CN108365181B - Modification method of high-nickel layered positive electrode material - Google Patents

Modification method of high-nickel layered positive electrode material Download PDF

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CN108365181B
CN108365181B CN201711178891.XA CN201711178891A CN108365181B CN 108365181 B CN108365181 B CN 108365181B CN 201711178891 A CN201711178891 A CN 201711178891A CN 108365181 B CN108365181 B CN 108365181B
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王波
蔡飞鹏
杨改
高剑
蒋波
秦显忠
陈花
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Shandong AIA kesimao New Material Co., Ltd
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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    • Y02E60/10—Energy storage using batteries

Abstract

A method for modifying a high-nickel layered cathode material comprises the following steps: (1) uniformly mixing a high-nickel layered transition metal oxide material with a precursor containing M-O and M-P; (2) through chemical reaction, M-O and M-P precursor coating layers formed on the surface of LiNixX1-xO2(x >0.5) are converted, and a layer of nanoscale and uniformly distributed M-O and M-P coating layers is formed on the surface of an active material; (3) and (3) carrying out heat treatment on the coating layer obtained in the step (2) to obtain the lithium battery anode material of which the surface of the electrode material contains M-O and/or L-M-O and M-P and/or L-M-P. The positive electrode material prepared by the method can greatly reduce the content of lithium residue on the surface, and can form an inert protective layer and a lithium conducting layer on the surface of the material, so that the rate performance and the cycling stability of the material are improved, and the safety performance is improved.

Description

Modification method of high-nickel layered positive electrode material
Technical Field
The invention relates to an electrode material of a lithium ion battery, in particular to a high-nickel layered anode material and a preparation method thereof.
Background art:
with the development of industry and the rapid increase of the number of automobiles, the emission of greenhouse gases is increasingly serious, which causes global warming, and becomes a global problem to be solved urgently. The consumption of fossil fuels is one of the important causes of this problem, and therefore, the development and utilization of renewable energy sources are increasingly urgent. However, renewable energy sources typified by solar energy and wind energy are intermittent. Therefore, there is a need to select an efficient energy storage system. Based on factors such as weight, storage capacity, size, and durability, lithium ion batteries are one of the most prominent energy storage devices.
The lithium ion battery mainly comprises a positive electrode, a negative electrode, electrolyte, a diaphragm and the like. Currently, the main cathode materials include layered LiCoO2Layered LiNi1-x-yCoxMnyO2Layered LiNi0.8Co0.15Al0.05O2Spinel Li2MnO4And olivine LiFePO4And the like. Wherein the layered structure LiNi1-x-yCoxMnyO2(1-x-y>0.5) and LiNi0.8Co0.15Al0.05O2The high-nickel ternary material has a thickness of more than 180mA · hg-1The specific discharge capacity and the operation voltage of nearly 3.8V can reach 800 Wh-kg-1The energy density of the lithium ion battery is expected to become one of the cathode materials of the next generation lithium ion battery.
Despite the obvious advantages, the high nickel ternary cathode material still has many problems, which hinder its practical application. Surface lithium retention is one of several serious problems. The main components of the surface lithium residue are LiOH and Li2CO3And the like. During operation, lithium impurities can react with the electrolyte to form CO2、N2And the like, causing the battery to swell, resulting in deterioration of the battery performance. In addition, in the slurry mixing process in the battery preparation, when the pH is high, gelation of the slurry can be caused. Therefore, the surface lithium residues must be effectively removed before the battery is prepared. Currently, the method for removing lithium residue is washing, and then secondary sintering. This process can partially remove lithium residues, but causes a decrease in capacity retention rate upon secondary sintering in air. Furthermore, this treatment method does not effectively protect the active material surface.
Another important problem with high nickel transition metal oxide positive electrode materials is the deterioration of the surface structure during cycling. This structural deterioration is caused by cation-mixing, starting from the surface of the material and gradually spreading towards the inner layer. At high operating voltages and high temperatures. In addition, with the accompanying deterioration of the structure,O2and is released from the crystal lattice, and oxygen is released more vigorously at high temperature or high voltage operation. When O is present2When the electrolyte is contacted with an organic electrolyte and exposed to open fire, combustion and explosion are very easy to occur. Therefore, it is important to suppress the mixed discharge of cations and reduce the oxygen release, and to improve the cycle performance and safety performance of the material.
