CN116979059A - Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment - Google Patents

Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment Download PDF

Info

Publication number
CN116979059A
CN116979059A CN202310998171.7A CN202310998171A CN116979059A CN 116979059 A CN116979059 A CN 116979059A CN 202310998171 A CN202310998171 A CN 202310998171A CN 116979059 A CN116979059 A CN 116979059A
Authority
CN
China
Prior art keywords
positive electrode
ion battery
sodium ion
source
equal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310998171.7A
Other languages
Chinese (zh)
Inventor
程斯琪
王伟刚
李树军
唐堃
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Liyang Zhongke Haina Technology Co ltd
Original Assignee
Liyang Zhongke Haina Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Liyang Zhongke Haina Technology Co ltd filed Critical Liyang Zhongke Haina Technology Co ltd
Priority to CN202310998171.7A priority Critical patent/CN116979059A/en
Publication of CN116979059A publication Critical patent/CN116979059A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/13—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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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

Landscapes

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

Abstract

The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery positive electrode material, a preparation method thereof, a positive electrode plate, a sodium ion battery and electric equipment. The general formula of the positive electrode material of the sodium ion battery is Na δ Cu x Mn y Ni z Fe s Mg a Al b Zr c Ti d O 2 The method comprises the steps of carrying out a first treatment on the surface of the The sodium ion battery anode material is mainly prepared by sintering a mixed material containing a precursor material, a sodium source and a fluxing agent; the mass ratio of the fluxing agent to the mixture is gamma, and the gamma and delta in the general formula satisfy the following relation: the delta-1)/gamma is more than or equal to 1 and less than or equal to 65. The invention realizes the improvement of the hardness of the positive electrode material by regulating and controlling the ratio of Na proportion to the mass ratio of the fluxing agent, improves the compaction density of the positive electrode plate prepared from the positive electrode material with single crystal/polycrystal morphology, and reaches 3.2g/cm 3 The above method realizes that the section particles of the positive electrode material are broken to be less than 3 after rolling.

