CN116477670A - Sodium ion precursor material and preparation method and application thereof - Google Patents

Sodium ion precursor material and preparation method and application thereof Download PDF

Info

Publication number
CN116477670A
CN116477670A CN202310254255.XA CN202310254255A CN116477670A CN 116477670 A CN116477670 A CN 116477670A CN 202310254255 A CN202310254255 A CN 202310254255A CN 116477670 A CN116477670 A CN 116477670A
Authority
CN
China
Prior art keywords
sodium ion
source
manganese
nickel
solution
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
CN202310254255.XA
Other languages
Chinese (zh)
Inventor
张坤
贾冬鸣
李聪
许开华
薛晓斐
段少强
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.)
GEM Co Ltd China
Jingmen GEM New Material Co Ltd
Original Assignee
GEM Co Ltd China
Jingmen GEM New Material 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 GEM Co Ltd China, Jingmen GEM New Material Co Ltd filed Critical GEM Co Ltd China
Priority to CN202310254255.XA priority Critical patent/CN116477670A/en
Publication of CN116477670A publication Critical patent/CN116477670A/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
    • H01M4/52—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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

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

Abstract

The invention provides a sodium ion precursor material, a preparation method and application thereof. The sodium ion precursor material comprises a nickel-iron-manganese hydroxide material; the nickel-iron-manganese hydroxide material is doped with boron and potassium. According to the invention, B and K are simultaneously doped in the preparation process of the sodium ion precursor material by a coprecipitation method, so that B and K elements in the obtained sodium ion layered oxide positive electrode material are uniformly distributed, the structural stability of the sodium ion layered oxide positive electrode material is stabilized, the positive electrode release capacity of the sodium ion layered oxide positive electrode material is facilitated, and the cycle performance of the sodium ion layered oxide positive electrode material is improved.

Description

Sodium ion precursor material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to a sodium ion precursor material, a preparation method and application thereof.
Background
At present, with the advent of portable wearable equipment, electric vehicles and smart grids, the demand for lithium is increasingly high, and world lithium resource reserves rapidly enter the situation of short supply. Meanwhile, due to the limitations of the production process and the production expansion period, the cost of the battery grade lithium carbonate and the high-purity lithium carbonate with higher technical content is greatly increased, and the recent price exceeds 60 ten thousand yuan per ton. The contradiction between explosive demands and mismatch of lithium resources of lithium batteries is aggravated, and the development of sodium ion batteries is a good direction.
In recent years, transition metal layered oxide Na x TmO 2 Because of the advantages of high specific capacity, simple preparation method, reversible deintercalation and the like, the transition metal layered oxide is hopeful to become a candidate material of the positive electrode of the sodium ion battery, and thus, the related fields are widely studied, for example, CN108565457A provides a positive electrode material of the sodium ion battery, a preparation method thereof and the sodium ion battery. The chemical formula of the positive electrode material of the sodium ion battery provided by the invention is Na x Ni 0.167 Co 0.167 Mn 0.67 O 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.8, the positive electrode material of the sodium ion battery is spherical in shape, and the concentration of manganese and nickel is distributed in a gradient manner along the radial direction.
However, the transition metal layered oxide still has some problems, such as deformation of the structure caused by easy phase transition in the deintercalation process, thus degradation of the structure, serious attenuation of reversible capacity in the circulation process, and poor circulation stability.
And because the radius of the sodium ions is larger, the sodium ions not only need higher energy to drive the sodium ions to move, but also easily damage the anode structure in the deintercalation process, so the sodium ions are generally doped to obtain higher specific capacity and better cycle performance, but the existing doping technology is mostly a solid phase method, a sol-gel method or a solvent evaporation method, and the industrial expansion production is not facilitated.
