CN116247197B - Spherical high-voltage lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery - Google Patents
Spherical high-voltage lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention provides a lithium nickel manganese oxide positive electrode material which has a spherical particle morphology; the spherical particle morphology is a spherical secondary particle morphology formed by stacking truncated octahedral morphology primary particles. The spherical high-voltage lithium nickel manganese oxide material composed of the truncated octahedral primary particles has a specific shape and an arrangement mode, the spherical lithium nickel manganese oxide material composed of the truncated octahedral primary particles in a close-packed mode can reduce the void ratio and the specific surface area of the material, and the compaction performance, the multiplying power performance and the cycle performance of the material are improved, and particularly the high-temperature cycle performance is excellent. Meanwhile, crystal faces (111) of the spherical secondary particles are closely arranged, so that gaps among the primary particles are further reduced, the specific surface area of the material is reduced, the maximum accumulation of the surfaces and the interiors of the spherical secondary particles is ensured, and the compaction density of the material can be improved.
Description
Technical Field
The invention belongs to the technical field of lithium nickel manganese oxide positive electrode materials, relates to a lithium nickel manganese oxide positive electrode material and a preparation method thereof, and a lithium ion battery, and particularly relates to a spherical high-voltage lithium nickel manganese oxide positive electrode material and a preparation method thereof, and a lithium ion battery.
Background
The lithium ion battery is used as a novel energy storage device, has the advantages of high working voltage, long cycle life, no memory effect and the like, and provides electric energy for devices such as 3C digital products, aeromodelling, electric tools, electric automobiles and the like. With the continuous expansion of application fields, lithium ion batteries with larger energy density and power density are urgently needed, and the positive electrode material is taken as one of key components of the lithium ion batteries, so that the performance of the lithium ion batteries is directly affected. High voltage lithium nickel manganate has received extensive attention from research technicians due to higher discharge voltage, higher energy density and lower production cost. However, the current commercial lithium nickel manganese oxide positive electrode material also has the problems of side reaction with electrolyte, dissolution of manganese ions, poor cycle performance and poor rate performance, and the control of the morphology of the material is one of methods for improving the problems.
Some corresponding improvements are also disclosed in the prior art, for example, patent CN106684350 discloses a preparation method of high-voltage anode material lithium nickel manganese oxide, oxalate and carbonate are used as precipitants simultaneously, oxalic acid/nickel manganese carbonate composite precursors are obtained through a coprecipitation method, after presintering, the precursors are dispersed in aqueous solution of lithium hydroxide for spray drying, and high-temperature calcination is carried out to obtain the high-voltage anode material lithium nickel manganese oxide. The prepared material is spherical in shape and has the advantages of high voltage, high tap density, high capacity, excellent multiplying power performance and the like, but the surface of the spherical lithium nickel manganese oxide material has more void structures, the compaction density is lower, and the battery performance is degraded due to easy crushing in the pole piece compaction process; the specific surface area of the material is large, and the dissolution of manganese ions is easy to occur in the high-temperature circulation process, so that the circulation performance is poor.
Therefore, how to find a lithium nickel manganese oxide positive electrode material with a more suitable morphology, which solves the technical problems existing in the current research, has become one of the focus of attention for many first-line researchers and research and development enterprises in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery, in particular to a spherical high-voltage lithium nickel manganese oxide positive electrode material. The spherical high-voltage lithium nickel manganese oxide material is composed of truncated octahedron primary particles, the primary particles have specific shapes and arrangement modes, the truncated octahedron close-packed spherical lithium nickel manganese oxide material can reduce the void ratio and specific surface area of the material, the compaction performance, the multiplying power performance and the cycle performance of the material are improved, and the material is particularly excellent in high-temperature cycle performance, simple in process, mild and easy to control in condition and low in production cost, and is more beneficial to popularization and application of large-scale industrial production.
The invention provides a lithium nickel manganese oxide positive electrode material which has a spherical particle morphology;
the spherical particle morphology is a spherical secondary particle morphology formed by stacking truncated octahedral morphology primary particles.
Preferably, the truncated octahedral primary particles include (100) and (111) crystal planes;
the total area of the (111) crystal face accounts for 80% -99.9% of the external surface area of the lithium nickel manganese oxide anode material.
Preferably, the surface of the (111) crystal face is smooth and flat;
the (111) crystal face is parallel to the section of the spherical secondary particles.
Preferably, the length of the edge between the connected (100) crystal face and the connected (111) crystal face is the length I of the edge, the length of the edge between the connected two (111) crystal faces is the length II of the edge, and the length ratio of the length I of the edge to the length II of the edge is (0.01-1): 1, a step of;
the lithium nickel manganese oxide comprises spinel lithium nickel manganese oxide, spinel and layered structure composite lithium nickel manganese oxide.
Preferably, the compaction density of the lithium nickel manganese oxide positive electrode material is 3.0-3.4 g/cm 3 ；
The specific surface area of the lithium nickel manganese oxide positive electrode material is 0.1-0.6 m 2 /g。
The invention provides a preparation method of a lithium nickel manganese oxide positive electrode material, which comprises the following steps:
1) Mixing a lithium nickel manganese oxide precursor, lithium salt and mica micropowder, and pre-sintering to obtain a pre-sintered product, and removing the mica micropowder in the pre-sintered product to obtain an intermediate product;
2) And sintering the intermediate product obtained in the steps to obtain the lithium nickel manganese oxide anode material.
