CN115663139A - Nickel-cobalt-manganese multi-element positive electrode material, preparation method and application thereof, and lithium ion battery - Google Patents
Nickel-cobalt-manganese multi-element positive electrode material, preparation method and application thereof, and lithium ion battery Download PDFInfo
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 60
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007774 positive electrode material Substances 0.000 title claims description 85
- 239000010406 cathode material Substances 0.000 claims abstract description 65
- 239000010405 anode material Substances 0.000 claims abstract description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 58
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 54
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 54
- 150000001785 cerium compounds Chemical class 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 40
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- 239000011572 manganese Substances 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 26
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 24
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- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000008139 complexing agent Substances 0.000 claims description 14
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 9
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- 238000007873 sieving Methods 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 6
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 6
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 6
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- 229910017052 cobalt Inorganic materials 0.000 claims description 6
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
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- 229910052748 manganese Inorganic materials 0.000 claims description 5
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- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
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- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a nickel-cobalt-manganese multi-element cathode material, a preparation method and application thereof, and a lithium ion battery. The nickel-cobalt-manganese multi-element cathode material contains a doping element Ce, and CeO is coated on the surface of the nickel-cobalt-manganese multi-element cathode material 2 (ii) a Ce obtained by XRD of nickel-cobalt-manganese multi-element anode material occupies Ce in position of lattice 3b 3b Satisfies the following conditions: 2.1 per mill less than or equal to Ce 3b Less than or equal to 6 per thousand. The nickel-cobalt-manganese multi-element anode material contains a doping elementElement Ce, and CeO is coated on the surface of the nickel-cobalt-manganese multi-element anode material 2 And the occupancy rate of Ce in the position of the crystal lattice 3b in the anode material meets a specific range, so that the structural stability of the anode material is obviously improved, and further, the lithium ion battery containing the anode material has the advantages of high energy density, good rate capability and high cycle capacity retention rate.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a nickel-cobalt-manganese multi-element positive electrode material and a preparation method and application thereof.
Background
With the increase in environmental pollution and energy crisis, non-fossil fuel powered vehicles, pure Electric Vehicles (EV), plug-in hybrid electric vehicles (PHEV), and Hybrid Electric Vehicles (HEV), have attracted attention in recent years. The lithium ion battery for the vehicle is required to have the characteristics of high energy density, long cycle life, good safety and the like. The positive electrode material is used as a key core material of the power lithium battery, and various performances of the vehicle battery are influenced. And its performance determines the energy density, lifetime, safety, etc. of the battery. The improvement of the nickel content in the multi-element cathode material is a main means for realizing high energy density of the current battery, but the structural stability and the thermal stability of the multi-element material are reduced along with the improvement of the nickel content, so that the cycle performance and the safety performance index of the battery are deteriorated along with the increase of the nickel content. The method for improving the electrical property of the material mainly comprises bulk phase doping, surface coating and the like.
CN113258059A discloses a multiple modified lithium ion battery anode material, and CeO is prepared in the synthesis process of the anode material 2 Adding into a reaction kettle to synthesize a precursor, but CeO 2 The Ce is difficult to dissolve in water and alkaline solution, and the Ce is difficult to be introduced into a precursor through liquid phase reaction, so that large-amount uniform doping is difficult to realize; according to the method, a precursor, a lithium source and cerium nitrate are mixed and sintered to obtain the anode material, and nitrate radicals are directly introduced into the anode material without post-treatment such as water washing, so that the capacity and the electrical property are influenced.
CN109301207A discloses a surface layer doped with Ce 3+ And the surface layer is coated with CeO 2 The cerium nitrate and the NCM anode material are subjected to ultrasonic treatment in ethanol for 1-2h and then are ground and sintered, the anode material is only modified on the surface layer and is not subjected to bulk phase doping, the effect of stabilizing the internal structure is limited, andthe method is complex, ethanol is needed, potential safety hazards exist, industrial production is difficult to realize, and the material structure can be damaged by the ultrasonic wave of the anode material in the ethanol, so that the electrical property is influenced.
In order to improve the structural stability of the anode material, the doped coating compound and the process means are reasonably designed, so that the material performance is improved, and the industrial production is facilitated.
Disclosure of Invention
The invention aims to solve the problem that the structural stability, the thermal stability, the cycle performance, the safety performance and the energy density of a nickel-cobalt-manganese multi-element cathode material cannot be improved simultaneously in the prior art, and provides a nickel-cobalt-manganese multi-element cathode material, a preparation method and application thereof and a lithium ion battery 2 And the occupancy rate of Ce in the position of the crystal lattice 3b in the anode material meets a specific range, so that the structural stability of the anode material is obviously improved, and further, the lithium ion battery containing the anode material has the advantages of high energy density, good rate capability and high cycle capacity retention rate.
In order to achieve the above object, a first aspect of the present invention provides a nickel-cobalt-manganese multi-element positive electrode material, wherein the nickel-cobalt-manganese multi-element positive electrode material contains a doping element Ce, and the surface of the nickel-cobalt-manganese multi-element positive electrode material is coated with CeO 2 ；
Ce obtained by XRD of nickel-cobalt-manganese multi-element anode material occupies Ce in position of lattice 3b 3b Satisfies the following conditions: 2.1 thousandth of Ce is not more than 3b ≤6‰。
The second aspect of the invention provides a preparation method of a nickel-cobalt-manganese multi-element positive electrode material, which is characterized by comprising the following steps:
(1) Preparing a nickel source, a cobalt source and a manganese source into a mixed salt solution, preparing a precipitator into a precipitator solution, preparing a complexing agent into a complexing agent solution, and preparing a cerium salt into a cerium salt solution;
(2) Under the protection of nitrogen, introducing the mixed salt solution, the cerium compound I solution, the complexing agent solution and the precipitant solution into a reaction kettle, carrying out coprecipitation reaction, and then aging, filtering, washing and drying to obtain a nickel-cobalt-manganese hydroxide precursor;
(3) Mixing a nickel-cobalt-manganese hydroxide precursor, a lithium source and a cerium compound II, performing first sintering, crushing and sieving to obtain a positive electrode material process product;
(4) Mixing the positive electrode material process product with the cerium compound III, performing secondary sintering, crushing, and sieving to obtain a nickel-cobalt-manganese multi-element positive electrode material;
wherein the cerium compound I and the cerium compound II are added in an amount of 0< [ n (Ce) in a stoichiometric ratio 1 +n(Ce) 2 ]/[n(Ni)+n(Co)+n(Mn)]Adding the mixture to less than or equal to 0.03;
the addition amount of the cerium compound III is more than 0< n (Ce) 3 /[n(Ni)+n(Co)+n(Mn)]Adding the additive less than or equal to 0.03.
