CN110380018B - Preparation method of composite electrode material with foam-shaped coating layer - Google Patents
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Abstract
The invention discloses LiNi with a foam coating layer 0.6 Co 0.2 Mn 0.2 O 2 @Co 3 O 4 A preparation method of the composite electrode material. With Ni (CH) 3 COOH) 2 ·4H 2 O、Co(CH 3 COOH) 2 ·4H 2 O、Mn(CH 3 COOH) 2 ·4H 2 O as raw material and C 2 H 2 O 4 ·2H 2 O is used as a complexing agent and a precipitator, a mixed solution of water and glycol is used as a solvent, and a solvothermal method is adopted to synthesize Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 A precursor; LiOH. H 2 O as a lithium source, with Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 Mixing and grinding the precursors, and sintering the mixture in a tube furnace to obtain LiNi 0.6 Co 0.2 Mn 0.2 O 2 (ii) a Through wet coating process, and through precipitation and calcination, LiNi is obtained 0.6 Co 0.2 Mn 0.2 O 2 @Co 3 O 4 A composite electrode material. The process is simple, the raw material source is wide, and the large-scale industrial production is facilitated; the prepared lithium ion battery anode material has good rate charge-discharge performance and excellent cycle service life, and the capacity of the material is higher.
Description
Technical Field
The invention belongs to the technical field of new energy material preparation, and particularly relates to LiNi with a foam coating layer 0.6 Co 0.2 Mn 0.2 O 2 @Co 3 O 4 A preparation method of the composite electrode material.
Background
Today, the large consumption of fossil fuels leads to greenhouse gases (e.g., two)Carbon oxide, methane, etc.) are continuously released into the atmosphere, causing serious damage to the environment, and therefore, the development of sustainable energy is imperative. As a power energy storage medium with the greatest development prospect, lithium ion batteries have received much attention in the fields of portable electronic devices and electric automobiles. To date, many researchers have been working on developing and studying transition metal oxides as positive electrode materials for lithium ion batteries. Among the numerous positive electrode materials, the nickel-rich ternary material LiNi 0.6 Co 0.2 Mn 0.2 O 2 Are strong candidates in terms of reversible capacity, high rate performance and cost. However, nickel-rich materials still have many problems that need to be solved urgently. Firstly, the increase of the nickel content increases the surface alkalinity of the material in practical application. Because of residual lithium on the surface of the nickel-rich ternary material, such as LiOH and Li 2 O, will absorb H in the air 2 O and CO 2 Thereby forming LiOH/Li 2 CO 3 Layer, and LiOH will react with LiPF in the electrolyte 6 Reaction of Li under high pressure 2 CO 3 And also decomposed to generate gas, resulting in battery gassing. Second, transition metals (e.g., Ni) in nickel-rich materials 4+ ) Side reactions with the electrolyte can occur with the concomitant release of oxygen and heat, resulting in reduced thermal stability of the cell and potential risk of thermal runaway. Also, in electrochemical tests, the anisotropic shrinkage and expansion of the primary particle crystals cause cracking, resulting in poor cycle performance.
Currently, LiNi is synthesized 0.6 Co 0.2 Mn 0.2 O 2 There are many methods for the positive electrode material, such as a coprecipitation method, a solid phase method, a sol-gel method, a spray drying method, and a hydrothermal method. Lini et al (electrochim. acta 130(2014)82-89) synthesized spherical LiNi by coprecipitation 0.6 Co 0.2 Mn 0.2 O 2 A positive electrode material having a good initial discharge capacity in a voltage range of 2.8 to 4.3V at a low current density, but having a large particle diameter of spherical particles (>10 μm), electrolyte does not penetrate well into the inside of the active material, Li + Embedding/extraction in the material is also hindered. Ahn et al (J.alloy.Compd.609(2014)143-149) reported a low temperature combustionMethod for preparing LiNi from transition metal acetate and urea 0.6 Co 0.2 Mn 0.2 O 2 A cathode material, the nano material has excellent cycle performance but has a current density of 20mA · g -1 Under the voltage range of 2.8-4.3V, the initial discharge specific capacity is only 170mAh g -1 And the rate capability is also unstable.
