CN113725410B - Ternary positive electrode material coated with lithium metaphosphate in situ, and preparation method and application thereof - Google Patents
Ternary positive electrode material coated with lithium metaphosphate in situ, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a ternary positive electrode material coated with lithium metaphosphate in situ, and a preparation method and application thereof. The preparation method comprises the following steps: s1, fully mixing ammonium dihydrogen phosphate, lithium carbonate and ethanol according to a preset proportion, heating and dissolving, then adding a preset amount of ternary cathode material, and uniformly dispersing to obtain a mixture; then drying the position and carrying out combined calcination treatment twice to obtain a calcined product; s2, adding the calcined product into PVDF solution, and dispersing for 8-18 h; adding conductive carbon black, and continuing to disperse for 8-18 h to obtain mixed slurry; and S3, coating the mixed slurry on an aluminum foil, and sequentially carrying out two-step drying treatment of blast drying and vacuum drying after coating to prepare the lithium metaphosphate in-situ coated ternary anode material. According to the invention, the lithium metaphosphate is coated in situ, so that the interface stability of the ternary anode can be effectively improved, and the occurrence of side reaction of the interface can be inhibited; solves the problem of uneven coating caused by insolubility of lithium metaphosphate, and the method has simple operation and is suitable for industrialized application.
Description
Technical Field
The invention relates to the technical field of preparation of positive electrode materials, in particular to a ternary positive electrode material coated with lithium metaphosphate in situ, and a preparation method and application thereof.
Background
Lithium ion batteries are increasingly being used in a wide variety of applications due to their higher weight/volume energy density, longer service life, lower self-discharge rate, and the like. The positive electrode material accounts for about 40% of the production cost of the lithium ion battery, and is a key material for determining the performance of the lithium ion battery. Compared with the anode materials such as lithium cobaltate, lithium iron phosphate and the like which are widely used, the high-nickel ternary anode material (NCM) is one of the first-choice anode materials of the next-generation high-energy lithium ion battery due to the advantages of high voltage, high capacity and the like. Although the NCM positive electrode material has the advantages, the problems of cycle stability, rate capability, safety and the like of the NCM positive electrode material need to be solved before further practical application, and the problems mainly originate from unstable crystal structure of the NCM material, side reaction of an interface between a positive electrode and an electrolyte, high interface resistance and the like.
Mention is made in the literature of coating Li by atomic deposition (ALD) 3 PO 4 The method has the advantages of high cost, complex process and inapplicability to industrialized application.
In the prior art, common positive electrode materials can be modified by using a surface coating method, mainly because the coating layer can effectively regulate and control the physical, electrochemical and mechanical properties of the electrode particle surface. However, the interface impedance of the ternary positive electrode material coated by lithium phosphate can be obviously increased, the cycle and rate performance of the battery cannot be effectively improved, and the exertion of capacity is also influenced, so that the electrochemical performance of the ternary positive electrode material is seriously influenced. In contrast, lithium metaphosphate can reduce interfacial resistance due to the influence of polyanion groups, but because lithium metaphosphate is insoluble in organic solvents, only simple mixing can be performed, resulting in uneven coating effect.
In view of the foregoing, there is a need for an improved ternary positive electrode material coated in situ with lithium metaphosphate, and a preparation method and application thereof, so as to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a ternary positive electrode material coated with lithium metaphosphate in situ, and a preparation method and application thereof.
In order to achieve the aim of the invention, the invention provides a preparation method of a ternary positive electrode material coated with lithium metaphosphate in situ, which comprises the following steps:
s1, fully mixing ammonium dihydrogen phosphate, lithium carbonate and ethanol according to a preset proportion, heating and dissolving, then adding a preset amount of ternary cathode material, and uniformly dispersing to obtain a mixture; drying the mixture, and then carrying out twice combined calcination treatment at two different temperature settings to obtain a calcination product;
s2, adding the calcined product into PVDF solution, and dispersing for 8-18 h; adding conductive carbon black, and continuing to disperse for 8-18 h to obtain mixed slurry;
and S3, coating the mixed slurry on an aluminum foil, and sequentially carrying out two-step drying treatment of blast drying and vacuum drying after coating to prepare the lithium metaphosphate in-situ coated ternary anode material.
