CN112751006A - Cobalt-free lithium ion battery layered positive electrode material and preparation method and application thereof - Google Patents

Cobalt-free lithium ion battery layered positive electrode material and preparation method and application thereof Download PDF

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CN112751006A
CN112751006A CN202110062781.7A CN202110062781A CN112751006A CN 112751006 A CN112751006 A CN 112751006A CN 202110062781 A CN202110062781 A CN 202110062781A CN 112751006 A CN112751006 A CN 112751006A
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cobalt
lithium ion
ion battery
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electrode material
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CN112751006B (en
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潘锋
张明建
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Unnamed Battery Technology (Shenzhen) Co.,Ltd.
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Peking University Shenzhen Graduate School
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Abstract

The application discloses a cobalt-free lithium ion battery layered positive electrode material and a preparation method and application thereof. The layered positive electrode material of the cobalt-free lithium ion battery is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the lithium layer has 3-7% of cation inversion positions, and the cation inversion positions are formed by the transition metal in the transition metal oxide layer entering the lithium layer and occupying lithium ions. The cobalt-free lithium ion battery layered positive electrode material still has excellent electrochemical performance under the condition of not using cobalt ions; in addition, the use of expensive metal cobalt ions is not required, so that the problem of cost caused by cobalt dependence is solved. The preparation method of the cobalt-free lithium ion battery layered cathode material is simple and is easy for large-scale industrial production.

Description

Cobalt-free lithium ion battery layered positive electrode material and preparation method and application thereof
Technical Field
The application relates to the field of battery materials, in particular to a cobalt-free lithium ion battery layered positive electrode material and a preparation method and application thereof.
Background
As the automotive industry transitions to electrification, rechargeable batteries must also meet future demands. While efforts to improve battery performance have met with some success, current efforts have been hampered by excessive cost. These challenges associated with battery cost are primarily associated with rapidly rising prices and increased demand for Transition Metals (TMs), with a particular shortage of cobalt as a component of widely used commercial positive electrode core materials, such as LiCoO2，LiNixMnyCo1-x-yO2，LiNi0.8Co0.15Al0.05O2And the like. In recent years, Co has become economically unattractive due to increased royalties for mining franchises, and political and ethical issues in africa. To address these cost pressures, researchers have made significant efforts to develop low-cobalt and even cobalt-free positive electrodes that do not have to compromise cell performance too much. Despite including lithium-and manganese-rich positive electrodes, high voltage spinel LiNi0.5Mn1.5O4And unconventional rock salt phase materials have been highlighted as possible alternatives to cobalt-containing anodes, but these alternative anode materials have impractical capacities and stabilities for large-scale commercial use. Therefore, current research on low Co dependence has focused mainly on the layered oxide positive electrode. The nickel-rich layered oxide cathode material has high capacity and energy density. However, direct replacement of cobalt with nickel, such as LiNiO, results in significant degradation of battery performance and thermal stability2It is practically infeasible. Therefore, designing cobalt-free high-performance lithium ion layered cathode materials has become an important challenge.
It is generally believed that Co suppresses structural defects by reducing Li/Ni misclassification in the Ni-rich component and obtains a well-crystallized layered structure. This helps to ensure rate capability of the nickel-rich positive electrode, but the effect on structural stability during cycling is not clear.
Disclosure of Invention
The application aims to provide a novel cobalt-free lithium ion battery layered positive electrode material, and a preparation method and application thereof.
The following technical scheme is adopted in the application:
the application discloses a cobalt-free lithium ion battery layered positive electrode material, which is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the lithium layer has 3-7% of cation inversion positions, and the cation inversion positions are formed by the transition metal in the transition metal oxide layer entering the lithium layer and occupying lithium ions. Therefore, the lithium layer has 3 to 7% of cation inversion, which means that 3 to 7% of lithium ions in the lithium layer are replaced by transition metal ions to form an inversion structure.
The key point of the present application is that, under the condition that no Co is added, the cobalt-free lithium ion battery layered cathode material with a cation reversal ratio of 3-7% in the lithium layer is obtained by adjusting the amount and ratio of the transition metal in the layered cathode material and adjusting and controlling the preparation parameters. The cobalt-free lithium ion battery layered positive electrode material has excellent electrochemical performance under the condition of not using Co, and particularly, the cycling stability and the thermal stability are improved; in addition, the preparation method of the cobalt-free lithium ion battery layered positive electrode material is simple and is easy for large-scale industrial production.
In one implementation of the present application, the primary transition metals of the transition metal oxide layer are nickel and manganese.
Preferably, the molar ratio of nickel to manganese is from 6:4 to 99: 1.
Preferably, in the cobalt-free lithium ion battery layered positive electrode material, the molar ratio of the lithium element to other metal elements is 1-1.1: 1. Wherein, the other metal element refers to metal elements other than lithium, such as nickel and manganese, and if other doped metal elements exist, the doped metal elements are also included.
It should be noted that lithium-rich and manganese-rich cathode materials or nickel-rich layered oxide cathode materials are cathode materials already existing in the prior art; in one implementation mode of the application, manganese is added into a nickel-lithium layered oxide positive electrode material, the proportion of nickel and manganese is controlled, and the preparation process parameter is regulated, so that the positive ion reverse proportion in a lithium layer is 3-7%; li (Ni) thus obtainedαMnβ)O2The cobalt-free lithium ion battery layered cathode material has high cycle stability, and the rate capability can meet the use requirement of the lithium ion battery, so that the cobalt-free lithium ion battery layered cathode material has excellent electrochemical performance.
In one implementation of the present application, the transition metal oxide layer is further doped with at least one of metal ions Al, Ti, and Mg.
It should be noted that, in the transition metal oxide layer of the present application, doped metal ions such as Al, Ti, and Mg may be optionally added or not added according to requirements, and specifically, the properties of the layered positive electrode material of the lithium ion battery are determined according to the requirements, and are not specifically limited herein.
In one implementation of the present application, the layered positive electrode material of the cobalt-free lithium ion battery is a secondary microparticle formed by primary nanoparticles.
Preferably, the size of the primary nanoparticles is 10 to 300 nanometers and the size of the secondary microparticles is 1 to 20 micrometers.
In one implementation of the present application, the layered positive electrode material of the cobalt-free lithium ion battery is micron-sized single crystal particles.
Preferably, the size of the single crystal particles is 0.5 to 10 microns.
