CN110776021A - Nickel cobalt lithium manganate positive electrode material and preparation method thereof, lithium ion battery positive electrode slurry, lithium ion battery positive electrode and lithium ion battery - Google Patents
Nickel cobalt lithium manganate positive electrode material and preparation method thereof, lithium ion battery positive electrode slurry, lithium ion battery positive electrode and lithium ion battery Download PDFInfo
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Abstract
The invention provides a nickel cobalt lithium manganate positive electrode material and a preparation method thereof, lithium ion battery positive electrode slurry, a lithium ion battery positive electrode and a lithium ion battery. The preparation method of the nickel cobalt lithium manganate positive electrode material comprises the following steps: and mixing the precursor of the nickel cobalt lithium manganate positive electrode material with a copper source, carrying out first calcination, and then adding a lithium source to carry out second calcination to obtain the nickel cobalt lithium manganate positive electrode material. The nickel cobalt lithium manganate positive electrode material is prepared by the preparation method. The lithium ion battery anode slurry comprises the nickel cobalt manganese oxideA lithium positive electrode material. The lithium ion battery anode is prepared by using the lithium ion battery anode slurry. The lithium ion battery comprises the lithium ion battery anode. The application provides a nickel cobalt lithium manganate cathode material, is Cu
2+The doped anode material can effectively improve the structural stability and the conductivity of the material, thereby improving the electrochemical properties such as the rate capability, the cycle performance and the like of the anode material.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a nickel cobalt lithium manganate positive electrode material and a preparation method thereof, lithium ion battery positive electrode slurry, a lithium ion battery positive electrode and a lithium ion battery.
Background
As an environment-friendly lithium secondary battery, the lithium ion battery has been widely used in various electronic fields such as the 3C field and the EV field due to its characteristics of high specific energy, high specific power, long cycle life, good high and low temperature performance, and the like. With the continuous expansion of the application field, higher requirements are put forward on the energy density, the rate capability and the cycle performance of the lithium ion battery. At present, the method for improving the energy density mainly comprises the steps of gradually changing from lithium iron phosphate to lithium nickel cobalt manganese oxide positive electrode materials, lithium nickel cobalt aluminum positive electrode materials, lithium-rich manganese-based positive electrode materials and the like from improving the gram capacity of the positive electrode materials. However, the nickel cobalt lithium manganate positive electrode material has poor conductivity, large internal resistance and other problems, and finally affects rate performance, cycle performance and the like of the lithium ion battery.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a nickel cobalt lithium manganate positive electrode material and a preparation method thereof, lithium ion battery positive electrode slurry, a lithium ion battery positive electrode and a lithium ion battery, so as to solve the problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a nickel cobalt lithium manganate positive electrode material comprises the following steps:
mixing a precursor of the nickel cobalt lithium manganate positive electrode material with a copper source, carrying out first calcination, and then adding a lithium source to carry out second calcination to obtain a lithium nickel cobalt lithium manganate positive electrode material Li (Ni)
xCo
yMn
1-x-y-zCu
z)O
2Wherein x is more than 0 and less than 1,0＜y＜1，0＜z≤0.2，0＜1-x-y-z＜1；
the mol ratio of the nickel cobalt lithium manganate positive electrode material precursor to the copper element in the copper source is 1: (0.01-0.1), wherein the molar ratio of the precursor of the nickel cobalt lithium manganate positive electrode material to the lithium element in the lithium source is (0.5-1): 1.
Cu
2+the cathode material has special peripheral electron arrangement, can effectively improve the conductivity of the cathode material, further improves the rate capability and the cycle performance of the lithium ion battery, and adopts Cu to improve the rate capability and the cycle performance of the lithium ion battery
2+Substituted part of Mn
4+Enhancing the structural stability.
The precursor and copper doping step-by-step preparation method can ensure the performance of the precursor to the maximum extent, and further ensure the performance of the finally obtained anode material. In contrast, the method adopted by the application is superior to the one-step method of the manganese source, the cobalt source, the nickel source, the copper source and the lithium source adopted in the prior art.
