CN114573040A - Effectively doped lithium cobaltate material and preparation method thereof - Google Patents
Effectively doped lithium cobaltate material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an effectively doped lithium cobaltate material and a preparation method thereof, wherein organic metal salt is used for replacing metal oxide in the prior art for doping, the organic metal salt is in a molecular structure, crystals are combined by intermolecular force, the migration and fracture regeneration of the metal salt during melting are facilitated, and organic matters can emit a large amount of heat energy during sintering, so that the local temperature is increased, the local temperature where the metal exists is ensured to be higher, the migration of the metal and the doping of the metal are facilitated, and the prepared lithium cobaltate material has better effective doping effect and good doping uniformity.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an effectively doped lithium cobaltate material and a preparation method thereof.
Background
The high-voltage lithium cobaltate is one of the most ideal positive electrode materials of the current small-sized high-specific energy batteries. However, when the charging voltage is increased (> 4.2V), the phase structure of lithium cobaltate is changed, the stability is deteriorated, the structure is easily destroyed, and Co is continuously removed with lithium ions3+Is oxidized into Co4+Strongly oxidizing Co4+The decomposition of the electrolyte is accelerated, and further, the dissolution of cobalt is caused, so that the capacity of the battery is seriously attenuated, and the cycle performance is reduced. Therefore, a doping technique is needed to improve the bulk structure of the lithium cobaltate positive electrode material, so as to improve the electrochemical performance of the whole material.
Aiming at the doping process of the lithium cobaltate anode material, the doping elements adopted in the prior art are aluminum, magnesium and the like. The doping method is usually precursor doping, bulk doping (sintering doping), and the like. However, the existing characterization methods mainly characterize the doping content and the doping elements, such as ICP and other schemes, which cannot evaluate whether the product is doped, that is, when the metal exists in the form of a single oxide or a lithium salt, the metal is successfully detected by the scheme and is included in the doping amount, which causes the problem that the doping uniformity of the lithium cobaltate positive electrode material obtained by the existing doping method cannot be confirmed, the maximum effect cannot be exerted, and the performance of the material is reduced due to the part which is not effectively doped.
Disclosure of Invention
The invention aims to provide a lithium cobaltate material with effective doping.
The specific scheme is as follows:
an effectively doped lithium cobaltate material is lithium cobaltate substituted and doped by lithium sites, and the general formula of the matrix of the material is Li1+xMyCo1-zO2(ii) a Wherein x is more than or equal to-0.05 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.05, and z is more than 0 and less than or equal to 0.05; m is a doping element; the c value of the unit cell parameter of the lithium cobaltate material is between 14.05 and 14.085, and the a value of the unit cell parameter of the a axis is between 2.815 and 2.83.
Furthermore, the doping element M is one or more of Al, Mg, Ti, Mn and Ni.
The invention also provides a preparation method of the effectively doped lithium cobaltate material, which comprises the following steps:
s1, uniformly mixing cobalt salt, a lithium compound and a nano-scale additive containing an M element, controlling the molar ratio of Li to Co to be 1.00-1.06, and uniformly mixing to obtain a primary mixture; wherein, the M element is one or more of Al, Mg, Ti, Mn and Ni; the nano-scale additive is organic metal salt corresponding to M element;
s2, sintering the primary mixture obtained in the step S1 to obtain a primary sintered material;
s3, crushing and grading the primary sintered material obtained in the step S2 to obtain lithium battery positive electrode material semi-finished products with different particle sizes;
s4, performing secondary mixing on the semi-finished products of the lithium battery positive electrode materials with different particle sizes, adding a nanoscale additive containing an M element and a nanoscale additive containing an A element in the secondary mixing, and uniformly mixing to obtain a secondary mixture, wherein the M element is one or more of Al, Mg, Ti, Zr, Mn and Ni, and the A element is one or more of Mg, Al, Ti, Zr, Ni, Mn, Y, La, Ce, Pr and Sm;
s5, sintering the secondary mixture to obtain a secondary sintered material;
and S6, pulverizing the secondary sintering material to obtain the effectively doped lithium cobaltate material.
Further, the organic metal salt is one or more of acetylacetone metal salt, EDTA metal salt, oxalate metal salt and acetate metal salt.
