CN112701256A - All-solid-state lithium ion battery composite positive electrode material, preparation method thereof and lithium ion battery containing positive electrode material - Google Patents
All-solid-state lithium ion battery composite positive electrode material, preparation method thereof and lithium ion battery containing positive electrode material Download PDFInfo
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Abstract
A method for preparing a composite anode material of an all-solid-state lithium ion battery, the composite anode material prepared by the method and the lithium ion battery containing the anode material are disclosed. The method comprises (1) coating nanoscale zirconium source compound, lanthanum source compound and doped metal compound on the surface of spherical nickel-cobalt-manganese ternary precursor by ball milling; and (2) mixing the coated nickel-cobalt-manganese ternary precursor with a lithium source, and then calcining at high temperature to obtain the lanthanum-lithium zirconate coated nickel-cobalt-manganese ternary composite cathode material. The all-solid-state lithium ion battery prepared from the composite cathode material has the advantages of small interface resistance, good cycle stability, high safety performance and the like.
Description
Technical Field
The invention relates to a lithium ion battery positive electrode material, in particular to a preparation method of an all-solid-state lithium ion battery composite positive electrode material, the composite positive electrode material prepared by the method and a lithium ion battery containing the positive electrode material.
Background
At present, in the traditional lithium ion battery, because a large amount of flammable organic electrolyte such as carbonates, ethers and the like is used, under abnormal conditions such as overcharge, internal short circuit and the like, the danger of natural and even explosion exists, and serious potential safety hazards exist. The solid electrolyte is adopted to replace the organic electrolyte in the all-solid-state lithium ion battery, so that the potential safety hazard of the lithium ion battery can be greatly reduced, and the all-solid-state lithium ion battery is a necessary trend in the technical development of the lithium battery in the future. The all-solid-state lithium ion battery cannot be commercially applied in a large scale due to the defects of high interface resistance, low ionic conductivity and the like. Particularly, the matching between the solid electrolyte and the anode and cathode materials is one of the difficulties in research.
Disclosure of Invention
The invention aims to improve the matching between a solid electrolyte and the conventional commercial ternary cathode material, and provides a preparation method of a composite cathode material coated by the solid electrolyte.
In one aspect, the invention provides a method for preparing an all-solid-state lithium ion battery composite cathode material, which comprises the following steps:
(1) coating a nanoscale zirconium source compound, a nanoscale lanthanum source compound and a nanoscale doped metal compound on the surface of the spherical nickel-cobalt-manganese ternary precursor by using a ball milling method; and
(2) and mixing the coated nickel-cobalt-manganese ternary precursor with a lithium source, and then calcining at high temperature to obtain the lanthanum-lithium zirconate coated nickel-cobalt-manganese ternary composite cathode material.
In one embodiment of the method according to the present invention, the molar ratio Zr: La: M between the metal elements in the zirconium source compound, the lanthanum source compound and the doped metal compound is 2-x:3: x, wherein x is in the range of 0.2 to 1.5, preferably 0.5 to 1, where M represents the metal element in the doped metal compound. The proportion of doping elements is too low to form a cubic phase coating layer; the doping element proportion is too high, which is not beneficial to improving the conductivity of the coating layer lithium lanthanum zirconate. Therefore, a reasonable doping ratio needs to be selected.
In another embodiment of the method according to the present invention, the zirconium source compound is one or more selected from the group consisting of zirconium oxide, zirconium hydroxide, zirconium carbonate, zirconium nitrate, zirconium sulfate, zirconyl nitrate, zirconium acetate; the lanthanum source compound is one or more selected from lanthanum oxide, lanthanum hydroxide, lanthanum carbonate, lanthanum nitrate, lanthanum sulfate, lanthanum oxalate and lanthanum acetate; the doped metal compound is at least one selected from tantalum oxide and niobium oxide.
In another embodiment of the method according to the present invention, the ball milling method in step (1) uses at least one of isopropanol and ethanol as a ball milling medium, and ball milling is performed at a speed of 200 to 500rpm for 6 to 12 hours, preferably at a speed of 300 to 400rpm for 8 to 10 hours.