The invention also provides a nickel-cobalt-manganese multi-element cathode material prepared by the preparation method.
The fourth aspect of the invention provides an application of the nickel-cobalt-manganese multi-element positive electrode material in a lithium ion battery.
The fifth aspect of the invention provides a lithium ion battery, which is characterized in that the lithium ion battery comprises the nickel-cobalt-manganese multi-element cathode material.
By the technical scheme, the nickel-cobalt-manganese multi-element positive electrode material and the preparation method and application thereof provided by the invention have the following beneficial effects:
the nickel-cobalt-manganese multi-element cathode material contains a doping element Ce, and CeO is coated on the surface of the nickel-cobalt-manganese multi-element cathode material 2 And the occupancy rate Ce of Ce obtained by XRD of the nickel-cobalt-manganese multi-element cathode material at the position of crystal lattice 3b 3b The positive electrode material has a stable structure, and the rate capability and the cycle performance of the lithium ion battery containing the positive electrode material are improved. In particular, ceO coated on the surface of the cathode material 2 Can prevent side reaction between electrolyte and surface, and F element in crystal lattice can block electrolyteAnd the corrosion of HF inhibits the damage of electrolyte to the material in the battery circulation process, and further improves the structural stability of the positive electrode material in the battery circulation process.
Further, ce in the cathode material provided by the invention 4+ The Ce-doped ternary material metal layer can be doped, the radius of Ce ions is large, the interlayer spacing can be increased, li is easier to insert and remove, and the rate capability is improved; and Ce 4+ In the method, li vacancy can be introduced due to charge balance, so that the Li ion mobility is improved, and the rate capability of the lithium ion battery containing the cathode material is further improved.
Furthermore, in the anode material provided by the invention, the bonding strength of Ce doped in crystal lattices and O is strong, so that O atoms in the crystal lattices can be stabilized, the crystal lattice O is inhibited from coming out, and the material structure is stabilized; the strong bond between the F element and the metal can stabilize the metal element in the crystal lattice, inhibit the dissolution of the metal element, and further improve the structural stability and the cycle performance. Incorporation of Ce into the crystal lattice 4+ Based on the charge balance, ni in the positive electrode material can be stabilized 2+ Since the average valence of the metal layer is 3+ -, ce 4+ Into the metal layer, ni may be added 2+ The lithium-nickel composite positive electrode material is stably arranged in the metal layer and cannot migrate to the Li layer, so that the mixed arrangement of lithium and nickel is inhibited, and the charge-discharge capacity, the rate capability and the cycle performance of the lithium ion battery containing the positive electrode material are improved.
Furthermore, the nickel-cobalt-manganese multi-element anode material provided by the invention is prepared in a two-step doping mode, the preparation method is simple, specifically, a soluble cerium compound I is added during wet synthesis of a precursor, uniform doping of the precursor is realized, the precursor is easy to enter into crystal lattices after sintering, and anions such as nitrate radical, sulfate radical and chloride ion are removed through washing and filtering processes, and cannot be introduced into the anode material. Then, a cerium compound II (preferably cerium fluoride) is introduced in the sintering stage for doping, part of the doping is introduced into crystal lattices, and the redundant part of the doping can be left between grain boundaries; and then coated with a cerium compound III (preferably cerium oxide) to protect the surface of the material. The Ce element is introduced in the precursor synthesis process and the two sintering processes, so that the Ce can be uniformly doped into crystal lattices, distributed among crystal boundaries and uniformly coated on the surface of the material, the optimal doping and coating amount of the Ce is achieved, and the segregation condition is avoided. The method is easy to realize industrially, has low cost and is suitable for mass production.
Drawings
Fig. 1 is an SEM image of the positive electrode material prepared in example 1;
FIG. 2 is an XRD pattern of the positive electrode material obtained in example 1, in which the peak of the pentagram is CeO 2 Characteristic peak of (a);
fig. 3 is an SEM image of the positive electrode material prepared in comparative example 1;
fig. 4 is a graph of cycle performance at 1C rate of the positive electrode materials obtained in example 1 and comparative example 1, in which the test temperature was 45℃ and the voltage was in the range of 3.0 to 4.3V.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a nickel-cobalt-manganese multi-element positive electrode material, which is characterized in that the nickel-cobalt-manganese multi-element positive electrode material contains a doping element Ce, and CeO is coated on the surface of the nickel-cobalt-manganese multi-element positive electrode material 2 ；
Ce obtained by XRD of the nickel-cobalt-manganese multi-element anode material occupies Ce in lattice 3b position 3b Satisfies the following conditions: 2.1 per mill less than or equal to Ce 3b ≤6‰。
In the invention, the nickel-cobalt-manganese multi-element cathode material contains a doping element Ce, and CeO is coated on the surface of the nickel-cobalt-manganese multi-element cathode material 2 ，Ce 4+ Can be doped in the ternary metal layer due to Ce 4+ The ionic radius is large, so that the interlayer spacing can be increased, li is easier to insert and remove, and the multiplying power performance is improved; and Ce 4+ Exist, because of the introduction of Li vacancy due to charge balance, improve Li ionThe mobility further improves the rate capability of the lithium ion battery containing the cathode material.