Furthermore, the organic metal salt is a two-tooth to six-tooth chelate compound taking an organic matter as a chelating ligand.
Further, the sintering process in step S2 includes raising the temperature to 200-300 ℃, keeping the temperature for sintering for H1 hours, then continuing raising the temperature to 700-900 ℃, keeping the temperature for H2 hours, continuing raising the temperature to 900-1100 ℃, keeping the temperature for sintering for H3 hours to obtain a primary sintering material, wherein the sum of H1, H2 and H3 is 8-20 hours.
Further, the sintering temperature of the secondary sintering in the step S5 is 600-1100 ℃, and the time duration of the secondary sintering is 5-20 hours.
Further, the lithium cobaltate material obtained in the step S6 is subjected to effective doping characterization, and the c value of the cell parameter of the lithium cobaltate material is between 14.05 and 14.085, and the a value of the cell parameter of the a axis is between 2.815 and 2.83.
Further, effective doping is carried out on the lithium cobaltate material obtained in the step S6, XRD representation is carried out, XRD data are refined, and the difference value between the total doped metal content of the refined lithium cobaltate material and the total metal content of the actual fed material is less than 20%.
Compared with the prior art, the effectively doped lithium cobaltate material and the preparation method thereof provided by the invention have the following advantages: the lithium cobaltate material provided by the invention is doped by replacing metal oxides in the prior art with organic metal salts, the organic metal salts are in molecular structures, crystals are combined by virtue of intermolecular force, the migration and fracture regeneration of the metal salts during melting are facilitated, and a large amount of heat energy is generated by organic matters during sintering, so that the local temperature is increased, the higher temperature of the place where the metal exists is ensured, the migration of the metal and the doping of the metal are more facilitated, and the prepared lithium cobaltate material has a better effective doping effect and good doping uniformity.
Drawings
Fig. 1 shows a Scanning Electron Microscope (SEM) image and an elemental distribution diagram of the lithium cobaltate material obtained in example 1.
Fig. 2 shows a Scanning Electron Microscope (SEM) image and an elemental distribution diagram of the lithium cobaltate material obtained in example 2.
Fig. 3 shows a Scanning Electron Microscope (SEM) image and an elemental distribution diagram of the lithium cobaltate material obtained in example 3.
Fig. 4 shows a Scanning Electron Microscope (SEM) image and an elemental distribution diagram of the lithium cobaltate material obtained in example 4.
Fig. 5 shows XRD patterns of lithium cobaltate materials obtained in examples 1-4.
Detailed Description
To further illustrate the various embodiments, the invention provides the accompanying drawings. The accompanying drawings, which are incorporated in and constitute a part of this disclosure, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the embodiments. Those skilled in the art will appreciate still other possible embodiments and advantages of the present invention with reference to these figures.
The invention will now be further described with reference to the accompanying drawings and detailed description.
The invention provides an effectively doped lithium cobaltate material, which is lithium cobalt oxide substituted and doped at lithium position, and the general formula of the matrix of the material is Li1+xMyCo1-zO2(ii) a Wherein x is more than or equal to-0.05 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.05, and z is more than 0 and less than or equal to 0.05; m is a doping element; the c value of the unit cell parameter of the lithium cobaltate material is between 14.05 and 14.085, and the a value of the unit cell parameter of the a axis is between 2.815 and 2.83.
In the prior art, the introduction of sintering doping metal is mainly carried out by selecting oxide, and most of metal oxide is atomic crystal, so that the reaction temperature is high, the activity is poor, and the metal oxide can not be well doped and fused with lithium cobaltate, so that segregation or insufficient uniformity occurs, and the performance of doping elements is not well exerted on the whole.
Therefore, in order to realize the effective doping of the lithium cobaltate material, the invention adopts an introduction scheme of solid-phase sintering introduction, selects the introduction additive as organic metal salt (such as acetic acid metal salt, acetylacetone metal salt and the like), and uses the organic metal salt to replace the metal oxide in the prior art for doping, thereby realizing the purpose of effective doping, and the principle is as follows:
firstly, the organic metal salt is a molecular crystal, each unit in the crystal is combined through intermolecular force, but not through chemical bonds in an atomic crystal, and the structural energy is smaller than that of the atomic crystal of the oxide by more than one order of magnitude, so that the melting point of the material is generally less than 300 ℃, and the melting and doping process of the material is facilitated.
