CN115676822A - Nitrogen-phosphorus doped foamy porous carbon material and preparation method thereof - Google Patents
Nitrogen-phosphorus doped foamy porous carbon material and preparation method thereof Download PDFInfo
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Abstract
The application provides a nitrogen-phosphorus doped foam porous carbon material and a preparation method thereof, and the mass percentage contents of carbon, nitrogen and phosphorus elements in the nitrogen-phosphorus doped foam porous carbon material are regulated and controlled, so that the nitrogen-phosphorus doped foam porous carbon material meets the following requirements: 0<I D /I G <1.5, the obtained nitrogen-phosphorus doped foamed porous carbon material has high capacity, abundant electrochemical active sites, surface groups and pore channels, and is favorable for improving the electrochemical performance of the nitrogen-phosphorus doped foamed porous carbon material. The nitrogen-phosphorus doped foam porous carbon material provided by the application is used as a negative electrode material of a lithium ion battery, and is beneficial to improving the electrochemical performance of the lithium ion battery.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a nitrogen-phosphorus doped foamy porous carbon material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high energy storage density, high open circuit voltage, low self-discharge rate, long cycle life, good safety and the like, and is widely applied to the fields of electric energy storage, mobile electronic equipment, electric automobiles, aerospace equipment and the like. As mobile electronic devices and electric vehicles enter a high-speed development stage, the market puts higher and higher requirements on energy density, safety, cycle performance, service life and the like of lithium ion batteries.
The porous carbon material is widely applied to the electrochemical field due to the advantages of rich sources, developed pores, strong modifiability, environmental friendliness and the like. However, the porous material using carbon as the only constituent element has very few surface groups, so that the advantages of high specific surface area, high porosity and the like of the material cannot be effectively utilized, thereby limiting the electrochemical performance of the porous carbon material and also limiting the application of the porous carbon material in the lithium ion battery. Therefore, how to improve the electrochemical performance of the porous carbon material and further improve the electrochemical performance of the lithium ion battery becomes a problem to be solved urgently.
Disclosure of Invention
The application aims to provide a nitrogen-phosphorus doped foamed porous carbon material and a preparation method thereof, so as to prepare the nitrogen-phosphorus doped foamed porous carbon material with good electrochemical performance, and further improve the electrochemical performance of a lithium ion battery. The specific technical scheme is as follows:
the first aspect of the application provides a nitrogen-phosphorus doped foamed porous carbon material, based on the total mass of the nitrogen-phosphorus doped foamed porous carbon material, the mass percentage content of carbon element is 85% -93%, the mass percentage content of nitrogen element is 6% -12%, and the mass percentage content of phosphorus element is 1% -3%; in a Raman spectrum of the nitrogen-phosphorus doped foamed porous carbon material, the nitrogen-phosphorus doped foamed porous carbon material meets the following requirements: 0<I D /I G <1.5, wherein I D Indicating that the corresponding peak position of the Raman spectrum is 1360cm -1 ±10cm -1 Peak intensity of time I G Indicating that the corresponding peak position of the Raman spectrum is 1590cm -1 ±10cm -1 The peak at time is strong.
