CN113707875A - Spinel type lithium nickel manganese oxide, preparation method thereof and lithium ion battery - Google Patents
Spinel type lithium nickel manganese oxide, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention discloses spinel type lithium nickel manganese oxide, a preparation method thereof and a lithium ion batteryHas the chemical formula of [ LixNiaMnbMcO4]·[NdOe]fThe spinel type lithium nickel manganese oxide comprises a lithium nickel manganese oxide inner core LixNiaMnbMcO4And NdOeA coating layer; x is more than or equal to 1.00 and less than or equal to 1.12, a is more than or equal to 0.45 and less than or equal to 0.55, b is more than or equal to 1.45 and less than or equal to 1.85, c is more than or equal to 0.001 and less than or equal to 0.050, a + b + c are 2, d and e meet the NdOe valence balance, and f is less than 0.1; m comprises at least one of Cr, Al, Zr, V, Ti, Mo, Ru, Mg, Nb, Ba, Si, P, W, Co, Cu and Zn; n includes at least one of Al, Zn, Zr, Bi, Mg, B, Nb, Si, and P. Through doping and cladding, the specific capacity, the first effect and the cycle performance of the lithium nickel manganese oxide are obviously improved.
Description
Technical Field
The invention relates to the technical field of new energy, and relates to spinel lithium nickel manganese oxide, a preparation method thereof and a lithium ion battery.
Background
Along with the development of electric automobiles, the requirements on battery anode materials are higher and higher, and spinel lithium nickel manganese oxide LiNi0.5Mn1.5O4The material has a higher voltage platform (4.7V), so that the energy density of the material is as high as 650Wh/kg, and the material has the potential of being applied to high-energy-density lithium ion batteries. However, transition metal in the spinel lithium nickel manganese oxide is easy to react with HF in electrolyte, so that the spinel lithium nickel manganese oxide is dissolved, the capacity and the cycle performance of the battery are affected, and in order to realize large-scale application of the spinel lithium nickel manganese oxide cathode material in an electric automobile, the spinel lithium nickel manganese oxide needs to be modified to improve the electrochemical performance of the spinel lithium nickel manganese oxide.
CN101859895A discloses a method for improving LiNi which is a positive electrode material of a lithium ion battery0.5Mn1.5O4The electrochemical performance method adopts the ethanol water solution of chromium nitrate and combines the ultrasonic and water bath methods to the LiNi0.5Mn1.5O4Surface layer of (2) is doped with Cr3+Obtaining the lithium ion battery anode material LiNi with high electrochemical performance0.5Mn1.5O4. However, the method has the problems of water pollution and industrial disadvantage of synthesizing the product in a liquid phaseThe production is simplified, and the surface layer doping has limited improvement on the performance.
CN108023081A discloses a preparation method of Al-doped modified lithium nickel manganese oxide positive electrode material, which adopts alumina powder and lithium nickel manganese oxide LiNi0.5Mn1.5O4Mixing the positive electrode materials, carrying out ultrasonic treatment in absolute ethyl alcohol, drying and sintering the mixture to obtain Al-doped modified lithium nickel manganese oxide LiNi0.45Al0.05Mn1.5O4A positive electrode material powder. However, the patent uses absolute ethyl alcohol, experiments need to be carried out in an explosion-proof environment and explosion-proof equipment, certain dangerousness is caused, the industrial production is not facilitated, and meanwhile, due to the fact that aluminum is mixed with the synthesized lithium nickel manganese oxide, the effect that the aluminum cannot be better doped into the positive electrode material and even can only be coated on the surface is easily caused, and the effect of improving the product performance is limited. Therefore, it is necessary to provide a modification process for lithium nickel manganese oxide, so as to improve the capacity, the first effect and the cycle performance of the lithium nickel manganese oxide.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide spinel lithium nickel manganese oxide, a preparation method thereof and a lithium ion battery. According to the invention, the spinel type lithium nickel manganese oxide is doped and coated by adopting specific elements, so that the capacity, the first effect and the cycle performance of the obtained spinel type lithium nickel manganese oxide can be improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides spinel type lithium nickel manganese oxide, wherein the chemical general formula of the spinel type lithium nickel manganese oxide is [ Li [ ]xNiaMnbMcO4]·[NdOe]fThe spinel type lithium nickel manganese oxide comprises a lithium nickel manganese oxide inner core LixNiaMnbMcO4And NdOeA coating layer;
wherein x is more than or equal to 1.00 and less than or equal to 1.12, a is more than or equal to 0.45 and less than or equal to 0.55, b is more than or equal to 1.45 and less than or equal to 1.85, c is more than or equal to 0.001 and less than or equal to 0.050, a + b + c is 2, d and e satisfy the condition that N is equal todOeThe valence is balanced, and f is less than 0.1;
m comprises at least one of Cr, Al, Zr, V, Ti, Mo, Ru, Mg, Nb, Ba, Si, P, W, Co, Cu and Zn;
n includes at least one of Al, Zn, Zr, Bi, Mg, B, Nb, Si, and P.
