CN110364711B - Gradient rubidium doped nickel-cobalt-manganese positive electrode material and preparation method thereof - Google Patents
Gradient rubidium doped nickel-cobalt-manganese positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a gradient rubidium-doped nickel-cobalt-manganese positive electrode material and a preparation method thereof, wherein the theoretical chemical expression of the gradient rubidium-doped nickel-cobalt-manganese positive electrode material is L i1‑aRbaNi1‑X‑ YCoXMnYO2Wherein a is more than or equal to 0.001 and less than or equal to 0.02, X is more than or equal to 0.1 and less than or equal to 1/3, and Y is more than or equal to 0.1 and less than or equal to 1/3; the content of rubidium is gradually reduced from inside to outside in the rubidium-doped nickel-cobalt-manganese positive electrode material, and nickel-cobalt-manganese is uniformly distributed in the rubidium-doped nickel-cobalt-manganese positive electrode material. The preparation method is characterized by comprising the following steps: the method comprises the steps of mixing a nickel source, a cobalt source, a manganese source, a rubidium salt and a precipitator according to a certain proportion by utilizing the characteristic that the radiuses of lithium ions and rubidium ions are close to each other, then pumping solutions of alcohols with different volume concentrations by using a peristaltic pump, wherein the volume concentrations of the alcohols are 100% -20% in sequence, the deposition amount of the rubidium salt can change in a gradient manner, so that a gradient rubidium doped material is obtained, the lithium ions in the ternary material are replaced in the gradient doping manner of the rubidium ions, and a more stable layered structure is formed. The rubidium-doped nickel-cobalt-manganese cathode material prepared by the method has good circulation stability and high ionic conductivity.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a gradient rubidium-doped nickel-cobalt-manganese positive electrode material and a preparation method thereof.
Background
The nickel-rich ternary material is used as the lithium ion battery anode material, has higher reversible capacity, and becomes one of the most promising lithium ion battery anode materials in the field of new energy automobiles. However, too high nickel content is liable to cross-occupy with lithium, which is not favorable for the performance of electrochemical properties of the material. The capacity of the ternary material is improved along with the increase of the content of nickel, however, the safety problem caused by the unstable structure brought by the capacity is also the main problem for limiting the market application of the high-nickel ternary material.
At present, the high nickel content is improvedThe main method for improving the stability and ionic conductivity of the element material includes coating and doping to raise the stability of the material structure, raise the electronic conductivity and ionic conductivity of the material and lower the cationic mixed discharge to raise the output power density of the cell, and the patent CN201710338732.5 discloses a rubidium doping method, which is to dope rubidium ion into high-nickel ternary positive electrode material to enlarge the L i layer interval and thus increase L i layer interval in crystal lattice+Diffusion coefficient, which can significantly enhance the electrochemical performance of the high nickel ternary cathode material. However, excessive doping of rubidium ions can damage the lattice structure of the ternary material, and the problem of unstable cycle performance is caused. Patent CN201810954002.2 discloses a co-doped modified high-nickel ternary material and a preparation method thereof, wherein the prepared material has excellent electrochemical activity, rate capability and cycling stability, but the ion conductivity of the co-doped modified high-nickel ternary material is relatively low. In conclusion, the ternary material at the present stage also has the problems of low ionic conductivity and unstable cycle performance.
Disclosure of Invention
Aiming at the problems of low ionic conductivity and unstable cycle performance in the prior art, the invention provides a gradient rubidium-doped nickel-cobalt-manganese positive electrode material with high stability and high ionic conductivity and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a gradient rubidium doped nickel cobalt manganese anode material has a theoretical chemical expression of L i1-aRbaNi1-X-YCoXMnYO2Wherein a is more than or equal to 0.001 and less than or equal to 0.02, X is more than or equal to 0.1 and less than or equal to 1/3, and Y is more than or equal to 0.1 and less than or equal to 1/3; the rubidium content is gradually reduced from the center to the surface of the rubidium-doped nickel-cobalt-manganese positive electrode material particles, and the content of nickel, cobalt and manganese is uniformly distributed in the rubidium-doped nickel-cobalt-manganese positive electrode material particles.
