CN113845154B - Positive electrode solid solution material precursor, and preparation method and application thereof - Google Patents

Positive electrode solid solution material precursor, and preparation method and application thereof Download PDF

Info

Publication number
CN113845154B
CN113845154B CN202111092491.3A CN202111092491A CN113845154B CN 113845154 B CN113845154 B CN 113845154B CN 202111092491 A CN202111092491 A CN 202111092491A CN 113845154 B CN113845154 B CN 113845154B
Authority
CN
China
Prior art keywords
solution
positive electrode
solid solution
precursor
mixed 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.)
Active
Application number
CN202111092491.3A
Other languages
Chinese (zh)
Other versions
CN113845154A (en
Inventor
郭建
高秀玲
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.)
Tianjin EV Energies Co Ltd
Original Assignee
Tianjin EV Energies 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 Tianjin EV Energies Co Ltd filed Critical Tianjin EV Energies Co Ltd
Priority to CN202111092491.3A priority Critical patent/CN113845154B/en
Publication of CN113845154A publication Critical patent/CN113845154A/en
Application granted granted Critical
Publication of CN113845154B publication Critical patent/CN113845154B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/48—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
    • 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a positive electrode solid solution material precursor, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing a nickel source, a manganese source, a cobalt source and a first doped metal source with a solvent to obtain a mixed solution A; (2) Dissolving a second doped metal source in an iminodisuccinic acid sodium salt solution to obtain a mixed solution B, and dissolving sodium tungstate in ammonia water to obtain a mixed solution C; (3) The ammonia water is used as base solution for heating, the mixed solution A, the mixed solution B and the mixed solution C are added into the base solution, the pH value is regulated, and the precursor of the positive electrode solid solution material is obtained through ageing and filtering after the reaction is finished.