Particularly, when the nickel-cobalt-manganese multi-element cathode material obtains Ce in lattice 3b position occupancy rate Ce obtained by XRD 3b The positive electrode material has a stable structure, and the rate capability and the cycle performance of the lithium ion battery containing the positive electrode material are improved. In particular, ceO coated on the surface of the cathode material 2 The side reaction of the electrolyte and the surface can be prevented, the F element in the crystal lattice can block the corrosion of HF in the electrolyte, the damage of the electrolyte to the material in the battery circulation process is inhibited, and the structural stability of the anode material in the battery circulation process is further improved. Specifically, ce cannot play a role in charge balance and interlayer support when the occupancy rate of the lattice 3b position is too low, and the material capacity is reduced due to the absence of electrochemical activity of Ce when the occupancy rate is too high, and excessive Ce blocks lithium ion channels between layers, thereby affecting the rate capability.
Further, 2.3 ‰ Ce 3b ≤4‰。
According to the invention, the occupancy rate Ni of Ni obtained by XRD of the nickel-cobalt-manganese multi-element positive electrode material at the 3a position of crystal lattice 3a Satisfies the following conditions: ni 3a ≤2％。
In the invention, when the nickel-cobalt-manganese multi-element cathode material is obtained by XRD, the occupancy rate of Ni in the lattice 3a position is Ni 3a When the specific range is met, the occupancy rate of Ni in a Li layer is low, li ion insertion and extraction cannot be hindered, and the excellent rate performance of the lithium ion battery containing the cathode material is ensured.
Further, ni 3a 0.2 to 1.5 percent.
According to the invention, ceO exists in the XRD spectrogram of the nickel-cobalt-manganese multi-element cathode material at the position where 2 theta is 28-29 DEG 2 The characteristic peak of (1).
In the invention, ceO exists in the XRD spectrogram of the nickel-cobalt-manganese multi-element cathode material at the position where 2 theta is 28-29 DEG 2 Characteristic peak of (A), indicating the presence of CeO on the surface of the material 2 The positive electrode material can inhibit the corrosion of the electrolyte and stabilize the surface structure,thereby protecting the internal structure from being damaged and improving the cycle performance of the lithium ion battery containing the cathode material.
In the invention, the XRD spectrum of the nickel-cobalt-manganese multi-element cathode material has a characteristic peak (003) of the cathode material at the 2 theta of 18.5-19.4 degrees.
According to the invention, the nickel-cobalt-manganese multi-element anode material is CeO obtained by XRD 2 (111) Peak area G of characteristic peak (111) The peak area G of the characteristic peak of the nickel-cobalt-manganese multi-element positive electrode material (003) (003) The following relationship is satisfied:
2≤G (003) /G (111) ≤15。
in the present invention, when CeO is used 2 (111) Peak area G of characteristic peak (111) The peak area G of the characteristic peak of the nickel-cobalt-manganese multi-element cathode material (003) (003) When the above specific relationship is satisfied, it is indicated that the CeO on the surface of the positive electrode material 2 The coating amount is within a proper range if the surface is coated with CeO 2 Too little, only a small amount of point coating can be realized, and most surfaces are not protected and exposed in the electrolyte, so that the materials cannot be completely and uniformly coated; if the surface is coated with CeO 2 Too much of CeO, which is not electrochemically active 2 The charge and discharge capacity of the lithium ion battery containing the anode material is reduced, and CeO 2 The excessive coating amount causes the excessive thickness of the coating layer on the surface of the anode material, thereby influencing the intercalation and deintercalation of lithium ions.
Further, G is not less than 3 (003) /G (111) ≤10。
According to the invention, the cell parameter a of the nickel-cobalt-manganese multi-element anode material obtained by XRD satisfies the following conditions: a is more than or equal to 2.85nm and less than or equal to 2.90nm.
According to the invention, the cell parameter c of the nickel-cobalt-manganese multi-element anode material obtained by XRD satisfies the following conditions: c is more than or equal to 14.15nm and less than or equal to 14.25nm.
In the present invention, ce is used as a main component 4+ The ionic radius (0.104 nm) is larger than that of Ni 2+ (0.069nm)、Co 3+ (0.054 nm) and Mn 4+ (0.053nm)，Ce 4+ The support effect between the lattice layers leads to an increase in the cell parameters a and c, in particular, such that the cell parameters a and c satisfy the above rangesDuring the process, the distance between the anode material layers is increased, the lithium ion mobility is improved, and the rate capability of the lithium ion battery containing the anode material is improved.
According to the invention, the nickel-cobalt-manganese multi-element cathode material has a composition shown in formula I:
Li a Ni x Mn y Co z Ce b O 2-c/2 F c ·mCeO 2 formula I;
wherein 0.9. Ltoreq. A.ltoreq. 1.1,0.5. Ltoreq. X <1,0 yarn-y yarn-ties 0.5,0 yarn-z yarn-ties 0.5,0 yarn-b.ltoreq.0.03, 0 yarn-c yarn-ties 0.05,0 yarn-m.ltoreq.0.03.
In the invention, when the nickel-cobalt-manganese multi-element anode material has the composition shown in formula I, namely the multi-element anode material contains a doping element Ce with a specific content and a coating layer CeO with a specific content 2 The cathode material has a stable structure, and the rate capability and the cycle performance of the lithium ion battery containing the cathode material are improved.
Further, a is more than or equal to 1.02 and less than or equal to 1.06,0.5 and less than 1,0 yarn-woven-y yarn-woven 0.5,0 yarn-woven-z yarn-woven 0.5,0<b and less than or equal to 0.02,0 yarn-c yarn-woven 0.02 and 0 yarn-m is less than or equal to 0.02.