The key point of the application lies in that the cobalt-free lithium ion battery layered cathode material with the cation reversal ratio of 3-7% in the lithium layer is creatively found to have excellent electrochemical performance; the specific physical structure, particle size, single crystal structure, size and the like of the layered cathode material of the cobalt-free lithium ion battery can be regulated and controlled by the prior art according to the use requirements. For example, the cobalt-free lithium ion battery layered cathode material can be made into a cathode material with a core-shell structure or an element gradient structure to meet various use requirements.
Therefore, the other side of the application discloses a lithium ion battery layered anode material, which is of a core-shell structure, wherein a cladding layer material of the core-shell structure is the cobalt-free lithium ion battery layered anode material of the application, and a core anode material of the core-shell structure is at least one of lithium cobaltate, a ternary layered material, a spinel lithium manganate material and a lithium iron phosphate material.
The key point of the present application is that the cobalt-free lithium ion battery layered positive electrode material of the present application is applied to a lithium ion battery layered positive electrode material with a core-shell structure, and as for the specific preparation methods of the core positive electrode material and the core-shell structure, reference may be made to the prior art, which is not specifically limited herein.
The application further discloses a lithium ion battery layered anode material which is of an element gradient structure, wherein the outermost layer of the element gradient structure is made of the cobalt-free lithium ion battery layered anode material, the element gradient structure is made of a material with gradient change of nickel and manganese element components, the nickel content is increased from outside to inside in a gradient manner, and the manganese content is decreased from outside to inside in a gradient manner.
It can be understood that the key point of the present application is that the cobalt-free lithium ion battery layered cathode material of the present application is applied to a lithium ion battery layered cathode material with an element gradient structure, and as for the internal elements of the element gradient structure, the proportion control of the internal elements, and the specific preparation method of the lithium ion battery layered cathode material with the element gradient structure, reference may be made to the prior art, which is not specifically limited herein.
The application also discloses the cobalt-free lithium ion battery layered positive electrode material, or the application of the lithium ion battery layered positive electrode material adopting the cobalt-free lithium ion battery layered positive electrode material in power lithium batteries and 3C consumer electronic lithium ion batteries.
The cobalt-free lithium ion battery layered cathode material and the lithium ion battery layered cathode material adopting the cobalt-free lithium ion battery layered cathode material have excellent electrochemical performance, and can better meet the use requirements of power lithium batteries and 3C consumer electronic lithium ion batteries.
The present application further discloses a battery, wherein the cobalt-free lithium ion battery layered positive electrode material or the lithium ion battery layered positive electrode material of the present application is adopted in the battery.
The cobalt-free lithium ion battery layered positive electrode material or the lithium ion battery layered positive electrode material has excellent electrochemical performance, and can better meet various use requirements.
The application also discloses a preparation method of the cobalt-free lithium ion battery layered positive electrode material, wherein the cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a high-temperature sintering method; the high temperature sintering method comprises mixing the raw materials uniformly, and sintering at 700-1100 deg.C for 3-24 hours in air or oxygen atmosphere.
Preferably, after sintering, rapidly cooling to room temperature at a speed of more than 100 ℃/min to obtain the cobalt-free lithium ion battery layered positive electrode material.
It should be noted that in the high-temperature sintering method of the present application, too high or too low sintering temperature increases the amount of cation inversion; therefore, in one implementation manner of the present application, the cation inversion amount is controlled by controlling the sintering temperature of 700-1100 ℃ for 3-24 hours, so as to achieve the requirement of 3-7% cation inversion of the present application. For quenching with rapid cooling at a rate greater than 100 ℃/min, this approach increases the amount of cation reversal relative to normal cooling; thus, in one implementation of the present application, the amount of cation reversal is also regulated by controlling the rate of temperature reduction of the quench.
The application also discloses a preparation method of the cobalt-free lithium ion battery layered positive electrode material, wherein the cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a microwave sintering method; the microwave sintering method comprises mixing the raw materials uniformly, and treating for 3 minutes to 3 hours under the microwave power of 300-2000 watts.
In one implementation manner of the present application, before performing high-temperature sintering or microwave sintering, a coprecipitation method is further included to synthesize a hydroxide precursor; wherein the coprecipitation method comprises placing aqueous solution of transition metal salt in nitrogen atmosphere, and adding aqueous solution of NaOH and NH4OH aqueous solution is used as a precipitator and a complexing agent, reacts for 6 to 15 hours under the conditions of pH value of 10 to 11, temperature of 50 to 80 ℃, stirring speed of 500 and 1000rpm/s, and then is dried to obtain the hydroxide precursor of the transition metal. The transition metal is, for example, nickel or manganese in the transition metal oxide layer. After the transition metal hydroxide precursor is obtained, the transition metal hydroxide precursor and a lithium source are uniformly mixed, and then high-temperature sintering or microwave sintering is carried out to obtain the cobalt-free lithium ion battery layered anode material. If doping metal ions such as Al, Ti or Mg are contained, the hydroxide precursor can be prepared by mixing the metal salt aqueous solution doped with the metal ions with the transition metal salt aqueous solution when preparing the hydroxide precursor; or after obtaining the transition metal hydroxide precursor, uniformly mixing the transition metal hydroxide precursor, a lithium source and a metal oxide doped with metal ions, and performing high-temperature sintering or microwave sintering.
The beneficial effect of this application lies in:
the cobalt-free lithium ion battery layered positive electrode material still has excellent electrochemical performance under the condition of not using cobalt ions; in addition, the use of expensive metal cobalt ions is not required, so that the problem of cost caused by cobalt dependence is solved. The preparation method of the cobalt-free lithium ion battery layered cathode material is simple and is easy for large-scale industrial production.
Drawings
FIG. 1 is a schematic structural diagram of a layered positive electrode material having cation inversion in an example of the present application;
FIG. 2 is a scanning electron microscope image of a layered positive electrode material of a cobalt-free lithium ion battery prepared in the first embodiment of the present application;
FIG. 3 shows the results of the cycle performance test of the cobalt-free lithium ion battery layered positive electrode material prepared in the first embodiment of the present application under C/3 and 1C rate current in the voltage range of 2.8-4.5V;
FIG. 4 is a scanning electron microscope image of the layered positive electrode material of the cobalt-free lithium ion battery prepared in the second embodiment of the present application;
FIG. 5 is a powder diffraction pattern and a fine modification result chart of the layered positive electrode material of the cobalt-free lithium ion battery prepared in example II of the present application;
FIG. 6 shows the results of the cycle performance test of the cobalt-free lithium ion battery layered positive electrode material prepared in the second embodiment of the present application under C/2 rate current in the full cell within the voltage range of 2.8-4.45V;
FIG. 7 shows the results of cycle performance tests of five four positive electrode materials in examples two to five of the present application at a voltage range of 2.8-4.5V at a current rate of C/3;
fig. 8 is a scanning electron microscope image of a single crystal of the cobalt-free lithium ion battery layered positive electrode material prepared in example eight of the present application.
