CN113363459A - Nickel positive electrode material with stable high-temperature performance, preparation method of nickel positive electrode material, lithium battery positive electrode plate and lithium battery - Google Patents
Nickel positive electrode material with stable high-temperature performance, preparation method of nickel positive electrode material, lithium battery positive electrode plate and lithium battery Download PDFInfo
- Publication number
- CN113363459A CN113363459A CN202110390061.3A CN202110390061A CN113363459A CN 113363459 A CN113363459 A CN 113363459A CN 202110390061 A CN202110390061 A CN 202110390061A CN 113363459 A CN113363459 A CN 113363459A
- Authority
- CN
- China
- Prior art keywords
- nickel
- temperature
- positive electrode
- lithium battery
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
The invention relates to the technical field of lithium batteries and lithium battery nickel anode materials, and discloses a nickel anode material with stable high-temperature performance aiming at the problem that the high-temperature stability of the nickel anode material is influenced by lithium carbonate and the like, wherein the lithium carbonate concentration in the nickel anode material is less than or equal to 400ppm, and the lithium battery nickel anode material is realized by controlling the specific surface area of a precursor of the nickel anode material and the temperature of primary calcination. The high-nickel ternary cathode material disclosed by the invention pays more attention to the lithium carbonate content in the nickel cathode material. The content of lithium carbonate hidden in the nickel anode material is low, so that the stability of the nickel anode material and the prepared lithium battery after high-temperature storage and the stability of the lithium battery in circulating work at high temperature can be effectively improved.
Description
Technical Field
The invention relates to the technical field of lithium batteries and nickel cathode materials of lithium batteries, in particular to a nickel cathode material with stable high-temperature performance, a preparation method of the nickel cathode material, a lithium battery cathode plate and a lithium battery.
Background
With the increasing demand of high energy density lithium ion batteries, high nickel ternary materials are gaining wide attention due to their high capacity and low raw material cost. However, the high-temperature stability of the high-nickel ternary cathode material, including high-temperature cycle performance and high-temperature storage performance, is relatively low, mainly because the high-nickel ternary cathode material has very low stability in air and is easily decomposed to generate impurities such as lithium hydroxide and lithium carbonate, i.e., residual lithium. Lithium carbonate and the like generate gas in the battery cycle process, particularly under the high-temperature condition, and the cycle and storage performance of materials and batteries are seriously influenced. In addition, the high-compaction preparation of the positive plate can easily cause the secondary particles of the high-nickel ternary positive material to crack or break, and the gas generated by the lithium carbonate in the high-temperature circulation and storage processes of the lithium battery can further induce the particle breaking, so that the battery capacity is attenuated, and therefore, the control of the residual lithium content of the nickel positive material has important significance for maintaining the high-temperature performance of the lithium battery. Chinese patent CN106770244A discloses that the stability of the material is evaluated by measuring the content of lithium carbonate on the surface by acid-base neutralization titration, but the patent document does not give any teaching how to obtain a high nickel cathode material with high temperature stability.
Disclosure of Invention
The invention aims to provide a nickel positive electrode material with stable high-temperature performance aiming at the problem that the high-temperature stability of the nickel positive electrode material is influenced by lithium carbonate and the like, so as to improve the high-temperature stability of a lithium battery prepared from the high-nickel positive electrode material.
Another object of the present invention is to provide a method for preparing the nickel cathode material with stable high temperature performance.
Still another object of the present invention is to provide a positive electrode sheet for a lithium battery and a lithium battery using the nickel positive electrode material.
The invention provides the following technical scheme:
a nickel anode material with stable high-temperature performance has a general formula as follows:
Li1+a(NixMnyCozAb)1-aO2wherein:
0.5< x < 0.9, 0.1< z < 0.2 and x + y + z 1,
0<b≤0.01，
a is a high-nickel ternary anode doping element,
0.01≤a≤0.2，
the lithium carbonate concentration in the nickel cathode material is less than or equal to 400ppm expressed by carbon content.
