CN116154134A - Modified cobalt-free positive electrode material and preparation method and application thereof - Google Patents

Modified cobalt-free positive electrode material and preparation method and application thereof Download PDF

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Publication number
CN116154134A
CN116154134A CN202310191999.1A CN202310191999A CN116154134A CN 116154134 A CN116154134 A CN 116154134A CN 202310191999 A CN202310191999 A CN 202310191999A CN 116154134 A CN116154134 A CN 116154134A
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cobalt
free
positive electrode
electrode material
modified cobalt
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乔水伶
李崇
方向乾
王慧萍
李伟
马娜妮
张彩红
王子钰
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Caihong Group Co ltd
Shaanxi Rainbow New Materials Co ltd
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Shaanxi Rainbow New Materials Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

Abstract

The invention discloses a modified cobalt-free positive electrode material, a preparation method and application thereof, comprising an inner core Li 1+x Ni 0.75 Mn 0.25 O 2 And a coating layer attached to a surface thereof; the coating layer material is aluminum lithium hydride and zirconium phosphotungstate, wherein the aluminum lithium hydride can participate in counteracting irreversible capacity loss caused by formation of SEI film by first charge and discharge of the lithium ion battery, so that the first coulomb efficiency and charge and discharge cycle performance of the lithium ion battery are greatly improved, the conductivity of the material and the diffusion speed of lithium ions in the cobalt-free layered cathode material are improved, and the rate performance and the cycle stability of the lithium ion battery are remarkably improved. Compared with the method without coating the lithium aluminum hydride and zirconium phosphotungstateThe first coulomb efficiency of the modified cobalt-free positive electrode material prepared by coating lithium aluminum hydride and zirconium phosphotungstate is 87.5-89.8%, the first discharge specific capacity of 0.1C is 187.4-193.2 mAh/g, the 2C multiplying power performance is 87.0-89.1%, and the capacity retention rate after 100 circles of circulation is 98-99.2%. And the whole preparation process has simple process and good application prospect.

Description

Modified cobalt-free positive electrode material 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 a modified cobalt-free anode material, a preparation method and application thereof.
Background
Cobalt is used as one of important elements of the positive electrode material of the power battery, so that the structure of the material can be stabilized, and the cycle and rate performance of the material can be improved. However, the global cobalt metal has the problems of uneven storage capacity distribution, resource shortage and price rise, and the global battery materials, battery suppliers and vehicle enterprises are forced to reduce the content of cobalt in the ternary battery. Thus, technical routes of NCA, NCM ternary and NCMA quaternary appear, but the above technical routes cannot put cobalt resources on global battery materials, battery suppliers and vehicle enterprises.
The cobalt-free layered cathode material is recently developed, and the cobalt-free nickel-based cathode material has the advantages of low cost, high specific capacity and the like, so that the cobalt-free layered cathode material is attractive in the market, but the problems of poor rate performance, short cycle life and poor high-pressure cycle stability are solved. The modification method commonly used at present comprises particle size nanocrystallization, morphology control, surface coating, ion doping and the like, and after the three aspects of modification are combined, the electrical property of the cobalt-free layered cathode material can be greatly improved.
However, the improper selection of the coating agent or the doping agent also causes the increase of resistance, influences the transmission of electrons and ions, and further reduces the electrical performance, and the cobalt-free layered cathode material in the related art still has the problems of low initial efficiency and poor multiplying power and cycle performance due to the lack of cobalt element. Therefore, it is a key to solve the above problems to further modify the cobalt-free layered cathode material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a modified cobalt-free positive electrode material, and a preparation method and application thereof, so as to solve the technical problems of low initial efficiency, poor rate capability and poor cycle performance of the existing cobalt-free positive electrode material.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a modified cobalt-free positive electrode material, which comprises a cobalt-free positive electrode material and a coating layer; the coating layer is lithium aluminum hydride and zirconium phosphotungstate.