A doped modified P2 type sodium ion battery positive electrode material is disclosed as CN109962215 a. The method is characterized in that: doped modified P2 type sodium ion battery anode material is Na with doped structure 0.67 Mn x Fe 1-x O 2 Positive electrode material, cation doped material Na 0.67 Mn 0.6 Fe 0.4-x-y A x B y O 2 X is more than 0 and less than or equal to 0.1, y is more than 0 and less than or equal to 0.1, and doped cations comprise two parts: a is metal cation participating in oxidation-reduction reaction in the charge-discharge process, and B is inert metal cation in the charge-discharge process. The preparation method employed in this document is a solid phase method.
Therefore, how to obtain a structure of the sodium-ion oxide positive electrode material with uniformly distributed doping elements and stable performance and improve electrochemical performance is a technical problem to be solved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a sodium ion precursor material, and a preparation method and application thereof. According to the invention, B and K are simultaneously doped in the preparation process of the sodium ion precursor material by a coprecipitation method, so that B and K elements in the obtained sodium ion layered oxide positive electrode material are uniformly distributed, the structural stability of the sodium ion layered oxide positive electrode material is stabilized, the positive electrode release capacity of the sodium ion layered oxide positive electrode material is facilitated, and the cycle performance of the sodium ion layered oxide positive electrode material is improved.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a sodium ion precursor material comprising a nickel iron manganese hydroxide material; the nickel-iron-manganese hydroxide material is doped with boron and potassium.
In the sodium ion precursor material provided by the invention, B and K are simultaneously doped in the preparation process of the sodium ion precursor material, so that B and K elements in the obtained sodium ion layered oxide positive electrode material are uniformly distributed, the B doping can improve the structural stability of the sodium ion layered oxide positive electrode material, the cycle performance of the positive electrode material is improved, and K ions can stabilize the structure of the sodium ion layered oxide positive electrode material, thereby being more beneficial to the deintercalation of sodium ions in the layered oxide positive electrode material; in the invention, the doping of B and K synergistically act to realize the improvement of specific capacity and cycle performance, and if only B is doped, the purpose of improving specific capacity cannot be realized, and if only K is doped, the doping amount cannot be accurately controlled; and B and K, if not incorporated in the precursor stage, may be detrimental to uniform distribution of the elements.
Preferably, the sodium ion precursor material has a chemical formula zC 24 H 20 BK-Ni x Fe y Mn (1-x-y) (OH) 2 Wherein, z is more than or equal to 0.01 and less than or equal to 0.05, x is more than or equal to 0.1 and less than or equal to 0.34,0.1, and y is more than or equal to 0.34.
For example, the z can be 0.01, 0.013, 0.015, 0.018, 0.02, 0.023, 0.025, 0.028, 0.03, 0.033, 0.035, 0.038, 0.4, 0.043, 0.045, 0.05, or the like; the x may be 0.1, 0.13, 0.15, 0.18, 0.2, 0.23, 0.25, 0.28, 0.3, 0.32, or 0.34, etc., and the y may be 0.1, 0.13, 0.15, 0.18, 0.2, 0.23, 0.25, 0.28, 0.3, 0.32, or 0.34, etc.
In the sodium ion precursor material provided by the invention, the z value is too small, namely the doping of B and K is too small, which is unfavorable for improving the performance of a sodium ion positive electrode, and the z value is too large, namely the doping of B and K is too much, which can cause the reduction of specific capacity.
In a second aspect, the present invention also provides a method for preparing a sodium ion precursor material according to the first aspect, the method comprising the steps of:
and adding the nickel-iron-manganese-boron mixed salt solution, the potassium source solution and the precipitant solution into the base solution in parallel flow for coprecipitation reaction to obtain the sodium ion precursor material.
According to the preparation method provided by the invention, doping of B and K is carried out by a coprecipitation method, so that doping elements are uniformly distributed, in the preparation process, if a boron source is singly added (not used as one of mixed salts), the boron source is unfavorable for uniform distribution of the elements, and if a potassium source is not singly added, the boron source directly participates in the reaction, namely, the boron source is jointly added (used as the mixed salt) and the potassium source is singly added, so that a precursor material with uniform distribution of B, K is obtained, and the preparation method is easy to regulate and control, simple and suitable for large-scale production.