Detailed Description
The research shows that in the existing layered positive electrode material of the lithium ion battery, the main reason that the lithium layer and the transition metal oxide layer can generate interlayer mixed arrangement (cation disorder) of Li and transition metal ions in the preparation process is influenced by the super-exchange effect and the magnetic resistance error effect; the cobalt ions are needed to be added because the cobalt ions can release magnetic faults in the layers and reduce the super exchange effect between the layers, thereby inhibiting the structural defect of cation inversion. And further research shows that the manganese ions can enhance the exchange effect between super layers and aggravate magnetic resistance errors, so that more structural defects are generated.
Therefore, the addition of cobalt ions has the function of regulating the cation inversion. However, earlier studies in this application found that cation inversion is affected by both superexchange and magnetoresi stive errors; however, in the specific production process, the two factors can be regulated and controlled by adjusting the proportion of the transition metal element and the production process parameters. That is, the ratio of the cation inversion in the lithium layer can be controlled by adjusting the ratio of the transition metal elements, particularly the ratio of nickel and manganese, and the production process parameters.
Furthermore, more importantly, the research of the application finds that although cation inversion belongs to structural defects, the deintercalation barrier and the kinetics of lithium ions are reduced, and the crystallization of a layered structure is influenced; however, the proper proportion of cations to be inverted can improve the cycling stability of the material; so that the layered cathode material has excellent electrochemical performance.
The research and the recognition of the genes, the application creatively provides a novel cobalt-free lithium ion battery layered positive electrode material, the cobalt-free lithium ion battery layered positive electrode material is a layered positive electrode material formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, and the lithium layer has 3-7% of cation inversion. The structure of the layered cathode material of the cobalt-free lithium ion battery is schematically shown in fig. 1, and fig. 1 shows the layered cathode material with cation inversion.
The cation reverse proportion can be realized by adjusting the proportion of transition metal and adjusting and controlling preparation parameters, such as adjusting and controlling the proportion of nickel and manganese, controlling the temperature, time, atmosphere, quenching and the like of high-temperature sintering, controlling the power and time of microwave sintering and the like.
According to the application, the cation reverse position of the cobalt-free lithium ion battery layered positive electrode material is controlled to be 3-7%, and in the range, although structural defects exist, the influence on the performance of the battery positive electrode material is small, so that the layered positive electrode material still has excellent electrochemical performance. In addition, the cobalt-free lithium ion battery layered positive electrode material has high cycle stability; moreover, the method has the characteristic of low cost because cobalt ions are not required to be used. In addition, the cobalt-free lithium ion battery layered positive electrode material only needs to be sintered at high temperature or by microwaves, the hydroxide precursor at the early stage only needs to be sintered by conventional coprecipitation equipment, generation equipment does not need to be updated, the preparation method is simple, and industrialization is easy to realize.
The present application will be described in further detail with reference to specific examples. The following examples are intended to be illustrative of the present application only and should not be construed as limiting the present application.
Example one
The layered positive electrode material of the cobalt-free lithium ion battery of this example is a layered positive electrode material in which lithium layers and cobalt-free transition metal oxide layers are alternately stacked, wherein the cobalt-free transition metal oxide layer is a nickel-cobalt oxide layer, and the lithium layer has 5% of cation inversion. The cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a high-temperature sintering method, and the method specifically comprises the following steps:
(1) synthesis of hydroxide precursor Ni by coprecipitation method0.7Mn0.3(OH)2: the concentration is 2.0mol L-1NiSO (D)4·6H2O and MnSO4·5H2The mixed aqueous solution of O was pumped into a self-made continuous stirred tank reactor (4L) under nitrogen atmosphere. Simultaneously, 4.0mol L of-1And 5.0mol L of NaOH-1NH of (2)4The OH aqueous solution is used as a precipitator and a complexing agent to be respectively pumped into the reactor. The pH value of the precursor solution is kept between 10.5 and 11, the temperature is kept at 60 ℃, and the stirring speed is kept at 1000 rpm/s. The reaction is carried out for 10 hours, and then the reaction product is filtered, washed for 3 times by deionized water and dried in a vacuum oven at 80 ℃ overnight.
(2) Adopting high-temperature solid phase sintering to obtain a product: reacting LiOH & H2O and Ni obtained above0.7Mn0.3(OH)2The precursor is mixed and ground uniformly according to the molar ratio of Li to TM which is 1.03 to 1, calcined for 12 hours at 825 ℃ in an oxygen atmosphere, and rapidly cooled at the speed of 110 ℃/min to obtain the product LiNi0.7Mn0.3O2(NM73) polycrystalline material, with an average particle size of 13 microns. The Li/Ni dislocation amount in the material is determined to be 5.0% by the structural refinement of an X-ray diffraction pattern. In the examples, TM means metal ions other than lithium ions, and the same shall apply to the following examples.
(3) Electrochemical testing: mixing NM73, carbon black and PVDF in a mass ratio of 80:10:10, grinding in a mortar to prepare a positive pole piece, wherein the loading capacity of active substances is about 5.2mg cm-2. The lithium half-cell was prepared using a 2032-type coin cell, using a Celgard 2325 separator and 1.2mol L-1GEN II electrolyte (LiPF)6Dissolving in EC/EMC mixed solvent with volume ratio of 3: 7), and mixing the solution with half-cell at 2.8-4.5V (vs Li)+/Li). For the full cell, the 2032 button cell is assembled by using a graphite cathode, the cycling is carried out in the voltage range of 2.8-4.45V, the N/P ratio of the full cell is about 1.2, and the commercial graphite Fujian is provided by Shenzhen BTR new energy materials company.
The results of observing the layered cathode material of the cobalt-free lithium ion battery prepared in the example by scanning an electron microscope are shown in fig. 2, and the results show that the preparation of the example obtains compact secondary particles with the average particle size of 13 μm; the scale bar in FIG. 2 is 2 μm.
The results of the cycle performance of the layered positive electrode material of the cobalt-free lithium ion battery under the current of C/3 and 1C multiplying power in the voltage range of 2.8-4.5V are shown in FIG. 3. In FIG. 3, the upper curve is the test result of C/3, and the lower curve is the test result of 1C. FIG. 3 shows that the capacity retention at C/3 magnification is 87.5%, and the capacity retention at 1C magnification is 87.7%.
The results show that the laminated cathode material of the cobalt-free lithium ion battery has higher capacity and better cycling stability and thermal stability.