Optionally, the molar ratio of the nickel cobalt lithium manganate positive electrode material precursor to the copper element in the copper source may be 1: 0.01, 1: 0.02, 1: 0.03, 1: 0.04, 1: 0.05, 1: 0.06, 1: 0.07, 1: 0.08, 1: 0.09, 1: 0.1 and 1: (0.01-0.1), the molar ratio of the nickel cobalt lithium manganate positive electrode material precursor to the lithium element in the lithium source can be 0.5: 1. 0.6: 1. 0.7: 1. 0.8: 1. 0.9: 1. 1: 1 is and (0.5-1): 1.
preferably, the preparation method of the precursor of the nickel cobalt lithium manganate positive electrode material comprises the following steps:
preparing a manganese source, a nickel source and a cobalt source into a mixed solution, then adding an alkali source, and reacting to obtain a precursor of the nickel cobalt lithium manganate positive electrode material;
preferably, the concentration of the metal ions in the mixed solution is 1.5-2.0 mol/L;
preferably, the manganese source comprises manganese sulfate, the nickel source comprises nickel sulfate, and the cobalt source comprises cobalt sulfate.
General formula (Ni) of precursor of nickel cobalt lithium manganate positive electrode material
xCo
yMn
1-x-y-z)(OH)
2X is more than 0 and less than 1, y is more than 0 and less than 1, and z is more than 0 and less than or equal to 0.2. The properties of the precursor may influenceAnd doping copper to obtain the performance of the cathode material. The liquid phase reaction, the control of the concentration of metal ions in the mixed solution and the optimization of the raw materials are all adopted to ensure the performance of the precursor to the greatest extent so as to be beneficial to copper doping and the performance of the prepared anode material is the best.
The manganese source, nickel source and cobalt source may be any of other manganese salts, nickel salts and cobalt salts, for example, carbonates and nitrates, and sulfates are preferably used as the raw material because of their good solubility and stable performance (non-oxidative and other unstable performances).
Alternatively, the concentration of the metal ions in the mixed solution may be any value between 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, 2.0mol/L, and 1.5-2.0 mol/L.
More preferably, the alkali source comprises aqueous sodium hydroxide and/or aqueous ammonia;
preferably, the alkali source comprises a mixture of alkali sources in a volume ratio of 1: (1-3) 2-4mol/L aqueous sodium hydroxide solution and 1-1.5mol/L aqueous ammonia;
preferably, the pH value of the reaction system is adjusted to 10-12 by adding the alkali source;
preferably, the temperature of the reaction is 40-60 ℃.
The alkali source is selected to optimize the process of forming the hydroxide precipitate and to reduce impurities in the precursor. Theoretically, the slower the generation speed, the better the shape and performance of the precipitate, and the less the impurities; the optimization of the alkali source concentration, the adjustment of the pH end point of the reaction system and the reaction temperature is to achieve the balance of precipitation performance and speed and improve the production efficiency on the basis of ensuring the quality of the precursor.
Alternatively, the volume ratio of the aqueous sodium hydroxide solution to the aqueous ammonia may be 1: 1. 1: 2. 1: 3 and 1: (1-3) any value therebetween; the concentration of the sodium hydroxide aqueous solution can be any value between 2mol/L, 3mol/L, 4mol/L and 2-4mol/L, and the concentration of the ammonia water can be any value between 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L and 1-1.5 mol/L; the end point of adding the alkali source to adjust the pH value of the reaction system can be any value between 10, 11, 12 and 10-12; the reaction temperature may be any of 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ and 40-60 ℃.
Preferably, the method also comprises a step of cleaning the product after the reaction is finished;
preferably, the step of washing the product comprises: washing the product with deionized water, and then putting the product into absolute ethyl alcohol;
preferably, the product is put into absolute ethyl alcohol for treatment for 0.5 to 1.5 hours;
preferably, the step of washing the product further comprises a drying step;
preferably, the drying temperature is 80-100 ℃ and the drying time is 10-14 h.