Disclosure of Invention
The invention provides a LiNi with a foam-shaped coating layer to solve the problems of poor conductivity of a nickel-cobalt-manganese ternary material, poor cycle performance caused by unstable structure under high voltage and the like 0.6 Co 0.2 Mn 0.2 O 2 @Co 3 O 4 A preparation method of the composite electrode material.
The technical solution for realizing the purpose of the invention is as follows: simple synthesis of high-performance LiNi 0.6 Co 0.2 Mn 0.2 O 2 @Co 3 O 4 A method of compounding an electrode material comprising the steps of:
(1) with Ni (CH) 3 COOH) 2 ·4H 2 O、Co(CH 3 COOH) 2 ·4H 2 O、Mn(CH 3 COOH) 2 ·4H 2 O as a raw material, C 2 H 2 O 4 ·2H 2 Using O as a complexing agent and a precipitating agent, using Sodium Dodecyl Sulfate (SDS) as a surfactant, using a mixed solution of water and glycol as a solvent, and precipitating metal ions under the stirring condition;
(2) then the precipitation mixture is subjected to hydrothermal reaction under certain conditions to obtain Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 A precursor;
(3) the obtained precursor and LiOH. H 2 Mixing and grinding O, and sintering in a tube furnace to obtain LiNi 0.6 Co 0.2 Mn 0.2 O 2 ；
(4) Reacting NH 4 HCO 3 Dissolved in water and added to LiNi 0.6 Co 0.2 Mn 0.2 O 2 Magnetically stirring the suspension at normal temperature. Weighing Co (NO) 3 ) 3 ·9H 2 Dissolving O in deionized waterAnd adding a proper amount of PVP (polyvinylpyrrolidone), then adding Co (NO) 3 ) 3 ·9H 2 Slowly dropwise adding mixed solution of O and PVP into LiNi 0.6 Co 0.2 Mn 0.2 O 2 And NH 4 HCO 3 The mixture of (1) was stirred for 5 hours, washed three times with centrifugal water, and dried at 80 ℃ overnight. Finally sintering for 4 hours at 600 ℃ in the oxygen atmosphere to obtain Co 3 O 4 Coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 @Co 3 O 4 A composite electrode material.
In the step (1), the volume ratio of water to glycol in the solvothermal system is 1: 1;
the hydrothermal reaction temperature in the step (2) is 200 ℃, and the hydrothermal reaction time is 14 h;
LiOH. H in the above step (3) 2 O as a lithium source and Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 The mass ratio of the precursor is as follows: 1.2: 1;
co (NO) in the above step (4) 3 ) 2 ·6H 2 O and NH 4 HCO 3 The ratio of the amount of the substances of (a) to (b) is 2: 5;
co in the above step (4) 3 O 4 And LiNi 0.6 Co 0.2 Mn 0.2 O 2 The mass ratio is 1-5: 100.
And (4) coating by a wet chemical method, and uniformly coating the precipitate on the surface of the material by using PVP as a dispersing agent.
Compared with the prior art, the invention has the following remarkable advantages: (1) oxalic acid is used as a complexing agent and a precipitator, a small amount of Sodium Dodecyl Sulfate (SDS) is used as a surfactant, and Ni with uniform morphology and particle size is formed in an ethylene glycol solution 0.6 Co 0.2 Mn 0.2 C 2 O 4 A precursor; (2) the hydrothermal reaction is carried out for 14 hours, the hydrothermal temperature is 200 ℃, the growth of the material can be promoted, the excessive agglomeration and crystallization of the material can be prevented, and a certain size is controlled; (3) ni in oxygen atmosphere 0.6 Co 0.2 Mn 0.2 C 2 O 4 The precursor is mixed with lithium salt and then sintered at high temperature, so that the crystallinity of the material is improved, and LiNi with uniform size is synthesized 0.6 Co 0.2 Mn 0.2 O 2 A material; (4) LiNi 0.6 Co 0.2 Mn 0.2 O 2 、Co(NO 3 ) 2 ·6H 2 O and NH 4 HCO 3 In the wet precipitation process, Co (NO) 3 ) 2 ·6H 2 O and NH 4 HCO 3 Reaction to Co (OH) 2 CO 3 Adding PVP as dispersant to precipitate cobalt salt homogeneously on the surface of the material, and sintering at high temperature to obtain LiNi 0.6 Co 0.2 Mn 0.2 O 2 The surface of the main material is uniformly coated with Co 3 O 4 Thereby the electrode material structure is more stable, and the cycle performance is improved.