Description

Positive electrode solid solution material precursor, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to an anode solid solution material precursor, a preparation method and application thereof.
Background
With the progress of economic globalization and the massive use of fossil fuels, environmental pollution and energy shortage problems are increasingly serious. In order to reduce pollution in the use process of fossil fuel, sustainable renewable energy sources, novel power batteries and high-efficiency energy storage systems are developed, reasonable allocation of renewable resources is realized, and the method has important strategic significance for solving energy crisis and protecting environment. The lithium ion battery is paid attention to as a novel high-energy green battery, and compared with other energy storage systems, the lithium ion battery has the outstanding advantages of high storage energy per unit volume, long cycle life, good safety, no memory effect and the like. The method has wide application prospect and potential huge economic benefit in the aspects of portable electronic equipment, electric automobiles, space technology, national defense industry and the like, and rapidly becomes the focus of attention in recent years.
The positive electrode materials of lithium ion batteries which have been put into practical use at present can be classified into three types according to their structures, including lithium gold having a hexagonal layered structureBelongs to oxide, spinel material and polyanion structure compound. Among them, the layered oxide has been attracting attention because of its high energy density, ease of preparation, strong structural stability, and excellent reversibility of lithium ion extraction/intercalation. To further enhance the performance of the layered structure material, different metal ions are introduced into LiTMO 2 The TM lattice position of the system.
High Entropy Oxide (HEO) is a new compound that has been of interest to the scientific community because of its unique properties. Where HEO stands for a multi-element metal oxide system that can crystallize as a single phase. Typically, 5 or more elements share the same atomic sites in HEO, forming a stable solid solution.
The lithium ion battery anode material in the current market is mainly prepared by a coprecipitation-high temperature solid phase method, the precursor performance plays a decisive role in the lithium ion battery anode material, and the high-entropy solid solution material precursor is prepared by the coprecipitation method, so that different metal elements occupy transition metal ion sites in the coprecipitation process to form a stable solid solution material, and the process can realize the atomic level mixing of the materials and realize mass production, and has wide application prospect.
CN110233257B discloses a preparation method of a solid spherical multiple annular lithium-rich manganese-based solid solution positive electrode material precursor, wherein the lithium-rich manganese-based solid solution positive electrode material precursor has a solid spherical multiple annular structure, a liquid-liquid coprecipitation method is adopted to obtain a carbonate precursor, and the solid spherical multiple annular lithium-rich manganese-based solid solution positive electrode material precursor is obtained by performing special calcination treatment on the carbonate precursor. The lithium-rich manganese-based solid solution positive electrode material prepared by adopting the solid spherical oxide precursor with the multiple annular structures has excellent electrochemical performance and large compaction density, and the positive electrode material prepared by adopting the precursor circularly generates phase change under high voltage to cause irreversible structural phase change, so that the circulation stability is poor.
CN103606667a discloses a preparation method of a precursor of a solid solution of manganese as a lithium ion positive electrode material, which comprises the steps of reacting a mixed solution of nickel, manganese and aluminum ions with a precipitant under nitrogen atmosphere, aging, washing and dryingAnd drying to obtain the nickel-manganese-aluminum hydroxide precursor, wherein the synthesized precursor has spherical morphology, ideal particle size distribution and higher tap density. The positive electrode material has low electron conductivity and poor doubling rate caused by Li/Ni mixed arrangement, and Ni is in a high lithium removal state 4+ Is prone to reduction to Ni 3+ Releasing O 2 Resulting in poor thermal stability.
The problems of poor cycling stability, poor multiplying power, low conductivity and the like exist in the scheme, so that the development of the precursor with good cycling stability, good multiplying power and high electronic conductivity is necessary to be applied to the lithium ion battery anode material.
Disclosure of Invention
Aiming at the performance improvement requirement of the existing layered structure lithium ion battery anode material in the market, the invention prepares the multi-metal element hydroxide precursor through coprecipitation on the basis of not changing the process of production materials and not increasing the cost of production raw materials, so that different metal elements occupy transition metal ion sites in the coprecipitation process, and a high-entropy solid solution material precursor is formed.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a precursor of a solid solution material for a positive electrode, the method comprising the steps of:
(1) Mixing a nickel source, a manganese source, a cobalt source and a first doped metal source with a solvent to obtain a mixed solution A;
(2) Dissolving a second doped metal source in an iminodisuccinic acid sodium salt solution to obtain a mixed solution B, and dissolving sodium tungstate in ammonia water to obtain a mixed solution C;