The purpose of the deionized water cleaning is to remove water-soluble impurities on the surface of the obtained precipitate, and the purpose of the absolute ethyl alcohol soaking is to further remove the impurities. The drying temperature and time are preferably selected to avoid high temperature to reduce the stability of the precursor, generate impurities, and ensure the drying efficiency.
Alternatively, the time for treating the product in absolute ethyl alcohol can be any value between 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h and 0.5-1.5 h; the drying temperature can be any value between 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ and 80-100 ℃, and the drying time can be any value between 10h, 11h, 12h, 13h, 14h and 10-14 h.
Preferably, the lithium source comprises lithium carbonate and/or lithium hydroxide;
preferably, the lithium source is lithium carbonate;
preferably, the copper source is basic copper carbonate;
preferably, the molar ratio of the nickel cobalt lithium manganate positive electrode material precursor to the copper carbonate is 1: (0.02-0.06);
preferably, the precursor of the nickel cobalt lithium manganate positive electrode material is Ni
0.5Co
0.2Mn
0.3-z(OH)
2、Ni
0.6Co
0.2Mn
0.2-z(OH)
2Or Ni
0.8Co
0.1Mn
0.1-z(OH)
2。
Lithium carbonate is used as a lithium source, basic copper carbonate is used as a copper source, carbon dioxide is generated by decomposition in the sintering process, impurities such as sulfate radicals and nitrate radicals are not introduced, and the obtained positive electrode material has more excellent performance.
When Cu
2+When the doping proportion is smaller, the crystallinity and the order degree of the material can be reduced; when Cu
2+The doping proportion is increased within a certain range, the interlayer spacing of the material is increased, the embedding and the separation of ions are facilitated, the rate capability of the material is further improved, and Cu
2+The doped lithium ion battery has larger ionic radius, and the unit cell parameters of the doped lithium ion battery are increased, so that the impedance of the lithium ion battery is reduced in the charging and discharging processes, the cycle performance of the lithium ion battery is improved, and the energy density of the lithium ion battery is influenced when the increase proportion is too large.
On the basis of controlling the amount of copper doping, the optimal performance of the material can be obtained by optimizing the amount of nickel and cobalt. In addition, Ni is a precursor of the above-mentioned nickel cobalt lithium manganate positive electrode material
0.5Co
0.2Mn
0.3-z(OH)
2、Ni
0.6Co
0.2Mn
0.2-z(OH)
2Or Ni
0.8Co
0.1Mn
0.1-z(OH)
2The content of manganese is more than 0.
Optionally, the molar ratio of the nickel cobalt lithium manganate positive electrode material precursor to the copper carbonate may be 1: 0.02, 1: 0.03, 1: 0.04, 1: 0.05, 1: 0.06 and 1: (0.02-0.06).
Optionally, the temperature of the first calcination is 400-500 ℃, and the time is 4-6 h; the temperature of the second calcination is 850-900 ℃, and the time is 22-26 h;
preferably, ball milling is carried out after the nickel cobalt lithium manganate positive electrode material precursor and the copper source are mixed and the lithium source is added.
The optimization of the calcining temperature and time can control the doping and ion replacement processes, and ensure the rate capability and the cycle performance of the cathode material.
Alternatively, the temperature of the first calcination may be any value between 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃ and 400-; the temperature of the second calcination may be any value between 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃ and 850-.
A nickel cobalt lithium manganate positive electrode material is prepared by the preparation method.
The lithium ion battery anode slurry comprises the nickel cobalt lithium manganate anode material.
The lithium ion battery anode is prepared by using the lithium ion battery anode slurry.
A lithium ion battery comprises the lithium ion battery anode.
The required soft package lithium ion battery is obtained through the working procedures of sheet making, lamination, welding, packaging, liquid injection, formation, capacity grading and the like.