The invention also provides a preparation method of the gradient rubidium-doped nickel-cobalt-manganese positive electrode material, which comprises the following steps:
(1) mixing a nickel source, a cobalt source, a manganese source and a rubidium salt according to the molar ratio of metal elements contained in the nickel source, the cobalt source, the manganese source and the rubidium salt (1-X-Y) to obtain a precursor mixture, adding a certain amount of precipitator, and then sequentially pumping alcoholic solutions with different concentrations by using a peristaltic pump, wherein the alcoholic solutions with different concentrations are sequentially pumped from high concentration to low concentration, the deposition amount of the rubidium salt is subjected to gradient change, and a gradient rubidium-doped precipitate material is obtained;
(2) filtering, washing and drying the gradient rubidium-doped precipitate material prepared in the step (1) to obtain a precursor of the gradient rubidium-doped nickel-cobalt-manganese positive electrode material;
(3) mixing the gradient rubidium-doped nickel-cobalt-manganese positive electrode material precursor prepared in the step (2) with a lithium source according to the mass ratio of (2-3) to (1), and sintering at 700-900 ℃ for 8-12h to obtain a gradient rubidium-doped nickel-cobalt-manganese positive electrode material;
(4) performing ultrasonic treatment on the gradient rubidium-doped nickel cobalt manganese positive electrode material prepared in the step (3), a conductive agent and a binder for 2-4 hours according to the mass ratio of (7-8) to (2-1) to 1 to obtain gradient rubidium-doped nickel cobalt manganese positive electrode material slurry;
(5) and (3) coating the gradient rubidium-doped nickel-cobalt-manganese positive electrode material slurry prepared in the step (4) on the surface of an aluminum foil in a blade coating mode, and then drying the aluminum foil in vacuum at the temperature of 80-120 ℃ for 8-12 hours to obtain the gradient rubidium-doped nickel-cobalt-manganese positive electrode material.
According to the scheme, the precipitator is one of urea, amino formamide and the like, and the proportion relation between the mass of the precipitator and the total mass of the precursor mixture is 1: (4-25).
According to the scheme, the alcohol is selected from ethanol, ethylene glycol and the like, and pure water is used as a solvent to prepare the alcohol solution.
According to the scheme, the proportion relation between the total volume of the alcohol solutions with different concentrations and the total mass of the precursor mixture is (100-400) m L (15-30) g, wherein the volume concentration of the alcohol solutions with different concentrations ranges from 100% to 20%, such as 100%, 80%, 60%, 40% and 20%, preferably, the respective volumes of the alcohol solutions with different concentrations are equal, and the reaction time of each alcohol solution with different concentrations is 0.5-2 hours.
According to the scheme, the rubidium salt is rubidium chloride (RbCl)) Rubidium carbonate (Rb)2CO3) And the like.
According to the scheme, the nickel source, the cobalt source and the manganese source are respectively one or more of soluble salts of nickel, cobalt and manganese, such as nickel chloride hexahydrate, cobalt chloride, manganese chloride, rubidium chloride, nickel sulfate hexahydrate, cobalt sulfate heptahydrate, manganese sulfate, rubidium carbonate, nickel nitrate, cobalt nitrate hexahydrate, manganese nitrate and the like.
According to the scheme, the lithium source is lithium carbonate (L i)2CO3) Lithium hydroxide (L iOH. H)2O), and the like.
According to the scheme, the conductive agent is any one of acetylene black, Super-P and the like; the binder is any one of polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC) and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, after a nickel source, a cobalt source, a manganese source and a rubidium salt are mixed, solutions of alcohols with different volume concentrations are sequentially pumped by using a peristaltic pump under the condition of a precipitator, the deposition amount of the rubidium salt is subjected to gradient change, and a gradient rubidium-doped precipitation material with the rubidium ion concentration sequentially reduced from inside to outside is obtained. Furthermore, the problem of low ionic conductivity is solved by doping the rubidium ions with higher concentration in the inner layer, and the problem of unstable cycle performance is solved by doping the rubidium ions with low concentration in the outer layer, so that the problems of low ionic conductivity and unstable cycle performance are finally solved.
(2) The ion conductivity, the cycling stability and other properties of the gradient rubidium-doped nickel-cobalt-manganese positive electrode material prepared by the method are greatly improved.
Drawings
Fig. 1 is an XRD comparison graph of a sample (experimental group) prepared from the gradient rubidium-doped nickel cobalt manganese cathode material obtained in example 1, a sample of a control group 1 and a reference group.
Fig. 2 is a graph comparing the capacity change of 100 cycles of charge and discharge cycles of the sample (experimental group) prepared from the gradient rubidium-doped nickel cobalt manganese cathode material obtained in example 1 and the sample of the control group 2 at a current density of 0.2C.