(3) And heating by taking ammonia water as base solution, adding the mixed solution A, the mixed solution B and the mixed solution C into the base solution, adjusting the pH, and aging and filtering after the reaction is completed to obtain the precursor of the positive solid solution material.
The order of arrangement of the mixed solution A, the mixed solution B and the mixed solution C is not limited.
The method prepares the hydroxide precursor of the multi-metal element through coprecipitation, so that different metal elements occupy transition metal ion sites in the coprecipitation process; meanwhile, because various metal ions are introduced and Ksp is different when various metal ion hydroxides precipitate, the complex precipitation of all metal ions can not be realized by using ammonia water as a complexing agent, and the simultaneous precipitation of various metal ions can be promoted by using a polyion copolymerization chelating agent iminodisuccinate sodium salt IDS.
Taking a hydroxide precursor as an example: since the precipitation solution transition products of various metal ion hydroxides are different, the state of the early-stage solution is improved according to the solution transition product constant and Ksp Ni(OH)2 ＝2×10 -15 ，Ksp Co(OH)2 ＝1.9×10 -15 ，Ksp Mn(OH)2 ＝1.6×10 -13 ，Ksp Zn(OH)2 ＝7.1×10 -18 ，Ksp Mg(OH)2 ＝1.8×10 -11 ，Ksp Al(OH)3 ＝1.3×10 -33 ，Ksp Cr(OH)2 ＝2×10 -16 ，Ksp Ti(OH)3 ＝1×10 -40 ，Ksp Sn(OH)2 ＝6.3×10 -27 ；
According to the different dissolution products of various metal hydroxides, the invention can adopt different configuration modes for various metal salt solutions.
Preferably, the first dopant metal source of step (1) comprises any one or a combination of at least two of Ti, V, cr, zr, mn, fe, co, ni, zn, mg, ca, ru, sn, sb, al, mo, Y, nb, la, ce, eu or Er salts.
Preferably, the second dopant metal source of step (2) comprises any one or a combination of at least two of Ti, V, cr, zr, mn, fe, co, ni, zn, mg, ca, ru, sn, sb, al, mo, Y, nb, la, ce, eu or Er salts.
Preferably, NH in the aqueous ammonia of step (3) 3 The concentration of (2) is 10 to 25%, for exampleSuch as: 10%, 12%, 15%, 20% or 25%, etc.
Preferably, the temperature of the heating is 40 to 60 ℃, for example: 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, or the like.
Preferably, the feeding speed of the mixed liquor A, the mixed liquor B and the mixed liquor C is independently 100-200 mL/h, for example: 100mL/h, 120mL/h, 150mL/h, 180mL/h, 200mL/h, etc.
Preferably, the stirring is carried out simultaneously with the feeding.
Preferably, the stirring speed is 500 to 800rpm, for example: 500rpm, 550rpm, 600rpm, 700rpm, 800rpm, etc.
Preferably, the pH in step (3) is 10 to 12, for example: 10. 10.5, 11, 11.5 or 12, etc.
Preferably, the solution for adjusting the pH comprises any one or a combination of at least two of sodium hydroxide solution, sodium carbonate solution or sodium bicarbonate solution.
Preferably, the reaction time of step (3) is 24 to 40 hours, for example: 24h, 30h, 32h, 35h or 40h, etc.
Preferably, the aging time is from 6 to 10 hours, for example: 6h, 7h, 8h, 9h or 10h, etc.
Preferably, the filtration is followed by a drying treatment.
Preferably, the temperature of the drying treatment is 90 to 150 ℃, for example: 90 ℃, 100 ℃, 110 ℃, 120 ℃, 140 ℃ or 150 ℃ and the like.
Preferably, the drying treatment is performed for 10 to 30 hours, for example: 10h, 15h, 20h, 25h or 30h, etc.
In a second aspect, the present invention provides a positive electrode solid solution material precursor prepared by the method according to the first aspect, wherein the positive electrode solid solution material precursor has a chemical formula of Ni x Co y Mn 0.95-x-y A 0.05 (OH) 2 Wherein x+y<0.95, a+b+c+d+e=1, a being at least five of Ti, V, cr, mn, fe, co, ni, zn, mg, ca, ru, sn, sb, W, al, mo, Y, nb, la, ce, eu or Er.
The inventionThe solid solution material precursor introduces other metal elements capable of improving the performance of the positive electrode material precursor into the TM layer, wherein the metal elements comprise Ti, V, cr, mn, fe, co, ni, zn, mg, ca, ru, sn, sb, W, al, mo, Y, nb, la, ce, eu or Er and other elements, so that at least five metal elements exist in the system to form LiNi x Co y Mn 0.95-x-y ·(Sn a W b Cr c Al d Mg e ) 0.05 (OH) 2 ，[x+y<0.95，a+b+c+d+e＝1]The solid-liquid material with the structure ensures that the system at least contains five or more metal impurity elements. The solid solution structure comprises LiNi x Co y Mn 0.95-x-y (Sn a W b ) 0.05 (OH) 2 (x+y<0.95,a+b＝1)、LiNi x Co y Mn 0.95-x-y (Cr a Al b Mg c ) 0.05 (OH) 2 (x+y<0.95,a+b+c＝1)、LiNi x Co y Mn 0.95-x-y (Sn a W b Cr c Al d Mg e ) 0.05 (OH) 2 (x+y<0.95, a+b+c+d+e=1), and the like.
In a third aspect, the present invention provides a positive electrode solid solution material prepared from the positive electrode solid solution material precursor of the second aspect.
In a fourth aspect, the present invention provides a positive electrode sheet comprising the positive electrode solid solution material according to the third aspect.
In a fifth aspect, the present invention provides a lithium ion battery comprising the positive electrode sheet according to the fourth aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) Five or more elements in the solid solution structural material share the same atomic site to form a stable solid solution, and the solid solution material has complex composition, so that complementation of performances of different structural materials can be realized, and the appearance of the material shows excellent performances, including good structural stability, thermal stability, rate capability and the like.
(2) According to the invention, IDS is introduced into the preparation process of the positive electrode material precursor, the problem that the mixing uniformity is poor due to the fact that solid phase mixing doping cannot be used in coprecipitation in the current batch application, and the doped ions in the ternary material structure cannot be uniformly distributed is solved, the ion level mixing of most of the doping metal elements is realized, and a new technological scheme is found for improving the performance consistency of the industrial production material.