Preferably, the lithium nickel manganese oxide precursor comprises Ni 0.25 Mn 0.75 (OH) 2 ；
The molar ratio of the lithium nickel manganese oxide precursor to lithium in the lithium salt is 1: (0.5-0.75);
the molar ratio of the lithium nickel manganese oxide precursor to the mica micropowder is 1: (0.001-0.05).
Preferably, the temperature of the pre-sintering is 450-650 ℃;
the presintering time is 1-10 h.
Preferably, the mode of removing the mica micropowder comprises sieving and/or air classification;
the sintering temperature is 700-1000 ℃;
the presintering time is 5-20 h.
The invention provides a lithium ion battery, which comprises the lithium nickel manganese oxide positive electrode material prepared by any one of the technical schemes or the preparation method of any one of the technical schemes.
The invention provides a lithium nickel manganese oxide positive electrode material which has a spherical particle morphology; the spherical particle morphology is a spherical secondary particle morphology formed by stacking truncated octahedral morphology primary particles. Compared with the prior art, the nickel lithium manganate with the spherical structure morphology and the truncated octahedral structure is more beneficial to the diffusion of lithium ions and the improvement of the cycle performance due to the existence of the (110) crystal face, and researches show that the acute angle vertex angle of the octahedral morphology is easy to be corroded by HF in electrolyte, so that manganese ions in the material are dissolved, the stability of the crystal structure is damaged, and the cycle of the nickel lithium manganate material is newly deteriorated. Compared with spinel octahedral morphology, the truncated octahedral morphology is composed of eight (111) crystal faces and six (100) crystal faces, and has no high-activity acute angle vertex angle, so that the structure reduces the area of the crystal faces which are easy to dissolve manganese ions (111), is not easy to corrode by electrolyte, and improves the cycle performance of the material. Although corresponding technical schemes exist in the prior art, as disclosed in patent CN107253739, the anode material lithium nickel manganese oxide with a micron-sized truncated octahedral structure is made into a truncated octahedral structure, more gaps exist among particles, the size is in a micron-sized level, and the more gaps in the material structure can increase the specific surface area of the material, so that the contact area between electrolyte and the material is increased, the intercalation/deintercalation resistance of lithium ions is reduced, and the rate performance of the battery is improved.
However, the research of the invention considers that the spherical morphology lithium nickel manganese oxide prepared by the prior art has spinel morphology formed by (111) crystal faces on the surfaces of primary particles, and acute angle vertex angles are exposed at interfaces where materials are contacted with electrolyte, so that a large number of uneven undulations exist on the surfaces, the specific surface area of the materials is increased, more gaps exist among the primary particles, and side reactions of the materials and the electrolyte are further increased, so that the cycle performance of the materials is deteriorated. The truncated octahedral lithium nickel manganese oxide prepared in the prior art is single particles smaller than 3 microns, the smaller the particle size of the material is, the more obvious the nano effect is, the larger the specific surface area is, and the larger the area of side reaction occurs when the material contacts with electrolyte. In addition, the smaller the particles of the positive electrode material are after the battery pole piece is rolled, the more gaps are formed among the materials, the lower the compaction density is, and the improvement of the energy density of the battery is affected. Thus, high energy density batteries generally require that the positive electrode material be spherical particles greater than 5 microns.
Based on the above, the invention particularly designs a lithium nickel manganese oxide positive electrode material with a specific structure, which is a high-voltage lithium nickel manganese oxide material with spherical secondary particles composed of truncated octahedral primary particles. The primary particles provided by the invention are in a truncated octahedral shape, the interface of the material surface and electrolyte mainly in direct contact is a (111) crystal face, and the crystal face is basically parallel to the section of the spherical particles. The truncated octahedral structure reduces the area of crystal faces easy to dissolve manganese ions (111), is not easy to be corroded by electrolyte, and improves the cycle performance of the material. (111) The crystal face surface is smooth and flat, and crystal defects are few, so that the arrangement mode that the crystal face and the spherical section are kept parallel can enable the specific surface area of particles to be minimum, side reactions of the material and electrolyte are reduced, and the normal temperature and high temperature cycle performance of the material is improved. And the (100)/(111) crystal plane length I and the (111)/(111) crystal plane length II have a specific length ratio, and the (100) crystal plane is not substantially in direct contact with the electrolyte. The area ratio of the (111) crystal face and the (100) crystal face can be regulated and controlled by regulating and controlling the length ratio of the edge length I to the edge length II, the migration rate of lithium ions in the (100) crystal face is higher than that of the (111) crystal face, and when the (100) crystal face faces the inside of the material, the migration of lithium ions in the inside of the material is facilitated, and the rate capability of the material can be improved. Meanwhile, crystal faces (111) of the spherical secondary particles are closely arranged, so that gaps among the primary particles are further reduced, the specific surface area of the material is reduced, the maximum accumulation of the surfaces and the interiors of the spherical secondary particles is ensured, and the compaction density of the material can be improved.
