CN113540433A - Cathode material, preparation method, lithium ion battery cathode and lithium ion battery - Google Patents
Cathode material, preparation method, lithium ion battery cathode and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a positive electrode material, a preparation method, a lithium ion battery positive electrode and a lithium ion battery, wherein the positive electrode material comprises nickel cobalt lithium manganate, wherein Zr element is doped in the nickel cobalt lithium manganate; and is formed on the nickelA coating layer on the surface of lithium cobalt manganese oxide, wherein the coating layer is formed by H3BO3And Al2O3And (4) forming. The obtained anode material has small particle size and compact coating layer, and can effectively improve the electrochemical stability and cycle performance of the lithium ion battery, reduce residual alkali, reduce flatulence and improve the comprehensive performance of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a modified nickel cobalt lithium manganate ternary single crystal anode material and a preparation method thereof, a lithium ion battery anode containing the anode material, and a lithium ion battery containing the lithium ion battery anode.
Background
With the continuous development of new energy industry, people have higher and higher requirements on the endurance capacity of power batteries. The performance of the anode material, which is one of the key materials of the lithium ion battery, directly affects the final comprehensive performance of the lithium ion battery.
Lithium cobaltate is one of the most widely used battery materials, but cobalt resources are increasingly deficient, the price is high, and potential safety hazards exist in the use process of lithium cobaltate batteries. Therefore, the application of the nickel cobalt lithium manganate is gradually increased. Nickel cobalt lithium manganate is a key ternary cathode material of a lithium ion battery and has a chemical formula of LiNixCoyMn1-x-yO2It possesses higher specific capacity and lower cost than the cell positive electrode material. With the continuous increase of the content of nickel element in the ternary material and the decrease of the content of cobalt element, manganese element and the like, the lithium ion battery has some side effects, such as battery failure caused by the stability problem of the anode material, the matching problem of the electrolyte, the over-high charging temperature and the like. Therefore, the nickel-cobalt-manganese ternary single crystal material is produced, the stability of the anode material is enhanced, the voltage of the whole system can be increased to a new height, and a solution is provided for the requirement of higher energy density.
Chinese patent applications with publication numbers CN110854370A and CN110148744A both disclose a preparation method of a nickel cobalt lithium manganate positive electrode material, which is doped with metal elements and then utilizes Al2O3The surface is coated, thereby improving the cycle performance, rate capability and the like of the material. However, the existing coating agent can not completely prevent HF from corroding the anode material, and Ni-F, Mn-F can still be detected after coating, namely HF is not mixed with Al as the coating agent2O3Besides the reaction, the reaction also reacts with the NCM bulk, and the by-product generated by the reaction is attached to the surface of the anode, so that the resistance in the circulating process is increased.
In addition, chinese patent application publication No. CN109742346A discloses a Si/Al co-coated nickel-cobalt-manganese lithium ion battery positive electrode material and a preparation method thereof, which can reduce the reaction of an electrolyte and the positive electrode material to a certain extent. The coating layer is still not dense enough so that part of the electrolyte can react with the anode material.
Disclosure of Invention
In view of the above, the present invention needs to provide a cathode material and a preparation method thereof, in which a modified nickel-cobalt-manganese ternary single crystal cathode material is obtained by Zr doping and B/Al co-coating, and the cathode material has an excellent lithium ion de-intercalation rate, a stable crystal structure and electrochemical stability, and at the same time, has low residual alkali, improves ionic conductivity, and can effectively reduce the occurrence of side reactions.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a positive electrode material, which comprises:
the lithium nickel cobalt manganese oxide is doped with Zr element;
and the coating layer is formed on the surface of the nickel cobalt lithium manganate and consists of H3BO3And Al2O3And (4) forming.
According to a further scheme, the nickel-cobalt-manganese lithium manganate is prepared from a nickel-cobalt-manganese precursor, a Zr dopant and a lithium source, wherein the nickel-cobalt-manganese precursor and the lithium source are mixed according to a molar ratio Li/Me of 1.02-1.08, and Me is the sum of moles of nickel, cobalt and manganese.
In a further scheme, the chemical general formula of the nickel-cobalt-manganese precursor is Ni1-x-yCoxMny(OH)2，x＝0.05-0.2，y＝0.05-0.2，1-x-y＝0.6-0.9；
The lithium source is at least one selected from lithium hydroxide, lithium carbonate and lithium nitrate.