Surface coating is an effective method for improving material performance, and the coating material at present is mainly metal oxide (such as Al)2O3、MgO、ZnO、SiO2Etc.), metal fluorides (AlF)3、MgF2Etc.) and metal phosphates (AlPO)4、FePO4Etc.), which are inert coatings, essentially forming an inert layer on the surface of the active material to isolate the surface of the material from the organic electrolyte, thus serving as a physical protective layer and an HF scavenger. This surface modification method can improve the structural stability of the material, thus improving the cycle stability and safety, but may cause the reduction of the rate capability; another coating method is lithium conductive coating, which is to form a lithium conductive layer mainly containing LiAlO on the surface of active material2、Li2MnO3、Li2SiO3、Li3PO4And the like, the structural stability of the material can be improved, and the rate capability of the material can be improved. However, this method often requires additional lithium source to react with the coating precursor again during the coating process, and cannot effectively reduce the content of lithium impurities on the surface.
The invention content is as follows:
the invention provides a surface modification method for a high-nickel layered cathode material, which can greatly reduce the content of lithium residue on the surface and form an inert protective layer and a lithium conducting layer on the material, thereby improving the rate capability and the cycling stability of the material and improving the safety performance.
The invention provides a modified high-nickel layered positive electrode material, which comprises a high-nickel layered transition metal oxide object phase layer and a composite coating layer consisting of M-O and/or L-M-O, and M-P and/or L-M-P, wherein the high-nickel layered transition metal oxide can beWith LiNixX1-xO2Is represented by (1), wherein<x<1, X is one or more of Co, Mn, Al and the like; the M-O compound refers to an oxide containing M element; the M-P refers to a phosphate containing M element; the L-M-O compound refers to a lithium oxide of M element; the L-M-P refers to lithium phosphate of M element.
The M element is selected from one or more of Mg, Ca, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ni, Cu, Zn, B, Al, Ga, Si, Ge and Sn elements, and preferably is one or more of V, Mn, Fe, Co, Zr and B.
The high nickel layered transition metal oxide positive electrode material is preferably LiNi0.6Co0.2Mn0.2O2、LiNi0.7Co0.15Mn0.15O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Al0.05O2、LiNi0.9Co0.05Mn0.05O2。
The M-O compound is Al2O3、Co3O4、TiO2、TiO、Ti2O3、ZrO2、SnO2、SnO、MnO2、B2O3、SiO2、V2O5、V2O3、VO2、VO、Nb2O5、NbO、NbO2、Ta2O5、MoO3、RuO2、Fe3O4、Cr2O3、Ga2O3、GeO2、Rh2O3、P2O5、WO3Is preferably V2O5、V2O3、VO2、Fe3O4、Co3O4、ZrO2、B2O3One or more of (a).
Said M-P is AlPO4、CoPO4、Co3(PO4)2、Mn3(PO4)2、FePO4、Fe3(PO4)2、Mg3(PO4)2、Zn3(PO4)2、VPO4、Ni3(PO4)2Cu3(PO4)2、Ca3(PO4)2、YPO4、BPO4、W(PO4)2、TiPO4Is preferably CoPO4、Co3(PO4)2、FePO4、Fe3(PO4)2、VPO4、W(PO4)2One or more of (a).
The invention also provides a method for modifying the high-nickel layered cathode material, which comprises the following steps:
(1) uniformly mixing a high-nickel layered transition metal oxide material with a precursor containing M-O and M-P;
(2) through chemical reaction, the LiNi is subjected to chemical reactionxX1-xO2(x>0.5) converting the M-O and M-P precursor coating formed on the surface to form a layer of nanoscale and uniformly distributed M-O and M-P coating on the surface of the active material;
(3) and (3) carrying out heat treatment on the coating layer obtained in the step (2) to obtain the lithium battery anode material of which the surface of the electrode material contains M-O and/or L-M-O and M-P and/or L-M-P.