And secondly, the organic matter can react with oxygen under the current doping condition to be combusted, so that the final product does not contain related substances and impurities are not introduced. Meanwhile, the heat released during the combustion of the organic matter can cause the local temperature of the material to be higher than the set temperature, further increase the temperature near the organic metal salt, and can help the doped metal element to perform infiltration doping, thereby improving the doping effect.
Finally, in the organic metal salt, the valence state of the metal is generally low, and the valence state change is accompanied in the sintering process, so that the process of breaking and regenerating the metal oxygen bond in the doping process of the lithium cobaltate material is improved, and the uniformity of metal doping is improved.
The effective doping of the lithium cobaltate material is realized by the following modes:
s1, primary mixing: uniformly mixing cobalt salt, a lithium compound and a nano-scale additive containing an M element, controlling the molar ratio of Li/Co to be in the range of 1.00-1.07, controlling the particle size D50 of the cobalt salt to be between 12-18um, and uniformly mixing to obtain a primary mixed material, wherein the M element is one or more of Al, Mg, Ti, Mn and Ni; the nanoscale additive is an organic metal salt corresponding to the M element. The organic metal salt is one or more of acetylacetone metal salt, EDTA metal salt, oxalate metal salt and acetometallate salt, and is specifically a two-tooth to six-tooth chelate compound with an organic matter as a chelating ligand.
S2, primary sintering: and sintering the primary mixture obtained in the step S1, wherein the sintering process comprises the steps of firstly heating to 200-300 ℃, keeping the temperature for sintering for H1 hours, then continuously heating to 700-900 ℃, keeping the temperature for H2 hours, continuously heating to 900-1100 ℃, and keeping the temperature for sintering for H3 hours to obtain the primary sintered material, wherein the sum of H1, H2 and H3 is 8-20 hours.
S3, primary screening: and (5) crushing and grading the primary sintered material obtained in the step (S2) to obtain lithium battery positive electrode material semi-finished products with different particle sizes.
S4, secondary mixing: carrying out secondary mixing on semi-finished products of lithium battery positive electrode materials with different particle sizes, adding a nanoscale additive containing an M element and a nanoscale additive containing an A element in the secondary mixing process, and uniformly mixing to obtain a secondary mixture, wherein the M element is one or more of Al, Mg, Ti, Zr, Mn and Ni, and the A element is one or more of Mg, Al, Ti, Zr, Ni, Mn, Y, La, Ce, Pr and Sm.
S5, secondary sintering: and sintering the secondary mixture to obtain a secondary sintered material, wherein the sintering temperature is 600-1100 ℃, and the secondary sintering time is 5-20 hours.
S6, milling: and (4) pulverizing the secondary sintering material to obtain the effectively doped lithium cobaltate material.
The doped lithium cobaltate material obtained in the above manner is measured by performing XRD test characterization on the doped lithium cobaltate to confirm the c value of the unit cell parameter and the a value of the unit cell parameter of the a axis.
Example 1
According to the mol ratio of 1: 1: 0.02 weighing lithium carbonate, cobaltosic oxide and aluminum acetylacetonate, uniformly mixing the lithium carbonate, the cobaltosic oxide and the aluminum acetylacetonate, placing the mixture in a muffle furnace, heating up to 260 ℃ at the speed of 2 ℃/min, carrying out heat preservation sintering for 2 hours, then continuously heating up to 800 ℃ at the speed of 5 ℃/min, carrying out heat preservation for 3 hours, continuously heating up to 1060 ℃ at the speed of 5 ℃/min, carrying out heat preservation sintering for 7 hours to obtain a primary sintering material, naturally cooling to room temperature, and grinding and sieving to obtain a lithium cobaltate semi-finished product with the particle size of 2-20 mu m.
Uniformly mixing the lithium cobaltate semi-finished product and aluminum oxide according to the molar ratio of 1:0.01, placing the material in a muffle furnace, calcining for 6 hours at the temperature of 800 ℃, naturally cooling, crushing and sieving to obtain a doped finished product lithium cobaltate material, wherein the particle size of the doped finished product lithium cobaltate material is 2.05-20.5 mu m.