Further, the Zr dopant is selected from hydroxides, oxides or salts of Zr element.
In a further scheme, the total doping mole amount of the Zr element is 0.1-0.2% of Me in the nickel-cobalt-manganese precursor.
In the further scheme, in the positive electrode material, H3BO3And Al2O3The coating amount is 0.5-1.5 wt% per mill respectively.
The invention also provides a preparation method of the cathode material, which comprises the following steps:
fully mixing a nickel-cobalt-manganese precursor, a Zr dopant and a lithium source according to a stoichiometric ratio, and then sintering for the first time to obtain a Zr-doped base material;
mixing the Zr-doped base material with H3BO3And Al2O3And after fully and uniformly mixing, performing secondary sintering to obtain the Zr-doped B/Al co-coated double-modified nickel cobalt lithium manganate single-crystal positive electrode material.
In a further scheme, the first sintering process specifically comprises the following steps: after the temperature is kept for 5-8h at the temperature of 440-950 ℃, the temperature is raised to 950 ℃ and kept for 15-18 h;
the temperature of the second sintering is 380-450 ℃, and the heat preservation time is 6-8 h.
The invention further provides a lithium ion battery positive electrode which contains the positive electrode material.
The invention further provides a lithium ion battery, which comprises the lithium ion battery anode.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the doping of a small amount of Zr4+Ions to improve cyclability, structural properties and electrochemical properties. The doping of the metal zirconium does not affect the main structure of the material, and still belongs to a typical layered structure, but the unit cell parameters of the doped material are changed. The unit cell parameter c is gradually increased along with the increase of the Zr doping amount, and the main reason is that the Zr is doped4+Substitution of transition layer Metal ions (Ni)2+、Co3+And Mn4+) And is located in the transition metal layer. The grain size of the Zr-doped material is reduced, and the Li is shortened+Diffusion path of (2) in favor of Li+The de-intercalation in the layered structure improves the de-intercalation rate of lithium ions and improves the cycle stability of the batteryAnd (4) sex. Due to Zr4+Ni by strong electrostatic action of ions2+The migration resistance is increased, the phase transition from the layered structure to the spinel structure is suppressed, the crystal structure is stabilized, and the bond energy of the Zr-O bond formed by the combination of Zr and O is larger than the bond energy of the bonds of Ni-O, Co-O, Mn-O, and the like. Therefore, the structural stability of the doped material is enhanced. In addition, the proper amount of Zr doping can lead to Zr4+The solid solution formed by the solid solution transferred to the surface of the electrode is equivalent to a layer of coating, so that the oxidation-reduction reaction between the active material and the electrolyte is inhibited to a certain extent, the structural phase change of the electrode material and the expansion and contraction of a unit cell in the charging and discharging processes are inhibited, and the electrochemical stability of the material is improved. On the other hand, H3BO3/Al2O3The co-coated positive electrode material can form a compact coating layer on the surface of the positive electrode material, can effectively improve the cycle performance and ionic conductivity of the battery, reduce residual alkali and reduce flatulence, so that the co-coated double-modified nickel-cobalt-manganese ternary positive electrode material provided by the invention can effectively reduce the occurrence of side reactions and improve the comprehensive performance of the lithium ion battery.
Drawings
Fig. 1 is an SEM image of the modified nickel cobalt manganese ternary single crystal positive electrode material prepared in example 1 of the present invention.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The present invention provides, in a first aspect, a positive electrode material comprising:
the lithium nickel cobalt manganese oxide is doped with Zr element;
and the coating layer is formed on the surface of the nickel cobalt lithium manganate and consists of H3BO3And Al2O3And (4) forming.
The method utilizes Zr element to dope the nickel cobalt lithium manganate and simultaneously utilizes H3BO3And Al2O3The nickel cobalt lithium manganate is subjected to co-coating, so that the occurrence of side reactions is effectively reduced, and the comprehensive performance of the lithium ion battery is improved. Wherein, the nickel cobalt lithium manganate is a commonly used ternary cathode material in the field, and has a chemical formula of LiNixCoyMn1-x-yO2And will not be described in detail herein.