As a further improvement of the invention, in the mixture described in step S1, the mass ratio of monoammonium phosphate, lithium carbonate, ethanol and ternary cathode material is (4-6): (2-3): (450-550): (80-100).
As a further improvement of the present invention, the specific procedure of the two-time combined calcination treatment in step S1 is: calcining for 8-18 h at 200-300 ℃; calcining at 500-600 deg.c for 8-18 hr.
As a further improvement of the invention, in the mixed slurry in the step S2, the mass ratio of the ternary cathode material, PVDF and conductive carbon black is (80-100): (2-4): (1-3).
As a further improvement of the present invention, the ternary positive electrode material is NCM81.
As a further improvement of the present invention, the specific procedure of the two-step drying process in step S3 is as follows: drying at 70-90 deg.c in a blast oven, and stoving in a vacuum oven at-0.05 to-0.2 KPa for 8-18 hr.
As a further improvement of the invention, in the PVDF solution in step S2, the PVDF has a mass fraction of 3-8%.
As a further improvement of the present invention, in the two-time combined calcination treatment in step S1, the temperature rising rate of calcination is 5 ℃/min.
In order to achieve the aim of the invention, the invention also provides the ternary positive electrode material coated in situ by the lithium metaphosphate prepared by the preparation method, and the interface impedance of the ternary positive electrode material is as low as 50Ω or below.
In order to achieve the aim of the invention, the invention also provides application of the lithium metaphosphate in-situ coated ternary anode material in a lithium battery.
The beneficial effects of the invention are as follows:
1. according to the preparation method of the lithium metaphosphate in-situ coated ternary positive electrode material, the lithium metaphosphate in-situ coated ternary positive electrode material can effectively improve the interface stability of the ternary positive electrode material and inhibit the occurrence of interface side reactions; meanwhile, the method comprises the steps of firstly realizing the coating of the soluble raw materials on the surface of the ternary positive electrode material through the dissolution of the synthetic raw materials, then carrying out further two-step combined gradient calcination reaction on the ternary positive electrode material coated with the raw materials, thereby uniformly synthesizing lithium metaphosphate on the surface of the ternary positive electrode material in situ, and further solving the problem that the lithium metaphosphate cannot uniformly coat the positive electrode material due to the fact that the lithium metaphosphate is insoluble in organic solvents and water, and the coating effect of the positive electrode plate is influenced by LiPO 3 The particle size is influenced, so that the technical problems of powder falling and protrusion on the surface of the pole piece are easy to occur; the modification method is simple to operate and suitable for industrialized application.
2. According to the preparation method of the lithium metaphosphate in-situ coated ternary positive electrode material, provided by the invention, the in-situ coated substrate lithium metaphosphate is used as a lithium salt, has the capability of guiding lithium ions, a stable interface modification layer is formed on the surface of the ternary positive electrode through in-situ coating, so that the interface problem can be remarkably optimized, and the technical defect that the electrochemical performance of the ternary positive electrode material is influenced due to the remarkably increased interface impedance caused by the adoption of the lithium metaphosphate modified coated ternary positive electrode material is avoided.
3. The performance parameters of the lithium metaphosphate in-situ coated ternary positive electrode material provided by the invention are that the interface impedance is as low as 50 omega or below, and the 1C cycle number and the capacity retention rate respectively reach 437 cycles and 80 percent; the first circle coulomb efficiency reaches 91.5% and above.