At present, research aiming at residual lithium in the nickel cathode material is mainly focused on surface lithium carbonate, and the research on controlling the content of internal lithium carbonate is less. The research of the inventor finds that the high-temperature stability and the cycling stability of the lithium ion battery are influenced more obviously by the content of the internal lithium carbonate compared with the surface lithium carbonate. Therefore, the concentration of the lithium carbonate in the nickel cathode material provided by the technical scheme is mainly controlled, the quality content of the lithium carbonate in the nickel cathode material is controlled below 400ppm, the high-temperature performance of the lithium battery is remarkably improved, and particularly the high-temperature performance of the soft package lithium ion battery is improved. After high-temperature circulation or storage, the lithium ion battery such as a soft package lithium ion battery can keep higher capacity retention rate and capacity recovery rate, and the cycle performance of the lithium battery is improved.
Preferably, a is at least one of Al, Mg, Zr, and Ti.
The preparation method of the nickel cathode material with stable high-temperature performance is characterized by comprising the following steps:
(1) measured according to the quantityPrecursor Ni of nickel anode materialxMnyCozOOH and LiOH 2H2O, high-speed mixing to obtain a mixture, wherein the precursor NixMnyCozOOH specific surface area less than or equal to 25m2/g；
(2) Calcining the mixture at high temperature for the first time in an oxygen atmosphere, and then crushing to obtain crushed materials;
(3) mixing the crushed material with an oxide of A according to the amount and supplementary LiOH.2H according to the amount2Mixing O at a high speed, then calcining for the second time in an oxygen atmosphere, and crushing and sieving to obtain a nickel anode material;
current driver NixMnyCozSpecific surface area of OOH>20m2When the temperature is/g, the temperature of the first high-temperature calcination in the step (2) is 850-875 ℃;
current driver NixMnyCozOOH specific surface area less than or equal to 20m2When the temperature is/g, the temperature of the first high-temperature calcination in the step (2) is 800-875 ℃.
In the preparation method of the nickel cathode material, the content of lithium carbonate in the nickel cathode material can be reduced by controlling the specific surface area of the precursor of the inner cathode material and the temperature of primary calcination. The inventors' studies found that the specific surface area and the primary calcination temperature are important factors affecting the internal residual lithium carbonate, wherein the specific surface area is the main factor. The large specific surface area tends to generate lithium carbonate as a by-product on the particle surface and between the grains, and tends to cause the accumulation of lithium carbonate inside compared with the calcination temperature and the like. While increasing the temperature of the primary calcination can reduce the internal lithium carbonate content, this is probably because the high-temperature calcination tends to keep the calcined particle large in size, the specific surface area is relatively reduced, and therefore the internal lithium carbonate content is reduced. Since the increase in the calcination temperature has a small effect on the internal lithium carbonate content compared to the specific surface area which is sufficiently large to result in an inability to reduce the internal lithium carbonate content to 400ppm even if the calcination temperature is increased, the specific surface area BET of a suitable precursor should be 25m or less2(ii) in terms of/g. In the step (3), if necessary, LiOH 2H is supplemented2O is selected from nickel anode according to actual conditions0-10 mol% of the total molar amount of the material.
As preferred in the process of the invention, the precursor NixMnyCozOOH specific surface area less than or equal to 10m2(ii) in terms of/g. When the specific surface is less than or equal to 10m2When per g, the specific surface area is less than or equal to 25m under the same preparation conditions2The internal lithium carbonate content can be reduced very significantly, in principle by more than 100%.
Preferably, the oxygen flow rate during the calcination in the oxygen atmosphere in the step (2) is 1.5 to 3L/min, and the calcination time is 8 to 12 hours.
Preferably, in the step (3), the temperature of the secondary calcination is 750-850 ℃, the oxygen flow rate is 1.0-3.0 mL/min, and the calcination time is 10-15 hours.
A lithium battery positive plate using the nickel positive electrode material or the nickel positive electrode material obtained by the preparation method.
A lithium battery using the nickel anode material or the nickel anode material obtained by the preparation method or the lithium battery anode sheet. Compared with other lithium batteries under the same condition, the lithium battery provided by the technical scheme of the invention has obviously improved cycle stability after high-temperature work and storage.