Further, the nickel cobalt lithium manganate is prepared from a nickel cobalt manganese precursor, a Zr dopant and a lithium source, wherein the nickel cobalt manganese precursor mainly refers to nickel cobalt manganese hydroxide, and the chemical general formula of the nickel cobalt manganese hydroxide is Ni1-x-yCoxMny(OH)2The ratio of x is 0.05 to 0.2, y is 0.05 to 0.2, and 1-x-y is 0.6 to 0.9, and the composition of the nickel cobalt manganese pre-precursor and the ratio of the lithium source can be adjusted according to the stoichiometric ratio of the nickel cobalt lithium manganate to be finally prepared, and thus, the ratio is not particularly limited. In one or more embodiments of the present invention, the nickel-cobalt-manganese precursor and the lithium source are mixed in a molar ratio Li/Me of 1.02 to 1.08, where Me is the sum of nickel, cobalt and manganese moles, further preferably, Li/Me of 1.05; further, the selection of the lithium source is not particularly limited and may be a conventional one in the art, and specifically, there may be mentioned, but not limited to, at least one of lithium hydroxide, lithium carbonate, and lithium nitrate.
Further, the Zr dopant may be selected from hydroxides, oxides or salts of Zr element, which are conventional in the art, and specific mentioned examples include, but are not limited to, zirconium hydroxide, zirconium oxide or zirconium carbonate.
Furthermore, the doping amount of Zr is not particularly limited, and can be adjusted according to the performance of the anode material, and uniform ZrO can be formed by proper doping2Coating to improve residual alkali inhibiting effect and further protect active material from dissolving transition metalThe method comprises the steps of dissolving and releasing oxygen, further inhibiting structural phase change of an electrode material and expansion and contraction of unit cells in the charging and discharging processes, and improving the electrochemical stability of the material, wherein in one or more embodiments of the invention, the total doping mole amount of Zr element is 0.1-0.2% of Me in the nickel-cobalt-manganese precursor.
Further, in the positive electrode material, H3BO3And Al2O3The coating amounts of (a) are 0.5 to 1.5 wt%, respectively, more preferably 0.75 wt%, respectively, and the overall performance of the positive electrode material is further improved by optimizing the coating amounts.
In a second aspect, the present invention provides a method for preparing the cathode material according to the first aspect, including the steps of:
fully mixing a nickel-cobalt-manganese precursor, a Zr dopant and a lithium source according to a stoichiometric ratio, and then sintering for the first time to obtain a Zr-doped base material;
mixing the Zr-doped base material with H3BO3And Al2O3And after fully and uniformly mixing, performing secondary sintering to obtain the Zr-doped B/Al co-coated double-modified nickel cobalt lithium manganate single-crystal positive electrode material.
Further, the first sintering process specifically comprises the following steps: after the temperature is kept for 5-8h at the temperature of 440-950 ℃, the temperature is raised to 950 ℃ and kept for 15-18 h; in one or more embodiments of the invention, the ramp rate is constant, preferably 5 ℃/min, and the first sintering is performed in an oxygen-filled atmosphere.
The temperature of the second sintering is 380-450 ℃, and the heat preservation time is 6-8 h.
The third aspect of the invention discloses a lithium ion battery anode which contains the anode material of the first aspect of the invention.
In a fourth aspect of the invention, a lithium ion battery is disclosed, which comprises the lithium ion battery anode according to the third aspect of the invention.
The technical solution of the present invention will be more clearly and completely described below with reference to specific embodiments.
Example 1
Preparation of Zr-doped base material
100g of Ni are weighed0.75Co0.125Mn0.125(OH)2Precursor, 0.1% doping amount of ZrO2And lithium hydroxide are added into a high-speed mixer to be fully and uniformly mixed, wherein the molar ratio of the lithium hydroxide to the nickel-cobalt-manganese precursor is Li: me 1.05: 1, adding; and (3) placing the uniformly mixed material in an oxygen atmosphere of 99.9% for primary sintering, heating to 480 ℃ at the speed of 5 ℃/min, preserving heat for 5h, then continuously heating to 900 ℃ at the speed of 5 ℃/min, preserving heat for 15h, naturally cooling, crushing, and sieving with a 300-mesh sieve to obtain the Zr-doped base material.