The precursor coating layer in the step (1) is obtained by adopting a coating or dipping method.
The chemical reaction in the step (2) is to put the high-nickel layered transition metal oxide material loaded with the M-O and M-P precursor coating layer obtained in the step (1) into a solution of phosphoric acid or soluble phosphate to enable the M-P precursor to perform a precipitation reaction to obtain the M-P coating layer; then decomposing at high temperature to obtain the M-O coating layer, wherein the decomposition reaction temperature is 400-600 ℃.
The heat treatment atmosphere in the step (3) is performed in an oxygen, air or inert gas atmosphere; the heat treatment temperature is 500-750 ℃, and the heat treatment time is 4-8 h; such as nitrogen, argon.
The precursor of M-O refers to a compound containing M element capable of generating an M-O compound, specifically comprises one or more of a salt containing M and an organic matter containing M, and preferably contains nitrate, carbonate and organic acid salt containing M.
The precursor of M-P is a precursor containing M element capable of generating an M-P compound, and specifically includes one or more of a salt containing M, an acid containing M and an organic substance containing M, and preferably an organic acid containing M.
The L-M-O refers to one or more of lithium oxides containing M element, preferably LiAlO2、Li2TiO3、Li2ZrO3、Li2SiO3、Li2MnO3、Li2MnP2O7、Li3BO3、Li3B7O12、Li2B4O7、LiNbO2、LiNbO3、Li3NbO4、LiTaO3、Li2MoO4、Li2WO4、LiVO3、Li2SnO3、LiFeO2、Li5FeO4、Li2WO4And the like.
The Li-M-P refers to one or more of lithium phosphate containing M element, preferably LiCoPO4、Li2MnP2O7、Li2Fe3(P2O7)2、LiZnPO4、Li3V2(PO4)3、Li2Ti2(PO4)3And the like.
The mixing mode in the step (2) is one or more of grinding, ball milling, stirring and heating and rotary evaporation.
The invention has the advantages that:
according to the invention, through surface modification of the electrode material, the lithium impurity residue on the surface of the electrode material is greatly reduced, and the structural stability of the material is improved, so that the cycling stability and the safety are improved, and meanwhile, the reduction of the rate capability of the electrode is avoided.
Drawings
FIG. 1: the technical route map of the technical scheme of the invention;
FIG. 2: zr surface modified LiNi0.8Co0.1Mn0.1O2Scanning an electron microscope image by using an electrode material;
FIG. 3: zr surface modified LiNi0.8Co0.1Mn0.1O2Scanning an electron microscope image by using an electrode material;
FIG. 4: surface-modified LiNi0.6Co0.2Mn0.2O2Electrical properties of (d);
FIG. 5: surface-modified LiNi0.6Co0.2Mn0.2O2The rate capability of (a);
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1:
taking 20g of high nickel layered transition metal oxide material LiNi0.8Co0.1Mn0.1O2Dissolving 1g of vanadium nitrate in 100ml of water, heating to 95 ℃, continuously stirring, and ultrasonically dispersing for 30 min; adding phosphoric acid solution, and continuing to stir by ultrasonic wave until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi0.8Co0.1Mn0.1O2Transferring the mixture into a muffle furnace, carrying out heat treatment for 2h at 450 ℃ in air atmosphere, heating to 600 ℃ and carrying out treatment for 5h to obtain the surface-modified high-nickel layered transition metal oxide material LiNi0.8Co0.1Mn0.1O2。
Example 2:
taking 15g of high nickel layered transition metal oxide material LiNi0.8Co0.15Al0.05O2Dissolving 0.5g of zirconium nitrate and 0.2g of manganese nitrate in 100ml of water, heating to 90 ℃, continuously stirring, and ultrasonically dispersing for 20 min; adding phosphoric acid solution, and continuing to stir by ultrasonic wave until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi0.8Co0.15Al0.05O2Transferring into a muffle furnace, heat treating at 400 deg.C for 1 hr in air atmosphere, and heating to 65%Treating at 0 ℃ for 3h to obtain surface-modified high-nickel layered transition metal oxide material LiNi0.8Co0.15Al0.05O2。
Example 3:
25g of high nickel layered transition metal oxide material LiNi is taken0.6Co0.2Mn0.2O2Dissolving 1g of boric acid and 0.2g of vanadium nitrate in 100ml of water, heating to 80 ℃, continuously stirring, and ultrasonically dispersing for 40 min; adding ammonium hydrogen phosphate solution, and continuing to stir by ultrasonic waves until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi0.6Co0.2Mn0.2O2Transferring the mixture into a muffle furnace, carrying out heat treatment for 2h at 450 ℃ in an oxygen atmosphere, heating to 700 ℃ and carrying out treatment for 3h to obtain the surface-modified high-nickel layered transition metal oxide material LiNi0.6Co0.2Mn0.2O2。
Example 4:
taking 15g of high nickel layered transition metal oxide material LiNi0.8Co0.15Mn0.05O2Dissolving 0.5g of zirconium nitrate in 100ml of water, heating to 90 ℃, continuously stirring, and ultrasonically dispersing for 30 min; adding phosphoric acid solution, and continuing to stir by ultrasonic wave until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi0.8Co0.15Mn0.05O2Transferring the mixture into a muffle furnace, carrying out heat treatment for 2h at 400 ℃ in air atmosphere, heating to 700 ℃ and carrying out treatment for 5h to obtain the surface-modified high-nickel layered transition metal oxide material LiNi0.8Co0.15Mn0.05O2。
Example 5:
30g of high nickel layered transition metal oxide material LiNi is taken0.8Co0.15Mn0.05O2Dissolving 1g of zirconium nitrate and 0.5g of boric acid in 100ml of water, heating to 95 ℃, continuously stirring, and ultrasonically dispersing for 30 min; adding phosphoric acid solution, and continuing to stir by ultrasonic wave until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi0.8Co0.15Mn0.05O2Transferring the mixture into a muffle furnace, carrying out heat treatment for 2h at 400 ℃ in air atmosphere, heating to 650 ℃ and carrying out treatment for 4h to obtain the surface-modified high-nickel layered transition metal oxide material LiNi0.8Co0.15Mn0.05O2。
Example 6:
30g of high nickel layered transition metal oxide material LiNi is taken0.8Co0.15Mn0.05O2Dissolving 0.8g of ferric nitrate in 100ml of water, heating to 95 ℃, continuously stirring, and ultrasonically dispersing for 30 min; adding phosphoric acid solution, and continuing to stir by ultrasonic wave until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi0.8Co0.15Mn0.05O2Transferring the mixture into a muffle furnace, carrying out heat treatment for 2h at 440 ℃ in air atmosphere, heating to 600 ℃ and carrying out treatment for 4h to obtain the surface-modified high-nickel layered transition metal oxide material LiNi0.8Co0.15Mn0.05O2。
Example 7:
30g of high nickel layered transition metal oxide material LiNi is taken0.8Co0.15Al0.05O2Dissolving 1.2g of cobalt nitrate in 100ml of water, heating to 95 ℃, continuously stirring, and ultrasonically dispersing for 30 min; adding phosphoric acid solution, and continuing to stir by ultrasonic wave until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi0.8Co0.15Al0.05O2Transferring the mixture into a muffle furnace, carrying out heat treatment for 2h at 450 ℃ in air atmosphere, heating to 700 ℃ and carrying out treatment for 5h to obtain the surface-modified high-nickel layered transition metal oxide material LiNi0.8Co0.15Al0.05O2。
Example 8:
40g of high nickel layered transition metal oxide material LiNi is taken0.8Co0.1Mn0.1O2Dissolving 1.2g of cobalt nitrate and 0.5g of boric acid in 100ml of water, heating to 95 ℃, continuously stirring, and ultrasonically dispersing for 30 min; adding phosphoric acid solution, and continuing to stir by ultrasonic wave until the water content is completeVolatilizing; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi0.8Co0.1Mn0.1O2Transferring the mixture into a muffle furnace, carrying out heat treatment for 2h at 450 ℃ in air atmosphere, heating to 700 ℃ and carrying out treatment for 5h to obtain the surface-modified high-nickel layered transition metal oxide material LiNi0.8Co0.1Mn0.1O2。
Comparative example 1
