CN115286055B - Ternary cathode material, preparation method thereof, cathode and lithium ion battery - Google Patents
Ternary cathode material, preparation method thereof, cathode and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a ternary cathode material and a preparation method thereof, a cathode and a lithium ion battery, and relates to the technical field of lithium ion batteries. The preparation method of the ternary cathode material comprises the following steps: high-pressure low-temperature pretreatment: putting a mixture obtained by mixing the nickel-cobalt-manganese ternary precursor with a lithium source in an inert atmosphere, and reacting for 4 to 8h at the high-pressure environment temperature of 200 to 250 ℃ under the pressure of more than or equal to 0.5MPa to obtain an intermediate material; high-temperature treatment: and (3) placing the intermediate material in an environment with the temperature of 750-980 ℃ and the air or oxygen atmosphere for reaction for 4-8h. The ternary cathode material is prepared by the preparation method. The anode of the lithium ion battery comprises the ternary anode material, and the lithium ion battery comprises the anode. The ternary cathode material prepared by the preparation method provided by the application has good intercrystalline morphology and good cycling stability.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a ternary cathode material and a preparation method thereof, a cathode and a lithium ion battery.
Background
In the process of synthesizing the anode material, intergranular cracks and intracrystalline nanopores are generated in the material, which are not favorable for the circulation stability. The invention mainly discloses a method for synthesizing a ternary material, which reduces intergranular cracks and intracrystalline nanopores generated in the synthesis of a positive electrode material and achieves the purpose of improving the cycle stability of the positive electrode material.
The traditional ternary anode material high-temperature heat treatment process is mainly that the temperature is directly increased to a high-temperature section for heat preservation, and the material preparation is completed after the temperature is reduced to the room temperature. And part of material synthesis is carried out by firstly arranging a heat preservation platform at 400-600 ℃, preserving heat for a plurality of hours, carrying out pre-lithiation on the material, then heating to a high temperature section, preserving heat, and cooling to room temperature to complete material preparation. Because the temperature is directly raised to a higher high temperature, the time for lithium ions to diffuse into the precursor is shorter, so that the precursor forms a core-shell structure, the core region is hydroxide, and the shell region is a mixed phase of lithium and hydroxide. Directly heating or heating to 400-600 ℃ for heat preservation, so that the hydroxide in the nuclear area is directly decomposed, intergranular cracks and intracrystalline nanopores are generated, and the cycling stability of the anode material is reduced. The shell region has small structural change due to the existence of lithium, and intergranular cracks and intracrystalline nanopores are less generated.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a ternary cathode material, a preparation method thereof, a cathode and a lithium ion battery.
The invention is realized by the following steps:
in a first aspect, the present invention provides a method for preparing a ternary cathode material, comprising:
high-pressure low-temperature pretreatment: putting a mixture obtained by mixing the nickel-cobalt-manganese ternary precursor with a lithium source in an inert atmosphere, and reacting for 4 to 8h at the high-pressure environment temperature of 200 to 250 ℃ under the pressure of more than or equal to 0.5MPa to obtain an intermediate material;
high-temperature treatment: and (3) placing the intermediate material in an environment with the temperature of 750 to 980 ℃ and the air or oxygen atmosphere for reaction for 4 to 8h.
In an optional embodiment, after the mixture is placed in a high-pressure environment, the temperature is raised to 200-250 ℃ at a temperature rise rate of 1~5 ℃/min.
In an alternative embodiment, the temperature of the high-pressure low-temperature pretreatment is 220 to 230 ℃, and the reaction time is 5 to 7h.
In an alternative embodiment, the molar ratio of the metal element in the nickel-cobalt-manganese ternary precursor to the lithium element in the lithium source is 1.01 to 1.1.
In an alternative embodiment, the lithium source is lithium hydroxide.
In alternative embodiments, the pressure of the high pressure environment is from 0.5 to 1.5MPa.
In a second aspect, the present invention provides a ternary cathode material, which is prepared by the preparation method according to any one of the previous embodiments.
In a third aspect, the present invention provides a positive electrode of a lithium ion battery, comprising the ternary positive electrode material according to the previous embodiments.