Drawings
Fig. 1 is an SEM image of a positive electrode solid solution material precursor according to example 1 of the present invention.
Fig. 2 is a particle size distribution diagram of a positive electrode solid solution material precursor product according to example 1 of the present invention.
Fig. 3 is an SEM image of a positive electrode solid solution material precursor according to example 2 of the present invention.
Fig. 4 is a particle size distribution diagram of a positive electrode solid solution material precursor product according to example 2 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. 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 embodiment provides a positive electrode solid solution material precursor, which is characterized in that the preparation method of the positive electrode solid solution material precursor is as follows:
(1) Dissolving nickel sulfate, cobalt sulfate, manganese sulfate, zinc sulfate, magnesium sulfate and chromium sulfate in deionized water to prepare a solution A;
(2) Dissolving tin sulfate and aluminum sulfate in 10L of 0.5M IDS solution to prepare solution B, and preparing 10L of complexing agent with concentration of 0.4M, namely ammonia water solution, wherein 0.02M sodium tungstate is added as tungsten source to obtain solution C;
(3) Adding 5L deionized water into a 30L reaction kettle, adding 200mL25% concentrated ammonia water as base solution, adjusting pH to 11, maintaining temperature at 50deg.C, and reversingIntroducing nitrogen into the reactor for 4h, maintaining the inert gas environment, injecting the prepared solution A, solution B and solution C into a nitrogen protective atmosphere reactor with the rotating speed of 600rmp at the speed of 200mL/h, simultaneously adding the solution A, the solution B and the solution C into the base solution at a constant speed (namely 200 mL/h) in parallel, regulating the pH value in the reaction process by sodium hydroxide, taking care of regulating the flow rate of the alkaline solution, and controlling the pH value to be 11 by an online pH value regulator; ensuring the final Ni: co: mn: sn: zn: mg: w: cr: the molar ratio of Al is 0.82:0.1:0.03:0.01:0.01:0.01:0.01:0.005:0.005; after the reaction for 25 hours, the salt solution and the complexing agent are completely injected into the reaction kettle, the precursor preparation is completed, the coprecipitation process is finished after aging for 10 hours, the solid-liquid mixture is centrifugally filtered and separated, washed to be neutral by deionized water, and dried for 25 hours at 100 ℃ to obtain the Ni with the molecular formula 0.82 Co 0.1 Mn 0.03 (Sn 0.01 Zn 0.01 Mg 0.01 W 0.01 Cr 0.005 Al 0.005 (OH) 2 An SEM image of the precursor is shown in fig. 1, and a particle size distribution diagram of the precursor is shown in fig. 2.
Example 2
The embodiment provides a positive electrode solid solution material precursor, which is characterized in that the preparation method of the positive electrode solid solution material precursor is as follows:
(1) Dissolving nickel sulfate, cobalt sulfate, manganese sulfate, magnesium sulfate and chromium sulfate in deionized water to prepare a solution A;
(2) Dissolving aluminum sulfate and zirconium sulfate in 10L of 0.5M IDS solution to prepare solution B, preparing 10L of complexing agent with concentration of 0.4M, namely ammonia water solution, wherein 0.02M sodium tungstate is added as tungsten source to obtain solution C;
(3) Adding 5L deionized water into a 30L reaction kettle, adding 200mL of 25% concentrated ammonia water as a base solution, adjusting the pH to 11, maintaining the temperature at 50 ℃, introducing nitrogen into the reaction kettle for 4h, maintaining the inert gas environment, injecting the prepared solution A, solution B and solution C into a nitrogen protection atmosphere reaction kettle with the rotating speed of 600rmp at the speed of 200mL/h, simultaneously adding the solution A, the solution B and the solution C into the base solution at the constant speed (namely 200 mL/h) in parallel, and adjusting the reaction by sodium hydroxideThe pH in the process, taking care to adjust the alkaline solution flow rate, controlling ph=11 by an online pH; ensuring the final Ni: co: mn: cr: al: mg: zr=0.8: 0.1:0.05:0.01:0.01:0.01:0.01, after reacting for 25 hours, completely pumping the salt solution and the complexing agent into the reaction kettle, preparing the precursor, finishing the coprecipitation process after aging for 10 hours, centrifugally filtering and separating the solid-liquid mixture, washing with deionized water to be neutral, and drying at 100 ℃ for 25 hours to obtain the Ni with the molecular formula of 0.8 Co 0.1 Mn 0.05 Cr 0.01 Al 0.01 Mg 0.01 Zr 0.0 1 W 0.01 (OH) 2 An SEM image of the precursor is shown in fig. 3, and a particle size distribution diagram of the precursor is shown in fig. 4.
The positive electrode solid solution material precursors obtained in examples 1 to 2 were tested, and the test results are shown in table 1:
TABLE 1
D50(μm) Tap density (g/cm) 3 ) Specific surface area (m) 2 /g)
Example 1 8.15 2.05 13.7
Example 2 9.45 1.88 17.3
As can be seen from examples 1-2, the present invention introduces a polyion copolychelating agent iminodisuccinic acid sodium salt IDS in the coprecipitation process, and reduces the dosage of ammonia water; meanwhile, because a plurality of metal ions are introduced and Ksp is different when various metal ion hydroxides are precipitated, the complex precipitation of all metal ions can not be realized by using ammonia water as a complexing agent, and the simultaneous precipitation of a plurality of metal ions can be promoted by adopting a polyion copolymerization chelating agent iminodisuccinate sodium salt IDS.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (18)