FIG. 3 is a graph showing capacity retention at a large current density of 1C for the sample of control 1.
Fig. 4 is a capacity retention graph of a sample prepared from the gradient rubidium-doped nickel cobalt manganese cathode material obtained in example 1 at a large current density of 1C.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A gradient rubidium doped nickel cobalt manganese anode material has a theoretical chemical expression of L i1-aRbaNi1-X-YCoXMnYO2Wherein a is 0.007, X is 0.2, and Y is 0.3; the rubidium content is gradually reduced from the center to the surface of the rubidium-doped nickel-cobalt-manganese positive electrode material particles, and the content of nickel, cobalt and manganese is uniformly distributed in the rubidium-doped nickel-cobalt-manganese positive electrode material particles.
The preparation method of the gradient rubidium doped nickel cobalt manganese anode material comprises the following steps:
(1) respectively weighing 11.8795g of nickel chloride hexahydrate, 2.5966g of cobalt chloride, 3.7752g of manganese chloride, 0.08464g of rubidium chloride and 2.4g of urea, mixing, pumping 20ml of 100 volume percent ethanol solution by using a peristaltic pump, fully reacting for 1 hour, pumping 20ml of 80 volume percent ethanol solution again, and fully reacting for 1 hour; then sequentially pumping ethanol solutions with volume concentrations of 60%, 40% and 20%, wherein the reaction time of the ethanol solution with each concentration is 1h after pumping, so as to obtain the gradient rubidium doped material;
(2) filtering, washing and drying the gradient rubidium-doped precipitate material prepared in the step (1) to obtain a precursor of the gradient rubidium-doped nickel-cobalt-manganese positive electrode material;
(3) mixing 4.6106g of the gradient rubidium-doped nickel cobalt manganese positive electrode material precursor prepared in the step (2) with 2.2019g of lithium hydroxide, and sintering at 850 ℃ for 12h to obtain a gradient rubidium-doped nickel cobalt manganese positive electrode material;
(4) performing ultrasonic treatment on the gradient rubidium-doped nickel-cobalt-manganese positive electrode material prepared in the step (3), acetylene black and polyvinylidene fluoride (PVDF) for 2 hours according to the mass ratio of 7:2:1 to obtain gradient rubidium-doped nickel-cobalt-manganese positive electrode material slurry;
(5) and (3) coating the gradient rubidium-doped nickel-cobalt-manganese positive electrode material slurry prepared in the step (3) on the surface of an aluminum foil in a blade coating mode, and then performing vacuum drying for 12 hours at the temperature of 80 ℃ to obtain the gradient rubidium-doped nickel-cobalt-manganese positive electrode material.
Control 1 differs from example 1 in that: different from the step (1), the operation is as follows: respectively weighing 11.8795g of nickel chloride hexahydrate, 2.5966g of cobalt chloride, 3.7752g of manganese chloride, 0.08464g of rubidium chloride and 2.4g of urea, mixing, pumping 20ml of ethanol solution with the volume concentration of 60% by using a peristaltic pump, fully reacting for 1h, and repeating the step for 4 times to obtain a common rubidium-doped material; (ii) a Steps (2) - (4) are the same.
The control reference group differs from example 1 in that: different from the step (1), the operation is as follows: respectively weighing 11.8795g of nickel chloride hexahydrate, 2.5966g of cobalt chloride, 3.7752g of manganese chloride and 2.4g of urea, mixing, pumping 20ml of ethanol solution with the volume concentration of 60% by using a peristaltic pump, fully reacting for 1h, and repeating the step for 4 times to obtain an undoped common ternary material; steps (2) - (4) are the same.