Preparation of modified nickel-cobalt-manganese ternary single crystal positive electrode material
100g of Zr-doped base material and 0.75 per mill of H for coating are weighed3BO3And Al2O3And after uniformly mixing, performing secondary sintering in an oxygen atmosphere, heating to 400 ℃ at the speed of 5 ℃/min, preserving heat for 6h, finally naturally cooling, crushing, and sieving with a 300-mesh sieve to obtain the modified nickel-cobalt-manganese ternary single crystal cathode material.
Fig. 1 is an SEM image of the modified nickel-cobalt-manganese ternary single crystal positive electrode material in this embodiment, and it can be seen from the SEM image that particles of the modified nickel-cobalt-manganese ternary single crystal material prepared in this embodiment are in an agglomerated state, the particles are uniformly distributed, the average particle size is less than 2 μm, the specific surface area of the material is increased, a layer of compact small solid particles is provided on the surface of the material, and the small solid particles can effectively prevent direct contact between the positive electrode active material and the electrolyte, and are beneficial to improving the electrochemical performance of the material.
Comparative example 1
This comparative example uses the same embodiment as example 1 except that: does not carry out Zr element doping and H3BO3And Al2O3The other steps and parameters were the same as in example 1.
Comparative example 2
Of Zr-doped base materialsPreparation of
Same as example 1
Preparation of modified nickel-cobalt-manganese ternary single crystal positive electrode material
The same embodiment as in example 1 was used except that: the coating layer is composed of 1.5 per mill of H3BO3And (4) forming.
Comparative example 3
Preparation of Zr-doped base material
Same as example 1
Preparation of modified nickel-cobalt-manganese ternary single crystal positive electrode material
The same embodiment as in example 1 was used except that: the coating layer is made of 1.5 per mill of Al2O3And (4) forming.
Comparative example 4
Preparation of Zr-doped base material
Same as example 1
Preparation of modified nickel-cobalt-manganese ternary single crystal positive electrode material
The same embodiment as in example 1 was used except that: the coating layer is made of 0.75 per mill of SiO2And Al2O3And (4) forming.
Example 2
Preparation of Zr-doped base material
100g of Ni are weighed0.75Co0.125Mn0.125(OH)2Adding the precursor, zirconium hydroxide with the doping amount of 0.15% and lithium nitrate into a high-speed mixer, and fully and uniformly mixing, wherein the lithium hydroxide and the nickel-cobalt-manganese precursor are mixed according to the mol ratio of Li: me 1.02: 1, adding; and (3) placing the uniformly mixed material in an oxygen atmosphere of 99.9% for primary sintering, heating to 440 ℃ at the speed of 5 ℃/min, preserving heat for 6h, then continuously heating to 920 ℃ at the speed of 5 ℃/min, preserving heat for 16h, naturally cooling, crushing, and sieving with a 300-mesh sieve to obtain the Zr-doped base material.
Modified nickel cobaltPreparation of manganese ternary single crystal cathode material
100g of Zr-doped base material and 0.5 per mill of H for coating are weighed3BO3And Al2O3And after uniformly mixing, performing secondary sintering in an oxygen atmosphere, heating to 380 ℃ at the speed of 5 ℃/min, preserving heat for 7h, finally naturally cooling, crushing, and sieving with a 300-mesh sieve to obtain the modified nickel-cobalt-manganese ternary single crystal cathode material.
Example 3
Preparation of Zr-doped base material
100g of Ni are weighed0.75Co0.125Mn0.125(OH)2Adding the precursor, zirconium carbonate with the doping amount of 0.15% and lithium carbonate into a high-speed mixer, and fully and uniformly mixing, wherein the lithium hydroxide and the nickel-cobalt-manganese precursor are mixed according to the mol ratio Li: me 1.08: 1, adding; and (3) placing the uniformly mixed material in an oxygen atmosphere of 99.9% for primary sintering, heating to 500 ℃ at the speed of 5 ℃/min, preserving heat for 8h, then continuously heating to 950 ℃ at the speed of 5 ℃/min, preserving heat for 18h, naturally cooling, crushing, and sieving with a 300-mesh sieve to obtain the Zr-doped base material.