In another embodiment of the method according to the invention, the lithium source is one or more selected from the group consisting of lithium oxide, lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium sulfate, lithium oxalate, lithium acetate.
In another embodiment of the method according to the present invention, the mixing in step (2) is performed by ball milling at least one of isopropanol and ethanol as a ball milling medium at a speed of 200 to 500rpm for 6 to 12 hours, preferably at a speed of 300 to 400rpm for 8 to 10 hours.
In another embodiment of the process according to the invention, the high-temperature calcination in step (2) thereof is carried out by: heating to 700-1000 ℃ at a heating rate of 1-3 ℃/min, sintering at a constant temperature for 6-18 h, preferably heating to 800-900 ℃, and sintering at a constant temperature for 8-12 h; then heating to 1000-1400 ℃ at a heating rate of 1-3 ℃/min, sintering at constant temperature for 8-24 h, preferably heating to 1100-1200 ℃, and sintering at constant temperature for 12-18 h; then, the temperature is decreased to room temperature at a rate of 1-10 ℃/min, preferably at a rate of 3-5 ℃/min.
In another embodiment of the method according to the present invention, in the lanthanum lithium zirconate coated nickel cobalt manganese ternary composite positive electrode material, the mass ratio of the lanthanum lithium zirconate to the nickel cobalt manganese ternary material is 3 to 10%, preferably 5 to 8%.
In another embodiment of the method according to the invention, the spherical nickel cobalt manganese ternary precursor is selected from Ni1/3Co1/3Mn1/3(OH)2、Ni0.5Co0.3Mn0.2(OH)2、Ni0.6Co0.2Mn0.2(OH)2、Ni0.8Co0.1Mn0.1(OH)2At least one of; the median particle size D50 of the ternary precursor is 10-15 microns.
In another aspect, the present invention provides an all-solid-state lithium ion battery composite positive electrode material prepared according to the method of any one of the embodiments.
In yet another aspect, the present invention provides an all solid-state lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, characterized in that the positive electrode of the battery comprises the composite positive electrode material according to the present invention. The negative electrode used in the present invention may be natural graphite, artificial graphite, silicon carbon composite, metallic lithium; the electrolyte used in the present invention is a garnet-type lithium lanthanum zirconate solid electrolyte.
According to the preparation method of the composite cathode material, provided by the invention, through one-step calcination, when the nickel-cobalt-manganese ternary cathode material is prepared, the lanthanum-lithium zirconate electrolyte material is coated on the surface of the nickel-cobalt-manganese ternary cathode material in situ, so that the contact effect between the lanthanum-lithium zirconate electrolyte and the ternary cathode material is improved, the interface impedance is reduced, and the cycle performance of the all-solid-state battery is effectively improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which:
fig. 1 is a graph comparing the cycle performance of a battery made with the composite positive electrode material of the present invention with that of a battery made with an uncoated positive electrode material.
Detailed Description
The present invention will be further illustrated by the description of preferred forms thereof, but is not limited to these embodiments.
It should be noted that, in this context, "rpm" means "rpm/minute", "h" means "hour", "min" means "minute"; the raw materials/reagents used in the following examples are individually described, and are commercially available chemical reagents unless otherwise described, and are not particularly limited.
The method for preparing the all-solid-state lithium ion battery composite positive electrode material comprises the following steps of:
(1) coating a nanoscale zirconium source compound, a nanoscale lanthanum source compound and a nanoscale doped metal compound on the surface of the spherical nickel-cobalt-manganese ternary precursor by using a ball milling method; and
(2) and mixing the coated nickel-cobalt-manganese ternary precursor with a lithium source, and then calcining at high temperature to obtain the lanthanum-lithium zirconate coated nickel-cobalt-manganese ternary composite cathode material.
In the method according to the present invention, the ball milling method may be a ball milling method using any ball mill, for example, a model XQM-2 ball mill manufactured by Changsha powder technology Limited, and a jar and balls using a jar and balls made of zirconia.