The invention has the following beneficial effects:
the invention provides a high-nickel ternary cathode material with stable high-temperature performance, and the lithium carbonate content in the nickel cathode material is concerned. The content of lithium carbonate hidden in the nickel anode material is low, and the content of the lithium carbonate is not more than 400ppm expressed by carbon content, so that the stability of the nickel anode material and the prepared lithium battery after high-temperature storage and the stability of the lithium battery in circulating work at high temperature can be effectively improved.
Drawings
FIG. 1 is a high temperature cycle capacity retention curve at 45 ℃ for pouch batteries made from nickel positive electrode materials of examples 1-4.
Detailed Description
The following further describes the embodiments of the present invention.
The starting materials used in the present invention are commercially available or commonly used in the art, unless otherwise specified, and the methods in the following examples are conventional in the art, unless otherwise specified.
In the following examples with Li1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2For the purpose of illustration, it is shown,
that is, a is 0.02, x is 0.83, y is 0.12, z is 0.05, and b is 0.002;
the carbon sulfur analyzer used was a Leco brand model CS230 carbon sulfur analyzer.
Example 1
Nickel anode material Li with stable high-temperature performance1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2The preparation method comprises the following steps:
(1) measuring precursor Ni of nickel anode material according to chemical equivalent0.83Mn0.12Co0.05OOH and LiOH 2H2O, high-speed mixing to obtain a mixture, wherein the precursor Ni0.83Mn0.12Co0.05OOH specific surface area of 10m2/g；
(2) Calcining the mixture for the first time at 820 ℃ for 10 hours in an oxygen atmosphere at the oxygen flow rate of 2L/min, and then crushing to obtain crushed materials;
(3) mixing the crushed material with Al measured according to a certain weight2O3And a supplement of 5 mol% LiOH 2H2And O is mixed at a high speed, then the mixture is calcined for 12 hours at 800 ℃ in an oxygen atmosphere, the flow rate of oxygen is 1.5mL/min, and then the mixture is crushed and sieved to obtain the nickel anode material.
Example 2
Nickel anode material Li with stable high-temperature performance1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2The difference from example 1 is that the first calcination temperature in step (1) was 840 ℃.
Example 3
Nickel anode material Li with stable high-temperature performance1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2Comparison with example 1Characterized in that the temperature of the first calcination in the step (1) is 850 ℃.
Example 4
Nickel anode material Li with stable high-temperature performance1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2The difference from example 1 is that the first calcination temperature in step (1) was 875 ℃.
Example 5
Nickel anode material Li with stable high-temperature performance1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2The difference from example 1 is that the first calcination temperature in step (1) was 800 ℃.
Example 6
Nickel anode material Li with stable high-temperature performance1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2The difference from example 1 is that Ni is a precursorxMnyCozOOH having a specific surface area of 5m2/g。
Example 7
Nickel anode material Li with stable high-temperature performance1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2The difference from example 1 is that Ni is a precursorxMnyCozOOH having a specific surface area of 15m2/g。
Example 8
Nickel anode material Li with stable high-temperature performance1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2The difference from example 1 is that Ni is a precursorxMnyCozOOH specific surface area of 20m2/g。
Example 9
Nickel anode material Li with stable high-temperature performance1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2The difference from embodiment 1 is that,precursor NixMnyCozOOH having a specific surface area of 25m2The temperature of the first calcination in the step (1) is 850 ℃.
Example 10
Nickel anode material Li with stable high-temperature performance1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2The difference from example 1 is that Ni is a precursorxMnyCozOOH having a specific surface area of 25m2The temperature of the first calcination in the step (1) is 875 ℃.
Comparative example 1
Nickel cathode material Li1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2The difference from example 1 is that Ni is used as a precursorxMnyCozOOH having a specific surface area of 25m2/g。
Comparative example 2
Nickel cathode material Li1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2The difference from example 1 is that Ni is used as a precursorxMnyCozOOH having a specific surface area of 25m2The temperature of the first calcination in the step (1) is 840 ℃.