Example two
The layered positive electrode material of the cobalt-free lithium ion battery of this example was a layered positive electrode material in which a lithium layer and a transition metal oxide layer containing no cobalt were alternately stacked, wherein the transition metal oxide layer containing no cobalt was a nickel-cobalt oxide layer, and the lithium layer had a cation inversion of 5.5%. The cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a high-temperature sintering method, and the method specifically comprises the following steps:
(1) synthesis of hydroxide precursor Ni by coprecipitation method0.8Mn0.2(OH)2: the concentration is 2.0mol L-1NiSO (D)4·6H2O and MnSO4·5H2The mixed aqueous solution of O was pumped into a self-made continuous stirred tank reactor (4L) under nitrogen atmosphere. Simultaneously, 4.0mol L of-1And 5.0mol L of NaOH-1NH of (2)4The OH aqueous solution is used as a precipitator and a complexing agent to be respectively pumped into the reactor. The pH value of the precursor solution is kept between 10.5 and 11, the temperature is kept at 60 ℃, and the stirring speed is kept at 1000 rpm/s. Reaction for 10 hours, suction filtration and deionized water washing for 3 timesAnd dried in a vacuum oven at 80 ℃ overnight.
(2) Adopting high-temperature solid phase sintering to obtain a product: reacting LiOH & H2O and Ni obtained above0.8Mn0.2(OH)2The precursor is uniformly mixed and ground according to the molar ratio of Li to TM being 1.03 to 1, calcined for 12 hours at 800 ℃ in an oxygen atmosphere, and rapidly cooled at the speed of 110 ℃/min to obtain the product LiNi0.8Mn0.2O2(NM82) polycrystalline material, with an average particle size of 10 microns. The Li/Ni dislocation amount in the material is determined to be 5.5% by the structural refinement of an X-ray diffraction pattern. The powder diffraction pattern and the refinement result of the layered positive electrode material of the cobalt-free lithium ion battery of this example are shown in fig. 5.
(3) Electrochemical testing: mixing NM82, carbon black and PVDF in a mass ratio of 80:10:10, grinding in a mortar to prepare a positive pole piece, wherein the loading capacity of active substances is about 5.2mg cm-2. The lithium half-cell was prepared using a 2032-type coin cell, using a Celgard 2325 separator and 1.2mol L-1GEN II electrolyte (LiPF)6Dissolving in EC/EMC mixed solvent with volume ratio of 3: 7), and mixing the solution with half-cell at 2.8-4.5V (vs Li)+/Li). For the full cell, the 2032 button cell is assembled by using a graphite cathode, the cycling is carried out in the voltage range of 2.8-4.45V, the N/P ratio of the full cell is about 1.2, and the commercial graphite Fujian is provided by Shenzhen BTR new energy materials company.
The results of observing the layered cathode material of the cobalt-free lithium ion battery prepared in this example by scanning with an electron microscope are shown in fig. 4, which shows that the preparation of this example obtains dense secondary particles with an average particle size equivalent to that of the first example, and the scale bar in the figure is 2 μm.
The results of the cycle performance test of the cobalt-free lithium ion battery layered positive electrode material in the present example under the C/2 rate current in the full-cell voltage range of 2.8-4.45V are shown in FIG. 6. The results of the cycle performance test at a voltage range of 2.8-4.5V at C/3 rate current are shown in FIG. 7. Fig. 7 shows that the capacity retention of the positive electrode material NM82 of this example was 86.2%.
The results show that the laminated cathode material of the cobalt-free lithium ion battery has higher capacity and better cycling stability and thermal stability.
EXAMPLE III
The layered positive electrode material of the cobalt-free lithium ion battery is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the transition metal oxide layer without cobalt is a nickel-cobalt oxide layer and is doped with Al; the lithium layer had 4.5% cation inversion. The cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a high-temperature sintering method, and the method specifically comprises the following steps:
(1) synthesis of hydroxide precursor Ni by coprecipitation method0.8Mn0.15Al0.05(OH)2: the concentration is 2.0mol L-1NiSO (D)4·6H2O、MnSO4·5H2O、Al2(SO4)3·18H2The mixed aqueous solution of O was pumped into a self-made continuous stirred tank reactor (4L) under nitrogen atmosphere. Simultaneously, 4.0mol L of-1And 5.0mol L of NaOH-1NH of (2)4The OH aqueous solution is used as a precipitator and a complexing agent to be respectively pumped into the reactor. The pH value of the precursor solution is kept between 10.5 and 11, the temperature is kept at 60 ℃, and the stirring speed is kept at 1000 rpm/s. The reaction is carried out for 10 hours, and then the reaction product is filtered, washed for 3 times by deionized water and dried in a vacuum oven at 80 ℃ overnight.
(2) Adopting high-temperature solid phase sintering to obtain a product: reacting LiOH & H2O and Ni obtained above0.8Mn0.15Al0.05(OH)2The precursor is uniformly mixed and ground according to the molar ratio of Li to TM being 1.03 to 1, calcined for 12 hours at 800 ℃ in an oxygen atmosphere, and rapidly cooled at the speed of 110 ℃/min to obtain the product LiNi0.8Mn0.15Al0.05O2(NMA) polycrystalline material with an average grain size of 10 microns. The Li/Ni dislocation amount in the material is determined to be 4.5% by the structural refinement of an X-ray diffraction pattern.
(3) Electrochemical testing: mixing NMA, carbon black and PVDF according to a mass ratio of 80:10:10, grinding in a mortar to prepare a positive pole piece, wherein the loading capacity of active substances is about 5.2mg cm-2. The lithium half-cell was prepared using a 2032-type coin cell, using a Celgard 2325 separator and 1.2mol L-1GEN II electrolyte (LiPF)6Dissolving in EC/EMC mixed solvent with volume ratio of 3: 7), and mixing the solution with half-cell at 2.8-4.5V (vs Li)+/Li). For the full cell, the 2032 button cell is assembled by using a graphite cathode, the cycling is carried out in the voltage range of 2.8-4.45V, the N/P ratio of the full cell is about 1.2, and the commercial graphite Fujian is provided by Shenzhen BTR new energy materials company.
The results of the cycle performance test of the layered positive electrode material of the cobalt-free lithium ion battery in the present example under the current of C/3 rate in the voltage range of 2.8-4.5V are shown in FIG. 7. Fig. 7 shows that the capacity retention ratio of the positive electrode material NMA in this example was 92.1%.
The results show that the laminated cathode material of the cobalt-free lithium ion battery has higher capacity and better cycling stability and thermal stability.