1. The preparation method of the positive electrode solid solution material precursor is characterized by comprising the following steps of:
(1) Mixing a nickel source, a manganese source, a cobalt source and a first doped metal source with a solvent to obtain a mixed solution A;
(2) Dissolving a second doped metal source in an iminodisuccinic acid sodium salt solution to obtain a mixed solution B, and dissolving sodium tungstate in ammonia water to obtain a mixed solution C;
(3) Heating by taking ammonia water as a base solution, adding the mixed solution A, the mixed solution B and the mixed solution C into the base solution, adjusting the pH, and aging and filtering after the reaction is completed to obtain the precursor of the positive solid solution material;
the chemical formula of the positive electrode solid solution material precursor is Ni x Co y Mn 0.95-x-y A 0.05 (OH) 2 Wherein x+y<0.95, a is Ti, V, cr, mn, fe, co, ni, zn, mg, ca, ru, sn, sb, W, al, mo, Y, nb, la, ce, eu or at least five of Er.
2. The method of claim 1, wherein the first dopant metal source of step (1) comprises any one or a combination of at least two of Ti, V, cr, zr, mn, fe, co, ni, zn, mg, ca, ru, sn, sb, al, mo, Y, nb, la, ce, eu or Er salts.
3. The method of claim 1, wherein the second dopant metal source of step (2) comprises any one or a combination of at least two of Ti, V, cr, zr, mn, fe, co, ni, zn, mg, ca, ru, sn, sb, al, mo, Y, nb, la, ce, eu or Er salts.
4. The process according to claim 1, wherein NH in the aqueous ammonia of step (3) 3 The concentration of (2) is 10-25%.
5. The method of claim 1, wherein the heating is at a temperature of 40 to 60 ℃.
6. The method of claim 1, wherein the feed rates of mixed liquor a, mixed liquor B and mixed liquor C are independently 100 to 200mL/h.
7. The process of claim 6, wherein the stirring is performed while feeding.
8. The method according to claim 7, wherein the stirring speed is 500 to 800rpm.
9. The process according to claim 1, wherein the pH in the step (3) is 10 to 12.
10. The method of claim 1, wherein the pH adjusting solution comprises any one or a combination of at least two of sodium hydroxide solution, sodium carbonate solution, or sodium bicarbonate solution.
11. The process according to claim 1, wherein the reaction time in step (3) is 24 to 40 hours.
12. The process according to claim 1, wherein the aging time is from 6 to 10 hours.
13. The method of claim 1, wherein the filtration is followed by a drying process.
14. The method according to claim 13, wherein the temperature of the drying treatment is 90 to 150 ℃.
15. The method according to claim 13, wherein the drying treatment is performed for 10 to 30 hours.
16. A positive electrode solid solution material, characterized in that it is prepared from a positive electrode solid solution material precursor prepared by the method of any one of claims 1 to 15.
17. A positive electrode sheet, characterized in that it contains the positive electrode solid solution material according to claim 16.
18. A lithium ion battery comprising the positive electrode sheet of claim 17.
CN202111092491.3A 2021-09-17 2021-09-17 Positive electrode solid solution material precursor, and preparation method and application thereof Active CN113845154B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111092491.3A CN113845154B (en) 2021-09-17 2021-09-17 Positive electrode solid solution material precursor, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111092491.3A CN113845154B (en) 2021-09-17 2021-09-17 Positive electrode solid solution material precursor, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113845154A CN113845154A (en) 2021-12-28
CN113845154B true CN113845154B (en) 2023-10-13