The second aspect of the invention provides a preparation method of a nickel-cobalt-manganese multi-element positive electrode material, which is characterized by comprising the following steps:
(1) Preparing a nickel source, a cobalt source and a manganese source into a mixed salt solution, preparing a precipitator into a precipitator solution, preparing a complexing agent into a complexing agent solution, and preparing a cerium salt into a cerium salt solution;
(2) Under the protection of nitrogen, introducing the mixed salt solution, the cerium compound I solution, the complexing agent solution and the precipitant solution into a reaction kettle, carrying out coprecipitation reaction, and then aging, filtering, washing and drying to obtain a nickel-cobalt-manganese hydroxide precursor;
(3) Mixing a nickel-cobalt-manganese hydroxide precursor, a lithium source and a cerium compound II, performing first sintering, crushing and sieving to obtain a positive electrode material process product;
(4) Mixing the positive electrode material process product with the cerium compound III, performing secondary sintering, crushing, and sieving to obtain a nickel-cobalt-manganese multi-element positive electrode material;
wherein the cerium compound I solution and the cerium compound II are added in an amount of 0< [ n (Ce) in a stoichiometric ratio 1 +n(Ce) 2 ]/[n(Ni)+n(Co)+n(Mn)]Adding the mixture to less than or equal to 0.03;
the addition amount of the cerium compound III is more than 0< n (Ce) 3 /[n(Ni)+n(Co)+n(Mn)]Adding the additive less than or equal to 0.03.
According to the preparation method of the nickel-cobalt-manganese multi-element anode material, the nickel-cobalt-manganese multi-element anode material is prepared in a two-step doping mode, the soluble cerium compound I is added when a precursor is synthesized by a wet method, the precursor is uniformly doped, the precursor is easy to enter into crystal lattices after being sintered, and anions such as nitrate radicals, sulfate radicals and chloride ions are removed through a washing and filtering process and cannot be introduced into the anode material. Introducing a cerium compound II for doping in a sintering stage, introducing part of cerium into crystal lattices, and leaving the rest part among crystal boundaries; and then coating with a cerium compound III to protect the surface of the material.
The Ce element is introduced in the precursor synthesis process and the two sintering processes, so that the Ce can be uniformly doped into crystal lattices, distributed among crystal boundaries and uniformly coated on the surface of the material, the optimal doping and coating amount of the Ce element is achieved by controlling the addition amount of the Ce element in each step, the segregation condition is avoided, and finally the nickel-cobalt-manganese multi-element cathode material is prepared.
Furthermore, the preparation method is easy to realize industrially, has low cost and is suitable for mass production.
Further, when the cerium compound I and the cerium compound II are added in a stoichiometric ratio of 0.001 < [ n (Ce) 1 +n(Ce) 2 ]/[n(Ni)+n(Co)+n(Mn)]When the addition is less than or equal to 0.02, ce in the prepared cathode material has a proper occupancy rate at the lattice 3b position, so that the lithium-nickel mixed discharge can be inhibited, and the structural stability of the cathode material is improved.
Further, when the cerium compound III is added in a stoichiometric ratio of 0.001 < n (Ce) 3 /[n(Ni)+n(Co)+n(Mn)]When the addition is less than or equal to 0.02,CeO with appropriate coating amount on surface of cathode material 2 The lithium ion battery can protect the internal structure of the anode material, prevent the corrosion of the battery by electrolyte in the circulation process, and simultaneously, does not influence the charge and discharge capacity of the lithium ion battery and the insertion and the separation of lithium ions.
In one embodiment of the invention, the cerium compound I is added in a stoichiometric ratio 0< n (Ce) 1 /[n(Ni)+n(Co)+n(Mn)]Not more than 0.02, and the addition amount of the cerium compound II is more than 0 and less than n (Ce) according to the stoichiometric ratio 2 /[n(Ni)+n(Co)+n(Mn)]Adding the additive less than or equal to 0.02.
According to the invention, when the addition amounts of the Ce element in the nickel-cobalt-manganese hydroxide precursor and the positive electrode material process product are respectively controlled to meet the ranges, the Ce can be uniformly doped into the material phase, segregation and local enrichment can not occur, and the structural stability of the prepared positive electrode material is further remarkably improved.
Further, the cerium compound I is added in an amount of 0.0005 < n (Ce) in a stoichiometric ratio 1 /[n(Ni)+n(Co)+n(Mn)]Not more than 0.01, and the addition amount of the cerium compound II is 0.0005 < n (Ce) 2 /[n(Ni)+n(Co)+n(Mn)]Adding the additive in an amount less than or equal to 0.01.
According to the invention, the cerium compound I is selected from at least one of cerium sulfate, cerium chloride, cerium nitrate, cerium acetate, cerium hydroxide and cerium fluoride.
According to the invention, the cerium compound II is selected from at least one of cerium acetate, cerium hydroxide and cerium fluoride.
According to the invention, the cerium compound III is selected from at least one of cerium acetate, cerium hydroxide, cerium oxide and cerium fluoride.
In one embodiment of the present invention, the cerium compound II is cerium fluoride and the cerium compound III is cerium oxide.
In the present invention, the kind of the nickel source, the cobalt source, and the manganese source is not particularly limited, and may be a kind conventionally used in the art. For example, the nickel source, the cobalt source, and the manganese source are each independently selected from at least one of a sulfate, a chloride, a nitrate, and an acetate. The concentration of the mixed salt solution is also not particularly limited and may be adjusted according to the conventional practice in the art, for example, the concentration of the mixed salt solution is 1 to 3mol/L.
In the present invention, the kind of the precipitant is not particularly limited, and may be a kind of precipitant that is conventional in the art, for example, the precipitant is selected from sodium hydroxide and/or potassium hydroxide. The concentration of the precipitant solution is also not particularly limited, and may be adjusted according to the routine practice in the art.
In the present invention, the kind of the complexing agent is not particularly limited, and may be a kind of a complexing agent that is conventional in the art, and for example, the complexing agent is selected from at least one of ammonia water, disodium ethylenediaminetetraacetate, ammonium nitrate, ammonium chloride, and ammonium sulfate. The concentration of the complexing agent solution is also not particularly limited, and may be adjusted according to the routine practice in the art.
In the present invention, the kind of the lithium source is not particularly limited, and may be a kind of a lithium source that is conventional in the art, for example, the lithium source is selected from at least one of lithium carbonate, lithium hydroxide, lithium oxide, and lithium acetate.
According to the invention, the lithium source is added in a stoichiometric ratio of 0.9. Ltoreq. N (Li)/[ n (Ni) + n (Co) + n (Mn) ].ltoreq.1.1, preferably 1.02. Ltoreq. N (Li)/[ n (Ni) + n (Co) + n (Mn) ].ltoreq.1.06.