Example four
The layered positive electrode material of the cobalt-free lithium ion battery is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the transition metal oxide layer without cobalt is a nickel-cobalt oxide layer and is doped with Ti; the lithium layer had 5.8% cation inversion. The cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a high-temperature sintering method, and the method specifically comprises the following steps:
(1) synthesis of hydroxide precursor Ni by coprecipitation method0.8Mn0.2(OH)2: the concentration is 2.0mol L-1NiSO (D)4·6H2O and MnSO4·5H2The mixed aqueous solution of O was pumped into a self-made continuous stirred tank reactor (4L) under nitrogen atmosphere. Simultaneously, 4.0mol L of-1And 5.0mol L of NaOH-1NH of (2)4The OH aqueous solution is used as a precipitator and a complexing agent to be respectively pumped into the reactor. The pH value of the precursor solution is kept between 10.5 and 11, the temperature is kept at 60 ℃, and the stirring speed is kept at 1000 rpm/s. The reaction is carried out for 10 hours, and then the reaction product is filtered, washed for 3 times by deionized water and dried in a vacuum oven at 80 ℃ overnight.
(2) Adopting high-temperature solid phase sintering to obtain a product: first of all, Ni obtained above0.8Mn0.2(OH)2Precursor and nano-grade TiO2Mixing with LiOH. H2O is according toMixing and grinding Li and TM in the molar ratio of 1.03 to 1 uniformly, calcining at 800 ℃ for 12 hours in an oxygen atmosphere, and rapidly cooling at the speed of 110 ℃/min to obtain a product LiNi0.79Mn0.2Ti0.01O2(NMT) polycrystalline material, average particle size 10 microns. The Li/Ni dislocation amount in the material is determined to be 5.8% by the structural refinement of an X-ray diffraction pattern.
(3) Electrochemical testing: mixing NMT, carbon black and PVDF according to a mass ratio of 80:10:10, grinding in a mortar to prepare a positive pole piece, wherein the loading capacity of active substances is about 5.2mg cm-2. The lithium half-cell was prepared using a 2032-type coin cell, using a Celgard 2325 separator and 1.2mol L-1GEN II electrolyte (LiPF)6Dissolving in EC/EMC mixed solvent with volume ratio of 3: 7), and mixing the solution with half-cell at 2.8-4.5V (vs Li)+/Li). For the full cell, the 2032 button cell is assembled by using a graphite cathode, the cycling is carried out in the voltage range of 2.8-4.45V, the N/P ratio of the full cell is about 1.2, and the commercial graphite Fujian is provided by Shenzhen BTR new energy materials company.
The results of the cycle performance test of the layered positive electrode material of the cobalt-free lithium ion battery in the present example under the current of C/3 rate in the voltage range of 2.8-4.5V are shown in FIG. 7. Fig. 7 shows that the capacity retention ratio of the positive electrode material NMT in this example is 87.3%.
The results show that the laminated cathode material of the cobalt-free lithium ion battery has higher capacity and better cycling stability and thermal stability.
EXAMPLE five
The layered positive electrode material of the cobalt-free lithium ion battery is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the transition metal oxide layer without cobalt is a nickel-cobalt oxide layer and is doped with Mg; the lithium layer had 3.5% cation inversion. The cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a high-temperature sintering method, and the method specifically comprises the following steps:
(1) synthesis of hydroxide precursor Ni by coprecipitation method0.8Mn0.2(OH)2: the concentration is 2.0mol L-1NiSO (D)4·6H2O and MnSO4·5H2The mixed aqueous solution of O was pumped into a self-made continuous stirred tank reactor (4L) under nitrogen atmosphere. Simultaneously, 4.0mol L of-1And 5.0mol L of NaOH-1NH of (2)4The OH aqueous solution is used as a precipitator and a complexing agent to be respectively pumped into the reactor. The pH value of the precursor solution is kept between 10.5 and 11, the temperature is kept at 60 ℃, and the stirring speed is kept at 1000 rpm/s. The reaction is carried out for 10 hours, and then the reaction product is filtered, washed for 3 times by deionized water and dried in a vacuum oven at 80 ℃ overnight.
(2) Adopting high-temperature solid phase sintering to obtain a product: first of all, Ni obtained above0.8Mn0.2(OH)2Mixing the precursor with nano-scale MgO, and mixing with LiOH & H2Mixing and grinding O uniformly according to the molar ratio of Li to TM being 1.03 to 1, calcining for 12 hours at 800 ℃ in an oxygen atmosphere, and rapidly cooling at the speed of 110 ℃/min to obtain a product LiNi0.79Mn0.2Mg0.01O2(NMM) polycrystalline material, average particle size 10 microns. The Li/Ni dislocation amount in the material is determined to be 3.5% by the structural refinement of an X-ray diffraction pattern.
(3) Electrochemical testing: mixing NMM, carbon black and PVDF according to a mass ratio of 80:10:10, grinding in a mortar to prepare a positive pole piece, wherein the loading capacity of active substances is about 5.2mg cm-2. The lithium half-cell was prepared using a 2032-type coin cell, using a Celgard 2325 separator and 1.2mol L-1GEN II electrolyte (LiPF)6Dissolving in EC/EMC mixed solvent with volume ratio of 3: 7), and mixing the solution with half-cell at 2.8-4.5V (vs Li)+/Li). For the full cell, the 2032 button cell is assembled by using a graphite cathode, the cycling is carried out in the voltage range of 2.8-4.45V, the N/P ratio of the full cell is about 1.2, and the commercial graphite Fujian is provided by Shenzhen BTR new energy materials company.
The results of the cycle performance test of the layered positive electrode material of the cobalt-free lithium ion battery in the present example under the current of C/3 rate in the voltage range of 2.8-4.5V are shown in FIG. 7. Fig. 7 shows that the capacity retention rate of the positive electrode material NMM in this example is 88.2%.
The results show that the laminated cathode material of the cobalt-free lithium ion battery has higher capacity and better cycling stability and thermal stability.
EXAMPLE six
The layered positive electrode material of the cobalt-free lithium ion battery is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the transition metal oxide layer without cobalt is a nickel-cobalt oxide layer; the lithium layer had 7.0% cation inversion. The cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a high-temperature sintering method, and the method specifically comprises the following steps:
(1) synthesis of hydroxide precursor Ni by coprecipitation method0.8Mn0.2(OH)2: the concentration is 2.0mol L-1NiSO (D)4·6H2O and MnSO4·5H2The mixed aqueous solution of O was pumped into a self-made continuous stirred tank reactor (4L) under nitrogen atmosphere. Simultaneously, 4.0mol L of-1And 5.0mol L of NaOH-1NH of (2)4The OH aqueous solution is used as a precipitator and a complexing agent to be respectively pumped into the reactor. The pH value of the precursor solution is kept between 10.5 and 11, the temperature is kept at 60 ℃, and the stirring speed is kept at 1000 rpm/s. The reaction is carried out for 10 hours, and then the reaction product is filtered, washed for 3 times by deionized water and dried in a vacuum oven at 80 ℃ overnight.