In the present invention, x is, for example, 1.00, 1.02, 1.05, 1.08, 1.10 or 1.12, etc., a is, for example, 0.45, 0.47, 0.48, 0.50 or 0.55, etc., b is, for example, 1.45, 1.47, 1.50, 1.55, 1.60, 1.65, 1.70, 1.75, 1.80 or 1.85, etc., c is, for example, 0.001, 0.002, 0.003, 0.004 or 0.005, etc., d is, for example, 1, 2 or 3, etc., e is, for example, 1, 2, 3 or 5, etc., and f is, for example, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.08 or 0.09, etc.
According to the invention, the specific capacity, the first effect and the cycle performance of the obtained spinel type lithium nickel manganese oxide can be improved by doping and coating the lithium nickel manganese oxide with specific elements. The technical principle is as follows: firstly, doping element M is doped into crystal lattices of nickel cobalt lithium manganate, so that the electronic conductivity can be improved, and the bond energy of the doping element and oxygen atoms is more stable than Mn-O and Ni-O bonds, so that the structure of the anode material is stabilized, the insertion and extraction of lithium ions are facilitated, the specific capacity and the first effect of the anode material are improved, and the cycle performance of the material is improved; secondly, since the electrochemical reaction is generated at the interface of the electrode and the electrolyte, the performance of the material surface has great influence on the battery performance, and the anode material can be protected from being corroded by HF while the excellent electrical performance of the material is ensured through proper coating, so that the cycle performance of the anode material is also improved; again, by adding in LiMn2O4Based on the Ni element and the M element, the Ni element and the M element replace a part of Mn position to enter into crystal lattices, the content of the nickel element and the content of the manganese element are controlled, and the problem caused by LiMn can be solved2O4The low capacity caused by the low operating voltage of about 4V is a problem, and higher voltage is obtained, for example, spinel lithium nickel manganese oxide can have higher voltage (about 5V), and the capacity of the voltage-improved material is correspondingly improved.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, M is selected from at least one of Cr, Al and Zr, and N is selected from at least one of Zr, Zn, Bi, P and Si.
Preferably, the spinel type lithium nickel manganese oxide has a particle size of 7 μm to 9 μm, for example, 7 μm, 7.5 μm, 8 μm, 8.5 μm, or 9 μm.
In a second aspect, the present invention provides a method for preparing spinel-type lithium nickel manganese oxide according to the first aspect, comprising the following steps:
(1) mixing a lithium source, a manganese source, a nickel source and an M source by a dry method, and sintering at one time in an air atmosphere to obtain a primary sintered product;
(2) mixing the primary burned product with an N source, and sintering for the second time in an air atmosphere to obtain the spinel type lithium nickel manganese oxide;
the temperature of the secondary sintering is lower than that of the primary sintering.
By doping and coating the lithium nickel manganese oxide by the method, the capacity, the first effect and the cycle performance of the material can be obviously improved.
The invention adopts a solid phase method for bulk phase doping and surface coating, has no water pollution problem and is more environment-friendly.
The method of the present invention is not particularly limited in the kind of the lithium source, and for example, includes, but is not limited to, any one or a combination of two of lithium hydroxide or lithium carbonate, preferably lithium carbonate.
Preferably, the manganese source of step (1) comprises any one or a combination of at least two of manganese monoxide, manganese dioxide, manganese sesquioxide or manganomanganic oxide, preferably manganomanganic oxide.