In a fourth aspect, the present invention provides a lithium ion battery comprising a positive electrode as in the previous embodiments.
The invention has the following beneficial effects:
high-pressure low-temperature pretreatment is carried out before high-temperature heat treatment of the precursor and a lithium source, lithium can be ensured to fully enter the precursor in advance at a lower temperature in the process, and intergranular cracks and intragranular nanopores caused by dehydration among molecules of the precursor can be avoided as much as possible. Therefore, the preparation method of the ternary cathode material provided by the application can be used for preparing the ternary cathode material with good micro-morphology and high cycling stability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a micro-topography of a particle profile of a ternary cathode material made in example 1;
FIG. 2 is a micro-topography of a particle profile of the ternary cathode material prepared in example 2;
FIG. 3 is a micro-topography of a particle profile of the ternary cathode material prepared in example 3;
FIG. 4 is a micro-topography of a particle profile of the ternary cathode material prepared in example 4;
FIG. 5 is a micro-topography of a particle profile of the ternary cathode material prepared in example 5;
FIG. 6 is a micro-topography of a particle profile of the ternary cathode material prepared in example 6;
FIG. 7 is a micro-topography of a particle profile of the ternary cathode material made in example 7;
FIG. 8 is a micro-topography of a particle profile of the ternary cathode material made in example 8;
FIG. 9 is a micro-topography of a particle profile of the ternary cathode material prepared in example 9;
FIG. 10 is a micro-topography of a particle profile of the ternary cathode material made in example 10;
FIG. 11 is a micro-topography of a particle profile of the ternary cathode material prepared in comparative example 1;
FIG. 12 is a micro-topography of a particle profile of the ternary cathode material prepared in comparative example 2;
fig. 13 is a micro-topography of a cross section of particles of the ternary cathode material prepared in comparative example 3;
FIG. 14 is a micro-topography of a particle profile of the ternary cathode material prepared in comparative example 4;
FIG. 15 is a micro-topography of a particle profile of the ternary cathode material prepared in comparative example 5;
fig. 16 is a micro-topography of a particle profile of the ternary cathode material prepared in comparative example 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The ternary cathode material, the preparation method thereof, the cathode and the lithium ion battery provided by the embodiment of the invention are specifically described below.
The preparation method of the ternary cathode material provided by the embodiment of the invention comprises the following steps:
putting a mixture obtained by mixing the nickel-cobalt-manganese ternary precursor with a lithium source in an inert atmosphere, and reacting for 4 to 8h at the high-pressure environment temperature of 200 to 250 ℃ under the pressure of more than or equal to 0.5MPa to obtain an intermediate material;
and (3) placing the intermediate material in an environment with the temperature of 750-980 ℃ for reaction for 4-8h.
When the temperature is directly raised to high temperature (750 to 980 ℃) in the sintering process, the transition metal hydroxide is thermally decomposed into transition metal oxide with a rock salt structure, lithium is difficult to diffuse into an internal core area, the inside of the particle is uneven, so that the reaction occurs in different radial areas of the particle, and finally intergranular cracks and nano holes are generated. Therefore, according to the technical scheme provided by the embodiment of the application, a low-temperature (200-250 ℃) heat preservation platform is arranged in the synthesis process of the positive electrode material, a high-pressure environment is created, and high-pressure low-temperature pretreatment is carried out on the precursor, so that lithium can reach the core area in the precursor to the maximum extent. The thermal decomposition between hydroxide molecules can be reduced in a low-temperature environment (200 to 250 ℃) and lithium can be diffused into a precursor; the high pressure can ensure that lithium is fully diffused into the precursor, and the mechanism of the process is as follows: when the mixture is placed in a low-temperature (200 to 250 ℃) high-pressure (more than or equal to 0.5 MPa) environment, the thermal decomposition temperature of a precursor (the component is hydroxide of nickel, cobalt and manganese) is generally more than 350 ℃, so that the precursor is not decomposed, but lithium in lithium hydroxide and the precursor hydroxide can generate lithium hydrogen exchange due to the processes of dehydration of lithium hydroxide crystal water, exchange reaction of hydrogen ions and lithium ions and the like, the hydrogen in the precursor is gradually replaced, the original structure of the precursor is maintained, and the reaction formula can be expressed as follows:
Ni(OH) 2 +LiOH→ Ni(OLi)(OH)+ H 2 O
the technical scheme can avoid violent adjustment of the internal structure of the precursor during pyrolysis, and can ensure that all lithium ions enter the inside of the precursor, so that the inside of the whole particle is uniform during high-temperature reaction of the particle, and nanopores and grain cracks caused by nonuniform reaction inside the particle are reduced. The temperature of the technical scheme is not suitable to be too high, otherwise, the precursor is subjected to violent decomposition reaction; meanwhile, the lithium hydroxide crystal water exists in a liquid state or a supercritical state after being dehydrated through proper high-pressure conditions, so that the speed of hydrogen and lithium exchange is improved. If the temperature is too low or too low during high-pressure low-temperature treatment, it is difficult to ensure that lithium fully enters the interior of the precursor, and if the temperature is too high, intermolecular thermal decomposition of the precursor is caused, so that intergranular cracks and intracrystalline nanopores are obviously increased. Therefore, compared with the anode material synthesized by directly heating to a high-temperature section, the anode material synthesized by the precursor subjected to low-temperature high-pressure pretreatment has the advantages that intergranular cracks and intracrystalline nanopores of the material are obviously reduced, and the cycle stability of the anode material is improved.
The preparation method specifically comprises the following steps:
s1, fully mixing a nickel-cobalt-manganese precursor with a lithium source to obtain a mixture.
Specifically, the structural formula of the nickel-cobalt-manganese ternary precursor is Ni x Co y Mn (1-x-y) (OH) 2 。
The nickel-cobalt-manganese ternary precursor may be, for example, a high-nickel precursor, such as NCM811, NCM523, or NCM 622. Of course, it should be noted that any type of nickel-cobalt-manganese ternary precursor is suitable for use in the present application, such as a low-nickel ternary precursor.
Further, the molar ratio of the metal element in the nickel-cobalt-manganese ternary precursor to the lithium element in the lithium source is 1.01 to 1.1.
Further, the lithium source is at least one of lithium hydroxide and lithium carbonate.
S2, high-pressure low-temperature pretreatment
Putting the mixture into a high-pressure reaction kettle, introducing inert gas (such as nitrogen or argon and other rare gases) into the high-pressure reaction kettle for protection in order to avoid manganese oxidation and ensure that the crystal structure does not change, raising the temperature to 200-250 ℃ at a heating rate of 1~5 ℃/min (such as 1 ℃/min, 2 ℃/min, 3 ℃/min or 5 ℃/min), controlling the pressure in the reaction kettle to be more than or equal to 0.5MPa, and reacting for 4-8h to obtain the intermediate material.
Preferably, the pressure is 0.5 to 1.5MPa, so the pressure range is set to ensure that the high-pressure low-temperature pretreatment can be realized, and no operation difficulty exists, it should be noted that if the high-pressure reaction kettle used in the preparation process has very good high-pressure resistance, the high-pressure reaction kettle can also be treated in an environment of more than 1.5MPa.
Preferably, in order to ensure a better treatment effect, the temperature is 220 to 230 ℃ during high-pressure low-temperature pretreatment, and the reaction time is 5 to 7h.
Preferably, the high-pressure low-temperature pretreatment process can be carried out under stirring or vibration conditions, so that the pretreatment efficiency can be improved and the pretreatment can be more sufficient.
S3, high-temperature treatment
And (3) placing the intermediate material obtained in the last step into a box furnace, raising the temperature of the box furnace to 750-980 ℃, and reacting for 4-8h in the air or oxygen atmosphere to obtain the ternary cathode material.
If a high nickel ternary material (e.g., 7 series, 8 series, or 6 series) is prepared, the high temperature process ambient atmosphere is an oxygen-containing atmosphere with the objective of sufficiently oxidizing the nickel. If a low nickel ternary material (e.g., 5 series or 6 series) is prepared, the high temperature treatment process is performed in an air atmosphere.