Preferably, the preparation of the ferronickel manganese boron mixed salt solution comprises the following steps:
preparing a ternary mixed solution from a nickel source, an iron source and a manganese source, and then adding the boron source for mixing to obtain a nickel-iron-manganese-boron mixed salt solution.
Preferably, the molar concentration of the ternary mixed solution is 2 to 4mol/L, for example, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, or the like.
Preferably, the molar concentration of boron in the ferronickel manganese boron mixed salt solution is 0.15-0.8 mol/L, such as 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, 0.5mol/L, 0.55mol/L, 0.6mol/L, 0.65mol/L, 0.7mol/L, 0.75mol/L or 0.8mol/L, etc.
In the invention, the excessive molar concentration of boron in the nickel-iron-manganese-boron mixed salt solution can influence the electrochemical performance of the subsequent positive electrode material, and the excessive molar concentration can cause poor doping effect.
Preferably, the nickel source comprises any one or a combination of at least two of nickel nitrate, nickel sulfate or nickel chloride.
Preferably, the iron source comprises ferrous sulphate.
Preferably, the manganese source comprises any one or a combination of at least two of manganese nitrate, manganese sulfate or manganese chloride.
Preferably, the boron source comprises sodium tetraphenylboron.
In the invention, the sodium tetraphenylborate is selected as the boron source, the co-doping of B, K element can be better realized, and if other boron sources such as H are selected 3 BO 3 K can be caused to fail to precipitate.
Preferably, the potassium source comprises potassium oxalate.
In the invention, potassium oxalate is used asIs a potassium source, can provide K ions and also can serve as a complexing agent in a system, and other potassium salts, such as K 2 SO 4 Then a complexing agent solution needs to be additionally introduced, complicating the process.
Preferably, the molar concentration of the potassium source solution is 0.1 to 2.4mol/L, for example, 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, 2.4mol/L, or the like.
Preferably, the molar concentration of the precipitant solution is 1 to 12mol/L, for example 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L or 12mol/L, etc.
Preferably, the pH during the coprecipitation reaction is 9 to 11.8, for example 9, 9.3, 9.5, 9.8, 10, 10.3, 10.5, 10.8, 11, 11.3, 11.5 or 11.8, etc.
Preferably, the reaction temperature during the coprecipitation reaction is 40 to 60 ℃, for example 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, or the like.
Preferably, the reaction time during the coprecipitation reaction is 50 to 100 hours, for example, 50 hours, 55 hours, 60 hours, 65 hours, 70 hours, 75 hours, 80 hours, 85 hours, 90 hours, 95 hours, 100 hours, or the like.
Preferably, the stirring speed in the coprecipitation reaction process is 200-400 r/min, such as 200r/min, 230r/min, 250r/min, 280r/min, 300r/min, 330r/min, 350r/min, 380r/min or 400r/min, etc.
In the invention, the uniform doping of B and K in the precursor stage is realized jointly by the parameter coordination (pH, temperature, time and stirring rate) in the coprecipitation process.
As a preferred technical scheme, the preparation method comprises the following steps:
preparing a ternary mixed solution with the molar concentration of 2-4 mol/L from a nickel source, an iron source and a manganese source, and then adding a boron source for mixing to obtain a nickel-iron-manganese-boron mixed salt solution with the molar concentration of 0.15-0.8 mol/L;
and (3) adding the nickel-iron-manganese-boron mixed salt solution, the potassium source solution and the precipitant solution into the base solution in parallel, keeping the pH value to be 9-11.8, and performing coprecipitation reaction at the temperature of 40-60 ℃ at the stirring speed of 200-400 r/min for 50-100 h to obtain the sodium ion precursor material.
In a third aspect, the present invention provides a sodium ion positive electrode material, which is obtained by mixing and sintering a sodium ion precursor material and a sodium source according to the first aspect.
The sodium ion positive electrode material provided by the invention realizes doping of B and K in a precursor stage, and is further sintered to obtain the positive electrode material with stable structure and excellent performance.
