CN110649230A - Nano rivet core-shell structure cathode material and preparation method thereof - Google Patents

Nano rivet core-shell structure cathode material and preparation method thereof Download PDF

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CN110649230A
CN110649230A CN201810673912.3A CN201810673912A CN110649230A CN 110649230 A CN110649230 A CN 110649230A CN 201810673912 A CN201810673912 A CN 201810673912A CN 110649230 A CN110649230 A CN 110649230A
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刘孟
任重民
刘健
张胜其
林欢
王德宇
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention discloses a nano rivet core-shell structure cathode material, which comprises a particle unit formed by wrapping a core by a shell, wherein the core of the particle unit is a secondary spherical particle formed by lithium-containing multi-transition metal oxide primary particles; the primary particles of the lithium-containing multi-transition metal oxide are combined through the nano lithium-containing oxide which is filled in the gaps of the primary particles; the invention can effectively inhibit the interface pulverization of the secondary particles of the lithium ion battery anode material along the primary particles, so that the lithium ion battery has high specific capacity, excellent cycle performance and safety performance, and can form a uniform nano rivet core-shell structure anode material with an electrochemical active coating layer.

Description

Nano rivet core-shell structure cathode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a nano rivet core-shell structure anode material and a preparation method thereof.
Background
The gradual exhaustion of traditional energy sources makes the development and utilization of new energy sources get more and more attention. The lithium ion battery as a green novel energy source has the outstanding advantages of high energy density, long cycle life, low self-discharge efficiency, no memory effect, good safety and the like, and is widely applied to the fields of electronic products, power automobile batteries and the like. At present, lithium-containing multi-transition metal oxide materials are mainly spherical secondary particles in which primary particles are grown in an aggregated manner due to the limitation of synthesis techniques. After long-term electrochemical cycling, the secondary spherical material can be pulverized along the interface between the primary particles, so that the electrical contact between electrode materials is poor, the internal resistance is high, and the capacity of the battery is attenuated early. In addition, the high-nickel ternary material has the problems of high surface activity, instability in wet air and the like.
In order to solve the problem of material electrochemical performance attenuation caused by cracking of ternary material particles, the patents JP11329504A and EP2571083 respectively coat acetylene black and carbon fibers on the surface of primary particles of the positive electrode material, so that cracks can be filled when secondary particles are cracked, the conductivity of the positive electrode material is continuously maintained, and the cycle performance of the positive electrode material is maintained. However, acetylene black or carbon fibers coated on the surface of the primary particles are only filled between the primary particles, and the force between the carbon fibers and the primary particles is small, so that the contact internal resistance can be reduced only after the pulverization of the secondary particles, and the pulverization of the secondary particles cannot be well suppressed.
In order to solve the problem of unstable surface of ternary material, the conventional improvement method is to coat a layer of inert substance, such as MgO, TiO2、Al2O3 (Ultrathin Al2O3 Coatings for Improved Cycling Performance and Thermal Stability of LiNi0.5Co0.2Mn0.3O2Cathe, Material electric Acta 203 (2016) 154-: CN102332577A), SiO2(High-performance lithium ion batteries using SiO2-coated LiNi0.5Co0.2Mn0.3O2 microspheres as cathodes, Journal of Alloys and Compounds 709 (2017) 708-. Most of coating methods are to treat sintered materials, and because the coating process usually needs to treat the sintered ternary materials in water or an organic solvent, secondary calcination is needed, and a local spinel phase is inevitably generated in the calcination process, the capacity of the materials is reduced, the cycle is deteriorated, gas is generated, and the potential safety hazard of the battery is increased. In addition, the current coating method has a small coating amount, cannot form a uniform coating layer, and the coating layer material has no electrochemical activity and cannot have lithium ion deintercalation capability, thereby affecting the electrochemical performance of the cathode material.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: the method can effectively inhibit the interface pulverization of the secondary particles of the lithium ion battery anode material along the primary particles, so that the lithium ion battery has high specific capacity, excellent cycle performance and safety performance, and can form a uniform nano rivet core-shell structure anode material with an electrochemical active coating layer, and the preparation method thereof.
