CN115020699B - Low-cobalt or cobalt-free cathode material and preparation method and application thereof - Google Patents
Low-cobalt or cobalt-free cathode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a low-cobalt or cobalt-free cathode material and a preparation method and application thereof. The positive electrode material includes: a base material; having the formula Li a Ni x Co y Mn z O 2 Wherein a is more than or equal to 0.95 and less than or equal to 1.2,0.6 and less than 1.0,0 and less than or equal to y and less than or equal to 0.05,0 and less than or equal to z and less than or equal to 0.4, and a + x + y + z =2; the base material further contains a doping substance selected from at least one of oxides of B, zr, al, ga, ti, si, W and Mo elements; in an XRD diagram, the half-peak widths of diffraction peaks (104), (101), (012) and (003) are respectively a, b, c and m, and a/m is more than or equal to 0.62 and less than or equal to 1.05,0.80 and less than or equal to b/m and less than or equal to 1.25 and c/m is more than or equal to 0.76 and less than or equal to 1.15. The positive electrode material disclosed by the invention is good in structural stability, strong in battery cycle performance and extremely high in popularization and application values.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a low-cobalt or cobalt-free cathode material and a preparation method and application thereof.
Background
To realize sustainable personal transportation mode, pure electric vehicles are used for replacing gasoline powerThere is an increasing need for power cars. Li [ Ni ] x Co y Mn 1−x−y ]O 2 Ternary high nickel layered cathode materials have long been considered as ideal cathode materials for high energy density power cells.
However, since Co has disadvantages such as low storage capacity, high cost, and toxicity, research into a high nickel layered cathode material having low or no cobalt has been conducted. However, according to the research results of the prior art, the Co deficiency causes the deterioration of the layered structure, and often the stable crystal structure cannot be maintained, so that the structure is obviously attenuated during the electrochemical cycle, and the battery performance is seriously deteriorated. Therefore, in the current cathode material, the content of the Co element is still high, so as to ensure the structural stability in the electrochemical cycle process. For example:
in the prior art, CN 105895909A discloses a novel lithium ion battery anode material and a preparation method thereof, and the general formula of the anode material is Li y ( Ni a Co b X c ) O2, wherein X is an element which is more than or equal to +3 valence except Mn and comprises one or more of Ti, zr, ce, W, V, cr, sn, sr, mo, sc, la, P, nb, Y and Ga; y is more than or equal to 0.9 and less than or equal to 1.1,0.3 and less than or equal to a and less than or equal to 0.8,0.1 and less than or equal to b and less than or equal to 0.5,0.01 and less than or equal to c and less than or equal to 0.3, a +, b +, c =1, c and c +<b. However, the content of Co element in the positive electrode material is still high. In addition, CN 109390565A also discloses a positive electrode material and a lithium ion battery, wherein the general formula of the matrix material is Li x Co y M 1-y O 2 Wherein x is more than or equal to 1.0 and less than or equal to 1.2,0.8 and less than or equal to 1.0, M is selected from at least one of Mg, ti, al, zr, ni and Mn, and the content of Co element in the anode material is also higher.
Therefore, how to design a low-cobalt or cobalt-free high-nickel cathode material to keep the structure of the cathode material continuously and well stable in the electrochemical cycling process is a technical problem to be solved in the field.
Disclosure of Invention
In view of this, the present invention provides, first of all, a positive electrode material comprising: a base material;
the general formula of the matrix material is Li a Ni x Co y Mn z O 2 Wherein a is more than or equal to 0.95 and less than or equal to 1.2,0.6 and less than or equal to 1.0,0 and less than or equal to y is more than or equal to 0.05,0 and less than or equal to z is less than or equal to 0.4, and a + x + y + z =2; the base material also contains a doping substance, and the doping substance is selected from at least one of oxides of B, zr, al, ga, ti, si, W and Mo elements;
in an X-ray diffraction pattern of the cathode material, the half-peak width of a (104) diffraction peak is a, the half-peak width of a (101) diffraction peak is b, the half-peak width of a (012) diffraction peak is c, and the half-peak width of a (003) diffraction peak is m, and simultaneously, 0.62-1.05,0.80-b/m-1.25 and 0.76-c/m-1.15 are satisfied.