Preferably, the cobalt-free positive electrode material is Li 1+x Ni 0.75 Mn 0.25 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, 1.06 is less than or equal to 1+x is less than or equal to 1.08.
Preferably, the mass of lithium aluminum hydride is Li 1+x Ni 0.75 Mn 0.25 O 2 0.05 to 3 percent of the mass; zirconium phosphotungstate of mass Li 1+x Ni 0.75 Mn 0.25 O 2 0.03 to 4 percent of the mass.
The invention also discloses a preparation method of the modified cobalt-free positive electrode material, which comprises the following steps:
s1, lithium hydroxide and Ni 0.75 Mn 0.25 (OH) 2 Uniformly dispersing in a mixing manner to obtain a cobalt-free cathode material precursor;
s2, sintering the cobalt-free positive electrode material precursor obtained in the step S1 in an oxygen atmosphere, cooling to room temperature, crushing and sieving to obtain Li 1+x Ni 0.75 Mn 0.25 O 2 ；
S3, li prepared in the step S2 1+x Ni 0.75 Mn 0.25 O 2 Mixing with lithium aluminum hydride and zirconium phosphotungstate uniformlyAnd then sintering in air, cooling to room temperature, crushing and sieving to obtain the modified cobalt-free anode material.
Preferably, in step S1, li: ni: mn in a molar ratio of (1.06-1.08): 0.75:0.25.
preferably, in step S2, sintering is divided into a burn-in stage and a solid phase reaction stage.
Further preferably, the temperature rising rate of the presintering stage is 3 ℃/min, the temperature of the presintering stage is 550-750 ℃, and the heat preservation time is 2-3 h.
Further preferably, the temperature rising rate of the solid phase reaction stage is 3 ℃/min, the temperature of the solid phase reaction stage is 880-910 ℃, and the heat preservation time is 8-18 h.
Preferably, in the step S3, the sintering temperature is 200-600 ℃, and the heat preservation time is 6-12 h.
The invention also discloses application of the modified cobalt-free positive electrode material in preparation of a positive electrode material of a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a modified cobalt-free positive electrode material, which comprises a cobalt-free positive electrode material and a coating layer; the coating layer is lithium aluminum hydride and zirconium phosphotungstate; the lithium aluminum hydride can participate in counteracting irreversible capacity loss caused by the formation of an SEI film by the first charge and discharge of the lithium ion battery, so that the first coulomb efficiency and the charge and discharge cycle performance of the lithium ion battery are greatly improved; the zirconium phosphotungstate improves the conductivity of the material and the diffusion speed of lithium ions in the cobalt-free layered cathode material, obviously improves the rate capability and the cycle stability of a lithium ion battery, and compared with the cobalt-free cathode material without aluminum lithium hydride and zirconium phosphotungstate, the cobalt-free cathode material without aluminum lithium hydride and zirconium phosphotungstate has obviously improved initial coulomb efficiency and rate capability, and the cycle performance, the prepared modified cobalt-free cathode material has the initial coulomb efficiency of 87.5-89.8%, the initial discharge specific capacity of 187.4-193.2 mAh/g, the rate capability of 87.0-89.1% of 2C and the capacity retention rate of 98-99.2% after 100 circles of cycle.
The invention also discloses a preparation method of the modified cobalt-free positive electrode material, which comprises the steps of preparing a cobalt-free positive electrode material precursor in a mixing mode; presintering and solid phase reaction are carried out to prepare the cobalt-free anode material; and finally, uniformly mixing the cobalt-free positive electrode material with lithium aluminum hydride and zirconium phosphotungstate, and sintering under air to enable the lithium aluminum hydride and the zirconium phosphotungstate to be coated on the outer layer of the cobalt-free positive electrode material, so that the modified cobalt-free positive electrode material is obtained, and the whole preparation process is simple in process and has good application prospect.