The technical solution of the invention is as follows: a nanometer rivet core-shell structure anode material comprises a particle unit formed by wrapping a core by a shell, wherein the core of the particle unit is a secondary spherical particle formed by lithium-containing multi-transition metal oxide primary particles; the primary particles of the lithium-containing multi-transition metal oxide are combined through the nano lithium-containing oxide which is filled in the gaps of the primary particles;
the lithium-containing multi-transition metal oxide primary particle has a chemical composition of Li1+aNibCocAdM1-b-c-dO2One or more ofWherein a is more than or equal to 0.1 and less than or equal to 0.2, b is more than 0 and less than or equal to 1, c is more than 0 and less than or equal to 0.5, and d is more than 0 and less than or equal to 0.5; a is Mn or Al; the M is one or more of Cr, Mg, Ga, Ti, Fe, Cu, Sb, Sr, Ca, K, Na, Sn, Zn, V and Sc;
the chemical composition of the nano lithium-containing oxide is LieRfOgOne or more of; wherein, e + f × (valence of R) =2 g; r is selected from one or more of Nb, La, Ag, In, Te, Hf, Pb, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm and Yb;
the shell of the particle unit comprises at least one shell layer consisting of crystalline phase materials and/or amorphous phase materials;
the crystalline phase material is selected from at least one of compounds of chemical formulas shown in formulas (I), (II), (III) and (IV):
Li1+hNiiCojMn1-h-iO2 （I）
wherein h is more than or equal to-0.1 and less than or equal to 0.2, i is more than or equal to 0 and less than or equal to 1, and j is more than or equal to 0 and less than or equal to 0.5;
Li1+mMn2O4+n （II）
wherein m is more than or equal to-0.1 and less than or equal to 0.2, n is more than or equal to-0.14 and less than or equal to 0.5;
Li1+pNi0.5Mn1.5O4+q （III）
wherein p is more than or equal to-0.1 and less than or equal to-0.2, and q is more than or equal to-0.14 and less than or equal to 0.5;
Li1+tFe1-sMnsPO4 （IV）
wherein t is more than or equal to-0.1 and less than or equal to 0.2, and s is more than or equal to 0 and less than or equal to 1;
the amorphous phase material is selected from at least one of compounds of chemical formulas shown in formulas (V) and (VI):
LiuQvOw （V）
wherein u + v × (valence of Q) =2 w;
QxOy （VI）
wherein, x (valence of Q) =2 y;
q is selected from one or more of Zr, Ta, Y, Sb, Mo, Pb, Bi, W, Sn, Ga, Cd, Sc, Ba, V, Cr, Ti and Zn.
Concentration C of Ni in the shell layerNi ShellLess than the concentration C of Ni in the coreNi Core(ii) a Wherein, CNi Shell= (the sum of the number of moles of Ni in the shell layer/the number of moles of Ni and other metal elements in the shell layer) × 100%, CNi Core= (the sum of moles of Ni in the core/moles of Ni and other metal elements in the core) × 100%.
The particle size of the lithium-containing multi-transition metal oxide primary particles is 50-1000nm, and the particle size of the secondary spherical particles is 0.5-50 mu m.
The thickness of the shell of the particle unit is 1-500nm, and the particle unit is composed of 1-50 shell layers.
The outer surface of the shell of the particle unit also comprises at least one surface protection layer, and the material composition of the surface protection layer is Al2O3、MgO、ZrO2、ZnO、Y2O3、Ta2O5、Cr2O3、Nb2O5、Mo2O3、V2O5、TiO2、Ga2O3、SrO、BaO、WO2、Sb2O5、SnO、CdO、Bi2O3And PbO.
The preparation method of the nano rivet core-shell structure cathode material comprises the following steps:
1) stirring and mixing the precursor of the multi-element transition metal with the R element source, or settling or adsorbing the R element source on the surface of the precursor of the multi-element transition metal to obtain a precursor P1;
2) stirring and mixing the precursor P1 with a Q element source or settling or adsorbing the Q element source on the surface of the precursor P1 to obtain a precursor P2 coated with 1 layer of Q element source; or mixing and sintering the precursor P1 and a lithium source, and then stirring and mixing the precursor P1 and a Q element source, or settling or adsorbing the Q element source on the surface of the sintered material to obtain a precursor P2 coated with 1 layer of Q element source;
if a plurality of layers need to be coated, stirring and mixing the precursor P2 with a Q element source, or settling or adsorbing the Q element source on the surface of the precursor P2 to obtain a precursor P3 coated with 2 layers of Q element sources; repeating the coating to prepare a precursor P (n + 1) for coating n layers of Q element sources, wherein n is more than or equal to 2;
3) mixing the precursor P (n + 1) with the T element source to obtain a precursor P (n + 2);
4) and uniformly mixing the precursor P (n + 2) with a lithium source, and sintering to obtain the nano rivet core-shell structure cathode material.