Performance test of the nickel positive electrode materials of examples and comparative examples
1. Internal lithium carbonate concentration test
(1) Test method
S1: taking 5g of the nickel cathode material of each example and comparative example, dissolving the 5g of the nickel cathode material in 100mL (V1) of ethanol, stirring for 1 hour, filtering, taking a certain volume (V2) of filtrate, titrating the filtrate by using a hydrochloric acid solution with the concentration of 0.5mol/L in an automatic titrator to obtain 2 voltage plateaus, wherein the end point of the first plateaus is a1(mL), the end point of the second plateaus is a2(mL), calculating the lithium carbonate content on the surface of the nickel cathode material according to the following formula, and further calculating the carbon content on the surface:
surface lithium carbonate content: li2CO3(wt％)＝73.8909*(a2-a1)*c/(1000*m*V2/V1)；
Surface carbon content: t1 (wt%) (12.0107 × a2-a1) × c/(1000 × m × V2/V1);
wherein c is the concentration of hydrochloric acid, and m is the mass of the nickel anode material;
s2, calcining 1g of the same nickel cathode material in a carbon-sulfur analyzer at 1600 ℃ in the same time, and measuring the carbon content T2 (wt%);
s3: the content of hidden residual lithium in the nickel cathode material is expressed as carbon concentration, namely T2-T1 (wt%), and the results are shown in Table 1.
(2) Test results
Table 1 lithium carbonate concentration inside the nickel positive electrode material in each example and comparative example
| Sample (I) | BET m2/g | Temperature/. degree.C | T1(wt./ppm) | T2(wt./ppm) | T2-T1(wt./ppm) |
| Example 1 | 10 | 820 | 410 | 600 | 190 |
| Example 2 | 10 | 840 | 301 | 450 | 149 |
| Example 3 | 10 | 850 | 285 | 425 | 140 |
| Example 4 | 10 | 875 | 280 | 400 | 120 |
| Example 5 | 10 | 800 | 420 | 650 | 230 |
| Example 6 | 5 | 820 | 460 | 560 | 100 |
| Example 7 | 15 | 820 | 395 | 675 | 280 |
| Example 8 | 20 | 820 | 390 | 730 | 340 |
| Example 9 | 25 | 850 | 300 | 680 | 380 |
| Example 10 | 25 | 875 | 280 | 650 | 370 |
| Comparative example 1 | 25 | 820 | 395 | 850 | 545 |
| Comparative example 2 | 25 | 840 | 310 | 712 | 402 |
As can be seen from the above table, the nickel cathode material Li prepared by the method of the present invention1.02(Ni0.83Co0.12Mn0.05Al0.002)0.98O2Has a lower internal lithium carbonate concentration, wherein:
as can be seen from examples 1 and 2 to 5, the lithium carbonate content in the nickel positive electrode material gradually decreased as the primary calcination temperature increased. As can be seen from comparison of example 1 with examples 6, 7 and 8 and comparative example 1, the internal lithium carbonate content is lower as the specific surface area of the precursor is smaller, wherein when BET is less than or equal to 10m, at a constant calcination temperature2At/g, there was a significant decrease in lithium carbonate content. As can be seen from comparison of examples 9 and 10 with comparative examples 1 and 2, when BET is high to some extent, the internal lithium carbonate content can be reduced by increasing the calcination temperature, but the effect of reduction is limited.
2. High temperature storage performance of nickel anode material
The nickel positive electrode materials of examples 1 and 2 and comparative examples 1 and 2 were fabricated into pouch batteries having the following structure:
and (3) positive electrode: coating slurry of a nickel anode material on an aluminum foil to prepare an anode;
negative electrode: a lithium negative electrode;
electrolyte solution: 1mol L-1EC/EMC/DMC of LiPF6 (1:1:1, wt%).
Placing the prepared soft package battery at 55 ℃ for 3 months, and then carrying out charge and discharge tests under the following test conditions: the results are shown in Table 2, at 25 ℃ and 100% SOC, 2.7-4.2V, 1C/1C.