(2) Adopting high-temperature solid phase sintering to obtain a product: reacting LiOH & H2O and Ni obtained above0.8Mn0.2(OH)2The precursor is uniformly mixed and ground according to the molar ratio of Li to TM being 1.03 to 1, calcined for 12 hours at 800 ℃ in air atmosphere, and rapidly cooled at the speed of 130 ℃/min to obtain the product LiNi0.8Mn0.2O2(NM82) a polycrystalline material. The Li/Ni dislocation amount in the material is determined to be 7.0% by the structural refinement of an X-ray diffraction pattern.
(3) Electrochemical testing: mixing NM82, carbon black and PVDF in a mass ratio of 80:10:10, grinding in a mortar to prepare a positive pole piece, wherein the loading capacity of active substances is about 5.2mg cm-2. The lithium half-cell was prepared using a 2032-type coin cell, using a Celgard 2325 separator and 1.2mol L-1GEN II electrolyte (LiPF)6Dissolving in EC/EMC mixed solvent with volume ratio of 3: 7), and mixing the solution with half-cell at 2.8-4.5V (vs Li)+/Li). For full cell, 2032 button cell was assembled using graphite negative electrode, at 2.8-4.45VThe voltage range is cycled, the N/P ratio of the full cell is about 1.2, and the commercial graphite Fujian is provided by Shenzhen BTR new energy materials.
The cycle performance test is carried out on the cobalt-free lithium ion battery layered positive electrode material under the current of C/3 and 1C multiplying power within the voltage range of 2.8-4.5V. The results show that the laminated cathode material of the cobalt-free lithium ion battery has higher capacity and better cycling stability and thermal stability.
EXAMPLE seven
The layered positive electrode material of the cobalt-free lithium ion battery is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the transition metal oxide layer without cobalt is a nickel-cobalt oxide layer; the lithium layer had 4.0% cation inversion. The cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a high-temperature sintering method, and the method specifically comprises the following steps:
(1) synthesis of hydroxide precursor Ni by coprecipitation method0.8Mn0.2(OH)2: the concentration is 2.0mol L-1NiSO (D)4·6H2O and MnSO4·5H2The mixed aqueous solution of O was pumped into a self-made continuous stirred tank reactor (4L) under nitrogen atmosphere. Simultaneously, 4.0mol L of-1And 5.0mol L of NaOH-1NH of (2)4The OH aqueous solution is used as a precipitator and a complexing agent to be respectively pumped into the reactor. The pH value of the precursor solution is kept between 10.5 and 11, the temperature is kept at 60 ℃, and the stirring speed is kept at 1000 rpm/s. The reaction is carried out for 10 hours, and then the reaction product is filtered, washed for 3 times by deionized water and dried in a vacuum oven at 80 ℃ overnight.
(2) Adopting high-temperature solid phase sintering to obtain a product: reacting LiOH & H2O and Ni obtained above0.8Mn0.2(OH)2The precursor is mixed and ground uniformly according to the molar ratio of Li to TM which is 1.03 to 1, calcined for 12 hours at 850 ℃ in an oxygen atmosphere, and naturally cooled to obtain the product LiNi0.8Mn0.2O2(NM82) a polycrystalline material. The Li/Ni dislocation amount in the material is determined to be 4.0% by the structural refinement of an X-ray diffraction pattern.
(3) Electrochemical testing: NM82 and carbon black and PVDF in a mass ratio of 80:1010 in proportion and ground in a mortar to prepare a positive electrode plate, the active material loading is about 5.2mg cm-2. The lithium half-cell was prepared using a 2032-type coin cell, using a Celgard 2325 separator and 1.2mol L-1GEN II electrolyte (LiPF)6Dissolving in EC/EMC mixed solvent with volume ratio of 3: 7), and mixing the solution with half-cell at 2.8-4.5V (vs Li)+/Li). For the full cell, the 2032 button cell is assembled by using a graphite cathode, the cycling is carried out in the voltage range of 2.8-4.45V, the N/P ratio of the full cell is about 1.2, and the commercial graphite Fujian is provided by Shenzhen BTR new energy materials company.
The cycle performance test is carried out on the cobalt-free lithium ion battery layered positive electrode material under the current of C/3 and 1C multiplying power within the voltage range of 2.8-4.5V. The results show that the laminated cathode material of the cobalt-free lithium ion battery has higher capacity and better cycling stability and thermal stability.
Example eight
The layered positive electrode material of the cobalt-free lithium ion battery is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the transition metal oxide layer without cobalt is a nickel-cobalt oxide layer; the lithium layer had 4.8% cation inversion. The cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a high-temperature sintering method, and the method specifically comprises the following steps:
(1) synthesis of hydroxide precursor Ni by coprecipitation method0.8Mn0.2(OH)2: the concentration is 2.0mol L-1NiSO (D)4·6H2O and MnSO4·5H2The mixed aqueous solution of O was pumped into a self-made continuous stirred tank reactor (4L) under nitrogen atmosphere. Simultaneously, 4.0mol L of-1And 5.0mol L of NaOH-1NH of (2)4The OH aqueous solution is used as a precipitator and a complexing agent to be respectively pumped into the reactor. The pH value of the precursor solution is kept between 10.5 and 11, the temperature is kept at 60 ℃, and the stirring speed is kept at 1000 rpm/s. The reaction is carried out for 10 hours, and then the reaction product is filtered, washed for 3 times by deionized water and dried in a vacuum oven at 80 ℃ overnight.
(2) Adopting high-temperature solid phase sintering to obtain a product: reacting LiOH & H2O and Ni obtained above0.8Mn0.2(OH)2The precursor is uniformly mixed and ground according to the molar ratio of Li to TM which is 1.03 to 1, calcined for 12 hours at 850 ℃ in an oxygen atmosphere, and quenched at 110 ℃ per minute to obtain the product LiNi0.8Mn0.2O2(NM82) a polycrystalline material. The Li/Ni dislocation amount in the material is determined to be 4.8% by the structural refinement of an X-ray diffraction pattern.