In some embodiments of the present application, the nitrogen-phosphorus doped foamy porous carbon material has a specific surface area of 150m 2 /g-300m 2 /g。
In some embodiments of the present application, a nitrogen-phosphorus doped foamed porous carbon material comprising pores having a pore size of 1nm to 28nm, the nitrogen-phosphorus doped foamed porous carbon material having a porosity of 0.150cm 3 /g-0.250cm 3 /g。
A second aspect of the present application provides a method of preparing a nitrogen-phosphorus doped foamy porous carbon material of any of the above embodiments, comprising the steps of:
(1) Adding the milk powder into deionized water, and uniformly mixing to obtain milk powder emulsion; wherein based on the total mass of the milk powder, the mass percentage of the protein is 12-25%, and the mass percentage of the fat is 10-40%; the solid content of the milk powder emulsion is 1-10 wt%;
(2) Carrying out hydro-thermal synthesis reaction on the milk powder emulsion, and drying after the reaction is finished to obtain a carbon precursor; wherein the reaction temperature of the hydro-thermal synthesis reaction is 100-140 ℃, and the reaction time is 16-20 h;
(3) Carrying out high-temperature heat treatment on the carbon precursor, cooling to room temperature, cleaning, and drying to obtain nitrogen-phosphorus doped foamed porous carbon; wherein the step of high-temperature heat treatment comprises the steps of heating to 390-410 ℃ at the heating rate of 2-8 ℃/min, preserving heat for 1.5-2.5 h, heating to 500-650 ℃ at the heating rate of 2-8 ℃/min, and preserving heat for 0.5-3 h.
In some embodiments of the present application, the step of washing comprises washing with an acid solution for 0.5h to 1.5h, and then washing with absolute ethanol and deionized water alternately for 3 times to 7 times; the acid in the acid solution is selected from HCl and H 2 SO 4 、HNO 3 At least one of (1).
A third aspect of the present application provides a negative electrode tab comprising a negative electrode material layer comprising a negative electrode material comprising a nitrogen-phosphorus doped foamy porous carbon material of any of the above embodiments.
In some embodiments of the present application, the nitrogen-phosphorus doped foamy porous carbon material is in a mass percentage of 70% to 95% based on the total mass of the anode material layer.
A fourth aspect of the present application provides a lithium ion battery comprising the negative electrode tab of any of the above embodiments.
The application provides a nitrogen-phosphorus doped foamed porous carbon material and a preparation method thereof, and the nitrogen-phosphorus doped foamed porous carbon material can meet the requirements by regulating and controlling the mass percentage content of carbon, nitrogen and phosphorus elements: 0<I D /I G <1.5, the obtained nitrogen-phosphorus doped foamed porous carbon material has good electrochemical properties, such as higher capacity, electrochemical activity, electrical conductivity and ion transport capacity. The nitrogen-phosphorus doped foam porous carbon material provided by the application is used as a negative electrode material of a lithium ion battery, and is beneficial to improving the electrochemical performance of the lithium ion battery.
Of course, not all advantages described above need necessarily be achieved at the same time in the practice of any embodiment of the present application.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following descriptions are only some embodiments of the present application, and those skilled in the art may obtain other embodiments according to the drawings.
FIG. 1 is an X-ray diffraction (XRD) pattern of a nitrogen-phosphorus doped foamed porous carbon material of example 1;
FIG. 2 is a Raman (Raman) spectrum of the nitrogen-phosphorus doped foamy porous carbon material of example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the nitrogen-phosphorus doped foamed porous carbon material of example 1;
FIG. 4 is a scanning electron microscope-X ray energy dispersive spectroscopy (SEM-EDX) spectrum of the nitrogen-phosphorus doped foamed porous carbon material in example 1;
FIG. 5 is a graph of the cycle performance of the nitrogen-phosphorus doped foamed porous carbon material of example 1;
FIG. 6 is a nitrogen adsorption-desorption graph of the nitrogen-phosphorus doped foamy porous carbon material in example 1;
FIG. 7 is a graph showing the pore size distribution of the nitrogen-phosphorus doped foamy porous carbon material in example 1.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the description herein are intended to be within the scope of the present disclosure. The specific technical scheme is as follows:
the first aspect of the application provides a nitrogen-phosphorus doped foamed porous carbon material, wherein based on the total mass of the nitrogen-phosphorus doped foamed porous carbon material, the mass percentage of carbon element is 85% -93%, the mass percentage of nitrogen element is 6% -12%, and the mass percentage of phosphorus element is 1% -3%; in a Raman spectrum of the nitrogen-phosphorus doped foamed porous carbon material, the nitrogen-phosphorus doped foamed porous carbon material meets the following requirements: 0<I D /I G <1.5, preferably 0.6<I D /I G <1.1, wherein I D Indicating that the corresponding peak position of the Raman spectrum is 1360cm -1 ±10cm -1 Peak intensity of time, I G Shows that the corresponding peak position of the Raman spectrum is 1590cm -1 ±10cm -1 The peak at time is strong.