According to the preparation method provided by the invention, the mica micropowder is used as a crystal face growth control agent, and the length ratio of the edge length I to the edge length II is controlled by adjusting the addition amount of the mica micropowder, so that the area ratio of the (100) crystal face to the (111) crystal face is adjusted, and the preparation method is simple and controllable in process, low in production cost and suitable for large-scale industrial production.
Experimental results show that under the same sintering condition, the length ratio of the ridge length I to the ridge length II gradually decreases along with the increase of the addition amount of the mica micropowder, the specific surface area of the lithium nickel manganese oxide also gradually decreases, and the compaction of the material also gradually increases. When the mole ratio of the lithium nickel manganese oxide precursor to the mica micropowder is 1: in the case of (0.002-0.01), the length ratio of the (100)/(111) crystal plane length I to the (111)/(111) crystal plane length II of the primary particles is 0.01-0.3: the total area of the (111) crystal faces accounts for 90% -99% of the external surface area of the lithium nickel manganese oxide anode material. The compaction density of the lithium nickel manganese oxide anode material is 3.15-3.25 g/cm 3 A specific surface area of 0.3 to 0.4m 2 /g。
Drawings
FIG. 1 is a schematic representation of truncated octahedral particles, surface expansions and crystal planes edges prepared according to the present invention;
FIG. 2 is an SEM image of spherical lithium nickel manganese oxide prepared according to example 1 of the invention;
FIG. 3 is an SEM image of lithium nickel manganese oxide prepared according to comparative example 1 of the present invention;
FIG. 4 is an SEM image of lithium nickel manganese oxide prepared according to comparative example 2;
FIG. 5 is a graph showing the comparison of the rate and cycle performance of the batteries fabricated in example 1 and comparative example 1 of the present invention;
FIG. 6 is a graph showing the comparison of the 55℃high-temperature cycle performance of the batteries fabricated in example 1 and comparative example 1 according to the present invention.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further the features and advantages of the invention and are not limiting of the patent claims of the invention.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All raw materials of the invention have no special limitation on the purity, and the invention preferably adopts the purity requirement of the analytical purity or the routine preparation field of the lithium nickel manganese oxide anode material.
All raw materials of the invention, the brands and abbreviations of which belong to the conventional brands and abbreviations in the field of the related application are clear and definite, and the person skilled in the art can purchase from the market or prepare by the conventional method according to the brands, abbreviations and the corresponding application.
The process used in the invention, the abbreviations thereof belong to the conventional abbreviations in the field, the specific steps and the conventional parameters of each abbreviation are clear and definite in the related field, and the process can be realized by a conventional method according to the abbreviations by a person skilled in the art.
The invention provides a lithium nickel manganese oxide positive electrode material which has a spherical particle morphology;
the spherical particle morphology is a spherical secondary particle morphology formed by stacking truncated octahedral morphology primary particles.
In the present invention, the features indicated above are all microscopic features, and are not related to macroscopic features.
In the present invention, the truncated octahedral primary particles preferably include (100) crystal planes and (111) crystal planes.
In the invention, the total area of the (111) crystal face preferably accounts for 80% -99.9% of the external surface area of the lithium nickel manganese oxide anode material. More preferably 85 to 99%; more preferably 90 to 99%.
In the invention, the (111) crystal face is the interface of the lithium nickel manganese oxide positive electrode material (the surface of the secondary spherical particles) mainly in direct contact with the electrolyte, and occupies the vast majority of the surface area of the secondary particles, and only the (100) crystal face exists in the stacked gaps to be in small contact with the electrolyte.
In the present invention, the surface of the (111) crystal plane is preferably a surface having a smooth and flat surface.
In the present invention, the (111) plane is preferably parallel to the plane of the spherical secondary particles.
In the present invention, the length of the edge between the connected (100) crystal plane and (111) crystal plane is the length of the edge I, the length of the edge between the connected two (111) crystal planes is the length of the edge II, and the length ratio of the length of the edge I to the length of the edge II is preferably (0.01 to 1): 1, more preferably (0.1 to 0.5): 1, more preferably (0.1 to 0.3): 1.
in the present invention, the lithium nickel manganese oxide preferably includes spinel lithium nickel manganese oxide, or spinel and layered structure composite lithium nickel manganese oxide. Specifically, the general formula of the lithium nickel manganese oxide is preferably Li 1+x Ni 0.5 Mn 1.5 O 4 . Wherein x is more than or equal to 0 and less than or equal to 0.5, and preferably x is more than or equal to 0 and less than or equal to 0.2; more preferably 0.ltoreq.x.ltoreq.0.1.
In the invention, the compaction density of the lithium nickel manganese oxide positive electrode material is preferably 3.0-3.4 g/cm 3 More preferably 3.05 to 3.35g/cm 3 More preferably 3.1 to 3.3g/cm 3 More preferably 3.15 to 3.25g/cm 3 。
In the invention, the specific surface area of the lithium nickel manganese oxide positive electrode material is preferably 0.1-0.6 m 2 Preferably 0.2 to 0.5m 2 Preferably 0.3 to 0.4m 2 /g。
In the invention, the lithium nickel manganese oxide positive electrode material is preferably a high-voltage lithium nickel manganese oxide material.