The ternary cathode material provided by the embodiment of the invention is prepared by the preparation method provided by the embodiment of the invention. The ternary cathode material has a better intercrystalline structure and good cycle performance.
The positive electrode of the lithium ion battery provided by the embodiment of the invention comprises the ternary positive electrode material provided by the embodiment of the invention. Because the positive electrode comprises the ternary positive electrode material provided by the embodiment of the application, the positive electrode has a long service life.
The lithium ion battery provided by the embodiment of the invention comprises the anode of the lithium ion battery provided by the embodiment of the invention. Because the lithium ion battery comprises the positive electrode provided by the embodiment of the application, the lithium ion battery has longer service life.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Fully mixing a precursor (NCM 811) and lithium hydroxide according to a molar ratio of metal elements of 1.02 to obtain a mixture, placing the mixture in a high-pressure reaction kettle, introducing oxygen into the high-pressure reaction kettle, heating to 225 ℃ according to a heating rate of 3 ℃/min, keeping the pressure of the reaction kettle at 0.75MPa, and keeping the temperature for 6 hours; and then transferring the anode material to a box furnace, heating to 780 ℃, keeping the temperature for 6 hours in an oxygen atmosphere, and naturally cooling to room temperature to prepare the anode material.
Example 2
This embodiment is substantially the same as embodiment 1 except that: the pressure of the high-pressure reaction kettle is kept at 0.5MPa.
Example 3
This embodiment is substantially the same as embodiment 1 except that: the pressure of the high-pressure reaction kettle is kept at 1MPa.
Example 4
This embodiment is substantially the same as embodiment 1 except that: the temperature was set at 220 ℃ during the treatment in the autoclave.
Example 5
This embodiment is substantially the same as embodiment 1 except that: when the mixture is treated in a high-pressure reaction kettle, the temperature is set to be 230 ℃, and the pretreatment time is 4 hours.
Example 6
This embodiment is substantially the same as embodiment 1 except that: when the mixture is treated in a high-pressure reaction kettle, the temperature is set to be 200 ℃, and the pretreatment time is 8 hours.
Example 7
This embodiment is substantially the same as embodiment 1 except that: the temperature was set to 250 ℃ during the treatment in the autoclave.
Example 8
This embodiment is substantially the same as embodiment 1 except that: the treatment temperature in the box furnace was 750 ℃ and the treatment time was 8 hours.
Example 9
This embodiment is substantially the same as embodiment 1 except that: the treatment temperature in the box furnace was 800 ℃ and the treatment time was 4 hours.
Example 10
This embodiment is substantially the same as embodiment 1 except that: the ternary precursor is NCM523, the treatment temperature in a box type furnace is 900 ℃, and the treatment time is 8h.
Comparative example 1
This comparative example is essentially the same as example 1 except that: and after mixing the precursor with a lithium source, heating to 780 ℃ at the speed of 3 ℃/min under the conditions of normal pressure and oxygen atmosphere, and carrying out heat treatment for 12h.
Comparative example 2
This comparative example is essentially the same as example 1, except that: and (3) mixing the precursor with a lithium source, heating to 500 ℃ at the speed of 3 ℃/min under the conditions of normal pressure and oxygen atmosphere, keeping the temperature for 6h, heating to 780 ℃ and keeping the temperature for 6h, and naturally cooling to room temperature to prepare the cathode material.
Comparative example 3
This comparative example is essentially the same as example 1 except that: controlling the air pressure in the high-pressure reaction kettle to be normal pressure.
Comparative example 4
This comparative example is essentially the same as example 1 except that: the treatment temperature in the autoclave was 150 ℃.
Comparative example 5
This comparative example is essentially the same as example 1 except that: the treatment temperature in the autoclave was 300 ℃.
Comparative example 6
This comparative example is essentially the same as example 1 except that: the treatment time in the high-pressure reaction kettle is 2 hours.
Experimental example 1
The sectional microscopic morphology observation of the positive electrode material particles prepared in examples 1 to 10 and comparative example 1~6 is respectively shown in fig. 1 to 16.
It can be seen from the figure that the particles of the positive electrode materials prepared in examples 1 to 10 have significantly fewer intergranular cracks and intracrystalline nanopores, and have significantly better intergranular morphology.