Drawings
Fig. 1 is an SEM image (scale: 5 μm) of lithium metaphosphate provided in example 1 of the present invention after in-situ coating.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of a ternary positive electrode material coated with lithium metaphosphate in situ, which comprises the following steps:
s1, fully mixing ammonium dihydrogen phosphate, lithium carbonate and ethanol according to a preset proportion, heating and dissolving, then adding a preset amount of ternary cathode material, and uniformly dispersing to obtain a mixture; drying the mixture, and then carrying out twice combined calcination treatment at two different temperature settings to obtain a calcination product;
s2, adding the calcined product into PVDF solution, and dispersing for 8-18 h; adding conductive carbon black, and continuing to disperse for 8-18 h to obtain mixed slurry;
and S3, coating the mixed slurry on an aluminum foil, and sequentially carrying out two-step drying treatment of blast drying and vacuum drying after coating to prepare the lithium metaphosphate in-situ coated ternary anode material.
Preferably, in the mixture described in step S1, the mass ratio of monoammonium phosphate, lithium carbonate, ethanol and ternary cathode material is (4-6): (2-3): (450-550): (80-100).
Preferably, the specific process of the two combined calcination treatments in step S1 is as follows: calcining for 8-18 h at 200-300 ℃; calcining at 500-600 deg.c for 8-18 hr.
Preferably, in the mixed slurry in step S2, the mass ratio of the ternary cathode material, PVDF, and conductive carbon black is (80-100): (2-4): (1-3).
Preferably, the ternary positive electrode material is NCM811.
Preferably, the specific process of the two-step drying treatment in step S3 is as follows: drying at 70-90 deg.c in a blast oven, and stoving in a vacuum oven at-0.05 to-0.2 KPa for 8-18 hr.
Preferably, in the PVDF solution in step S2, the mass fraction of PVDF is 3-8%.
Preferably, in the two-time combined calcination treatment in step S1, the temperature rising rate of calcination is 5 ℃/min.
Example 1
The embodiment 1 of the invention provides a preparation method of a ternary positive electrode material coated with lithium metaphosphate in situ, which comprises the following steps:
s1, fully mixing raw materials of 5 parts of monoammonium phosphate, 2.5 parts of lithium carbonate and 500 parts of ethanol, heating and dissolving, then adding 90 parts of ternary positive electrode material NCM811, and uniformly dispersing to obtain a mixture; then drying the mixture, and then carrying out two-time combined calcination treatments at two different temperature settings, specifically, carrying out primary calcination at 250 ℃ for 12 hours; secondary calcination is carried out for 12 hours at 550 ℃ to obtain a calcination product;
s2, adding the calcined product into 60 parts by mass of PVDF solution (5 parts by mass of PVDF powder and 95 parts by mass of NMP solvent) with the mass fraction of 5%, and dispersing for 12 hours; adding 2 parts of conductive carbon black, and continuing to disperse for 12 hours to obtain mixed slurry;
and S3, coating the mixed slurry on an aluminum foil by using a 200-micrometer scraper, putting the coated aluminum foil into a blast oven for drying at 80 ℃, putting the dried aluminum foil into a vacuum oven, and drying for 12 hours under the vacuum degree of-0.1 KPa to prepare the lithium metaphosphate in-situ coated ternary cathode material (refer to figure 1).
And S4, rolling, cutting and assembling the prepared ternary positive electrode material coated with the lithium metaphosphate in situ, and testing.
As can be seen from fig. 1, the lithium metaphosphate is uniformly coated on the surface of the ternary cathode material.
Comparative example 1
Comparative example 1 only used ternary positive electrode material NCM811 as a blank comparative example, and performance test was performed by the following specific procedures:
s1, preparing a 5% PVDF solution: 5 parts by mass of PVDF powder, 95 parts by mass of NMP solvent, and magnetically stirring to transparent liquid; taking 60 parts of 5% PVDF solution, 50 parts of NMP, 95 parts of N CM811, and dispersing for 12 hours; adding 2 parts of conductive carbon black in a grafting way, and dispersing for 12 hours;
s2, coating an aluminum foil by using a 200-micrometer scraper, putting the coated aluminum foil into a blast oven for drying at 80 ℃, putting the aluminum foil into a vacuum oven, and drying for 12 hours under the vacuum degree of minus 0.1KPa to prepare a ternary anode material;
and S3, rolling, cutting and assembling the lithium metaphosphate coated ternary positive electrode material into pieces, and testing the assembled battery.