Drawings
In FIG. 1 are TEM images of uncoated NCM and coated amounts of 1 wt.%, 3 wt.%, 5 wt.% corresponding a NCM, b CO-NCM1, c CO-NCM2, dCO-NCM 3.
FIG. 2 is an XRD pattern of NCM, CO-NCM1, CO-NCM2, CO-NCM 3.
FIG. 3 is a graph of the first discharge specific capacities under 0.1C conditions of NCM, CO-NCM1, CO-NCM2, and CO-NCM 3.
FIG. 4 is a graph of discharge specific capacities of four materials, namely NCM, CO-NCM1, CO-NCM2 and CO-NCM3, under different multiplying power conditions.
FIG. 5 is a discharge specific capacity cycle diagram of four materials of NCM, CO-NCM1, CO-NCM2 and CO-NCM3 circulating 100 times under 0.2C multiplying power
Detailed Description
The embodiments of the present invention will be described in detail with reference to the accompanying drawings so that the advantages and features of the invention can be more easily understood by those skilled in the art, and the scope of the invention will be more clearly defined.
EXAMPLES target product of the invention LiNi 0.6 Co 0.2 Mn 0.2 O 2 @Co 3 O 4 The composite material is prepared by the following steps:
example 1
LiNi which is a target product of the invention 0.6 Co 0.2 Mn 0.2 O 2 The preparation method comprises the following steps:
(1) synthesis of stable Ni by coprecipitation method 0.6 Co 0.2 Mn 0.2 C 2 O 4 Precursor: 6.164g of Ni (CH) were weighed 3 COOH) 2 ·4H 2 O、2.056gCo(CH 3 COOH) 2 ·4H 2 O、2.002g Mn(CH 3 COOH) 2 ·4H 2 Dissolving O in a mixed solution of 60ml water and 60ml ethylene glycol, and weighing 6.240g C 2 H 2 O 4 ·2H 2 O and 0.2g SDS were dissolved in another mixed solution of 60ml water and 60ml ethylene glycol, and a metal salt solution was slowly added dropwise to C under stirring 2 H 2 O 4 ·2H 2 In the mixed solution of O and SDS, light green precipitate is generated in the solution, and the stirring is continued for 6 hours;
(2) stirring, putting the solution into a hydrothermal kettle, placing the hydrothermal kettle in a muffle furnace, reacting for 14h at 200 ℃, centrifugally washing, and drying overnight to obtain Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 A precursor;
(3) mix Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 Precursor and LiOH. H 2 Mixing and grinding O according to the mass ratio of 1:1.05, then placing the mixture into a tube furnace, presintering the mixture for 4 hours at 500 ℃ in an oxygen atmosphere, and sintering the mixture for 15 hours at 850 ℃ to obtain LiNi 0.6 Co 0.2 Mn 0.2 O 2 And is denoted as NCM.
Example 2
The target product of the invention is 1 wt.% Co 3 O 4 Coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 The composite material is prepared by the following steps:
(1) synthesis of stable Ni by coprecipitation method 0.6 Co 0.2 Mn 0.2 C 2 O 4 Precursor: 6.164g of Ni (CH) were weighed 3 COOH) 2 ·4H 2 O、2.056gCo(CH 3 COOH) 2 ·4H 2 O、2.002g Mn(CH 3 COOH) 2 ·4H 2 Dissolving O in a mixed solution of 60ml water and 60ml ethylene glycol, and weighing 6.240g C 2 H 2 O 4 ·2H 2 O and 0.2g SDS were dissolved in another mixed solution of 60ml water and 60ml ethylene glycolSlowly dripping the metal salt solution into the C under the stirring condition 2 H 2 O 4 ·2H 2 In the mixed solution of O and SDS, light green precipitate is generated in the solution, and the stirring is continued for 6 hours;
(2) stirring, putting the solution into a hydrothermal kettle, placing the hydrothermal kettle in a muffle furnace, reacting for 14h at 200 ℃, centrifugally washing, and drying overnight to obtain Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 A precursor;
(3) mixing Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 Precursor and LiOH. H 2 Mixing and grinding O according to the mass ratio of 1:1.05, then placing the mixture into a tube furnace, presintering the mixture for 4 hours at 500 ℃ in an oxygen atmosphere, and sintering the mixture for 15 hours at 850 ℃ to obtain LiNi 0.6 Co 0.2 Mn 0.2 O 2 ；
(4)LiNi 0.6 Co 0.2 Mn 0.2 O 2 @Co 3 O 4 Preparation: weighing 4.0g LiNi 0.6 Co 0.2 Mn 0.2 O 2 Dispersing the material in 100ml deionized water, ultrasonically dispersing for 1h, and then adding 0.098g NH under the condition of magnetic stirring 4 HCO 3 . 0.145gCo (NO) 3 ) 2 ·6H 2 O and 0.2g PVP were dissolved in 50ml deionized water and then slowly added dropwise to LiNi 0.6 Co 0.2 Mn 0.2 O 2 And NH 4 HCO 3 The mixture of (1) was further stirred for 5 hours. Centrifugally washing, drying overnight at 80 ℃, and finally sintering in a tube furnace at 600 ℃ for 4 hours in an oxygen atmosphere to obtain 1 wt.% Co 3 O 4 Coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 Composite material, noted CO-NCM 1.
Example 3
The target product of the invention is 3 wt.% Co 3 O 4 Coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 The composite material is prepared by the following steps:
(1) synthesis of stable Ni by coprecipitation method 0.6 Co 0.2 Mn 0.2 C 2 O 4 Precursor: 6.164g of Ni (CH) were weighed 3 COOH) 2 ·4H 2 O、2.056gCo(CH 3 COOH) 2 ·4H 2 O、2.002g Mn(CH 3 COOH) 2 ·4H 2 Dissolving O in a mixed solution of 60ml water and 60ml ethylene glycol, and weighing 6.240g C 2 H 2 O 4 ·2H 2 O and 0.2g SDS were dissolved in another mixed solution of 60ml water and 60ml ethylene glycol, and a metal salt solution was slowly added dropwise to C under stirring 2 H 2 O 4 ·2H 2 In the mixed solution of O and SDS, light green precipitate is generated in the solution, and the stirring is continued for 6 hours;
(2) stirring, putting the solution into a hydrothermal kettle, placing the hydrothermal kettle in a muffle furnace, reacting for 14h at 200 ℃, centrifugally washing, and drying overnight to obtain Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 A precursor;
(3) mixing Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 Precursor and LiOH. H 2 Mixing and grinding O according to the mass ratio of 1:1.05, then placing the mixture into a tube furnace, presintering the mixture for 4 hours at 500 ℃ in an oxygen atmosphere, and sintering the mixture for 15 hours at 850 ℃ to obtain LiNi 0.6 Co 0.2 Mn 0.2 O 2 ；
(4)LiNi 0.6 Co 0.2 Mn 0.2 O 2 @Co 3 O 4 Preparation: weighing 4.0g LiNi 0.6 Co 0.2 Mn 0.2 O 2 Dispersing the material in 100ml deionized water, ultrasonically dispersing for 1h, and then adding 0.296g NH under the condition of magnetic stirring 4 HCO 3 . 0.436gCo (NO) 3 ) 2 ·6H 2 O and 0.4g PVP were dissolved in 75ml deionized water and then slowly added dropwise to LiNi 0.6 Co 0.2 Mn 0.2 O 2 And NH 4 HCO 3 The mixture of (1) was further stirred for 5 hours. Centrifugally washing, drying at 80 ℃ overnight, and sintering in a tube furnace at 600 ℃ for 4h in an oxygen atmosphere to obtain 3 wt.% Co 3 O 4 Coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 Composite material, noted CO-NCM 2.
Example 4
The target product of the invention is 5 wt.% Co 3 O 4 Coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 The composite material is prepared by the following steps:
(1) synthesis of stable Ni by coprecipitation method 0.6 Co 0.2 Mn 0.2 C 2 O 4 Precursor: 6.164g of Ni (CH) are weighed 3 COOH) 2 ·4H 2 O、2.056gCo(CH 3 COOH) 2 ·4H 2 O、2.002g Mn(CH 3 COOH) 2 ·4H 2 Dissolving O in a mixed solution of 60ml water and 60ml ethylene glycol, and weighing 6.240g C 2 H 2 O 4 ·2H 2 O and 0.2g SDS were dissolved in another mixed solution of 60ml water and 60ml ethylene glycol, and a metal salt solution was slowly added dropwise to C under stirring 2 H 2 O 4 ·2H 2 In the mixed solution of O and SDS, light green precipitate is generated in the solution, and the stirring is continued for 6 hours;
(2) stirring, putting the solution into a hydrothermal kettle, placing the hydrothermal kettle in a muffle furnace, reacting for 14h at 200 ℃, centrifugally washing, and drying overnight to obtain Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 A precursor;
(3) mix Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 Precursor and LiOH. H 2 Mixing and grinding O according to the molar ratio of 1:1.05, then placing the mixture into a tube furnace, presintering the mixture for 4 hours at 500 ℃ in an oxygen atmosphere, and sintering the mixture for 15 hours at 850 ℃ to obtain LiNi 0.6 Co 0.2 Mn 0.2 O 2 ；
(4)LiNi 0.6 Co 0.2 Mn 0.2 O 2 @Co 3 O 4 Preparation: weighing 4.0g LiNi 0.6 Co 0.2 Mn 0.2 O 2 Dispersing the material in 100ml deionized water, ultrasonically dispersing for 1h, and then adding 0.493g NH under the condition of magnetic stirring 4 HCO 3 . 0.727gCo (NO) 3 ) 2 ·6H 2 O and 0.6g PVP were dissolved in 100ml deionized water and then added dropwise slowly to LiNi 0.6 Co 0.2 Mn 0.2 O 2 And NH 4 HCO 3 The mixture of (1) was further stirred for 5 hours. Washing with water by centrifugation, drying at 80 deg.C overnight, and placing in tubeSintering the mixture for 4 hours in a formula furnace at 600 ℃ in an oxygen atmosphere to obtain 5 wt.% Co 3 O 4 Coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 Composite material, noted CO-NCM 3.
(5) The morphology of the product was observed and analyzed by scanning electron microscopy SEM, and in FIG. 1, (a), (b), (c) and (d) correspond to TEM images of NCM, CO-NCM1, CO-NCM2 and CO-NCM3, respectively. Uncoated pure phase LiNi in Panel (a) 0.6 Co 0.2 Mn 0.2 O 2 The particle size of the material is between 300-500nm, and the shape is irregular; the material in graph (b) is 1 wt.% Co 3 O 4 Coated ternary material with significant Co on the surface 3 O 4 The coating layer is in a foam shape and is provided with a plurality of mesopores, but the coating layer is not uniform, a plurality of parts of particles are still exposed outside, and the corrosion of the electrolyte to the main body material can not be relieved well in the charging and discharging process. The graph (c) is a TEM image of the coating amount of 3 wt.%, and the coating is relatively uniform, so that the side reaction of the material and the electrolyte is well reduced, and the structural stability of the material is maintained. And the coating layer still has a plurality of mesopores, and compared with the compact coating layer in the prior literature, the foam-shaped coating layer is beneficial to Li in the charge and discharge process + Diffusion at material surface and mitigation of Li + Change in volume of material during the extraction/insertion process. 5 wt.% Co in graph (d) 3 O 4 The coating makes the coating layer too thick, and increases Li in the process of charging and discharging + Diffusion path on the surface of the material, reduction of Li + The diffusion rate may affect the electrochemical performance of the battery material. In FIG. 2, a, b, c and d are XRD patterns of NCM, CO-NCM1, CO-NCM2 and CO-NCM3, respectively, obtained by Co 3 O 4 The characteristic diffraction peaks of the coated material and the unmodified material correspond one to one, which shows that the crystal structure of the modified material is not changed and is still in a layered structure. FIG. 3 is a graph showing the first discharge specific capacities of the NCM, CO-NCM1, CO-NCM2 and CO-NCM3 under 0.1C, respectively, under which the discharge specific capacity of the uncoated NCM is only 180mAh g -1 Through Co 3 O 4 After modified coating, CO-NCM1, CO-NCM2 and CO-NCM3 are