Comparative examples 1 and 2 are high-temperature heat treatment methods of conventional cathode materials, and the inter-crystalline morphology of the cathode material prepared by the method is obviously inferior to that of the cathode material prepared by the examples.
Comparative example 3, which was not performed under high pressure at the time of low temperature heat treatment, started to enter a high temperature stage when lithium was not completely dispersed inside the particles due to a slow diffusion rate of lithium into the particles at normal pressure, resulting in intergranular cracks and crystalline nanopores inside the particles of the positive electrode material.
Comparative example 4 since the temperature of the high-pressure low-temperature pretreatment was too low and the temperature of the low-temperature treatment did not reach a temperature at which lithium diffuses into the crystal, the preparation method was actually closer to comparative example 1, and the positive electrode material obtained by the high-temperature heat treatment had significant intergranular cracks and intragranular nanopores.
In the comparative example 5, due to the fact that the temperature in the high-pressure low-temperature pretreatment process is high, intermolecular dehydration is performed on substances such as nickel hydroxide, and therefore obvious intergranular cracks and intragranular nano holes exist in the positive electrode material obtained through high-temperature heat treatment.
In the comparative example 6, the high-pressure low-temperature pretreatment time is short, so that lithium does not completely enter the interior of the crystal in the high-pressure low-temperature pretreatment process, lithium enters the interior of the crystal in the subsequent high-temperature treatment process, and intermolecular dehydration occurs in the subsequent high-temperature treatment process, thereby causing obvious intergranular cracks and intracrystalline nanopores.
Experimental example 2
The positive electrode materials prepared in examples 1 to 10 and comparative example 1~6 were made into button cells, and the cycling performance was tested at 45 ℃ at 1C rate, with the results shown in table 1.
TABLE 1 Properties of the respective groups of positive electrode materials
| Group of | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| 50 cycles of cycle performance | 97.61% | 97.25% | 98.13% | 97.48% | 97.35% | 96.15% | 95.45% | 96.98% |
| 100 cycles cycle performance | 95.23% | 94.84% | 95.66% | 95.09% | 95.13% | 93.47% | 93.12% | 95.13% |
| Example 9 | Example 10 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| 50 cycles of cycle performance | 97.14% | 94.32% | 94.30% | 94.15% | 95.40% | 94.67% | 94.12% | 95.88% |
| 100 cycles cycle performance | 95.37% | 90.18% | 91.34% | 90.87% | 92.25% | 91.21% | 91.18% | 93.43% |
As can be seen from the above table, the positive electrode materials prepared in the examples of the present application have significantly better cycle performance than the comparative examples. Particularly, examples 1 to 5, 8 and 9 are clearly the best, and comparing examples 6 and 7 with example 1, examples 6 and 7 are relatively poor in performance, while the high-pressure low-temperature pretreatment temperature of examples 6 and 7 is not within a preferred range, so that the performance of the prepared cathode material is clearly better when the high-pressure low-temperature pretreatment temperature is 220 to 230 ℃.
In conclusion, the preparation method of the ternary cathode material provided by the application carries out high-pressure low-temperature pretreatment before the high-temperature heat treatment of the precursor and the lithium source, ensures that lithium can fully enter the interior of the precursor in advance at a lower temperature in the process, and can avoid intergranular cracks and intragranular nanopores caused by the dehydration among molecules of the precursor as much as possible. Therefore, the preparation method of the ternary cathode material provided by the application can be used for preparing the ternary cathode material with good micro-morphology and high cycling stability.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a ternary cathode material is characterized by comprising the following steps:
high-pressure low-temperature pretreatment: putting a mixture obtained by mixing a nickel-cobalt-manganese ternary precursor and lithium hydroxide in an inert atmosphere, keeping the pressure of the mixture in a high-pressure environment of more than or equal to 0.5MPa, and reacting for 4 to 8h at the temperature of 200 to 250 ℃ to obtain an intermediate material;
high-temperature treatment: and (3) placing the intermediate material in an environment with the temperature of 750-980 ℃ and the air or oxygen atmosphere for reaction for 4-8h.
