CN114188528B - Preparation method of ternary positive electrode material with low residual alkali content and high capacity retention rate - Google Patents

Preparation method of ternary positive electrode material with low residual alkali content and high capacity retention rate Download PDF

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CN114188528B
CN114188528B CN202111421637.4A CN202111421637A CN114188528B CN 114188528 B CN114188528 B CN 114188528B CN 202111421637 A CN202111421637 A CN 202111421637A CN 114188528 B CN114188528 B CN 114188528B
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CN114188528A (en
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李佰康
张文静
朱用
程春雷
黄帅杰
朱涛
顾春芳
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Nantong Kington Energy Storage Power New Material Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Low residueThe preparation method of the ternary positive electrode material with alkali content and high capacity retention rate comprises the following steps: 1. dehydrating nickel cobalt manganese hydroxide to obtain Ni 1‑x‑y Co x Mn y (OH) 2 X is more than or equal to 0 and less than 1, y is more than or equal to 0 and less than 1, and x+y is more than or equal to 0 and less than or equal to 0.2; 2. drying nickel cobalt manganese hydroxide at the temperature of less than 210 ℃, and selectively using a crystallinity regulator for pickling according to FWHM (001) to obtain a product with the FWHM (001) of which the value is less than or equal to 0.30 and less than or equal to 0.60; 3. calcining the product at high temperature to obtain Ni with the general formula of 1‑x‑y Co x Mn y O Z Ternary precursor with FWHM (111) less than or equal to 0.60 and less than or equal to 0.80 is mixed with lithium and sintered to obtain the positive electrode material. The ternary precursor with uniform crystallinity can be obtained by the method, and the problems of high residual alkali content and low high nickel positive electrode circularity of the high nickel ternary precursor are solved.

Description

Preparation method of ternary positive electrode material with low residual alkali content and high capacity retention rate
Technical Field
The invention relates to the field of lithium battery anode materials, in particular to a preparation method of a ternary anode material with low residual alkali content and high capacity retention rate.
Background
The ternary positive electrode material of the lithium battery is the first choice material of the lithium battery because of low price and stable performance, and the high energy density is the greatest advantage. Along with the increase of the content of nickel element, the specific capacity of the ternary positive electrode material is gradually increased, and the energy density of the battery core is also increased. At present, the positive electrode material for the domestic power lithium battery mainly takes NCM523 as a main material, and the energy density of a battery core reaches 160-200 wh/kg. The high-nickel ternary positive electrode material increases the number of reactive electrons of the battery, so that the energy density of the battery is improved, the energy density of a battery core is expected to be 300wh/kg, the energy density of the battery reaches 200wh/kg, the current energy density is improved by 30%, and compared with the ternary materials of different types, the energy density NCM811 is larger than NCM622 and larger than NCM523, the energy density of other battery materials can be improved by improving the nickel content, the grouping efficiency is improved, and the like.
The high-nickel ternary positive electrode material has high energy density and mid-long term development advantage, and meanwhile, the production technology of the high-nickel ternary positive electrode material also faces great challenges. The residual alkali on the surface is high in content, side reactions are easy to occur with PVDF and electrolyte of the positive electrode slurry, the processing difficulty is high, and serious flatulence is generated when the material is stored at high temperature. And the higher the nickel content, the higher the total alkali content. The high total alkali content means that the lithium residues on the surface of the particles are more, so that carbon dioxide and water in the air are easily absorbed, and Li is formed on the surface of the particles 2 CO 3 And LiOH layers consume Li in the material and are not electrochemically active, thus causing capacity fade.
Aiming at the problem of high residual alkali content, a process of washing a high-nickel material with water and then secondarily sintering at a lower temperature is generally adopted at present, so that the residual alkali content of the surface of the high-nickel material is reduced, but the multiplying power and the cycle performance of the treated high-nickel material are obviously reduced, and the large-scale application of the high-nickel material is limited.
Therefore, how to solve the above-mentioned drawbacks of the prior art is a subject to be studied and solved by the present invention.