Description

Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery positive electrode material, a preparation method thereof, a positive electrode plate, a sodium ion battery and electric equipment.
Background
Compared with a lithium ion battery, the sodium ion battery has lower cost and rich sodium element reserves, and the energy density of the sodium ion battery can be compared with that of lithium ion batteries such as lithium iron phosphate and the like.
Although the positive electrode material of the sodium ion battery has higher theoretical capacity, the pole piece compaction density of the positive electrode material of the sodium ion battery is generally lower than that of the lithium ion battery, and the pole piece compaction density of the positive electrode material of the sodium ion battery is generally lower than 3g/cm 3 This not only results in the energy density of the sodium ion battery being difficult to increase, but also the pole piece has the phenomenon that particles are broken more after rolling, thereby resulting in the increase of the expansion rate of the pole piece and the increase of side reactions in the circulating process, and the cycle life is poor.
Therefore, the sodium ion battery positive electrode material which can not only improve the compaction density of the sodium ion positive electrode plate, but also reduce the technical problem of particle fragmentation in the electrode plate rolling process has important significance.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a positive electrode material of a sodium ion battery, which solves the technical problems that the energy density of the sodium ion battery is difficult to improve and particles of the positive electrode material are more broken after rolling due to low compaction density of a pole piece of a conventional sodium ion positive electrode material.
The second object of the invention is to provide a preparation method of the positive electrode material of the sodium ion battery.
A third object of the present invention is to provide a positive electrode sheet.
A fourth object of the present invention is to provide a sodium ion battery.
A fifth object of the present invention is to provide a powered device.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a sodium ion battery anode material, which has a general formula of Na δ Cu x Mn y Ni z Fe s Mg a Al b Zr c Ti d O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein 1 is<δ≤1.2，0.08≤x≤0.14，0.32≤y≤0.35，0.18≤z≤0.24，0.3≤s≤0.36，x+y+z+s＝1，0≤a+b≤0.05，0<c≤0.03，0<d≤0.02；
The sodium ion battery anode material is mainly prepared by sintering a mixed material containing a precursor material, a sodium source and a fluxing agent; the mass ratio of the fluxing agent to the mixed material is gamma, and delta in the general formula and gamma satisfy the following relation: delta-1)/gamma is more than or equal to 1 and less than or equal to 65;
wherein the general formula of the precursor material is Cu x Mn y Ni z Fe s (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.08 and less than or equal to 0.14,0.32, y is more than or equal to 0.35,0.18 and z is more than or equal to 0.24,0.3 and s is more than or equal to 0.36, and x+y+z+s=1;
the fluxing agent contains a zirconium source and a titanium source; optionally, at least one of a magnesium source and an aluminum source is also included in the fluxing agent.
The invention also provides a preparation method of the sodium ion battery anode material, which comprises the following steps:
sintering a mixed material containing a precursor material, a sodium source and a fluxing agent to obtain the sodium ion battery anode material; wherein the mass ratio of the fluxing agent to the mixture is gamma, and the excess coefficient delta of the gamma and sodium element in the sodium source satisfies the following relation: delta-1)/gamma is more than or equal to 1 and less than or equal to 65;
the general formula of the precursor material is Cu x Mn y Ni z Fe s (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.08 and less than or equal to 0.14,0.32, y is more than or equal to 0.35,0.18 and z is more than or equal to 0.24,0.3 and s is more than or equal to 0.36, and x+y+z+s=1;
the fluxing agent contains a zirconium source and a titanium source; optionally, the fluxing agent further comprises at least one of a magnesium source and an aluminum source;
the molar ratio of the precursor material to sodium element in the sodium source is 1:1.01 to 1.2;
the molar ratio of the precursor material to the zirconium element in the zirconium source is 1:0.001 to 0.03;
the molar ratio of the precursor material to the titanium element in the titanium source is 1:0.001 to 0.02;
the ratio of the molar amount of the precursor material to the sum of the molar amounts of magnesium element in the magnesium source and aluminum element in the aluminum source is 1:0 to 0.05.
The invention also provides a positive electrode plate which is mainly made of the positive electrode material of the sodium ion battery.
The invention also provides a sodium ion battery, which comprises the positive electrode plate.
The invention further provides electric equipment, which comprises the sodium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) The sodium ion battery positive electrode material provided by the invention can realize the improvement of the hardness of the positive electrode material by regulating and controlling the ratio of Na ratio to the mass ratio of the fluxing agent, the compaction density of the positive electrode plate prepared from the monocrystal/polycrystal morphology positive electrode material is improved, and the fracture of the section particles of the positive electrode material after rolling is less than 3.
(2) The compaction density of the positive electrode plate prepared from the positive electrode material of the sodium ion battery is more than or equal to 3.2g/cm 3 。
(3) The positive electrode material of the sodium ion battery provided by the invention has excellent electrochemical performance, high capacity, high initial efficiency and good cycle performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a positive electrode material of example 1 after rolling;
FIG. 2 is an SEM image of a positive electrode material of example 2 after rolling;
FIG. 3 is an SEM image of a positive electrode material of comparative example 1 after rolling;
FIG. 4 is an SEM image of a positive electrode material of comparative example 3 after rolling;
FIG. 5 is a sectional SEM image of a positive electrode material of example 2 after rolling;
FIG. 6 is a sectional SEM image of a positive electrode material of comparative example 6 after rolling.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, the present invention provides a positive electrode material for a sodium ion battery, the positive electrode material for a sodium ion battery is a layered oxide positive electrode material, the microstructure of the positive electrode material for a sodium ion battery comprises at least one of a single crystal morphology and a polycrystalline morphology, and the positive electrode material for a sodium ion battery has a general formula of Na δ Cu x Mn y Ni z Fe s Mg a Al b Zr c Ti d O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein 1 is<δ≤1.2，0.08≤x≤0.14，0.32≤y≤0.35，0.18≤z≤0.24，0.3≤s≤0.36，x+y+z+s＝1，0≤a+b≤0.05，0<c≤0.03，0<d≤0.02。