Family

ID=78974587

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111092491.3A Active CN113845154B (en) 2021-09-17 2021-09-17 Positive electrode solid solution material precursor, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113845154B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102496708A (en) * 2011-12-12 2012-06-13 江南大学 Multi-element lamellar positive pole material of lithium ion battery and preparation method for multi-element lamellar positive pole material
CN102723475A (en) * 2012-06-06 2012-10-10 株洲泰和高科技有限公司 Preparation method of ternary layered lithium-ion battery anode material
CN104134798A (en) * 2014-08-08 2014-11-05 湖北金泉新材料有限责任公司 Composite doping type nickel-cobalt positive electrode material and preparation method thereof
CN105900276A (en) * 2014-01-09 2016-08-24 日产自动车株式会社 Process for producing lithium ion secondary battery
CN106025238A (en) * 2016-07-22 2016-10-12 哈尔滨工业大学 Preparation method of lithium-ion-battery anode material with bulk-phase-doped metal elements
CN106848297A (en) * 2017-03-31 2017-06-13 中国科学院青海盐湖研究所 The preparation method of rich lithium tertiary cathode material in lithium ion battery
CN108550822A (en) * 2018-04-25 2018-09-18 成都新柯力化工科技有限公司 A kind of lanthanum, the nickelic ternary anode material of lithium battery of magnesium codope and preparation method
CN109301189A (en) * 2018-09-11 2019-02-01 天津市捷威动力工业有限公司 The preparation method of the one nickelic multicomponent material of type monocrystalline type
CN109704411A (en) * 2018-11-22 2019-05-03 银隆新能源股份有限公司 Nickel lithium manganate cathode material and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102496708A (en) * 2011-12-12 2012-06-13 江南大学 Multi-element lamellar positive pole material of lithium ion battery and preparation method for multi-element lamellar positive pole material
CN102723475A (en) * 2012-06-06 2012-10-10 株洲泰和高科技有限公司 Preparation method of ternary layered lithium-ion battery anode material
CN105900276A (en) * 2014-01-09 2016-08-24 日产自动车株式会社 Process for producing lithium ion secondary battery
CN104134798A (en) * 2014-08-08 2014-11-05 湖北金泉新材料有限责任公司 Composite doping type nickel-cobalt positive electrode material and preparation method thereof
CN106025238A (en) * 2016-07-22 2016-10-12 哈尔滨工业大学 Preparation method of lithium-ion-battery anode material with bulk-phase-doped metal elements
CN106848297A (en) * 2017-03-31 2017-06-13 中国科学院青海盐湖研究所 The preparation method of rich lithium tertiary cathode material in lithium ion battery
CN108550822A (en) * 2018-04-25 2018-09-18 成都新柯力化工科技有限公司 A kind of lanthanum, the nickelic ternary anode material of lithium battery of magnesium codope and preparation method
CN109301189A (en) * 2018-09-11 2019-02-01 天津市捷威动力工业有限公司 The preparation method of the one nickelic multicomponent material of type monocrystalline type
CN109704411A (en) * 2018-11-22 2019-05-03 银隆新能源股份有限公司 Nickel lithium manganate cathode material and preparation method thereof