According to the invention, the conditions of the coprecipitation reaction include: the reaction temperature is 40-70 ℃, the reaction time is 5-20h, the pH value is 11-13, and the stirring speed is 50-90rpm.
Further, the conditions of the coprecipitation reaction include: the reaction temperature is 50-65 ℃, the reaction time is 10-20h, the pH value is 11.5-12.5, and the stirring speed is 60-80rpm.
According to the invention, the conditions of the first sintering comprise: in the presence of air and/or oxygen, the sintering temperature is 700-1200 ℃, and the sintering time is 5-30h.
Further, the conditions of the first sintering include: in the presence of air and/or oxygen, the sintering temperature is 700-1100 ℃, and the sintering time is 10-30h.
According to the invention, the conditions of the second sintering include: in the presence of air and/or oxygen, the sintering temperature is 500-900 ℃, and the sintering time is 3-15h.
Further, the conditions of the second sintering include: in the presence of air and/or oxygen, the sintering temperature is 500-800 ℃, and the sintering time is 6-10h.
In the present invention, the mixing in step (3) is mechanical mixing, and no solvent is added.
In the present invention, the aging, press-filtering, washing, drying in the step (2) and the crushing and screening in the steps (3) and (4) are carried out according to a conventional method well known to those skilled in the art.
The invention also provides a nickel-cobalt-manganese multi-element cathode material prepared by the preparation method.
The fourth aspect of the invention provides an application of the nickel-cobalt-manganese multi-element positive electrode material in a lithium ion battery.
The fifth aspect of the invention provides a lithium ion battery, which is characterized by comprising the nickel-cobalt-manganese multi-element cathode material.
In the following examples, all the raw materials are commercially available products unless otherwise specified.
The room temperature in the present invention means 25. + -. 2 ℃ unless otherwise specified.
In the following examples and comparative examples, relevant parameters were measured by the following methods:
(1) And (3) morphology testing: obtained by a scanning electron microscope test of type S-4800 of Hitachi, japan;
(2) XRD test: obtained by testing with a Smart Lab 9KW X-ray diffractometer from Japan science company;
(3) And (3) electrochemical performance testing:
in the following examples and comparative examples, electrochemical performance of the multi-component positive electrode material was tested using 2025 button cell batteries.
The preparation process of the 2025 type button cell is as follows:
preparing a pole piece: a multi-element cathode material, acetylene black and polyvinylidene fluoride (PVDF) are mixed according to the formula95:3:2 and a proper amount of N-methyl pyrrolidone (NMP) to form uniform slurry, coating the slurry on an aluminum foil, drying at 120 ℃ for 12h, and performing punch forming on the aluminum foil by using 100MPa pressure to prepare a positive pole piece with the diameter of 12mm and the thickness of 120 mu m, wherein the loading amount of the multi-element positive pole material is 15-16mg/cm 2 。
Assembling the battery: and assembling the positive pole piece, the diaphragm, the negative pole piece and the electrolyte into a 2025 type button cell in an argon-filled gas glove box with the water content and the oxygen content of less than 5ppm, and standing for 6 hours. Wherein, the negative pole piece uses a metal lithium piece with the diameter of 17mm and the thickness of 1 mm; the separator used was a polyethylene porous membrane (Celgard 2325) having a thickness of 25 μm; liPF of 1mol/L is used as electrolyte 6 And a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in equal amounts.
And (3) electrochemical performance testing:
in the following examples and comparative examples, electrochemical performance of 2025 type button cell was tested by Shenzhen New Willebell test system, and the charge and discharge current density at 0.1C was 200mA/g.
And controlling the charging and discharging voltage interval to be 3.0-4.3V, and carrying out charging and discharging tests on the button cell at 0.1C at room temperature to evaluate the first discharging specific capacity of the multi-element anode material.
And (3) testing the cycle performance: controlling the charging and discharging voltage interval to be 3.0-4.3V, and carrying out charging and discharging circulation on the button cell for 2 times at the constant temperature of 45 ℃ at 0.1 ℃, and then carrying out charging and discharging circulation for 80 times at 1 ℃ to evaluate the high-temperature capacity retention rate of the multi-element anode material.
And (3) rate performance test: controlling the charging and discharging voltage interval to be 3.0-4.3V, at room temperature, performing charging and discharging circulation on the button cell for 2 times at 0.1C, then performing charging and discharging circulation for 1 time at 0.2C, 0.33C, 0.5C and 1C respectively, and evaluating the rate capability of the multielement anode material by the ratio of the first discharging specific capacity at 0.1C to the discharging specific capacity at 1C. Wherein, the first discharge specific capacity of 0.1C is the discharge specific capacity of the button cell in the 1 st cycle, and the 1C discharge specific capacity is the discharge specific capacity of the button cell in the 6 th cycle.
Example 1
(1) To be provided withNickel sulfate, cobalt sulfate and manganese sulfate are used as raw materials, and the molar ratio of Ni: co: mn =80:10:10 are prepared into 2mol/L even nickel, cobalt and manganese salt mixed solution and 0.2mol/L Ce 2 (SO 4 ) 3 And preparing a solution, namely preparing an 8mol/L NaOH solution as a precipitator and directly using 25wt% ammonia water as a complexing agent.
Under the protection of nitrogen, the solution is introduced into a reaction kettle in a cocurrent flow mode, and n (Ce) is controlled 1 ：[n(Ni)+n(Co)+n(Mn)]=0.004:1, stirring at 70rpm, maintaining the reaction temperature at 55 ℃ and carrying out the reaction for 20h under the condition of pH value of 12.3. And (3) performing filter pressing, washing, drying and screening to obtain a nickel-cobalt-manganese hydroxide precursor, wherein the precursor is spherical or spheroidal single particle and has a loose structure.
