CN114122379A - Positive electrode material and preparation method and application thereof - Google Patents
Positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a positive electrode material and a preparation method and application thereof. According to the invention, the surface of the core of the anode material is respectively coated with the first coating layer and the second coating layer, and the first coating layer and the second coating layer both comprise cobalt compounds, so that the ionic and electronic conductivity of the surface of the material can be effectively improved, and the internal resistance of the battery is reduced; meanwhile, the first coating layer and the second coating layer are good in combination effect, the interface structure is stable, the prepared battery has low direct current resistance and high capacity retention rate, and the battery also has good electrochemical performance at low temperature.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a positive electrode material and a preparation method and application thereof.
Background
With the growing demand for energy and the depletion of fossil fuels, the energy crisis is becoming a global problem. In order to solve the problem of conventional energy exhaustion, researchers have been developing green, sustainable energy, and lithium ion batteries have shown great advantages in application. Ternary layered material LiNixCoyMn1-x-yO2(y is less than 0.13), has large capacity and low cost, is a battery anode material with excellent performance, and is widely applied to lithium ion batteries. However, the low-cobalt ternary layered material contacts with electrolyte in the charging and discharging processes, which can cause the dissolution of active substances, collapse the surface structure of the material and affect the electrochemical performance of the battery.
The current common method for improving the electrochemical performance of the cathode material is to coat the surface of the material. One prior art scheme is to mix Al2O3The coating is coated on the surface of the anode material to isolate the contact of the electrode material and the electrolyte, so that the stability of the material in the electrochemical cycle process can be improved. Another prior art scheme introduces a carbon source and a precursor into the reaction mixtureAnd performing operations such as freeze drying, sintering and the like to coat carbon in the active material and on the surface of the active material, thereby improving the high-voltage stability of the electrode material. In another technical scheme, a gas phase coating mode is adopted, a compact coating layer is formed on the surface of the ternary cathode material, the contact between the ternary cathode material and electrolyte is reduced, and the cycle performance of the ternary cathode material is improved.
However, in the prior art, the coating layer has poor conductive effect, the interface structure is unstable during multilayer coating, and the material has low ionic and electronic conductivity, which is not beneficial to the diffusion of lithium ions and limits the further development of lithium ion batteries.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a positive electrode material and a preparation method and application thereof. According to the invention, the surface of the core of the anode material is respectively coated with the first coating layer and the second coating layer, and the first coating layer and the second coating layer both comprise cobalt compounds, so that the ionic and electronic conductivity of the surface of the material can be effectively improved, and the internal resistance of the battery is reduced; meanwhile, the first coating layer and the second coating layer are good in combination effect, the interface structure is stable, the prepared battery has low direct current resistance and high capacity retention rate, and the battery also has good electrochemical performance at low temperature.
In the present invention, "low temperature" means a temperature of less than-20 ℃.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode material, including a positive electrode material core, a first coating layer coated on a surface of the positive electrode material core, and a second coating layer coated on a surface of the first coating layer, where the first coating layer includes a first cobalt compound, and the second coating layer includes a second cobalt compound.
According to the invention, the surface of the core of the anode material is sequentially coated with the first coating layer and the second coating layer from inside to outside, the first coating layer and the second coating layer both comprise cobalt compounds, the cobalt compounds have strong conductivity and stable structure, the coating effect on the surface of the core of the anode material is good, the direct current resistance of the material can be reduced, the stability of the material is improved, and the electrochemical performance of the material at low temperature is improved; simultaneously, compare with the individual layer cladding, double-deck cladding stability is higher, and is more anti-strain in long circulation, and because first cladding and second cladding all contain cobalt compound for first cladding and second cladding combine effectually, and interface structure is stable, can effectively promote the ion and the electron conductivity on material surface, has further improved the electric conductivity and the stability of material.
Preferably, the ratio of the mass of the positive electrode material core to the total mass of the first and second coating layers in the positive electrode material is (100-p): p, where p is 0.005 to 2, and may be, for example, 0.005, 0.006, 0.008, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 0.8, 1, 1.5, or 2, etc.
Preferably, the mass ratio of the first coating layer to the second coating layer is q (100-q), wherein q is 7 to 26, and may be, for example, 7, 8, 9, 10, 12, 15, 18, 20, 22, 24, 26, etc., preferably 21 to 23.
Preferably, the first cladding layer and the second cladding layer both comprise cobalt oxide.
As a further preferable aspect of the positive electrode material of the present invention, the first coating layer is distributed in a planar manner on the surface of the positive electrode material core. The first coating layer is distributed in a surface shape, so that the surface of the anode material is protected, and the continuous side reaction of the anode material and the electrolyte is inhibited.
Preferably, the crystalline form of the first cobalt compound is amorphous.