The multi-transition metal precursor is composed of a plurality of transition metal compounds; the transition metal compound is one or more of transition metal oxide, hydroxide, oxyhydroxide and carbonate;
the R element source is an oxide, carbonate or hydroxide of an element R, and the R is selected from one or more of Nb, La, Ag, In, Te, Hf, Pb, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm and Yb; the Q element source is an oxide, carbonate or hydroxide of an element Q, and the Q is selected from one or more of Zr, Ta, Y, Sb, Mo, Pb, Bi, W, Sn, Ga, Cd, Sc, Ba, V, Cr, Ti and Zn; the source of the T element is oxide, carbonate or hydroxide of the element T, and the T is selected from one or more of Ni, Co, Mn and Fe.
As optimization, the preparation method of the nano rivet core-shell structure cathode material further comprises a step 5), and specifically comprises the following steps: sintering and coating at least one of the following surface protection layer materials on the surface of the nano rivet core-shell structure cathode material in the step 4) to prepare the nano rivet core-shell structure cathode material containing the protection layer: al (Al)2O3、MgO、ZrO2、ZnO、Y2O3、Ta2O5、Cr2O3、Nb2O5、Mo2O3、V2O5、TiO2、Ga2O3、SrO、BaO、WO2、Sb2O5、SnO、CdO、Bi2O3、PbO。
The lithium source is one or more of lithium carbonate, lithium hydroxide, lithium chloride, lithium nitrate and lithium acetate.
The sintering in the steps 2) and 4) is firstly sintering at the temperature of 450-700 ℃ for 2-24 hours and then sintering at the temperature of 700-1000 ℃ for 10-36 hours.
The invention has the beneficial effects that: the lithium ion battery anode material with the nano rivet structure is obtained by a simple and easy-to-implement synthesis method, and the nano lithium-containing oxide filling gaps among the primary particles can effectively generate lattice deformation or dislocation, so that the deformation stress of the lithium ion battery anode material is eliminated, the pulverization of secondary particles of the lithium ion battery anode material along the interface among the primary particles can be effectively inhibited, and the lithium ion battery can have high specific capacity, excellent cycle performance and safety performance. By adopting the method, the lithium ion battery anode material with the nano rivet structure can be obtained, secondary particles of the lithium ion battery anode material can be effectively inhibited from being pulverized along the interface between primary particles, the transmission distance of lithium ions between the primary particles is reduced, the lithium ion battery can have high specific capacity, excellent cycle performance and safety performance, meanwhile, the uniform core-shell structure with the electrochemical active coating layer is formed, the performance of the anode material is greatly improved, the surface composite coating layer shell has good lithium ion transmission capability, the surface side reaction is effectively inhibited, and the discharge capacity, the rate capability and the cycle performance of the anode material are obviously improved.
Drawings
Fig. 1 is a topographical view of precursor P1 prepared in comparative example 1.
FIG. 2 is a topographical view of precursor P4 prepared in example 2.
FIG. 3 is a topographical view of precursor P5 prepared in example 3.
FIG. 4 is preparation 3 of example 1#Topography of the sample.
FIG. 5 is preparation 5 of example 3#Topography of the sample.
FIG. 6 is a graph showing a comparative example 1Prepare 1#And (4) a morphology graph of the sample after charge and discharge cycles.
FIG. 7 is preparation 5 of example 3#And (4) a morphology graph of the sample after charge and discharge cycles.
FIG. 8 preparation 5 of example 3#Transmission electron micrograph of sample.
FIG. 9 preparation 5 of example 3#Transmission electron micrograph of sample.
FIG. 10 shows example 3 in which 5#X-ray diffraction contrast plots of the samples.
FIG. 11 shows example 7 in which 9#X-ray diffraction contrast plots of the samples.