Disclosure of Invention
The invention aims to provide a preparation method of a ternary positive electrode material with low residual alkali content and high capacity retention rate.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the ternary positive electrode material with low residual alkali content and high capacity retention rate comprises the following steps:
step one, dehydrating nickel cobalt manganese hydroxide to obtain Ni with the general formula of 1-x-y Co x Mn y (OH) 2 Wherein x is more than or equal to 0 and less than 1, y is more than or equal to 0 and less than 1, and x+y is more than or equal to 0 and less than or equal to 0.2;
drying the nickel cobalt manganese hydroxide in the first step at the temperature of less than 210 ℃ to ensure that the moisture content of the nickel cobalt manganese hydroxide is less than or equal to 0.2%, and then performing XRD test;
if FWHM (001) is less than 0.3, dispersing nickel cobalt manganese hydroxide in the aqueous solution, adding a first crystallinity regulator, and carrying out pickling;
if FWHM (001) > 0.6 is measured, dispersing nickel cobalt manganese hydroxide in the aqueous solution, adding a second crystallinity regulator, and carrying out pickling;
after immersion washing, a product with FWHM (001) of more than or equal to 0.30 and less than or equal to 0.60 is obtained;
calcining the product obtained in the step two at a high temperature of 300-600 ℃, and washing and drying the product with water to obtain FWHM (111) which is less than or equal to 0.60 and less than or equal to 0.80, wherein the general formula is Ni 1-x-y Co x Mn y O Z Is a ternary precursor of (a);
and step four, mixing the ternary precursor obtained in the step three with lithium, and sintering to obtain the ternary positive electrode material with low residual alkali content and high capacity retention rate.
The relevant content explanation in the technical scheme is as follows:
1. in the scheme, the nickel cobalt manganese hydroxide in the first step is synthesized by a coprecipitation method.
2. In the scheme, the drying time of the second step is 1-2 hours.
3. In the above scheme, the XRD test refers to FWHM (full width at half maximum) of a substance measured by an X-ray powder diffractometer.
Wherein FWHM (001) represents the half-width of the (001) diffraction peak, FWHM (111) represents the half-width of the (111) diffraction peak, and FWHM (200) represents the half-width of the (200) diffraction peak.
4. In the above scheme, the soaking and washing comprises soaking or/and washing.
5. In the scheme, the calcination time in the third step is 1-7 h.
6. In the above scheme, in the second step, the first crystallinity regulator is one or more of ammonia water, ammonium nitrate, ammonium sulfate and sodium hydroxide, and the total concentration of the first crystallinity regulator is 0.001-0.01 mol/L.
7. In the above scheme, in the second step, the second crystallinity regulator is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide, and the total concentration of the second crystallinity regulator is 0.01-0.5 mol/L.
8. In the scheme, in the second step, FWHM (100) is less than or equal to 0.15 and less than or equal to 0.50 of the product after pickling.
9. In the scheme, in the third step, FWHM (200) is less than or equal to 0.7 and less than or equal to 1.0 of the ternary precursor after calcination.
10. In the above scheme, in the third step, the high temperature calcination is a gradient high temperature calcination, the calcination temperature during calcination is increased in gradient at least two different temperature values, and the calcination is performed for 0.5-1 h at each temperature value, wherein the temperature values comprise 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ and 600 ℃.
The crystallinity of the ternary precursor finally obtained in the third step can be more effectively controlled through echelon calcination, so that the crystallinity meets the control range, the calcination has obvious influence on the Na/S impurity content of the precursor, and the Na/S impurity content of the precursor can be controlled through echelon calcination.
11. In the above scheme, in the second step, the atmosphere introduced during drying is nitrogen or inert gas.
12. In the above scheme, in the third step, the atmosphere introduced during calcination is air or oxygen.
13. In the scheme, the precursor in the fourth step is mixed with lithium and sintered to form the surface Li of the positive electrode material 2 CO 3 The residual quantity is less than or equal to 1500ppm, the surface LiOH residual quantity is less than or equal to 1000ppm, and the capacity retention rate after 100 weeks circulation is more than 90%.
14. In the scheme, the lithiation ratio during lithium mixing is 1.0-1.15, and lithium carbonate, lithium hydroxide and the like can be adopted as a lithium source.
The working principle and the advantages of the invention are as follows:
the invention relates to a preparation method of a ternary positive electrode material with low residual alkali content and high capacity retention rate, which comprises the following steps: 1. dehydrating nickel cobalt manganese hydroxide to obtain Ni 1-x-y Co x Mn y (OH) 2 X is more than or equal to 0 and less than 1, y is more than or equal to 0 and less than 1, and x+y is more than or equal to 0 and less than or equal to 0.2; two (II)Drying the nickel cobalt manganese hydroxide at the temperature of less than 210 ℃, and selectively using a crystallinity regulator for pickling according to FWHM (001) to obtain a product with the FWHM (001) of which the value is less than or equal to 0.30 and less than or equal to 0.60; 3. calcining the product at high temperature to obtain Ni with the general formula of 1-x-y Co x Mn y O Z Ternary precursor with FWHM (111) less than or equal to 0.60 and less than or equal to 0.80 is mixed with lithium and sintered to obtain the positive electrode material. The ternary precursor with uniform crystallinity can be obtained by the method, and the problems of high residual alkali content and low high nickel positive electrode circularity of the high nickel ternary precursor are solved.