As can be seen from fig. 1, the gradient rubidium-doped nickel cobalt manganese positive electrode material prepared in the present embodiment and the common rubidium-doped nickel cobalt manganese positive electrode material prepared in the comparison group 1 are both successfully doped, and the comparison with the comparison reference group proves that the product conforms to the theoretical chemical expression of L i1-aRbaNi1-X-YCoXMnYO2。
The gradient rubidium-doped nickel-cobalt-manganese positive electrode material obtained in the embodiment 1 adopts an electrochemical workstation to test that the cycle performance of the gradient rubidium-doped nickel-cobalt-manganese positive electrode material still maintains 99.27% of initial discharge capacity after 100 cycles of cycle; as comparative group 1, the conventional rubidium-doped nickel cobalt manganese positive electrode material maintained only 82.87% of the initial discharge capacity after 100 cycles. Compared with the common rubidium-doped nickel-cobalt-manganese positive electrode material, the gradient rubidium-doped nickel-cobalt-manganese positive electrode material prepared by the invention has the advantages that the deposition amount of rubidium salt is changed in a gradient manner by adding the solutions with different volume concentrations of ethanol, the gradient rubidium-doped nickel-cobalt-manganese positive electrode material with the rubidium ion concentration sequentially reduced from inside to outside is obtained, the problem of low ionic conductivity is solved by doping the rubidium ions with higher concentration at the inner layer, and meanwhile, the problem of unstable cycle performance is solved by doping the rubidium ions with low concentration at the outer layer, so that the problems of low ionic conductivity and unstable cycle performance are finally solved.
FIG. 1 shows that the gradient rubidium-doped Ni-Co-Mn positive electrode material obtained in the embodiment and a reference group are successfully doped with rubidium, and the comparison with the reference group proves that the product conforms to the theoretical chemical expression of L i1-aRbaNi1-X-YCoXMnYO2. Fig. 2 shows that the ion conductivity and the cycling stability of the gradient rubidium-doped nickel cobalt manganese cathode material obtained in example 1 are superior to those of the sample of the control group 1. Fig. 3 and 4 collectively illustrate that the gradient rubidium-doped nickel-cobalt-manganese cathode material sample obtained in example 1 has higher cycling stability than the sample of the control group 1 under a high current density.
Example 2
A gradient rubidium doped nickel cobalt manganese anode material has a theoretical chemical expression of L i1-aRbaNi1-X-YCoXMnYO2Wherein a is 0.01, X is 0.1, and Y is 0.1; the rubidium content is gradually reduced from the center to the surface of the rubidium-doped nickel-cobalt-manganese positive electrode material particles, and the content of nickel, cobalt and manganese is uniformly distributed in the rubidium-doped nickel-cobalt-manganese positive electrode material particles.
The preparation method of the gradient rubidium doped nickel cobalt manganese anode material comprises the following steps:
(1) respectively weighing 21g of nickel sulfate hexahydrate, 2.81g of cobalt sulfate heptahydrate, 1.51g of manganese sulfate, 0.231g of rubidium carbonate and 1.2g of urea, and mixing; pumping 40ml of ethanol solution with the volume concentration of 100% by using a peristaltic pump, fully reacting for 1h, pumping 40ml of ethanol solution with the volume concentration of 80% again, and fully reacting for 1 h; then sequentially pumping ethanol solutions with volume concentrations of 60%, 40% and 20%, wherein the reaction time of the ethanol solution with each concentration after pumping is 1h, so as to obtain the gradient rubidium doped material;
(2) filtering, washing and drying the gradient rubidium-doped precipitate material prepared in the step (1) to obtain a precursor of the gradient rubidium-doped nickel-cobalt-manganese positive electrode material;
(3) mixing 4.6597g of the gradient rubidium-doped nickel cobalt manganese positive electrode material precursor prepared in the step (2) with 2.2019g of lithium hydroxide, and sintering at 700 ℃ for 10h to obtain a gradient rubidium-doped nickel cobalt manganese positive electrode material;
(4) performing ultrasonic treatment on the gradient rubidium-doped nickel-cobalt-manganese positive electrode material prepared in the step (3), Super-P and sodium carboxymethyl cellulose (CMC) for 2 hours according to the mass ratio of 7:2:1 to obtain gradient rubidium-doped nickel-cobalt-manganese positive electrode material slurry;
(5) and coating the gradient rubidium-doped nickel-cobalt-manganese positive electrode material slurry on the surface of an aluminum foil in a blade coating mode at 120 ℃ and drying for 8 hours to obtain the gradient rubidium-doped nickel-cobalt-manganese positive electrode with high stability and high ionic conductivity.
The gradient rubidium-doped nickel-cobalt-manganese positive electrode material obtained in the embodiment 2 adopts an electrochemical workstation to test that the cycle performance of the gradient rubidium-doped nickel-cobalt-manganese positive electrode material still maintains 96.3% of initial discharge capacity after 100 cycles of cycle; as control 2, the common rubidium-doped nickel cobalt manganese positive electrode material only maintained 82.1% of the initial discharge capacity after 100 cycles.