The invention is a complete and refined whole technical scheme, better guarantees the microstructure morphology and composition of the lithium nickel manganese oxide anode material, further improves the compaction performance, the multiplying power performance and the cycle performance of the lithium nickel manganese oxide anode material, especially the high-temperature cycle performance, and the spherical high-voltage lithium nickel manganese oxide material can specifically comprise the following structures:
the spherical high-voltage lithium nickel manganese oxide anode material provided by the invention has the advantages that primary particles of lithium nickel manganese oxide are in truncated octahedral morphology; the interface of the material surface in direct contact with the electrolyte is a (111) crystal face, and the crystal face is basically parallel to the section of the spherical particles; the truncated octahedral primary particles are 0.5-3 microns, and the diameter of the spherical secondary particles is 5-20 microns.
Specifically, the truncated octahedral primary particles are 0.5-3 microns, and the diameter of the spherical secondary particles is 5-15 microns; more preferably, the truncated octahedral primary particles are 0.5-3 microns and the spherical secondary particles have a diameter of 5-8 microns.
Specifically, the length ratio of the (100)/(111) crystal plane edge length I to the (111)/(111) crystal plane edge length II of the primary particles is 0.01-1: 1, and the (100) crystal plane is not substantially in direct contact with the electrolyte.
Specifically, the length ratio of the (100)/(111) crystal face edge length I to the (111)/(111) crystal face edge length II is 0.1 to 0.5:1, a step of; more preferably, the length ratio of the (100)/(111) crystal face length I to the (111)/(111) crystal face length II is 0.1 to 0.3:1.
the spherical high-voltage lithium nickel manganese oxide material formed by the truncated octahedral primary particles has a specific shape and a specific arrangement mode, and the spherical lithium nickel manganese oxide material formed by the truncated octahedral close-packed structure can reduce the void ratio and specific surface area of the material, improve the compaction performance, multiplying power performance and cycle performance of the material, and is particularly excellent in high-temperature cycle performance.
The shape and arrangement of the truncated octahedral morphology primary particles in the invention have the following characteristics: the interface of the material surface and the electrolyte mainly and directly contacts is a (111) crystal face, and the crystal face is basically parallel to the section of the spherical particles; (100) The length ratio of the (111) crystal face edge length I to the (111)/(111) crystal face edge length II is 0.01-1: 1, and the (100) crystal face is not substantially in direct contact with the electrolyte; the truncated octahedral primary particles are 0.5-3 microns, and the diameter of the spherical secondary particles is more than 5 microns; this shape and arrangement ensures maximum packing of the spherical particles on the surface and inside.
Referring to fig. 1, fig. 1 is a schematic view of truncated octahedral particles, surface expansions, and crystal planes edges prepared according to the present invention.
The invention provides a preparation method of a lithium nickel manganese oxide positive electrode material, which comprises the following steps:
1) Mixing a lithium nickel manganese oxide precursor, lithium salt and mica micropowder, and pre-sintering to obtain a pre-sintered product, and removing the mica micropowder in the pre-sintered product to obtain an intermediate product;
2) And sintering the intermediate product obtained in the steps to obtain the lithium nickel manganese oxide anode material.
Firstly, mixing a lithium nickel manganese oxide precursor, lithium salt and mica micropowder, and then pre-sintering to obtain a pre-sintered product, and removing the mica micropowder in the pre-sintered product to obtain an intermediate product.
In the present invention, the general formula or chemical formula of the lithium nickel manganese oxide precursor is preferably Ni 0.25 Mn 0.75 (OH) 2 。
In the present invention, the molar ratio of the lithium nickel manganese oxide precursor to lithium in the lithium salt is preferably 1: (0.5 to 0.75), more preferably 1: (0.5 to 0.6), more preferably 1: (0.5-0.55).
In the invention, the molar ratio of the lithium nickel manganese oxide precursor to the mica micropowder is preferably 1: (0.001 to 0.05), more preferably 1: (0.001 to 0.02), more preferably 1: (0.002-0.01).
In the present invention, the temperature of the pre-sintering is preferably 450 to 650 ℃, more preferably 490 to 610 ℃, and even more preferably 540 to 570 ℃.
In the present invention, the pre-sintering time is preferably 1 to 10 hours, more preferably 3 to 8 hours, and still more preferably 5 to 6 hours.
In the present invention, the means for removing the fine mica powder preferably includes sieving and/or air classification, more preferably sieving or air classification.
In the present invention, the sintering temperature is preferably 700 to 1000 ℃, more preferably 750 to 950 ℃, and preferably 800 to 900 ℃.
In the present invention, the time for the pre-sintering is preferably 5 to 20 hours, more preferably 8 to 17 hours, and still more preferably 11 to 14 hours.