Preparation of modified nickel-cobalt-manganese ternary single crystal positive electrode material
100g of Zr doped base material and H with the coating amount of 1.5wt ‰ are weighed3BO3And Al2O3And after uniformly mixing, performing secondary sintering in an oxygen atmosphere, heating to 450 ℃ at the speed of 5 ℃/min, preserving heat for 8 hours, finally naturally cooling, crushing, and sieving with a 300-mesh sieve to obtain the modified nickel-cobalt-manganese ternary single crystal cathode material.
Test example
The positive electrode materials in example 1 and comparative examples 1 to 4 were prepared into positive electrode sheets of lithium batteries, and then assembled into button cells, respectively, and the results of the performance tests were shown in tables 1 and 2. Wherein, button cell equipment specifically does: weighing the active substance, the SP and the PVDF according to the mass ratio of 8:1:1, grinding and mixing the active substance, the SP and the PVDF uniformly in an agate mortar, then dropwise adding a proper amount of organic solvent NMP, and grinding the slurry to be in a fluid state. And uniformly coating the slurry on an aluminum foil, placing the aluminum foil in a vacuum drying oven at 120 ℃ for 6 hours, then preparing a disk-shaped positive plate with the diameter of 14mm, placing the disk-shaped positive plate in an argon-protected glove box, and assembling the disk-shaped positive plate, a diaphragm (polypropylene film), a negative plate (a lithium plate with the diameter of 15mm and the thickness of 0.3 mm) and electrolyte into the button cell.
Table 1 electrical property test results
TABLE 2 residual alkali test results
Note: the residual alkali test in table 2 employs a titration test method conventionally employed in the art.
As can be seen from the test results in tables 1 and 2, compared with example 1, in comparative example 1, since there is no doping and no cladding, the single crystal has a larger grain size, resulting in lower first effect and capacity, and a large residual alkali amount; in contrast, comparative examples 2 and 3, which are doped and then coated with a single component, have improved performance compared to comparative example 1, but are still inferior to example 1. While comparative example 4 uses SiO2And Al2O3Although the electrochemical performance of the co-coating is improved, the residual alkali content is still higher, the electrochemical performance is excellent in the example 1, and the residual alkali content is low, which is mainly because on one hand, the particle size of the Zr-doped material is reduced, and the Li is shortened+Diffusion path of (2) in favor of Li+The de-intercalation in the layered structure improves the de-intercalation rate of lithium ions, improves the cycling stability of the battery and improves the electrochemical performance of the material; and B has an ionic radius of half that of Al, so that a dense coating layer can be formed, and H3BO3With residual LiOH/Li on the surface of NCM2CO3Reaction, reducing residual alkali, therefore, H3BO3/Al2O3The co-coated anode material can effectively improve the cycle performance and ionic conductivity of the battery, reduce residual alkali and reduce flatulence, so the battery has the advantages of high cycle performance, high ionic conductivity, low residual alkali content, high yield, high safety, and good service lifeThe co-coated double-modified nickel-cobalt-manganese ternary cathode material provided by the invention can effectively reduce the occurrence of side reactions and improve the comprehensive performance of the lithium ion battery.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A positive electrode material comprising:
the lithium nickel cobalt manganese oxide is doped with Zr element;
and the coating layer is formed on the surface of the nickel cobalt lithium manganate and consists of H3BO3And Al2O3And (4) forming.
2. The positive electrode material according to claim 1, wherein the nickel cobalt lithium manganate is prepared from a nickel cobalt manganese precursor, a Zr dopant and a lithium source, and the nickel cobalt manganese precursor and the lithium source are mixed according to a molar ratio Li/Me of 1.02-1.08, wherein Me is the sum of moles of nickel, cobalt and manganese.
3. The positive electrode material of claim 2, wherein the nickel-cobalt-manganese precursor has a chemical formula of Ni1-x- yCoxMny(OH)2，x＝0.05-0.2，y＝0.05-0.2，1-x-y＝0.6-0.9；
The lithium source is at least one selected from lithium hydroxide, lithium carbonate and lithium nitrate.
4. The positive electrode material according to claim 2, wherein the Zr dopant is selected from hydroxides, oxides or salts of Zr element.
5. The positive electrode material according to claim 2, wherein the total doping molar amount of the Zr element is 0.1% to 0.2% of Me in the nickel-cobalt-manganese precursor.