(2) Lithium hydroxide, cerium fluoride and nickel cobalt manganese hydroxide precursor are mixed according to the proportion of n (Li): n (Ce) 2 ：[n(Ni)+n(Co)+n(Mn)]=1.04:0.002:1, evenly mixing, sintering for 12h at 900 ℃ in an oxygen atmosphere, naturally cooling to room temperature, crushing and sieving to obtain the process product of the cathode material.
(3) Mixing the positive electrode material process product and cerium oxide according to n (Ce) 3 ：[n(Ni)+n(Co)+n(Mn)]And the components are uniformly mixed according to the proportion of =0.01 1.04 (Ni 0.8 Co 0.1 Mn 0.1 Ce 0.006 )O 1.994 F 0.012 ·0.01CeO 2 . Cell parameters
Examples 2 to 9
According to the method of example 1, except that the adopted formula and the process parameters are different, as shown in table 1, the rest is the same as example 1, and the multi-element cathode material is prepared.
Comparative examples 1 to 5
According to the method of example 1, except that the adopted formula and the process parameters are different, as shown in table 1 (continuation), the rest is the same as example 1, and the multi-element cathode material is prepared.
Comparative example 6
The process of example 1 was followed except that: in the step (1), cerium oxide is adopted to replace Ce 2 (SO 4 ) 3 Solution, directly adding cerium oxide into a reaction kettle;
in the step (2), cerium nitrate is adopted to replace cerium fluoride. Other formulations and process parameters are shown in table 1 (continuation).
Comparative example 7
The process of example 1 was followed except that: in the step (1), ce is not added 2 (SO 4 ) 3 ；
Cerium fluoride is not added in the step (2);
and (3) replacing cerium oxide with cerium nitrate, ultrasonically treating the uniformly mixed mixture in ethanol for 1.5h, grinding, and sintering at 650 ℃ for 5h to obtain the cathode material.
Other formulations and process parameters are shown in table 1 (continuation).
TABLE 1
TABLE 1 (continue)
TABLE 1 (continuation)
The compositions of the examples and comparative cathode materials are shown in table 2.
TABLE 2
Test example
(1) Topography testing
The present invention tests scanning electron microscope images of the positive electrode materials prepared in the above examples and comparative examples, as shown in fig. 1 and 3, and it can be seen from fig. 1 and 3 that CeO on the surface of the positive electrode material obtained in example 1 2 Uniformly coating; it can be seen from fig. 3 that the positive electrode material obtained in comparative example 1 has a smooth surface and no coating.
(2)XRD
The XRD of the cathode materials prepared in the above examples and comparative examples was tested, fig. 2 is a XRD pattern of the cathode material prepared in example 1, and it can be seen from fig. 2 that CeO is present in XRD pattern at 28 ° -29 ° at 2 θ 2 The characteristic peak of (1) indicates that the material surface has CeO 2 And (4) coating. Table 3 shows the peak position 2. Theta. Of the characteristic peak of the positive electrode material (003) (003) Sum peak integral area G (003) 、CeO 2 Peak position 2 θ of characteristic peak of (111) (111) Sum peak integral area G (111) Integral area G of characteristic peak of positive electrode material (003) (003) With CeO 2 Integral area G of characteristic peak of (111) (111) Ratio G of (003) /G (111) Cell parameter a and cell parameter c, and refining to obtain Ni occupying rate of Ni in position of lattice 3a 3a And the occupancy rate Ce of Ce in the lattice 3b position 3b 。
TABLE 3
(3) Electrochemical performance test
The electrochemical performance of the positive electrode materials prepared in the above examples and comparative examples was tested, including the first discharge specific capacity of 0.1C, the specific discharge capacity of 1C, the rate capability and the cycle performance, and the specific test results are shown in table 4. Fig. 4 is a graph of cycle performance at 1C rate of the positive electrode materials obtained in example 1 and comparative example 1, in which the test temperature was 45℃ and the voltage was in the range of 3 to 4.3V. It can be seen from fig. 4 that the cycle capacity and cycle performance at 45 ℃ of example 1 are significantly better than those of comparative example 1.
TABLE 4
As can be seen from tables 2, 3, and 4, the positive electrode materials obtained in examples 1 to 9 of the present invention contain the doping element Ce, and the surfaces of the nickel-cobalt-manganese multi-element positive electrode materials are coated with CeO, as compared to comparative examples 1 to 7 2 And the occupancy rate Ce of Ce obtained by XRD of the nickel-cobalt-manganese multi-element cathode material at the position of crystal lattice 3b 3b The range limited by the invention is met, and when the cathode material is used for the lithium ion battery, the first discharge specific capacity, the rate capability and the cycle performance of the lithium ion battery can be obviously improved and promoted.
Further, the positive electrode materials obtained in examples 1 to 6 contained the doping element Ce and CeO in comparison with examples 7 to 9 2 The coating amount of the lithium ion battery is in an optimal range, and when the cathode material is used for the lithium ion battery, the lithium ion battery can have high first discharge specific capacity, rate capability and cycle performance, and the comprehensive performance of the battery is optimal.
Further, as can be seen from examples 1-2, ce is more easily incorporated into the crystal lattice by doping Ce in a liquid phase at the precursor stage than at the sintering stage, and Ce cannot be completely incorporated into the crystal lattice when the doping amount is too large, and remains between grain boundaries and on the surface.
Further, example 2 has less doping at the precursor stage, more doping at sintering, and less Ce into the crystal lattice than example 1, so that the positive electrode material is includedThe rate capability of the lithium ion battery is reduced; in the embodiment 3, the total content of the doped and coated Ce element is increased, the first discharge specific capacity of the lithium ion battery containing the cathode material is slightly reduced, but the multiplying power and the cycle performance are slightly good; example 4 the content of the doping element Ce is high and the CeO layer is coated 2 The content of (a) is small, so that the rate performance of a lithium ion battery containing the cathode material is slightly good but the cycle performance is slightly poor.
Therefore, when the specific range defined by the invention is met, the increased doping element Ce can play a supporting role between crystal lattice layers, so that Li ions can be more easily inserted and extracted, the rate capability of the lithium ion battery containing the cathode material is improved, and CeO (cerium oxide) of the coating layer is improved 2 The content of (b) is increased, and the cycle performance of a lithium ion battery containing the positive electrode material can be improved.