Preferably, the chemical formula of the sodium ion positive electrode material is Na 0.67-z K z B z Ni x Fe y Mn (1-x-y) O 2 Wherein, z is more than or equal to 0.01 and less than or equal to 0.05, x is more than or equal to 0.1 and less than or equal to 0.34,0.1, and y is more than or equal to 0.34.
For example, the z can be 0.01, 0.013, 0.015, 0.018, 0.02, 0.023, 0.025, 0.028, 0.03, 0.033, 0.035, 0.038, 0.4, 0.043, 0.045, 0.05, or the like; the x may be 0.1, 0.13, 0.15, 0.18, 0.2, 0.23, 0.25, 0.28, 0.3, 0.32, or 0.34, etc., and the y may be 0.1, 0.13, 0.15, 0.18, 0.2, 0.23, 0.25, 0.28, 0.3, 0.32, or 0.34, etc.
Preferably, the sodium source comprises sodium carbonate.
Preferably, the sintering includes primary sintering and secondary sintering.
Preferably, the temperature of the primary sintering is 300 to 500 ℃, for example 300 ℃, 350 ℃,400 ℃, 450 ℃, 500 ℃, or the like.
Preferably, the time of the primary sintering is 3 to 6 hours, for example, 3 hours, 4 hours, 5 hours, 6 hours, or the like.
Preferably, the secondary sintering is performed at a temperature of 700 to 900 ℃, for example 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, or the like.
Preferably, the secondary sintering time is 12 to 24 hours, for example 12 hours, 15 hours, 18 hours, 20 hours, 22 hours or 24 hours, etc.
In a fourth aspect, the present invention also provides a sodium ion battery comprising a sodium ion positive electrode material according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the sodium ion precursor material provided by the invention, B and K are simultaneously doped in the preparation process of the sodium ion precursor material, so that B and K elements in the obtained sodium ion layered oxide positive electrode material are uniformly distributed, the B doping can improve the structural stability of the sodium ion layered oxide positive electrode material, the circulating performance of the positive electrode material is improved, K ions can stabilize the structure of the sodium ion layered oxide positive electrode material, and the B and K cooperate to improve the capacity and the circulating performance of the sodium ion positive electrode material. The positive electrode in the sodium ion battery is prepared from the sodium ion precursor provided by the invention, and when z in the precursor is more than or equal to 0.01 and less than or equal to 0.05, the initial specific capacity of the battery at 0.1C can reach 170.85 mAh.g under the voltage of 2-4V -1 The capacity retention rate after 100 circles of circulation can reach more than 90.8 percent.
(2) According to the preparation method provided by the invention, B and K are doped by a coprecipitation method, the boron source is added together (used as mixed salt), and the potassium source is added independently, so that the doping elements are uniformly distributed, the sodium ion precursor material with stable structure is obtained, the regulation and control are easy, and the preparation method is simple and suitable for large-scale production.
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present embodiment provides a sodium ion precursor material having a chemical formula of 0.01C 24 H 20 BK-Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 。
The preparation method of the sodium ion precursor material comprises the following steps:
weighing nickel sulfate, ferrous sulfate and manganese sulfate according to the stoichiometric ratio of Ni to Fe to Mn=1 to 1 to prepare a ternary solution with the concentration of 2mol/L, then adding sodium tetraphenylborate into the ternary solution, stirring and dissolving the ternary solution to enable B to be preparedThe concentration is 0.5mol/L; adding base solution (adding water to 1/3 of the reaction kettle, adding oxalic acid to make oxalic acid radical concentration 1-7g/L, adding liquid alkali to control pH at 11-12), introducing N 2 Heating to 50deg.C, adding quaternary solution, 2mol/L sodium hydroxide solution and 0.1mol/L potassium oxalate solution into a reaction kettle, stirring continuously at 360r/min, maintaining pH of the reaction system at 10, and reacting for 80 hr to obtain the product with structural formula of 0.01C 24 H 20 BK-Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Is a quasi-spherical five-membered precursor.