2. The preparation method of the ternary cathode material as claimed in claim 1, wherein the temperature of the mixture is raised to 200-250 ℃ at a temperature raising rate of 1~5 ℃/min after the mixture is placed in a high-pressure environment.
3. The preparation method of the ternary cathode material as claimed in claim 1, wherein the temperature of the high-pressure low-temperature pretreatment is 220 to 230 ℃.
4. The method for preparing the ternary cathode material of claim 1~3, wherein the molar ratio of the metal element in the nickel-cobalt-manganese ternary precursor to the lithium element in the lithium source is 1.01 to 1.1.
5. The method for preparing the ternary cathode material as claimed in claim 1~3, wherein the pressure of the high-pressure environment is 0.5 to 1.5MPa.
6. A ternary positive electrode material, characterized by being prepared by the preparation method of any one of claims 1~5.
7. A positive electrode for a lithium ion battery, comprising the ternary positive electrode material according to claim 6.
8. A lithium ion battery comprising the positive electrode according to claim 7.
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Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050038905A (en) * | 2003-10-23 | 2005-04-29 | 삼성에스디아이 주식회사 | Lithium polymer secondary battery |
| CN103066269A (en) * | 2012-12-25 | 2013-04-24 | 贵州省开阳安达磷化工有限公司 | Preparation method for ternary positive electrode active material and battery |
| CN106450187A (en) * | 2016-10-11 | 2017-02-22 | 绍兴文理学院 | High-performance ternary positive electrode material and preparation method thereof |
| CN107134571A (en) * | 2017-05-11 | 2017-09-05 | 浙江工业职业技术学院 | A kind of preparation method of low particle diameter tertiary cathode material |
| CN107195863A (en) * | 2017-06-07 | 2017-09-22 | 四川科能锂电有限公司 | The preparation method of nickel-cobalt-manganternary ternary anode material |
| EP3296267A1 (en) * | 2016-09-18 | 2018-03-21 | Guizhou Zhenhua E-CHEM Co., Ltd | Spherical or spherical-like lithium ion battery cathode material, preparation method and application thereof |
| CN108206281A (en) * | 2016-12-20 | 2018-06-26 | 比亚迪股份有限公司 | A kind of ternary material and preparation method thereof and cell size and anode and lithium battery |
| CN108807933A (en) * | 2018-06-29 | 2018-11-13 | 深圳市德方纳米科技股份有限公司 | A kind of positive electrode and preparation method thereof |
| CN109987650A (en) * | 2019-04-26 | 2019-07-09 | 清华大学深圳研究生院 | Nickel-cobalt lithium manganate cathode material, preparation method and application |
| CN111180724A (en) * | 2020-02-26 | 2020-05-19 | 黄冈林立新能源科技有限公司 | Preparation method of ternary single crystal cathode material |
| CN111533182A (en) * | 2020-05-08 | 2020-08-14 | 潍坊学院 | Solvothermal preparation method of high-lithium-ion-diffusion ternary cathode material |
| CN112080800A (en) * | 2020-05-26 | 2020-12-15 | 宜宾锂宝新材料有限公司 | Modification method of single crystal ternary cathode material |
| CN112993239A (en) * | 2019-12-17 | 2021-06-18 | 天津国安盟固利新材料科技股份有限公司 | High-pressure-resistant low-cobalt ternary cathode material and preparation method thereof |
| EP3930036A1 (en) * | 2020-06-25 | 2021-12-29 | Basf Se | All-solid-state lithium ion electrochemical cells and their manufacture |
| CN113871610A (en) * | 2021-09-07 | 2021-12-31 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
| CN113896253A (en) * | 2021-09-24 | 2022-01-07 | 合肥国轩电池材料有限公司 | Ternary cathode material and preparation method and application thereof |
| CN114436345A (en) * | 2022-02-14 | 2022-05-06 | 中南大学 | Ternary cathode material of lithium ion battery and preparation method thereof |