Fig. 12 is an elemental distribution plot of a cross-section of a particle of precursor P5 prepared in example 3.
FIG. 13 is 5 prepared in example 3#Elemental profile of the cross section of the sample particle.
Fig. 14 is a discharge graph of the positive electrode materials prepared in comparative example 1, example 1 and example 3.
Fig. 15 is a graph of rate performance of the positive electrode materials prepared in comparative example 1, example 1 and example 3.
Fig. 16 is a graph showing cycle performance of the positive electrode materials prepared in comparative example 1, example 1 and example 3.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
the morphological test analysis was performed using a scanning electron microscope S4800H manufactured by Hitachi, Japan and a transmission electron microscope Tecnai F20 manufactured by FEI, the Netherlands.
Electrochemical performance test analysis was performed using the LAND electrochemical test system CT2001A manufactured by Wuhanxinnuo electronics Co.
The performance test method of the anode material comprises the following steps:
uniformly mixing a positive electrode material, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVdF) in a Nitrogen Methyl Pyrrolidone (NMP) solvent, wherein the mass ratio of the positive electrode material to the conductive agent to the binder is 85: 10: and 5, coating the uniformly mixed slurry on an aluminum foil, and performing vacuum drying at 120 ℃ for 12 hours to obtain the lithium ion battery anode.
The CR2032 type button lithium ion battery is assembled by using the pole piece as a positive electrode, using metal lithium as a negative electrode, adopting a solution of ethylene carbonate and dimethyl carbonate of 1mol/L lithium hexafluorophosphate as an electrolyte and adopting a polyethylene and polypropylene composite material with the thickness of 20 microns as a diaphragm. The assembled button cell is subjected to charge and discharge tests, and the voltage range is 2.8-4.3 volts.
Comparative example 1
According to the molar ratio of Ni, Co and Mn of 8: 1: 1 preparing a mixed solution, respectively weighing 232.63g, 29.10g and 25.10g of nickel nitrate hexahydrate, cobalt nitrate hexahydrate and manganese nitrate tetrahydrate, and adding 500mL of water for dissolving. 1000mL of a 5mol/L NaOH solution and 1000mL of a 2mol/L aqueous ammonia solution were prepared.
Adding 200mL of water into a reaction kettle protected by argon, simultaneously adding the mixed solution, a 5mol/L NaOH solution and a 2mol/L ammonia water solution into the reaction kettle, and controlling the final pH value of the solution to be 7-14. And after the sedimentation is finished, filtering and washing the precipitate, and drying at 80 ℃ to obtain a precursor P1.
The precursor P1100 g was weighed, and Li OH.H was weighed so that the molar ratio of the lithium source to the precursor P1 was 1.052O47.71 g and precursor P1 are mixed evenly, sintered for 4 hours at 550 ℃, and then sintered for 12 hours at 850 ℃ to obtain the cathode material LiNi0.8Co0.1Mn0.1O2Is marked as 1#。
Comparative example 2
According to the molar ratio of Ni, Co and Mn of 5: 2: 3 preparing a mixed solution, weighing 131.42g of nickel sulfate hexahydrate, cobalt sulfate heptahydrate, and manganese sulfate monohydrate, 56.22g and 50.70g respectively, and adding 500mL of water for dissolving. 1000mL of a 4mol/L NaOH solution and 1000mL of a 2mol/L aqueous ammonia solution were prepared.
200mL of water is added into a reaction kettle protected by nitrogen, the mixed solution, a 4mol/L NaOH solution and a 2mol/L ammonia water solution are simultaneously added into the reaction kettle, and the final pH value of the solution is controlled to be 11.5. And after the sedimentation is finished, filtering and washing the precipitate, and drying at 80 ℃ to obtain a precursor P2.