Further, it can be seen from examples 5 and 6 that the same effect can be obtained also for different NCM compositions, except that the characteristic peak positions of the positive electrode materials of different compositions are slightly different.
Further, in example 7, ceO was added to the positive electrode material in accordance with the content of Ce as a dopant element 2 Less coating amount of G (003) /G (111) Large, ce 3b And the lithium-nickel mixed discharge can not be well inhibited, so that the improvement degree of the rate capability and the cycle performance of the lithium ion battery containing the cathode material is reduced.
In the positive electrode material obtained in example 8, ceO was included in the positive electrode material in comparison with example 1 2 Greater coating amount of (G) (003) /G (111) Smaller and excessive CeO 2 Leading to increase of inert elements introduced into the anode material, and slightly reducing the first discharge specific capacity of the lithium ion battery containing the anode material; further, since CeO 2 The coating amount of (2) is large, and the surface coating layer is thick, so that the conduction of lithium ions on the surface of the cathode material is hindered, and the rate capability of the lithium ion battery containing the cathode material is slightly reduced.
Compared with the embodiment 1, in the cathode material prepared in the embodiment 9, the content of the doping element Ce is larger, so that the amount of the inert element introduced into the cathode material is increased, and the first discharge specific capacity of the lithium ion battery containing the cathode material is slightly reduced; and Ce occupies a higher rate at the position of the crystal lattice 3b, so that the conduction of lithium ions on the surface of the anode material is hindered, and the rate capability of the lithium ion battery containing the anode material is slightly reduced.
Comparative examples 1 to 3 were conducted to obtain positive electrode materials not containing coating layer CeO 2 The positive electrode material does not contain CeO 2 The (111) characteristic peak of (a), which makes the cycle performance of a lithium ion battery including the above-described cathode material poor.
Specifically, the positive electrode material prepared in comparative example 1 did not contain the doping element Ce and did not contain the coating layer CeO, as compared with example 1 2 And the lithium-nickel mixed arrangement is serious, so that the rate capability and the cycle performance of the lithium ion battery containing the cathode material are poor.
In comparative example 2, the Ce element was introduced only at the precursor stage, and the surface of the obtained positive electrode material had no CeO 2 And the occupancy rate of Ce in the crystal lattice 3b position in the anode material is low, so that uniform doping cannot be realized, and the rate capability and the cycle performance of the lithium ion battery containing the anode material are poor.
Comparative example 3 Ce was introduced only at the primary sintering stage, and the surface of the prepared positive electrode material was free of CeO 2 And the occupancy rate of Ce in the crystal lattice 3b position in the anode material is low, so that uniform doping cannot be realized, and the rate capability and the cycle performance of the lithium ion battery containing the anode material are poor.
Comparative example 4 only Ce is introduced in the secondary sintering stage, and the prepared anode material does not contain the doping element Ce and only CeO 2 The coating cannot inhibit the lithium-nickel mixing, so that the rate performance of the lithium ion battery containing the cathode material is poor, and the cycle performance is inferior to that of example 1.
Comparative example 5 content of doping element Ce and coating layer CeO 2 Too much of, G (003) /G (111) The small size of the positive electrode material causes the first discharge specific capacity of the lithium ion battery containing the positive electrode material to be reduced, the rate capability to be poor, and the small amount of Ce is doped, so that the Li ions are easier to be embedded and extracted, the material capacity is easier to be exerted, but the excessive Ce is moreThe doping material can block Li ion channels, so that the rate capability of the battery is reduced, ce has no electrochemical activity, and the doping cladding adds excessive Ce element to influence the first discharge specific capacity of the battery.
Comparative example 6 cerium oxide was added to the precursor, the cerium oxide being insoluble in water, the cerium oxide introduced at the precursor stage could not be doped into the crystal lattice, and more cerium nitrate was added at the sintering stage, and could be partially doped into the crystal lattice, but the introduction of an inert nitrate ion into the material resulted in a lower material capacity. In comparative example 6, surface coating was not performed, and part of the cerium nitrate added in the sintering step was left, but most of the cerium nitrate was left in the grain boundary, and the excess cerium nitrate was converted into CeO 2 Remains at grain boundaries, and is difficult to uniformly coat the surface of the material, resulting in deterioration of cycle performance of a battery comprising the positive electrode material.
Comparative example 7 no cerium element was doped in the preparation process of the positive electrode material, only cerium nitrate was coated on the surface, and a small portion of cerium nitrate was introduced into the surface layer lattice, so bulk phase doping could not be achieved, and lithium-nickel mixing was severe in the sintering process of preparing the positive electrode material, which could not play a good role in inhibiting by coating, resulting in poor rate performance and cycle performance of the battery comprising the positive electrode material, and the initial specific discharge capacity of the battery comprising the positive electrode material was low due to introduction of an inert nitrate ion into the material. Further, grinding the positive electrode material in ethanol can weaken the bonding force between primary particles, destroy the material structure, and further reduce the cycle retention rate of the battery.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. The nickel-cobalt-manganese multi-element cathode material is characterized by containing doping element CeAnd CeO is coated on the surface of the nickel-cobalt-manganese multi-element cathode material 2 ；
Ce obtained by XRD of the nickel-cobalt-manganese multi-element anode material occupies Ce in lattice 3b position 3b Satisfies the following conditions: 2.1 per mill less than or equal to Ce 3b ≤6‰。
2. The nickel-cobalt-manganese multi-element positive electrode material according to claim 1, wherein 2.3 ‰ Ce 3b ≤4‰。
3. The nickel-cobalt-manganese multi-element positive electrode material according to claim 1 or 2, wherein Ni obtained by XRD of the nickel-cobalt-manganese multi-element positive electrode material has an occupation ratio Ni of lattice 3a sites 3a Satisfies the following conditions: ni 3a 2 percent or less, preferably 0.2 to 1.5 percent.