According to the invention, through a large number of experimental researches, the composition of the base material is regulated and controlled, so that when the half-peak width of the characteristic peak of an X-ray diffraction pattern of the cathode material meets the relation, the structural phase transformation of the cathode material with low cobalt or no cobalt and high nickel can be obviously inhibited, the stability of unit cell parameters in the electrochemical cycle process is kept, and the NiO phase is not easily generated in the cathode material, so that the structural stability of the cathode material is improved, and the improvement of the electrochemical cycle performance is realized.
As a preferred embodiment of the present invention, the doping materials are B, zr and Al oxide, and the present invention has found that when doping such materials, the crystal structure stability and the microstructure stability of the particles can be more optimally balanced, enabling the above half-peak aspect ratio range to be better achieved.
As a preferred embodiment of the present invention, the matrix material has the general formula Li a Ni x Mn z O 2 Wherein a is more than or equal to 0.95 and less than or equal to 1.2,0.6 and less than 1.0,0 and more than z and less than or equal to 0.4, and a + x + z =2.
The invention discovers that the use of the cobalt-free element can be realized in the base material, and the stable crystal structure can be kept as well as the half-peak width of the characteristic peak in the X-ray diffraction pattern of the anode material is ensured to meet the relationship, so that the anode material has good cycle performance in the electrochemical cycle process.
As a preferred embodiment of the present invention, the positive electrode material satisfies both 0.71. Ltoreq. A/m. Ltoreq. 0.9,0.89. Ltoreq. B/m. Ltoreq.1.07 and 0.83. Ltoreq. C/m. Ltoreq.0.97 in an X-ray diffraction pattern.
Under the condition of satisfying the relation between the half peak widths of the characteristic peaks of the X-ray diffraction patterns, the structural stability of the anode material can be further improved, and the electrochemical cycle performance is better.
As a preferred embodiment of the present invention, the median particle size of the positive electrode material is 2~5 microns.
As a preferred embodiment of the present invention, the positive electrode material includes a single crystal and/or a polycrystal.
In a preferred embodiment of the present invention, the specific surface area of the positive electrode material is 0.3 to 6 m 2 (ii)/g, and/or the tap density is 1.5 to 4.0 g/cm 3 。
Further, the present invention provides a method for preparing the positive electrode material in any one of the above embodiments, comprising:
(1) Preparing hydroxide precursors of other elements except Li and O in the general formula of the matrix material;
(2) Coating the doping substance on the surface of the hydroxide precursor to prepare a modified precursor;
(3) And mixing the modified precursor with a lithium source, and then roasting for the first time to obtain the matrix material.
As a preferred embodiment of the present invention, the primary calcination is carried out at 690 ℃ to 780 ℃.
As a preferred embodiment of the present invention, the preparation method further comprises: and mixing the base material and the coating material, and then carrying out secondary roasting at the temperature of 450-550 ℃.
In specific implementations, the cladding material includes, but is not limited to, at least one of oxides of elements selected from the group consisting of B, zr, al, ga, ti, si, W, mo.
As a preferred embodiment of the present invention, the preparation method comprises:
(1) Preparing hydroxide precursors of other elements except Li and O in the general formula of the base material;
(2) Coating the oxide of at least one element of Zr, al, ga, ti, W and Mo on the surface of the hydroxide precursor to prepare a modified precursor;
(3) Mixing the modified precursor with a lithium source and then roasting for the first time to prepare a matrix material;
(4) And mixing the base material and the coating material, and then carrying out secondary roasting at the temperature of 450-550 ℃.
More preferably, in the step (3), the modified precursor is mixed with a lithium source and a non-metal oxide and then is subjected to primary calcination to obtain the matrix material.
In specific implementations, the non-metal oxide includes, but is not limited to, an oxide of B, si.
In specific implementations, the lithium source includes, but is not limited to, liOH.
Further, the present invention also provides a positive electrode plate, including: a positive current collector; the positive electrode diaphragm is in contact with the positive electrode current collector; the positive electrode membrane comprises the positive electrode material in any one of the embodiments or the positive electrode material prepared by any one of the preparation methods.
In addition, the invention also provides a lithium ion battery which comprises the positive pole piece.
