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Single crystal ternary positive electrode material with good dispersibility, lithium-nickel mixed arrangement and low residual alkali, and preparation method and application thereof

A positive electrode material and single crystal technology, applied in the field of single crystal ternary positive electrode materials, can solve the problems of cycle performance degradation, serious agglomeration and decline of single crystal materials, and achieve the effect of reducing lithium-nickel mixing and improving electrochemical performance

Active Publication Date: 2019-12-17
SHENZHEN CITY BATTERY NANOMETER TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the bottleneck limiting the application of ternary cathode materials is the safety issue caused by gas production, which is due to the residual Li on the surface of ternary materials. 2 O and CO in the air 2 and H 2 O reacts to form the residual base Li 2 CO 3 and LiOH, which generate CO during battery cycling 2 、H 2 O gas, causing the battery to swell and causing safety hazards
In addition, most of the ternary cathode materials currently on the market are secondary spherical particles formed by the agglomeration of primary particles. As the number of cycles increases, the secondary particles will appear pulverized at the primary particle interface, resulting in increased internal resistance and capacity decay. Soon, cycle performance degrades
[0003] Making the material into a single crystal morphology can improve the cycle performance and safety performance of the material. However, compared with the non-single crystal material, the calcination temperature of the single crystal ternary material is higher, and it is easier to produce lithium volatilization and cause lithium loss, resulting in lithium Severe mixed discharge of nickel and reduced capacity
[0004] The patent No. CN 101847722 A discloses a micron-sized single crystal ternary material, the synthesized single crystal material is seriously agglomerated, and the distribution of primary particles is uneven
The patent No. CN101707252A discloses a method for preparing polycrystalline oxide ternary positive electrode materials by mixing various metal salts and lithium salts by wet ball milling. Spherical particles, agglomerated secondary spherical particles affect the improvement of material compaction density and volume energy density, the preparation process is complicated, the cost is too high and the processability is poor

Method used

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  • Single crystal ternary positive electrode material with good dispersibility, lithium-nickel mixed arrangement and low residual alkali, and preparation method and application thereof
  • Single crystal ternary positive electrode material with good dispersibility, lithium-nickel mixed arrangement and low residual alkali, and preparation method and application thereof
  • Single crystal ternary positive electrode material with good dispersibility, lithium-nickel mixed arrangement and low residual alkali, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0068] This embodiment uses Ir 2 o 3 Auxiliary synthesis of Li 1.04 Ni 0.5 co 0.2 mn 0.27 Zn 0.01 Ba 0.02 o 2 The single crystal material specifically includes the following steps:

[0069] (1) According to the stoichiometric ratio Li 1.04 Ni 0.5 co 0.2 mn 0.27 Zn 0.01 Ba 0.02 o 2 , weighed 38.42g lithium carbonate, 89.92gNi 0.5 co 0.2 mn 0.27 (OH) 2Precursor, 0.814g ZnO, 3.067g BaO and 0.06g Ir 2 o 3 Additives (Ir 3+ with you 0.5 co 0.2 mn 0.27 (OH) 2 The molar ratio is 0.000275:1), put it in a three-dimensional mixer, add polyurethane balls, and mix well.

[0070] (2) Put the uniformly mixed material in a sagger for heat treatment, and calcinate it in an oxygen atmosphere. At a rate of 4°C / min, first raise the temperature to 450°C and keep it for 3 hours, then raise the temperature to 900°C and keep it for 15 hours, and then heat it at 5°C / min to cool down to room temperature.

Embodiment 2

[0072] In this example, iridium nitrate and tellurium oxide are used to assist in the synthesis of Li 1.025 Ni 0.6 co 0.2 mn 0.15 B 0.04 V 0.01 o 2 The single crystal material specifically includes the following steps:

[0073] (1) According to the stoichiometric ratio Li 1.025 Ni 0.6 co 0.2 mn 0.15 B 0.04 V 0.01 o 2 , weighed 18.93g lithium carbonate and 21.5g lithium hydroxide, 89.24g Ni 0.6 co 0.2 mn 0.15 (OH) 2 Precursor, 2.785g B 2 o 3 , 1.82g V 2 o 5 , 0.2458g of iridium nitrate and 0.0319g tellurium oxide additive (Ir 3+ and Y 3+ with you 0.6 co 0.2 mn 0.15 (OH) 2 The molar ratios are 0.00065:1 and 0.0002:1 respectively), placed in a three-dimensional mixer, adding polyurethane balls, and mixing evenly.