The other procedures are the same as example 1, but only M metal oxide is loaded on the high nickel layered transition metal oxide material. The preparation process comprises the following steps:
taking 20g of high nickel layered transition metal oxide material LiNi0.8Co0.1Mn0.1O2Dissolving 1g of vanadium nitrate in 100ml of water, heating to 95 ℃, continuously stirring, and ultrasonically dispersing for 30 min; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi0.8Co0.1Mn0.1O2Transferring the mixture into a muffle furnace, carrying out heat treatment for 2h at 450 ℃ in air atmosphere, heating to 600 ℃ and carrying out treatment for 5h to obtain the surface-modified high-nickel layered transition metal oxide material LiNi0.8Co0.1Mn0.1O2。
Comparative example 2
The other procedures are the same as example 1, but only M metal phosphate is loaded on the high nickel layered transition metal oxide material. The preparation process comprises the following steps:
taking 20g of high nickel layered transition metal oxide material LiNi0.8Co0.1Mn0.1O2Dissolving 1g of vanadium nitrate and 5g of phosphoric acid in 100ml of water, heating to 95 ℃, continuously stirring, and ultrasonically dispersing for 30 min; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi0.8Co0.1Mn0.1O2Transferring the mixture into a muffle furnace, carrying out heat treatment for 2h at 450 ℃ in air atmosphere, heating to 600 ℃ and carrying out treatment for 5h to obtain the surface-modified high-nickel layered transition metal oxide material LiNi0.8Co0.1Mn0.1O2。
The performance tests of discharge capacity and discharge cycle retention rate were performed on examples 1 to 8 obtained according to the technical scheme of the present invention and comparative examples 1 to 2 prepared according to the prior art, and the results are shown in the following table:
Figure BDA0001478786790000051
Figure BDA0001478786790000061
from the experimental data in the table, it can be seen that the electrode material prepared by the method of the present invention has good discharge performance, and meanwhile, the aging-resistant discharge performance is also obviously improved, and a significant progress is made.
The lithium battery electrode according to the present invention is described above by way of specific examples. It will be readily appreciated by those of ordinary skill in the art that the details for implementing the invention are not limited by the foregoing description. Although only an example of the electrode for a lithium battery is provided, it will be apparent to those skilled in the art after having obtained the teachings of the present invention that the spirit of the present invention can be applied to other secondary batteries as well, and therefore, the scope of the present invention is not limited to the electrode for a lithium battery, but the claims should be defined as follows.

Claims (1)

1. A method for modifying a high-nickel layered cathode material comprises the following steps: taking 15g of high nickel layered transition metal oxide material LiNi0.8Co0.15Al0.05O2Dissolving 0.5g of zirconium nitrate and 0.2g of manganese nitrate in 100ml of water, heating to 90 ℃, continuously stirring, and ultrasonically dispersing for 20 min; adding phosphoric acid solution, and continuing to stir by ultrasonic wave until the water is completely volatilized; the obtained transition metal-loaded high-nickel layered transition metal oxide material LiNi0.8Co0.15Al0.05O2Transferring the mixture into a muffle furnace, carrying out heat treatment for 1h at 400 ℃ in air atmosphere, heating to 650 ℃ and carrying out treatment for 3h to obtain the surface-modified high-nickel layered transition metal oxide material LiNi0.8Co0.15Al0.05O2(ii) a Wherein the surface of the surface-modified high-nickel layered transition metal oxide material contains M-O and/or L-M-O, and M-P and/or L-M-P; wherein said M-O means an oxide containing M element; the M-P refers to a phosphate containing M element; the L-M-O refers to a lithium oxide of M element; the L-M-P refers to lithium phosphate of M element; m is zirconium and manganese.
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