.5 and less than or equal to 1.
Specifically, the positive electrode material is O3 type layered oxide.
Preferably, the average peak height ratio (003)/(104) of the positive electrode material is 0.01-5.5, and the average peak area ratio is 0.05-4.5.
In the preferred scheme, HI is more than or equal to 0.5 and less than or equal to 4,0.5 and AI is more than or equal to 3.
The larger HI indicates that the effective area of the scanned material (003) surface is large, namely the area perpendicular to the (003) surface is wide, and further indicates that the lamellar structure of the material is more than the spheroid structure; the smaller HI indicates that the crystallization temperature or crystallization reaction of the positive electrode material is not complete, and the lower the crystallinity is exhibited. The AI also has a rule similar to HI in size, and the AI also characterizes how wide the half peak width of the characteristic peak is, the wider the half peak width is, which indicates that the impurity phase is more or the crystallinity is low.
In the invention, XRD test is carried out on the prepared positive electrode material for multiple times, and the peak position report is obtained through analysis and treatment by searching peaks through Jade6.0 software.
In the analysis, the raw materials and the proportion of the positive electrode material are controlled, so that the obtained positive electrode material has better morphology and better consistency.
Specifically, the repose angle psi of the positive electrode material is less than or equal to 40 degrees.
In a preferred scheme, the repose angle psi of the positive electrode material is less than or equal to 30 degrees.
In the present invention, the reference to the angle of repose test was GB/T11986-1989, and it was found that the positive electrode material of the present invention was excellent in fluidity.
In another embodiment of the invention, a preparation method of the positive electrode material is disclosed, wherein a sodium-containing metal source raw material and other metal source raw materials are weighed according to stoichiometric ratio, and the other metal source raw materials and the sodium metal source raw materials are uniformly mixed, calcined at high temperature, crushed and screened to obtain the positive electrode material.
Specifically, the high-temperature calcination temperature is 700-1200 ℃, such as 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃ and the calcination time is 8-36 hours, such as 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours and 36 hours.
In the preferred scheme, the high-temperature calcination temperature is 800-1100 ℃ and the calcination time is 12-20 h.
Specifically, the temperature rising rate in the high-temperature calcination process is 1-10 ℃/min.
Exemplary heating rates are 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min.
In the preferred scheme, the temperature rising rate in the high-temperature calcination process is 2-5 ℃/min.
The invention adopts the above-mentioned required calcining temperature for solid phase reaction, the temperature is too high to form other structures, the required solid phase reaction does not occur when the temperature is too low, the calcining time is the required reaction time, the time is too long to form other structures, the time is too short, the solid phase reaction is not thoroughly performed, the heating rate adopts the specific heating rate of the invention, the heating rate is too fast to cause the reaction to be performed before the next reaction occurs or the reaction can be continued when the heating rate is too high, the subsequent reaction does not occur when the heating rate is too slow, the heat treatment time is greatly prolonged, and the energy consumption is further increased.
Specifically, the atmosphere for calcination is selected to be an air atmosphere or an oxygen atmosphere.
Specifically, the pH value of the positive electrode material is 11.40-12.05.
In another embodiment of the invention, a sodium ion battery is disclosed comprising the positive electrode material.
Compared with the prior art, the positive electrode material forms a high ion conduction coating layer composed of the inactive metal oxide and the residual alkali on the surface of the material on the basis of controlling the morphology, so that the positive electrode material is easy to harden, high in alkalinity, unstable in thermodynamics and the like, and a sodium ion battery prepared by using the positive electrode material has good battery capacity and rate capability, wherein the battery capacity (0.1C specific capacity) is 130-136mAh/g, the 0.5C/0.1C rate is greater than 94%, the 1C/0.1C rate is greater than 82%, and the 0.1C initial week coulomb efficiency is greater than 94%.
The positive electrode material of the present invention has a schematic shape and structure as shown in fig. 7, and the positive electrode material structure is composed of a matrix material layer with an irregular outer surface and a coating material layer coated on the outer surface of the matrix material layer, and is a core-shell structure in which the coating material 1 is coated on the surface of the matrix material 2, and the surface shape of the matrix material 2 is irregularly connected with the coating material 1 based on the difference of the ionic radius, the oxygen binding capacity, and the like of each metal element in the present invention. According to the invention, through the comprehensive effect of each metal element and the combination of the preparation method, al, ti and Zr cannot diffuse into the matrix material 2, the microscopic particles of the anode material are arranged in a layered manner, the coating material 1 can play roles in protecting an interface, inhibiting electrolyte decomposition and certain high-temperature flame retardance on the surface of the anode material, the consumption of residual alkali on the surface can be realized, and the stability of the anode material is further improved.