Preferably, the nickel source in step (1) comprises any one or a combination of at least two of nickel monoxide, nickel sesquioxide, nickel hydroxide, nickel chloride or nickel sulfate, preferably nickel sesquioxide.
Preferably, the M source in step (1) is selected from at least one of an oxide or a hydroxide of M, preferably at least one of chromium sesquioxide, aluminum oxide, molybdenum dioxide, ruthenium tetroxide, cobaltosic oxide and cobalt hydroxide, preferably at least one of chromium sesquioxide and aluminum oxide.
Preferably, the lithium source, the manganese source, the nickel source and the M source are used in the step (1) in amounts satisfying a molar ratio Li: Ni: Mn: M (1.00 to 1.12): 0.45 to 0.55): 1.45 to 1.85): 0.001 to 0.05, which corresponds to respective molar ratios of Li to Mn, Ni and M, as exemplified by:
the molar ratio of Li to Ni is (1.00 to 1.12) to (0.45 to 0.55), for example, 1:0.45, 1:0.46, 1:0.48, 1:0.50, 1:0.51, 1:0.52, 1:0.53, or 1: 0.55.
The molar ratio Li to Mn is (1.00 to 1.12): (1.45 to 1.85), for example, 1:1.45, 1:1.47, 1:1.50, 1:1.55, 1:1.60, 1:1.65, 1:1.70, 1:1.75, 1:1.80, or 1: 1.85.
The molar ratio Li: M is (1.00 to 1.12): (0.001 to 0.050), for example, 1:0.001, 1:0.003, 1:0.005, 1:0.008, 1:0.010, 1:0.020, 1:0.040, or 1: 0.050.
Preferably, the temperature of the primary sintering in the step (1) is 750-980 ℃, such as 750 ℃, 770 ℃, 780 ℃, 800 ℃, 825 ℃, 850 ℃, 900 ℃, 950 ℃ or 980 ℃, etc.; the time of the primary sintering is 8h to 16h, such as 8h, 10h, 12h, 13h, 15h or 16 h.
Preferably, the step (1) is carried out by cooling, crushing and sieving after the primary sintering.
In a preferred embodiment of the method of the present invention, in the step (2), the N source is at least one selected from the group consisting of an oxide of N and a salt of N, preferably at least one selected from the group consisting of zirconia, zinc oxide, bismuth oxide, lithium phosphate and silica, and preferably at least one selected from the group consisting of zirconia, zinc oxide and lithium phosphate.
Preferably, the molar ratio of the N element in the N source in the step (2) to the calcined product is (0.001-0.050): 1, such as 0.001:1, 0.003:1, 0.005:1, 0.007:1, 0.010:1, 0.020:1, 0.030:1, 0.040:1 or 0.050: 1.
Preferably, the temperature of the secondary sintering in the step (2) is 550 ℃ to 700 ℃, such as 550 ℃, 575 ℃, 585 ℃, 600 ℃, 620 ℃, 640 ℃, 660 ℃ or 700 ℃, and the like; the time of the secondary sintering is 6h to 10h, such as 6h, 7h, 8h, 8.5h, 9h or 10 h.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
s1: the lithium source, the manganese source, the nickel source and the doping element M source are respectively mixed according to the molar ratio of Li to Ni to Mn to M (1.00-1.12) to (0.45-0.55) to (1.45-1.85): (0.001-0.05) weighing, wherein the doping element M is at least one of Cr, Al, Zr, V, Ti, Mo, Ru, Mg, Nb, Ba, Si, P, W, Co, Cu and Zn;
uniformly mixing a lithium source, a manganese source, a nickel source and a doping element M source by a dry method, keeping the temperature at 750-980 ℃ for 8-16 h in the air atmosphere, cooling, crushing and sieving to obtain the spinel lithium nickel manganese oxide which is sintered for the first time;
s2: and (4) uniformly mixing the primary sintered product obtained in the step (S1) with a coating agent in a dry method to ensure that the coating agent is uniformly coated on the surface of the anode material, wherein the coating agent is at least one of a Zr source, a Zn source, a Bi source, a P source or a Si source, carrying out secondary sintering on the material after the dry method mixing for 6-10 h at 550-700 ℃ in an air atmosphere, cooling, crushing and sieving to obtain the coated spinel lithium nickel manganese oxide.