The invention is a complete and refined whole technical proposal, better ensures the microstructure morphology and composition of the lithium nickel manganese oxide anode material, further improves the compaction performance, the multiplying power performance and the cycle performance, especially the high-temperature cycle performance of the lithium nickel manganese oxide anode material, and the preparation method of the spherical high-voltage lithium nickel manganese oxide material specifically comprises the following steps:
the preparation method of the spherical high-voltage lithium nickel manganese oxide positive electrode material provided by the invention comprises the following steps:
s1: lithium nickel manganese oxide precursor, lithium salt and mica micropowder according to a mole ratio of 1:0.5 to 0.75: mixing 0.001-0.05 evenly, sintering for 1-10 h at 450-650 ℃ to obtain an intermediate product I;
s2: sieving or air-classifying the obtained intermediate product I, and removing mica micropowder to obtain an intermediate product II;
s3: sintering the intermediate product II at 700-1000 ℃ for 5-20 hours, cooling and sieving to obtain the spherical high-voltage lithium nickel manganese oxide anode material.
Specifically, the mass ratio of the lithium nickel manganese oxide precursor, the lithium salt and the mica micro powder in the step S1 is 100: 20-35: mixing 0.001-0.02 evenly, sintering for 2-10 h at 450-600 ℃; more preferably, the mass ratio of the lithium nickel manganese oxide precursor, the lithium salt and the mica micro powder in the step S1 is 100: 20-25: mixing 0.002-0.01 homogeneously and sintering at 500-600 deg.c for 2-4 hr.
Specifically, the sintering temperature of the intermediate product II in the step S3 is 750-950 ℃ and the sintering time is 5-20 h; more preferably, the sintering temperature of the intermediate product II is 800-900 ℃ and the sintering time is 8-12 h.
The invention also provides a lithium ion battery, which comprises the lithium nickel manganese oxide positive electrode material according to any one of the technical schemes or the lithium nickel manganese oxide positive electrode material prepared by the preparation method according to any one of the technical schemes.
The invention provides a spherical high-voltage lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery. The lithium nickel manganese oxide anode material with a specific structure is a high-voltage lithium nickel manganese oxide material with spherical secondary particles composed of truncated octahedral primary particles. The primary particles provided by the invention are in a truncated octahedral shape, the interface of the material surface and electrolyte mainly in direct contact is a (111) crystal face, and the crystal face is basically parallel to the section of the spherical particles. The truncated octahedral structure reduces the area of crystal faces easy to dissolve manganese ions (111), is not easy to be corroded by electrolyte, and improves the cycle performance of the material. (111) The crystal face surface is smooth and flat, and crystal defects are few, so that the arrangement mode that the crystal face and the spherical section are kept parallel can enable the specific surface area of particles to be minimum, side reactions of the material and electrolyte are reduced, and the normal temperature and high temperature cycle performance of the material is improved. And the (100)/(111) crystal plane length I and the (111)/(111) crystal plane length II have a specific length ratio, and the (100) crystal plane is not substantially in direct contact with the electrolyte. The area ratio of the (111) crystal face and the (100) crystal face can be regulated and controlled by regulating and controlling the length ratio of the edge length I to the edge length II, the migration rate of lithium ions in the (100) crystal face is higher than that of the (111) crystal face, and when the (100) crystal face faces the inside of the material, the migration of lithium ions in the inside of the material is facilitated, and the rate capability of the material can be improved. Meanwhile, crystal faces (111) of the spherical secondary particles are closely arranged, so that gaps among the primary particles are further reduced, the specific surface area of the material is reduced, the maximum accumulation of the surfaces and the interiors of the spherical secondary particles is ensured, and the compaction density of the material can be improved.
According to the preparation method provided by the invention, the mica micropowder is used as a crystal face growth control agent, and the length ratio of the edge length I to the edge length II is controlled by adjusting the addition amount of the mica micropowder, so that the area ratio of the (100) crystal face to the (111) crystal face is adjusted, and the preparation method is simple and controllable in process, low in production cost and suitable for large-scale industrial production.
Experimental results show that under the same sintering condition, the length ratio of the ridge length I to the ridge length II gradually decreases along with the increase of the addition amount of the mica micropowder, the specific surface area of the lithium nickel manganese oxide also gradually decreases, and the compaction of the material also gradually increases. When the mole ratio of the lithium nickel manganese oxide precursor to the mica micropowder is 1: in the case of (0.002-0.01), the length ratio of the (100)/(111) crystal plane length I to the (111)/(111) crystal plane length II of the primary particles is 0.01-0.3: 1, (111) total crystal face area90% -99% of the external surface area of the lithium nickel manganese oxide anode material. The compaction density of the lithium nickel manganese oxide anode material is 3.15-3.25 g/cm 3 A specific surface area of 0.3 to 0.4m 2 /g。
For further explanation of the present invention, the following describes in detail a lithium nickel manganese oxide positive electrode material, a preparation method thereof and a lithium ion battery according to the present invention with reference to the examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and detailed implementation and specific operation procedures are given, which are only for further explaining the features and advantages of the present invention, and not limiting the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
S1: lithium nickel manganese oxide precursor, lithium carbonate and mica micropowder according to a mole ratio of 1:0.25:0.005, mixing uniformly, and sintering at 500 ℃ for 4 hours to obtain an intermediate product I;
s2: sieving or air-classifying the obtained intermediate product I, and removing mica micropowder to obtain an intermediate product II;
s3: sintering the intermediate product II at 850 ℃ for 10 hours, cooling and sieving to obtain the spherical high-voltage lithium nickel manganese oxide anode material LiNi 0.5 Mn 1.5 O 4 。
The spherical high-voltage lithium nickel manganese oxide positive electrode material prepared in the embodiment 1 of the invention is characterized.