Example 2
The present embodiment provides a sodium ion precursor material having a chemical formula of 0.03C 24 H 20 BK-Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 。
The preparation method of the sodium ion precursor material comprises the following steps:
weighing nickel sulfate, ferrous sulfate and manganese sulfate according to the stoichiometric ratio of Ni to Fe to Mn=1 to 1, preparing a ternary solution with the concentration of 3mol/L, then adding sodium tetraphenylborate into the ternary solution, and stirring for dissolution to ensure that the concentration of B is 0.5mol/L; adding base solution (adding water to 1/3 of the reaction kettle, adding oxalic acid to make oxalic acid radical concentration 1-7g/L, adding liquid alkali to control pH at 11-12), introducing N 2 Heating to 40 ℃, adding a quaternary solution, a 5mol/L sodium hydroxide solution and a 1mol/L potassium oxalate solution into a reaction kettle in parallel flow, continuously stirring at a stirring speed of 200r/min, maintaining the pH of the reaction system at 11, and reacting for 100h to obtain a structural formula of 0.03C 24 H 20 BK-Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Is a quasi-spherical five-membered precursor.
Example 3
The present embodiment provides a sodium ion precursor material having a chemical formula of 0.05C 24 H 20 BK-Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 。
The preparation method of the sodium ion precursor material comprises the following steps:
weighing sulfuric acid according to stoichiometric ratio of Ni to Fe to Mn=1:1:1Preparing a ternary solution of nickel, ferrous sulfate and manganese sulfate into a ternary solution of 4mol/L, then adding sodium tetraphenylborate into the ternary solution, and stirring and dissolving the ternary solution to ensure that the concentration of B is 0.8mol/L; adding base solution (adding water to 1/3 of the reaction kettle, adding oxalic acid to make oxalic acid radical concentration 1-7g/L, adding liquid alkali to control pH at 11-12), introducing N 2 Heating to 60 ℃, adding a quaternary solution, a 12mol/L sodium hydroxide solution and a 2mol/L potassium oxalate solution into a reaction kettle in parallel flow, continuously stirring at a stirring speed of 400r/min, maintaining the pH of the reaction system at 9, and reacting for 50h to obtain a structural formula of 0.05C 24 H 20 BK-Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Is a quasi-spherical five-membered precursor.
Example 4
The difference between this example and example 1 is that the chemical formula of the sodium ion precursor material in this example is 0.01C 24 H 20 BK-Ni 0.2 Fe 0.2 Mn 0.6 (OH) 2 。
The remaining preparation methods and parameters were consistent with example 1.
Example 5
The difference between this example and example 1 is that the chemical formula of the sodium ion precursor material in this example is 0.01C 24 H 20 BK-Ni 0.1 Fe 0.1 Mn 0.8 (OH) 2 。
The remaining preparation methods and parameters were consistent with example 1.
Example 6
The difference between this example and example 1 is that the chemical formula of the sodium ion precursor material in this example is 0.06C 24 H 20 BK-Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 。
The remaining preparation methods and parameters were consistent with example 1.
Example 7
The difference between this example and example 1 is that the chemical formula of the sodium ion precursor material in this example is 0.005C 24 H 20 BK-Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 。
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 1
The difference between this comparative example and example 1 is that only boron is doped, potassium is not doped, potassium oxalate is not added in the preparation process, and sodium oxalate is used.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 2
The difference between this comparative example and example 1 is that in this comparative example only potassium was doped, no boron was doped, and no sodium tetraphenylborate was added during the preparation.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 3
The difference between this comparative example and example 1 is that the boron source in this comparative example was added separately, i.e., the ferronickel manganese ternary mixed salt solution, the sodium tetraphenylboron solution, the potassium oxalate solution and the sodium hydroxide solution were added in parallel to the base solution.
The remaining preparation methods and parameters were consistent with example 1.
The sodium ion precursor materials provided in examples 1 to 7 and comparative examples 1 to 3 were mixed with sodium carbonate in a molar ratio of 1:0.7 (ratio to sodium element), and after primary sintering at 400 ℃ for 5 hours, the temperature was continuously raised to 800 ℃ for secondary sintering for 18 hours, to obtain a sodium ion positive electrode material, the specific chemical formulas of which are shown in table 1.