The invention also discloses application of the modified cobalt-free cathode material in preparing a lithium ion battery cathode material, when the cobalt-free cathode material is coated with 0.3% of aluminum lithium hydride and 0.25% of zirconium phosphotungstate, the initial coulomb efficiency of the prepared modified cobalt-free cathode material is 89.8%, the initial specific capacity of 0.1C is 193.2mAh/g, the 2C multiplying power performance is 89.1%, and the capacity retention rate of 100 circles under the condition of 0.1C is 99.2%.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and in the claims are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below in connection with specific examples:
the preparation method of the modified cobalt-free positive electrode material comprises the following steps:
s1, lithium hydroxide and Ni 0.75 Mn 0.25 (OH) 2 Uniformly dispersing in a certain mixing mode according to a certain proportion;
s2, sintering the uniformly dispersed material under the condition of oxygen-containing atmosphere, naturally cooling to room temperature, crushing and sieving to obtain the cobalt-free anode material Li 1+x Ni 0.75 Mn 0.25 O 2 ；
S3, li is again 1+x Ni 0.75 Mn 0.25 O 2 Mixing with lithium aluminum hydride and zirconium phosphotungstate uniformly in proportion, sintering under the air condition, crushing, and sieving with a 400-mesh sieve to obtain the modified cobalt-free anode material.
In step S1, li: ni: mn in a molar ratio of (1.06-1.08): 0.75:0.25, preferably 1.08.
In the step S2, sintering is divided into a presintering stage and a solid phase reaction stage;
the presintering stage is to raise the temperature from room temperature to 550-750 ℃, preferably 650 ℃; preserving the heat for 2-3 hours, preferably 2.5 hours;
the solid phase reaction stage is heated to 880-910 ℃ at a heating rate of 3 ℃/min, preferably 905 ℃; preserving the heat for 8-18 h, preferably 12h.
In the step S3, the lithium aluminum hydride and the zirconium phosphotungstate respectively account for 0.05 to 3 percent and 0.03 to 4 percent, preferably 0.3 percent and 0.25 percent of the mass of the cobalt-free positive electrode material;
the sintering temperature in S3 is raised from room temperature to 200-600 ℃, preferably 500 ℃; the temperature is kept for 6 to 12 hours, preferably 12 hours.
Example 1
The preparation method of the modified cobalt-free positive electrode material specifically comprises the following steps:
s1, lithium hydroxide and Ni 0.75 Mn 0.25 (OH) 2 Uniformly dispersing the materials according to the molar ratio of 1.06:1;
s2, dividing intoSintering the uniformly dispersed material under the condition of oxygen-containing atmosphere, wherein the heating rate is 3 ℃/min, and sintering is carried out at two sections of temperatures, the sintering temperature in the first section of presintering stage is 550 ℃, the heat preservation is carried out for 2 hours, the sintering temperature in the second section of solid phase reaction stage is 880 ℃, and the heat preservation is carried out for 8 hours; naturally cooling the sintered product to room temperature, crushing and sieving to obtain cobalt-free positive electrode material Li 1.06 Ni 0.75 Mn 0.25 O 2 ；
S3, li is 1.06 Ni 0.75 Mn 0.25 O 2 Mixing with lithium aluminum hydride and zirconium phosphotungstate according to a proportion, wherein the lithium aluminum hydride and the zirconium phosphotungstate respectively account for 0.05 percent and 0.03 percent of the mass of the cobalt-free positive electrode material, sintering under the air condition after uniform mixing, heating to 200 ℃ from room temperature, sintering for 6 hours, cooling to room temperature, crushing, and sieving by a 400-mesh sieve to finally obtain the modified cobalt-free positive electrode material.