The matrix material and the coating material of the positive electrode material form an irregular interface, have certain particle size distribution (including D10, D50 and D90), and have regular external surface, good consistency and good fluidity.
The positive electrode material of the present invention is explained below with reference to specific examples.
Example 1
The composite layered oxide cathode material of the embodiment is an O3 type material, and has the following general formula: na (Na) 0.93 Li 0.04 Cu 0.07 Mn 0.37 Ni 0.15 Fe 0.37 O 2 /0.1(Na 0.49 Al 0.49 Ti 0.17 Zr 0.34 O 2 )。
The positive electrode material is prepared by the following method: weighing Na according to stoichiometric ratio 2 CO 3 、 Li 2 CO 3 、 CuO、 Fe 2 O 3 、 Ni(OH) 2 、Al 2 O 3 、 TiO 2 、 ZrO 2 And MnO 2 Mixing uniformly, drying, calcining at 930 ℃ under compressed air atmosphere for 12 hours at high temperature, heating at a rate of 3 ℃/min to obtain a precursor of the positive electrode material, crushing and screening to obtainThe positive electrode material, denoted as B1, has a particle size distribution satisfying the following conditions: d10 is more than or equal to 4 mu m and less than or equal to 6 mu m, D50 is more than or equal to 9 mu m and less than or equal to 20 mu m, D90 is more than or equal to 16 mu m and less than or equal to 30 mu m, and D50/(D90-D10) is more than or equal to 0.5 and less than or equal to 1.
Example 1-1
The composite layered oxide cathode material of the embodiment is an O3 type material, and has the following general formula: na (Na) 0.93 Li 0.04 Cu 0.07 Mn 0.37 Ni 0.15 Fe 0.37 O 2 /0.01(Na 0.49 Al 0.49 Ti 0.17 Zr 0.34 O 2 ). The other preparation method was the same as in example 1, and the obtained positive electrode material was designated as B1-1.
Example 2
The composite layered oxide cathode material of the embodiment is an O3 type material, and has the following general formula: na (Na) 0.93 Li 0.04 Cu 0.14 Mn 0.37 Ni 0.08 Fe 0.37 O 2 /0.01(Na 0.49 Al 0.49 Ti 0.17 Zr 0.34 O 2 )。
The positive electrode material is prepared by the following method: weighing Na according to stoichiometric ratio 2 CO 3 、 Li 2 CO 3 、 CuO、 Fe 2 O 3 、 Ni(OH) 2 、Al 2 O 3 、TiO 2 、ZrO 2 And MnO 2 Mixing uniformly, drying, calcining at high temperature for 15h in a compressed air atmosphere at 920 ℃ at a heating rate of 3 ℃/min to obtain a positive electrode material precursor, crushing, screening to obtain the positive electrode material, and marking as B3, wherein the particle size distribution of the obtained positive electrode material meets the following conditions: d10 is more than or equal to 4 mu m and less than or equal to 6 mu m, D50 is more than or equal to 9 mu m and less than or equal to 20 mu m, D90 is more than or equal to 16 mu m and less than or equal to 30 mu m, and D50/(D90-D10) is more than or equal to 0.5 and less than or equal to 1.
Example 3
The composite layered oxide cathode material of the embodiment is an O3 type material, and has the following general formula: na (Na) 0.93 Li 0.04 Cu 0.16 Mn 0.37 Ni 0.08 Fe 0.37 O 2 /0.01(Na 0.3 Al 0.3 Ti 0.2 Zr 0.5 O 2 )。
The positive electrode material is prepared by the following method: weighing Na according to stoichiometric ratio 2 CO 3 、 Li 2 CO 3 、 CuO、 Fe 2 O 3 、 Ni(OH) 2 、Al 2 O 3 、TiO 2 、ZrO 2 And MnO 2 Mixing uniformly, drying, calcining at high temperature for 15 hours in a compressed air atmosphere at 920 ℃ and with a heating rate of 3 ℃/min to obtain a precursor of the positive electrode material, crushing, screening to obtain the positive electrode material, and marking as B5, wherein the particle size distribution of the obtained positive electrode material meets the following conditions: d10 is more than or equal to 4 mu m and less than or equal to 6 mu m, D50 is more than or equal to 9 mu m and less than or equal to 20 mu m, D90 is more than or equal to 16 mu m and less than or equal to 30 mu m, and D50/(D90-D10) is more than or equal to 0.5 and less than or equal to 1.