In the method according to the present invention, the nanoscale zirconium source compound, lanthanum source compound, doped metal compound may be zirconium, lanthanum, doped metal oxide, hydroxide, carbonate, nitrate, sulfate, acetate, etc., and their oxide or hydroxide is preferably used. These nanoscale compounds are commercially available, for example, from reagent suppliers such as mecillin, alatin, and the like.
In the method according to the present invention, the lithium source is one or more selected from the group consisting of lithium oxide, lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium sulfate, lithium oxalate, lithium acetate, preferably one or more selected from the group consisting of lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate. The lithium source serves as a reactant for coating the core spherical ternary material and also serves as a reactant for coating lanthanum lithium zirconate. And according to different compositions of coating layers, the molar ratio of the lithium source to the nickel-cobalt-manganese ternary precursor is 1.05-1.15: 1, so that the mass ratio of the lanthanum lithium zirconate to the nickel-cobalt-manganese ternary composite positive electrode material in the finally obtained lanthanum lithium zirconate coated nickel-cobalt-manganese ternary composite positive electrode material is 3-10%, and preferably 5-8%.
In the method according to the present invention, the doped metal compound is at least one selected from tantalum oxide and niobium oxide, and the molar ratio of the metal elements in the zirconium source compound, the lanthanum source compound and the doped metal compound is Zr, La, M is 2-x:3: and x, wherein the value of x is 0.2-1.5, preferably 0.5-1, and M represents a metal element in the doped metal compound. Wherein, the main function of the doped metal is to promote the formation of a cubic phase coating layer.
In the method, the ball milling coating in the step (1) and the ball milling mixing in the step (2) are ball milled for 6-12 h at the speed of 200-500 rpm, preferably for 8-10 h at the speed of 300-400 rpm, so as to respectively realize good coating and sufficient mixing. In the ball milling coating process in the step (1), isopropanol is used as a ball milling medium, and other media with similar properties, such as ethanol, can also be used. The mass ratio of the materials to the ball milling medium is 1: 1-2.
In the method according to the invention, the spherical nickel cobalt manganese ternary precursor is selected from Ni1/3Co1/3Mn1/3(OH)2、Ni0.5Co0.3Mn0.2(OH)2、Ni0.6Co0.2Mn0.2(OH)2、Ni0.8Co0.1Mn0.1(OH)2At least one of the three-element precursor, wherein the median particle diameter D50 of the three-element precursor is 10-15 microns. Wherein these precursors, for example Ni1/3Co1/3Mn1/3(OH)2The preparation method can be as follows: respectively preparing a transition metal salt solution with the molar ratio of Ni to Mn to Co of 1 to 1 and a sodium hydroxide solution added with a proper amount of ammonia water, adding the transition metal salt solution and the sodium hydroxide solution into a coprecipitation reaction kettle in parallel, fully stirring the mixture under the protection of nitrogen, controlling the reaction temperature to be 50 ℃ and the reaction pH to be about 11, continuously feeding the mixture, carrying out overflow reaction for more than 40 hours, collecting the product after the particle size and the sphericity of a precursor in the kettle meet the requirements, filtering, washing and drying the product to obtain Ni1/3Co1/3Mn1/3(OH)2A precursor. By adjusting the proportion of the nickel, the cobalt and the manganese, the ternary precursor with other proportion can be obtained.
In the process according to the invention, the high-temperature calcination described in step (2) is carried out in such a way that:
firstly, heating to 700-1000 ℃ at a heating rate of 1-3 ℃/min, sintering at a constant temperature for 6-18 h, preferably heating to 800-900 ℃, and sintering at a constant temperature for 8-12 h, wherein the generation of a ternary cathode material and the generation of a lanthanum lithium zirconate coating layer are mainly generated in the temperature section;
heating to 1000-1400 ℃ at a heating rate of 1-3 ℃/min, sintering at constant temperature for 8-24 h, preferably heating to 1100-1200 ℃, and sintering at constant temperature for 12-18 h, wherein the temperature is mainly a crystal structure stabilizing process of the lanthanum lithium zirconate coating layer;
then cooling to room temperature at a cooling rate of 1-10 ℃/min, preferably at a cooling rate of 3-5 ℃/min.