Preferably, the Zr source includes, but is not limited to, zirconium oxide (ZrO)2) Zirconium hydroxide (Zr (OH)4) Or zirconium chloride (ZrCl)4) Preferably zirconium oxide and/or zirconium hydroxide.
Preferably, the Zn source includes, but is not limited to, zinc oxide (ZnO), zinc chloride (ZnCl)2) Or zinc hydroxide (Zn (OH)2) Preferably zinc oxide.
Preferably, the source of Bi includes, but is not limited to, bismuth phosphate (Bi)3(PO4)5) Bismuth sulfate (Bi)2(SO4)3) Bismuth oxide (Bi)2O3) Bismuth chlorate (Bi (ClO)3)3) Bismuth chromide (Bi)2(CrO4)3) Or bismuth hydroxide (Bi (OH)3) Preferably bismuth oxide.
Preferably, the P source includes, but is not limited to, phosphorus trichloride (PCl)3) Phosphorus pentachloride (PCl)5) Or phosphorusAcid (H)3PO4) Preferably phosphoric acid.
Preferably, the Si source includes, but is not limited to, silicon dioxide (SiO)2) Sodium silicate (Na)2SiO3) Aluminum silicate (Al)2(SiO3)3) Or silicic acid (H)2SiO3) Preferably silica.
In a third aspect, the present invention provides a lithium ion battery, which includes a positive electrode, a negative electrode, a separator and an electrolyte, and is characterized in that the lithium ion battery includes the spinel type lithium nickel manganese oxide according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the spinel type lithium nickel manganese oxide is doped and coated by adopting specific elements, so that the electronic conductivity, the structural stability and the higher working voltage of the obtained spinel type lithium nickel manganese oxide can be improved, and the specific capacity, the first effect and the cycle performance of the material are obviously improved.
Drawings
FIG. 1 is an SEM photograph of the coated spinel lithium nickel manganese oxide obtained in example 1.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
This example provides a coated lithium nickel manganese oxide, which has a chemical general formula of [ Li1.05Ni 0.48Mn1.5Cr0.02O4]·[ZrO2]0.004Including lithium nickel manganese oxide core Li1.05Ni0.48Mn1.5Cr0.02O4And ZrO2And (4) coating.
The embodiment also provides a preparation method of the spinel type lithium nickel manganese oxide, which comprises the following steps:
(1) weighing Li according to the mol ratio of Li to Ni to Mn to Cr of 1.05 to 0.48 to 1.5 to 0.022CO3、Mn3O4NiO and a dopant Cr2O3After being uniformly mixed by a dry method, the mixture is sintered for 10 hours at 850 ℃ in the air atmosphere, cooled, crushed and sieved to obtain the spinel lithium nickel manganese oxide Li which is sintered for one time1.05Ni0.48Mn 1.5Cr0.02O4。
(2) Performing primary sintering on the spinel lithium nickel manganese oxide Li obtained in the step (1)1.05Ni0.48Mn 1.5Cr0.02O4Mixing with coating agent zirconium oxide (wherein, spinel lithium nickel manganese oxide Li1.05Ni 0.48Mn1.5Cr0.02O4The molar ratio of the coating agent to Zr element in zirconia is 1:0.004) to ensure that the coating agent is uniformly coated on the surface of the spinel lithium nickel manganese oxide, the mixed material is subjected to secondary sintering for 6 hours at the temperature of 600 ℃ in the air atmosphere, and the material is cooled, crushed and sieved to obtain the coated spinel lithium nickel manganese oxide [ Li1.05Ni 0.48Mn1.5Cr0.02O4]·[ZrO2]0.004Namely the coated lithium nickel manganese oxide.
Fig. 1 is an SEM image of the coated spinel lithium nickel manganese oxide obtained in example 1, and it can be seen that the obtained product is an irregularly shaped lithium nickel manganese oxide positive electrode material with good crystallinity.
Example 2
This example is different from example 1 in that Cr in step (1) is added2O3Zirconium oxide was substituted and the molar amount of zirconium element was the same as that of the Cr element in example 1.
Example 3
This example is different from example 1 in that Cr in step (1) is added2O3Titanium oxide was substituted and the molar amount of titanium element was the same as that of Cr element in example 1.