Compared with the prior art, the invention has the beneficial effects that at least:
1. the invention is through Cu
2+Part of Mn in the positive electrode material of nickel cobalt lithium manganate is replaced
4+，Cu
2+With special peripheral electron arrangement, Cu
2+Has larger ion radius, increases the unit cell parameter of the material after doping, increases the interlayer spacing of the material, is beneficial to the embedding and the separation of ions, reduces the impedance of the material in the charging and discharging processes, and obtains Cu
2+The doped anode material can effectively improve the structural stability and the conductivity of the material, so that the electrochemical properties such as the rate capability, the cycle performance and the like of the anode material are improved;
2. the positive electrode slurry prepared from the nickel cobalt lithium manganate positive electrode material provided by the application is used for further preparing a lithium ion battery positive electrode and a lithium ion battery, and has excellent electrical properties.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is a graph comparing the cycle curves of example 2, example 3 and comparative example 1.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Preparing a nickel cobalt lithium manganate positive electrode material:
mixing NiSO
4·6H
2O、CoSO
4·7H
2O、MnSO
4·H
2Mixing O according to the molar ratio of 0.6:0.2:0.19, placing the mixture in a beaker, and dissolving the mixture in deionized water to obtain a solution with the metal ion concentration of 1.5 mol/L;
mixing 3.0mol/L NaOH solution and 1.2mol/L ammonia water according to a volume ratio of 1: 1, slowly adding the mixture into the solution, adjusting the pH value to 10, stirring the mixture in a water bath kettle at 50 ℃ until the precipitate is completely precipitated, and simultaneously washing the mixture for multiple times by using deionized water; soaking the obtained precipitate in absolute ethyl alcohol for 1h, and then drying the precipitate in a constant-temperature vacuum box at 85 ℃ for 12h to obtain a precursor Ni of the nickel cobalt lithium manganate positive electrode material
0.6Co
0.2Mn
0.19(OH)
2。
Nickel is mixed withThe method comprises the following steps of (1) preparing a precursor of a lithium cobalt manganese oxide positive electrode material and basic copper carbonate according to a molar ratio of 1: mixing and ball-milling the mixture according to the proportion of 0.01, calcining the mixture for 5 hours at the temperature of 450 ℃, and then mixing the mixture according to the molar ratio of the precursor of the nickel cobalt lithium manganate positive electrode material to lithium carbonate of 1: 1 adding lithium carbonate, ball-milling and mixing uniformly, then putting into a mortar, calcining at 880 ℃ for 24h to obtain Cu
2+Doped lithium nickel cobalt manganese oxide positive electrode material Li (Ni)
0.6Co
0.2Mn
0.19Cu
0.01)O
2And is referred to as positive electrode material LNCM 1C.
Preparation of a battery containing a positive electrode material LNCM 1C:
s1, weighing 95 parts of cathode material LNCM1C, 2.5 parts of acetylene black and 2.5 parts of PVDF;
s2, weighing a solvent NMP according to the proportion that the solid content of the glue solution is 6 wt%, adding PVDF, controlling the stirring speed to be 35 r/min and the dispersion speed to be 30 r/min, and obtaining uniform and transparent glue solution after 4 hours; then adding conductive agent acetylene black, and operating for 1.5h according to the stirring speed of 35 r/min and the dispersion speed of 35 r/min; adding an anode material LNCM1C, and operating for 4 hours according to the stirring speed of 35 r/min and the dispersion speed of 30 r/min to obtain the anode slurry of the lithium ion battery;
s3, uniformly coating the positive electrode slurry of the lithium ion battery on the surface of a positive electrode current collector, and baking to obtain the lithium ion battery with the surface density of 380g/m
2The positive electrode plate of (1);
s4, rolling, die cutting, laminating and the like are carried out on the pole pieces to assemble the lithium ion battery, the lithium ion battery is marked as a battery LNCM1C, and electrochemical performance test is carried out.