Table 2 pouch cell high temperature storage 3 months test results
| Sample (I) | Capacity retention (%) | Capacity recovery ratio (%) | Volume increase (%) |
| Example 1 | 88.02 | 89.40 | 112.54 |
| Example 2 | 89.09 | 90.53 | 105.34 |
| Comparative example 1 | 86.84 | 88.81 | 121.76 |
| Comparative example 2 | 87.05 | 88.95 | 120.10 |
As can be seen from the above table, the high-temperature storage performance of the battery core is better for the nickel cathode material with low lithium carbonate content inside. Of these, comparative example 1 performed the worst of the 4 samples for capacity retention, capacity recovery and volume retention due to the highest lithium carbonate content inside.
3. High temperature cycle performance of nickel positive electrode materials the nickel positive electrode materials of examples 1 and 2 and comparative examples 1 and 2 were fabricated into pouch cells, and then high temperature cycle charge and discharge tests were performed at a working temperature of 45 ℃, with the following test conditions: the change curve of the capacity retention rate of each soft package battery along with the cycle number after high-temperature circulation at 45 ℃ and 1C/1C and 2.7-4.2V is shown in figure 1.
As can be seen from fig. 1, the internal lithium carbonate content in the nickel positive electrode material significantly affects its high temperature cycle performance. The pouch battery corresponding to example 2 had the highest high-temperature cycle retention, and the pouch battery corresponding to comparative example 1 had the lowest capacity retention, and the cycle results were explained by the internal lithium carbonate content of the material in table 1.
Thus, in general, the lithium carbonate content inside the secondary particles of the high nickel material can affect the high temperature cycling and storage performance of its cells.
Claims (8)
1. A nickel cathode material with stable high-temperature performance is characterized in that the general formula of the nickel cathode material is as follows:
Li1+a(NixMnyCozAb)1-aO2wherein:
0.5< x < 0.9, 0.1< z < 0.2 and x + y + z =1,
0<b≤0.01，
a is a high-nickel ternary anode material doping element,
0.01≤a≤0.2，
the lithium carbonate concentration in the nickel cathode material is less than or equal to 400ppm expressed by carbon content.
2. The high-temperature performance stable nickel positive electrode material according to claim 1, wherein a is at least one of Al, Mg, Zr, and Ti.
3. A method for preparing a nickel positive electrode material stable in high temperature performance according to any one of claims 1 or 2, comprising the steps of:
(1) measuring precursor Ni of nickel anode material according to quantityxMnyCozOOH and LiOH are subjected to 2H2O, high-speed mixing to obtain a mixture, wherein the precursor NixMnyCozOOH specific surface area less than or equal to 25m2/g；
(2) Calcining the mixture at high temperature for the first time in an oxygen atmosphere, and then crushing to obtain crushed materials;
(3) crushed materials, an oxide A which is taken according to the amount and supplementary LiOH which is taken according to the requirement are subjected to 2H2Mixing O at a high speed, then calcining for the second time in an oxygen atmosphere, and crushing and sieving to obtain a nickel anode material;
current driver NixMnyCozSpecific surface area of OOH>20m2When the temperature is/g, the temperature of the first high-temperature calcination in the step (2) is 850-875 ℃;
current driver NixMnyCozOOH specific surface area less than or equal to 20m2When the temperature is/g, the temperature of the first high-temperature calcination in the step (2) is 800-875 ℃.
4. The method for preparing the nickel cathode material with stable high-temperature performance according to claim 3, wherein a precursor Ni is usedxMnyCozOOH specific surface area less than or equal to 10m2/g。
5. The method for preparing a nickel cathode material with stable high-temperature performance according to claim 3, wherein the flow rate of oxygen during the calcination in the oxygen atmosphere in the step (2) is 1.5 to 3L/min, and the calcination time is 8 to 12 hours.
6. The method for preparing the nickel cathode material with stable high-temperature performance according to claim 3, wherein the temperature of the secondary calcination in the step (3) is 750-850 ℃, the oxygen flow rate is 1.0-3.0 mL/min, and the calcination time is 10-15 hours.