And (3) performing effective doping characterization on lithium cobaltate, and confirming the c value of the unit cell parameter and the a value of the unit cell parameter of the a axis.
Example 2
According to the mol ratio of 1: 1: 0.02 weighing lithium carbonate, cobaltosic oxide and EDTA titanium salt, uniformly mixing the lithium carbonate, the cobaltosic oxide and the EDTA titanium salt, putting the mixture into a muffle furnace, heating to 300 ℃ at the speed of 2 ℃/min, carrying out heat preservation sintering for 1.5 hours, then continuously heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat preservation for 3 hours, continuously heating to 1000 ℃ at the speed of 5 ℃/min, carrying out heat preservation sintering for 8 hours to obtain a primary sintering material, naturally cooling to room temperature, and grinding and sieving to obtain a lithium cobaltate semi-finished product with the particle size of 2-20 mu m.
Uniformly mixing the lithium cobaltate semi-finished product and aluminum oxide according to the molar ratio of 1:0.01, placing the material in a muffle furnace, calcining at the temperature of 800 ℃ for 8 hours, naturally cooling, crushing and sieving to obtain a doped finished product lithium cobaltate material, wherein the particle size of the doped finished product lithium cobaltate material is 2.05-20.5 mu m.
And (3) performing effective doping characterization on lithium cobaltate, and confirming the c value of the unit cell parameter and the a value of the unit cell parameter of the a axis.
Example 3
According to the mol ratio of 1: 1: 0.02 weighing lithium carbonate, cobaltosic oxide and nickel oxalate, uniformly mixing the lithium carbonate, the cobaltosic oxide and the nickel oxalate, placing the mixture in a muffle furnace, heating to 200 ℃ at the speed of 2 ℃/min, carrying out heat preservation sintering for 2 hours, then continuously heating to 750 ℃ at the speed of 5 ℃/min, carrying out heat preservation for 3 hours, continuously heating to 1100 ℃ at the speed of 5 ℃/min, carrying out heat preservation sintering for 5 hours to obtain a primary sintering material, naturally cooling to room temperature, and grinding and sieving to obtain a lithium cobaltate semi-finished product with the particle size of 2-20 mu m.
Uniformly mixing the lithium cobaltate semi-finished product and aluminum oxide according to the molar ratio of 1:0.01, placing the material in a muffle furnace, calcining at 900 ℃ for 8 hours, naturally cooling, crushing and sieving to obtain a doped finished product lithium cobaltate material, wherein the particle size of the doped finished product lithium cobaltate material is 2.05-20.5 mu m. And (3) performing effective doping characterization on lithium cobaltate, and confirming the c value of the unit cell parameter and the a value of the unit cell parameter of the a axis.
Example 4
According to the mol ratio of 1: 1: 0.02 weighing lithium carbonate, cobaltosic oxide and ethyl manganese propionate, uniformly mixing the lithium carbonate, the cobaltosic oxide and the ethyl manganese propionate, putting the mixture into a muffle furnace, heating to 200 ℃ at the speed of 2 ℃/min, carrying out heat preservation sintering for 2 hours, then continuously heating to 750 ℃ at the speed of 5 ℃/min, carrying out heat preservation for 3 hours, continuously heating to 1100 ℃ at the speed of 5 ℃/min, carrying out heat preservation sintering for 5 hours to obtain a primary sintering material, naturally cooling to room temperature, and grinding and sieving to obtain a lithium cobaltate semi-finished product with the particle size of 2-20 mu m.
Uniformly mixing the lithium cobaltate semi-finished product and titanium oxide according to the molar ratio of 1:0.01, placing the material in a muffle furnace, calcining at the temperature of 1000 ℃ for 8 hours, naturally cooling, crushing and sieving to obtain a doped finished product lithium cobaltate material, wherein the particle size of the doped finished product lithium cobaltate material is 2.05-20.5 mu m. And (3) performing effective doping characterization on lithium cobaltate, and confirming the c value of the unit cell parameter and the a value of the unit cell parameter of the a axis.