Example 3
A gradient rubidium doped nickel cobalt manganese anode material has a theoretical chemical expression of L i1-aRbaNi1-X-YCoXMnYO2Wherein a is 0.02, X is 1/3, and Y is 1/3; the rubidium content is gradually reduced from the center to the surface of the rubidium-doped nickel-cobalt-manganese positive electrode material particles, and the content of nickel, cobalt and manganese is uniformly distributed in the rubidium-doped nickel-cobalt-manganese positive electrode material particles.
The preparation method of the gradient rubidium doped nickel cobalt manganese anode material comprises the following steps:
(1) respectively weighing 6.0901g of nickel nitrate, 9.7016g of cobalt nitrate hexahydrate, 5.965g of manganese nitrate, 0.24g of rubidium chloride and 4.0536g of formamide, mixing, pumping 80ml of 100 volume percent ethylene glycol solution by using a peristaltic pump, fully reacting for 1h, pumping 80ml of 80 volume percent ethylene glycol solution again, and fully reacting for 1 h; then sequentially pumping ethylene glycol solutions with volume concentrations of 60%, 40% and 20%, wherein the reaction time of the ethanol solution with each concentration after pumping is 1h, so as to obtain a gradient rubidium doped material;
(2) filtering, washing and drying the gradient rubidium-doped precipitate material prepared in the step (1) to obtain a precursor of the gradient rubidium-doped nickel-cobalt-manganese positive electrode material;
(3) mixing 4.6614g of the gradient rubidium-doped nickel cobalt manganese positive electrode material precursor prepared in the step (2) with 1.9425g of lithium carbonate, and sintering at 900 ℃ for 8h to obtain a gradient rubidium-doped nickel cobalt manganese positive electrode material;
(4) performing ultrasonic treatment on the gradient rubidium-doped nickel-cobalt-manganese positive electrode material prepared in the step (3), Super-P and sodium carboxymethyl cellulose (CMC) for 1 hour according to the mass ratio of 8:1:1 to obtain gradient rubidium-doped nickel-cobalt-manganese positive electrode material slurry;
(5) and coating the gradient rubidium-doped nickel-cobalt-manganese positive electrode material slurry on the surface of an aluminum foil in a blade coating mode at 100 ℃ and drying for 10 hours to obtain the gradient rubidium-doped nickel-cobalt-manganese positive electrode with high stability and high ionic conductivity.
Control 3 differs from example 3 in that: different from the step (1), the operation is as follows: respectively weighing 6.0901g of nickel nitrate, 9.7016g of cobalt nitrate hexahydrate, 5.965g of manganese nitrate, 0.24g of rubidium chloride and 4.0536g of formamide, mixing, pumping 80ml of 20% ethylene glycol solution by using a peristaltic pump, fully reacting for 1h, and repeating the step for 4 times to obtain a common rubidium-doped material; steps (2) - (4) are the same.
The gradient rubidium-doped nickel-cobalt-manganese positive electrode material obtained in the embodiment 3 adopts an electrochemical workstation to test that the cycle performance of the gradient rubidium-doped nickel-cobalt-manganese positive electrode material still maintains 96.6% of initial discharge capacity after 100 cycles of cycle; as control 3, the conventional rubidium-doped nickel cobalt manganese positive electrode material maintained only 84.6% of the initial discharge capacity after 100 cycles.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (7)
1. A preparation method of a gradient rubidium doped nickel cobalt manganese anode material is characterized by comprising the following steps:
(1) according to a theoretical chemical expression L i, a nickel source, a cobalt source, a manganese source and a rubidium salt1-aRbaNi1-X-YCoXMnYO2Mixing the metal elements in a molar ratio of (1-X-Y) to X: Y: a to obtain a precursor mixture, adding a precipitator, and then sequentially pumping alcoholic solutions with different concentrations by using a peristaltic pump, wherein the alcoholic solutions with different concentrations are sequentially pumped from high to low to obtain gradient rubidium doped precipitate material; wherein a is more than or equal to 0.001 and less than or equal to 0.02, X is more than or equal to 0.1 and less than or equal to 1/3, and Y is more than or equal to 0.1 and less than or equal to 1/3;
(2) filtering, washing and drying the gradient rubidium-doped precipitate material prepared in the step (1) to obtain a precursor of the gradient rubidium-doped nickel-cobalt-manganese positive electrode material;
(3) mixing the gradient rubidium-doped nickel cobalt manganese positive electrode material precursor prepared in the step (2) with a lithium source according to the mass ratio of (2-3) to (1) at 700-900 ℃, and sintering for 8-12h to obtain a gradient rubidium-doped nickel cobalt manganese positive electrode material, wherein the content of rubidium is gradually reduced from the center to the surface of the rubidium-doped nickel cobalt manganese positive electrode material particles;
(4) mixing the gradient rubidium-doped nickel-cobalt-manganese positive electrode material prepared in the step (3) with a conductive agent and a binder according to the mass ratio of (7-8) to (2-1) to 1, and performing ultrasonic treatment for 2-4 hours to obtain gradient rubidium-doped nickel-cobalt-manganese positive electrode material slurry;
(5) and (3) coating the gradient rubidium-doped nickel-cobalt-manganese positive electrode material slurry prepared in the step (4) on the surface of an aluminum foil in a blade coating mode, and then drying the aluminum foil in vacuum at the temperature of 80-120 ℃ for 8-12 hours to obtain the gradient rubidium-doped nickel-cobalt-manganese positive electrode material.