Also Published As

Publication number Publication date
CN113845154A (en) 2021-12-28

Similar Documents

Publication Publication Date Title
CN111916687B (en) Positive electrode material, preparation method thereof and lithium ion battery
CN112599781B (en) Double-concentration gradient doped lithium ion battery anode material and preparation method thereof
CN115000399B (en) Spherical-like sodium ion battery positive electrode material, preparation method thereof and sodium ion battery
CN108483516B (en) Lithium ion battery anode material with superlattice ordered structure and synthesis method thereof
CN109244390B (en) Phosphorus-doped lithium-rich manganese-based positive electrode material for lithium ion battery and preparation method thereof
WO2015139482A1 (en) High-voltage lithium-ion battery positive electrode material having spinel structure and preparation method thereof
CN104134791A (en) High-voltage mono-crystal lithium nickel cobalt manganese oxide anode material and preparation method thereof
WO2015039490A1 (en) Lithium-rich anode material and preparation method thereof
CN102208607A (en) Synthesis and surface modification method of lithium excessive laminar oxide anode material
CN113889619A (en) Sodium-ion battery positive electrode material and preparation method and application thereof
CN109678219B (en) Preparation method of nano layered lithium nickel cobalt manganese oxide
CN107579223B (en) Method for preparing nickel-cobalt-manganese ternary material
CN113772748B (en) Preparation method of lithium ion battery anode material
CN112010356A (en) Lanthanum-aluminum-magnesium in-situ co-doped cobaltosic oxide material and preparation method thereof
CN111029561A (en) Ternary lithium battery positive electrode material precursor and preparation method thereof, ternary lithium battery positive electrode material and preparation method and application thereof
CN113851641A (en) High-entropy solid solution cathode material and preparation method and application thereof
CN106920959A (en) A kind of lithium-rich manganese-based polynary positive pole material of monocrystalline and preparation method thereof
CN113845153A (en) Multi-element high-entropy solid solution cathode material and preparation method and application thereof
CN110534737A (en) A kind of high magnification doping type nickel-cobalt-manganese ternary material and preparation method thereof
CN103303982B (en) Preparation method of high-pressure solid lithium cobalt oxide precursor
CN113555545B (en) Crystal face controllable anion/cation co-doped alpha/beta composite nickel-cobalt-aluminum precursor and preparation method thereof
CN110911652B (en) Nano spherical alpha-MnO 2 /Bi 2 O 3 Material, preparation method and application thereof
CN113830841A (en) Anode solid solution material and preparation method and application thereof
CN108807971B (en) Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof
CN113845154B (en) Positive electrode solid solution material precursor, and preparation method and application thereof

Legal Events

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