Referring to fig. 2, fig. 2 is an SEM image of spherical lithium nickel manganese oxide prepared in example 1 of the present invention.
As can be seen from fig. 2, the spherical lithium nickel manganese oxide primary particles prepared in example 1 have a truncated octahedral morphology, the interface of the material surface in direct contact with the electrolyte is a (111) crystal plane, and the crystal plane is basically parallel to the tangent plane of the spherical particles; the truncated octahedral primary particles are 1-3 microns and the spherical secondary particles have a diameter of about 7 microns.
Example 2
S1: lithium nickel manganese oxide precursor, lithium carbonate and mica micropowder according to a mole ratio of 1:0.26:0.002 is evenly mixed and sintered for 3 hours at 650 ℃ to obtain an intermediate product I;
s2: sieving or air-classifying the obtained intermediate product I, and removing mica micropowder to obtain an intermediate product II;
s3: sintering the intermediate product II at 850 ℃ for 15 hours, cooling and sieving to obtain the spherical high-voltage lithium nickel manganese oxide anode material Li 1.04 Ni 0.5 Mn 1.5 O 4 。
Example 3
S1: lithium nickel manganese oxide precursor, lithium hydroxide and mica micropowder according to a mole ratio of 1:0.55:0.003, and sintering at 530 ℃ for 1.5 hours to obtain an intermediate product I;
s2: sieving or air-classifying the obtained intermediate product I, and removing mica micropowder to obtain an intermediate product II;
s3: sintering the intermediate product II at 920 ℃ for 8 hours, cooling and sieving to obtain the spherical high-voltage lithium nickel manganese oxide anode material Li 1.1 Ni 0.5 Mn 1.5 O 4 。
Example 4
S1: lithium nickel manganese oxide precursor, lithium carbonate, lithium hydroxide and mica micropowder according to a mole ratio of 1:0.25:0.03:0.01, and sintering at 600 ℃ for 2 hours to obtain an intermediate product I;
s2: sieving or air-classifying the obtained intermediate product I, and removing mica micropowder to obtain an intermediate product II;
s3: sintering the intermediate product II at 780 ℃ for 15 hours, cooling and sieving to obtain the spherical high-voltage lithium nickel manganese oxide anode material Li 1.06 Ni 0.5 Mn 1.5 O 4 。
Example 5
S1: lithium nickel manganese oxide precursor, lithium nitrate and mica micropowder according to a mole ratio of 1:0.54:0.02, and sintering for 1h at 450 ℃ to obtain an intermediate product I;
s2: sieving or air-classifying the obtained intermediate product I, and removing mica micropowder to obtain an intermediate product II;
s3: sintering the intermediate product II at 1000 ℃ for 12 hours, cooling and sieving to obtain the spherical high-strength ceramic materialLithium nickel manganese oxide positive electrode material Li 1.08 Ni 0.5 Mn 1.5 O 4 。
Example 6
S1: lithium nickel manganese oxide precursor, lithium carbonate and mica micropowder according to a mole ratio of 1:0.3:0.01, and sintering at 480 ℃ for 5 hours to obtain an intermediate product I;
s2: sieving or air-classifying the obtained intermediate product I, and removing mica micropowder to obtain an intermediate product II;
s3: sintering the intermediate product II for 16 hours at 830 ℃, cooling and sieving to obtain the spherical high-voltage lithium nickel manganese oxide positive electrode material Li 1.2 Ni 0.5 Mn 1.5 O 4 。
Example 7
S1: lithium nickel manganese oxide precursor, lithium carbonate and mica micropowder according to a mole ratio of 1:0.255: mixing evenly at 0.008, and sintering at 510 ℃ for 2.5h to obtain an intermediate product I;
s2: sieving or air-classifying the obtained intermediate product I, and removing mica micropowder to obtain an intermediate product II;
s3: sintering the intermediate product II for 9 hours at 810 ℃, cooling and sieving to obtain the spherical high-voltage lithium nickel manganese oxide positive electrode material Li 1.02 Ni 0.5 Mn 1.5 O 4 。
Example 8
S1: lithium nickel manganese oxide precursor, lithium hydroxide and mica micropowder according to a mole ratio of 1:0.75: mixing uniformly 0.004, and sintering at 600 ℃ for 2 hours to obtain an intermediate product I;
s2: sieving or air-classifying the obtained intermediate product I, and removing mica micropowder to obtain an intermediate product II;
s3: sintering the intermediate product II at 980 ℃ for 6 hours, cooling and sieving to obtain the spherical high-voltage lithium nickel manganese oxide positive electrode material Li 1.5 Ni 0.5 Mn 1.5 O 4 。
Comparative example 1
S1: according to the mole ratio of Ni: mn=1: 3 preparing a mixed solution A with the concentration of nickel sulfate and manganese sulfate of 2.0mol/L according to molSpecific CO 3 2- ：C 2 O 4 2- =1: 8.5, weighing ammonium oxalate and ammonium carbonate, and adding a proper amount of distilled water to prepare a precipitant solution B with the total concentration of 3.0 mol/L;
s2: the mixed solution A, B is subjected to reaction for 15 hours at the stirring speed of 600r/min and the reaction temperature of 50 ℃, the pH value in the reaction solution is regulated to be about 5.5 by controlling the speed of adding ammonium sulfate and adding the precipitant solution B, and then the mixture is washed and dried to obtain a spherical oxalic acid/nickel manganese carbonate composite precursor;
s3: pre-sintering the precursor for 8 hours at the temperature of 450 ℃, and mixing the pre-sintered product with lithium hydroxide according to the molar ratio of Li: (ni+mn) =1.03: 2, mixing and dispersing in distilled water, carrying out spray drying, calcining the spray dried product at 850 ℃ for 12 hours, and then annealing at 600 ℃ for 10 hours to obtain the high-voltage lithium nickel manganese oxide positive electrode material described in comparative example 1.