Example 2
Preparing a nickel cobalt lithium manganate positive electrode material:
mixing NiSO
4·6H
2O、CoSO
4·7H
2O、MnSO
4·H
2Mixing O according to the molar ratio of 0.6:0.2:0.18, placing the mixture in a beaker, and dissolving the mixture in deionized water to obtain a solution with the metal ion concentration of 1.5 mol/L;
mixing 2.0mol/L NaOH solution and 1.5mol/L ammonia water according to a volume ratio of 1: 3, slowly adding the mixture into the solution, adjusting the pH value to 12, stirring the mixture in a water bath kettle at the temperature of 40 ℃ until the precipitate is completely precipitated, and simultaneously washing the mixture for multiple times by using deionized water; soaking the obtained precipitate in anhydrous ethanol for 1.5 hr, and soakingThe precipitate is dried for 14 hours in a constant temperature vacuum box at 80 ℃ to obtain a precursor Ni of the nickel cobalt lithium manganate positive electrode material
0.6Co
0.2Mn
0.18(OH)
2。
Preparing a precursor of a nickel cobalt lithium manganate positive electrode material and basic copper carbonate according to a molar ratio of 1: mixing and ball-milling according to the proportion of 0.02, calcining for 4 hours at 500 ℃, and then mixing and ball-milling according to the molar ratio of the precursor of the nickel cobalt lithium manganate positive electrode material to lithium carbonate of 0.5: 1 adding lithium carbonate, ball-milling and mixing uniformly, then putting into a mortar, calcining at 850 ℃ for 26h to obtain Cu
2+Doped lithium nickel cobalt manganese oxide positive electrode material Li (Ni)
0.6Co
0.2Mn
0.18Cu
0.02)O
2And is referred to as the positive electrode material LNCM 2C.
Preparation of a battery containing a positive electrode material LNCM 2C:
s1, weighing 95 parts of cathode material LNCM2C, 2.5 parts of acetylene black and 2.5 parts of PVDF;
s2, weighing a solvent NMP according to the proportion that the solid content of the glue solution is 6 wt%, adding PVDF, controlling the stirring speed to be 35 r/min and the dispersion speed to be 30 r/min, and obtaining uniform and transparent glue solution after 4 hours; then adding conductive agent acetylene black, and operating for 1.5h according to the stirring speed of 35 r/min and the dispersion speed of 35 r/min; adding an anode material LNCM1C, and operating for 4 hours according to the stirring speed of 35 r/min and the dispersion speed of 30 r/min to obtain the anode slurry of the lithium ion battery;
s3, uniformly coating the positive electrode slurry of the lithium ion battery on the surface of a positive electrode current collector, and baking to obtain the lithium ion battery with the surface density of 380g/m
2The positive electrode plate of (1);
and S4, rolling, die cutting, laminating and the like the pole pieces to assemble the lithium ion battery, recording the lithium ion battery as a battery LNCM2C, and carrying out electrochemical performance testing.
Example 3
Preparing a nickel cobalt lithium manganate positive electrode material:
mixing NiSO
4·6H
2O、CoSO
4·7H
2O、MnSO
4·H
2Mixing O according to the molar ratio of 0.6:0.2:0.14, placing the mixture in a beaker, and dissolving the mixture in deionized water to obtain a solution with the metal ion concentration of 2.0 mol/L;
slowly adding 4.0mol/L NaOH solution into the solutionAdjusting pH to 11, stirring in a water bath kettle at 60 ℃ until the precipitate is completely precipitated, and simultaneously washing with deionized water for multiple times; soaking the obtained precipitate in absolute ethyl alcohol for 0.5h, and then drying the precipitate in a constant-temperature vacuum box at 100 ℃ for 10h to obtain a precursor Ni of the nickel cobalt lithium manganate positive electrode material
0.6Co
0.2Mn
0.14(OH)
2。
Preparing a precursor of a nickel cobalt lithium manganate positive electrode material and basic copper carbonate according to a molar ratio of 1: mixing and ball-milling according to the proportion of 0.06, calcining for 6 hours at 400 ℃, and then mixing and ball-milling according to the molar ratio of the precursor of the nickel cobalt lithium manganate positive electrode material to lithium carbonate of 0.8: 1 adding lithium carbonate, ball-milling and mixing uniformly, then putting into a mortar, calcining at 900 ℃ for 22h to obtain Cu
2+Doped lithium nickel cobalt manganese oxide positive electrode material Li (Ni)
0.6Co
0.2Mn
0.14Cu
0.06)O
2And is referred to as the positive electrode material LNCM 6C.