Example 4
The composite layered oxide cathode material of the embodiment is an O3 type material, and has the following general formula: na (Na) 0.95 Cu 0.18 Mn 0.33 Ni 0.08 Fe 0.40 Li 0.01 O 2 /0.01(Na 0.3 Al 0.3 Ti 0.2 Zr 0.5 O 2 )。
The positive electrode material is prepared by the following method: weighing Na according to stoichiometric ratio 2 CO 3 、 Li 2 CO 3 、 CuO、 Fe 2 O 3 、 Ni(OH) 2 、Al 2 O 3 、TiO 2 、ZrO 2 And MnO 2 Mixing uniformly, drying, calcining at high temperature for 15 hours in a compressed air atmosphere at 920 ℃ and with a heating rate of 3 ℃/min to obtain a precursor of the positive electrode material, crushing, screening to obtain the positive electrode material, and marking as B7, wherein the particle size distribution of the obtained positive electrode material meets the following conditions: d10 is more than or equal to 4 mu m and less than or equal to 6 mu m, D50 is more than or equal to 9 mu m and less than or equal to 20 mu m, D90 is more than or equal to 16 mu m and less than or equal to 30 mu m, and D50/(D90-D10) is more than or equal to 0.5 and less than or equal to 1.
Example 5
The composite layered oxide cathode material of the embodiment is an O3 type material, and has the following general formula: na (Na) 0.92 Cu 0.2 Mn 0.38 Ni 0.08 Fe 0.33 Li 0.01 O 2 /0.01(Na 0.3 Al 0.3 Ti 0.2 Zr 0.5 O 2 )。
The positive electrode material is prepared by the following method: weighing Na according to stoichiometric ratio 2 CO 3 、 Li 2 CO 3 、 CuO、 Fe 2 O 3 、 Ni(OH) 2 、Al 2 O 3 、TiO 2 、ZrO 2 And MnO 2 Mixing uniformly, drying, calcining at high temperature for 15 hours in a compressed air atmosphere at 920 ℃ and with a heating rate of 3 ℃/min to obtain a precursor of the positive electrode material, crushing, screening to obtain the positive electrode material, and marking as B8, wherein the particle size distribution of the obtained positive electrode material meets the following conditions: d10 is more than or equal to 4 mu m and less than or equal to 6 mu m, D50 is more than or equal to 9 mu m and less than or equal to 20 mu m, D90 is more than or equal to 16 mu m and less than or equal to 30 mu m, and D50/(D90-D10) is more than or equal to 0.5 and less than or equal to 1.
Comparative example 1
The Al coating material of example 1 was replaced with Co, and the Al in the raw material 2 O 3 Replaced by Co 3 O 4 Otherwise, the same as in example 1 was conducted to obtain a positive electrode material precursor, and the precursor was pulverized and sieved to obtain a precursor having the general formula:
Na 0.93 Li 0.04 Cu 0.07 Mn 0.37 Ni 0.15 Fe 0.37 O 2 /0.1(Na 0.49 Co 0.49 Ti 0.17 Zr 0.34 O 2 ) The positive electrode material designated as A1), the particle size distribution of the obtained positive electrode material satisfies the following condition: d10 is more than or equal to 4 mu m and less than or equal to 6 mu m, D50 is more than or equal to 9 mu m and less than or equal to 20 mu m, D90 is more than or equal to 16 mu m and less than or equal to 30 mu m, and D50/(D90-D10) is more than or equal to 0.5 and less than or equal to 1.
Comparative example 2
The positive electrode material of this comparative example has the following general formula:
Na 0.93 Li 0.04 Cu 0.07 Mn 0.37 Ni 0.15 Fe 0.37 O 2 /0.1(Na 0.50 Mg 0.25 Ti 0.35 Zr 0.40 O 2 )。
the positive electrode material of the comparative example was prepared by the following method: weighing Na according to stoichiometric ratio 2 CO 3 、 Li 2 CO 3 、 CuO、 Fe 2 O 3 、 Ni(OH) 2 、MnO 2 、 Mg(OH) 2 、TiO 2 、ZrO 2 The preparation method is the same as that of example 1, the positive electrode material is obtained, and is marked as A3, and the particle size distribution of the obtained positive electrode material meets the following conditions: d10 is more than or equal to 4 mu m and less than or equal to 6 mu m, D50 is more than or equal to 9 mu m and less than or equal to 20 mu m, D90 is more than or equal to 16 mu m and less than or equal to 30 mu m, and D50/(D90-D10) is more than or equal to 0.5 and less than or equal to 1.