(3) Electrochemical testing: mixing NM82, carbon black and PVDF in a mass ratio of 80:10:10, grinding in a mortar to prepare a positive pole piece, wherein the loading capacity of active substances is about 5.2mg cm-2. The lithium half-cell was prepared using a 2032-type coin cell, using a Celgard 2325 separator and 1.2mol L-1GEN II electrolyte (LiPF)6Dissolving in EC/EMC mixed solvent with volume ratio of 3: 7), and mixing the solution with half-cell at 2.8-4.5V (vs Li)+/Li). For the full cell, the 2032 button cell is assembled by using a graphite cathode, the cycling is carried out in the voltage range of 2.8-4.45V, the N/P ratio of the full cell is about 1.2, and the commercial graphite Fujian is provided by Shenzhen BTR new energy materials company.
The results of observing the layered cathode material of the cobalt-free lithium ion battery prepared in this example by a scanning electron microscope are shown in fig. 8.
The cycle performance test is carried out on the cobalt-free lithium ion battery layered positive electrode material under the current of C/3 and 1C multiplying power within the voltage range of 2.8-4.5V. The results show that the laminated cathode material of the cobalt-free lithium ion battery has higher capacity and better cycling stability and thermal stability.
Example nine
The layered positive electrode material of the cobalt-free lithium ion battery is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the transition metal oxide layer without cobalt is a nickel-cobalt oxide layer; the lithium layer had 4.3% cation inversion. The cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a high-temperature sintering method, and the method specifically comprises the following steps:
(1) synthesis of hydroxide precursor Ni by coprecipitation method0.8Mn0.2(OH)2: the concentration is 2.0mol L-1NiSO (D)4·6H2O and MnSO4·5H2The mixed aqueous solution of O was pumped into a self-made continuous stirred tank reactor (4L) under nitrogen atmosphere. Simultaneously, 4.0mol L of-1And 5.0mol L of NaOH-1NH of (2)4The OH aqueous solution is used as a precipitator and a complexing agent to be respectively pumped into the reactor. The pH value of the precursor solution is kept between 10.5 and 11, the temperature is kept at 60 ℃, and the stirring speed is kept at 1000 rpm/s. The reaction is carried out for 10 hours, and then the reaction product is filtered, washed for 3 times by deionized water and dried in a vacuum oven at 80 ℃ overnight.
(2) Adopting high-temperature solid phase sintering to obtain a product: reacting LiOH & H2O and Ni obtained above0.8Mn0.2(OH)2The precursor is mixed and ground uniformly according to the molar ratio of Li to TM being 1.2 to 1, calcined for 20 hours at 950 ℃ in an oxygen atmosphere, and rapidly cooled at the speed of 110 ℃/min to obtain the product LiNi0.8Mn0.2O2(NM82) single crystal material with an average particle size of about 2 microns. The amount of Li/Ni dislocations in the material was determined to be 4.3%.
(3) Electrochemical testing: mixing NM82, carbon black and PVDF in a mass ratio of 80:10:10, grinding in a mortar to prepare a positive pole piece, wherein the loading capacity of active substances is about 5.2mg cm-2. The lithium half-cell was prepared using a 2032-type coin cell, using a Celgard 2325 separator and 1.2mol L-1GEN II electrolyte (LiPF)6Dissolving in EC/EMC mixed solvent with volume ratio of 3: 7), and mixing the solution with half-cell at 2.8-4.5V (vs Li)+/Li). For the full cell, the 2032 button cell is assembled by using a graphite cathode, the cycling is carried out in the voltage range of 2.8-4.45V, the N/P ratio of the full cell is about 1.2, and the commercial graphite Fujian is provided by Shenzhen BTR new energy materials company.
The cycle performance test is carried out on the cobalt-free lithium ion battery layered positive electrode material under the current of C/3 and 1C multiplying power within the voltage range of 2.8-4.5V. The results show that the laminated cathode material of the cobalt-free lithium ion battery has higher capacity and better cycling stability and thermal stability.
Example ten
The layered positive electrode material of the cobalt-free lithium ion battery is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the transition metal oxide layer without cobalt is a nickel-cobalt oxide layer; the lithium layer had 6.0% cation inversion. The present embodiment adopts a microwave sintering method to synthesize a cobalt-free lithium ion battery layered positive electrode material, which specifically comprises:
(1) synthesis of hydroxide precursor Ni by coprecipitation method0.8Mn0.2(OH)2: the concentration is 2.0mol L-1NiSO (D)4·6H2O and MnSO4·5H2The mixed aqueous solution of O was pumped into a self-made continuous stirred tank reactor (4L) under nitrogen atmosphere. Simultaneously, 4.0mol L of-1And 5.0mol L of NaOH-1NH of (2)4The OH aqueous solution is used as a precipitator and a complexing agent to be respectively pumped into the reactor. The pH value of the precursor solution is kept between 10.5 and 11, the temperature is kept at 60 ℃, and the stirring speed is kept at 1000 rpm/s. The reaction is carried out for 10 hours, and then the reaction product is filtered, washed for 3 times by deionized water and dried in a vacuum oven at 80 ℃ overnight.
(2) Adopting microwave sintering to obtain a product: reacting LiOH & H2O and Ni obtained above0.8Mn0.2(OH)2The precursor is mixed and ground uniformly according to the mol ratio of Li to TM which is 1.2 to 1, and the mixture reacts for 1 hour under the constant power microwave of 500W to obtain the product LiNi0.8Mn0.2O2(NM82) a polycrystalline material. The amount of Li/Ni dislocations in the material was determined to be 6.0%.
(3) Electrochemical testing: mixing NM82, carbon black and PVDF in a mass ratio of 80:10:10, grinding in a mortar to prepare a positive pole piece, wherein the loading capacity of active substances is about 5.2mg cm-2. The lithium half-cell was prepared using a 2032-type coin cell, using a Celgard 2325 separator and 1.2mol L-1GEN II electrolyte (LiPF)6Dissolving in EC/EMC mixed solvent with volume ratio of 3: 7), and mixing the solution with half-cell at 2.8-4.5V (vs Li)+/Li). For the full cell, the 2032 button cell is assembled by using a graphite cathode, the cycling is carried out in the voltage range of 2.8-4.45V, the N/P ratio of the full cell is about 1.2, and the commercial graphite Fujian is provided by Shenzhen BTR new energy materials company.
The cycle performance test is carried out on the cobalt-free lithium ion battery layered positive electrode material under the current of C/3 and 1C multiplying power within the voltage range of 2.8-4.5V. The results show that the laminated cathode material of the cobalt-free lithium ion battery has higher capacity and better cycling stability and thermal stability.