The above general formula Na δ Cu x Mn y Ni z Fe s Mg a Al b Zr c Ti d O 2 Where 0.ltoreq.a+b.ltoreq.0.05, it being understood that a may be 0 alone, b may be 0 alone, or a and b may also be 0 simultaneously. That is, when a=0, 0.ltoreq.b.ltoreq.0.05; alternatively, when b=0, 0.ltoreq.a.ltoreq.0.05.
The above general formula Na δ Cu x Mn y Ni z Fe s Mg a Al b Zr c Ti d O 2 Delta includes, but is not limited to, a point value of any one of 1.01, 1.03, 1.05, 1.08, 1.10, 1.12, 1.14, 1.15, 1.17, 1.19 or a range value therebetween; x includes, but is not limited to, a point value of any one of 0.09, 0.10, 0.11, 0.12, 0.13 or a range value therebetween; y includes, but is not limited to, a point value of any one of 0.325, 0.330, 0.335, 0.340, 0.345 or a range value therebetween; z includes, but is not limited to, a point value of any one of 0.19, 0.20, 0.21, 0.22, 0.23 or a range value therebetween; s includes, but is not limited to, a point value of any one of 0.31, 0.32, 0.33, 0.34, 0.35, or a range value between any two; a includes, but is not limited to, a point value of any one of 0.01, 0.02, 0.03, 0.04, 0.05 or a range value therebetween; b includes, but is not limited to, a point value of any one of 0.01, 0.02, 0.03, 0.04, 0.05 or a range value therebetween; c includes, but is not limited to, a point value of any one of 0.001, 0.003, 0.005, 0.008, 0.01, 0.015, 0.02, 0.025, or a range value therebetween; d includes, but is not limited to, a dot value of any one of 0.001, 0.003, 0.005, 0.008, 0.01, 0.012, 0.015, 0.018, or a range value therebetween.
The sodium ionsThe battery anode material is mainly prepared by sintering a mixed material containing a precursor material, a sodium source and a fluxing agent. The general formula of the precursor material is Cu x Mn y Ni z Fe s (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.08 and less than or equal to 0.14,0.32, y is more than or equal to 0.35,0.18 and z is more than or equal to 0.24,0.3, s is more than or equal to 0.36, and x+y+z+s=1.
The fluxing agent contains a zirconium source and a titanium source; optionally, at least one of a magnesium source and an aluminum source is also included in the fluxing agent. It will be appreciated that optionally means optionally that the flux may or may not contain at least one of a magnesium source and an aluminum source.
The fluxing agent m Auxiliary aid With the mixture m Total (S) The ratio of the masses (abbreviated as flux mass ratio) is γ, i.e., γ=m Auxiliary aid /m Total (S) 。
The gamma and delta in the general formula satisfy the following relation: 1-65, i.e., (delta-1)/gamma=1-65. Wherein the value of (delta-1)/gamma includes, but is not limited to, a point value of any one of 2, 3, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 63 or a range value therebetween.
Delta in the general formula represents the excess coefficient of sodium element, and the excess coefficient delta-1 of sodium element is the excess proportion of sodium element. The ratio of the excess ratio of sodium element to the mass ratio of the fluxing agent is the combination amount of the fluxing agent and the residual sodium, which is equal to 1, is similar to the residual sodium or the material sodium persulfate is completely combined with the fluxing agent to form sodium salt, and similar to vitrification, the hardness can be improved to a certain extent, if the sodium persulfate amount is more, the structure is more favorable, and the redundant Na can also be used as an all-electric sodium supplement agent. But the ratio should not be too high because too much sodium residue would lead to difficulties in mixing the slurry and material instability.
According to the sodium ion battery positive electrode material provided by the invention, the hardness of the positive electrode material can be improved by adjusting and controlling the ratio of the Na ratio to the mass ratio of the fluxing agent, the compaction density of the positive electrode plate prepared from the positive electrode material with single crystal/polycrystal morphology can be improved, and less than 3 section particles are broken after the positive electrode material is rolled.
Therefore, the positive electrode material of the sodium ion battery provided by the invention has excellent electrochemical performance, high capacity, high initial efficiency and good cycle performance.
In a preferred embodiment, the sodium source comprises NaOH, na 2 CO 3 、NaHCO 3 And NaNO 3 At least one of them.
In a preferred embodiment, the fluxing agent is an oxide and/or hydroxide. For example, the zirconium source comprises at least one of zirconium oxide and zirconium hydroxide; the titanium source comprises at least one of titanium dioxide and titanium hydroxide; the magnesium source comprises at least one of magnesium oxide and magnesium hydroxide; the aluminum source includes at least one of aluminum oxide and aluminum hydroxide.
In a preferred embodiment, the general formula Na δ Cu x Mn y Ni z Fe s Mg a Al b Zr c Ti d O 2 Wherein a is more than or equal to 0 and less than or equal to 0.03; including but not limited to a point value of any one of 0.01, 0.05, 0.1, 0.15, 0.2, 0.25 or a range value therebetween.
In a preferred embodiment, the general formula Na δ Cu x Mn y Ni z Fe s Mg a Al b Zr c Ti d O 2 B is more than or equal to 0 and less than or equal to 0.03; including but not limited to a point value of any one of 0.01, 0.05, 0.1, 0.15, 0.2, 0.25 or a range value therebetween.
In a preferred embodiment, the general formula Na δ Cu x Mn y Ni z Fe s Mg a Al b Zr c Ti d O 2 Wherein, delta is equal to or greater than 1.01 and equal to or less than 1.2, including but not limited to a point value of any one of 1.03, 1.05, 1.08, 1.10, 1.12, 1.14, 1.15, 1.17, 1.19 or a range value between any two.
In a preferred embodiment, in order to comprehensively consider the hardness of the positive electrode material and the compacted density of the positive electrode sheet prepared therefrom, the ratio γ=0.001 to 0.05 of the mass of the flux to the mixture, including, but not limited to, a point value of any one of 0.002, 0.003, 0.005, 0.008, 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045 or a range value between any two.
In a preferred embodiment, the D50 particle size of the positive electrode material of the sodium ion battery is 5-20 μm, including but not limited to a dot value of any one of 5 μm, 8 μm, 10 μm, 13 μm, 15 μm, 18 μm, 20 μm or a range value between any two.