Because the lithium ion battery contains the anode material, the lithium ion battery also has excellent electrochemical cycle performance.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares a high nickel anode material with low cobalt or even no cobalt, and overcomes the technical problems of poor structural stability and poor battery cycle performance of the low cobalt anode material in the prior art. The cathode material disclosed by the invention can reduce the utilization of Co element, save economic cost and natural resources, and reduce potential hazards brought by toxicity, so that the lithium ion battery is safer and more environment-friendly in application, and has extremely high popularization and application values.
Drawings
Fig. 1 is a graph showing a particle size distribution of a positive electrode material of example 1.
Fig. 2 is an X-ray diffraction pattern of the positive electrode material of example 1.
Fig. 3 is a first cycle charge and discharge curve diagram of the positive electrode material of example 1.
Fig. 4 is a graph comparing electrochemical cycling curves of the cathode materials of example 1 and comparative example 1 at 25 ℃.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The specific techniques or conditions not indicated in the examples are all conventional methods or techniques or conditions described in the literature of the field or according to the product specifications. The reagents and instruments used are conventional products which are available from normal commercial vendors, not indicated by manufacturers.
In the following examples and comparative examples, a high-speed mixer was used to mix the materials uniformly.
In the X-ray diffraction patterns (XRD patterns) of the positive electrode materials in the following examples and comparative examples, (104) the half-width of the diffraction peak is a, (101) the half-width of the diffraction peak is b, (012) the half-width of the diffraction peak is c, and (003) the half-width of the diffraction peak is m.
The precursors in the following examples were prepared by conventional coprecipitation method, and the parameters of the preparation conditions were controlled such that the particle size D of the precursor was 50 1.5 to 4.5 μm. The method comprises the following specific steps:
(1) Preparing a salt solution from nickel salt, cobalt salt and manganese salt; dissolving alkali into an alkali solution; dissolving a complexing agent into a complexing agent solution;
(2) Adding the salt solution, the alkali solution and the complexing agent solution in the step (1) into a reaction kettle in a concurrent flow manner for reaction, wherein the stirring rotation speed is constant, the reaction pH is controlled to be 10.5-12.5, the reaction temperature is controlled to be 40-70 ℃, and the precursor granularity D is controlled by adjusting different reaction times 50 ；
(3) And (3) carrying out solid-liquid separation, washing, drying and screening on the hydroxide precursor slurry prepared in the step (2) to obtain the required spherical hydroxide precursor material.
Example 1
This example provides a positive electrode material, the matrix material of which has a chemical formula of LiNi 0.92 Mn 0.08 O 2 The doping substance is ZrO 2 、B 2 O 3 (ii) a The coating material is Al 2 O 3 (ii) a The median particle diameter of the positive electrode material was 3.7 μm, and the specific surface area was 0.712m 2 (ii)/g, tap density of 3.2g/cm 3 . a. The proportional relationship among b, c and m is shown in Table 1.
The preparation method of the cathode material in the embodiment comprises the following steps:
(1) Preparation of Ni 0.92 Mn 0.08 (OH) 2 A precursor;
(2) ZrO 2 is mixed with 2 Coated with Ni 0.92 Mn 0.08 (OH) 2 Preparing a modified precursor on the surface of the precursor;
(3) Mixing the modified precursor with LiOH and B as lithium sources 2 O 3 Mixing, placing into an atmosphere furnace for primary roasting at 690 deg.C for 10 hr, crushing, sieving to obtain primary roasted sample, and coating Al on the surface of the primary roasted sample 2 O 3 (0.03 wt.%) and then carrying out secondary roasting at 500 ℃ for 5 hours to obtain the anode material;
wherein, the lithium source LiOH, the precursor and ZrO are added according to the dosage relation of 1.03 2 And B 2 O 3 。
Through testing, the particle size distribution curve of the cathode material of the embodiment is shown in fig. 1; the XRD pattern is shown in figure 2; the first cycle charge-discharge curve (0.1C, 25 ℃) is shown in FIG. 3; the 25 ℃ electrochemical cycling profile is shown in figure 4.
Example 2
This example provides a positive electrode material which differs from example 1 only in that the chemical formula of the matrix material is LiNi 0.88 Mn 0.12 O 2 . a. The proportional relationship among b, c and m is shown in Table 1. The median diameter of the anode material is 3.9 microns, and the specific surface area is 0.835m 2 (iv)/g, tap density of 3.1 g/cm 3 。
The preparation method of the anode material onlyExample 1 differs in that: the precursor is Ni 0.88 Mn 0.12 (OH) 2 (ii) a The primary calcination temperature was 710 ℃.