6. The positive electrode material according to claim 1, wherein H is in the positive electrode material3BO3And Al2O3The coating amount is 0.5-1.5 wt% per mill respectively.
7. A method for preparing a positive electrode material according to any one of claims 1 to 6, comprising the steps of:
fully mixing a nickel-cobalt-manganese precursor, a Zr dopant and a lithium source according to a stoichiometric ratio, and then sintering for the first time to obtain a Zr-doped base material;
mixing the Zr-doped base material with H3BO3And Al2O3And after fully and uniformly mixing, performing secondary sintering to obtain the Zr-doped B/Al co-coated double-modified nickel cobalt lithium manganate single-crystal positive electrode material.
8. The preparation method according to claim 7, wherein the first sintering process specifically comprises: after the temperature is kept for 5-8h at the temperature of 440-950 ℃, the temperature is raised to 950 ℃ and kept for 15-18 h;
the temperature of the second sintering is 380-450 ℃, and the heat preservation time is 6-8 h.
9. A positive electrode for a lithium ion battery, comprising the positive electrode material according to any one of claims 1 to 6.
10. A lithium ion battery comprising the positive electrode for a lithium ion battery according to claim 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094067A (en) * | 2021-11-09 | 2022-02-25 | 远景动力技术(江苏)有限公司 | Ternary positive electrode material, preparation method and application thereof |
| CN114314693A (en) * | 2021-12-29 | 2022-04-12 | 合肥融捷能源材料有限公司 | Modified ternary cathode material, preparation method thereof and lithium ion battery |
| WO2024016662A1 (en) * | 2022-07-22 | 2024-01-25 | 宁波容百新能源科技股份有限公司 | Composite coating agent for positive electrode material, high-nickel single-crystal positive electrode material, and battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110416511A (en) * | 2019-07-19 | 2019-11-05 | 宁德新能源科技有限公司 | Positive electrode and anode and electrochemical appliance including it |
| CN110504432A (en) * | 2019-08-29 | 2019-11-26 | 桑顿新能源科技(长沙)有限公司 | Nickle cobalt lithium manganate composite material and preparation method, lithium battery anode and preparation method thereof, lithium battery and power supply unit |
| CN111430700A (en) * | 2019-10-10 | 2020-07-17 | 蜂巢能源科技有限公司 | Quaternary positive electrode material for lithium ion battery, preparation method of quaternary positive electrode material and lithium ion battery |
| CN111435738A (en) * | 2019-12-18 | 2020-07-21 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
| CN111463411A (en) * | 2019-01-18 | 2020-07-28 | 天津国安盟固利新材料科技股份有限公司 | High-nickel ternary cathode material with single crystal morphology and preparation method thereof |
-
2021
- 2021-06-28 CN CN202110719449.3A patent/CN113540433A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463411A (en) * | 2019-01-18 | 2020-07-28 | 天津国安盟固利新材料科技股份有限公司 | High-nickel ternary cathode material with single crystal morphology and preparation method thereof |
| CN110416511A (en) * | 2019-07-19 | 2019-11-05 | 宁德新能源科技有限公司 | Positive electrode and anode and electrochemical appliance including it |
| CN110504432A (en) * | 2019-08-29 | 2019-11-26 | 桑顿新能源科技(长沙)有限公司 | Nickle cobalt lithium manganate composite material and preparation method, lithium battery anode and preparation method thereof, lithium battery and power supply unit |
| CN111430700A (en) * | 2019-10-10 | 2020-07-17 | 蜂巢能源科技有限公司 | Quaternary positive electrode material for lithium ion battery, preparation method of quaternary positive electrode material and lithium ion battery |
| CN111435738A (en) * | 2019-12-18 | 2020-07-21 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094067A (en) * | 2021-11-09 | 2022-02-25 | 远景动力技术(江苏)有限公司 | Ternary positive electrode material, preparation method and application thereof |
| CN114314693A (en) * | 2021-12-29 | 2022-04-12 | 合肥融捷能源材料有限公司 | Modified ternary cathode material, preparation method thereof and lithium ion battery |
| WO2024016662A1 (en) * | 2022-07-22 | 2024-01-25 | 宁波容百新能源科技股份有限公司 | Composite coating agent for positive electrode material, high-nickel single-crystal positive electrode material, and battery |
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