[0074] (2) Put the uniformly mixed materials in a sagger for heat treatment, and calcined in an oxygen atmosphere. First, the temperature was raised to 500° C. for 2 hours at a rate of 3° C. / min, and then the temperature was raised to 880° C. ...

Embodiment 3

[0076] In this embodiment, iridium oxalate is used to assist in the synthesis of Li 1.0 Ni 0.55 co 0.25 mn 0.17 Ti 0.02 Bi 0.01 o 2 The single crystal material specifically includes the following steps:

[0077] (1) According to the stoichiometric ratio Li 1.0 Ni 0.55 co 0.25 mn 0.17 Ti 0.02 Bi 0.01 o 2 , weighed 36.95g lithium carbonate, 87.42g Ni 0.5 co 0.25 mn 0.17 (OH) 2 Precursor, 1.6g TiO 2 , 4.66g Bi 2 o 3 And 0.0648g iridium oxalate additive (Ir 3+ with you 0.5 co 0.25 mn 0.17 (OH) 2 The molar ratio is 0.0001:1), put it in a three-dimensional mixer, add polyurethane balls, and mix well.

[0078] (2) Put the uniformly mixed materials in a sagger for heat treatment, and calcined in an oxygen atmosphere. First, the temperature was raised to 450° C. for 2.5 hours at a rate of 3° C. / min, and then heated to 890° C. for 13 hours, and then heated for 8 hours. Cool to room temperature at a rate of °C / min.

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Abstract

The invention discloses a single crystal ternary positive electrode material with good dispersibility, lithium-nickel mixed arrangement and low residual alkali, and a preparation method and an application thereof. In the preparation process of the single crystal ternary positive electrode material, the raw materials comprise a cationic additive, and the cationic additive is any one or a combination of at least two of an iridium source, an yttrium source, a tellurium source, an indium source and a gallium source. By adding the cationic additives such as Ir<3+>, Y<3+>, Te<4+>, In<3+> and Ga<3+>,the surface energy of the ternary material can be promoted to be reduced on the one hand, so that the sintering temperature of the material is reduced, and the volatilization of lithium salt is reduced; and on the other hand, the lithium-nickel mixed arrangement can be reduced, the directional growth of the crystal face of the material is controlled, and the adsorption effect and reaction activity of the crystal face and CO2 and H2O in the air are inhibited, so that residual alkali on the surface of the ternary material is reduced, the processing performance of the material is improved, and the rate discharge capacity and cycle performance of the single crystal ternary material are improved.

Description

technical field [0001] The invention belongs to the field of positive electrode materials for lithium ion batteries, and relates to a single crystal ternary positive electrode material, its preparation method and application, in particular to a single crystal ternary positive electrode material with good dispersibility, lithium-nickel mixed discharge and low residual alkali, Its preparation method and its application in lithium ion battery. Background technique [0002] Existing layered ternary cathode materials have been widely used in fields such as electric vehicles and hybrid electric vehicles due to their advantages such as high energy density, long cycle life, and low production cost. However, the bottleneck limiting the application of ternary cathode materials is the safety issue caused by gas production, which is due to the residual Li on the surface of ternary materials. 2 O and CO in the air 2 and H 2 O reacts to form the residual base Li 2 CO 3 and LiOH, whic...

Claims

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Application Information

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IPC IPC(8): H01M4/36H01M4/505H01M4/525H01M4/62H01M10/0525
CPCH01M4/364H01M4/505H01M4/525H01M4/628H01M10/0525Y02E60/10
Inventor 杨春香严武渭黄友军温伟城杨顺毅黄友元
Owner SHENZHEN CITY BATTERY NANOMETER TECH
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