For example, the carbon element may be present in an amount of 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, or any two of these ranges; the mass percentage of the nitrogen element can be 6%, 7%, 8%, 9%, 10%, 11%, 12% or the range formed by any two numerical values; the phosphorus element may be present in an amount of 1%, 2%, 3%, or any two of these ranges. By controlling the mass percentage of the carbon, nitrogen and phosphorus elements within the range, the nitrogen-phosphorus doped foamed porous carbon material can keep higher capacity, simultaneously can change the pore structure of the carbon material and generate more electrochemical active sites, and can induce carbon atoms to redistribute charges so as to increase the charge density of a doped region, thereby improving the electrochemical activity and the conductivity of the nitrogen-phosphorus doped foamed porous carbon material. In addition, various nitrogen and phosphorus-containing groups can be formed on the surface of the carbon material, and the surface chemical activity of the carbon material can be improved. For example, the interface compatibility and the wettability between the nitrogen-phosphorus doped foamy porous carbon material and the electrolyte are enhanced, and the diffusion resistance of lithium ions in pores is effectively relieved. Therefore, the nitrogen-phosphorus doped foamed porous carbon material has high capacity and abundant electrochemical active sites and surface groups by regulating and controlling the mass percentage of the carbon, nitrogen and phosphorus elements, and is favorable for improving the capacity, the electrochemical activity, the conductivity and the ion transmission capability of the nitrogen-phosphorus doped foamed porous carbon material, and further improving the electrochemical properties, such as the capacity, the cycle performance and the like, of the lithium ion battery. It should be noted that, the nitrogen-phosphorus doped porous carbon foam material usually contains some impurity elements with a low content (for example, a mass percentage content of less than or equal to 0.1%), and in the present application, when calculating the mass percentages of the above carbon element, nitrogen element and phosphorus element, "based on the total mass of the nitrogen-phosphorus doped porous carbon foam material" means the total mass obtained by excluding the above impurity elements, that is, based on the total mass of the carbon element, nitrogen element and phosphorus element, the mass percentages of the carbon element, nitrogen element and phosphorus element are further obtained.
For example, I D /I G The value of (b) can be 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.5, or a range consisting of any two of the foregoing values. By mixing I D /I G The value of (2) is controlled within the range, so that the nitrogen-phosphorus doped foamed porous carbon material has proper graphitization degree, the nitrogen-phosphorus doped foamed porous carbon material has higher specific capacity and good conductivity, and the electrochemical performance of the lithium ion battery is further improved.
On the whole, the mass percentage contents of carbon, nitrogen and phosphorus elements are regulated and controlled within the range, and the nitrogen-phosphorus doped foam porous carbon material meets the following requirements: 0<I D /I G <1.5, the obtained nitrogen-phosphorus doped foamed porous carbon material has high capacity, abundant electrochemical active sites, surface groups, pore channels and proper graphitization degree, and is beneficial to improving the capacity, electrochemical activity, conductivity and ion transmission capability of the nitrogen-phosphorus doped foamed porous carbon material. The nitrogen-phosphorus doped foam porous carbon material provided by the application is used as a negative electrode material of a lithium ion battery, and is beneficial to improving the electrochemical performance of the lithium ion battery.