Compared with the prior art, the method has the advantages that the half-peak width of the precursor after calcination is controlled by controlling the presintering condition and the sintering temperature, so that the ternary precursor with controllable crystallinity is obtained, the redundant moisture generated when the existing ternary precursor of the lithium battery is mixed and calcined with lithium salt is reduced, the precursor with uniform crystallinity is more beneficial to simplifying the positive electrode calcination process, the residual alkali amount on the surface of the ternary positive electrode material is reduced, and the cycle retention rate of the ternary positive electrode material is finally improved.
Drawings
FIG. 1 is an XRD pattern of the product obtained in step two of example 2 of the present invention;
FIG. 2 is an XRD pattern of the product obtained in step three of example 2 of the present invention;
FIG. 3 is an SEM image of the product of step three of example 2 of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings and examples:
the present invention will be described in detail with reference to the drawings, wherein modifications and variations are possible in light of the teachings of the present invention, without departing from the spirit and scope of the present invention, as will be apparent to those of skill in the art upon understanding the embodiments of the present invention.
The term (terms) as used herein generally has the ordinary meaning of each term as used in this field, in this disclosure, and in the special context, unless otherwise noted. Certain terms used to describe the present disclosure are discussed below, or elsewhere in this specification, to provide additional guidance to those skilled in the art in connection with the description herein.
Comparative example 1:
step one, water content is 13%, and the proportion of metal elements is 85:05:10, drying the nickel cobalt manganese hydroxide at 180 ℃, mixing the dried nickel cobalt manganese hydroxide with lithium hydroxide according to the lithium mixing amount of 1.05, and sintering to obtain the ternary positive electrode material.
Comparative example 2:
step one, 12% of water and 96% of metal elements: 02:02, drying the nickel cobalt manganese hydroxide at 160 ℃, mixing the dried nickel cobalt manganese hydroxide with lithium hydroxide according to the lithium mixing amount of 1.05, and sintering the mixture under the same process as in comparative example 1 to obtain the ternary positive electrode material.
Example 1:
step one, mixing the synthesized metal elements with the proportion of 85:05:10, dehydrating the nickel cobalt manganese hydroxide precursor until the water content is 13%;
step two, the moisture content is 13%, and the metal element proportion is 85:05:10, drying the nickel cobalt manganese hydroxide precursor at 180 ℃ and measuring half-peak width to obtain a process product;
calcining the process product obtained in the step two at 300 ℃, 450 ℃ and 600 ℃ for 30 minutes respectively, and washing and drying to obtain a ternary precursor;
and step four, mixing the ternary precursor obtained in the step three with lithium hydroxide according to the lithium distribution amount of 1.05, and sintering under the same process as that of the comparative example 1 to obtain the ternary positive electrode material.
Example 2:
step one, mixing the synthesized metal elements with the proportion of 85:05:10, dehydrating the nickel cobalt manganese hydroxide precursor until the water content is 13%;
step two, the moisture content is 13%, and the metal element proportion is 85:05:10, drying the nickel cobalt manganese hydroxide precursor at 180 ℃, measuring half-width, soaking in a mixed solution of ammonia water and ammonium nitrate for 1h, and then performing centrifugal washing and drying at 180 ℃ to obtain a process product;
and thirdly, respectively calcining the process products obtained in the second step for 30 minutes at the temperature of 300 ℃, 450 ℃ and 600 ℃ in sequence, and washing and drying the process products to obtain the ternary precursor.
And step four, mixing the ternary precursor obtained in the step three with lithium hydroxide according to the lithium distribution amount of 1.05, and sintering under the same process as that of the comparative example 1 to obtain the ternary positive electrode material.
Example 3:
step one, the ratio of the synthesized metal elements is 96:02:02, dehydrating the nickel cobalt manganese hydroxide precursor until the water content is 12%;
step two, 12% of water and 96% of metal elements: 02:02, drying at 180 ℃, measuring half-peak width, soaking in a mixed solution of sodium carbonate and sodium hydroxide for 2 hours, and then centrifugally washing and drying at 180 ℃ to obtain a process product;
calcining the process products obtained in the step two at 300 ℃, 450 ℃ and 600 ℃ for 30 minutes respectively, and washing and drying the process products to obtain a ternary precursor;
and step four, mixing the ternary precursor obtained in the step three with lithium hydroxide according to the lithium distribution amount of 1.05, and sintering under the same process as that of the comparative example 1 to obtain the ternary positive electrode material.