4. The nickel cobalt manganese multi-positive electrode material of any one of claims 1 to 3, wherein the nickel cobalt manganese multi-positive electrode material has an XRD spectrum with CeO present at 28 ° to 29 ° at 2 θ 2 The (111) characteristic peak of (1);
preferably, the nickel-cobalt-manganese multi-element cathode material is CeO obtained by XRD 2 Peak area G of characteristic peak of (111) (111) The peak area G of the characteristic peak of (003) of the nickel-cobalt-manganese multi-element cathode material (003) The following relationship is satisfied:
2≤G (003) /G (111) 15, preferably 3.ltoreq.G (003) /G (111) ≤10。
5. The nickel-cobalt-manganese multi-positive electrode material according to any one of claims 1 to 4, wherein a unit cell parameter a of the nickel-cobalt-manganese multi-positive electrode material obtained by XRD satisfies: a is more than or equal to 2.85nm and less than or equal to 2.90nm;
preferably, the nickel-cobalt-manganese multi-element cathode material has a unit cell parameter c obtained by XRD which satisfies: c is more than or equal to 14.15nm and less than or equal to 14.25nm.
6. The nickel cobalt manganese multi-positive electrode material of any one of claims 1 to 5, wherein the nickel cobalt manganese multi-positive electrode material has a composition represented by formula I:
Li a Ni x Mn y Co z Ce b O 2-c/2 F c ·mCeO 2 formula I;
wherein 0.9. Ltoreq. A.ltoreq. 1.1,0.5. Ltoreq. X <1,0 yarn-y yarn-ties 0.5,0 yarn-z yarn-ties 0.5,0 yarn-b.ltoreq.0.03, 0 yarn-c yarn-ties 0.05,0 yarn-m.ltoreq.0.03.
7. The preparation method of the nickel-cobalt-manganese multi-element cathode material is characterized by comprising the following steps of:
(1) Preparing a nickel source, a cobalt source and a manganese source into a mixed salt solution, preparing a precipitator into a precipitator solution, preparing a complexing agent into a complexing agent solution, and preparing a cerium salt into a cerium salt solution;
(2) Under the protection of nitrogen, introducing the mixed salt solution, the cerium compound I solution, the complexing agent solution and the precipitant solution into a reaction kettle, carrying out coprecipitation reaction, and then aging, filtering, washing and drying to obtain a nickel-cobalt-manganese hydroxide precursor;
(3) Mixing a nickel-cobalt-manganese hydroxide precursor, a lithium source and a cerium compound II, performing first sintering, crushing and sieving to obtain a positive electrode material process product;
(4) Mixing the positive electrode material process product with the cerium compound III, performing secondary sintering, crushing, and sieving to obtain a nickel-cobalt-manganese multi-element positive electrode material;
wherein the cerium compound I and the cerium compound II are added in an amount of 0< [ n (Ce) in a stoichiometric ratio 1 +n(Ce) 2 ]/[n(Ni)+n(Co)+n(Mn)]Adding the mixture to less than or equal to 0.03;
the addition amount of the cerium compound III is more than 0< n (Ce) 3 /[n(Ni)+n(Co)+n(Mn)]Adding the additive less than or equal to 0.03.
8. The preparation method according to claim 7, wherein the cerium compound I and the cerium compound II are added in a stoichiometric ratio of 0.001 < [ n (Ce) ] 1 +n(Ce) 2 ]/[n(Ni)+n(Co)+n(Mn)]Adding the mixture to less than or equal to 0.02;
preferably, the cerium compound III is added in an amount according toThe stoichiometric ratio is 0.001 < n (Ce) 3 /[n(Ni)+n(Co)+n(Mn)]≤0.02。
9. The process according to claim 7 or 8, wherein the cerium compound I is added in a stoichiometric ratio of 0< n (Ce) 1 /[n(Ni)+n(Co)+n(Mn)]Addition of up to 0.02, preferably 0.0005 < n (Ce) 1 /[n(Ni)+n(Co)+n(Mn)]≤0.01；
Preferably, the cerium compound II is added in a stoichiometric ratio of 0< n (Ce) 2 /[n(Ni)+n(Co)+n(Mn)]Addition of up to 0.02, preferably 0.0005 < n (Ce) 2 /[n(Ni)+n(Co)+n(Mn)]≤0.01。
10. The production method according to any one of claims 7 to 9, wherein the cerium compound I is at least one selected from the group consisting of cerium sulfate, cerium chloride, cerium nitrate, cerium acetate, cerium hydroxide and cerium fluoride;
preferably, the cerium compound II is selected from at least one of cerium acetate, cerium hydroxide and cerium fluoride;
preferably, the cerium compound III is selected from at least one of cerium acetate, cerium hydroxide, cerium oxide and cerium fluoride;
preferably, the cerium compound II is cerium fluoride and the cerium compound III is cerium oxide;
preferably, the lithium source is added in a stoichiometric ratio of 0.9. Ltoreq. N (Li)/[ n (Ni) + n (Co) + n (Mn) ]. Ltoreq.1.1, preferably 1.02. Ltoreq. N (Li)/[ n (Ni) + n (Co) + n (Mn) ]. Ltoreq.1.06.
11. The production method according to any one of claims 7 to 10, wherein the conditions of the coprecipitation reaction include: the reaction temperature is 40-70 ℃, the reaction time is 5-20h, the pH value is 11-13, and the stirring speed is 50-90rpm;
preferably, the conditions of the first sintering include: in the presence of air and/or oxygen, the sintering temperature is 700-1200 ℃, and the sintering time is 5-30h;
preferably, the conditions of the second sintering include: in the presence of air and/or oxygen, the sintering temperature is 500-900 ℃, and the sintering time is 3-15h.
12. A nickel-cobalt-manganese multi-element positive electrode material obtained by the preparation method according to any one of claims 7 to 11.
13. Use of the nickel cobalt manganese multi-element positive electrode material of any one of claims 1 to 6 and 12 in a lithium ion battery.
14. A lithium ion battery comprising the nickel-cobalt-manganese multi-element positive electrode material of any one of claims 1 to 6 and 12.
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