In addition, the invention also provides the all-solid-state lithium ion battery composite positive electrode material prepared by the method and the all-solid-state lithium ion battery with the positive electrode containing the composite positive electrode material.
Alternatively, the negative electrode for the all solid-state lithium ion battery of the present invention may be natural graphite, artificial graphite, silicon, a silicon carbon composite material, metallic lithium.
Alternatively, the electrolyte used in the all solid-state lithium ion battery of the present invention is lanthanum lithium zirconate. It should be noted that after the preparation of the lithium lanthanum zirconate coated nickel-cobalt-manganese ternary composite positive electrode material, the all-solid-state lithium ion battery can be prepared according to the following method:
(1) respectively dissolving lanthanum lithium zirconate coated nickel-cobalt-manganese ternary cathode material, lithium borate and indium tin oxide conductive additive (mass ratio 6:3:1) in a solvent to prepare cathode layer slurry, wherein ethyl cellulose is a binder, the solvent is butyl carbitol, and the solid content is 40 wt%;
(2) coating and printing the positive electrode layer slurry on the surface of the surface-treated lanthanum lithium zirconate solid electrolyte, and then carrying out heat treatment at 700 ℃;
(3) sputtering gold foil as a positive current collector on the surface of the positive layer;
(4) attaching a solid electrolyte layer on the surface of the positive electrode layer which is not sputtered with the gold foil;
(5) directly sticking a lithium sheet on the other surface of the solid electrolyte to be used as a negative electrode;
(6) attaching a stainless steel current collector to the other side of the lithium sheet to serve as a negative current collector;
(7) and respectively leading out leads from the positive current collector and the negative current collector to obtain the all-solid-state lithium ion battery.
In the invention, the all-solid-state battery prepared in the way is subjected to charge and discharge performance test at room temperature, wherein the test voltage interval is 2.7-4.3V, and the test current is 5 muA/cm2。
The following examples are given for further understanding of the contents, features and effects of the present invention, but the present invention is not limited thereto.
Example 1
This example is intended to illustrate the preparation of the all-solid-state lithium ion battery composite positive electrode material of the present invention.
Coating a precursor: quasi-drugDefinite quantity of Ni0.6Co0.2Mn0.2(OH)2Precursor 94.9g, nano La2O32.77g of nano ZrO21.05g of nano Ta2O50.63g, adding the materials into a ball milling tank and ball milling for 8 hours at 400 rpm. Isopropanol is used as a ball milling medium, and the material-liquid ratio is 1: 1.5.
High-temperature calcination: 47.08g of battery-grade LiOH. H is accurately weighed2And O, adding the mixture into the ball-milled and coated precursor, and carrying out ball milling at 400rpm for 8 hours again. Heating to 800 ℃ at the heating rate of 2 ℃/min, sintering at constant temperature for 12h, heating to 1100 ℃ at the heating rate of 2 ℃/min, sintering at constant temperature for 12h, and cooling to room temperature at the cooling rate of 5 ℃/min. To obtain Li6.5La3Zr1.5Ta0.5O12Coated LiNi0.6Co0.2Mn0.2O2And compounding the positive electrode material, and assembling the positive electrode material into an all-solid-state battery for testing.
Example 2
This example is intended to illustrate the preparation of the all-solid-state lithium ion battery composite positive electrode material of the present invention.
Coating a precursor: accurately weighing Ni0.6Co0.2Mn0.2(OH)2Precursor 94.9g, nano La2O32.77g of nano ZrO21.05g of nano Nb2O50.38g, adding the materials into a ball milling tank and milling for 8 hours at 400 rpm. Isopropanol is used as a ball milling medium, and the material-liquid ratio is 1: 1.5.