Example 2
The preparation method of the modified cobalt-free positive electrode material specifically comprises the following steps:
s1, lithium hydroxide and Ni 0.75 Mn 0.25 (OH) 2 Uniformly dispersing the materials according to the molar ratio of 1.08:1;
s2, sintering the uniformly dispersed material under the oxygen-containing atmosphere condition, wherein the heating rate is 3 ℃/min, and sintering is carried out at two sections of temperatures, the sintering temperature in the first section of presintering stage is 650 ℃, the heat preservation is carried out for 2.5 hours, the sintering temperature in the second section of solid phase reaction stage is 905 ℃, and the heat preservation is carried out for 12 hours; naturally cooling the sintered product to room temperature, crushing and sieving to obtain cobalt-free positive electrode material Li 1.08 Ni 0.75 Mn 0.25 O 2 ；
S3, li is 1.08 Ni 0.75 Mn 0.25 O 2 Mixing with lithium aluminum hydride and zirconium phosphotungstate according to a proportion, wherein the lithium aluminum hydride and the zirconium phosphotungstate respectively account for 0.3 percent and 0.25 percent of the mass of the cobalt-free positive electrode material, sintering under the air condition after uniform mixing, heating to 500 ℃ from room temperature, sintering for 8 hours, cooling to room temperature, crushing, and sieving with a 400-mesh sieve to finally obtain the modified cobalt-free positive electrode material.
Example 3
The preparation method of the modified cobalt-free positive electrode material specifically comprises the following steps:
s1, lithium hydroxide and Ni 0.75 Mn 0.25 (OH) 2 Uniformly dispersing the materials according to the molar ratio of 1.07:1;
s2, sintering the uniformly dispersed material under the oxygen-containing atmosphere condition, wherein the heating rate is 3 ℃/min, and sintering is carried out at two sections of temperatures, the sintering temperature in the first section of presintering stage is 750 ℃, the heat preservation is 3h, the sintering temperature in the second section of solid phase reaction stage is 910 ℃, and the heat preservation is 18h; naturally cooling the sintered product to room temperature, crushing and sieving to obtain cobalt-free positive electrode material Li 1.07 Ni 0.75 Mn 0.25 O 2 ；
S3, li is 1.07 Ni 0.75 Mn 0.25 O 2 Mixing with lithium aluminum hydride and zirconium phosphotungstate according to a proportion, wherein the lithium aluminum hydride and the zirconium phosphotungstate respectively account for 3 percent and 4 percent of the mass of the cobalt-free positive electrode material, sintering under the air condition after uniform mixing, heating to 600 ℃ from room temperature, sintering for 12 hours, cooling to room temperature, crushing, and sieving with a 400-mesh sieve to finally obtain the modified cobalt-free positive electrode material.
Comparative example
The preparation method of the modified cobalt-free positive electrode material specifically comprises the following steps:
s1, lithium hydroxide and Ni 0.75 Mn 0.25 (OH) 2 Uniformly dispersing the materials according to the molar ratio of 1.08:1;
s2, sintering the uniformly dispersed material under the oxygen-containing atmosphere condition, wherein the heating rate is 3 ℃/min, and sintering is carried out at two sections of temperatures, the sintering temperature in the first section of presintering stage is 650 ℃, the heat preservation is carried out for 2.5 hours, the sintering temperature in the second section of solid phase reaction stage is 905 ℃, and the heat preservation is carried out for 12 hours; naturally cooling the sintered product to room temperature, crushing and sieving to obtain cobalt-free positive electrode material Li 1.08 Ni 0.75 Mn 0.25 O 2 。
2025 buckling was performed on the above examples 1 to 3 and comparative examples, electrochemical performance was tested at room temperature, the test voltage was 3.0 to 4.3V, and 0.1c,0.5c,1c, and 2c charge and discharge tests were sequentially performed, and resistance tests were performed. The multiplying power performance calculating method comprises the following steps: 2C discharge capacity/0.1C discharge capacity.