Characterization was performed on the high-voltage lithium nickel manganese oxide positive electrode material prepared in comparative example 1 of the present invention.
Referring to fig. 3, fig. 3 is an SEM image of lithium nickel manganese oxide prepared in comparative example 1 of the present invention.
As can be seen from fig. 3, the primary particles of lithium nickel manganese oxide prepared in comparative example 1 have spinel octahedral morphology, the secondary particles have spherical morphology, the acute angle vertex angle can be exposed at the interface where the material contacts with the electrolyte, a large number of uneven undulations exist on the surface, and a large number of gaps exist between the primary particles.
Comparative example 2
S1: adding deionized water with the volume ratio of 1:8, then adding manganese sulfate monohydrate; preparing ammonium bicarbonate solution with the concentration of 0.3 mol/L; adding ammonium bicarbonate solution into manganese sulfate solution to obtain manganese carbonate powder;
s2: sintering manganese carbonate powder at 520 ℃ for 6 hours to obtain manganese sesquioxide;
s3: lithium hydroxide monohydrate, nickel nitrate hexahydrate and manganese sesquioxide are mixed according to a mole ratio of 1:0.5:1.5, dropwise adding 5mL of absolute ethyl alcohol into the mixture, stirring, drying and grinding to obtain mixed powder;
s4: and sintering the mixed powder in air at 600 ℃ for 6 hours to obtain the high-voltage lithium nickel manganese oxide positive electrode material in comparative example 2.
Characterization was performed on the high-voltage lithium nickel manganese oxide positive electrode material prepared in comparative example 2 of the present invention.
Referring to fig. 4, fig. 4 is an SEM image of lithium nickel manganese oxide prepared in comparative example 2 according to the present invention.
As can be seen from fig. 4, the lithium nickel manganese oxide prepared in comparative example 2 is mostly single particles having a diameter of 1 to 4 μm, and sharp corners and edges of grain boundaries can be exposed at the interface where the material and the electrolyte are in contact.
The high-voltage lithium nickel manganese oxide positive electrode materials prepared in the examples and the comparative examples are detected.
Referring to table 1, table 1 is a comparative table of the compacted densities of examples 1 to 8 of the present invention and comparative examples 1 and 2.
TABLE 1
As can be seen from Table 1, the compacted densities of examples 1 to 10 are significantly better than those of comparative examples 1 and 2.
Referring to table 2, table 2 shows comparative tables of specific surface areas of examples 1 to 8 of the present invention and comparative examples 1 and 2.
TABLE 2
As can be seen from Table 2, the specific surface areas of examples 1 to 10 are significantly smaller than those of comparative examples 1 and 2.
The positive electrode materials in example 1, comparative example 1 and comparative example 2 were fabricated into lithium ion batteries by the following specific methods: 9g of positive electrode material, 0.5g of acetylene black and polyvinylidene fluoride solution with 5% of solid content are mixed at normal temperature and normal pressure to form slurry, and the slurry is uniformly coated on the surface of aluminum foil to prepare the pole piece.
The pole piece obtained in the last step is dried at 80 ℃ and then is pressed, a round slice with the area of 1.32cm < 2 > is cut into a positive pole, a pure lithium slice is taken as a negative pole, 1mol/L of LiPF6 Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution is taken as electrolyte, wherein the volume ratio of EC to DMC is 1:1, then assembled into a lithium ion battery in a glove box filled with argon.
The normal temperature cycle performance of the prepared lithium ion battery is tested, and the result is shown in fig. 5, and fig. 5 is a comparison chart of multiplying power and cycle performance of the battery prepared by the invention example 1 and the comparative example 1.
As can be seen from FIG. 5, in example 1, the specific discharge capacity of the battery 0.2C was 137.8mAh/g, the specific discharge capacity of 0.5C was 135.7mAh/g, the specific discharge capacity of 1C was 130mAh/g, the specific discharge capacity of 2C was 120.5mAh/g, the ratio of 2C to 0.2C was 87.4%, and the retention rates of 0.5C and 50 cycles were 97.9%;
comparative example 1 produced a battery with a specific discharge capacity of 133mAh/g at 0.2C, a specific discharge capacity of 114.1mAh/g at 0.5C, a specific discharge capacity of 118.3mAh/g at 1C, a specific discharge capacity of 107.1mAh/g at 2C, a ratio of 2C/0.2C of 80.5%, and a capacity retention rate of 85.5% at 0.5C for 50 cycles;
comparative example 2 a battery was produced with a specific discharge capacity of 133.4mAh/g at 0.5C, a specific discharge capacity of 121.9mAh/g at 1C, a specific discharge capacity of 126.4mAh/g at 2C, a specific discharge capacity of 116.3mAh/g at 2C, a ratio of 2C/0.2C of 87.1%, a capacity retention rate of 91.9% at 0.5C for 50 cycles;
the cycle performance and rate performance of example 1 were both superior to those of comparative examples 1 and 2.