The precursor P250 g was weighed, and the molar ratio of lithium source to precursor was 1.05: 1 weigh LiOH.H2O23.94 g and precursor P2 are mixed evenly, sintered for 6 hours at 400 ℃ and then sintered for 12 hours at 850 ℃ to obtain LiNi0.5Co0.2Mn0.3O2Material, marked 2#。
Example 1
Weigh precursor P110 g, with Nb2O5 1.6g of the precursor P3 is obtained after uniform mixing; the precursor P310 g was weighed, and LiOH. H was weighed so that the molar ratio of the lithium source to the precursor P3 was 1.052Mixing O4.56 g and precursor P3 uniformly, sintering at 650 deg.C for 6 hr, and sintering at 900 deg.C for 12 hr to obtain anode material, labeled as 3#。
Example 2
Precursor P350 g was weighed, 200mL water was added, and the mixture was stirred to form a dispersion. Preparing 1mol/L ammonia water solution. 11.32g of Zr (SO) were weighed4)2.H2O, dissolved in 60mL of water.
Zr (SO)4)2Adding the solution into the dispersion of the precursor P3, adjusting the pH value to 8.0 by using ammonia water after the addition is finished, filtering, washing for three times, and drying at 100 ℃ to obtain ZrO (OH) coated on the surface2Precursor P4.
Weighing 10g of the P4 precursor, and mixing the lithium salt and the precursor according to a molar ratio of 1.2:1, weighing LiOH2O5.30 g and a precursor P4 are uniformly mixed, sintered for 6 hours at 600 ℃ and sintered for 12 hours at 900 ℃ to obtain the LiNi with the nano rivet structure as the core0.8Co0.1Mn0.1O2The shell layer is Li6Zr2O7Core-shell material of (1), denoted by 4#。
Example 3
Weighing the precursor P450 g in example 2, adding 200mL of water, and stirring to form a dispersion liquid; 11.93g of Co (CH) were weighed3COO)2•4H2O, dissolved in 50mL of water. Fitting for mixing4mol/L LiOH solution and 1mol/L ammonia solution are prepared.
Mixing Co (CH)3COO)2The solution was added to a dispersion of precursor P4 simultaneously with 4mol/L LiOH and aqueous ammonia solution, Co (OH)2Depositing on the surface of precursor P4, controlling the pH value of deposition at 12, filtering, washing with water, and drying at 100 deg.C to obtain composite precursor P5.
50g of the P5 precursor is weighed, and the molar ratio of the lithium salt to the precursor is 1.2:1, weighing LiOH2O26.65 g, and the precursor P5 are evenly mixed, sintered for 6 hours at 480 ℃ and sintered for 12 hours at 950 ℃ to obtain the LiNi with the nano rivet structure as the core0.8Co0.1Mn0.1O2The shell is crystal phase LiCoO2And amorphous phase Li6Zr2O7Core-shell material of (1), labeled 5#。
Example 4
Core-shell material 5 after sintering in example 3 was weighed#50g of water (100 mL) was added to form a suspension. Weighing Mg (CH)3COO)2•4H2O5.59 g was dissolved in 50mL of water to prepare a 1mol/L NaOH solution.
Mixing Mg (CH)3COO)2Is slowly added to the suspension of the positive electrode material together with a NaOH solution to form Mg (OH)2Sedimentating on the surface of the anode material, and the end point pH value is 11.5; filtering, washing, calcining the material at 500 ℃ for 6 hours to obtain LiNi with MgO coated surface and nano rivet structure as core0.8Co0.1Mn0.1O2The shell layer is crystal phase LiMn2O4And amorphous phase Li6Zr2O7Core-shell material of (1), denoted by 6#。
Example 5
Precursor P210 g was weighed and 100ml of deionized water was added and stirred to form a dispersion. 1mol/L ammonia solution is prepared, 7.04g of TaCl is weighed5And adding 14mL of deionized water for dissolution.
Adding TaCl5Adding the solution into the dispersion of the precursor P2, adjusting the pH to 8.0-9.0 with ammonia water after the addition is finished, filtering, washing with water for three times,drying at 100 ℃ to obtain surface coating Ta (OH)5Precursor P6.
The precursor P610 g was weighed, and LiOH.H was weighed in such a manner that the molar ratio of the lithium source to the precursor P6 was 1.2:12O5.34 g and a precursor P6 are uniformly mixed, sintered for 6 hours at 600 ℃ and sintered for 12 hours at 850 ℃ to obtain LiNi with a nano rivet structure0.5Co0.2Mn0.3O2Positive electrode material, reference numeral 7#。
Example 6
Precursor P650 g was weighed, 200mL water was added, and the mixture was stirred to form a dispersion. Preparing 1mol/L ammonia water solution. 11.36g of Zr (SO) were weighed4)2.H2O, dissolved in 30mL of water.