Example 4
This example differs from example 1 in that the zirconium oxide in step (2) is replaced by bismuth oxide and spinel lithium nickel manganese oxide Li1.05Ni0.48Mn1.5Cr0.02O4The molar ratio of Bi element in bismuth oxide is 1: 0.004.
Example 5
This example differs from example 1 in that the zirconium oxide in step (2) is replaced by ZrP2O7And spinel lithium nickel manganese oxide Li1.05Ni0.48Mn1.5Cr0.02O4And ZrP2O7The molar ratio of P element in the lithium nickel manganese oxide is 1:0.004, and spinel lithium nickel manganese oxide Li1.05Ni0.48Mn 1.5Cr0.02O4And ZrP2O7The molar ratio of Zr element in (1) to (0.002).
Example 6
This example differs from example 1 in that the zirconium oxide in step (2) was replaced with AlPO4And spinel lithium nickel manganese oxide Li1.05Ni0.48Mn1.5Cr0.02O4And AlPO4The molar ratio of Al element in the lithium nickel manganese oxide is 1:0.002, and the spinel lithium nickel manganese oxide Li1.05Ni0.48Mn1.5Cr0.02O4And AlPO4The molar ratio of the P element in (B) is 1: 0.002.
Example 7
This example differs from example 1 in that in step (2) spinel lithium nickel manganese oxide Li1.05Ni0.48Mn1.5Cr0.02O4The molar ratio of Zr element in the zirconia was 1: 0.001.
Example 8
This example differs from example 1 in that in step (2) spinel lithium nickel manganese oxide Li1.05Ni0.48Mn1.5Cr0.02O4The molar ratio of Zr element in the zirconium oxide to Zr element was 1: 0.02.
Comparative example 1
The comparative example provides lithium nickel manganese oxide, and the preparation method comprises the following steps:
(1) weighing Li according to the molar ratio of Li to Ni to Mn of 1.05 to 0.5 to 1.52CO3、Mn3O4And NiO, uniformly mixing by a dry method, performing primary sintering for 10 hours at 850 ℃ in the air atmosphere, cooling, crushing and sieving to obtain the primary sintered spinel lithium nickel manganese oxide Li1.05Mn0.5Ni1.5O4。
(2) Carrying out secondary sintering on the primary sintered spinel lithium nickel manganese oxide obtained in the step (1) for 6h at 600 ℃ in the air atmosphere, cooling, crushing and sieving to obtain spinel lithium nickel manganese oxide Li1.05Ni0.5Mn1.5O4。
Comparative example 2
The comparative example provides lithium nickel manganese oxide, and the preparation method comprises the following steps:
(1) weighing Li according to the mol ratio of Li to Ni to Mn to Cr of 1.05 to 0.48 to 1.5 to 0.022CO3、Mn3O4NiO and a dopant Cr2O3After being uniformly mixed by a dry method, the mixture is sintered for 10 hours at 850 ℃ in the air atmosphere, cooled, crushed and sieved to obtain the spinel lithium nickel manganese oxide Li which is sintered for one time1.05Mn0.48Ni1.5Cr0.02O4。
(2) Carrying out secondary sintering on the primary sintered spinel lithium nickel manganese oxide obtained in the step (1) for 6h at 600 ℃ in the air atmosphere, cooling, crushing and sieving to obtain spinel lithium nickel manganese oxide Li1.05Mn0.48Ni1.5Cr0.02O4。
Comparative example 3
The comparative example provides lithium nickel manganese oxide, and the preparation method comprises the following steps:
(1) weighing Li according to the mol ratio of Li to Ni to Mn of 1.05 to 0.5 to 1.52CO3、Mn3O4And NiO, uniformly mixing by a dry method, performing primary sintering for 10 hours at 850 ℃ in the air atmosphere, cooling, crushing and sieving to obtain the primary sintered spinel lithium nickel manganese oxide Li1.05Mn0.5Ni1.5O4。
(2) Mixing the spinel lithium nickel manganese oxide obtained in the step (1) and a coating agent ZrO2Uniformly mixing Zr element in the mixed material according to a molar ratio of 1:0.04 to ensure that the coating agent is uniformly coated on the surface of the spinel lithium nickel manganese oxide, carrying out secondary sintering on the mixed material for 6 hours at 600 ℃ in an air atmosphere, cooling, crushing and sieving to obtain the coated spinel lithium nickel manganese oxide [ Li1.05Ni0.5Mn1.5O4]·[ZrO2]0.04。
Comparative example 4
This example differs from example 1 in the molar ratio Li: Ni: Mn: Cr of 1.05:0.35:1.6:0.05 in step (1).