In some embodiments of the present application, the nitrogen-phosphorus doped foamy porous carbon material has a specific surface area of 150m 2 /g-300m 2 (iv) g. For example, the nitrogen-phosphorus doped foamed porous carbon material may have a specific surface area of 150m 2 g -1 、180m 2 /g、200m 2 /g、220m 2 /g、250m 2 /g、270m 2 /g、290m 2 /g、300m 2 In terms of/g or any two of the above ranges. By controlling the specific surface area of the nitrogen-phosphorus doped foamed porous carbon material within the above range, the contact area between the nitrogen-phosphorus doped foamed porous carbon material and the electrolyte is increased, the transmission capability of lithium ions is improved, and the side reaction between the nitrogen-phosphorus doped foamed porous carbon material and the electrolyte is reduced, so that the electrochemical performance of the lithium ion battery is improved.
In some embodiments of the present application, the nitrogen-phosphorus doped porous foam carbon material comprises pores having a pore size of 1nm to 28nm, and the nitrogen-phosphorus doped porous foam carbon material has a porosity of 0.150cm 3 /g-0.250cm 3 (ii) in terms of/g. When the nitrogen-phosphorus doped foamed porous carbon material comprises pores with the size and the porosity is in the range, the contact area between the nitrogen-phosphorus doped foamed porous carbon material and the electrolyte is increased, a rapid lithium ion transportation channel is provided, the lithium ion transportation capacity is improved, and the electrochemical performance of the lithium ion battery is further improved.
A second aspect of the present application provides a method for preparing a nitrogen-phosphorus doped foamy porous carbon material provided by the first aspect of the present application, comprising the steps of:
(1) Adding milk powder into deionized water, and uniformly mixing to obtain milk powder emulsion; wherein based on the total mass of the milk powder, the mass percentage of the protein is 12-25%, and the mass percentage of the fat is 10-40%; the solid content of the milk powder emulsion is 1-10 wt%; the milk powder can be commercially available milk powder with the mass percentage of protein and fat within the range, and the brand and the type of the milk powder are not particularly limited;
(2) Carrying out hydro-thermal synthesis reaction on the milk powder emulsion, and drying after the reaction is finished to obtain a carbon precursor; wherein the reaction temperature of the hydro-thermal synthesis reaction is 100-140 ℃, and the reaction time is 16-20 h;
(3) Carrying out high-temperature heat treatment on the carbon precursor, cooling to room temperature, cleaning, and drying to obtain nitrogen-phosphorus doped foam porous carbon; wherein the step of high-temperature heat treatment comprises the steps of heating to 390-410 ℃ at the heating rate of 2-8 ℃/min, preserving heat for 1.5-2.5 h, heating to 500-650 ℃ at the heating rate of 2-8 ℃/min, and preserving heat for 0.5-3 h.
According to the preparation method of the nitrogen-phosphorus doped foamed porous carbon material, firstly, the milk powder is added into deionized water, milk powder emulsion is obtained after the milk powder is uniformly mixed, and then the nitrogen-phosphorus doped foamed porous carbon material is obtained through hydrothermal synthesis reaction and high-temperature heat treatment. The milk powder used in the application is also milk powder which can be directly purchased in the market, and the milk powder contains nitrogen elements and phosphorus elements, so that the nitrogen elements and the phosphorus elements do not need to be additionally introduced, the preparation method is simplified, and the cost and the difficulty of operation are reduced. Meanwhile, if the purchased milk powder is overdue and can not be eaten, the milk powder can still be used as the milk powder in the preparation method, the method is green and environment-friendly, unnecessary waste can be reduced, and the cost is reduced. In addition, compared with the prior art, the preparation of the negative active material carbon material usually needs to be completed at a high temperature (for example, the temperature is greater than or equal to 2000 ℃), the energy consumption is reduced, and the safety potential exists, while the reaction temperature of the hydrothermal synthesis reaction and the high-temperature heat treatment in the application is lower and is not more than 600 ℃, so that the energy consumption can be reduced, and the reaction safety is improved.
In some embodiments of the present application, the step of washing in step (3) comprises washing with an acid solution for 0.5h to 1.5h, and then washing with anhydrous ethanol and deionized water alternately for 3 times to 7 times; the acid in the acid solution is selected from HCl and H 2 SO 4 、HNO 3 At least one of (1). By selecting the cleaning step and the acid solution, impurities (such as metal oxide salt and the like) can be removed conveniently, and the nitrogen-phosphorus doped foamy porous carbon material with pure components can be obtained. The acid solution in this application is an aqueous solution of the above-mentioned acids. The concentration of the acid solution is not particularly limited as long as the object of the present application can be achieved, and for example, the concentration of the acid solution may be 0.5mol/L to 1.5mol/L.
The manner and speed of the "mixing" in step (1) are not particularly limited, as long as the purpose of the present invention can be achieved, for example, the mixing can be performed by magnetic stirring, specifically, the rotation speed of the magnetic stirring can be 300-800 rpm.
The temperature and time of the drying treatment in the step (2) and the step (3) are not particularly limited as long as the object of the present application can be achieved, and for example, the temperature of the drying treatment may be 40 ℃ to 80 ℃ and the time may be 18h to 30h.
The protein and fat in the milk powder are those commonly used in milk powder, and illustratively, the protein may include, but is not limited to, raw milk, whey protein powder, and the like, and the fat may include, but is not limited to, vegetable oil (e.g., rapeseed oil, sunflower oil, coconut oil, and the like), vegetable blend oil, and the like. It is understood that other necessary or optional ingredients may also be included in the milk powder, such as carbohydrates, vitamins, minerals, and the like, illustratively, carbohydrates may include, but are not limited to, and the like, vitamins may include, but are not limited to, vitamin a, vitamin B, vitamin D, vitamin E, and the like, and minerals may include, but are not limited to, calcium, sodium, iron, zinc, phosphorus, magnesium, and the like. The mass percentage of the other essential and optional ingredients is 100% minus the sum of the mass percentages of protein and fat, based on the total mass of the milk powder.
The mass percentages of carbon element, nitrogen element and phosphorus element in the nitrogen-phosphorus doped foamed porous carbon material mainly depend on the mass percentages of protein and fat in the milk powder in the preparation process, for example, the mass percentages of the protein and fat in the milk powder are increased, and the mass percentages of the nitrogen element and the phosphorus element in the nitrogen-phosphorus doped foamed porous carbon material are increased; the mass percentage of protein and fat in the milk powder is reduced, and the mass percentage of nitrogen and phosphorus in the nitrogen-phosphorus doped foam porous carbon material is reduced; the mass percentage of the carbon element in the nitrogen-phosphorus doped foam porous carbon material is changed along with the mass percentage of the nitrogen element and the phosphorus element. In general, the mass percentage of nitrogen and phosphorus in the nitrogen-phosphorus doped foamed porous carbon material can be regulated by changing the temperature and time of the high-temperature heat treatment. For example, when the temperature of the high-temperature heat treatment is increased, the mass percentage of nitrogen elements and the mass percentage of phosphorus elements in the nitrogen-phosphorus doped foamed porous carbon material are reduced; the temperature of high-temperature heat treatment is reduced, the mass percentage of nitrogen elements in the nitrogen-phosphorus doped foamed porous carbon material is increased, and the mass percentage of phosphorus elements in the nitrogen-phosphorus doped foamed porous carbon material is increased. The high-temperature heat treatment time is prolonged, the mass percentage content of nitrogen elements in the nitrogen-phosphorus doped foam porous carbon material is reduced, and the mass percentage content of phosphorus elements is reduced; the time of high-temperature heat treatment is shortened, the mass percentage of nitrogen elements in the nitrogen-phosphorus doped foam-like porous carbon material is increased, and the mass percentage of phosphorus elements in the nitrogen-phosphorus doped foam-like porous carbon material is increased. The mass percentage of the carbon element in the nitrogen-phosphorus doped foamed porous carbon material is changed along with the change of the mass percentage of the nitrogen element and the phosphorus element.
In general, the temperature rise rate and the time of the high-temperature heat treatment can be changed to regulate and control the I of the nitrogen-phosphorus doped foamed porous carbon material D /I G Specific surface area and pore size. For example, increasing the temperature of high temperature heat treatment, I of Nitrogen-phosphorus doped foamed porous carbon Material D /I G Will be reduced and the specific surface area will be reducedThe pore size will decrease; lowering the temperature of high-temperature heat treatment, nitrogen-phosphorus doped foamed porous carbon Material I D /I G The specific surface area increases and the pore diameter increases. Increasing the rate of temperature rise of high temperature heat treatment, nitrogen-phosphorus doped foamed porous carbon materials I D /I G The specific surface area and the pore diameter are reduced; nitrogen-phosphorus doped foamed porous carbon material I for reducing the rate of temperature rise in high temperature heat treatment D /I G The specific surface area is increased and the pore diameter is increased. Extended duration high temperature Heat treatment of Nitrogen-phosphorus doped foamed porous carbon Material I D /I G The specific surface area and the pore diameter are reduced; shortening of high-temperature Heat treatment time, nitrogen-phosphorus doped foamed porous carbon Material I D /I G The specific surface area increases and the pore diameter increases.
A third aspect of the present application provides a negative electrode sheet comprising a negative electrode material layer comprising a negative electrode material comprising a nitrogen-phosphorus doped foamed porous carbon material as provided in the first aspect of the present application.
In some embodiments of the present application, the nitrogen-phosphorus doped foamy porous carbon material is in a mass percentage of 70% to 95% based on the total mass of the anode material layer. For example, the nitrogen-phosphorus doped foamed porous carbon material may be present in an amount of 70%, 75%, 80%, 85%, 90%, 95%, or any combination thereof. By controlling the mass percentage of the nitrogen-phosphorus doped foamy porous carbon material within the range, the negative pole piece with high capacity and good conductivity can be obtained, and the electrochemical performance of the lithium ion battery can be further improved.
In the present application, the negative electrode material layer may further include a conductive agent and a binder, and the conductive agent and the binder known in the art may be used, which is not limited in the present application. In the present application, the negative electrode tab includes a negative electrode current collector and a negative electrode material layer disposed on at least one surface of the negative electrode current collector. The above-mentioned "negative electrode material layer disposed on at least one surface of the negative electrode current collector" means that the negative electrode material layer may be disposed on one surface of the negative electrode current collector in the thickness direction of the negative electrode current collector, or may be disposed on both surfaces of the negative electrode current collector in the thickness direction of the negative electrode current collector. The "surface" herein may be the entire region of the negative electrode current collector or a partial region of the negative electrode current collector, and the present application is not particularly limited as long as the object of the present application can be achieved. The negative electrode current collector may be any one known in the art, and is not limited in this application.
A fourth aspect of the present application provides a lithium ion battery comprising a positive electrode sheet, an electrolyte, a separator, and a negative electrode sheet in any of the above embodiments of the present application. Therefore, the lithium ions provided by the application have good electrochemical performance. The positive electrode plate, the electrolyte and the separator may be those known in the art, and the application is not limited thereto. The preparation process of the lithium ion battery of the present application is well known to those skilled in the art, and the present application is not limited thereto.
Examples
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. Various tests and evaluations were carried out according to the following methods. Unless otherwise specified, "part" and "%" are based on mass.
The test method and the test equipment are as follows:
XRD test:
the sample powder of the nitrogen-phosphorus doped foamed porous carbon material in the example or the negative active material in the comparative example was placed in an XRD test instrument sample stage, and an XRD diffractogram was obtained using a scanning rate of 5 °/min at a scanning angle ranging from 10 ° to 80 °. The phase analysis was performed on the characteristic peaks of the sample powder in combination with the analysis software MDI Jade 6.0.