In a preferred embodiment, the specific surface area of the positive electrode material of the sodium ion battery is 0.1-0.6 m 2 /g, including but not limited to 0.1m 2 /g、0.2m 2 /g、0.3m 2 /g、0.4m 2 /g、0.5m 2 /g、0.6m 2 A point value of any one of/g or a range value between any two.
In a preferred embodiment, the tap density (TD for short) of the positive electrode material of the sodium ion battery is more than or equal to 1.8g/cm 3 Including but not limited to 1.8g/cm 3 、1.9g/cm 3 、2.0g/cm 3 Any one of the point values or a range value between any two.
In a preferred embodiment, the D50 particle size of the precursor material is 4-10 μm; including but not limited to a dot value of any one of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or a range value between any two.
In a preferred embodiment, the precursor material has a specific surface area of 5 to 50m 2 /g; including but not limited to 10m 2 /g、15m 2 /g、20m 2 /g、25m 2 /g、30m 2 /g、35m 2 /g、40m 2 /g、45m 2 A point value of any one of/g or a range value between any two.
In a preferred embodiment, the precursor material has a tap density of 1.6g/cm or more 3 Including but not limited to 1.7g/cm 3 、1.8g/cm 3 、1.9g/cm 3 、2.0g/cm 3 Any one of the point values or a range value between any two.
The D50 particle diameter of the precursor material is controlled within the above range, and both high yield and high yield can be obtained.
The specific surface area (BET) of the precursor material is controlled within the range, so that the sintering activity is improved, the sintering difficulty is reduced, and the sintering is easy.
The tap density of the precursor material is controlled, so that the deposition time and the sintering difficulty can be reduced, and the sintering efficiency is high.
It will be appreciated that unavoidable impurities such as impurities contained in the starting materials, as well as impurities introduced or formed during the preparation process, are also included in the precursor material and/or the sodium ion battery cathode material. Wherein the impurity element comprises at least one of Na, S, ca, mg, al, zn, co and Li, and the impurity element content is less than 5000ppm.
In a preferred embodiment, the compacted density of the positive electrode plate prepared from the positive electrode material of the sodium ion battery is more than or equal to 3.2g/cm 3 。
In a second aspect, the invention provides a preparation method of the positive electrode material of the sodium ion battery, which specifically comprises the following steps:
and sintering the mixed material containing the precursor material, the sodium source and the fluxing agent to obtain the sodium ion battery anode material.
Wherein the mass ratio of the fluxing agent to the mixture is gamma, and the excess coefficient delta of the gamma and sodium element in the sodium source satisfies the following relation: the delta-1)/gamma is more than or equal to 1 and less than or equal to 65.
According to the preparation method of the sodium ion battery positive electrode material, provided by the invention, by controlling the ratio of gamma to the sodium element excess coefficient delta, the compaction density of the sodium ion positive electrode plate can be improved, particle fragmentation in the rolling process of the electrode plate can be reduced, and the electrochemical performance of the sodium ion positive electrode material is improved.
The general formula of the precursor material is Cu x Mn y Ni z Fe s (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.08 and less than or equal to 0.14,0.32, y is more than or equal to 0.35,0.18 and z is more than or equal to 0.24,0.3, s is more than or equal to 0.36, and x+y+z+s=1.
The fluxing agent contains a zirconium source and a titanium source; optionally, at least one of a magnesium source and an aluminum source is also included in the fluxing agent.
The molar ratio of the precursor material to sodium element in the sodium source is 1:1.01 to 1.2; including but not limited to a dot value of any one of 1:1.03, 1:1.05, 1:1.08, 1:1.10, 1:1.13, 1:1.15, 1:1.18, or a range value therebetween.
The molar ratio of the precursor material to the zirconium element in the zirconium source is 1:0.001 to 0.03; including but not limited to a dot value of any one of 1:0.003, 1:0.005, 1:0.008, 1:0.01, 1:0.015, 1:0.02, 1:0.025, or a range value therebetween.
The molar ratio of the precursor material to the titanium element in the titanium source is 1:0.001 to 0.02; including but not limited to a dot value of any one of 1:0.003, 1:0.005, 1:0.008, 1:0.01, 1:0.015, or a range value therebetween.
The ratio of the molar amount of the precursor material to the sum of the molar amounts of magnesium element in the magnesium source and aluminum element in the aluminum source is 1:0 to 0.05, including but not limited to any one of, or a range of values between, 1:0.003, 1:0.005, 1:0.008, 1:0.01, 1:0.015, 1:0.02, 1:0.03, 1:0.04, 1:0.05.
In a preferred embodiment, the sodium source comprises NaOH, na 2 CO 3 、NaHCO 3 And NaNO 3 At least one of them.
In a preferred embodiment, the zirconium source comprises at least one of zirconium oxide and zirconium hydroxide.
In a preferred embodiment, the titanium source comprises at least one of titanium dioxide and titanium hydroxide.
In a preferred embodiment, the magnesium source comprises at least one of magnesium oxide and magnesium hydroxide.
In a preferred embodiment, the aluminum source comprises at least one of aluminum oxide and aluminum hydroxide.
In a preferred embodiment, the sintering temperature is 700-1200 ℃, including but not limited to any one of 800 ℃, 900 ℃, 1000 ℃, 1100 ℃ or a range of values between any two. The sintering heat preservation time is 8-24 h, including but not limited to any one of 10h, 12h, 15h, 18h, 20h and 22h or a range of values between any two.
In a preferred embodiment, the sintering is performed in an oxygen-containing atmosphere.
In a preferred embodiment, the oxygen-containing atmosphere comprises an air atmosphere or an oxygen atmosphere.
In a preferred embodiment, the rate of temperature rise during sintering is 1 to 10 ℃ per minute, including but not limited to any one of a point value or a range of values between any two of 2 ℃/min, 3 ℃/min, 5 ℃/min, 7 ℃/min, 9 ℃/min.
In a preferred embodiment, the sintering further comprises the steps of crushing and sieving.
In a third aspect, the invention provides a positive electrode plate, which is mainly made of the positive electrode material of the sodium ion battery.
In a fourth aspect, the invention provides a sodium ion battery, comprising the positive electrode plate of the sodium ion battery.
The sodium ion battery has high capacity and excellent cycle stability.
In a fifth aspect, the present invention provides an electrical device, including the sodium ion battery.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The present embodiment provides an O3 type Na 1.15 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 Ti 0.01 Zr 0.01 O 2 The preparation method of the sodium ion battery anode material comprises the following steps:
weighing 2.6864kg of Na 2 CO 3 (purity is 99.86%)4kg of precursor material Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 、0.0355kg TiO 2 (purity 99.13%) and 0.0055kg ZrO 2 (purity is 99.32%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 12h under the air atmosphere at 980 ℃ with the heating rate of 3 ℃/min.
Example 2
The embodiment provides O3 type Na 1.2 Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 Mg 0.003 Ti 0.001 Zr 0.002 O 2 The preparation method of the sodium ion battery anode material comprises the following steps:
weighing 2.7982kg of Na 2 CO 3 (purity 99.86%), 4kg of precursor material Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 (OH) 2 、0.0078kg Mg(OH) 2 (purity 99.06%), 0.0036kg TiO 2 (purity 99.13%) and 0.0109kg ZrO 2 (purity is 99.32%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 12h under the air atmosphere at 1000 ℃ with the temperature rising rate of 3 ℃/min.
Example 3
The embodiment provides O3 type Na 1.1 Cu 0.14 Mn 0.32 Ni 0.18 Fe 0.36 Mg 0.03 Al 0.01 Ti 0.01 Zr 0.02 O 2 The preparation method of the sodium ion battery anode material comprises the following steps:
weighing 2.5614kg of Na 2 CO 3 (purity 99.86%), 4kg of precursor material Cu 0.14 Mn 0.32 Ni 0.18 Fe 0.36 (OH) 2 、0.0776kg Mg(OH) 2 (purity 99.06%), 0.0226kg Al 2 O 3 (purity 99.07%), 0.0354kg TiO 2 (99.13%) and 0.1089kg ZrO 2 (purity is 99.32%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 24 hours in an air atmosphere at 900 ℃ with a heating rate of 3 ℃/min.
Example 4
The embodiment provides O3 type Na 1.05 Cu 0.12 Mn 0.35 Ni 0.23 Fe 0.3 Mg 0.01 Al 0.03 Ti 0.01 Zr 0.02 O 2 The preparation method of the sodium ion battery anode material comprises the following steps:
weighing 2.4460kg of Na 2 CO 3 (purity 99.86%), 4kg of precursor material Cu 0.12 Mn 0.35 Ni 0.23 Fe 0.3 (OH) 2 、0.0258kg Mg(OH) 2 (purity 99.06%), 0.0678kg Al 2 O 3 (purity 99.07%), 0.0354kg TiO 2 (purity 99.13%) and 0.1089kg ZrO 2 (purity is 99.32%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 18h in air atmosphere at 950 ℃ with a heating rate of 10 ℃/min.
Example 5
This example, O3 type Na 1.02 Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 Mg 0.001 Al 0.003 Ti 0.001 Zr 0.002 O 2 The preparation method of the sodium ion battery anode material comprises the following steps:
weighing 2.0986kg of Na 2 CO 3 (purity 99.86%), 0.3753kg NaNO 3 (purity 99.52%), 4kg precursor material Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 (OH) 2 、0.0026kg Mg(OH) 2 (purity 99.06%), 0.0104kg Al (OH) 3 (purity 99.18%), 0.0035kg TiO 2 (purity 99.13%) and 0.0109kg ZrO 2 (purity is 99.32%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 15h under the air atmosphere at 980 ℃ with the heating rate of 8 ℃/min.
Example 6
The embodiment provides O3 type Na 1.03 Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 Al 0.003 Ti 0.001 Zr 0.002 O 2 The preparation method of the sodium ion battery anode material comprises the following steps:
weighing 0.2332kg of Na 2 CO 3 (purity of 99.86)%), 1.5943kg NaOH (purity 99.21%), 4kg precursor material Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 (OH) 2 、0.0104kg Al(OH) 3 (purity 99.18%), 0.0035kg TiO 2 (purity 99.13%) and 0.0109kg ZrO 2 (purity is 99.32%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 18h under the oxygen atmosphere at 750 ℃ with the temperature rising rate of 5 ℃/min.
Example 7
The embodiment provides O3 type Na 1.1 Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 Al 0.03 Ti 0.01 Zr 0.02 O 2 The preparation method of the sodium ion battery anode material comprises the following steps:
1.7715kg NaOH (purity 99.21%) and 4kg precursor Cu were weighed 0.11 Mn 0.33 Ni 0.22 Fe 0.34 (OH) 2 、0.1037kg Al(OH) 3 (purity 99.18%), 0.0354kg TiO 2 (purity 99.13%) and 0.1090kg ZrO 2 (purity is 99.32%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 20h under the oxygen atmosphere at 700 ℃ with the temperature rising rate of 3 ℃/min.
Example 8
The embodiment provides O3 type Na 1.05 Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 Mg 0.03 Ti 0.01 Zr 0.02 O 2 The preparation method of the sodium ion battery anode material comprises the following steps:
weighing 3.7034kg NaHCO 3 (purity 99.67%), 4kg precursor material Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 (OH) 2 、0.0776kg Mg(OH) 2 (purity 99.06%), 0.0354kg TiO 2 (purity 99.13%) and 0.1090kg ZrO 2 (purity is 99.32%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 15h under the oxygen atmosphere at 800 ℃ with the heating rate of 1 ℃/min.
Comparative example 1
O3 type Na provided in this comparative example 1.02 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 Zr 0.02 O 2 The preparation method of the positive electrode material comprises the following steps:
weighing 2.3828kg of Na 2 CO 3 (purity 99.86%), 4kg of precursor material Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 And 0.1092kg ZrO 2 (purity is 99.32%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 15h under the air atmosphere at 980 ℃ with the heating rate of 3 ℃/min.
Comparative example 2
O3 type Na provided in this comparative example 1.02 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 Mg 0.02 O 2 The preparation method of the positive electrode material comprises the following steps:
weighing 2.3828kg of Na 2 CO 3 (purity 99.86%), 4kg of precursor material Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 And 0.0518kg of Mg (OH) 2 (purity is 99.06%), mixing evenly at high speed to obtain a mixed material, sintering at high temperature for 15h under the air atmosphere at 980 ℃, and heating up at a speed of 3 ℃/min.
Comparative example 3
O3 type Na provided in this comparative example 1.02 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 Ti 0.02 O 2 The preparation method of the positive electrode material comprises the following steps:
weighing 2.3828kg of Na 2 CO 3 (purity 99.86%), 4kg of precursor material Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 And 0.0709kg TiO 2 (purity is 99.13%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 15h under the air atmosphere at 980 ℃ with the heating rate of 3 ℃/min.
Comparative example 4
O3 type Na provided in this comparative example 1.03 Cu 0.12 Mn 0.35 Ni 0.23 Fe 0.3 Mg 0.01 Al 0.03 Ti 0.01 Zr 0.02 O 2 The preparation method of the positive electrode material comprises the following steps:
weighing 2.3995kg of Na 2 CO 3 (purity 99.86%), 4kg of precursor material Cu 0.12 Mn 0.35 Ni 0.23 Fe 0.3 (OH) 2 、0.0258kg Mg(OH) 2 (purity 99.06%), 0.0678kg Al 2 O 3 (purity 99.07%), 0.0354kg TiO 2 (purity 99.13%) and 0.1089kg ZrO 2 (purity is 99.32%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 18h in air atmosphere at 950 ℃ with a heating rate of 10 ℃/min.
Comparative example 5
Comparative example O3 Na 1.21 Cu 0.12 Mn 0.35 Ni 0.23 Fe 0.3 Mg 0.0009 Al 0.0028 Ti 0.0009 Zr 0.0018 O 2 The preparation method of the positive electrode material comprises the following steps:
weighing 2.8188kg of Na 2 CO 3 (purity 99.86%), 4kg of precursor material Cu 0.12 Mn 0.35 Ni 0.23 Fe 0.3 (OH) 2 、0.0023kg Mg(OH) 2 (purity 99.06%), 0.0062kg Al 2 O 3 (purity 99.07%), 0.0032kg TiO 2 (purity 99.13%) and 0.0099kg ZrO 2 (purity is 99.32%), mixing evenly at high speed to obtain a mixed material, and sintering at high temperature for 18h in air atmosphere at 950 ℃ with a heating rate of 10 ℃/min.
Comparative example 6
O3 type Na provided in this comparative example 1.2 Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 Mg 0.003 Ti 0.001 Zr 0.002 O 2 The preparation method of the positive electrode material is basically the same as that of example 2, except that the precursor material Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 (OH) 2 Tap density of 1.4g/cm 3 。
The ratio gamma of the mass of the flux to the mass of the mixture, the excess ratio delta-1 of sodium element, and the (delta-1)/gamma values in the above examples and comparative examples are shown in Table 1.
Table 1 groups of gamma, delta-1 and (delta-1)/gamma values
In each of the above examples and comparative examples, the D50 particle diameter, specific surface area (BET) and tap density of the precursor material, and the D50 particle diameter and specific surface area of the sodium ion battery cathode material are shown in table 2.
TABLE 2D 50, BET and tap Density of precursors, D50 and BET of cathode materials
Experimental example 1
After the layered oxide cathode materials prepared in example 1, example 2, comparative example 1 and comparative example 3 were rolled into a pole piece, SEM image analysis was performed, the acceleration voltage was 1KV, the magnification was 5K, and the area percentage of the fracture was used as a criterion for particle fracture.
Wherein, the SEM image of the positive electrode material of example 1 after being rolled is shown in fig. 1, the SEM image of the positive electrode material of example 2 after being rolled is shown in fig. 2, the SEM image of the positive electrode material of comparative example 1 after being rolled is shown in fig. 3, and the SEM image of the positive electrode material of comparative example 3 after being rolled is shown in fig. 4.
As can be seen from fig. 1 to 4, the fragmentation of comparative examples 1 and 3 using the single element flux was serious, the area occupied by the fragmented particles was 50% or more (comparative example 1 occupied by the fragmented particles > 90% and comparative example 3 occupied by the fragmented particles > 80%), while example 1 was fluxed with Ti element and Zr element simultaneously, example 1 was fluxed with Mg element, ti element and Zr element simultaneously, and the area occupied by the fragmented particles was less than 30%.
Further, after the electrode sheets made of the layered oxide cathode materials of example 2 and comparative example 6 were rolled, the sections were polished with an argon ion polisher, and SEM image analysis was performed, with an acceleration voltage of 1KV, a magnification of 500K, and the degree of chipping and bouncing of the electrode sheet particles was checked. The SEM of the cut surface of the positive electrode material of example 2 after rolling is shown in fig. 5, and the SEM of the cut surface of the positive electrode material of comparative example 6 after rolling is shown in fig. 5.
As can be seen from fig. 5 and 6, the pole piece of comparative example 6 is stressed unevenly after being rolled, and has internal stress rebound, and more particles are broken; whereas the pole piece compaction of example 2 meets the standard and has substantially no bounce.
The pole piece rolling steps are as follows: the positive electrode materials, the conductive agent SP and the binder PVDF prepared in the examples and the comparative examples are respectively mixed with solvent N-methyl pyrrolidone and anhydrous oxalic acid according to the mass percent of 97.3 percent, 0.7 percent and 2.0 percent to form positive electrode slurry, the positive electrode slurry is coated on the surface of a current collector aluminum foil and dried, and then the positive electrode slurry is pressed by rolling until the equipment limit or the aluminum foil is not broken or the average value of the compacted density is kept at 3.3+/-0.1 g/cm 3 。
Experimental example 2
The positive electrode materials prepared in each example and each comparative example are respectively used as active substances, the active substances are mixed according to the mass ratio of SP to PVDF of 90:5:5, NMP is added to prepare adhesive glue solution with viscosity, the adhesive glue solution is coated on aluminum foil, and the aluminum foil is baked for 12 hours at 120 ℃ in a vacuum drying oven, so that the positive electrode plate is obtained. And a metallic sodium sheet is used as a counter electrode, glass fiber (Waterman) is used as a diaphragm, and 1mol/L NaPF 6 EC/dmc=1:1 (Alfa) as electrolyte, 2032 coin cell was assembled in an Ar protection glove box. Each set of cells was then tested at a voltage range of 2.5 to 4.0V, cycled for 3 weeks at 0.1C, and the specific discharge capacity and initial effect of 5 cells at 0.1C for 3 weeks on average were recorded, with the results shown in table 3.
Further, tap Densities (TDs) of the positive electrode materials prepared in each example and each comparative example, and the compacted densities of the electrode sheets prepared in each positive electrode material were measured, respectively, and the state after rolling was observed.
TABLE 3 results of tap Density, pole piece compaction Density and electrochemical Property of Positive electrode Material
As can be seen from comparison of the experimental data of comparative examples 1 to 3 and examples (especially examples 1 to 2) in tables 1, 2 and 3, the fluxing of single Mg, zr and Ti elements was difficult to reach 3.2g/cm 3 The pole piece has the compacted density.
As is clear from the experimental results of comparative examples 4 and 5, the value of (delta-1)/gamma is lower or higher than the set value, and it is difficult to achieve 3.2g/cm even if the pole piece is pressed until the pole piece breaks 3 The pole piece has the compacted density. Whereas example 2 and example 4 in the set value range can each reach 3.2g/cm 3 The pole piece compaction density above, and even though the same precursor was only different in sodium dose and flux dose, example 4 was higher in both capacity exertion and initial efficiency than comparative examples 4 and 5.
As can be seen from a comparison of example 2 and comparative example 6, the compacted density of the pole piece produced from the low tap precursor is difficult to reach the standard.
In addition, the above examples 1-5 are monocrystalline morphology materials, and examples 6-7 are polycrystalline morphology materials, which demonstrate that both morphology materials can achieve an increase in material hardness, and an increase in positive pole piece compaction density, and achieve less than 3 fracture of the tangent plane particles after rolling of the positive pole material.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.