Zr (SO)4)2Adding the solution into the dispersion of the precursor P6, adjusting the pH to 8.0 with ammonia water after the addition is finished, filtering, washing with water for three times, and drying at 100 ℃ to obtain ZrO (OH) coated on the surface2Precursor P7.
Weighing 10g of the P7 precursor, and mixing the lithium salt and the precursor according to a molar ratio of 1.2:1, weighing LiOH2O5.31 g and a precursor P7 are uniformly mixed, sintered for 6 hours at 600 ℃ and sintered for 12 hours at 900 ℃ to obtain the LiNi with the nano rivet structure as the core0.5Co0.2Mn0.3O2The shell layer is Li6Zr2O7Core-shell material of (1), denoted by 8#。
Example 7
Precursor P750 g in example 6 was weighed, 200mL of water was added, and the mixture was stirred to form a dispersion; 14.32g of Mn (CH) are weighed3COO)2•4H2O, dissolved in 60mL of water. 4mol/L LiOH solution and 1mol/L ammonia solution are prepared.
Mixing Mn (CH)3COO)2The solution was added to a dispersion of precursor P7 simultaneously with 4mol/L LiOH and an aqueous ammonia solution, Mn (OH)2The precipitate is settled on the surface of precursor P7, and the settlement pH value is controlled at 12. Filtering, washing with water, and drying at 100 ℃ to obtain the composite precursor P8.
50g of the P8 precursor was weighed, and the molar ratio of lithium salt to precursor was 1.1: 1, weighing LiOH224.40g of O, and the precursor P8 are uniformly mixed, sintered for 6 hours at 500 ℃ and sintered for 12 hours at 950 ℃ to obtain the LiNi with the nano rivet structure as the core0.5Co0.2Mn0.3O2The shell layer is crystal phase LiMn2O4And amorphous phase Li6Zr2O7Core-shell material of (1), denoted by 9#。
Example 8
Core-shell material 9 after sintering in example 7 was weighed#50g of water (100 mL) was added to form a suspension. Weighing MgSO4•7H2O6.45 g was dissolved in 50mL of water to prepare a 1mol/L NaOH solution.
MgSO (MgSO)4Is slowly added to the reaction mixture 9 together with a solution of NaOH#In the suspension of (3), Mg (OH)2Sedimentating on the surface of the anode material, and the end point pH value is 11.5; filtering, washing, calcining the material at 500 ℃ for 6 hours to obtain LiNi with MgO coated surface and nano rivet structure as core0.5Co0.2Mn0.3O2The shell is crystal phase LiCoO2And amorphous phase Li6Zr2O7Core-shell material of (1), denoted by 10#。
Performance testing
FIGS. 1-3 are topographical views of the precursors prepared in comparative example 1, example 2 and example 3, from which it can be seen that the precursor material is spherical and has a diameter of 10-40 μm; fig. 4 and 5 are morphology diagrams of the cathode materials prepared in comparative example 1 and example 3, and it can be seen from the diagrams that the materials are spherical, and the morphology of other materials is similar. As is clear from FIGS. 1 to 5, the prepared precursor and the positive electrode material are spherical secondary particles having a particle size of about 10 μm, and the particles are composed of primary particles having a size of 200-500 nm.
Fig. 6 and 7 are morphology diagrams of the positive electrode materials prepared in comparative example 1 and example 3 after charge and discharge cycles, and it can be seen from the diagrams that secondary particles crack after charge and discharge cycles of the 1# positive electrode material, and the integrity of the secondary particles is better and no cracking phenomenon occurs after charge and discharge cycles of the 5# novel structure positive electrode material.
FIGS. 8 and 9 are projection electron micrographs of the core-shell material prepared in # 5, from which it can be seen that LiNbO3The nanocrystalline is interstitial among the primary particles to form a nano rivet structure, and more tiny crystalline regions and amorphous regions exist on the surface.
FIGS. 10 and 11 are views 5 of example 3#Sample, 9 in example 7#The X-ray diffraction contrast diagram of the sample, and the test result of XRD shows 5#The sample is alpha-NaFeO with space group of R-3m2And (4) a type lattice structure. 10#The sample is a structure in which a space group is a layered structure of R-3m and a spinel structure of Fd-3m are intergrowth.