Example 4:
step one, the ratio of the synthesized metal elements is 96:02:02, dehydrating the nickel cobalt manganese hydroxide precursor until the water content is 12%;
step two, the moisture content is 11%, and the metal element proportion is 90:05: drying the nickel cobalt manganese hydroxide precursor at 160 ℃ and measuring the half-peak width to obtain a process product;
calcining the process product obtained in the step two at 300 ℃, 400, 500 ℃ and 600 ℃ for 30 minutes respectively in sequence, and washing and drying to obtain a ternary precursor;
and step four, mixing the ternary precursor obtained in the step three with lithium hydroxide according to the lithium distribution amount of 1.05, and sintering under the same process as that of the comparative example 1 to obtain the ternary positive electrode material.
Example 5:
step one, the ratio of the synthesized metal elements is 90:05:05, dehydrating the nickel cobalt manganese hydroxide precursor until the water content is 11%;
step two, the moisture content is 11%, and the metal element proportion is 90:05:05, drying the nickel cobalt manganese hydroxide precursor at 160 ℃, measuring half-width, soaking in a mixed solution of dilute sulfuric acid and ammonium sulfate for 1h, and then performing centrifugal washing and drying at 160 ℃ to obtain a process product;
calcining the process product obtained in the step two at 300 ℃, 400, 500 ℃ and 600 ℃ for 30 minutes respectively in sequence, and washing and drying to obtain a ternary precursor;
and step four, mixing the ternary precursor obtained in the step three with lithium hydroxide according to the lithium distribution amount of 1.05, and sintering under the same process as that of the comparative example 1 to obtain the ternary positive electrode material.
Example 6:
step one, mixing the synthesized metal elements with the proportion of 93:02:05, dehydrating the nickel cobalt manganese hydroxide precursor until the water content is 11%;
step two, 11% of water and 93% of metal elements: 02:05, drying the nickel cobalt manganese hydroxide precursor at 160 ℃, measuring half-peak width, soaking in a mixed solution of sodium carbonate and sodium hydroxide for 2 hours, and then centrifugally washing and drying at 160 ℃ to obtain a process product;
and thirdly, respectively calcining the process products obtained in the second step for 30 minutes at 300 ℃, 400 and 500 ℃ in sequence, and washing and drying the process products to obtain the ternary precursor.
And step four, mixing the ternary precursor obtained in the step three with lithium hydroxide according to the lithium distribution amount of 1.05, and sintering under the same process as that of the comparative example 1 to obtain the ternary positive electrode material.
Table 1: half-width data table for hydroxides of comparative example and hydroxides obtained in step two of example
Figure 279034DEST_PATH_IMAGE002
Table 2: step in the examples half-width data sheet for oxide precursor
Figure DEST_PATH_IMAGE004
The positive electrode materials obtained in the comparative examples and examples were subjected to residual lithium amount and electrochemical performance test, and the test data are shown in table 3 below:
Figure DEST_PATH_IMAGE006
table 1 shows XRD data of the products obtained after the end of step two in the comparative example and the example, and it can be seen from the data that the half-width of the nickel cobalt manganese hydroxide having different crystallinity can be adjusted by using the crystallinity modifier in step two to reach the desired range.
Table 2 shows XRD data of the product obtained after step three, which indicates that the half-width adjustment of the final product is achieved by performing step three after the treatment of step two, i.e. the control of the crystallinity of the product of step three is achieved by controlling the crystallinity of the product of step two.
Table 3 is a representation of the residual lithium amount and electrochemical performance data of the positive electrode material obtained by using the same sintering process, and the data can show that the precursor with uniform crystallinity obtained by using the method of the invention is sintered, so that the problems of high residual alkali content and low high nickel positive electrode circularity of the high nickel ternary precursor are solved.
FIG. 1 is an XRD pattern of the product obtained in step two of example 2, wherein the first peak is the (001) peak and the second peak is the (100) peak.
FIG. 2 is an XRD pattern of the product obtained in step three of example 2, wherein the first peak is the (111) peak and the second peak is the (200) peak.