EXAMPLE eleven
The layered positive electrode material of the cobalt-free lithium ion battery is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the transition metal oxide layer without cobalt is a nickel-cobalt oxide layer; the lithium layer had 6.9% cation inversion. The present embodiment adopts a microwave sintering method to synthesize a cobalt-free lithium ion battery layered positive electrode material, which specifically comprises:
(1) synthesis of hydroxide precursor Ni by coprecipitation method0.8Mn0.2(OH)2: the concentration is 2.0mol L-1NiSO (D)4·6H2O and MnSO4·5H2The mixed aqueous solution of O was pumped into a self-made continuous stirred tank reactor (4L) under nitrogen atmosphere. Simultaneously, 4.0mol L of-1And 5.0mol L of NaOH-1NH of (2)4The OH aqueous solution is used as a precipitator and a complexing agent to be respectively pumped into the reactor. The pH value of the precursor solution is kept between 10.5 and 11, the temperature is kept at 60 ℃, and the stirring speed is kept at 1000 rpm/s. The reaction is carried out for 10 hours, and then the reaction product is filtered, washed for 3 times by deionized water and dried in a vacuum oven at 80 ℃ overnight.
(2) Adopting microwave sintering to obtain a product: reacting LiOH & H2O and Ni obtained above0.8Mn0.2(OH)2The precursor is mixed and ground uniformly according to the mol ratio of Li to TM which is 1.2 to 1, and the mixture reacts for 10 minutes under the constant power microwave of 1500W to obtain the product LiNi0.8Mn0.2O2(NM82) a polycrystalline material. The amount of Li/Ni dislocations in the material was determined to be 6.9%.
(3) Electrochemical testing: mixing NM82, carbon black and PVDF in a mass ratio of 80:10:10, grinding in a mortar to prepare a positive pole piece, wherein the loading capacity of active substances is about 5.2mg cm-2. The lithium half-cell was prepared using a 2032-type coin cell, using a Celgard 2325 separator and 1.2mol L-1GEN II electrolyte (LiPF)6Dissolved in EC/EMC mixed solvent with volume ratio of 3: 7), half of the mixture is addedThe battery is at 2.8-4.5V (vs Li)+/Li). For the full cell, the 2032 button cell is assembled by using a graphite cathode, the cycling is carried out in the voltage range of 2.8-4.45V, the N/P ratio of the full cell is about 1.2, and the commercial graphite Fujian is provided by Shenzhen BTR new energy materials company.
The cycle performance test is carried out on the cobalt-free lithium ion battery layered positive electrode material under the current of C/3 and 1C multiplying power within the voltage range of 2.8-4.5V. The results show that the laminated cathode material of the cobalt-free lithium ion battery has higher capacity and better cycling stability and thermal stability.
The foregoing is a more detailed description of the present application in connection with specific embodiments thereof, and it is not intended that the present application be limited to the specific embodiments thereof. It will be apparent to those skilled in the art from this disclosure that many more simple derivations or substitutions can be made without departing from the spirit of the disclosure.

Claims (10)

1. A cobalt-free lithium ion battery layered cathode material is characterized in that: the laminated positive electrode material of the cobalt-free lithium ion battery is formed by alternately stacking a lithium layer and a transition metal oxide layer without cobalt, wherein the lithium layer has 3-7% of cation inversion positions, and the cation inversion positions are formed by the transition metal in the transition metal oxide layer entering the lithium layer and occupying lithium ions.
2. The cobalt-free lithium ion battery layered positive electrode material according to claim 1, wherein: the main transition metals of the transition metal oxide layer are nickel and manganese;
preferably, the molar ratio of nickel to manganese is from 6:4 to 99: 1;
preferably, in the layered positive electrode material of the cobalt-free lithium ion battery, the molar ratio of the lithium element to other metal elements is 1-1.1: 1.
3. The cobalt-free lithium ion battery layered cathode material according to claim 2, wherein: the transition metal oxide layer is also doped with at least one of metal ions Al, Ti and Mg.
4. The cobalt-free lithium ion battery layered positive electrode material according to any one of claims 1 to 3, wherein: the layered positive electrode material of the cobalt-free lithium ion battery is secondary microparticles consisting of primary nanoparticles;
preferably, the size of the primary nano-particles is 10-300 nanometers, and the size of the secondary micro-particles is 1-20 micrometers;
preferably, the cobalt-free lithium ion battery layered positive electrode material is micron-sized single crystal particles;
preferably, the size of the single crystal particles is 0.5 to 10 μm.
5. A lithium ion battery layered positive electrode material is characterized in that: the lithium ion battery layered positive electrode material is of a core-shell structure, the coating layer material of the core-shell structure is the cobalt-free lithium ion battery layered positive electrode material of any one of claims 1 to 4, and the core positive electrode material of the core-shell structure is at least one of lithium cobaltate, a ternary layered material, a spinel lithium manganate material and a lithium iron phosphate material.
6. A lithium ion battery layered positive electrode material is characterized in that: the layered positive electrode material of the lithium ion battery is of an element gradient structure, the outermost layer material of the element gradient structure is the cobalt-free layered positive electrode material of the lithium ion battery as claimed in any one of claims 1 to 4, the inside of the element gradient structure is a material with gradient change of nickel and manganese elements, the nickel content is increased from outside to inside in a gradient manner, and the manganese content is decreased from outside to inside in a gradient manner.
7. Use of the cobalt-free lithium ion battery layered cathode material according to any one of claims 1 to 4 or the lithium ion battery layered cathode material according to claim 5 or 6 in power lithium batteries, 3C consumer electronics lithium ion batteries.
8. A battery, characterized by: the laminated positive electrode material of the cobalt-free lithium ion battery as defined in any one of claims 1 to 4 or the laminated positive electrode material of the lithium ion battery as defined in claim 5 or 6 is used in the battery.
9. The method for preparing the layered cathode material of the cobalt-free lithium ion battery according to any one of claims 1 to 4, wherein the method comprises the following steps: the cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a high-temperature sintering method;
the high-temperature sintering method comprises the steps of uniformly mixing the raw materials, and sintering at the temperature of 700-1100 ℃ for 3-24 hours in the atmosphere of air or oxygen;
preferably, after sintering, rapidly cooling to room temperature at a speed of more than 100 ℃/min to obtain the cobalt-free lithium ion battery layered cathode material.
10. The method for preparing the layered cathode material of the cobalt-free lithium ion battery according to any one of claims 1 to 4, wherein the method comprises the following steps: the cobalt-free lithium ion battery layered positive electrode material is synthesized by adopting a microwave sintering method;
the microwave sintering method comprises the steps of uniformly mixing the raw materials, and treating for 3 minutes to 3 hours under the microwave power of 300-2000 watts.
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