High-temperature calcination: 47.08g of battery-grade LiOH. H is accurately weighed2And O, adding the mixture into the ball-milled and coated precursor, and carrying out ball milling at 400rpm for 8 hours again. Heating to 800 ℃ at the heating rate of 2 ℃/min, sintering at constant temperature for 12h, heating to 1100 ℃ at the heating rate of 2 ℃/min, sintering at constant temperature for 12h, and cooling to room temperature at the cooling rate of 5 ℃/min. To obtain Li6.5La3Zr1.5Nb0.5O12Coated LiNi0.6Co0.2Mn0.2O2And compounding the positive electrode material, and assembling the positive electrode material into an all-solid-state battery for testing.
Example 3
This example is intended to illustrate the preparation of the all-solid-state lithium ion battery composite positive electrode material of the present invention.
Coating a precursor: accurately weighing Ni0.6Co0.2Mn0.2(OH)2Precursor 94.9g, nano La2O32.91g of nano ZrO21.47g, the material is added into a ball milling tank and ball milled for 8 hours at 400 rpm. Isopropanol is used as a ball milling medium, and the material-liquid ratio is 1: 1.5.
High-temperature calcination: 47.31g of battery-grade LiOH. H are accurately weighed2And O, adding the mixture into the ball-milled and coated precursor, and carrying out ball milling at 400rpm for 8 hours again. Heating to 800 ℃ at the heating rate of 2 ℃/min, sintering at constant temperature for 12h, heating to 1100 ℃ at the heating rate of 2 ℃/min, sintering at constant temperature for 12h, and cooling to room temperature at the cooling rate of 5 ℃/min. To obtain Li7La3Zr2O12Coated LiNi0.6Co0.2Mn0.2O2And compounding the positive electrode material, and assembling the positive electrode material into an all-solid-state battery for testing.
Comparative example 1
This comparative example serves to illustrate the effect of a positive electrode material that is not coated with lanthanum lithium zirconate.
Accurately weighing Ni0.6Co0.2Mn0.2(OH)294.9g of precursor and battery-grade LiOH. H2And 45.47g of O, adding the materials into a ball milling tank, and milling for 8 hours at 400 rpm. Isopropanol is used as a ball milling medium, and the material-liquid ratio is 1: 1.5. Heating to 800 ℃ at the heating rate of 2 ℃/min, sintering at constant temperature for 12h, and finally cooling to room temperature at the cooling rate of 5 ℃/min. Obtaining LiNi0.6Co0.2Mn0.2O2And assembling the positive electrode material into an all-solid-state battery for testing.
As can be seen from fig. 1, the all-solid-state battery assembled by the composite cathode material prepared by the method of the present invention has good cycle performance and high capacity utilization rate. Ta-doped lanthanum lithium zirconate Li as in example 16.5La3Zr1.5Ta0.5O12The cycle performance after coating the ternary material was superior to example 3, which was not coated with Ta-doped lanthanum lithium zirconate. The same is true for example 2. This is because of the zirconic acid after Ta and Nb dopingThe ionic conductivity of lanthanum lithium is improved. And the comparison shows that the Ta doping effect is better than the Nb doping effect. The comparative example 1 has poor cycle stability, rapid capacity fading, low actual capacity and low capacity utilization rate (ratio between actual capacity and theoretical capacity), which shows that the coating of the lanthanum lithium zirconate can remarkably improve the contact effect between the cathode material and the solid electrolyte and reduce the interface resistance.
These are merely examples and are not intended to limit the present invention. The endpoints of the ranges and any numerical values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass ranges or values near those ranges or values. For numerical ranges, combinations of values between the endpoints of each range, between the endpoints of each range and separate values, and between separate values can be made with each other, resulting in one or more new numerical ranges, which should be considered as specifically disclosed herein.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (12)
1. A method for preparing an all-solid-state lithium ion battery composite cathode material comprises the following steps:
(1) coating a nanoscale zirconium source compound, a nanoscale lanthanum source compound and a nanoscale doped metal compound on the surface of the spherical nickel-cobalt-manganese ternary precursor by using a ball milling method; and
(2) and mixing the coated nickel-cobalt-manganese ternary precursor with a lithium source, and then calcining at high temperature to obtain the lanthanum-lithium zirconate coated nickel-cobalt-manganese ternary composite cathode material.