Fig. 12 is an element distribution diagram of a cross section of the precursor P5 particle prepared in example 3, and it can be seen from the diagram that the concentration of Ni element in the prepared precursor is gradually reduced from the core to the shell, the content of Co element in the shell is higher than that in the core, and the highest peak of Zr element concentration appears on the right side of the highest peak of Co element concentration. The results indicate that the synthesized precursor has Ni as the core0.8Co0.1Mn0.1(OH)2The middle layer is ZrO (OH)2The outermost layer is Co (OH)2The shell-core-shell structure of (1). FIG. 13 is 5 prepared in example 3#The element distribution diagram of the cross section of the sample particle shows that the distribution of Co element and Zr element does not have a peak with higher concentration. Because the oxide precursor is decomposed and reacts to form crystalline phase LiCoO in the high-temperature sintering process2And amorphous phase Li6Zr2O7A homogeneous mixing zone of (a).
Fig. 14 to 16 are discharge curves, rate performance curves and cycle performance curves of the positive electrode materials prepared in comparative example 1, example 2 and example 3, and discharge voltages were 4.3V to 2.8V. The comparison shows that the cathode material effectively inhibits secondary particle pulverization to reduce internal resistance, the surface composite coating shell layer has good lithium ion transmission capability and effectively inhibits surface side reaction, and the discharge capacity, rate capability and cycle performance of the cathode material are obviously improved.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.

Claims (10)

1. The nanometer rivet core-shell structure cathode material comprises a particle unit formed by wrapping an inner core by a shell, and is characterized in that:
the inner core of the particle unit is a secondary spherical particle consisting of lithium-containing multi-element transition metal oxide primary particles; the primary particles of the lithium-containing multi-transition metal oxide are combined through the nano lithium-containing oxide which is filled in the gaps of the primary particles;
the lithium-containing multi-transition metal oxide primary particle has a chemical composition of Li1+aNibCocAdM1-b-c-dO2Wherein a is more than or equal to 0.1 and less than or equal to 0.2, b is more than 0 and less than or equal to 1, c is more than 0 and less than or equal to 0.5, and d is more than 0 and less than or equal to 0.5; a is Mn or Al; the M is one or more of Cr, Mg, Ga, Ti, Fe, Cu, Sb, Sr, Ca, K, Na, Sn, Zn, V and Sc;
the chemical composition of the nano lithium-containing oxide is LieRfOgOne or more of; wherein, e + f × (valence of R) =2 g; r is selected from one or more of Nb, La, Ag, In, Te, Hf, Pb, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm and Yb;
the shell of the particle unit comprises at least one shell layer consisting of crystalline phase materials and/or amorphous phase materials;
the crystalline phase material is selected from at least one of compounds of chemical formulas shown in formulas (I), (II), (III) and (IV):
Li1+hNiiCojMn1-h-iO2 （I）
wherein h is more than or equal to-0.1 and less than or equal to 0.2, i is more than or equal to 0 and less than or equal to 1, and j is more than or equal to 0 and less than or equal to 0.5;
Li1+mMn2O4+n （II）
wherein m is more than or equal to-0.1 and less than or equal to 0.2, n is more than or equal to-0.14 and less than or equal to 0.5;
Li1+pNi0.5Mn1.5O4+q （III）
wherein p is more than or equal to-0.1 and less than or equal to-0.2, and q is more than or equal to-0.14 and less than or equal to 0.5;
Li1+tFe1-sMnsPO4 （IV）
wherein t is more than or equal to-0.1 and less than or equal to 0.2, and s is more than or equal to 0 and less than or equal to 1;
the amorphous phase material is selected from at least one of compounds of chemical formulas shown in formulas (V) and (VI):
LiuQvOw （V）
wherein u + v × (valence of Q) =2 w;
QxOy （VI）
wherein, x (valence of Q) =2 y;
q is selected from one or more of Zr, Ta, Y, Sb, Mo, Pb, Bi, W, Sn, Ga, Cd, Sc, Ba, V, Cr, Ti and Zn.