The high temperature cycle performance at 55 ℃ of the prepared lithium ion battery is tested, the result is shown in fig. 6, and fig. 6 is a graph comparing the high temperature cycle performance at 55 ℃ of the battery prepared in example 1 and comparative example 1 of the invention.
As can be seen from fig. 6, the specific discharge capacity of example 1 battery 1C was 130.3mAh/g, and the capacity retention rate at 50 cycles was 91.7%;
comparative example 1 produced a battery with a 1C discharge specific capacity of 121.2mAh/g and a 50-cycle capacity retention of 55.6%;
comparative example 2 battery 1C has a specific discharge capacity of 125.1mAh/g and a 50-cycle capacity retention of 70.8%;
the high temperature cycle performance of example 1 is superior to that of comparative examples 1 and 2.
The spherical high-voltage lithium nickel manganese oxide positive electrode material, the preparation method thereof and the lithium ion battery provided by the invention are described in detail, and specific examples are used for describing the principles and the implementation modes of the invention, and the description of the examples is only used for helping understand the method and the core idea of the invention, including the best mode, and also enables any person skilled in the art to practice the invention, including making and using any device or system and implementing any combined method. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. The lithium nickel manganese oxide positive electrode material is characterized by having a spherical particle morphology;
the spherical particle morphology is a spherical secondary particle morphology formed by stacking truncated octahedral primary particles;
the preparation method of the lithium nickel manganese oxide positive electrode material comprises the following steps:
1) Mixing a lithium nickel manganese oxide precursor, lithium salt and mica micropowder, and pre-sintering to obtain a pre-sintered product, and removing the mica micropowder in the pre-sintered product to obtain an intermediate product;
2) And sintering the intermediate product obtained in the steps to obtain the lithium nickel manganese oxide anode material.
2. The lithium nickel manganese oxide positive electrode material according to claim 1, wherein the truncated octahedral primary particles include a (100) crystal plane and a (111) crystal plane;
the total area of the (111) crystal face accounts for 80% -99.9% of the external surface area of the lithium nickel manganese oxide anode material.
3. The lithium nickel manganese oxide positive electrode material according to claim 2, wherein the surface of the (111) crystal face is smooth and flat;
the (111) crystal face is parallel to the section of the spherical secondary particles.
4. The lithium nickel manganese oxide positive electrode material according to claim 2, wherein the length of the edge between the connected (100) crystal plane and (111) crystal plane is the length I of the edge, the length of the edge between the connected two (111) crystal planes is the length II of the edge, and the length ratio of the length I of the edge to the length II of the edge is (0.01 to 1): 1, a step of;
the lithium nickel manganese oxide comprises spinel lithium nickel manganese oxide, spinel and layered structure composite lithium nickel manganese oxide.
5. The lithium nickel manganese oxide positive electrode material according to claim 1, wherein the compacted density of the lithium nickel manganese oxide positive electrode material is 3.0 to 3.4g/cm 3 ；
The specific surface area of the lithium nickel manganese oxide positive electrode material is 0.1-0.6 m 2 /g。
6. The lithium nickel manganese oxide positive electrode material according to claim 1, wherein the lithium nickel manganese oxide precursor comprises Ni 0.25 Mn 0.75 (OH) 2 。
7. The lithium nickel manganese oxide positive electrode material according to claim 1, wherein the molar ratio of the lithium nickel manganese oxide precursor to lithium in the lithium salt is 1: (0.5-0.75);
the molar ratio of the lithium nickel manganese oxide precursor to the mica micropowder is 1: (0.001-0.05).
8. The lithium nickel manganese oxide positive electrode material according to claim 1, wherein the pre-sintering temperature is 450-650 ℃;
the presintering time is 1-10 h.
9. The lithium nickel manganese oxide positive electrode material according to claim 1, wherein the mode of removing mica micropowder comprises sieving and/or air classification;
the sintering temperature is 700-1000 ℃;
the sintering time is 5-20 h.
10. A lithium ion battery comprising the lithium nickel manganese oxide positive electrode material according to any one of claims 1 to 9.
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| CN107253739A (en) * | 2017-06-20 | 2017-10-17 | 兰州理工大学 | The preparation method of micron order rescinded angle octahedral structure positive electrode nickel ion doped |
| CN112993241A (en) * | 2021-04-02 | 2021-06-18 | 中南大学 | Preparation method of single-crystal lithium manganate material |
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| CN107253739A (en) * | 2017-06-20 | 2017-10-17 | 兰州理工大学 | The preparation method of micron order rescinded angle octahedral structure positive electrode nickel ion doped |
| CN112993241A (en) * | 2021-04-02 | 2021-06-18 | 中南大学 | Preparation method of single-crystal lithium manganate material |
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