7. A positive electrode sheet for a lithium battery using the nickel positive electrode material according to any one of claims 1 to 2 or the nickel positive electrode material obtained by the production method according to any one of claims 3 to 6.
8. A lithium battery using the nickel positive electrode material according to any one of claims 1 to 2 or the nickel positive electrode material obtained by the production method according to any one of claims 3 to 6 or the positive electrode sheet for a lithium battery according to claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110390061.3A CN113363459B (en) | 2021-04-12 | 2021-04-12 | Nickel positive electrode material with stable high-temperature performance, preparation method of nickel positive electrode material, lithium battery positive electrode plate and lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110390061.3A CN113363459B (en) | 2021-04-12 | 2021-04-12 | Nickel positive electrode material with stable high-temperature performance, preparation method of nickel positive electrode material, lithium battery positive electrode plate and lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113363459A true CN113363459A (en) | 2021-09-07 |
| CN113363459B CN113363459B (en) | 2022-05-13 |
Family
ID=77525091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110390061.3A Active CN113363459B (en) | 2021-04-12 | 2021-04-12 | Nickel positive electrode material with stable high-temperature performance, preparation method of nickel positive electrode material, lithium battery positive electrode plate and lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113363459B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090121198A1 (en) * | 2004-11-02 | 2009-05-14 | Nippon Mining & Metals Co., Ltd. | Cathode Material for Lithium Secondary Battery and Manufacturing Method Thereof |
| CN110192297A (en) * | 2016-12-26 | 2019-08-30 | 住友化学株式会社 | Positive active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery |
| CN110620230A (en) * | 2019-08-30 | 2019-12-27 | 恒大新能源科技集团有限公司 | Positive active material, preparation method thereof, positive plate and lithium battery |
| CN111052463A (en) * | 2017-12-27 | 2020-04-21 | 日立金属株式会社 | Positive electrode active material for lithium ion secondary battery, method for producing positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery |
| CN111162249A (en) * | 2018-11-07 | 2020-05-15 | 天津国安盟固利新材料科技股份有限公司 | Positive electrode material for improving first discharge capacity and preparation method thereof |
| CN111653767A (en) * | 2020-02-27 | 2020-09-11 | 乳源东阳光磁性材料有限公司 | Washing process and preparation method of high-nickel polycrystalline ternary cathode material |
| CN111971826A (en) * | 2018-04-06 | 2020-11-20 | 松下知识产权经营株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN112133890A (en) * | 2019-06-24 | 2020-12-25 | 比亚迪股份有限公司 | Lithium-containing ternary precursor and preparation method thereof, ternary cathode material and preparation method thereof, and lithium ion battery |
| CN112151775A (en) * | 2019-06-28 | 2020-12-29 | 宁德时代新能源科技股份有限公司 | Ternary cathode material with low gas production and high capacity |
| CN112340784A (en) * | 2020-09-30 | 2021-02-09 | 宜宾锂宝新材料有限公司 | Method for reducing residual alkali on surface of high-nickel ternary cathode material, high-nickel ternary cathode material prepared by method and lithium ion battery |
-
2021
- 2021-04-12 CN CN202110390061.3A patent/CN113363459B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090121198A1 (en) * | 2004-11-02 | 2009-05-14 | Nippon Mining & Metals Co., Ltd. | Cathode Material for Lithium Secondary Battery and Manufacturing Method Thereof |
| CN110192297A (en) * | 2016-12-26 | 2019-08-30 | 住友化学株式会社 | Positive active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery |
| CN111052463A (en) * | 2017-12-27 | 2020-04-21 | 日立金属株式会社 | Positive electrode active material for lithium ion secondary battery, method for producing positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery |
| CN111971826A (en) * | 2018-04-06 | 2020-11-20 | 松下知识产权经营株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN111162249A (en) * | 2018-11-07 | 2020-05-15 | 天津国安盟固利新材料科技股份有限公司 | Positive electrode material for improving first discharge capacity and preparation method thereof |
| CN112133890A (en) * | 2019-06-24 | 2020-12-25 | 比亚迪股份有限公司 | Lithium-containing ternary precursor and preparation method thereof, ternary cathode material and preparation method thereof, and lithium ion battery |