Example 3
This example provides a positive electrode material, which is different from example 1 only in that the chemical formula of the matrix material is LiNi 0.83 Mn 0.17 O 2 . a. The proportional relationship among b, c and m is shown in Table 1. The median diameter of the anode material is 4.0 microns, and the specific surface area is 0.982m 2 (iv)/g, tap density of 3.4 g/cm 3 。
The preparation method of the cathode material is different from that of the embodiment 1 only in that: the precursor is Ni 0.83 Mn 0.17 (OH) 2 (ii) a The primary calcination temperature was 710 ℃.
Example 4
This example provides a cathode material which differs from example 1 only in that the chemical formula of the matrix material is Li 0.98 Ni 0.90 Mn 0.12 O 2 . a. The proportional relationship among b, c and m is shown in Table 1. The median diameter of the anode material is 4.2 microns, and the specific surface area is 0.912m 2 (iv)/g, tap density of 2.7 g/cm 3 。
The preparation method of the cathode material is different from that of the embodiment 1 only in that: the precursor is Ni 0.90 Mn 0.12 (OH) 2 (ii) a The primary roasting temperature is 700 ℃; adding LiOH source, precursor and ZrO according to the dosage relation of 1.01 2 And B 2 O 3 。
Example 5
This example provides a cathode material which differs from example 1 only in that the chemical formula of the matrix material is Li 1.1 Ni 0.85 Mn 0.05 O 2 . a. The proportional relationship among b, c and m is shown in Table 1. The median particle diameter of the cathode material is 3.9 microns, and the specific surface area is 0.642m 2 (iv)/g, tap density of 3.3 g/cm 3 。
The preparation method of the cathode material is different from that of the embodiment 1 only in that: the precursor is Ni 0.85 Mn 0.05 (OH) 2 (ii) a The primary roasting temperature is 720 DEG C(ii) a Adding a lithium source LiOH, a precursor and ZrO according to the dosage relation of 1.13 2 And B 2 O 3 。
Example 6
This example provides a positive electrode material, which is different from example 1 only in that the chemical formula of the matrix material is LiNi 0.92 Mn 0.06 Co 0.02 O 2 . a. The proportional relationship among b, c and m is shown in Table 1. The median particle diameter of the cathode material is 3.6 microns, and the specific surface area is 1.125m 2 (iv)/g, tap density of 2.6 g/cm 3 。
The preparation method of the cathode material is different from that of the embodiment 1 only in that: the precursor is Ni 0.92 Mn 0.06 Co 0.02 (OH) 2 。
Example 7
This example provides a positive electrode material which differs from example 1 only in that the chemical formula of the matrix material is LiNi 0.88 Mn 0.09 Co 0.03 O 2 . a. The proportional relationship among b, c and m is shown in Table 1. The median particle diameter of the anode material is 4.3 microns, and the specific surface area is 1.624m 2 (iv)/g, tap density of 3.0 g/cm 3 。
The preparation method of the cathode material is different from the embodiment 2 only in that: the precursor is Ni 0.88 Mn 0.09 Co 0.03 (OH) 2 。
Example 8
This example provides a positive electrode material, which is different from example 1 only in that the chemical formula of the matrix material is LiNi 0.83 Mn 0.12 Co 0.05 O 2 . a. The proportional relationship among b, c and m is shown in Table 1. The median diameter of the anode material is 3.8 microns, and the specific surface area is 0.859m 2 (iv)/g, tap density of 3.1 g/cm 3 。
The preparation method of the cathode material is different from that of the embodiment 3 only in that: the precursor is Ni 0.83 Mn 0.12 Co 0.05 (OH) 2 。
In addition, in the concrete implementation process, the invention also provides a positive electrode material prepared by the methodThe positive pole piece and the lithium ion battery. And the positive current collector in the positive pole piece adopts copper foil. In the lithium ion battery, the negative electrode material adopts graphite material, the isolating membrane adopts ceramic-coated isolating membrane, and the electrolyte adopts LiPF 6 And (3) an electrolyte. The positive electrode plate and the lithium ion battery in the examples were prepared in a conventional manner in the art.