Comparative example 3
The positive electrode material prepared in this comparative example was prepared without coating material, and was otherwise the same as in example 1 to give a positive electrode material having the general formula Na 0.93 Li 0.04 Cu 0.07 Mn 0.37 Ni 0.15 Fe 0.37 O 2 Is designated as A5.
Comparative example 4
The general formula and the preparation method of the positive electrode material prepared in this comparative example are the same as those of example 1, except that the particle size distribution of the prepared positive electrode material satisfies the following conditions: d10 is less than or equal to 1 mu m and less than 4 mu m, D50 is less than or equal to 5 mu m and less than or equal to 9 mu m, D90 is less than or equal to 10 mu m and less than or equal to 16 mu m, D50/(D90-D10) is less than or equal to 0.5 and less than or equal to 1, and the positive electrode material prepared in the comparative example is marked as C1.
Comparative example 5
The general formula and the preparation method of the positive electrode material prepared in this comparative example are the same as those of example 1, except that the particle size distribution of the prepared positive electrode material satisfies the following conditions: the positive electrode material prepared in this comparative example was designated as C2, with D10 < 6 μm < 8 μm, D50 < 20 μm < 24 μm, D90 < 30 μm and D50/(D90-D10). Ltoreq.1, and D50 < 25 μm.ltoreq.D90.
Comparative example 6
The general formula of the positive electrode material prepared in the comparative example is as follows:
Na 0.93 Li 0.04 Cu 0.07 Mn 0.37 Ni 0.15 Fe 0.37 O 2 /0.11（Na 0.49 Al 0.49 Ti 0.17 Zr 0.34 O 2 ) Otherwise, the positive electrode material prepared in this comparative example was designated as C3 in the same manner as in example 1.
Comparative example 7
The general formula of the positive electrode material prepared in the comparative example is as follows:
Na 0.93 Li 0.04 Cu 0.07 Mn 0.37 Ni 0.15 Fe 0.37 O 2 /0.01（Na 0.2 Al 0.2 Ti 0.27 Zr 0.53 O 2 ) The positive electrode material prepared in this comparative example was designated as C4, in the same manner as in example 1.
Comparative example 8
The general formula of the positive electrode material prepared in the comparative example is as follows:
Na 0.93 Li 0.04 Cu 0.07 Mn 0.37 Ni 0.15 Fe 0.37 O 2 /0.01（Na 0.6 Al 0.6 Ti 0.13 Zr 0.27 O 2 ) Otherwise, the same as in example 1 was conducted, and the positive electrode material prepared in this comparative example was designated as C5.
Comparative example 9-1
The general formula and the preparation method of the positive electrode material prepared in this comparative example are the same as those of example 2, except that the high-temperature calcination temperature in the preparation method is 1250 ℃, and the positive electrode material prepared in this comparative example is designated as C9-1.
Comparative example 9-2
The general formula and the preparation method of the positive electrode material prepared in this comparative example are the same as those of example 2, except that the high-temperature calcination temperature in the preparation method is 690 ℃, and the positive electrode material prepared in this comparative example is designated as C9-2.
Comparative examples 9 to 3
The general formula and the preparation method of the positive electrode material prepared in this comparative example are the same as those of example 2, except that the time of high-temperature calcination in the preparation method is 37 hours, and the positive electrode material prepared in this comparative example is designated as C9-3.
Comparative examples 9 to 4
The general formula and the preparation method of the positive electrode material prepared in this comparative example are the same as those of example 2, except that the time of high-temperature calcination in the preparation method is 7 hours, and the positive electrode material prepared in this comparative example is designated as C9-4.
Comparative examples 9 to 5
The general formula and the preparation method of the positive electrode material prepared in this comparative example are the same as those of example 2, except that the temperature rising rate in the high-temperature calcination in the preparation method is 11 ℃/min, and the positive electrode material prepared in this comparative example is designated as C9-5.
Comparative examples 9 to 6
The general formula and the preparation method of the positive electrode material prepared in this comparative example are the same as those of example 2, except that the temperature rising rate in the high temperature calcination in the preparation method is 0.5 ℃/min, and the positive electrode material prepared in this comparative example is designated as C9-6.