FIG. 3 is an SEM image of the product from step three of example 2.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a ternary positive electrode material with low residual alkali content and high capacity retention rate is characterized by comprising the following steps: the method comprises the following steps:
step one, dehydrating nickel cobalt manganese hydroxide to obtain Ni with the general formula of 1-x-y Co x Mn y (OH) 2 Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and x+y is more than 0 and less than or equal to 0.2;
drying the nickel cobalt manganese hydroxide obtained in the first step at the temperature of less than 210 ℃ to ensure that the moisture content of the nickel cobalt manganese hydroxide is less than or equal to 0.2%, and then performing XRD test;
if FWHM (001) is less than 0.3, dispersing nickel cobalt manganese hydroxide in the aqueous solution, adding a first crystallinity regulator, and carrying out pickling;
if FWHM (001) > 0.6 is measured, dispersing nickel cobalt manganese hydroxide in the aqueous solution, adding a second crystallinity regulator, and carrying out pickling;
after immersion washing, a product with FWHM (001) of more than or equal to 0.30 and less than or equal to 0.60 is obtained;
calcining the product obtained in the step two at a high temperature of 300-600 ℃, and washing and drying the product with water to obtain FWHM (111) which is less than or equal to 0.60 and less than or equal to 0.80, wherein the general formula is Ni 1-x-y Co x Mn y O Z Is a ternary precursor of (a);
and step four, mixing the ternary precursor obtained in the step three with lithium, and sintering to obtain the ternary positive electrode material with low residual alkali content and high capacity retention rate.
2. The method of manufacturing according to claim 1, characterized in that: in the second step, the first crystallinity regulator is one or more of ammonia water, ammonium nitrate, ammonium sulfate and sodium hydroxide, and the total concentration of the first crystallinity regulator is 0.001-0.01 mol/L.
3. The method of manufacturing according to claim 1, characterized in that: in the second step, the second crystallinity regulator is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide, and the total concentration of the second crystallinity regulator is 0.01-0.5 mol/L.
4. The method of manufacturing according to claim 1, characterized in that: in the second step, FWHM (100) of the product after pickling is more than or equal to 0.15 and less than or equal to 0.50.
5. The method of manufacturing according to claim 1, characterized in that: in the third step, FWHM (200) of the calcined ternary precursor is not less than 0.7 and not more than 1.0.
6. The method of manufacturing according to claim 1, characterized in that: in the third step, the high-temperature calcination is gradient high-temperature calcination, and the calcination temperature is gradient increased at least two different temperature values during calcination, and the calcination is performed for 0.5-1 h, wherein the temperature values comprise 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ and 600 ℃.
7. The method of manufacturing according to claim 1, characterized in that: in the second step, the atmosphere introduced during drying is nitrogen or inert gas.
8. The method of manufacturing according to claim 1, characterized in that: in the third step, the atmosphere introduced during calcination is air or oxygen.
9. The method of manufacturing according to claim 1, characterized in that: mixing and sintering ternary precursor in the fourth step with lithium to obtain the surface Li of the ternary positive electrode material 2 CO 3 The residual quantity is less than or equal to 1500ppm, and the surface LiOH residual quantity is less than or equal to 1000ppm.
10. The method of manufacturing according to claim 1, characterized in that: and (3) the capacity retention rate of the ternary positive electrode material after 100-week circulation of the ternary precursor mixed lithium sintering in the step (IV) is more than 90%.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1717823A (en) * 2002-11-29 2006-01-04 清美化学股份有限公司 Method for preparing positive electrode active material for lithium secondary cell
JP2013173632A (en) * 2012-02-23 2013-09-05 Toyota Industries Corp Lithium-manganese-based composite oxide, positive electrode active material for secondary battery, and secondary battery
CN107968193A (en) * 2017-11-22 2018-04-27 江门市科恒实业股份有限公司 A kind of preparation method and battery of high power capacity tertiary cathode material
CN110534733A (en) * 2019-07-21 2019-12-03 浙江美都海创锂电科技有限公司 A kind of large single crystal lithium ion battery nickle cobalt lithium manganate method for preparing anode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1717823A (en) * 2002-11-29 2006-01-04 清美化学股份有限公司 Method for preparing positive electrode active material for lithium secondary cell
JP2013173632A (en) * 2012-02-23 2013-09-05 Toyota Industries Corp Lithium-manganese-based composite oxide, positive electrode active material for secondary battery, and secondary battery
CN107968193A (en) * 2017-11-22 2018-04-27 江门市科恒实业股份有限公司 A kind of preparation method and battery of high power capacity tertiary cathode material
CN110534733A (en) * 2019-07-21 2019-12-03 浙江美都海创锂电科技有限公司 A kind of large single crystal lithium ion battery nickle cobalt lithium manganate method for preparing anode material

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