And (3) detection:
and (3) making the buckle electric: the spinel type lithium nickel manganese oxide prepared in each example and the lithium nickel manganese oxide prepared in each comparative example are respectively used as positive electrode materials, the carbon black conductive agent and the binder PVDF (solid content is 6.25%) are weighed according to the mass ratio of 92:4:4, NMP is added to adjust the solid content of the slurry to be 48.37%, and the slurry is uniformly mixed to prepare the battery positive electrode slurry. Coating the slurry on an aluminum foil with the thickness of 20-40 um, and preparing a positive electrode plate by vacuum drying and rolling, wherein a lithium metal plate is used as a negative electrode, and the electrolyte ratio is 1.15M LiPF6EC: DMC (1:1 vol%), and assembling the button cell.
The electrical property test of the material adopts a blue battery test system to test at 25 ℃, and the test voltage range is 3.5V-5V; the 0.1C first discharge capacity, first effect and 1C 50 cycle capacity retention rate were tested. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the specific capacity, the first effect and the cycle performance of the lithium nickel manganese oxide can be obviously improved by doping and coating the lithium nickel manganese oxide with elements of specific types and contents.
The comparison between the embodiment 1 and the embodiments 2 to 3 shows that the types of the doping elements are different, and the nickel lithium manganate synthesized by adopting the doping method and the doping content of the invention has higher specific capacity, first effect and good cycle performance.
The comparison between example 1 and example 4 shows that the coating layer is made of zirconium oxide or bismuth oxide, which can provide the material with good electrochemical performance, and the zirconium oxide coating layer has better effect.
It can be seen from a comparison of example 1 with examples 5-6 that coating of multiple elements and better electrochemical performance can be achieved by using a single type of coating source.
It can be seen from the comparison between example 1 and examples 7-8 that, within a certain range, the content of the coating element is different, which has a slight influence on the specific capacity, the first effect and the cycle performance of the synthesized lithium nickel manganese oxide, and a preferable coating range exists to better balance the above effects.
As can be seen from the comparison between the example 1 and the comparative example 1, after the lithium nickel manganese oxide is doped and coated, the capacity, the first effect and the cycle are all obviously improved.
It can be seen from the comparison between example 1 and comparative example 2 that the first discharge capacity of the material is reduced after the lithium nickel manganese oxide is coated, but the cycle performance is obviously improved, mainly because the coating layer reduces the direct contact area between the electrode surface and the electrolyte, and inhibits the decomposition of the electrolyte and the occurrence of side reactions.
As can be seen from the comparison between the example 1 and the comparative example 3, the electrochemical performance of the material is improved after the nickel lithium manganate is doped, mainly because the electronic conductivity of the material is improved by doping Cr, and the Cr-O bond energy is stronger than that of Mn-O and Ni-O bond energy, so that the material has better chemical and structural stability.
It is understood from the comparison between example 1 and comparative example 4 that too little doping amount of nickel element and too much doping amount of chromium element cause a large decrease in first discharge capacity, first effect and cycle performance.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The spinel type lithium nickel manganese oxide is characterized in that the chemical general formula of the spinel type lithium nickel manganese oxide is [ Li [ ]xNiaMnbMcO4]·[NdOe]fThe spinel type lithium nickel manganese oxide comprises a lithium nickel manganese oxide inner core LixNiaMnbMcO4And NdOeA coating layer;
wherein x is more than or equal to 1.00 and less than or equal to 1.12, a is more than or equal to 0.45 and less than or equal to 0.55, b is more than or equal to 1.45 and less than or equal to 1.85, c is more than or equal to 0.001 and less than or equal to 0.050, a + b + c is 2, d and e satisfy the condition that N is equal todOeThe valence is balanced, and f is less than 0.1;
m comprises at least one of Cr, Al, Zr, V, Ti, Mo, Ru, Mg, Nb, Ba, Si, P, W, Co, Cu and Zn;
n includes at least one of Al, Zn, Zr, Bi, Mg, B, Nb, Si, and P.