Scanning Electron Microscope (SEM) images, elemental distribution diagrams, and XRD patterns of the doped lithium cobaltate materials prepared in examples 1-4 above are shown in fig. 1-5. Wherein a in fig. 1 is a scanning electron micrograph of the lithium cobaltate material obtained in example 1, and b in fig. 1 is an element distribution diagram of the lithium cobaltate material obtained in example 1. Fig. 2 a is a scanning electron micrograph of the lithium cobaltate material obtained in example 2, and fig. 2 b is a distribution diagram of elements of the lithium cobaltate material obtained in example 2. Fig. 3 a is a scanning electron micrograph of the lithium cobaltate material obtained in example 3, and fig. 3 b is a distribution diagram of elements of the lithium cobaltate material obtained in example 3. Fig. 4 a is a scanning electron micrograph of the lithium cobaltate material obtained in example 4, and fig. 4 b is an elemental distribution diagram of the lithium cobaltate material obtained in example 4. Fig. 5 is an XRD pattern of the lithium cobaltate material prepared in examples 1-4.
As can be seen from fig. 1 to 4, the doping element can be effectively doped into the lithium cobaltate material, and has good doping uniformity.
The XRD data of examples 1-4 were subjected to fitting refinement using Rietveld structure refinement method and data analysis using EVA, TOPAS software, to obtain XRD refinement data as shown in table 1 below.
TABLE 1
| Description of the invention | Cell parameter a | Cell parameter c | Content of refining element |
| Example 1 | 2.8254 | 14.73045 | 1.93％ |
| Example 2 | 2.8236 | 14.65403 | 1.86％ |
| Example 3 | 2.8203 | 14.06239 | 1.88％ |
| Example 4 | 2.8164 | 14.06033 | 1.79％ |
From table 1, it can be seen that the cell parameter c value of the lithium cobaltate material provided by the present invention is between 14.05 and 14.085, the cell parameter a value of the a-axis is between 2.815 and 2.83, and the difference between the XRD data doping element content refinement value and the theoretical charging chemical formula value of the lithium cobaltate material is less than 20%, which indicates that the doped lithium cobaltate material has good doping effect, excellent electrochemical performance and good stability.
Lithium cobaltate materials prepared in examples 1 to 4 were prepared into lithium batteries, and the prepared lithium batteries were tested under the test conditions and the results shown in table 2.
TABLE 2
The lithium cobaltate material used in the comparative example in table 2 is a commercial product (4.48V product of tungsten new energy materials ltd. of mansion), and it can be seen from the data in table 2 that the lithium batteries prepared from the lithium cobaltate materials obtained in examples 1 to 4 have almost the same charge capacity and discharge capacity as the commercial product, but have better cycle retention compared to the commercial product.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. An efficiently doped lithium cobaltate material, characterized by: the lithium cobaltate material is lithium cobaltate substituted and doped at a lithium position, and the general formula of a matrix of the lithium cobaltate material is Li1+xMyCo1-zO2(ii) a Wherein x is more than or equal to-0.05 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.05, and z is more than 0 and less than or equal to 0.05; m is a doping element; the c value of the unit cell parameter of the lithium cobaltate material is between 14.05 and 14.085, and the a value of the unit cell parameter of the a axis is between 2.815 and 2.83.
2. The lithium cobaltate material of claim 1, wherein: the doping element M is one or more of Al, Mg, Ti, Mn and Ni.
3. A preparation method of an effectively doped lithium cobaltate material is characterized by comprising the following steps:
s1, uniformly mixing cobalt salt, a lithium compound and a nano-scale additive containing an M element, controlling the molar ratio of Li to Co to be 1.00-1.07, and uniformly mixing to obtain a primary mixture; wherein, the M element is one or more of Al, Mg, Ti, Mn and Ni; the nano-scale additive is organic metal salt corresponding to M element;
s2, sintering the primary mixture obtained in the step S1 to obtain a primary sintered material;
s3, crushing and grading the primary sintered material obtained in the step S2 to obtain lithium battery positive electrode material semi-finished products with different particle sizes;
s4, performing secondary mixing on the semi-finished products of the lithium battery positive electrode materials with different particle sizes, adding a nanoscale additive containing an M element and a nanoscale additive containing an A element in the secondary mixing, and uniformly mixing to obtain a secondary mixture, wherein the M element is one or more of Al, Mg, Ti, Zr, Mn and Ni, and the A element is one or more of Mg, Al, Ti, Zr, Ni, Mn, Y, La, Ce, Pr and Sm;
s5, sintering the secondary mixture to obtain a secondary sintered material;
and S6, pulverizing the secondary sintering material to obtain the effectively doped lithium cobaltate material.