Preferably, the second cladding layers are distributed on the surface of the first cladding layer in a dot shape. The second coating layer is distributed in a point shape, so that the conductivity of the surface of the material is increased, and the dynamic performance is further improved.
Preferably, the crystalline form of the second cobalt compound is crystalline.
According to the invention, the first coating layer is preferably distributed in a planar manner, the second coating layer is preferably distributed in a point manner, the second coating layer can be uniformly dispersed on the first coating layer and cooperates with the first coating layer to construct a three-dimensional coating structure, the interface bonding effect is good, the material structure is stable, the diffusion efficiency and the electron conduction efficiency of lithium ions are high, the direct current resistance of the material is reduced, and the capacity retention rate of the material is improved.
Preferably, the chemical composition of the positive electrode material core is LiNixCoyMn1-x-yO2Wherein 0.5. ltoreq. x.ltoreq.0.9, 0. ltoreq. y.ltoreq.0.13, wherein x can be, for example, 0.5, 0.6, 0.7, 0.8 or 0.9, etc.; y may be, for example, 0, 0.01, 0.03, 0.05, 0.08, 0.1, 0.12, 0.13, or the like.
Preferably, the inner core of the cathode material is in a shape of a quadratic sphere.
Preferably, the cathode material inner core is a single crystal material.
Preferably, the positive electrode material core is in a shape of a quadratic sphere, and the particle size D50 of the positive electrode material core is 9 μm to 25 μm, and may be 9 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 25 μm, or the like.
Preferably, the cathode material core is a single crystal material, and the particle size D50 of the cathode material core is 2 μm to 6 μm, and may be, for example, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 5 μm, or 6 μm.
In a second aspect, the present invention provides a method for preparing the positive electrode material according to the first aspect, the method comprising:
mixing the positive electrode material core and a first cobalt source, and performing first sintering; and
and mixing the product obtained after the first sintering with a second cobalt source, and carrying out second sintering to obtain the cathode material.
According to the invention, the first coating layer and the second coating layer are respectively coated on the surface of the anode material core through two-step sintering, so that the bonding performance of the coating layers and the anode material core can be improved, and the stability and the conductivity of the anode material are enhanced.
Preferably, the ratio of the total mass of the first and second cobalt sources to the mass of the positive electrode material core is m (100-m), wherein m is 0.01 to 2, and may be, for example, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 0.8, 1, 1.1, 1.2, 1.5, 1.8, 2, etc., preferably 1.4 to 1.6.
Preferably, the mass ratio of the first cobalt source and the second cobalt source is n (100-n), wherein n is 10 to 30, and may be, for example, 10, 11, 12, 15, 20, 22, 25, 28 or 30, and preferably 24 to 26.
As a further preferable technical scheme of the preparation method, the first cobalt source comprises CoOOH and CoCO3、Co(NO3)2And Co (NO)3)4Any one or a combination of at least two of these, for example, CoOOH and CoCO3Combination of (1), Co (NO)3)2And Co (NO)3)4Combination of (1), CoCO3And Co (NO)3)2Or CoOOH, CoCO3And Co (NO)3)2Combinations of (3) and (3), and the like, preferably CoOOH.
Preferably, the second cobalt source comprises CoF2、CoF3、CoO、CoO2、Co3O4、CoN、Co2N、CoH、Co3H and Co3(BO3)2Any one or a combination of at least two of them, for example, CoF2And CoF3Combination of (A) and (B), Co3H and Co3(BO3)2Combination of (A) and (B), Co3O4And CoN, CoF3And CoO, or CoF2、Co3H and Co3(BO3)2Combinations of (A) and (B), preferably CoN and/or Co2N, more preferably CoN.
The cobalt source selected in the invention has different activity and structure, and the crystal form of the prepared cobalt compound is different accordingly. The first cobalt source is preferably a cobalt source with higher activity, which is favorable for generating the amorphous first cobalt compound, and the second cobalt source is preferably a cobalt source with lower activity, which is favorable for generating the crystalline second cobalt compound; meanwhile, the two cobalt sources have different melting points, the first cobalt source has a lower melting point, the second cobalt source has a higher melting point, and the two cobalt sources can be distributed on the surface of the anode material in different modes by matching with different sintering temperatures. The two cobalt compounds with different crystal forms and distribution modes are matched with each other to jointly construct a three-dimensional structure, so that the combination effect between the first cobalt compound and the second cobalt compound can be improved, the interface performance between the first coating layer and the second coating layer is further improved, and the conductivity and the capacity retention rate of the anode material are improved.
Preferably, the temperature of the first sintering is 700 ℃ to 900 ℃, for example 700 ℃, 730 ℃, 750 ℃, 780 ℃, 800 ℃, 830 ℃, 850 ℃ or 900 ℃, preferably 750 ℃ to 850 ℃.
Preferably, the time of the first sintering is 12h to 30h, for example, 12, 14h, 15h, 18h, 20h, 22h, 25, 28h or 30h, etc., preferably 15h to 25 h.
Preferably, the temperature of the second sintering is 600 ℃ to 700 ℃, for example, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃ or the like, preferably 650 ℃ to 690 ℃.
Preferably, the time of the second sintering is 6h to 12h, for example, 6, 7h, 8h, 9h, 10h, 11h or 12h, etc., preferably 8h to 10 h.
The first sintering and the second sintering have different optimal temperatures, and are matched with different cobalt sources, so that the first coating layer and the second coating layer with different forms are formed. The first sintering is preferably carried out at a relatively high temperature of 700-900 ℃, which is beneficial to enabling the first cobalt source to form a surface-distributed first coating layer on the surface of the positive electrode material core; the second sintering is preferably carried out at a relatively low temperature of 600 ℃ to 700 ℃, which is beneficial to enabling the second cobalt source to form a second coating layer distributed in a point shape on the surface of the first coating layer, so that the second coating layer can be uniformly dispersed on the first coating layer, a three-dimensional structure constructed by the point-shaped coating layer and the planar coating layer is presented, the interface combination effect is improved, the structural stability of the anode material is improved, the direct current resistance of the anode material is further reduced, and the capacity retention rate of the anode material is improved.
As a further preferable technical solution of the preparation method of the present invention, mixing the positive electrode material core and the first cobalt source for the first sintering includes: mixing the positive electrode material core with CoOOH, and sintering at 700-900 ℃ for 12-30 h;
mixing the product after the first sintering with a second cobalt source, and performing second sintering to obtain the cathode material, wherein the second sintering comprises the following steps: and mixing the sintered product with CoN, and sintering at 600-700 ℃ for 6-12 h to obtain the cathode material.
In a third aspect, the invention provides a positive electrode sheet comprising the positive electrode material according to the first aspect.
Preferably, the positive electrode sheet further comprises conductive carbon black, carbon nanotubes and a binder, and the mass ratio of the positive electrode material, the conductive carbon black, the carbon nanotubes and the binder in the positive electrode sheet is (90 to 99):1:0.5:1, for example, 90:1:0.5:1, 91:1:0.5:1, 92:1:0.5:1, 93:1:0.5:1, 94:1:0.5:1, 95:1:0.5:1, 96:1:0.5:1, 97:1:0.5:1, 98:1:0.5:1 or 99:1:0.5: 1.
In a fourth aspect, the invention provides a lithium ion battery, wherein the lithium ion battery comprises the positive plate according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the surface of the core of the anode material is respectively coated with the first coating layer and the second coating layer, and the first coating layer and the second coating layer both comprise cobalt compounds, so that the ionic and electronic conductivity of the surface of the material can be effectively improved, and the internal resistance of the battery is reduced; meanwhile, the first coating layer and the second coating layer are good in combination effect, the interface structure is stable, the prepared battery has low direct current resistance and high capacity retention rate, and the battery also has good electrochemical performance at low temperature.
(2) According to the invention, cobalt sources with different activities and different sintering temperatures are preferably adopted to prepare the anode material, the forms and crystal forms of the first coating layer and the second coating layer can be regulated and controlled, the interface combination effect is improved, the structural stability of the anode material is improved, the direct current resistance of the anode material is further reduced, and the capacity retention rate of the anode material is improved.
Drawings
FIG. 1 is a DC resistance diagram at 25 ℃ for example 1 and comparative example 1.
FIG. 2 is a DC resistance diagram at-20 ℃ for example 1 and comparative example 1.
FIG. 3 is a graph showing the capacity retention at-20 ℃ in example 1 and comparative example 1.
Detailed Description
In the prior art, the electrochemical performance of the cathode material is improved by coating, but in the prior art, the coating layer has poor conductive effect, the interface structure is unstable during multilayer coating, and the material has low ionic and electronic conductivity, so that the diffusion of lithium ions is not facilitated, and the further development of the lithium ion battery is limited.
In order to at least solve the problems, the invention provides a positive electrode material and a preparation method and application thereof.
The embodiment of the invention provides a positive electrode material, which comprises a positive electrode material core, a first coating layer and a second coating layer, wherein the first coating layer is coated on the surface of the positive electrode material core, the second coating layer is coated on the surface of the first coating layer, the first coating layer comprises a first cobalt compound, and the second coating layer comprises a second cobalt compound.
According to the invention, the surface of the core of the anode material is respectively coated with the first coating layer and the second coating layer, and the first coating layer and the second coating layer both comprise cobalt compounds, so that the ionic and electronic conductivity of the surface of the material can be effectively improved, and the internal resistance of the battery is reduced; meanwhile, the first coating layer and the second coating layer are good in combination effect, the interface structure is stable, the prepared battery has low direct current resistance and high capacity retention rate, and the battery also has good electrochemical performance at low temperature.
In some embodiments, the ratio of the mass of the positive electrode material core to the total mass of the first and second cladding layers in the positive electrode material is (100-p): p, where p is from 0.005 to 2.
In some embodiments, the mass ratio of the first cladding layer to the second cladding layer is q (100-q), wherein q is 7 to 26, preferably 21 to 23.
In some embodiments, the first cladding layer and the second cladding layer each comprise cobalt oxide.
In some embodiments, the first coating layer is distributed on the surface of the positive electrode material core in a planar mode.
In some embodiments, the crystalline form of the first cobalt compound is amorphous.
In some embodiments, the second cladding layer is distributed in dots on the surface of the first cladding layer.
In some embodiments, the crystalline form of the second cobalt compound is crystalline.
In some embodiments, the chemical composition of the positive electrode material core is LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.13.
In some embodiments, the positive electrode material core is a quadratic sphere.
In some embodiments, the cathode material core is a single crystal material.
In some embodiments, the positive electrode material core is spherical quadratic and the particle size D50 of the positive electrode material core is 9 μm to 25 μm.
In some embodiments, the cathode material core is a single crystal material, and the particle size D50 of the cathode material core is 2 μm to 6 μm.
Still another embodiment provides a method for preparing the positive electrode material, the method comprising:
mixing the positive electrode material core and a first cobalt source, and performing first sintering; and
and mixing the product obtained after the first sintering with a second cobalt source, and carrying out second sintering to obtain the cathode material.
In some embodiments, the ratio of the total mass of the first and second cobalt sources to the mass of the cathode material core is m (100-m), wherein m is from 0.01 to 2, preferably from 1.4 to 1.6.
In some embodiments, the mass ratio of the first cobalt source to the second cobalt source is n (100-n), wherein n is 10 to 30, preferably 24 to 26.
In some embodiments, the first cobalt source comprises CoOOH, CoCO3、Co(NO3)2And Co (NO)3)4Preferably CoOOH, or a combination of at least two thereof.
In some embodiments, the second cobalt source comprises CoF2、CoF3、CoO、CoO2、Co3O4、CoN、Co2N、CoH、Co3H and Co3(BO3)2Any one or a combination of at least two of them, preferably CoN and/or Co2N, more preferably CoN.
In some embodiments, the temperature of the first sintering is 700 ℃ to 900 ℃, preferably 750 ℃ to 850 ℃.
In some embodiments, the time for the first sintering is from 12h to 30h, preferably from 15h to 25 h.
In some embodiments, the temperature of the second sintering is 600 ℃ to 700 ℃, preferably 650 ℃ to 690 ℃.
In some embodiments, the time for the second sintering is 6 to 12 hours, preferably 8 to 10 hours.
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The present embodiment provides a positive electrode material including single-crystal LiNi0.53Co0.11Mn0.36O2The core is coated on the single crystal LiNi in a planar form0.53Co0.11Mn0.36O2The positive electrode material comprises a first coating layer on the surface of an inner core and a second coating layer coated on the surface of the first coating layer in a dot-shaped mode, wherein the first coating layer comprises amorphous cobalt oxide, the second coating layer comprises crystalline cobalt oxide, the mass ratio of the inner core of the positive electrode material to the total mass of the first coating layer and the second coating layer in the positive electrode material is 98.54:1.46, and the mass ratio of the first coating layer to the second coating layer is 21: 79.
The embodiment also provides a preparation method of the cathode material, and the preparation method comprises the following steps:
(1) mixing CoOOH and single crystal LiNi0.53Co0.11Mn0.36O2Mixing the cores, and sintering at 800 ℃ for 20 h;
(2) and (2) mixing the product sintered in the step (1) with CoN, and sintering at 650 ℃ for 20h to obtain the cathode material.
Wherein the mass ratio of CoOOH in the step (1) to CoN in the step (2) is 25:75, and the total mass of CoOOH and CoN is equal to that of single-crystal LiNi0.53Co0.11Mn0.36O2The mass ratio of the cores was 1.5: 98.5.
Example 2
The present embodiment provides a positive electrode material including a secondary spherical LiNi0.53Co0.11Mn0.36O2The inner core is coated on the secondary spherical LiNi in a planar form0.53Co0.11Mn0.36O2The positive electrode material comprises a first coating layer on the surface of an inner core and a second coating layer coated on the surface of the first coating layer in a dot-shaped mode, wherein the first coating layer comprises amorphous cobalt oxide, the second coating layer comprises crystalline cobalt oxide, the mass ratio of the inner core of the positive electrode material to the total mass of the first coating layer and the second coating layer in the positive electrode material is 99.25:0.75, and the mass ratio of the first coating layer to the second coating layer is 12.6: 87.4.
The embodiment also provides a preparation method of the cathode material, and the preparation method comprises the following steps:
(1) mixing CoCO3And secondary spherical LiNi0.53Co0.11Mn0.36O2Mixing the cores, and sintering at 750 ℃ for 25 h;
(2) mixing the sintered product obtained in the step (1) with CoF2Mixing, and sintering at 700 ℃ for 7h to obtain the cathode material;
wherein, CoCO in the step (1)3And CoF in step (2)2In a mass ratio of 15:85, CoCO3And CoF2Total mass of (2) and secondary spherical LiNi0.53Co0.11Mn0.36O2The mass ratio of the cores was 1: 99.
Example 3
The present embodiment provides a positive electrode material including single-crystal LiNi0.53Co0.11Mn0.36O2The core is coated on the single crystal LiNi in a planar form0.53Co0.11Mn0.36O2The positive electrode material comprises a first coating layer on the surface of an inner core and a second coating layer coated on the surface of the first coating layer in a dot-shaped mode, wherein the first coating layer comprises amorphous cobalt oxide, the second coating layer comprises crystalline cobalt oxide, the ratio of the mass of the inner core of the positive electrode material to the total mass of the first coating layer and the second coating layer in the positive electrode material is 98.34:1.66, and the mass ratio of the first coating layer to the second coating layer is 15: 85.
The embodiment also provides a preparation method of the cathode material, and the preparation method comprises the following steps:
(1) mixing Co (NO)3)2And single crystal LiNi0.53Co0.11Mn0.36O2Mixing the cores, and sintering at 850 ℃ for 15 h;
(2) and (2) mixing the product sintered in the step (1) with CoO, and sintering at 600 ℃ for 10h to obtain the cathode material.
Wherein, in the step (1), Co (NO)3)2And the mass ratio of CoO in the step (2) is 30:70, Co (NO)3)2And total mass of CoO and Single Crystal LiNi0.53Co0.11Mn0.36O2The mass ratio of the cores was 2: 98.
Example 4
The same as in example 1, except that CoOOH was replaced with CoN in step (1) so that the first clad layer included crystalline cobalt oxide.
Example 5
The same as in example 1 except that CoN in step (2) was replaced with CoOOH so that the second cladding layer included amorphous cobalt oxide.
Example 6
Except that CoOOH in the step (1) is replaced by Co (NO)3)2Otherwise, the same procedure as in example 1 was repeated.
Example 7
The procedure was as in example 1 except that CoN was replaced with CoO in the step (2).
Example 8
Except that the sintering temperature in the step (1) is replaced by 280 ℃ so that the first coating layer is coated on the single crystal LiNi in a dotted form0.53Co0.11Mn0.36O2The same as example 1 except for the surface of the inner core.
Example 9
The same procedure as in example 1 was repeated, except that the sintering temperature in step (2) was changed to 750 ℃ so that the second clad layer was coated on the surface of the first clad layer in a planar form.
Example 10
The procedure was as in example 1 except that the mass ratio of CoOOH in step (1) to CoN in step (2) was 35: 65.
Example 11
The procedure was as in example 1 except that the mass ratio of CoOOH in step (1) to CoN in step (2) was 8: 92.
Comparative example 1
LiNi except single crystal0.53Co0.11Mn0.36O2The surface of the core was not covered with the coating layer, and the rest was the same as in example 1.
Comparative example 2
Except that the operation of step (1) is not conducted, i.e., single-crystal LiNi0.53Co0.11Mn0.36O2The core surface was the same as in example 1 except that the first coating layer was not included.
Comparative example 3
Except that the operation of step (2) is not conducted, i.e., single-crystal LiNi0.53Co0.11Mn0.36O2The same as example 1 was repeated except that the surface of the inner core did not contain the second coating layer.
Comparative example 4
Except that CoOOH in the step (1) is replaced by Ni (NO)3)2Otherwise, the same procedure as in example 1 was repeated.
The positive electrode materials prepared in examples 1 to 11 and comparative examples 1 to 4 were used to prepare a 1Ah pouch cell, and the preparation method included the following steps:
dispersing and stirring conductive carbon black, carbon nano tubes, NMP and polyvinylidene fluoride at a mass ratio of 1:0.5:40:1 for 2h to prepare conductive slurry, then stirring and mixing the positive electrode materials prepared in examples 1 to 11 and comparative examples 1 to 4 with the conductive slurry at a high speed to prepare positive electrode slurry with certain viscosity, wherein the mass ratio of the positive electrode materials, the conductive carbon black, the carbon nano tubes, the NMP and the polyvinylidene fluoride in the positive electrode slurry is 97.5:1:0.5:40:1, uniformly coating the positive electrode slurry on an aluminum foil by using a scraper, placing the aluminum foil in a blast drying oven, and drying at 120 ℃ for 20min to obtain a positive electrode sheet; rolling and cutting the positive plate, taking graphite as a negative electrode and LiPF6And (4) assembling the 1Ah soft package battery by using the ester-based solution as an electrolyte.
First, DC resistance test
After the formation and aging process was performed on the 1Ah pouch cells containing the positive electrode materials of examples 1 to 11 and comparative examples 1 to 4, the cells were charged to 4.3V at a rate of 0.33C and discharged to 2.8V at room temperature, to obtain a capacity C0Then, after the state of charge (SOC) of the battery is adjusted to 70% SOC, the battery is discharged at 4C rate for 30s, and the voltage difference between before and after discharge is divided by the current density to obtain the dc resistance value of the battery at the SOC. The DC resistance values of 50% SOC and 20% SOC can be measured by the method, and the test results are shown in Table 1.
Similarly, the 1Ah pouch cells containing the positive electrode sheets of examples 1 to 11 and comparative examples 1 to 4 were placed in a constant temperature oven at-20 ℃ to test the DC resistance of the cells at-20 ℃ and the test results are shown in Table 1.
Second, capacity retention rate side amount
Placing the 1Ah soft package battery subjected to direct current resistance test in a constant-temperature oven at-20 ℃, charging and discharging twice at a voltage window of 2.8V to 4.3V with a rate of 0.33C, and recording the discharge capacity C of the second time1，C1/C0Namely, the capacity retention rate of the battery at a low temperature of-20 ℃, and the test results are shown in table 1.
TABLE 1
It can be seen from the above embodiments 1 to 11 that, in the present invention, the first cladding layer and the second cladding layer are respectively clad on the surface of the core of the positive electrode material, and both the first cladding layer and the second cladding layer include cobalt compounds, which can effectively improve the ionic and electronic conductivity of the surface of the material, thereby reducing the internal resistance of the battery; meanwhile, the first coating layer and the second coating layer are good in combination effect, the interface structure is stable, the prepared battery has low direct current resistance and high capacity retention rate, and the battery also has good electrochemical performance at low temperature.
As can be seen from comparison of example 1 with examples 4 to 5, the crystalline form of the cobalt compound in the first coating layer and the second coating layer in the positive electrode material affects the performance of the battery produced. In the embodiments 4 and 5, the same cobalt source is used for sintering, and the surface of the core of the positive electrode material is coated with the coating layer with the same crystal form, so that the cobalt oxide in the second coating layer cannot be uniformly dispersed on the cobalt oxide of the first coating layer, the stable three-dimensional structure between the first coating layer and the second coating layer is affected, the interface effect is poor, and the conductivity and the stability of the positive electrode material are further affected, so that the conductivity and the capacity retention rate of the positive electrode material in the embodiments 4 and 5 at 25 ℃ and-20 ℃ are slightly lower than those in the embodiment 1; while both the first and second cobalt sources are preferred, it is seen from a comparison of example 1 with examples 6 to 7 that the first cobalt source is CoOOH and the second cobalt source is CoN, which is the most effective.
It is understood from a comparison of example 1 with examples 8 to 9 that the morphology of the coating layer affects the performance of the prepared positive electrode material. In example 8 and example 9, the sintering temperature in the step (1) and the sintering temperature in the step (2) were changed, respectively, so that the first cladding layer and the second cladding layer had the same cladding morphology; when the first coating layer and the second coating layer are both distributed in a surface shape or in a point shape, the three-dimensional structure is difficult to form, and the interface combination effect is affected, so that the direct current resistance and the capacity retention rate of the cathode material are affected, and therefore the direct current resistance and the capacity retention rate of the embodiments 8 to 9 at different temperatures are slightly higher than those of the embodiment 1, and the capacity retention rate is slightly lower than that of the embodiment 1.
It can be seen from the comparison between example 1 and examples 10 to 11 that the optimum charge ratio of the second cobalt source of the first cobalt source is present, and when the content of the first cobalt source is more or less, the improvement effect of low temperature dc resistance and capacity retention is not obvious.
As can be seen from the comparison between example 1 and comparative examples 1 to 3, when only one coating layer is included in the positive electrode material, even if the coating layer is not included, the ionic and electronic conductivity of the surface of the material cannot be effectively improved, fig. 1 is a direct current resistance diagram at 25 ℃ of the pouch battery including the positive electrode material of example 1 and comparative example 1, fig. 2 is a direct current resistance diagram at-20 ℃ of the pouch battery including the positive electrode material of example 1 and comparative example 1, fig. 3 is a capacity retention diagram at-20 ℃ of the pouch battery including the positive electrode material of example 1 and comparative example 1, it can be seen from fig. 1 to 3 that the direct current resistance of the battery manufactured without the coating layer at different temperatures is high and the capacity retention ratio is poor, and the coating layer is included in comparative example 2 and comparative example 3 even if the distribution state of the coating layer is different from that of the coating layer, the conductivity and capacity retention rate thereof are also poor.
As can be seen from the comparison of example 1 with comparative example 4, the selection of the coating layer affects the performance of the positive electrode material. The coating layer in comparative example 4 contains cobalt oxide and nickel oxide, wherein nickel oxide has poor conductivity, has a different melting point from cobalt oxide, has poor interface bonding effect during sintering, is prone to chemical distortion during charge-discharge cycles, and affects interface structure stability, so that the conductivity and capacity retention rate of comparative example 4 are inferior to those of example 1.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The positive electrode material is characterized by comprising a positive electrode material core, a first coating layer and a second coating layer, wherein the first coating layer is coated on the surface of the positive electrode material core, the second coating layer is coated on the surface of the first coating layer, the first coating layer comprises a first cobalt compound, and the second coating layer comprises a second cobalt compound.
2. The positive electrode material according to claim 1, wherein a ratio of a mass of the positive electrode material core to a total mass of the first clad layer and the second clad layer in the positive electrode material is (100-p): p, wherein p is 0.005 to 2;
preferably, the mass ratio of the first coating layer to the second coating layer is q (100-q), wherein q is 7 to 26, preferably 21 to 23;
preferably, the first cladding layer and the second cladding layer both comprise cobalt oxide.
3. The cathode material according to claim 1 or 2, wherein the first coating layer is distributed on the surface of the cathode material core in a planar manner;
preferably, the crystalline form of the first cobalt compound is amorphous;
preferably, the second coating layers are distributed on the surface of the first coating layer in a dotted manner;
preferably, the crystalline form of the second cobalt compound is crystalline.
4. The positive electrode material according to any one of claims 1 to 3, wherein the chemical composition of the positive electrode material core is LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.5 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.13;
preferably, the positive electrode material inner core is in a shape of a quadratic sphere;
preferably, the cathode material inner core is a single crystal material;
preferably, the positive electrode material core is in a shape of a quadratic sphere, and the particle size D50 of the positive electrode material core is 9-25 μm;
preferably, the cathode material core is a single crystal material, and the particle size D50 of the cathode material core is 2-6 μm.
5. A method for producing the positive electrode material according to any one of claims 1 to 4, characterized by comprising:
mixing the positive electrode material core and a first cobalt source, and performing first sintering; and
and mixing the product obtained after the first sintering with a second cobalt source, and carrying out second sintering to obtain the cathode material.
6. The production method according to claim 5, wherein the ratio of the total mass of the first cobalt source and the second cobalt source to the mass of the positive electrode material core is m (100-m), wherein m is 0.01 to 2, preferably 1.4 to 1.6;
preferably, the mass ratio of the first cobalt source to the second cobalt source is n (100-n), wherein n is 10 to 30, preferably 24 to 26;
preferably, the first cobalt source comprises CoOOH, CoCO3、Co(NO3)2And Co (NO)3)4Any one or a combination of at least two of them, preferably CoOOH;
preferably, the second cobalt source comprises CoF2、CoF3、CoO、CoO2、Co3O4、CoN、Co2N、CoH、Co3H and Co3(BO3)2Any one or a combination of at least two of them, preferably CoN and/or Co2N, more preferably CoN.
7. The method for preparing according to claim 5 or 6, wherein the temperature of the first sintering is 700 ℃ to 900 ℃, preferably 750 ℃ to 850 ℃;
preferably, the time of the first sintering is 12h to 30h, preferably 15h to 25 h;
preferably, the temperature of the second sintering is 600 ℃ to 700 ℃, preferably 650 ℃ to 690 ℃;
preferably, the time of the second sintering is 6 to 12 hours, preferably 8 to 10 hours.
8. The production method according to any one of claims 5 to 7, wherein mixing the positive electrode material core and the first cobalt source to perform the first sintering includes: mixing the positive electrode material core with CoOOH, and sintering at 700-900 ℃ for 12-30 h;
mixing the product after the first sintering with a second cobalt source, and performing second sintering to obtain the cathode material, wherein the second sintering comprises the following steps: and mixing the sintered product with CoN, and sintering at 600-700 ℃ for 6-12 h to obtain the cathode material.
9. A positive electrode sheet, characterized in that the positive electrode sheet comprises the positive electrode material according to any one of claims 1 to 4;
preferably, the positive plate further comprises conductive carbon black, carbon nanotubes and a binder, and the mass ratio of the positive electrode material, the conductive carbon black, the carbon nanotubes and the binder in the positive plate is (90-99): 1:0.5: 1.
10. A lithium ion battery, characterized in that the positive electrode sheet according to claim 9 is included in the lithium ion battery.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218046B1 (en) * | 1997-09-10 | 2001-04-17 | Matsushita Electric Industrial Co., Ltd. | Positive electrode material for alkaline storage battery and method of producing the same |
| CN103985857A (en) * | 2014-05-19 | 2014-08-13 | 青岛乾运高科新材料股份有限公司 | Mixed lithium battery positive material and preparation method thereof |
| KR20160040116A (en) * | 2014-10-02 | 2016-04-12 | 주식회사 엘지화학 | Positive electrode active material for lithium secondary battery, method for preparing the same, and lithium secondary battery comprising the same |
| CN109713262A (en) * | 2018-12-17 | 2019-05-03 | 浙江衡远新能源科技有限公司 | A kind of preparation method of cobalt/cobalt oxide cladding tertiary cathode material |
| CN110459736A (en) * | 2018-05-07 | 2019-11-15 | 宁德新能源科技有限公司 | Positive electrode and anode pole piece and lithium ion battery containing the positive electrode |
| CN111200120A (en) * | 2018-11-20 | 2020-05-26 | 深圳市贝特瑞纳米科技有限公司 | Ternary cathode material, preparation method thereof and lithium ion battery |
| CN112117454A (en) * | 2020-10-09 | 2020-12-22 | 中伟新材料股份有限公司 | Ternary cathode material, preparation method thereof, lithium ion battery and power utilization equipment |
| CN112382741A (en) * | 2020-10-12 | 2021-02-19 | 深圳市贝特瑞纳米科技有限公司 | High-nickel positive electrode material, preparation method thereof and lithium ion secondary battery |
| US20210119209A1 (en) * | 2018-12-29 | 2021-04-22 | Contemporary Amperex Technology Co., Limited | Positive electrode material, preparation method and uses thereof |
| JP2021096901A (en) * | 2019-12-13 | 2021-06-24 | Tdk株式会社 | Lithium ion secondary battery |
| CN113036105A (en) * | 2021-03-09 | 2021-06-25 | 欣旺达电动汽车电池有限公司 | Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery |
| CN113346069A (en) * | 2018-02-11 | 2021-09-03 | 宁德时代新能源科技股份有限公司 | Positive electrode material, preparation method thereof and battery |
-
2021
- 2021-11-09 CN CN202111319925.9A patent/CN114122379B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6218046B1 (en) * | 1997-09-10 | 2001-04-17 | Matsushita Electric Industrial Co., Ltd. | Positive electrode material for alkaline storage battery and method of producing the same |
| CN103985857A (en) * | 2014-05-19 | 2014-08-13 | 青岛乾运高科新材料股份有限公司 | Mixed lithium battery positive material and preparation method thereof |
| KR20160040116A (en) * | 2014-10-02 | 2016-04-12 | 주식회사 엘지화학 | Positive electrode active material for lithium secondary battery, method for preparing the same, and lithium secondary battery comprising the same |
| CN113346069A (en) * | 2018-02-11 | 2021-09-03 | 宁德时代新能源科技股份有限公司 | Positive electrode material, preparation method thereof and battery |
| CN110459736A (en) * | 2018-05-07 | 2019-11-15 | 宁德新能源科技有限公司 | Positive electrode and anode pole piece and lithium ion battery containing the positive electrode |
| CN111200120A (en) * | 2018-11-20 | 2020-05-26 | 深圳市贝特瑞纳米科技有限公司 | Ternary cathode material, preparation method thereof and lithium ion battery |
| CN109713262A (en) * | 2018-12-17 | 2019-05-03 | 浙江衡远新能源科技有限公司 | A kind of preparation method of cobalt/cobalt oxide cladding tertiary cathode material |
| US20210119209A1 (en) * | 2018-12-29 | 2021-04-22 | Contemporary Amperex Technology Co., Limited | Positive electrode material, preparation method and uses thereof |
| JP2021096901A (en) * | 2019-12-13 | 2021-06-24 | Tdk株式会社 | Lithium ion secondary battery |
| CN112117454A (en) * | 2020-10-09 | 2020-12-22 | 中伟新材料股份有限公司 | Ternary cathode material, preparation method thereof, lithium ion battery and power utilization equipment |
| CN112382741A (en) * | 2020-10-12 | 2021-02-19 | 深圳市贝特瑞纳米科技有限公司 | High-nickel positive electrode material, preparation method thereof and lithium ion secondary battery |
| CN113036105A (en) * | 2021-03-09 | 2021-06-25 | 欣旺达电动汽车电池有限公司 | Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| HONGQIANG WANG等: "Enhanced interfacial reaction interface stability of Ni-rich cathode materials by fabricating dual-modified layer coating for lithium-ion batteries", ELECTROCHIMICA ACTA, vol. 366, pages 1 - 11 * |
| 蔡济钧等: "CoAl2O4包覆LiNi(1/3)Co(1/3)Mn(1/3)O2的电化学性能", 电化学, vol. 21, no. 02, pages 145 - 151 * |
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