2. The spinel-type lithium nickel manganese oxide according to claim 1, wherein M is at least one member selected from the group consisting of Cr, Al and Zr, and N is at least one member selected from the group consisting of Zr, Zn, Bi, P and Si.
3. The spinel type lithium nickel manganese oxide according to claim 1 or 2, wherein the particle size of the spinel type lithium nickel manganese oxide is 7 μm to 9 μm.
4. A method for preparing spinel-type lithium nickel manganese oxide according to any one of claims 1 to 3, comprising the steps of:
(1) mixing a lithium source, a manganese source, a nickel source and an M source by a dry method, and sintering at one time in an air atmosphere to obtain a primary sintered product;
(2) mixing the primary burned product with an N source, and sintering for the second time in an air atmosphere to obtain the spinel type lithium nickel manganese oxide;
the temperature of the secondary sintering is lower than that of the primary sintering.
5. The method of claim 4, wherein the lithium source of step (1) comprises any one or a combination of two of lithium hydroxide or lithium carbonate, preferably lithium carbonate;
preferably, the manganese source of step (1) comprises any one or a combination of at least two of manganese monoxide, manganese dioxide, manganese sesquioxide or manganomanganic oxide, preferably manganomanganic oxide;
preferably, the nickel source in step (1) comprises any one or a combination of at least two of nickel monoxide, nickel sesquioxide, nickel hydroxide, nickel chloride or nickel sulfate, preferably nickel sesquioxide;
preferably, the M source in the step (1) is selected from at least one of an oxide or a hydroxide of M, preferably at least one of chromic oxide, aluminum oxide, molybdenum dioxide, ruthenium tetroxide, cobaltosic oxide and cobalt hydroxide, preferably at least one of chromic oxide and aluminum oxide;
preferably, the lithium source, the nickel source, the manganese source and the M source are used in the step (1) in such amounts that the molar ratio Li: Ni: Mn: M (1.00-1.12): (0.45-0.55): (1.45-1.85): (0.001-0.050).
6. The method according to claim 4 or 5, wherein the temperature of the primary sintering in the step (1) is 750-980 ℃, and the time of the primary sintering is 8-16 h;
preferably, the step (1) is carried out by cooling, crushing and sieving after the primary sintering.
7. The method according to any one of claims 4 to 6, wherein the N source in step (2) is selected from at least one of an oxide or a salt of N, preferably at least one of zirconia, zinc oxide, bismuth oxide, lithium phosphate and silica, preferably at least one of zirconia, zinc oxide and lithium phosphate;
preferably, the molar ratio of the N element in the N source in the step (2) to the primary combustion product is (0.001-0.050): 1.
8. The method according to any one of claims 4 to 7, wherein the temperature of the secondary sintering in the step (2) is 550 ℃ to 700 ℃ and the time of the secondary sintering is 6h to 10 h.
9. Method according to any of claims 4-8, characterized in that the method comprises the steps of:
s1: the lithium source, the manganese source, the nickel source and the doping element M source are respectively mixed according to the molar ratio of Li to Ni to Mn to M (1.00-1.12) to (0.45-0.55) to (1.45-1.85): (0.001-0.05) weighing, wherein the doping element M is at least one of Cr, Al, Zr, V, Ti, Mo, Ru, Mg, Nb, Ba, Si, P, W, Co, Cu and Zn;
uniformly mixing a lithium source, a manganese source, a nickel source and a doping element M source by a dry method, keeping the temperature at 750-980 ℃ for 8-16 h in the air atmosphere, cooling, crushing and sieving to obtain the spinel lithium nickel manganese oxide which is sintered for the first time;
s2: and (4) uniformly mixing the primary sintered product obtained in the step (S1) with a coating agent in a dry method to ensure that the coating agent is uniformly coated on the surface of the anode material, wherein the coating agent is at least one of a Zr source, a Zn source, a Bi source, a P source or a Si source, carrying out secondary sintering on the material after the dry method mixing for 6-10 h at 550-700 ℃ in an air atmosphere, cooling, crushing and sieving to obtain the coated spinel lithium nickel manganese oxide.
10. A lithium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the lithium ion battery comprises the spinel type lithium nickel manganese oxide according to any one of claims 1 to 3.
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