CN114249355A - Layered cobaltosic oxide material and preparation method and application thereof - Google Patents
Layered cobaltosic oxide material and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a layered cobaltosic oxide material, a preparation method and an application thereof. The layered cobaltosic oxide material comprises a plurality of loose layers and a plurality of compact layers, wherein the loose layers and the compact layers are arranged in an overlapped mode from inside to outside, the loose layers are located in the center, the compact layers are located on the outermost layers, and the density of the loose layers is smaller than that of the compact layers. The layered cobaltosic oxide material provided by the application has a regular shape, is internally of a multilayer loose and compact alternate layered structure, is stable and ordered in structure and uniform in shape, and can be used for preparing a lithium ion battery to improve the cycling stability of the battery material.
Description
Technical Field
The application relates to the technical field of lithium ion battery anode materials, in particular to a layered cobaltosic oxide material and a preparation method and application thereof.
Background
With the rapid development of social economy, worldwide problems such as energy shortage, environmental protection, carbon peak reaching, carbon neutralization and the like are paid more and more attention, and the utilization of clean renewable energy becomes a future development trend.
The lithium cobaltate anode material has high voltage, high power and stable cycle performance and is widely applied to the fields of 3C, electric automobiles, electric tools, energy storage, wearable electronic products and the like. Lithium cobaltate is usually prepared by taking lithium carbonate and cobaltosic oxide as raw materials and adopting a high-temperature solid-phase method; wherein, the cobaltosic oxide is used as a precursor of the lithium cobaltate positive electrode material, and the granularity, consistency, surface appearance and internal structure of the cobaltosic oxide have important influence on the performance of the lithium cobaltate positive electrode material. For example, the internal structure of the cobaltosic oxide can influence the development of primary particles of the lithium cobaltate, and further influence the cycle performance of the lithium ion battery, so that the control of the internal structure of the cobaltosic oxide has important significance.
In the prior art, a coprecipitation method is generally adopted in combination with calcination to prepare a cobaltosic oxide material with a nano structure. However, the prepared nano-structure material is generally small in size and loose in structure, so that the density is low, the cycling stability of the battery material is not facilitated, and the energy density of the battery is reduced. Patent CN110078132A discloses a method for preparing doped cobaltosic oxide by intermittent coating, wherein the doping distribution of aluminum in the cobaltosic oxide material is uniform and the structure is compact by controlling the gradient addition of cobalt salt in the coprecipitation process; the prepared large-particle-size particle IVThe laser granularity D50 of the cobaltosic oxide is 17-19 mu m, and the laser granularity D50 of the small-granularity cobaltosic oxide is 3-5 mu m. However, as can be seen from the scanning electron microscope image, the prepared cobaltosic oxide material has irregular shape, a plurality of macropores on the surface, uneven external structure and tap density of only 2.0g/cm3On the left and right sides, the cycle performance of the lithium cobaltate cathode material is not improved.
Therefore, the cobaltosic oxide material which is regular in appearance, uniform in inner and outer structures and adjustable has important research significance and application value.
Disclosure of Invention
In order to solve the above problems, the present application provides a layered cobaltosic oxide material.
Another object of the present application is to provide a method for preparing a layered cobaltosic oxide material.
Another object of the present application is to provide an application of the layered cobaltosic oxide material in the preparation of a lithium ion battery.
The application provides a stratiform cobaltosic oxide material, including a plurality of loose layers and a plurality of compact layer, loose layer with compact layer is by interior outside overlap setting, loose level in the center, compact layer is located outermost, loose layer's density is less than compact layer's density.
The application also provides a preparation method of the layered cobaltosic oxide material.
The application of the layered cobaltosic oxide material in the preparation of the lithium ion battery is also within the protection scope of the application.
Compared with the prior art, the beneficial effects of this application are:
the layered cobaltosic oxide material provided by the application has the advantages that the interior is of a multilayer loose and dense alternate layered structure, the structure is stable and ordered, the appearance is uniform, and the cyclic stability of the material can be improved when the layered cobaltosic oxide material is used for preparing a lithium ion battery.
Drawings
Fig. 1 is a schematic structural diagram of a layered cobaltosic oxide material prepared in an example, wherein: 1-a first loose layer, 2-a first dense layer, 3-a second loose layer, and 4-a second dense layer;
fig. 2 is an SEM image of the layered cobaltosic oxide material prepared in the example.
Fig. 3 is a cross-sectional SEM image of the layered cobaltosic oxide material prepared in example 1.
Fig. 4 is a cross-sectional SEM image of the tricobalt tetraoxide material prepared in comparative example 1.
Description of the main elements
First porous layer 1
First dense layer 2
Second porous layer 3
Second dense layer 4
Detailed Description
The present application is further illustrated below with reference to examples. These examples are intended to be illustrative of the present application only and are not intended to limit the scope of the present application. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present disclosure are intended to be covered by the claims.
An embodiment of the application provides a stratiform cobaltosic oxide material, including a plurality of loose layers and a plurality of compact layers, loose layer with compact layer is by inside to outside overlap setting, loose level in center, compact layer is located outmost, loose layer's density is less than compact layer's density.
The cobaltosic oxide is used as a matrix of the lithium cobaltate positive electrode material, and the internal structure of the cobaltosic oxide can influence the structure of lithium cobaltate particles, so that the electrochemical performance of the lithium ion battery is influenced. In the lithium ion battery, the loose structure can shorten the diffusion distance of lithium ions, is beneficial to the removal and the embedding of the lithium ions in the charging and discharging process, has small damage to the structure and is beneficial to improving the cycle performance of the material. However, if the structure of the positive electrode material is too loose, the pressure resistance is poor, the roll is fragile, the structure is damaged, and the cycle is deteriorated.
The application provides a layered cobaltosic oxide material with multiple layers of loose and dense layers, wherein the layered structure has higher crystallinity, and the loose and dense layers are favorable for improving the compression resistance of the material, the loose structure can improve the diffusion performance of lithium ions, and the dense layer can maintain the structural stability of the material, so that the electrochemical performance of the material is improved.
In the embodiment, the particle size of the layered cobaltosic oxide material is 12-18 μm, the porosity is 5-30%, and the true density is 5.94-6.09 g/cm3。
When the particle size of the cobaltosic oxide material is 12-14 mu m, the particle radius is smaller while other properties of the material are ensured, the diffusion of lithium ions is facilitated, and the cobaltosic oxide material is mainly applied to a fast-charging material; when the particle size of the cobaltosic oxide material is 14-18 mu m, the high-temperature cycle performance of the anode material is improved, and the electrochemical performance of the material under high voltage is improved. The porosity is 5-30%, and the true density is 5.94-6.09 g/cm3And in addition, the crystallinity is improved in the sintering process, and the electrochemical performance of the anode material is favorably optimized.
Fig. 1 is a schematic structural diagram of a layered cobaltosic oxide material provided in the present application, and as can be seen from the diagram, the layered cobaltosic oxide material sequentially includes, from inside to outside, a first loose layer 1, a first dense layer 2, a second loose layer 3, and a second dense layer 4.
In the present embodiment, the first porous layer 1 has a thickness of 2 to 4 μm, a porosity of 10 to 35%, and a true density of 5.94 to 6.0g/cm3(ii) a The first dense layer 2 has a thickness of 1 to 3 μm, a porosity of 0.8 to 4%, and a true density of 6.05 to 6.09g/cm3(ii) a The thickness of the second loose layer 3 is 0.1-0.5 mu m, the porosity is 8-20%, and the true density is 6.01-6.04 g/cm3(ii) a The thickness of the second compact layer 4 is 2-5 μm, the porosity is 1% -5%, and the true density is 6.04-6.07 g/cm3。
In the present application, the porosity is the percentage value of the volume of all pores inside the bulk particulate material to the total volume of the material in a natural state. The porosity of the material directly reflects the degree of compaction of the material, and low porosity of the material indicates high degree of compaction, whereas high porosity of the material indicates low degree of compaction, and indicates that the interior of the material is relatively loose. The testing principle of porosity in this patent is: carrying out ion grinding cutting (such as argon ion beam cutting) on the bulk granular material to obtain a relatively flat and clear material internal section electron microscope image, and carrying out automatic intelligent identification on the material section electron microscope image by using image processing software to obtain the porosity of each layer region such as a plurality of loose layers, compact layers and the like in the material.
The true density is the ratio of the actual mass of the particulate material to the volume of the material (excluding the volume of the open pores of the material), and is a test value obtained by analysis of a true densitometer, wherein the test gas used for analysis of the true densitometer is helium. The working principle of the true density instrument is that an Archimedes principle-gas displacement method is applied, according to a formula PV ═ nRT (Bohr's law), under a certain condition, small-molecule (small-diameter) inert gas is used for entering the interior of a material, pores can be formed, the true volume (also called skeleton volume) of the sample is accurately measured by measuring the change of the gas volume of a sample cabin caused by placing the sample in the sample cabin, and the actual mass of the material and the skeleton volume of the material are subjected to division operation to obtain the true density of the material.
The layered cobaltosic oxide material provided by the application has a regular and ordered internal structure, a plurality of layers of compact layers and loose layers are arranged in order, the true density is high, the porosity is high, and the improvement on the cycle performance of a battery anode material and the energy density of a lithium ion battery is facilitated.
In this embodiment, there is also provided a method for preparing the layered cobaltosic oxide material, including the steps of:
s1: adding water into the reaction kettle as a base solution, adding 200kg of cobalt carbonate as a seed crystal, wherein the granularity of the seed crystal is 8-14 mu m, and adjusting the pH to 7.5-8.5; adding a cobalt salt solution, a soluble metal salt solution and a precipitant solution into a reaction kettle in a concurrent flow manner, wherein the feeding flow ratio of the cobalt salt solution, the precipitant solution and the soluble metal salt solution is (10-20): (20-32): 1; wherein the feeding flow rate of the initial cobalt salt solution is 25-30 g/L, after 5-25 h, the feeding flow rate of the cobalt salt solution is adjusted to be 5-25 g/L, and after 15-40 h, the feeding flow rate of the cobalt salt solution is adjusted to be 65 g/L; meanwhile, the feeding flow rates of the precipitant solution and the soluble metal salt solution are adjusted in proportion;
s2: aging, filtering and washing a product obtained after the coprecipitation reaction in the S1;
s3: calcining the product obtained in S2 under an atmosphere, wherein the calcining process comprises a drying section: the temperature is 150-200 ℃; a pyrolysis section: the temperature is 200-300 ℃; high-temperature oxidation crystallization section: the temperature is 350-750 ℃, and the layered cobaltosic oxide material is obtained after calcination.
Although the lithium cobaltate material has the advantages of high voltage, stable structure, good cycling stability and the like, when more than 50% of lithium is removed by charging the lithium cobaltate, irreversible phase change can occur to further influence the cycling performance and the safety performance of the lithium ion battery. At present, the method mainly adopted is to dope a metal element (mainly aluminum), and the structure of lithium cobaltate is stabilized by using the stability of the metal element in the charging and discharging processes. However, in the process of preparing doped cobaltosic oxide by coprecipitation, the stacking order of cobaltosic oxide is deteriorated due to the existence of metal elements, particles with looseness and low tap density are easily formed, and the structural stability is poor.
The method comprises the steps of carrying out gradient cocurrent feeding on each component, and initially forming a first loose layer in the inner part; the feeding flow is changed while the reaction time is controlled, after the flow is adjusted, the growth speed of the particles is accelerated, after a period of time is caused by the change of the growth speed of the inner layer and the outer layer, the gaps on the surfaces of the particles are filled and leveled to become compact (a first compact layer), the growth speed is accelerated at the moment, primary particles are refined and are stacked on the surfaces to form a loose structure (a second loose layer), and the surfaces of the primary particles become more and more compact (a second compact layer) along with the increase of the solid content in the reaction system. Then, by regulating and controlling the calcining atmosphere, the crystal seeds of the loose layer grow up quickly, the structure is loose, the distance between the primary particles inside is large, the calcining shrinkage is serious, a large loose layer is formed, the small structure of the primary particles in the precipitation process of the compact layer is compact, and the layered cobaltosic oxide material with a compact structure is obtained by calcining.
In this embodiment, the cobalt salt is at least one of cobalt nitrate, cobalt sulfate, or cobalt chloride; the soluble metal salt is at least one of nickel salt, manganese salt, aluminum salt, magnesium salt, calcium salt, zirconium salt or yttrium salt; the precipitant is at least one of ammonium bicarbonate, ammonia water or urea.
In the embodiment, the concentrations of the cobalt salt solution, the soluble metal salt solution and the precipitant solution are respectively 110-150 g/L, 20-40 g/L and 140-200 g/L.
In the embodiment, the temperature of the coprecipitation reaction in S1 is 45-55 ℃, and the precipitation time is 85-105 h; the aging time in S2 was 2 h.
In the present embodiment, the washing temperature in S2 is 20 to 60 ℃; washed to TDS (Total dissolved solids) < 50 ppm.
In this embodiment, the atmosphere in the drying section and the pyrolysis section in S3 is one of nitrogen gas and helium gas; the atmosphere of the high-temperature oxidation crystallization section is air or oxygen.
Further, the calcining atmosphere is in a low-pressure or negative-pressure state.
The preparation and properties of the layered cobaltosic oxide material of the present application are illustrated below using specific examples and comparative examples.
It should be noted that the feeding flow rate of the solution in the present application is limited by the used equipment, and is not limited to a specific value, and the solution can be implemented by using other equipment corresponding to different gradient feeding flow rates.
Example 1
A layered cobaltosic oxide material is prepared by the following steps:
s1: preparing 20g/L of aluminum sulfate solution, 100g/L of cobalt chloride solution and 130g/L of ammonium bicarbonate solution by using deionized water;
s2: adding 200L of deionized water as a base solution into a reaction system, adding 200kg of cobalt carbonate as a seed crystal, wherein the granularity of the seed crystal is about 10 mu m, and adjusting the pH to 8.0; then adding the prepared cobalt chloride solution, ammonium bicarbonate solution and aluminum sulfate solution into a reaction kettle simultaneously in a parallel flow feeding mode, wherein the feeding flow ratio of the cobalt chloride solution, the ammonium bicarbonate solution and the aluminum sulfate solution is 12:23.8: 1; the temperature of the reaction kettle is 48 ℃, and the stirring speed is 280 r/min; the feeding flow of the cobalt chloride solution is gradually increased in the feeding process, the initial cobalt chloride solution flow is 30L/h, and the cobalt chloride solution flow is adjusted to 48L/h after the cobalt chloride solution is fed for 24 hours; after feeding for 40 hours, the flow rate of the cobalt chloride solution is adjusted to 65L/h; the feeding flow rates of the corresponding ammonium bicarbonate solution and the corresponding aluminum sulfate solution are synchronously adjusted according to the proportion, and the reaction is stopped after 95 hours;
s3: transferring the product of the coprecipitation reaction in S2 to an aging tank for aging for 2h, washing with 50 deg.C salt-free water in a centrifuge for 6 times (1 m each time)3After the water is washed, the water is washed until the TDS of the washing water is less than 50 ppm;
s4: and (3) carrying out sectional calcination on the washed product in the S3, wherein the drying section: calcining at 200 deg.C for 2h without opening air pressure; a pyrolysis section: calcining at 300 ℃ for 3h without opening air pressure; high-temperature oxidation crystallization section: calcining at 740 deg.C for 1h, and introducing air under appropriate pressure to obtain layered cobaltosic oxide material.
Fig. 2 and 3 are SEM images of cross-sectional SEM images of the layered cobaltosic oxide material prepared in example 1, respectively, and it can be seen from the SEM images that the prepared layered cobaltosic oxide material is regular spherical, the particle size is about 18 μm, the interior of the material particle has a regular ordered layered structure, the boundary between the layers is obvious, and the first loose layer, the first dense layer, the second loose layer and the second dense layer are sequentially arranged from inside to outside. Table 1 shows the physicochemical properties of the layered cobaltosic oxide material prepared in example 1.
TABLE 1 physicochemical Properties of the layered Cobaltosic oxide Material prepared in example 1
Example 2
A layered cobaltosic oxide material is prepared by the following steps:
s1: preparing 40g/L of aluminum nitrate solution, 150g/L of cobalt sulfate solution and 180g/L of ammonium bicarbonate solution by using deionized water;
s2: adding 200L of deionized water as a base solution into a reaction system, adding 200kg of cobalt carbonate as a seed crystal, wherein the granularity of the seed crystal is about 12 mu m, and adjusting the pH to 7.5; then adding the prepared cobalt nitrate solution, ammonium bicarbonate solution and aluminum sulfate solution into a reaction kettle simultaneously in a parallel flow feeding mode, wherein the feeding flow ratio of the cobalt sulfate solution to the ammonium bicarbonate solution to the aluminum nitrate solution is 10:22: 1; the temperature of the reaction kettle is 50 ℃, and the stirring speed is 280 r/min; the feeding flow of the cobalt salt solution is gradually increased in the feeding process, the initial cobalt flow is 30L/h, and the cobalt salt flow is adjusted to 48L/h after 15 hours of feeding; after feeding for 30 hours, the flow rate of the cobalt sulfate solution is adjusted to 65L/h; the feeding flow rates of the corresponding ammonium bicarbonate solution and the aluminum nitrate solution are synchronously adjusted according to the proportion, and the reaction is stopped after the reaction time reaches 105 hours;
s3: transferring the product of the coprecipitation reaction in S2 to an aging tank for aging for 2h, washing with 50 deg.C salt-free water in a centrifuge for 6 times (1 m each time)3After the water is washed, the water is washed until the TDS of the washing water is less than 50 ppm;
s4: and (3) performing sectional calcination on the washed product in the S3, wherein the drying section comprises the following steps: calcining at 200 deg.C for 1h without opening air pressure; a pyrolysis section: calcining at 300 ℃ for 4h without opening air pressure; high-temperature oxidation crystallization section: calcining at 740 deg.C for 1.5h, and introducing air under appropriate pressure to obtain layered cobaltosic oxide material.
The shape and structure of the layered cobaltosic oxide material prepared in example 2 are substantially similar to those of example 1, and the physicochemical properties of the layered cobaltosic oxide material prepared in example 2 are shown in table 2.
Table 2 physicochemical properties of the layered cobaltosic oxide material prepared in example 2
Example 3
A layered cobaltosic oxide material and a preparation method thereof are disclosed, the method comprises the following steps:
s1: preparing 30g/L of aluminum sulfate solution, 120g/L of cobalt chloride solution and 160g/L of ammonium bicarbonate solution by using deionized water;
s2: adding 200L of deionized water into the reaction system as a base solution, adding 200kg of cobalt carbonate as a seed crystal, wherein the granularity of the seed crystal is about 14 mu m, and adjusting the pH to 8.2; then adding the prepared cobalt chloride solution, ammonium bicarbonate solution and aluminum sulfate solution into a reaction kettle simultaneously in a parallel flow feeding mode, wherein the feeding flow ratio of the cobalt chloride solution, the ammonium bicarbonate solution and the aluminum sulfate solution is 15:28: 1; the temperature of the reaction kettle is 52 ℃, and the stirring speed is 280 r/min; the feeding flow of the cobalt chloride solution is gradually increased in the feeding process, the initial cobalt flow is 25L/h, and the flow of the cobalt chloride solution is adjusted to 45L/h after 12 hours of feeding; after 24 hours of feeding, the flow rate of the cobalt chloride solution is adjusted to 65L/h; the feeding flow rates of the corresponding ammonium bicarbonate solution and the corresponding aluminum sulfate solution are synchronously adjusted according to the proportion, and the reaction is stopped after 100 hours;
s3: transferring the product of the coprecipitation reaction in S2 to an aging tank for aging for 2h, washing with 50 deg.C salt-free water in a centrifuge for 6 times (1 m each time)3After the water is washed, the water is washed until the TDS of the washing water is less than 50 ppm;
s4: calcining the washed product in the S3 by sections at the calcining temperature of 300 ℃ for 3h, and opening nitrogen atmosphere; calcining at the high temperature of 720 ℃ for 2h, and opening air to pressurize to a proper atmosphere to obtain the layered cobaltosic oxide material.
The shape and structure of the layered cobaltosic oxide material prepared in example 3 are substantially similar to those of example 1, and the physicochemical properties of the layered cobaltosic oxide material prepared in example 3 are shown in table 3.
TABLE 3 physicochemical Properties of the layered Cobaltosic oxide Material prepared in example 3
Example 4
A layered cobaltosic oxide material is prepared by the following steps:
s1: preparing 25g/L of aluminum nitrate solution, 120g/L of cobalt sulfate solution and 140g/L of ammonium bicarbonate solution by using deionized water;
s2: adding 200L of deionized water into the reaction system as a base solution, adding 200kg of cobalt carbonate as a seed crystal, wherein the granularity of the seed crystal is about 8 mu m, and adjusting the pH to 8.5; then adding the prepared cobalt sulfate solution, ammonium bicarbonate solution and aluminum nitrate solution into a reaction kettle simultaneously in a parallel flow feeding mode, wherein the feeding flow ratio of the cobalt sulfate solution to the ammonium bicarbonate solution to the aluminum nitrate solution is 16:30: 1; the temperature of the reaction kettle is 48 ℃, and the stirring speed is 280 r/min; the feeding flow of the cobalt salt solution is gradually increased in the feeding process, the feeding flow of the initial cobalt sulfate solution is 25L/h, and the feeding flow of the cobalt sulfate solution is adjusted to 45L/h after feeding for 6 hours; after 15 hours of feeding, the feeding flow rate of the cobalt sulfate solution is adjusted to 65L/h; the feeding flow rates of the corresponding ammonium bicarbonate solution and the aluminum nitrate solution are synchronously adjusted according to the proportion, and the reaction is stopped after 85 hours;
s3: transferring the product of the coprecipitation reaction in S2 to an aging tank for aging for 2h, washing with 50 deg.C salt-free water in a centrifuge for 6 times (1 m each time)3After the water is washed, the water is washed until the TDS of the washing water is less than 50 ppm;
s3: calcining the washed product in the S3 for segments at the calcining temperature of 300 ℃ for 4h, and opening a nitrogen atmosphere; calcining at the high temperature of 720 ℃ for 2h, and opening air to pressurize to a proper atmosphere to obtain the layered cobaltosic oxide material.
The shape and structure of the layered cobaltosic oxide material prepared in example 4 are substantially similar to those of example 1, and the physicochemical properties of the layered cobaltosic oxide material prepared in example 4 are shown in table 4.
Table 4 physicochemical properties of the layered cobaltosic oxide material prepared in example 4
Comparative example 1
A large-particle-size cobaltosic oxide material is prepared by the following steps:
s1: preparing 20g/L aluminum nitrate solution, 100g/L cobalt sulfate solution and 130g/L ammonium bicarbonate solution by using deionized water;
s2: adding 200L of deionized water into a reaction kettle as a base solution, adding 200kg of cobalt carbonate as a seed crystal, wherein the granularity of the seed crystal is about 10 mu m, and adjusting the pH to 8.0; then adding the prepared cobalt sulfate solution, ammonium bicarbonate solution and aluminum nitrate solution into a reaction kettle simultaneously in a parallel flow feeding mode, controlling the temperature of the reaction kettle to be 48 ℃, stirring at a speed of 280r/min, feeding the cobalt sulfate solution at a feeding flow rate of 45L/h, feeding the ammonium bicarbonate at a flow rate of 89.5L/h, feeding the aluminum nitrate solution at a flow rate of 3.75L/h, and feeding the cobalt sulfate solution, the ammonium bicarbonate and the aluminum nitrate solution at a flow rate ratio of 12:23.8:1), and stopping after the reaction lasts for 95 h;
s3: transferring the product of the coprecipitation reaction in S2 to an aging tank for aging for 2h, washing with 50 deg.C salt-free water in a centrifuge for 6 times (1 m each time)3After the water is washed, the water is washed until the TDS of the washing water is less than 50 ppm;
s4: and (3) performing sectional calcination on the washed product in the S3, wherein the drying section comprises the following steps: calcining at 200 deg.C for 2h without opening air pressure; a pyrolysis section: calcining at 300 ℃ for 3h without opening air pressure; high-temperature oxidation crystallization section: calcining at 740 deg.C for 1h, and introducing air under appropriate pressure to obtain layered cobaltosic oxide material.
The layered cobaltosic oxide material prepared in comparative example 1 was in a regular spherical shape with a particle size of about 18 μm, a porosity of 12%, and a true density of 6.03g/cm3. FIG. 4 is a SEM image of the cross-section of the tricobalt tetroxide material prepared in comparative example 1, from whichThe cobaltosic oxide material prepared by the method has uniform and compact internal structure, compact internal structure and loose external structure, and has no obvious loose and compact layered structure.
Performance testing
The cobaltosic oxide material prepared in the example 1 and the comparative example 1 is added with lithium carbonate according to the same process conditions to carry out secondary sintering to prepare a lithium cobaltoxide positive electrode material, the positive electrode material is respectively added with acetylene black and polyvinylidene fluoride (PVDF) to be uniformly mixed, then the mixture is ground into uniform slurry to be coated on an aluminum foil to prepare a positive electrode, and a button cell is prepared by taking a metal lithium sheet as a negative electrode and LiPF6 as an electrolyte. The electrochemical test voltage is 4.53V, the 1C high-temperature cycle test is carried out, the temperature is 50 ℃, and the test results are shown in Table 5:
TABLE 5 electrochemical Properties of example 1 and comparative example 1
| Performance of | Retention ratio of 48 cycles | Retention ratio of 66 cycles |
| Example 1 | 90.2％ | 79.9％ |
| Comparative example 1 | 84.2％ | 70.8％ |
From the above results, the layered cobaltosic oxide prepared by the method has higher cycle retention rate than that of a cobaltosic oxide material with a conventional structure under the same conditions. In addition, the preparation process is simple, convenient to operate and easy for industrial production.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present application and not for limiting, and although the present application is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application.
Claims (10)
1. The layered cobaltosic oxide material is characterized by comprising a plurality of loose layers and a plurality of compact layers, wherein the loose layers and the compact layers are arranged in an overlapped mode from inside to outside, the loose layers are located in the center, the compact layers are located on the outermost layers, and the density of the loose layers is smaller than that of the compact layers.
2. The layered cobaltosic oxide material of claim 1, wherein the layered cobaltosic oxide material has a particle size of 12 to 18 μm, a porosity of 5 to 30%, and a true density of 5.94 to 6.09g/cm3。
3. The layered cobaltosic oxide material of claim 1, wherein the layered cobaltosic oxide material comprises, in order from the inside out, a first porous layer, a first dense layer, a second porous layer, and a second dense layer.
4. The layered cobaltosic oxide material as claimed in claim 3, wherein said first porous layer has a thickness of 2 to 4 μm, a porosity of 10 to 35%, and a true density of 5.94 to 6.0g/cm3(ii) a The first dense layer has a thickness of 1-3 μm, a porosity of 0.8-4%, and a true density of 6.05-6.09 g/cm3(ii) a The thickness of the second loose layer is 0.1-0.5 mu m, the porosity is 8-20%, and the true density is 6.01-6.04 g/cm3(ii) a The second dense layer has a thickness of 2-5 μm, a porosity of 1-5%, and a true density of 6.04-6.07 g/cm3。
5. A method of preparing a layered cobaltosic oxide material as claimed in any one of claims 1 to 4, comprising the steps of:
s1: adding water into the reaction kettle as a base solution, adding 200kg of cobalt carbonate as a seed crystal, wherein the granularity of the seed crystal is 8-14 mu m, and adjusting the pH to 7.5-8.5; adding a cobalt salt solution, a soluble metal salt solution and a precipitant solution into a reaction kettle in a concurrent flow manner, wherein the feeding flow ratio of the cobalt salt solution, the precipitant solution and the soluble metal salt solution is (10-20): (20-32): 1; wherein the feeding flow rate of the initial cobalt salt solution is 25-30 g/L, after 5-25 h, the feeding flow rate of the cobalt salt solution is adjusted to be 5-25 g/L, and after 15-40 h, the feeding flow rate of the cobalt salt solution is adjusted to be 65 g/L; meanwhile, the feeding flow rates of the precipitant solution and the soluble metal salt solution are adjusted in proportion;
s2: aging, filtering and washing a product obtained after the coprecipitation reaction in the S1;
s3: calcining the product obtained in S2 under an atmosphere, wherein the calcining process comprises a drying section: the temperature is 150-200 ℃; a pyrolysis section: the temperature is 200-300 ℃; high-temperature oxidation crystallization section: the temperature is 350-750 ℃, and the layered cobaltosic oxide material is obtained after calcination.
6. The method according to claim 5, wherein the cobalt salt is at least one of cobalt nitrate, cobalt sulfate, or cobalt chloride; the soluble metal salt is at least one of nickel salt, manganese salt, aluminum salt, magnesium salt, calcium salt, zirconium salt or yttrium salt; the precipitant is at least one of ammonium bicarbonate, ammonia water or urea.
7. The method according to claim 5, wherein the concentrations of the cobalt salt solution, the soluble metal salt solution and the precipitant solution are 110 to 150g/L, 20 to 40g/L and 140 to 200g/L, respectively.
8. The preparation method according to claim 5, wherein the temperature of the coprecipitation reaction in S1 is 45-55 ℃, and the precipitation time is 85-105 h; the aging time in S2 was 2 h.
9. The method according to claim 5, wherein the atmosphere of the drying section and the pyrolysis section in S3 is nitrogen or helium; the atmosphere of the high-temperature oxidation crystallization section is air or oxygen.
10. Use of a layered cobaltosic oxide material according to any one of claims 1 to 4 in the preparation of a lithium ion battery.
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