Test example 1
(1) The positive electrode materials prepared in examples 1-5 and comparative examples 1-9-6 were used as active materials, respectively, according to mass ratio: SP: mixing PVDF in a ratio of 90:5:5, adding NMP to prepare adhesive liquid with viscosity, coating the adhesive liquid on aluminum foil, and baking the adhesive liquid for 12 hours at 120 ℃ in a vacuum drying oven to obtain the positive electrode plate. Sodium metal sheet is used as counter electrode, glass fiber (Waterman) is used as diaphragm, 1mol/L NaPF 6 EC/dmc=1:1 (Alfa) as electrolyte, 2032 coin cell was assembled in an Ar protection glove box. The battery was tested in a voltage range of 2.5 to 4.0v, activated for three weeks at 0.1C, cycled for 3 weeks at 0.5C, cycled for 3 weeks at 1C, and the specific capacity and coulombic efficiency at 0.1C, the specific capacity at 0.5C and the specific capacity at 1C were recorded, and the results are shown in table 1.
Wherein, the physical properties are characterized as follows:
pH test: taking a positive electrode material with the mass ratio: distilled water=1:20, magnetically stirring for 10min, standing for 5min, and measuring the pH value and recording as the pH value of the material;
XRD test: the range is 10-80 degrees, the step length is 0.02 degree, the time is 0.2, and the total duration is 712 seconds;
SEM test: accelerating voltage is 10kV, resolution is 10k, and universal morphology shooting is carried out;
angle of repose test: see GB/T11986-1989.
The pH, angle of repose ψ and XDR related data are shown in Table 2.
As can be seen from table 1, the substitution of Co for Al in the clad material compared with B1, and the performance of Co and Al was relatively close, but the specific capacity of 0.1C first-week discharge of the battery was reduced by 4.22mAh/g after substitution of Co for Al. A3 compared with B1, when the coating material is replaced by Al-Ti-Zr to be Mg-Ti-Zr, the specific capacity of the battery in the initial discharge of 0.1C is reduced by 3mAh/g, and the matrix material and the coating material are required to be combined in a specific way to play a role in improving the capacity of the battery.
B1 has similar results in specific capacity and coulombic efficiency at smaller values of 0.01 and larger values of 0.1 than B1-1, and no significant decrease in capacity and rate performance at larger values of 0.1. The positive electrode material prepared by the invention can keep capacity and multiplying power performance not to be reduced even if the molar ratio of the coating material is 0.1 by adopting a specific proportion, and more coating materials can reduce contact between the material and electrolyte to reduce side reaction, thereby prolonging the cycle life.
C1-C2 has reduced battery capacity and coulombic efficiency compared to B1 because only the particle size of the positive electrode material employing the present invention has higher battery capacity and coulombic efficiency.
C3-C5 has reduced battery capacity and coulombic efficiency compared to B1 because the positive electrode material prepared only with the ratios of the elements of the present invention has higher battery capacity and coulombic efficiency.
Compared with C9-1-C9-6, the temperature, time and heating rate of the high-temperature calcination are required to be controlled within the range defined by the invention, and too high or too low has larger influence on the battery capacity and the coulombic efficiency.
As can be seen from Table 2, A5 does not use a coating material, the repose angle psi is more than 40 DEG, and A1 and A3 use Co-Ti-Ni and Mg-Ti-Zr, compared with A5, the repose angle and pH value of the coating material are reduced to a certain extent, but compared with B1, the repose angle is less than 30 DEG and the pH value is less than 12, the effect is not obvious enough.
As the repose angle is less than 30 degrees, the flowability is very good in the process definition, the flowability is good in 31-35 degrees, the flowability of the repose angle is more than 40 degrees, the flowability is qualified, the flowability of the repose angle is more than 45 degrees, the flowability of the repose angle is more than 55 degrees, the flowability is very poor, the repose angle is more than 66 degrees, the materials are difficult to flow, and the flowability of the coated materials is good as can be seen from the repose angles of the B1-B8 materials.
The angle of repose is larger for C1-C2 than B1 because the fluidity of the prepared cathode material is better with the particle size of the invention.
C3-C5 in comparison with B1, it is stated that either the alpha or the sodium content of the coating material is outside the limits defined by the invention, not only affecting the electrochemistry of the material, but also the angle of repose and the pH.
Compared with B3, the temperature, time and heating rate of the high-temperature calcination of C9-1 to C9-6 are required to be controlled within the range defined by the invention, and too high or too low has great influence on the pH and repose angle of the material.
(2) The positive electrode materials prepared in comparative examples 1 to 3 and example 1 and example 2 were subjected to SEM and XRD tests, as shown in fig. 1 to 6, respectively.