| CN112151775A (en) * | 2019-06-28 | 2020-12-29 | 宁德时代新能源科技股份有限公司 | Ternary cathode material with low gas production and high capacity |
| CN110620230A (en) * | 2019-08-30 | 2019-12-27 | 恒大新能源科技集团有限公司 | Positive active material, preparation method thereof, positive plate and lithium battery |
| CN111653767A (en) * | 2020-02-27 | 2020-09-11 | 乳源东阳光磁性材料有限公司 | Washing process and preparation method of high-nickel polycrystalline ternary cathode material |
| CN112340784A (en) * | 2020-09-30 | 2021-02-09 | 宜宾锂宝新材料有限公司 | Method for reducing residual alkali on surface of high-nickel ternary cathode material, high-nickel ternary cathode material prepared by method and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113363459B (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6380608B2 (en) | Method for producing lithium composite compound particle powder, method for using lithium composite compound particle powder in non-aqueous electrolyte secondary battery | |
| US10056612B2 (en) | Lithium manganate particles for non-aqueous electrolyte secondary battery, process for producing the same, and nonaqueous electrolyte secondary battery | |
| CN110931738B (en) | Complex-phase high-voltage cathode material and preparation method thereof | |
| EP2910528A1 (en) | Li-Ni COMPLEX OXIDE PARTICLE POWDER AND NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY | |
| KR20120132485A (en) | Positive electrode active material precursor particulate powder and positive electrode active material particulate powder, and non-aqueous electrolyte secondary battery | |
| CN109461893B (en) | Novel lithium ion battery anode material and preparation method thereof | |
| EP4159897A1 (en) | Single-crystal-type multi-element positive electrode material, and preparation method therefor and application thereof | |
| WO2012118052A1 (en) | Non-aqueous electrolyte secondary battery, and positive electrode for non-aqueous electrolyte secondary battery | |
| CN114068912B (en) | Binary high-nickel monocrystal positive electrode material and preparation method thereof | |
| CN114620777B (en) | Ultrahigh nickel ternary precursor and preparation method thereof | |
| CN114436344B (en) | Preparation method and application of positive electrode material precursor with large channel | |
| EP4321486A1 (en) | Fluorine-doped lithium positive electrode material, preparation method therefor and use thereof | |
| CN113582254B (en) | Layered positive electrode material and preparation method and application thereof | |
| CN113903909A (en) | Cobalt nano coating modified nickel-rich low-cobalt single crystal multi-element positive electrode material and preparation method thereof | |
| CN112133904A (en) | High-nickel ternary cathode material of lithium ion battery and preparation method thereof | |
| CN113363459B (en) | Nickel positive electrode material with stable high-temperature performance, preparation method of nickel positive electrode material, lithium battery positive electrode plate and lithium battery | |
| CN114604904B (en) | Preparation method and application of tellurium-doped lithium cobalt oxide precursor | |
| CN116053458A (en) | Doped NCM ternary positive electrode material, preparation method thereof, positive electrode and lithium ion battery | |
| CN115911315A (en) | High-nickel anode precursor material and preparation method and application thereof | |
| CN114455643A (en) | High-rate high-nickel single crystal NCA precursor and preparation method thereof | |
| CN113764671A (en) | Anode material of lithium ion battery | |
| CN112624209A (en) | Na-Ti-Mg co-doped ternary material and preparation method and application thereof | |
| CN115986108A (en) | Ternary polycrystalline positive electrode material and preparation method thereof | |
| CN117902637A (en) | Preparation method of Na-doped cobalt carbonate, positive electrode material and lithium battery | |
| CN117317168A (en) | Metal atom doped layered oxide positive electrode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20211115 Address after: 311215 No. 855, Jianshe Second Road, economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant after: Wanxiang A123 Co.,Ltd. Address before: 311215 No. 855, Jianshe Second Road, Xiaoshan Economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant before: Wanxiang A123 Co.,Ltd. Applicant before: WANXIANG GROUP Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |