CN113921789B - Preparation method of carbon quantum dot modified NCM ternary cathode material and prepared NCM ternary cathode material - Google Patents
Preparation method of carbon quantum dot modified NCM ternary cathode material and prepared NCM ternary cathode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon quantum dot modified NCM ternary cathode material, which relates to the technical field of ternary cathode materials and comprises the following steps: (1) coating the intermediate layer; (2) TiO coated with doped carbon quantum dots 2 (ii) a And (3) alkaline etching. The invention has the beneficial effects that: with NCM as the inner core of the material, tiO 2 As a material shell, a cavity structure is formed in the middle, and TiO is used 2 The doping enters the carbon quantum dots while protecting and supporting the NCM core, so that the conductivity of the material is enhanced. Thereby improving the stability and rate capability of the material in two aspects.
Description
Technical Field
The invention relates to the technical field of ternary cathode materials, in particular to a preparation method of a carbon quantum dot modified NCM ternary cathode material and the prepared NCM ternary cathode material.
Background
The lithium ion secondary battery has the advantages of high capacity, no pollution, no memory effect, small self-discharge, good cycle performance and the like, and is secondary battery energy storage equipment with excellent performance. The lithium ion battery has great advantages in the portable electronic equipment industry, and has good development prospects in the fields of power batteries and large-scale energy storage in the future. The positive electrode material of the lithium ion battery is a key factor for restricting the capacity and the service life of the lithium ion battery.
Based on ternary transition metal oxides (LiNi) x Mn y Co z O 2 NCM) has been regarded as the most promising lithium ion battery material, compared to the traditional cathode material LiCoO 2 The ternary material has the characteristics of high energy density, low cost, low toxicity and the like. In addition, the nickel, cobalt and manganese have good synergistic effect, so the method is widely applied. The nickel is a main component in redox energy storage, and how to effectively improve the specific capacity of the material by improving the content of the nickel in the material is one of the hot spots of the current research. Generally, the high-nickel ternary cathode material refers to a material in which the mole fraction of nickel is greater than 0.6, and such a ternary material has the characteristics of high specific capacity and low cost, but also has the defects of low capacity retention rate, poor thermal stability and the like.
The high nickel ternary material has many problems, and due to the polarization phenomenon, the resistance in the use process seriously influences the material performance, wastes unnecessary resources and limits the rate capability of the material. In addition, the material is in contact with the electrolyte and is disturbed by external factors, and the corrosion of the anode material itself can seriously affect the circulation capacity of the material. Moreover, gases released during the corrosion of the material by the electrolyte are also one of the causes of cell swelling.
The ternary material is a novel material developed from doping, and it is considered that if other elements are doped in the ternary material, the electrochemical performance of the ternary material is not affected unknown, more requirements are also provided for the preparation process, the application of the ternary material in power is limited by the increase of the cost, and the consistency of the product is affected by the coating process, so that the improvement of the safety performance of the material on the premise of ensuring the product to be suitable for industrialization is the best method for enabling the ternary material to be really applied to the power battery.
The change of the structural morphology of the material has an important effect on the performance of the material. 1) The micron-sized primary particles have a more complete layered structure, and the more complete the layered structure is, the better the stability of the material is, which is reflected by the improvement of the cycle performance and the safety performance. 2) The primary particles with larger particle size have better dynamic stability. 3) The other advantage of making the primary particle size larger is that the specific surface area is reduced, the damage of the side reaction of the material caused by the contact with the electrolyte to the material structure is reduced, and the method is helpful to the circulation and the material stability.
Doping modification generally improves the electrochemical performance and structural stability of a material by changing the lattice constant of the material or the valence state of some elements in the material. Commonly used metal elements, non-metal elements and rare earth elements. The doping amount of these ions is very important, and too much or too little will affect the material properties, since researchers are always searching for the optimum content of these elements. By doping some metal ions (Zr, al, fe, cr, ce, mg and the like) and non-metal ions (F, si and the like) in the crystal lattice of the ternary material, the electronic conductivity and the ionic conductivity can be improved, the output power density of the battery is improved, and the stability, especially the thermal stability, of the structure of the ternary material can be improved.
Coating the surface of the ternary material with a metal compound (AlF) with proper thickness 3 、FePO 4 、ZrO 2 、V 2 O 5 、Al 2 O 3 、TiO 2 、ZnO、ZrO 2 Etc.), lithium salts (Li) 2 MnO 3 、LiCoO 2 Etc.) or some simple substances (carbon, graphene, etc.), which can physically isolate the active substance from the electrolyte in the battery, reduce the side reaction of the material and the electrolyte, and inhibit the dissolution of transition metal ions in the electrolyte. In addition, the coating can prevent impedance from increasing in the charge and discharge process and improve the cycle performance of the material. At the same time, having a certain mechanical strengthThe inactive coating layer may also slow down the collapse of the electrode material structure during long-term cycling. In addition, the coating layer with high conductivity can improve the conductivity of the electrode, thereby improving the rate performance. On the premise of high safety performance, the appropriate coating substance can also improve the charge-discharge cut-off voltage of the ternary material, so that the specific capacity of the material is improved. Therefore, in industrial production, on one hand, the performance of the material is improved by improving the synthesis process, and on the other hand, the appropriate bulk phase doping and surface coating of the commercial ternary material are necessary.
The patent application with the publication number of CN113206236A discloses a preparation method of an NCM ternary cathode material with a Yolk-shell structure, wherein the NCM ternary material is used as a core of the material, and a mesoporous SiO is adopted 2 The NCM inner core is supported as a shell of the material, but the capacity retention of the material is 95.2 percent after 50 cycles, and the material is to be further improved. The patent application with the publication number of CN109860534A discloses a ternary cathode material modified by carbon quantum dots and a preparation method thereof, wherein an organic carbon source is dissolved in water and/or ethanol and is uniformly mixed with the ternary material, and carbon quantum dots are formed on the surface of the ternary cathode material with the particle size of 5-15 microns after microwave pyrolysis. There is still room for further improvement in terms of the structure of the ternary material itself, the type of coating, and the method of preparation. Compared with the water system which introduces a carbon source to treat the ternary material, the oil phase system can reduce the contact of the ternary material and water and improve the formation of residual alkali.
Disclosure of Invention
The invention aims to solve the technical problem that the stability of a coated ternary cathode material in the prior art is to be further improved, and provides a preparation method of a carbon quantum dot modified random-type NCM ternary cathode material and the prepared carbon quantum dot modified random-type NCM ternary cathode material.
The invention solves the technical problems through the following technical means:
a preparation method of a carbon quantum dot modified NCM ternary cathode material comprises the following steps:
step one, coating an intermediate layer
Mixing a lithium source and a ternary precursor, sintering, and then crushing and sieving to obtain a sintered material;
dispersing the sintering material into a first organic solvent, stirring, adding ammonia water and a silicon source precursor, reacting, and drying to obtain a ternary material coated with the middle layer;
step two, coating TiO doped with carbon quantum dots 2
Dispersing the ternary material coated with the middle layer in the first step into a second organic solvent, adding carbon quantum dots, adding hydrochloric acid, dropwise adding a titanium source, stirring to form sol, drying, and calcining to obtain an intermediate product;
step three, alkaline etching
And adding the intermediate product into an alkaline solution for reaction, and purifying the product to obtain the carbon quantum dot modified NCM ternary cathode material with a battle-type structure.
Has the advantages that: the invention takes ternary material as inner core, tiO 2 As a material shell, a cavity structure is formed in the middle, and TiO is used 2 The carbon quantum dots are doped while the NCM core is protected and supported, so that the conductivity of the material is enhanced, the titanium dioxide modified by the carbon quantum dots and the surface porous structure enable the material to have good lithium ion transmission capability, the gram capacity exertion, the rate capability and the cycle retention rate of the material are enhanced, and the 50-cycle capacity retention rate reaches more than 98.3%.
The surface of the ternary cathode material with the battle-type structure prepared by the invention is provided with the hole structure, so that the contact wettability of the core NCM material and the electrolyte can be ensured, and the double-layer battle-type structure effectively buffers the volume expansion of the material in the charging and discharging processes, and prevents the material from being pulverized and the structure from collapsing.
Preferably, in the first step, the mixed material is sintered for 10 to 30 hours under the conditions that the volume concentration of the oxygen atmosphere is 30 to 99 percent and the temperature is 600 to 1000 ℃.
Preferably, the lithium source comprises one or more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium nitrate.
Preferably, the lithium source is lithium hydroxide or lithium carbonate.
Preferably, the first organic solvent is ethanol, propanol or isopropanol, the ratio of the mass of the sintering material to the volume of the first organic solvent is 1g (1-5) mL, and the volume ratio of the first organic solvent to the ammonia water and the silicon source precursor is 1.
The first organic solvent serves for dissolution.
Preferably, the silicon source precursor comprises any one or more of methyl orthosilicate, ethyl orthosilicate and butyl orthosilicate.
Preferably, the preparation method of the carbon quantum dots in the second step comprises the following steps: dissolving a carbon source and cysteine hydrochloride in paraffin oil, uniformly stirring and heating to 150-280 ℃, continuously stirring and heating at the temperature, carrying out heat preservation reaction for a period of time, cooling and purifying to obtain the carbon quantum dots.
Has the beneficial effects that: the invention adopts a solvothermal method, and is simpler compared with a high-pressure reaction kettle which needs stricter reaction conditions.
Preferably, the carbon source is selected from at least one of citric acid, glucose, vitamins, lactic acid, fructose, sucrose.
Preferably, the carbon source is glucose.
Preferably, the mass ratio of the carbon source to the cysteine hydrochloride is 1.2-1.5, and the ratio of the volume of the paraffin oil to the mass of the carbon source is 10-20mL.
Preferably, the heat preservation time is 5-60 min.
Preferably, the second organic solvent is ethanol, propanol or isopropanol, and the mass of the ternary material coating the intermediate layer and the volume of the second organic solvent are prepared to be 1g (1-5) mL.
The second organic solvent serves for dissolution.
Preferably, the titanium source is at least one of tetrabutyl titanate, tetrapropyl titanate, titanium tetrachloride and titanyl sulfate.
Preferably, the amount of the carbon quantum dots accounts for 0.05-0.5wt% of the ternary material coating the intermediate layer.
I.e. the mass ratio of the mass of the carbon quantum dots to the mass of the material obtained in step 1.
Preferably, the ratio of the mass of the ternary material coating the intermediate layer to the volume of the hydrochloric acid is 1g.
Preferably, the calcination temperature in the second step is 450-550 ℃, and the calcination time is 1-4 h.
Preferably, the alkaline solution in the third step is a NaOH solution, and the concentration of the NaOH solution is 2mol/L.
Preferably, the ratio of the mass of the intermediate product to the volume of the NaOH solution is 1g to 5mL.
Preferably, the reaction time is 1 to 5 hours.
Preferably, the purification step comprises washing the product with ethanol, filtering, and drying.
Preferably, the drying temperature is 100-300 ℃, and the drying time is 2-8 h.
The carbon quantum dot modified NCM ternary cathode material with the Rattle-type structure is prepared by the method.
The invention has the advantages that: the invention takes ternary material as inner core, tiO 2 As a material shell, a cavity structure is formed in the middle, and TiO is used 2 The carbon quantum dots are doped while the NCM core is protected and supported, so that the conductivity of the material is enhanced, the titanium dioxide modified by the carbon quantum dots and the surface porous structure enable the material to have good lithium ion transmission capability, the gram capacity exertion, the rate capability and the cycle retention rate of the material are enhanced, and the 50-cycle capacity retention rate reaches more than 98.3%.
The surface of the ternary cathode material with the battle-type structure prepared by the invention is provided with the hole structure, so that the contact wettability of the core NCM material and the electrolyte can be ensured, and the double-layer battle-type structure effectively buffers the volume expansion of the material in the charging and discharging processes, and prevents the material from being pulverized and the structure from collapsing.
Drawings
FIG. 1 is an SEM image of an NCM ternary cathode material with a lattice-type structure modified by carbon quantum dots in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Those skilled in the art who do not specify any particular technique or condition in the examples can follow the techniques or conditions described in the literature in this field or follow the product specification.
Example 1
The preparation method of the NCM ternary cathode material with the battle-type structure modified by the carbon quantum dots comprises the following steps:
step one, coating an intermediate layer
Mixing lithium hydroxide with a commercial ternary precursor Ni 70 Co 10 Mn 20 (OH) 2 According to the molar ratio of the lithium element to the nickel-cobalt-manganese element in the precursor of 1.08:1, weighing materials, uniformly mixing, sintering the mixed materials for 10 hours at the volume concentration of 50% in an oxygen atmosphere and the temperature of 800 ℃, and then crushing and sieving the materials by using a 200-mesh sieve to obtain a primary sintered material A;
and dispersing the sintered material A into absolute ethyl alcohol, adding ammonia water and methyl orthosilicate after stirring, reacting for 5 hours at normal temperature and normal pressure, filtering, washing with alcohol, and drying in vacuum at 120 ℃ to obtain a material, namely a sample B coated with the middle layer. Wherein the ratio of the mass of the sintering material A to the volume of the absolute ethyl alcohol, the volume of the ammonia water and the volume of the methyl orthosilicate is 1g:1mL of: 0.1mL:0.01mL.
Step two, preparing the carbon quantum dots
Glucose and cysteine hydrochloride were mixed according to a 1: weighing 0.2 by mass ratio, dissolving in paraffin oil, wherein the ratio of the volume of the paraffin oil to the mass of the glucose is 10mL:1g, stirring uniformly, heating to 150 ℃, continuously stirring, heating and preserving heat at the temperature for reaction for 30min, cooling, adding deionized water, ultrasonically cleaning, centrifuging, and drying to obtain the carbon quantum dots.
Step three, coating the TiO doped with the carbon quantum dots 2
Dispersing the sample B in the step one into absolute ethyl alcohol, adding the carbon quantum dots in the step two, wherein the amount of the carbon quantum dots accounts for 0.1wt% of the sample B, adding a certain amount of hydrochloric acid, adding 0.1mL of hydrochloric acid into 1g of the sample B, dropwise adding tetrabutyl titanate, adding 1mL of tetrabutyl titanate into 1g of the sample B, continuously stirring to form sol, drying, and calcining at 500 ℃ for 1h to obtain a product named as C.
Step four, etching under alkaline condition to form a battle-type structure
To obtain a material with a battle-type structure, the material C is added into a 2mol/L NaOH solution, and the reaction is continued for 1 hour, wherein the ratio of the mass of the material C to the volume of the NaOH solution is 1g:1mL, etching off the middle SiO layer by using an alkaline environment 2 The obtained product is cleaned by ethanol at normal temperature, filtered, kept at 120 ℃ for 2 hours and dried to obtain the material with the battle-type structure, the appearance of the prepared product is shown in figure 1, and the surface of the material has a hole structure.
Example 2
The preparation method of the carbon quantum dot modified NCM ternary cathode material with the letter-type structure comprises the following steps:
step one, coating an intermediate layer
Mixing lithium hydroxide with a commercial ternary precursor Ni 70 Co 10 Mn 20 (OH) 2 According to the condition that the molar ratio of the lithium element to the total nickel, cobalt and manganese elements in the precursor is 1.07:1, weighing and uniformly mixing materials, carrying out primary sintering on the mixed materials for 12 hours under the conditions that the volume concentration of an oxygen atmosphere is 70% and the temperature is 850 ℃, and then crushing and sieving the mixed materials by using a 200-mesh sieve to obtain a primary sintered material A;
and dispersing the sintering material A into absolute ethyl alcohol, adding ammonia water and ethyl orthosilicate after stirring, reacting for 5 hours at normal temperature and normal pressure, filtering, washing with alcohol, and drying in vacuum at 120 ℃ to obtain a material, namely a sample B coated with the middle layer. Wherein the ratio of the mass of the sintering material A to the volume of the absolute ethyl alcohol, the volume of the ammonia water and the volume of the methyl orthosilicate is 1g:1mL:0.1mL:0.01mL.
Step two, preparing carbon quantum dots
Glucose and cysteine hydrochloride were mixed according to a 1: weighing according to the mass ratio of 1.5, dissolving in paraffin oil, wherein the ratio of the volume of the paraffin oil to the mass of glucose is 20mL:1g, stirring uniformly, heating to 150 ℃, continuously stirring, heating, preserving heat and reacting for 60min at the temperature, cooling, adding deionized water, carrying out ultrasonic cleaning, then carrying out centrifugal treatment, and drying to obtain the carbon quantum dots.
Step three, coating the TiO doped with carbon quantum dots 2
Dispersing the sample B in the step one into absolute ethyl alcohol, adding the carbon quantum dots in the step two, wherein the amount of the carbon quantum dots accounts for 0.5wt% of the sample B, adding a certain amount of hydrochloric acid, adding 2mL of hydrochloric acid into 1g of the sample B, dropwise adding tetrapropyl titanate, adding 2mL of tetrapropyl titanate into 1g of the sample B, continuously stirring to form sol, drying, and calcining at 450 ℃ for 4 hours to obtain a product named as C.
Step four, etching under alkaline condition to form a battle-type structure
To obtain a material with a battle-type structure, the material C is added into a 2mol/L NaOH solution, and the reaction is continued for 1 hour, wherein the ratio of the mass of the material C to the volume of the NaOH solution is 1g:2mL, etching off the middle SiO by using alkaline environment 2 And washing the obtained product with ethanol at normal temperature, filtering, keeping the temperature at 300 ℃ for 2 hours, and drying to obtain the material with the battle-type structure.
Example 3
The preparation method of the carbon quantum dot modified NCM ternary cathode material with the letter-type structure comprises the following steps:
step one, coating an intermediate layer
Mixing lithium hydroxide with a commercial ternary precursor Ni 70 Co 10 Mn 20 (OH) 2 According to the condition that the molar ratio of the lithium element to the total nickel, cobalt and manganese elements in the precursor is 1.06:1 weighing materials, mixing uniformly in oxygen atmosphereUnder the conditions that the volume concentration of the raw materials is 90% and the temperature is 800 ℃, the mixed materials are sintered for 10 hours for the first time, and then are crushed and sieved by a 200-mesh screen to obtain a first-time sintered material A;
and dispersing the sintering material A into absolute ethyl alcohol, adding ammonia water and ethyl orthosilicate after stirring, reacting for 5 hours at normal temperature and normal pressure, filtering, washing with alcohol, and drying in vacuum at 120 ℃ to obtain a material, namely a sample B coated with the middle layer. Wherein the ratio of the mass of the sintering material A to the volume of the absolute ethyl alcohol, the volume of the ammonia water and the volume of the methyl orthosilicate is 1g:1mL:0.1mL:0.01mL.
Step two, preparing the carbon quantum dots
Glucose and cysteine hydrochloride were mixed according to a 1:1.5, dissolving the mixture in paraffin oil, wherein the ratio of the volume of the paraffin oil to the mass of the glucose is 20mL:1g, stirring uniformly, heating to 150 ℃, continuously stirring, heating and preserving heat at the temperature for reaction for 60min, cooling, adding deionized water, ultrasonically cleaning, centrifuging, and drying to obtain the carbon quantum dots.
Step three, coating the TiO doped with carbon quantum dots 2
Dispersing the sample B in the step one into absolute ethyl alcohol, adding the carbon quantum dots in the step two, wherein the amount of the carbon quantum dots accounts for 0.05wt% of the sample B, adding a certain amount of hydrochloric acid, adding 1mL of hydrochloric acid into 1g of the sample B, dropwise adding titanyl sulfate, adding 2mL of titanyl sulfate into 1g of the sample B, continuously stirring to form sol, drying, and calcining at 450 ℃ for 4 hours to obtain a product named as C.
Step four, etching under alkaline condition to form a random-type structure
To obtain a material with a battle-type structure, the material C is added into a 2mol/L NaOH solution, and the reaction is continued for 1 hour, wherein the ratio of the mass of the material C to the volume of the NaOH solution is 1g:3mL, etching off the middle SiO by using alkaline environment 2 And washing the obtained product with ethanol at normal temperature, filtering, keeping the temperature at 100 ℃ for 8 hours, and drying to obtain the material with the battle-type structure.
Example 4
The preparation method of the NCM ternary cathode material with the battle-type structure modified by the carbon quantum dots comprises the following steps:
step one, coating an intermediate layer
Mixing lithium hydroxide with a commercial ternary precursor Ni 70 Co 10 Mn 20 (OH) 2 According to the molar ratio of the lithium element to the nickel-cobalt-manganese element in the precursor of 1.05:1, weighing materials, uniformly mixing, sintering the mixed materials for 10 hours at the volume concentration of 60% in an oxygen atmosphere and the temperature of 900 ℃, and crushing and sieving the materials by using a 200-mesh sieve to obtain a primary sintered material A;
and dispersing the sintering material A into absolute ethyl alcohol, adding ammonia water and ethyl orthosilicate after stirring, reacting for 5 hours at normal temperature and normal pressure, filtering, washing with alcohol, and drying in vacuum at 120 ℃ to obtain a material, namely a sample B coated with the middle layer. Wherein the ratio of the mass of the sintering material A to the volume of absolute ethyl alcohol, the volume of deionized water, the volume of ammonia water and the volume of methyl orthosilicate is 1g:1mL of: 0.1mL:0.01mL.
Step two, preparing carbon quantum dots
Glucose and cysteine hydrochloride were mixed according to a 1: weighing according to the mass ratio of 1.5, dissolving in paraffin oil, wherein the ratio of the volume of the paraffin oil to the mass of glucose is 20mL:1g, stirring uniformly, heating to 150 ℃, continuously stirring, heating, preserving heat and reacting for 60min at the temperature, cooling, adding deionized water, carrying out ultrasonic cleaning, then carrying out centrifugal treatment, and drying to obtain the carbon quantum dots.
Step three, coating the TiO doped with the carbon quantum dots 2
Dispersing the sample B in the step one into absolute ethyl alcohol, adding the carbon quantum dots in the step two, wherein the amount of the carbon quantum dots accounts for 0.5wt% of the sample B, adding a certain amount of hydrochloric acid, adding 1mL of hydrochloric acid into 1g of the sample B, dropwise adding tetrapropyl titanate, adding 2mL of tetrapropyl titanate into 1g of the sample B, continuously stirring to form sol, drying, and calcining at 550 ℃ for 4 hours to obtain a product named as C.
Step four, etching under alkaline condition to form a battle-type structure
To obtain a material with a Rattle-type structure, the C material is added into a 2mol/L NaOH solution, and the reaction is continued for 1 hour, wherein the ratio of the mass of the C material to the volume of the NaOH solution is 1g:4mL, etching off the middle SiO by using an alkaline environment 2 And washing the obtained product with ethanol at normal temperature, filtering, keeping the temperature at 110 ℃ for 4 hours, and drying to obtain the material with the battle-type structure.
Example 5
The preparation method of the NCM ternary cathode material with the battle-type structure modified by the carbon quantum dots comprises the following steps:
step one, coating an intermediate layer
Lithium carbonate and a commercial ternary precursor Ni 60 Co 20 Mn 20 (OH) 2 According to the molar ratio of the lithium element to the nickel-cobalt-manganese element in the precursor of 1.02:1, weighing materials, uniformly mixing, sintering the mixed materials for 30 hours at the volume concentration of 80% in an oxygen atmosphere and the temperature of 600 ℃, and crushing and sieving the materials by using a 200-mesh sieve to obtain a primary sintered material A;
and dispersing the sintered material A into absolute ethyl alcohol, adding ammonia water and tetraethoxysilane after stirring, reacting for 5 hours at normal temperature and normal pressure, filtering, washing with alcohol, and drying in vacuum at 120 ℃ to obtain a material, namely a sample B coated with the middle layer. Wherein the ratio of the mass of the sintering material A to the volume of the absolute ethyl alcohol, the volume of the ammonia water and the volume of the methyl orthosilicate is 1g:1mL of: 0.1mL:0.01mL.
Step two, preparing the carbon quantum dots
Glucose and cysteine hydrochloride were mixed according to a 1:1.5, dissolving the mixture in paraffin oil, wherein the ratio of the volume of the paraffin oil to the mass of the glucose is 20mL:1g, stirring uniformly, heating to 150 ℃, continuously stirring, heating, preserving heat and reacting for 60min at the temperature, cooling, adding deionized water, ultrasonically cleaning, and centrifuging to obtain the carbon quantum dots.
Step three, coating the TiO doped with carbon quantum dots 2
Dispersing the sample B in the step one into absolute ethyl alcohol, adding the carbon quantum dots in the step two, wherein the amount of the carbon quantum dots accounts for 0.3wt% of the sample B, adding a certain amount of hydrochloric acid, adding 1.2mL of hydrochloric acid into 1g of the sample B, dropwise adding tetrapropyl titanate, adding 2mL of tetrapropyl titanate into 1g of the sample B, continuously stirring to form sol, drying, and calcining at 450 ℃ for 1h to obtain a product named as C.
Step four, etching under alkaline condition to form a random-type structure
To obtain a material with a battle-type structure, the material C is added into a 2mol/L NaOH solution, and the reaction is continued for 1 hour, wherein the ratio of the mass of the material C to the volume of the NaOH solution is 1g:5mL, etching off the middle SiO by using alkaline environment 2 And washing the obtained product with ethanol at normal temperature, filtering, keeping the temperature at 100 ℃ for 8 hours, and drying to obtain the material with the battle-type structure.
Example 6
The preparation method of the NCM ternary cathode material with the battle-type structure modified by the carbon quantum dots comprises the following steps:
step one, coating an intermediate layer
Lithium carbonate and a commercial ternary precursor Ni 50 Co 20 Mn 30 (OH) 2 According to the molar ratio of the lithium element to the nickel-cobalt-manganese element in the precursor of 1.2:1, weighing materials, uniformly mixing, sintering the mixed materials for 10 hours at the volume concentration of 30% in an oxygen atmosphere and the temperature of 900 ℃, and crushing and sieving the materials by using a 200-mesh sieve to obtain a primary sintered material A;
and dispersing the sintered material A into absolute ethyl alcohol, adding ammonia water and tetraethoxysilane after stirring, reacting for 5 hours at normal temperature and normal pressure, filtering, washing with alcohol, and drying in vacuum at 120 ℃ to obtain a material, namely a sample B coated with the middle layer. Wherein the ratio of the mass of the sintering material A to the volume of absolute ethyl alcohol, the volume of deionized water, the volume of ammonia water and the volume of methyl orthosilicate is 1g:1mL:0.1mL:0.01mL.
Step two, preparing carbon quantum dots
Glucose and cysteine hydrochloride were mixed according to a 1:1.5, dissolving the mixture in paraffin oil, wherein the ratio of the volume of the paraffin oil to the mass of the glucose is 20mL:1g, stirring uniformly, heating to 150 ℃, continuously stirring, heating, preserving heat and reacting for 60min at the temperature, cooling, adding deionized water, carrying out ultrasonic cleaning, then carrying out centrifugal treatment, and drying to obtain the carbon quantum dots.
Step three, coating the TiO doped with carbon quantum dots 2
Dispersing the sample B in the step one into absolute ethyl alcohol, adding a carbon quantum dot in the step two, wherein the amount of the carbon quantum dot accounts for 0.2wt% of the sample B, adding a certain amount of hydrochloric acid, adding 0.5mL of hydrochloric acid into 1g of the sample B, dropwise adding titanium tetrachloride, adding 2mL of titanium tetrachloride into 1g of the sample B, continuously stirring to form sol, drying, and calcining at 550 ℃ for 2 hours to obtain a product named as C.
Step four, etching under alkaline condition to form a battle-type structure
To obtain a material with a battle-type structure, the material C is added into a 2mol/L NaOH solution, and the reaction is continued for 1 hour, wherein the ratio of the mass of the material C to the volume of the NaOH solution is 1g:5mL, etching off the middle SiO by using alkaline environment 2 And washing the obtained product with ethanol at normal temperature, filtering, keeping the temperature at 200 ℃ for 2 hours, and drying to obtain the material with the battle-type structure.
Comparative example 1
The comparative example differs from example 1in that: only comprises the sintering step in the step one, and the material A is obtained after primary sintering.
Comparative example 2
The comparative example differs from example 2 in that: only comprises the sintering step in the step one, and the material A is obtained after primary sintering.
Comparative example 3
The comparative example differs from example 3 in that: only comprises the sintering step in the first step, and the material A is obtained after primary sintering.
Comparative example 4
The comparative example differs from example 4 in that: only comprises the sintering step in the step one, and the material A is obtained after primary sintering.
Comparative example 5
This comparative example differs from example 5 in that: only comprises the sintering step in the first step, and the material A is obtained after primary sintering.
Comparative example 6
This comparative example differs from example 6 in that: only comprises the sintering step in the first step, and the material A is obtained after primary sintering.
Comparative example 7
This comparative example differs from example 1in that: and step four, only using the carbon quantum dots obtained in the step two, namely, replacing the same amount of the C material in the step four with the carbon quantum dots obtained in the step two. The remaining steps remain the same.
Comparative example 8
The comparative example differs from example 1in that: only comprises the steps one, two and three, and does not carry out the step four alkaline etching.
Comparative example 9
The comparative example differs from example 1in that: and (4) directly mixing the sintering material A obtained in the step one with a paraffin oil solution of glucose and cysteine hydrochloride to obtain a sample B, and directly entering the step three, wherein the rest steps are the same.
Specific preparation process parameters of examples 1 to 6 are shown in table 1, and a series of materials with regular and collapse-free random-type structures are finally obtained and can be used as lithium ion battery anode materials. Comparative examples 1-8 are samples a with each example completing one sintering condition.
Table 1 shows the process parameters of the examples
The electrochemical performance of the ternary cathode materials prepared in examples 1-6 and comparative examples 1-6 was tested, and the test method was as follows:
and adopting 2016 button cells for electrochemical performance test: according to the active material: carbon black: and the polyvinylidene fluoride is dissolved in N-methyl pyrrolidone according to the mass ratio of 90. The cathode is a lithium plate, the diaphragm is Celgard 2400, and the electrolyte is 1M LiPF 6 Dissolved in EC/DMC/DEC (1. The assembly process of the battery is completed in the glove box. The charge and discharge test of the battery is carried out on Xinwei CT-3008The process is carried out. The material adopts a voltage range of 2.8-4.35V to test electrochemical performance, and comprises discharge capacity of 0.2C/0.33C/1C/2C at different multiplying factors and cycle retention rate of 50 weeks at 1C multiplying factor. The test results are shown in table 2.
Table 2 shows the results of electrochemical performance tests of the ternary cathode materials in each example and comparative example
As can be seen from table 2, the ternary cathode materials in examples 1 to 6, whether the gram capacity exertion, the first efficiency, the rate capability or the cycle capacity retention rate, are greatly improved compared with those in comparative examples 1 to 9.
The above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a carbon quantum dot modified NCM ternary positive electrode material is characterized by comprising the following steps:
step one, coating an intermediate layer
Mixing a lithium source and a ternary precursor, sintering, and then crushing and sieving to obtain a sintered material;
dispersing the sintering material into a first organic solvent, adding ammonia water and a silicon source precursor after stirring, reacting, and drying to obtain a ternary material coated with the middle layer;
step two, coating TiO doped with carbon quantum dots 2
Dispersing the ternary material coated with the middle layer in the first step into a second organic solvent, adding carbon quantum dots, adding hydrochloric acid, dropwise adding a titanium source, stirring to form sol, drying, and calcining to obtain an intermediate product;
step three, alkaline etching
And adding the intermediate product into an alkaline solution for reaction, and purifying the product to obtain the carbon quantum dot modified NCM ternary cathode material with the battle-type structure.
2. The method for preparing the carbon quantum dot modified NCM ternary cathode material according to claim 1, wherein in the first step, the mixed material is sintered for 10-30h under the conditions that the volume concentration of the oxygen atmosphere is 30-99% and the temperature is 600-1000 ℃.
3. The method for preparing the carbon quantum dot modified NCM ternary cathode material as claimed in claim 1, wherein the lithium source comprises one or more of lithium hydroxide, lithium carbonate, lithium nitrate and lithium oxalate.
4. The method for preparing the carbon quantum dot modified NCM ternary cathode material according to claim 1, wherein the first organic solvent is ethanol, propanol or isopropanol, the ratio of the mass of the sintering material to the volume of the first organic solvent is lg (1-5) mL, and the volume ratio of the first organic solvent to ammonia water and the silicon source precursor is 1.
5. The preparation method of the carbon quantum dot modified NCM ternary cathode material according to claim 1, wherein the preparation method of the carbon quantum dot in the second step comprises the following steps of dissolving a carbon source and cysteine hydrochloride in paraffin oil, uniformly stirring and heating to 150-280 ℃, continuously stirring and heating at the temperature for a heat preservation reaction for a period of time, cooling and purifying to obtain the carbon quantum dot.
6. The method for preparing the carbon quantum dot modified NCM ternary cathode material according to claim 5, wherein the carbon source is at least one selected from citric acid, glucose, vitamins, lactic acid, fructose and sucrose; the mass ratio of the carbon source to the cysteine hydrochloride is 1.2-1.5, and the ratio of the volume of the paraffin oil to the mass of the carbon source is 10-20mL.
7. The preparation method of the carbon quantum dot modified NCM ternary cathode material is characterized in that the second organic solvent is ethanol, and the ratio of the mass of the ternary material coated with the intermediate layer to the volume of the second organic solvent is 1g (1-5) mL.
8. The method for preparing the carbon quantum dot modified NCM ternary cathode material according to claim 1, wherein the amount of the carbon quantum dots accounts for 0.05-0.5wt% of the ternary material coating the intermediate layer.
9. The method for preparing the carbon quantum dot modified NCM ternary cathode material is characterized in that the ratio of the mass of the ternary material coated with the intermediate layer to the volume of hydrochloric acid is 1g to 0.1-2mL, and the ratio of the mass of the ternary material coated with the intermediate layer to the volume of a titanium source is 1g to 10mL.
10. The carbon quantum dot modified Rattle-type NCM ternary cathode material prepared by the method of any one of claims 1 to 9.
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