2. The method according to claim 1, wherein the molar ratio Zr: La: M between the metal elements in the zirconium source compound, the lanthanum source compound and the doped metal compound is 2-x:3: x, wherein x is 0.2-1.5, preferably 0.5-1, and M represents the metal element in the doped metal compound.
3. The method according to claim 1 or 2, wherein the zirconium source compound is one or more selected from the group consisting of zirconium oxide, zirconium hydroxide, zirconium carbonate, zirconium nitrate, zirconium sulfate, zirconyl nitrate, zirconium acetate; the lanthanum source compound is one or more selected from lanthanum oxide, lanthanum hydroxide, lanthanum carbonate, lanthanum nitrate, lanthanum sulfate, lanthanum oxalate and lanthanum acetate; the doped metal compound is at least one selected from tantalum oxide and niobium oxide.
4. The method according to claim 3, wherein the ball milling method in step (1) uses at least one of isopropanol and ethanol as a ball milling medium, and ball milling is carried out at a speed of 200-500 rpm for 6-12 h, preferably at a speed of 300-400 rpm for 8-10 h.
5. The method of claim 3, wherein the lithium source is one or more selected from the group consisting of lithium oxide, lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium sulfate, lithium oxalate, lithium acetate.
6. The method according to claim 3, wherein the mixing in step (2) is performed by ball milling at least one of isopropanol and ethanol as a ball milling medium at a speed of 200 to 500rpm for 6 to 12 hours, preferably at a speed of 300 to 400rpm for 8 to 10 hours.
7. The method of claim 3, wherein the high temperature calcination in step (2) is performed by: heating to 700-1000 ℃ at a heating rate of 1-3 ℃/min, sintering at a constant temperature for 6-18 h, preferably heating to 800-900 ℃, and sintering at a constant temperature for 8-12 h; then heating to 1000-1400 ℃ at a heating rate of 1-3 ℃/min, sintering at constant temperature for 8-24 h, preferably heating to 1100-1200 ℃, and sintering at constant temperature for 12-18 h; then, the temperature is decreased to room temperature at a rate of 1-10 ℃/min, preferably at a rate of 3-5 ℃/min.
8. The method according to claim 1, wherein in the lithium lanthanum zirconate coated nickel cobalt manganese ternary composite positive electrode material, the mass ratio of the lithium lanthanum zirconate to the nickel cobalt manganese ternary material is 3-10%, preferably 5-8%.
9. The method of claim 1, wherein the spherical nickel cobalt manganese ternary precursor is selected from Ni1/3Co1/3Mn1/3(OH)2、Ni0.5Co0.3Mn0.2(OH)2、Ni0.6Co0.2Mn0.2(OH)2、Ni0.8Co0.1Mn0.1(OH)2At least one of; the median particle size D50 of the ternary precursor is 10-15 microns.
10. An all-solid-state lithium ion battery composite positive electrode material prepared according to the method of any one of the preceding claims 1 to 9.
11. An all-solid-state lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, characterized in that the positive electrode of the battery comprises the composite positive electrode material of claim 10.
12. The all solid-state lithium ion battery according to claim 11, wherein the negative electrode is natural graphite, artificial graphite, silicon, a silicon-carbon composite material, or metallic lithium; the electrolyte is garnet-type lithium lanthanum zirconate solid electrolyte.
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| CN114068894A (en) * | 2021-10-27 | 2022-02-18 | 荆门市格林美新材料有限公司 | Preparation method of lanthanum lithium zirconate coated ternary cathode material |
| CN115043444A (en) * | 2022-08-16 | 2022-09-13 | 宜宾锂宝新材料有限公司 | High-nickel ternary positive electrode material, preparation method thereof and battery |
| CN116779871A (en) * | 2023-08-24 | 2023-09-19 | 浙江帕瓦新能源股份有限公司 | Lithium lanthanum zirconate coated and modified cathode material, preparation method thereof and lithium ion battery |
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