SEM images of the analytical materials are specifically as follows:
as can be seen from fig. 4-5, the SEM images of the B1, B3 materials are shown in fig. 4 and 5, respectively, where the particle surfaces of the materials are cleaner overall, although some fine particles are attached, with fig. 4 being most evident. The positive electrode material is coated by the coating material, so that the contact with air is reduced in the preparation and testing processes, and the surface side reaction is basically avoided.
SEM images of A1, A3 and A5 materials are shown in fig. 1-3, respectively, with the particle surfaces of the materials packed with punctiform particles and other fine particles, of which fig. 3 is most pronounced and larger flaky particles. The positive electrode material prepared without the coating material or the coating material defined by the invention has serious side reaction only when the air is contacted in the preparation and testing processes, the material is easy to be thickened, particles are adhered, and the fluidity is poor.
As can be seen from fig. 6, the characteristic peaks of the layered cathode material (asterisk (003), asterisk (104)) are compared, and HI and AI can be within a defined range after being coated with the coating material. The sodium salt coating of the specific three oxides can lead HI and AI to be in a limited range, and the morphology of the particles is in a spherical shape.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.

Claims (8)

1. The composite layered oxide positive electrode material is characterized by comprising a matrix material and a coating material, wherein the coating material comprises three elements of Al, ti and Zr;
the general formula of the positive electrode material is shown as follows:
Na x1 Cu y1 Mn z1 Li s1 Ni t1 Fe u1 O 2+nδ /α(Na a1 Al b1 Ti c1 Zr d1 O 2 ) Wherein 0.9 < x1 is less than or equal to 0.95,0.05 is less than or equal to y1 is less than or equal to 0.20,0.33 is less than or equal to z1 is less than or equal to 0.40,0.01 is less than or equal to s1 is less than or equal to 0.07,0.08 is less than or equal to t1 is less than or equal to 0.22,0.33 is less than or equal to u1 is less than or equal to 0.40,0 is less than or equal to 0.05, -1 is less than or equal to delta is less than or equal to 3,0 < alpha is less than or equal to 0.1,0.3 is less than or equal to a1 is less than or equal to 0.5,0.3 is less than or equal to b1 is less than or equal to 0.6,0.1 is less than or equal to c1 is less than or equal to 0.2,0.2 is less than or equal to 0.5, a1+3b1+4c1+4d1=4, b1+d1+d1=1=1=1, x1+2y1+3u1+s1+s1+2t1+2t1 < 4t1 < 4 < 2t1 < 21 < 4 < 2t1+4+ 21+4t1+21+21+1+t1+t1+1+1+1+1+1+1+1+1+1, 4.
The particle size distribution of the positive electrode material is as follows: d10 is more than or equal to 4 mu m and less than or equal to 6 mu m, D50 is more than or equal to 9 mu m and less than or equal to 20 mu m, D90 is more than or equal to 16 mu m and less than or equal to 30 mu m, and D50/(D90-D10) is more than or equal to 0.5 and less than or equal to 1;
the positive electrode material is prepared by the following steps:
weighing a sodium-containing metal source raw material and other metal source raw materials according to a stoichiometric ratio, uniformly mixing the other metal source raw materials and the sodium metal source raw material, calcining at a high temperature, crushing and screening to obtain the anode material;
the high-temperature calcination temperature is 800-1100 ℃, the calcination time is 12-20 h, and the temperature rising rate in the high-temperature calcination process is 1-10 ℃/min.
2. The composite layered oxide cathode material of claim 1, wherein the three elements of Al, ti and Zr are added as one or more of metal oxides, carbonates or hydroxides when preparing the cathode material.
3. The composite layered oxide cathode material according to claim 1 or 2, wherein the cathode material is an O3 type layered oxide.
4. The composite layered oxide cathode material according to claim 3, wherein the average peak height ratio of (003)/(104) satisfies 0.01.ltoreq.HI.ltoreq.5.5 and the average peak area ratio of 0.05.ltoreq.AI.ltoreq.4.5 in XRD test.
5. The composite layered oxide cathode material of claim 1, wherein the angle of repose ψ of the cathode material is less than or equal to 40 °.
6. The composite layered oxide cathode material of claim 5, wherein the angle of repose ψ of the cathode material is less than or equal to 30 °.
7. The composite layered oxide cathode material of claim 1, wherein the pH of the cathode material is 11.40-12.05.
8. A sodium ion battery comprising the positive electrode material of any one of claims 1-7.
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