Comparative example 2
The difference from example 1 is that: the lithium metaphosphate is directly used for coating, and the specific process is as follows:
s1, preparing a 5% PVDF solution: 5 parts by mass of PVDF powder, 95 parts by mass of NMP solvent, and magnetically stirring to transparent liquid; mixing 60 parts of the 5% PVDF solution, 5 parts of lithium metaphosphate and 50 parts of NMP, and dispersing for 12 hours; adding 90 parts of N CM811, and dispersing for 12 hours; adding 2 parts of conductive carbon black in a grafting way, and dispersing for 12 hours;
s2, coating an aluminum foil by using a 200-micrometer scraper, putting the coated aluminum foil into a blast oven for drying at 80 ℃, putting the aluminum foil into a vacuum oven, and drying for 12 hours at a vacuum degree of-0.1 KPa to prepare a lithium metaphosphate coated ternary anode material;
and S3, rolling, cutting and assembling the lithium metaphosphate coated ternary positive electrode material into pieces, and testing the assembled battery.
Comparative example 3
The difference from example 1 is that: the lithium phosphate is directly used for coating, and the specific process is as follows:
s1, preparing a 5% PVDF solution: 5 parts by mass of PVDF powder, 95 parts by mass of NMP solvent, and magnetically stirring to transparent liquid; mixing 60 parts of the 5% PVDF solution, 5 parts of lithium phosphate and 50 parts of NMP, and dispersing for 12 hours; adding 90 parts of N CM811, and dispersing for 12 hours; adding 2 parts of conductive carbon black in a grafting way, and dispersing for 12 hours;
s2, coating an aluminum foil by using a 200-micrometer scraper, putting the coated aluminum foil into a blast oven for drying at 80 ℃, putting the aluminum foil into a vacuum oven, and drying for 12 hours under the vacuum degree of minus 0.1KPa to prepare a lithium phosphate coated ternary anode material;
and S3, rolling the ternary positive electrode material coated by the lithium phosphate, cutting pieces, and assembling the battery for testing.
The results of the performance test of the ternary cathode materials of example 1 and comparative examples 1 to 3 after performance test are shown in Table 1.
Table 1 shows the results of the performance tests of example 1 and comparative examples 1-3
| Examples | Interface impedance | 1C cycle number and capacity retention rate | First circle coulombic efficiency |
| Example 1 | 50Ω | 437 turns, 80% | 91.5％ |
| Comparative example 1 | 120Ω | 235 turns, 80% | 90.95％ |
| Comparative example 2 | 65Ω | 294 turns, 80% | 90.95％ |
| Comparative example 3 | 500Ω | 40 turns, 79.75% | 90.88％ |
As can be seen from table 1, the performance of the lithium metaphosphate in-situ coated ternary cathode material prepared in example 1 is significantly better than the electrochemical performance of comparative examples 1-3, which indicates that the in-situ coating method under the two-step gradient calcination process provided by the invention can effectively improve the interfacial stability and electrochemical performance of the ternary cathode material, and solve the technical problem that the ternary cathode material cannot be uniformly coated in comparative example 2 because the lithium metaphosphate is insoluble in organic solvent and water.
Examples 2 to 7
The difference from example 1 is that: the ratio setting of the raw materials and the setting of the calcination temperature are different, as shown in table 2, and the other components are the same as those in example 1, and are not described here again.
Table 2 shows the raw material ratio settings and the performance test results of examples 1 to 5
As can be seen from table 2, the effect of the ratio setting of the raw materials on the performance of the lithium metaphosphate in-situ coated ternary cathode material is: the secondary calcination temperature is too low to cause incomplete reaction, the coating effect is affected, lithium metaphosphate can be completely generated at 550 ℃, and the further temperature improvement effect is not obvious, mainly because the further temperature improvement can improve the crystal formation speed within the range of lithium metaphosphate generation and decomposition temperature, so that the crystallization speed is high, and the crystal grains become large.
When the coating amount is small, the interface cannot be effectively coated, the interface impedance is improved, but there is still room for improvement, and when the coating amount is large, the thickness of the formed coating layer is increased, which also leads to an increase in the interface impedance.