And preparing the sodium ion positive electrode materials provided in the examples 1-7 and the comparative examples 1-3 to obtain positive electrode plates, and further preparing the sodium ion battery.
The sodium ion batteries provided in examples 1 to 7 and comparative examples 1 to 3 were subjected to performance tests with a test voltage ranging from 2.0 to 4.0V and a current density of 0.1C, and the test results are shown in table 1.
TABLE 1
As can be seen from the data in examples 1 and 6 and 7, the excessive z value in the sodium precursor material can cause the doped element to occupy the Na sites too much, which in turn reduces the specific capacity of the material, while the excessively small z value is detrimental to improving the material properties.
From the data obtained in example 1 and comparative examples 1-2, it is clear that the synergy of B and K doping in the present invention can achieve both an increase in specific capacity and an improvement in cycle performance; b is doped only, so that the cycle performance of the material can be improved; the K element cannot be precipitated by doping K alone, only a small amount of adsorbed K element can be obtained in the material, accurate quantification cannot be achieved, and the distribution range of the K element in the material cannot be controlled.
As can be seen from the data results of example 1 and comparative example 3, in the preparation method provided by the invention, the boron source and the ferronickel manganese ternary mixed salt solution are added together as mixed salt, otherwise, the doping elements are unevenly distributed, and the doping effect is affected.
In summary, the doping of B and K is performed by the coprecipitation method, the boron source is added together (as a mixed salt), and the potassium source is added separately, so that the doping elements are uniformly distributed, the B and K elements in the obtained sodium-ion layered oxide cathode material are uniformly distributed, the structural stability of the sodium-ion layered oxide cathode material can be improved by B doping, the cycle performance of the cathode material is improved, the K ions can stabilize the structure of the sodium-ion layered oxide cathode material, and the capacity and cycle performance of the sodium-ion cathode material are improved by B and K synergism. The positive electrode in the sodium ion battery is prepared from the sodium ion precursor provided by the invention, and when z in the precursor is more than or equal to 0.01 and less than or equal to 0.05, the initial specific capacity of the battery at 0.1C can reach 170.85 mAh.g under the voltage of 2-4V -1 The capacity retention rate after 100 circles of circulation can reach more than 90.8 percent.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. A sodium ion precursor material, wherein the sodium ion precursor material comprises a nickel iron manganese hydroxide material; the nickel-iron-manganese hydroxide material is doped with boron and potassium.
2. The sodium ion precursor material of claim 1, wherein the sodium ion precursor material has a chemical formula zC 24 H 20 BK-Ni x Fe y Mn (1-x-y) (OH) 2 Wherein, z is more than or equal to 0.01 and less than or equal to 0.05, x is more than or equal to 0.1 and less than or equal to 0.34,0.1, and y is more than or equal to 0.34.
3. A method of preparing a sodium ion precursor material according to claim 1 or 2, comprising the steps of:
and adding the nickel-iron-manganese-boron mixed salt solution, the potassium source solution and the precipitant solution into the base solution in parallel flow for coprecipitation reaction to obtain the sodium ion precursor material.
4. A method of preparing a sodium ion precursor material according to claim 3, wherein the preparation of the nickel iron manganese boron mixed salt solution comprises:
preparing a ternary mixed solution from a nickel source, an iron source and a manganese source, and then adding the boron source for mixing to obtain a nickel-iron-manganese-boron mixed salt solution;
preferably, the molar concentration of the ternary mixed solution is 2-4 mol/L;
preferably, the molar concentration of boron in the ferronickel manganese boron mixed salt solution is 0.15-0.8 mol/L;
preferably, the nickel source comprises any one or a combination of at least two of nickel nitrate, nickel sulfate or nickel chloride;
preferably, the iron source comprises ferrous sulfate;
preferably, the manganese source comprises any one or a combination of at least two of manganese nitrate, manganese sulfate or manganese chloride;
preferably, the boron source comprises sodium tetraphenylboron;
preferably, the potassium source comprises potassium oxalate;
preferably, the molar concentration of the potassium source solution is 0.1-2.4 mol/L;
preferably, the molar concentration of the precipitant solution is 1 to 12mol/L.