Preparation of a battery containing a positive electrode material LNCM 6C:
s1, weighing 95 parts of cathode material LNCM6C, 2.5 parts of acetylene black and 2.5 parts of PVDF;
s2, weighing a solvent NMP according to the proportion that the solid content of the glue solution is 6 wt%, adding PVDF, controlling the stirring speed to be 35 r/min and the dispersion speed to be 30 r/min, and obtaining uniform and transparent glue solution after 4 hours; then adding conductive agent acetylene black, and operating for 1.5h according to the stirring speed of 35 r/min and the dispersion speed of 35 r/min; adding an anode material LNCM6C, and operating for 4 hours according to the stirring speed of 35 r/min and the dispersion speed of 30 r/min to obtain the anode slurry of the lithium ion battery;
s3, uniformly coating the positive electrode slurry of the lithium ion battery on the surface of a positive electrode current collector, and baking to obtain the lithium ion battery with the surface density of 380g/m
2The positive electrode plate of (1);
and S4, rolling, die cutting, laminating and the like the pole pieces to assemble the lithium ion battery, recording the lithium ion battery as a battery LNCM6C, and carrying out electrochemical performance testing.
Example 4
Preparing a nickel cobalt lithium manganate positive electrode material:
mixing NiSO
4·6H
2O、CoSO
4·7H
2O、MnSO
4·H
2O is in a molar ratio of 0.6:0.2:0.11Proportionally mixing, placing in a beaker, and dissolving in deionized water to obtain a solution with the metal ion concentration of 1.8 mol/L;
slowly adding 1.0mol/L ammonia water into the solution, adjusting the pH value to 10, stirring in a 50 ℃ water bath until the precipitate is completely precipitated, and simultaneously washing with deionized water for multiple times; soaking the obtained precipitate in absolute ethyl alcohol for 1h, and then drying the precipitate in a constant-temperature vacuum box at 85 ℃ for 12h to obtain a precursor Ni of the nickel cobalt lithium manganate positive electrode material
0.6Co
0.2Mn
0.11(OH)
2。
Preparing a precursor of a nickel cobalt lithium manganate positive electrode material and basic copper carbonate according to a molar ratio of 1: mixing and ball-milling the mixture according to the proportion of 0.09, calcining the mixture for 5 hours at the temperature of 450 ℃, and mixing the mixture according to the molar ratio of the precursor of the nickel cobalt lithium manganate positive electrode material to lithium carbonate of 1: 1 adding lithium carbonate, ball-milling and mixing uniformly, then putting into a mortar, calcining at 880 ℃ for 24h to obtain Cu
2+Doped lithium nickel cobalt manganese oxide positive electrode material Li (Ni)
0.6Co
0.2Mn
0.11Cu
0.09)O
2And is referred to as the positive electrode material LNCM 9C.
Preparation of a battery containing a positive electrode material LNCM 9C:
s1, weighing 95 parts of cathode material LNCM1C, 2.5 parts of acetylene black and 2.5 parts of PVDF;
s2, weighing a solvent NMP according to the proportion that the solid content of the glue solution is 6 wt%, adding PVDF, controlling the stirring speed to be 35 r/min and the dispersion speed to be 30 r/min, and obtaining uniform and transparent glue solution after 4 hours; then adding conductive agent acetylene black, and operating for 1.5h according to the stirring speed of 35 r/min and the dispersion speed of 35 r/min; adding an anode material LNCM9C, and operating for 4 hours according to the stirring speed of 35 r/min and the dispersion speed of 30 r/min to obtain the anode slurry of the lithium ion battery;
s3, uniformly coating the positive electrode slurry of the lithium ion battery on the surface of a positive electrode current collector, and baking to obtain the lithium ion battery with the surface density of 380g/m
2The positive electrode plate of (1);
and S4, rolling, die cutting, laminating and the like the pole pieces to assemble the lithium ion battery, recording the lithium ion battery as a battery LNCM9C, and carrying out electrochemical performance testing.