| CN114477314A (en) * | 2022-01-28 | 2022-05-13 | 齐鲁工业大学 | Preparation method and application of nickel-cobalt-manganese ternary cathode material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10680242B2 (en) * | 2016-05-18 | 2020-06-09 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing positive electrode active material, and lithium ion battery |
| KR102095508B1 (en) * | 2016-11-22 | 2020-03-31 | 주식회사 엘지화학 | Positive Electrode Active Material Particle Comprising Core Having Lithium Cobalt Oxide and Shell Having Lithium Cobalt Phosphate and Method of Manufacturing the Same |
| CN110265634A (en) * | 2019-05-09 | 2019-09-20 | 浙江美都海创锂电科技有限公司 | A kind of preparation method of the nickelic NCM anode material for lithium-ion batteries of monocrystalline |
-
2022
- 2022-10-08 CN CN202211219713.8A patent/CN115286055B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050038905A (en) * | 2003-10-23 | 2005-04-29 | 삼성에스디아이 주식회사 | Lithium polymer secondary battery |
| CN103066269A (en) * | 2012-12-25 | 2013-04-24 | 贵州省开阳安达磷化工有限公司 | Preparation method for ternary positive electrode active material and battery |
| EP3296267A1 (en) * | 2016-09-18 | 2018-03-21 | Guizhou Zhenhua E-CHEM Co., Ltd | Spherical or spherical-like lithium ion battery cathode material, preparation method and application thereof |
| CN106450187A (en) * | 2016-10-11 | 2017-02-22 | 绍兴文理学院 | High-performance ternary positive electrode material and preparation method thereof |
| CN108206281A (en) * | 2016-12-20 | 2018-06-26 | 比亚迪股份有限公司 | A kind of ternary material and preparation method thereof and cell size and anode and lithium battery |
| CN107134571A (en) * | 2017-05-11 | 2017-09-05 | 浙江工业职业技术学院 | A kind of preparation method of low particle diameter tertiary cathode material |
| CN107195863A (en) * | 2017-06-07 | 2017-09-22 | 四川科能锂电有限公司 | The preparation method of nickel-cobalt-manganternary ternary anode material |
| CN108807933A (en) * | 2018-06-29 | 2018-11-13 | 深圳市德方纳米科技股份有限公司 | A kind of positive electrode and preparation method thereof |
| CN109987650A (en) * | 2019-04-26 | 2019-07-09 | 清华大学深圳研究生院 | Nickel-cobalt lithium manganate cathode material, preparation method and application |
| CN112993239A (en) * | 2019-12-17 | 2021-06-18 | 天津国安盟固利新材料科技股份有限公司 | High-pressure-resistant low-cobalt ternary cathode material and preparation method thereof |
| CN111180724A (en) * | 2020-02-26 | 2020-05-19 | 黄冈林立新能源科技有限公司 | Preparation method of ternary single crystal cathode material |
| CN111533182A (en) * | 2020-05-08 | 2020-08-14 | 潍坊学院 | Solvothermal preparation method of high-lithium-ion-diffusion ternary cathode material |
| CN112080800A (en) * | 2020-05-26 | 2020-12-15 | 宜宾锂宝新材料有限公司 | Modification method of single crystal ternary cathode material |
| EP3930036A1 (en) * | 2020-06-25 | 2021-12-29 | Basf Se | All-solid-state lithium ion electrochemical cells and their manufacture |
| CN113871610A (en) * | 2021-09-07 | 2021-12-31 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
| CN113896253A (en) * | 2021-09-24 | 2022-01-07 | 合肥国轩电池材料有限公司 | Ternary cathode material and preparation method and application thereof |
| CN114477314A (en) * | 2022-01-28 | 2022-05-13 | 齐鲁工业大学 | Preparation method and application of nickel-cobalt-manganese ternary cathode material |
| CN114436345A (en) * | 2022-02-14 | 2022-05-06 | 中南大学 | Ternary cathode material of lithium ion battery and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| correlation between dissolution behavior and electrochemical cycling performance of LiNi1/3Co1/3Mn1/3O2-based cells;honghe zheng等;《journal of power sources》;20120208;第207卷;第134-140页 * |
| 高镍三元正极材料LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2的合成及改进研究进展;陈绍军等;《惠州学院学报》;20200628(第03期);第972-986页 * |
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