5. The method for preparing a sodium ion precursor material according to claim 3 or 4, wherein the pH value during the coprecipitation reaction is 9 to 11.8;
preferably, the reaction temperature in the coprecipitation reaction process is 40-60 ℃;
preferably, the reaction time in the coprecipitation reaction process is 50-100 hours;
preferably, the stirring speed in the coprecipitation reaction process is 200-400 r/min.
6. The method of preparing a sodium ion precursor material according to any one of claims 3-5, comprising the steps of:
preparing a ternary mixed solution with the molar concentration of 2-4 mol/L from a nickel source, an iron source and a manganese source, and then adding a boron source for mixing to obtain a nickel-iron-manganese-boron mixed salt solution with the molar concentration of 0.15-0.8 mol/L;
and (3) adding the nickel-iron-manganese-boron mixed salt solution, the potassium source solution and the precipitant solution into the base solution in parallel, keeping the pH value to be 9-11.8, and performing coprecipitation reaction at the temperature of 40-60 ℃ at the stirring speed of 200-400 r/min for 50-100 h to obtain the sodium ion precursor material.
7. A sodium ion positive electrode material, wherein the sodium ion positive electrode material is obtained by mixing and sintering the sodium ion precursor material according to claim 1 or 2 and a sodium source.
8. The sodium ion positive electrode material according to claim 7, wherein the sodium ion positive electrode material has a chemical formula of Na 0.67-z K z B z Ni x Fe y Mn (1-x-y) O 2 Wherein, z is more than or equal to 0.01 and less than or equal to 0.05, x is more than or equal to 0.1 and less than or equal to 0.34,0.1, and y is more than or equal to 0.34.
9. The sodium ion positive electrode material according to claim 7 or 8, wherein the sodium source comprises sodium carbonate;
preferably, the sintering includes primary sintering and secondary sintering therewith;
preferably, the temperature of the primary sintering is 300-500 ℃;
preferably, the time of the primary sintering is 3-6 hours;
preferably, the temperature of the secondary sintering is 700-900 ℃;
preferably, the secondary sintering time is 12-24 hours.
10. A sodium ion battery, characterized in that it comprises a sodium ion positive electrode material according to any one of claims 7-9.
CN202310254255.XA 2023-03-16 2023-03-16 Sodium ion precursor material and preparation method and application thereof Pending CN116477670A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310254255.XA CN116477670A (en) 2023-03-16 2023-03-16 Sodium ion precursor material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310254255.XA CN116477670A (en) 2023-03-16 2023-03-16 Sodium ion precursor material and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116477670A true CN116477670A (en) 2023-07-25

Family

ID=87224053

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310254255.XA Pending CN116477670A (en) 2023-03-16 2023-03-16 Sodium ion precursor material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116477670A (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108448109A (en) * 2018-03-23 2018-08-24 中南大学 A kind of stratiform lithium-rich manganese-based anode material and preparation method thereof
EP3415470A1 (en) * 2017-06-14 2018-12-19 Karlsruher Institut für Technologie Boron-doped sodium-ion cathode material, method of producing same and its use
CN110429268A (en) * 2019-08-19 2019-11-08 国联汽车动力电池研究院有限责任公司 A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof
CN111916687A (en) * 2019-05-09 2020-11-10 深圳市贝特瑞纳米科技有限公司 Cathode material, preparation method thereof and lithium ion battery
CN113506685A (en) * 2021-08-18 2021-10-15 中国地质大学（北京） Boron-sulfur co-doped spongy porous carbon, preparation method thereof, carbon electrode and zinc ion hybrid capacitor
CN113889603A (en) * 2021-01-13 2022-01-04 浙江钠创新能源有限公司 Sodium ion battery positive electrode material and preparation method thereof
CN114988494A (en) * 2022-06-10 2022-09-02 宁波容百新能源科技股份有限公司 Boron-doped high-nickel ternary precursor material, preparation method thereof and high-nickel ternary cathode material