4. The production method according to claim 3, characterized in that: the organic metal salt is one or more of acetylacetone metal salt, EDTA metal salt, oxalate metal salt and acetate metal salt.
5. The method of claim 4, wherein: the organic metal salt is a two-tooth to six-tooth chelate with an organic substance as a chelating ligand.
6. The production method according to claim 3, characterized in that: the sintering process in the step S2 includes raising the temperature to 200-300 ℃, keeping the temperature for sintering for H1 hours, then continuing raising the temperature to 700-900 ℃, keeping the temperature for H2 hours, continuing raising the temperature to 900-1100 ℃, keeping the temperature for sintering for H3 hours to obtain a primary sintering material, wherein the sum of H1, H2 and H3 is 8-20 hours.
7. The production method according to claim 3, characterized in that: the sintering temperature of the secondary sintering in the step S5 is 600-1100 ℃, and the secondary sintering time is 5-20 hours.
8. The production method according to claim 3, characterized in that: and performing effective doping characterization on the lithium cobaltate material obtained in the step S6, wherein the unit cell parameter c value of the lithium cobaltate material is between 14.05 and 14.085, and the unit cell parameter a value of the a axis is between 2.815 and 2.83.
9. The production method according to claim 3, characterized in that: and (5) performing effective doping on the lithium cobaltate material obtained in the step (S6) to perform XRD characterization, and refining the XRD data, wherein the difference value between the total doped metal content of the refined lithium cobaltate material and the total actual fed metal content is less than 20%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007095571A (en) * | 2005-09-29 | 2007-04-12 | Seimi Chem Co Ltd | Manufacturing method of lithium-contained complex oxide |
| CN103825021A (en) * | 2014-03-12 | 2014-05-28 | 刘洋 | Preparation method for rare earth element doped composite lithium cobalt oxide cathode material |
| CN104701534A (en) * | 2015-03-31 | 2015-06-10 | 南通瑞翔新材料有限公司 | High-energy-density Ni-Co-based lithium ion positive electrode material and preparation method thereof |
| CN105118991A (en) * | 2015-08-27 | 2015-12-02 | 北大先行科技产业有限公司 | Lithium ion secondary battery positive electrode material and preparation method thereof |
| WO2018095053A1 (en) * | 2016-11-28 | 2018-05-31 | 华为技术有限公司 | Lithium cobalt oxide positive electrode material and preparation method therefor and lithium ion secondary battery |
| CN109786738A (en) * | 2017-11-15 | 2019-05-21 | 华为技术有限公司 | A kind of high voltage lithium cobalt oxide anode and preparation method thereof and lithium ion battery |
-
2022
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007095571A (en) * | 2005-09-29 | 2007-04-12 | Seimi Chem Co Ltd | Manufacturing method of lithium-contained complex oxide |
| CN103825021A (en) * | 2014-03-12 | 2014-05-28 | 刘洋 | Preparation method for rare earth element doped composite lithium cobalt oxide cathode material |
| CN104701534A (en) * | 2015-03-31 | 2015-06-10 | 南通瑞翔新材料有限公司 | High-energy-density Ni-Co-based lithium ion positive electrode material and preparation method thereof |
| CN105118991A (en) * | 2015-08-27 | 2015-12-02 | 北大先行科技产业有限公司 | Lithium ion secondary battery positive electrode material and preparation method thereof |
| WO2018095053A1 (en) * | 2016-11-28 | 2018-05-31 | 华为技术有限公司 | Lithium cobalt oxide positive electrode material and preparation method therefor and lithium ion secondary battery |
| CN109786738A (en) * | 2017-11-15 | 2019-05-21 | 华为技术有限公司 | A kind of high voltage lithium cobalt oxide anode and preparation method thereof and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 郑长春;宋顺林;刘亚飞;陈彦彬;: "元素掺杂在钴酸锂正极材料中的研究进展", 化学试剂, no. 10 * |
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