firstly coated under the condition of 0.1CThe specific capacity of the secondary discharge reaches 182 mAh.g -1 、191mAh·g -1 And 178 Ah.g -1 The modified CO-NCM2 material has the highest specific discharge capacity for the first time. FIG. 4 shows that the discharge specific capacities of the four materials under different multiplying power conditions are respectively lower than that of the unmodified NCM material under the 5C high multiplying power, and are only 71 mAh.g -1 The discharge specific capacity of the modified material under various multiplying power conditions is obviously improved, particularly under the condition of 5C, Co 3 O 4 The specific discharge capacity of the CO-NCM2 material reaches 100mAh g when the coating amount is 3 wt% -1 It is demonstrated that a proper amount of coating can effectively improve the stability of the material at a large rate. FIG. 5 is a discharge specific capacity cycle diagram of NCM, CO-NCM1, CO-NCM2 and CO-NCM3 under 0.2C multiplying power and circulating for 100 times without Co 3 O 4 The discharge capacity retention rate of the coated NCM material after 100 charge-discharge cycles is 61.2%, the discharge capacity retention rates of the three materials of CO-NCM1, CO-NCM2 and CO-NCM3 after coating modification are 77%, 87% and 75%, and the cycle stability is improved. Through comparison of multiplying power, circulation and the like of the four materials, 3 wt.% Co 3 O 4 The foam-like coating layer obviously improves the electrochemical performance of the material, and indicates that proper amount of Co 3 O 4 The coating prevents the main material and the electrolyte from generating adverse reaction to generate harmful substances such as HF and the like to corrode the material, so that the material structure is more stable in the large-rate charge-discharge cycle process. Thus, 3 wt.% Co was prepared 3 O 4 Coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 The material has excellent electrochemical performance and wide application prospect when being used as the anode material of the lithium ion battery.
Claims (5)
1. LiNi with foam-shaped coating layer 0.6 Co 0.2 Mn 0.2 O 2 @Co 3 O 4 The preparation method of the composite electrode material is characterized in that Ni (CH) 3 COOH) 2 ·4H 2 O、Co(CH 3 COOH) 2 ·4H 2 O、Mn(CH 3 COOH) 2 ·4H 2 O is taken as raw material， C 2 H 2 O 4 ·2H 2 O is taken as a complexing agent and a precipitator, and Sodium Dodecyl Sulfate (SDS) is added as a surfactant; taking a mixed solution of water and ethylene glycol as a solvent, adopting a solvothermal method, controlling the reaction temperature to be 200 ℃, reacting in a hydrothermal kettle for 14h, then centrifugally washing and drying to obtain Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 A precursor;
LiOH·H 2 o as a lithium source, with Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 Mixing and grinding the precursors, then placing the mixture in a tube furnace, presintering for 4h at 500 ℃ in an oxygen atmosphere, and then continuously sintering for 15h at 850 ℃ to obtain LiNi 0.6 Co 0.2 Mn 0.2 O 2 A material;
weighing LiNi 0.6 Co 0.2 Mn 0.2 O 2 Dispersing in deionized water, and performing ultrasonic dispersion; reacting NH 4 HCO 3 Dissolved in water and added to LiNi 0.6 Co 0.2 Mn 0.2 O 2 Magnetically stirring the suspension at normal temperature;
weighing Co (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water, adding polypyrrolidone, and adding Co (NO) 3 ) 3 ·9H 2 Slowly dropwise adding mixed solution of O and PVP into LiNi 0.6 Co 0.2 Mn 0.2 O 2 And NH 4 HCO 3 Stirring for 5h, centrifuging, washing for three times, and drying at 80 deg.C overnight; finally sintering for 4 hours at 600 ℃ in the oxygen atmosphere to obtain Co 3 O 4 Coated LiNi 0.6 Co 0.2 Mn 0.2 O 2 A material.
2. The method according to claim 1, wherein Ni (CH) 3 COOH) 2 ·4H 2 O、Co(CH 3 COOH) 2 ·4H 2 O、Mn(CH 3 COOH) 2 ·4H 2 The mass ratio of O is 6:2:2, and the volume ratio of water to glycol in the solvothermal system is 1:1.
3. The method according to claim 1, wherein LiOH. H 2 O as a lithium source and Ni 0.6 Co 0.2 Mn 0.2 C 2 O 4 The mass ratio of the precursors was 1.2: 1.
4. The method of claim 1, wherein n (Co (NO) 3 ) 2 ·6H 2 O):n(NH 4 HCO 3 )=2:5。
5. The method of claim 1, wherein Co is selected from the group consisting of 3 O 4 And LiNi 0.6 Co 0.2 Mn 0.2 O 2 The mass ratio is 1-5: 100.
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