Referring to Table 1, the three-way samples of examples 1 to 3 of the present invention and comparative example were buckled to a data comparison of 0.1C initial discharge specific capacity, rate capability, cycle performance and resistance. The results in the table show that compared with the comparative example, the first coulomb efficiency and the multiplying power performance of the cobalt-free positive electrode material coated with lithium aluminum hydride and zirconium phosphotungstate are obviously improved, the cycle performance is obviously improved, when 0.3 percent of lithium aluminum hydride and 0.25 percent of zirconium phosphotungstate are coated, the first coulomb efficiency of the prepared modified cobalt-free positive electrode material is 89.8 percent, the first discharge specific capacity of 0.1C is 193.2mAh/g, the multiplying power performance of 2C is 89.1 percent, and the capacity retention rate of 100 circles under the condition of 0.1C is 99.2 percent.
Table 1, examples and comparative examples sample 0.1C initial discharge specific capacity, rate capability, cycle performance and resistance
Figure SMS_1
Figure SMS_2
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (10)

1. The modified cobalt-free positive electrode material is characterized by comprising a cobalt-free positive electrode material and a coating layer; the coating layer is lithium aluminum hydride and zirconium phosphotungstate.
2. The modified cobalt-free positive electrode material according to claim 1, wherein the cobalt-free positive electrode material is Li 1+ x Ni 0.75 Mn 0.25 O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, 1.06 is less than or equal to 1+x is less than or equal to 1.08.
3. The modified cobalt-free cathode material according to claim 1, wherein the mass of lithium aluminum hydride is Li 1+ x Ni 0.75 Mn 0.25 O 2 0.05 to 3 percent of the mass; zirconium phosphotungstate of mass Li 1+x Ni 0.75 Mn 0.25 O 2 0.03 to 4 percent of the mass.
4. A method for preparing the modified cobalt-free cathode material according to any one of claims 1 to 3, comprising the steps of:
s1, lithium hydroxide and Ni 0.75 Mn 0.25 (OH) 2 Uniformly dispersing in a mixing manner to obtain a cobalt-free cathode material precursor;
s2, sintering the cobalt-free positive electrode material precursor obtained in the step S1 in an oxygen atmosphere, cooling to room temperature, crushing and sieving to obtain Li 1+x Ni 0.75 Mn 0.25 O 2 ；
S3, li prepared in the step S2 1+x Ni 0.75 Mn 0.25 O 2 Mixing with lithium aluminum hydride and zirconium phosphotungstate uniformly, sintering in air, cooling to room temperature, crushing and sieving to obtain the modified cobalt-free anode material.
5. The method for producing a modified cobalt-free positive electrode material according to claim 4, wherein in step S1, li: ni: mn in a molar ratio of (1.06-1.08): 0.75:0.25.
6. the method for producing a modified cobalt-free positive electrode material according to claim 4, wherein in step S2, sintering is divided into a pre-sintering stage and a solid phase reaction stage.
7. The method for preparing a modified cobalt-free cathode material according to claim 6, wherein the temperature rising rate in the pre-sintering stage is 3 ℃/min, the temperature in the pre-sintering stage is 550-750 ℃, and the heat preservation time is 2-3 h.
8. The method for preparing a modified cobalt-free cathode material according to claim 6, wherein the temperature rising rate in the solid phase reaction stage is 3 ℃/min, the temperature in the solid phase reaction stage is 880-910 ℃, and the heat preservation time is 8-18 h.
9. The method for preparing a modified cobalt-free cathode material according to claim 4, wherein in the step S3, the sintering temperature is 200-600 ℃ and the heat preservation time is 6-12 h.
10. Use of the modified cobalt-free cathode material according to any one of claims 1 to 3 for preparing a cathode material for a lithium ion battery.
CN202310191999.1A 2023-03-02 2023-03-02 Modified cobalt-free positive electrode material and preparation method and application thereof Pending CN116154134A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116655004A (en) * 2023-07-03 2023-08-29 湖南镓睿科技有限公司 Cobalt-free positive electrode material and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116655004A (en) * 2023-07-03 2023-08-29 湖南镓睿科技有限公司 Cobalt-free positive electrode material and preparation method and application thereof
CN116655004B (en) * 2023-07-03 2023-11-17 湖南镓睿科技有限公司 Cobalt-free positive electrode material and preparation method and application thereof

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