2. The method for preparing the gradient rubidium-doped nickel cobalt manganese cathode material as claimed in claim 1, wherein the precipitant is urea or formamide, and the ratio of the mass of the precipitant to the total mass of the precursor mixture is 1: (4-25).
3. The method for preparing a gradient rubidium-doped nickel cobalt manganese positive electrode material as claimed in claim 1, wherein the alcohol is selected from ethanol or ethylene glycol, and pure water is used as a solvent to prepare an alcohol solution.
4. The method as claimed in claim 1, wherein the ratio of the total volume of the different concentrations of the alcohol solutions to the total mass of the precursor mixture is (100-400) m L (15-30) g, and the volume concentration of the different concentrations of the alcohol solutions is in the range of 100-20%.
5. The method of claim 1, wherein the alcohol solutions of different concentrations are pumped in equal volumes, and the reaction time of each alcohol solution is 0.5-2 hours.
6. The method of claim 1, wherein said rubidium salt is any one of rubidium chloride or rubidium carbonate; the nickel source, the cobalt source and the manganese source are respectively one or more of soluble salts of nickel, cobalt and manganese; the lithium source is lithium carbonate or lithium hydroxide.
7. The method for preparing the gradient rubidium-doped nickel cobalt manganese positive electrode material as claimed in claim 1, wherein the conductive agent is acetylene black or Super-P; the binder is polyvinylidene fluoride or sodium hydroxymethyl cellulose.
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| CN111952566A (en) * | 2020-08-18 | 2020-11-17 | 光鼎铷业(广州)集团有限公司 | Rubidium-doped high-rate lithium battery positive electrode material and preparation method thereof |
| CN111952585A (en) * | 2020-08-18 | 2020-11-17 | 光鼎铷业(广州)集团有限公司 | High-compaction-density rubidium-doped lithium battery positive electrode material and preparation method thereof |
| CN112201898A (en) * | 2020-08-26 | 2021-01-08 | 河北金力新能源科技股份有限公司 | Lithium battery gradient distribution coating diaphragm and preparation method thereof |
| CN112234203A (en) * | 2020-10-15 | 2021-01-15 | 光鼎铷业(广州)集团有限公司 | Conductive polymer coated rubidium-doped high-nickel ternary lithium battery positive electrode material and preparation method thereof |
| CN114530588B (en) * | 2022-04-21 | 2022-07-22 | 浙江帕瓦新能源股份有限公司 | Multi-element concentration gradient doped precursor material, preparation method thereof and positive electrode material |
| CN114906885B (en) * | 2022-05-23 | 2024-02-02 | 青海师范大学 | High-magnification positive electrode material of lithium ion battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904318A (en) * | 2012-12-28 | 2014-07-02 | 惠州比亚迪电池有限公司 | Lithium battery positive electrode material and preparation method thereof |
| CN109786736A (en) * | 2018-12-28 | 2019-05-21 | 中南大学 | A kind of nickel cobalt rubidium manganate lithium material and its preparation method and application |
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| KR100326460B1 (en) * | 2000-02-10 | 2002-02-28 | 김순택 | Positive active material for lithium secondary battery and method of preparing same |
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| CN108630923A (en) * | 2018-04-28 | 2018-10-09 | 南开大学 | Nickel cobalt lithium aluminate cathode material, preparation method and the lithium battery of gradient sodium ion doping |
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