Comparative example 1
The comparative example provides a positive electrode material whose base material has the chemical formula LiNi 0.92 Mn 0.08 O 2 The doping elements are Ga and Ti, and the cladding material is Al 2 O 3 (ii) a a. The proportional relationship among b, c and m is shown in Table 1.
The specific preparation method only differs from the example 1: doping Ga and Ti in the step (2); the primary calcination temperature was 710 ℃.
The electrochemical cycling curve at 25 ℃ for the positive electrode material of this comparative example is shown in fig. 4.
Comparative example 2
This comparative example provides a positive electrode material whose matrix material has the chemical formula LiNi 0.88 Mn 0.12 O 2 The doping elements are W and Si, and the cladding material is Al 2 O 3 (ii) a a. The proportional relationship among b, c and m is shown in Table 1.
The specific preparation method only differs from the example 2: doping W and Si elements in the step (2); the primary roasting temperature is 730 ℃.
Comparative example 3
This comparative example provides a positive electrode material whose matrix material has the chemical formula Li 1.1 Ni 0.85 Mn 0.05 O 2 The doping elements are Mo and In, and the cladding material is Al 2 O 3 (ii) a a. The proportional relationship among b, c and m is shown in Table 1.
The specific preparation method only differs from the example 5: doping Mo and In elements In the step (2); the primary roasting temperature is 730 ℃.
Test examples
The positive electrode materials prepared in the examples and the comparative examples, acetylene black and PVDF are prepared into a positive electrode piece by a coating method according to the mass ratio of 8.
The test performance includes 0.1C specific capacity and 1C cycle capacity retention at hundred cycles, with the results shown in table 1.
TABLE 1
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.
Claims (9)
1. A positive electrode material, comprising: a base material;
the general formula of the matrix material is Li a Ni x Co y Mn z O 2 Wherein a is more than or equal to 0.95 and less than or equal to 1.2,0.6 and less than or equal to 1.0,0 and less than or equal to y is more than or equal to 0.05,0 and less than or equal to z is less than or equal to 0.4, and a + x + y + z =2; the base material also contains a doping substance, and the doping substance is selected from at least one of oxides of B, zr and Al elements;
in an X-ray diffraction pattern of the cathode material, the half-peak width of a (104) diffraction peak is a, the half-peak width of a (101) diffraction peak is b, the half-peak width of a (012) diffraction peak is c, and the half-peak width of a (003) diffraction peak is m, and simultaneously, 0.62-1.05,0.80-b/m-1.25 and 0.76-c/m-1.15 are satisfied.
2. The positive electrode material according to claim 1, wherein the matrix material has a general formula of Li a Ni x Mn z O 2 Wherein a is more than or equal to 0.95 and less than or equal to 1.2,0.6 and less than 1.0,0 and more than z and less than or equal to 0.4, and a + x + z =2.
3. The positive electrode material according to claim 1 or 2, wherein 0.71. Ltoreq. A/m. Ltoreq. 0.9,0.89. Ltoreq. B/m. Ltoreq.1.07 and 0.83. Ltoreq. C/m. Ltoreq.0.97 are simultaneously satisfied in an X-ray diffraction pattern of the positive electrode material.
4. The positive electrode material of claim 1, wherein the positive electrode material has a median particle size of 2~5 microns.
5. The positive electrode material as claimed in claim 1, wherein the specific surface area of the positive electrode material is 0.3 to 6 m 2 The tap density of the cathode material is 1.5 to 4.0 g/cm 3 。
6. A method of making the positive electrode material of any one of claims 1~5 comprising:
(1) Preparing hydroxide precursors of other elements except Li and O in the general formula of the matrix material;
(2) Coating the doping substance on the surface of the hydroxide precursor to prepare a modified precursor;
(3) And mixing the modified precursor with a lithium source, and roasting at 690-780 ℃ for one time to obtain the matrix material.
7. The method of claim 6, further comprising: and mixing the base material and the coating material, and then carrying out secondary roasting at the temperature of 450-550 ℃.
8. A positive electrode sheet comprising:
a positive current collector; and
the positive electrode diaphragm is arranged in contact with the positive electrode current collector;
the positive electrode membrane is characterized by comprising the positive electrode material of 1~5 or the positive electrode material prepared by the preparation method of claim 6 or 7.
9. A lithium ion battery comprising the positive electrode sheet according to claim 8.
Priority Applications (1)
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