It is noted that NiSO is used in the preparation of the nickel cobalt lithium manganate cathode material
4·6H
2O、CoSO
4·7H
2O、MnSO
4·H
2The molar ratio of O may be in the range of 5: 2: (3-z), 6: 2: (2-z), 8: 1: (1-z) was chosen (to correspond to NCM523/NCM622/NCM811, respectively).
Comparative example 1
Preparing a nickel cobalt lithium manganate positive electrode material:
mixing NiSO
4·6H
2O、CoSO
4·7H
2O、MnSO
4·H
2Mixing O according to the molar ratio of 0.6:0.2:0.2, placing the mixture in a beaker, and dissolving the mixture in deionized water to obtain 1.5mol/L solution;
mixing 3.0mol/L NaOH solution and 1.2mol/L ammonia water according to a volume ratio of 1: 1, slowly adding the mixture into the solution, adjusting the pH value to 10, stirring the mixture in a water bath kettle at 50 ℃ until the precipitate is completely precipitated, and simultaneously washing the mixture for multiple times by using deionized water; soaking the obtained precipitate in absolute ethyl alcohol for 1h, and then drying the precipitate in a constant-temperature vacuum box at 85 ℃ for 12h to obtain a precursor Ni of the nickel cobalt lithium manganate positive electrode material
0.6Co
0.2Mn
0.2(OH)
2。
The mol ratio of the precursor of the nickel cobalt lithium manganate positive electrode material to lithium carbonate is 1: 1 adding lithium carbonate, ball-milling and mixing uniformly, then placing into a mortar, calcining at 880 ℃ for 24h to obtain the lithium nickel cobalt manganese oxide positive electrode material Li (Ni)
0.6Co
0.2Mn
0.2)O
2And is referred to as the positive electrode material LNCM.
Preparing an LNCM battery containing a positive electrode material:
s1, weighing 95 parts of cathode material LNCM1C, 2.5 parts of acetylene black and 2.5 parts of PVDF;
s2, weighing a solvent NMP according to the proportion that the solid content of the glue solution is 6 wt%, adding PVDF, controlling the stirring speed to be 35 r/min and the dispersion speed to be 30 r/min, and obtaining uniform and transparent glue solution after 4 hours; then adding conductive agent acetylene black, and operating for 1.5h according to the stirring speed of 35 r/min and the dispersion speed of 35 r/min; adding an anode material LNCM, and operating for 4 hours according to the stirring speed of 35 rpm and the dispersion speed of 30 rpm to obtain the anode slurry of the lithium ion battery;
s3, uniformly coating the lithium ion battery anode slurry on the surface of the anode current collector, and baking to obtain the lithium ion battery anode slurry with the surface density of 380 g/greaterm
2The positive electrode plate of (1);
and S4, rolling, die cutting, laminating and the like are carried out on the pole piece to assemble the lithium ion battery, the lithium ion battery is marked as a battery LNCM, and the electrochemical performance test is carried out.
The batteries prepared in examples 1 to 4 and comparative example 1 were subjected to a 1C/1C charge-discharge cycle test at 25 ℃, and the capacity retention rate of the battery after 500 cycles was recorded, and the rate performance, internal resistance, and energy density of the battery were recorded, and the recorded results are shown in table 1.
TABLE 1 test data
As can be seen from the data in table 1, the lithium ion batteries made of the nickel cobalt lithium manganate positive electrode materials provided in examples 1 to 4 of the present application have better cycle performance, charge and discharge rate performance, and energy density than the lithium ion batteries made of the nickel cobalt lithium manganate positive electrode materials not doped with copper provided in comparative example 1. The internal resistance of the lithium ion battery prepared from the nickel cobalt lithium manganate positive electrode material provided by the embodiment 1-4 is smaller than that of the lithium ion battery prepared from the nickel cobalt lithium manganate positive electrode material which is not doped with copper and provided by the comparative example 1.
Examples 2 and 3 and comparative example 1 the cyclic curves are plotted versus the example 1. As can be seen from fig. 1, the capacity retention rates of examples 2 and 3 are significantly higher than that of comparative example 1 at the same number of cycles, and the difference is significant after 400 cycles.