The influence of the setting of the twice calcination process temperature on the performance of the ternary cathode material coated with the lithium metaphosphate in situ is as follows: the primary calcination is to completely remove the solvent, and the secondary calcination is to completely react to form lithium metaphosphate, and the reaction is incomplete due to the too low temperature.
In summary, the invention provides a ternary positive electrode material coated with lithium metaphosphate in situ, and a preparation method and application thereof. The preparation method comprises the following steps: s1, fully mixing ammonium dihydrogen phosphate, lithium carbonate and ethanol according to a preset proportion, heating and dissolving, then adding a preset amount of ternary cathode material, and uniformly dispersing to obtain a mixture; then drying the position and carrying out combined calcination treatment twice to obtain a calcined product; s2, adding the calcined product into PVDF solution, and dispersing for 8-18 h; adding conductive carbon black, and continuing to disperse for 8-18 h to obtain mixed slurry; and S3, coating the mixed slurry on an aluminum foil, and sequentially carrying out two-step drying treatment of blast drying and vacuum drying after coating to prepare the lithium metaphosphate in-situ coated ternary anode material. The lithium metaphosphate is coated in situ, so that the interface stability of the ternary anode material can be effectively improved, and the occurrence of side reactions of the interface can be restrained; solves the problem of uneven coating caused by insolubility of lithium metaphosphate, and the method has simple operation and is suitable for industrialized application.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of a ternary positive electrode material coated with lithium metaphosphate in situ is characterized by comprising the following steps: the method comprises the following steps:
s1, fully mixing ammonium dihydrogen phosphate, lithium carbonate and ethanol according to a preset proportion, heating and dissolving, then adding a preset amount of ternary cathode material, and uniformly dispersing to obtain a mixture; drying the mixture, and then carrying out twice combined calcination treatment at two different temperature settings to obtain a calcination product; the specific process of the twice combined calcination treatment is as follows: calcining for 8-18 h at 200-300 ℃; calcining at 500-600 deg.c for 8-18 hr; in the mixture, the mass ratio of the monoammonium phosphate, the lithium carbonate, the ethanol and the ternary positive electrode material is (4-6): (2-3): (450-550): (80-100);
s2, adding the calcined product into PVDF solution, and dispersing for 8-18 h; adding conductive carbon black, and continuing to disperse for 8-18 h to obtain mixed slurry;
s3, coating the mixed slurry on an aluminum foil, and sequentially carrying out two-step drying treatment of blast drying and vacuum drying after coating to prepare a lithium metaphosphate in-situ coated ternary anode material; the interface impedance of the ternary positive electrode material coated by the lithium metaphosphate in situ is as low as 50 omega or below.
2. The method for preparing the lithium metaphosphate in-situ coated ternary cathode material, which is characterized in that: in the mixed slurry in the step S2, the mass ratio of the ternary positive electrode material, PVDF and conductive carbon black is (80-100): (2-4): (1-3).
3. The method for preparing the lithium metaphosphate in-situ coated ternary cathode material, which is characterized in that: the ternary positive electrode material is NCM811.
4. The method for preparing the lithium metaphosphate in-situ coated ternary cathode material, which is characterized in that: the specific process of the two-step drying treatment in the step S3 is as follows: drying at 70-90 deg.c in a blast oven, and stoving in a vacuum oven at-0.05 to-0.2 KPa for 8-18 hr.
5. The method for preparing the lithium metaphosphate in-situ coated ternary cathode material, which is characterized in that: in the PVDF solution in the step S2, the mass fraction of PVDF is 3-8%.
6. The method for preparing the lithium metaphosphate in-situ coated ternary cathode material, which is characterized in that: in the two-time combined calcination treatment in step S1, the temperature rising rate of calcination is 5 ℃/min.
7. Use of the lithium metaphosphate in-situ coated ternary cathode material prepared by the preparation method of the lithium metaphosphate in-situ coated ternary cathode material according to any one of claims 1-6 in lithium batteries.
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