Claims (10)

1. A positive electrode material of a sodium ion battery is characterized in that the general formula of the positive electrode material of the sodium ion battery is Na δ Cu x Mn y Ni z Fe s Mg a Al b Zr c Ti d O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein 1 is<δ≤1.2，0.08≤x≤0.14，0.32≤y≤0.35，0.18≤z≤0.24，0.3≤s≤0.36，x+y+z+s＝1，0≤a+b≤0.05，0<c≤0.03，0<d≤0.02；
The sodium ion battery anode material is mainly prepared by sintering a mixed material containing a precursor material, a sodium source and a fluxing agent; the mass ratio of the fluxing agent to the mixed material is gamma, and delta in the general formula and gamma satisfy the following relation: delta-1)/gamma is more than or equal to 1 and less than or equal to 65;
wherein the general formula of the precursor material is Cu x Mn y Ni z Fe s (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.08 and less than or equal to 0.14,0.32, y is more than or equal to 0.35,0.18 and z is more than or equal to 0.24,0.3 and s is more than or equal to 0.36, and x+y+z+s=1;
the fluxing agent contains a zirconium source and a titanium source; optionally, at least one of a magnesium source and an aluminum source is also included in the fluxing agent.
2. The positive electrode material for sodium ion battery according to claim 1, wherein the general formula Na δ Cu x Mn y Ni z Fe s Mg a Al b Zr c Ti d O 2 Comprising at least one of the following features (1) to (3):
(1)0≤a≤0.03；
(2)0≤b≤0.03；
(3)1.01≤δ≤1.2。
3. the positive electrode material for sodium ion battery according to claim 1, wherein a ratio γ=0.001 to 0.05 of the mass ratio γ of the flux to the mixture.
4. The sodium ion battery positive electrode material according to claim 1, characterized in that the sodium ion battery positive electrode material comprises at least one of the following features (1) to (3):
(1) The particle diameter of D50 is 5-20 mu m;
(2) The specific surface area is 0.1-0.6 m 2 /g；
(3) Tap density is more than or equal to 1.8g/cm 3 。
5. The sodium ion battery cathode material of claim 1, wherein the precursor material comprises at least one of the following features (1) to (3):
(1) The particle diameter of D50 is 4-10 mu m;
(2) Specific surface area of 5-50 m 2 /g；
(3) Tap density is more than or equal to 1.6g/cm 3 。
6. The method for preparing a positive electrode material for sodium ion battery according to any one of claims 1 to 5, comprising the steps of:
sintering a mixed material containing a precursor material, a sodium source and a fluxing agent to obtain the sodium ion battery anode material; wherein the mass ratio of the fluxing agent to the mixture is gamma, and the excess coefficient delta of the gamma and sodium element in the sodium source satisfies the following relation: delta-1)/gamma is more than or equal to 1 and less than or equal to 65;
the general formula of the precursor material is Cu x Mn y Ni z Fe s (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.08 and less than or equal to 0.14,0.32, y is more than or equal to 0.35,0.18 and z is more than or equal to 0.24,0.3 and s is more than or equal to 0.36, and x+y+z+s=1;
the fluxing agent contains a zirconium source and a titanium source; optionally, the fluxing agent further comprises at least one of a magnesium source and an aluminum source;
the molar ratio of the precursor material to sodium element in the sodium source is 1:1.01 to 1.2;
the molar ratio of the precursor material to the zirconium element in the zirconium source is 1:0.001 to 0.03;
the molar ratio of the precursor material to the titanium element in the titanium source is 1:0.001 to 0.02;
the ratio of the molar amount of the precursor material to the sum of the molar amounts of magnesium element in the magnesium source and aluminum element in the aluminum source is 1:0 to 0.05.
7. The method of producing a sodium ion battery positive electrode material according to claim 6, further comprising at least one of the following features (1) to (7):
(1) The sodium source comprises NaOH and Na 2 CO 3 、NaHCO 3 And NaNO 3 At least one of (a) and (b);
(2) The zirconium source comprises at least one of zirconium oxide and zirconium hydroxide;
(3) The titanium source comprises at least one of titanium dioxide and titanium hydroxide;
(4) The magnesium source comprises at least one of magnesium oxide and magnesium hydroxide;
(5) The aluminum source includes at least one of aluminum oxide and aluminum hydroxide;
(6) The sintering temperature is 700-1200 ℃, and the sintering time is 8-24 hours;
(7) The sintering is performed in an oxygen-containing atmosphere.
8. A positive electrode sheet, characterized in that it is mainly made of the positive electrode material of sodium ion battery as claimed in any one of claims 1 to 5.
9. A sodium ion battery comprising the positive electrode sheet of claim 8.
10. A powered device comprising a sodium ion battery as defined in claim 9.
CN202310998171.7A 2023-08-08 2023-08-08 Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment Pending CN116979059A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310998171.7A CN116979059A (en) 2023-08-08 2023-08-08 Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310998171.7A CN116979059A (en) 2023-08-08 2023-08-08 Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment

Publications (1)

Publication Number Publication Date
CN116979059A true CN116979059A (en) 2023-10-31

Family

ID=88471310

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310998171.7A Pending CN116979059A (en) 2023-08-08 2023-08-08 Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment

Country Status (1)

Country Link
CN (1) CN116979059A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117199342A (en) * 2023-11-07 2023-12-08 宁波容百新能源科技股份有限公司 Sodium ion battery positive electrode material, and preparation method and application thereof
CN117239111A (en) * 2023-11-13 2023-12-15 北京中科海钠科技有限责任公司 Nickel-free layered oxide positive electrode material, preparation method thereof, positive electrode composition, sodium ion secondary battery and application
CN117276531A (en) * 2023-11-13 2023-12-22 北京中科海钠科技有限责任公司 Doped layered oxide positive electrode material, method for producing same, positive electrode composition, sodium ion secondary battery, and use
CN117303466A (en) * 2023-11-28 2023-12-29 广东省中科海钠科技有限责任公司 Layered positive electrode material, preparation method thereof and positive electrode plate
CN117457888A (en) * 2023-12-22 2024-01-26 成都碳合利科技有限公司 Sodium ion battery layered oxide single crystal positive electrode material and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117199342A (en) * 2023-11-07 2023-12-08 宁波容百新能源科技股份有限公司 Sodium ion battery positive electrode material, and preparation method and application thereof
CN117239111A (en) * 2023-11-13 2023-12-15 北京中科海钠科技有限责任公司 Nickel-free layered oxide positive electrode material, preparation method thereof, positive electrode composition, sodium ion secondary battery and application
CN117276531A (en) * 2023-11-13 2023-12-22 北京中科海钠科技有限责任公司 Doped layered oxide positive electrode material, method for producing same, positive electrode composition, sodium ion secondary battery, and use
CN117239111B (en) * 2023-11-13 2024-02-02 北京中科海钠科技有限责任公司 Nickel-free layered oxide positive electrode material, preparation method thereof, positive electrode composition, sodium ion secondary battery and application
CN117276531B (en) * 2023-11-13 2024-04-12 北京中科海钠科技有限责任公司 Doped layered oxide positive electrode material, method for producing same, positive electrode composition, sodium ion secondary battery, and use
CN117303466A (en) * 2023-11-28 2023-12-29 广东省中科海钠科技有限责任公司 Layered positive electrode material, preparation method thereof and positive electrode plate
CN117303466B (en) * 2023-11-28 2024-04-09 广东省中科海钠科技有限责任公司 Layered positive electrode material, preparation method thereof and positive electrode plate
CN117457888A (en) * 2023-12-22 2024-01-26 成都碳合利科技有限公司 Sodium ion battery layered oxide single crystal positive electrode material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN116979059A (en) Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment
JP6380608B2 (en) Method for producing lithium composite compound particle powder, method for using lithium composite compound particle powder in non-aqueous electrolyte secondary battery
JP4998753B2 (en) Cobalt oxide particle powder and production method thereof, positive electrode active material for non-aqueous electrolyte secondary battery, production method thereof, and non-aqueous electrolyte secondary battery
JP5879761B2 (en) Lithium composite compound particle powder, method for producing the same, and nonaqueous electrolyte secondary battery
CN109516509B (en) High-compaction single crystal ternary positive electrode material and preparation method and application thereof
JP2023534756A (en) Lithium ion battery positive electrode lithium replenishment additive and its preparation method and lithium ion battery
CN110649264B (en) Silicon-based negative electrode material and preparation method thereof
WO2022199389A1 (en) Silicon-oxygen composite negative electrode material, preparation method therefor, and lithium ion battery
JP5321802B2 (en) Lithium cobalt oxide particle powder and method for producing the same, and non-aqueous electrolyte secondary battery
CN108539131A (en) A kind of graphene is modified the preparation method of nickelic system&#39;s positive electrode
CN112047391A (en) Preparation method of single crystal type lithium nickel manganese aluminate anode material
CN110589901A (en) Preparation method of nickel cobalt lithium manganate positive electrode material (Ni is more than or equal to 0.8)
CN113764669A (en) Layered oxide positive electrode material of high-voltage sodium-ion battery
CN112661163B (en) Silica-based composite anode material, preparation method thereof and lithium ion battery
CN115924978B (en) Manganese-based layered sodium ion battery positive electrode material, and preparation method and application thereof
CN117080418B (en) Sodium ion battery positive electrode material, preparation method thereof, positive plate, sodium ion battery and electric equipment
CN117303466B (en) Layered positive electrode material, preparation method thereof and positive electrode plate
WO2024066809A1 (en) Positive electrode material, preparation method therefor, positive electrode sheet, secondary battery, and electronic device
CN115506021A (en) Single-crystal ternary cathode material and preparation method thereof, lithium ion battery cathode and lithium ion battery
CN115353085B (en) Lithium iron phosphate composite material containing lithium supplementing agent, preparation method and application thereof, and battery containing lithium iron phosphate composite material
JP5708939B2 (en) Lithium titanate particle powder and method for producing the same, negative electrode active material particle powder for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
CN115304104B (en) Manganese series lithium supplementing additive, preparation method and application thereof
JP5152456B2 (en) Positive electrode active material, method for producing the same, and nonaqueous electrolyte secondary battery
JP4305613B2 (en) Positive electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery
CN117285087B (en) Layered oxide, preparation method thereof and sodium battery

Legal Events

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