The application provides a nickel cobalt lithium manganate cathode material utilizes the characteristic of copper ion for cathode material impedance reduces at the charge-discharge in-process, promotes the multiplying power performance and the cycling performance of material, has solved nickel cobalt lithium manganate cathode material self poor, the big problem of internal resistance of structural stability in the cycling process, and then obtains the lithium ion battery that the performance is excellent.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. The preparation method of the nickel cobalt lithium manganate positive electrode material is characterized by comprising the following steps of:
mixing a precursor of the nickel cobalt lithium manganate positive electrode material with a copper source, carrying out first calcination, and then adding a lithium source to carry out second calcination to obtain a lithium nickel cobalt lithium manganate positive electrode material Li (Ni)
xCo
yMn
1-x-y-zCu
z)O
2Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than or equal to 0.2, and 0 and less than 1-x-y-z are less than 1;
the mol ratio of the nickel cobalt lithium manganate positive electrode material precursor to the copper element in the copper source is 1: (0.01-0.1), wherein the molar ratio of the precursor of the nickel cobalt lithium manganate positive electrode material to the lithium element in the lithium source is (0.5-1): 1.
2. the preparation method of claim 1, wherein the preparation method of the precursor of the nickel cobalt lithium manganate positive electrode material comprises the following steps:
preparing a manganese source, a nickel source and a cobalt source into a mixed solution, then adding an alkali source, and reacting to obtain a precursor of the nickel cobalt lithium manganate positive electrode material;
preferably, the concentration of the metal ions in the mixed solution is 1.5-2.0 mol/L;
preferably, the manganese source comprises manganese sulfate, the nickel source comprises nickel sulfate, and the cobalt source comprises cobalt sulfate.
3. The production method according to claim 2, wherein the alkali source comprises an aqueous sodium hydroxide solution and/or aqueous ammonia;
preferably, the alkali source comprises a mixture of alkali sources in a volume ratio of 1: (1-3) 2-4mol/L aqueous sodium hydroxide solution and 1-1.5mol/L aqueous ammonia;
preferably, the pH value of the reaction system is adjusted to 10-12 by adding the alkali source;
preferably, the temperature of the reaction is 40-60 ℃.
4. The method according to claim 2, further comprising a step of washing the product after the reaction is completed;
preferably, the step of washing the product comprises: washing the product with deionized water, and then putting the product into absolute ethyl alcohol;
preferably, the product is put into absolute ethyl alcohol for treatment for 0.5 to 1.5 hours;
preferably, the step of washing the product further comprises a drying step;
preferably, the drying temperature is 80-100 ℃ and the drying time is 10-14 h.
5. The production method according to claim 1, wherein the lithium source includes lithium carbonate and/or lithium hydroxide;
preferably, the lithium source is lithium carbonate;
preferably, the copper source is basic copper carbonate;
preferably, the molar ratio of the nickel cobalt lithium manganate positive electrode material precursor to the copper carbonate is 1: (0.02-0.06);
preferably, the precursor of the nickel cobalt lithium manganate positive electrode material is Ni
0.5Co
0.2Mn
0.3-z(OH)
2、Ni
0.6Co
0.2Mn
0.2-z(OH)
2Or Ni
0.8Co
0.1Mn
0.1-z(OH)
2。
6. The preparation method according to any one of claims 1 to 5, characterized in that the temperature of the first calcination is 400-500 ℃ and the time is 4-6 h; the temperature of the second calcination is 850-900 ℃, and the time is 22-26 h;
preferably, ball milling is carried out after the nickel cobalt lithium manganate positive electrode material precursor and the copper source are mixed and the lithium source is added.
7. A lithium nickel cobalt manganese oxide positive electrode material, which is prepared by the preparation method of any one of claims 1 to 6.
8. A lithium ion battery positive electrode slurry, which is characterized by comprising the nickel cobalt lithium manganate positive electrode material as defined in claim 7.
9. A positive electrode for a lithium ion battery, characterized by being produced using the positive electrode slurry for a lithium ion battery according to claim 8.
10. A lithium ion battery comprising the lithium ion battery positive electrode according to claim 9.
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