CN115321610A (en) * 2022-08-31 2022-11-11 荆门市格林美新材料有限公司 Zirconium-aluminum double-doped nickel-cobalt-manganese hydroxide and preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3415470A1 (en) * 2017-06-14 2018-12-19 Karlsruher Institut für Technologie Boron-doped sodium-ion cathode material, method of producing same and its use
CN108448109A (en) * 2018-03-23 2018-08-24 中南大学 A kind of stratiform lithium-rich manganese-based anode material and preparation method thereof
CN111916687A (en) * 2019-05-09 2020-11-10 深圳市贝特瑞纳米科技有限公司 Cathode material, preparation method thereof and lithium ion battery
CN110429268A (en) * 2019-08-19 2019-11-08 国联汽车动力电池研究院有限责任公司 A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof
CN113889603A (en) * 2021-01-13 2022-01-04 浙江钠创新能源有限公司 Sodium ion battery positive electrode material and preparation method thereof
CN113506685A (en) * 2021-08-18 2021-10-15 中国地质大学（北京） Boron-sulfur co-doped spongy porous carbon, preparation method thereof, carbon electrode and zinc ion hybrid capacitor
CN114988494A (en) * 2022-06-10 2022-09-02 宁波容百新能源科技股份有限公司 Boron-doped high-nickel ternary precursor material, preparation method thereof and high-nickel ternary cathode material
CN115321610A (en) * 2022-08-31 2022-11-11 荆门市格林美新材料有限公司 Zirconium-aluminum double-doped nickel-cobalt-manganese hydroxide and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN112599781B (en) Double-concentration gradient doped lithium ion battery anode material and preparation method thereof
CN103490051B (en) One is applicable to high-tension multielement cathode lithium electric material and preparation method thereof
CN103441265B (en) Rich lithium composite positive pole of a kind of codope and preparation method thereof
CN105958054A (en) Method for lanthanum phosphate coated lithium ion battery cathode material nickel cobalt lithium manganate
CN104810521A (en) Preparing method of nickel cobalt lithium manganate ternary positive electrode material
CN105355905A (en) Method for preparing high-voltage modified lithium ion cell cathode material lithium nickel manganese oxide
CN103094576A (en) Nickel-based positive electrode material, and preparation method thereof and battery
CN105932247A (en) Preparation method of nickel ferrite-coated lithium nickel manganese oxide positive electrode material
WO2022242714A1 (en) Iron-manganese-based positive electrode material, and preparation method therefor and use thereof
EP4220763A1 (en) Coated high nickel ternary material and preparation method therefor and use thereof
KR20240018648A (en) Cobalt-free anode material doped with multiple elements by partition and method for manufacturing the same
CN116504940A (en) Polyanion type sodium ion battery positive electrode material, preparation method and application thereof
CN115966687A (en) Layered sodium-ion battery positive electrode material and preparation method and application thereof
CN104733706B (en) A kind of preparation method of high-tap density composite positive pole
CN113422041A (en) Positive electrode material and preparation method and application thereof
CN117136443A (en) Preparation method of double-layer coated lithium-sodium composite lithium-rich manganese-based positive electrode material
CN114645314B (en) Preparation method of ternary positive electrode material with single crystal morphology
JP2024513948A (en) High nickel ternary core-shell precursor, positive electrode material and manufacturing method thereof
CN114142010B (en) Magnesium oxide and cerium fluoride composite coated lithium ion battery positive electrode material and preparation method thereof
CN113889616B (en) High tap density lithium-rich manganese-based positive electrode material and preparation method thereof
CN116477670A (en) Sodium ion precursor material and preparation method and application thereof
CN115611732A (en) Quaternary precursor and preparation method and application thereof
CN114335552B (en) Positive electrode material, modification process thereof and solid-state battery
CN104766968A (en) Improved ternary lithium ion material production technology method
CN115050955B (en) Preparation and modification method of high-nickel monocrystal ternary cathode material

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