2. The nano rivet core-shell structure cathode material according to claim 1, characterized in that: concentration C of Ni in the shell layerNi ShellLess than the concentration C of Ni in the coreNi Core(ii) a Wherein, CNi Shell= (the sum of the number of moles of Ni in the shell layer/the number of moles of Ni and other metal elements in the shell layer) × 100%, CNi Core= (the sum of moles of Ni in the core/moles of Ni and other metal elements in the core) × 100%.
3. The nano rivet core-shell structure cathode material according to claim 1, characterized in that: the particle size of the lithium-containing multi-transition metal oxide primary particles is 50-1000nm, and the particle size of the secondary spherical particles is 0.5-50 mu m.
4. The nano rivet core-shell structure cathode material according to claim 1, characterized in that: the thickness of the shell of the particle unit is 1-500nm, and the particle unit is composed of 1-50 shell layers.
5. The nano rivet core-shell structure cathode material according to claim 1, characterized in that: the outer surface of the shell of the particle unit also comprises at least one surface protection layer, and the material composition of the surface protection layer is Al2O3、MgO、ZrO2、ZnO、Y2O3、Ta2O5、Cr2O3、Nb2O5、Mo2O3、V2O5、TiO2、Ga2O3、SrO、BaO、WO2、Sb2O5、SnO、CdO、Bi2O3And PbO.
6. A preparation method of the nano rivet core-shell structure cathode material as claimed in any one of claims 1 to 4 is characterized in that: the method comprises the following steps:
1) stirring and mixing the precursor of the multi-element transition metal with the R element source, or settling or adsorbing the R element source on the surface of the precursor of the multi-element transition metal to obtain a precursor P1;
2) stirring and mixing the precursor P1 with a Q element source or settling or adsorbing the Q element source on the surface of the precursor P1 to obtain a precursor P2 coated with 1 layer of Q element source; or mixing and sintering the precursor P1 and a lithium source, and then stirring and mixing the precursor P1 and a Q element source, or settling or adsorbing the Q element source on the surface of the sintered material to obtain a precursor P2 coated with 1 layer of Q element source;
if a plurality of layers need to be coated, stirring and mixing the precursor P2 with a Q element source, or settling or adsorbing the Q element source on the surface of the precursor P2 to obtain a precursor P3 coated with 2 layers of Q element sources; repeating the coating to prepare a precursor P (n + 1) for coating n layers of Q element sources, wherein n is more than or equal to 2;
3) mixing the precursor P (n + 1) with the T element source to obtain a precursor P (n + 2);
4) and uniformly mixing the precursor P (n + 2) with a lithium source, and sintering to obtain the nano rivet core-shell structure cathode material.
7. The preparation method of the nano rivet core-shell structure cathode material according to claim 6, characterized in that: the multi-transition metal precursor is composed of a plurality of transition metal compounds; the transition metal compound is one or more of transition metal oxide, hydroxide, oxyhydroxide and carbonate.
8. The preparation method of the nano rivet core-shell structure cathode material according to claim 6, characterized in that: the R element source is an oxide, carbonate or hydroxide of an element R, and the R is selected from one or more of Nb, La, Ag, In, Te, Hf, Pb, Ce, Pr, Nd, Sm, Eu, Gd, Ho, Er, Tm and Yb; the Q element source is an oxide, carbonate or hydroxide of an element Q, and the Q is selected from one or more of Zr, Ta, Y, Sb, Mo, Pb, Bi, W, Sn, Ga, Cd, Sc, Ba, V, Cr, Ti and Zn; the source of the T element is oxide, carbonate or hydroxide of the element T, and the T is selected from one or more of Ni, Co, Mn and Fe.
9. The preparation method of the nano rivet core-shell structure cathode material according to claim 6, characterized in that: further comprising a step 5), specifically: sintering and coating at least one of the following surface protection layer materials on the surface of the nano rivet core-shell structure cathode material in the step 4) to prepare the nano rivet core-shell structure cathode material containing the protection layer: al (Al)2O3、MgO、ZrO2、ZnO、Y2O3、Ta2O5、Cr2O3、Nb2O5、Mo2O3、V2O5、TiO2、Ga2O3、SrO、BaO、WO2、Sb2O5、SnO、CdO、Bi2O3、PbO。
10. The preparation method of the nano rivet core-shell structure cathode material according to claim 6, characterized in that: the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium chloride, lithium nitrate and lithium acetate.
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