And (4) Raman testing:
the nitrogen-phosphorus doped foamed porous carbon material is tested by using a Raman spectrometer, an excitation light source is a He-Ne laser, the wavelength of the excitation light source is 532nm, and the test range is 250cm -1 To 3250cm -1 。
And (3) morphology characterization:
a conductive adhesive is stuck on a sample stage, a powder sample of the nitrogen-phosphorus doped foamed porous carbon material in the example or the negative electrode active material in the comparative example is spread on the conductive adhesive, the powder which is not adhered is blown away by an ear washing ball, gold spraying is performed, and morphology observation is performed on the powder sample by using a scanning electron microscope (model: HITACHI S-4800).
Testing of element content:
the nitrogen-phosphorus doped foamed porous carbon material in the test example or the element content by mass of the negative electrode active material in the comparative example was scanned under conditions of an acceleration voltage of 10kV and an emission current of 10mA using EDX equipped with a scanning electron microscope (model: HITACHI S-4800).
Nitrogen adsorption-desorption curves and specific surface area testing:
the nitrogen adsorption-desorption curves of the nitrogen-phosphorus doped foamed porous carbon material in the examples or the negative electrode active material in the comparative example were tested using a fully automatic nitrogen adsorption micropore distribution tester (manufacturer: congtar corporation, model: QUADRASORB SI) and the specific surface areas of the nitrogen-phosphorus doped foamed porous carbon material in the examples or the negative electrode active material in the comparative example were obtained.
Pore size distribution and porosity of the pores:
the porosity of the nitrogen-phosphorus doped foamed porous carbon material in the examples or the negative electrode active material in the comparative example and whether or not there is a pore having a pore diameter of 1nm to 28nm, if any, were recorded as "yes" were measured using a fully automatic nitrogen adsorption micropore distribution tester (manufacturer: congta, USA, model: QUADRASORB SI); if not, the result is recorded as 'no'.
Testing the coulombic efficiency for the first time:
at the test temperature of 25 ℃, the lithium ion battery is charged to 1.5V at a constant current of 400mA/g, stands for 10 seconds, then is discharged to 0.01V at 400mA/g, stands for 10 seconds, tests the first charge capacity and the first discharge capacity of the lithium ion battery, then carries out 300 discharge and charge cycles in the same steps, records the charge capacity and the discharge capacity of the lithium ion battery in each cycle, and calculates the first coulombic efficiency according to the following formula: primary coulombic efficiency = primary charge capacity/primary discharge capacity × 100%.
The nth coulombic efficiency = nth charge capacity/nth discharge capacity × 100%, and N is a positive integer of 1 to 300, so that a change curve of the coulombic efficiency of the lithium ion battery with the number of cycles can be obtained.
Testing of cycle capacity retention:
in an environment of 25 ℃, charging the lithium ion battery to 1.5V at a constant current of 400mA/g, standing for 10 seconds, then discharging to 0.01V at 400mA/g, standing for 10 seconds, and recording the discharge capacity of the first cycle. And then, carrying out 300 times of discharging and charging cycles in the same step, and recording the discharging capacity of the lithium ion battery in each cycle to obtain a variation curve of the capacity of the lithium ion battery along with the number of cycles.
Cycle capacity retention (%) of the lithium ion battery (300 th cycle discharge capacity/first cycle discharge capacity) × 100%.
Example 1
< preparation of Nitrogen-phosphorus doped foamed porous carbon Material >
(1) Weighing 5g of milk powder (Nestleyi Yun whole family nutritious milk powder, product standard code: GB 19644), adding 95mL of deionized water, and uniformly mixing to obtain milk powder emulsion with the solid content of 5wt%, wherein the mass percentage of protein and the mass percentage of fat in the milk powder are respectively 18% and 11.7%.
(2) And then transferring 50mL of the milk powder emulsion into a 100mL reaction kettle, reacting for 18h at 120 ℃, naturally cooling to room temperature, performing suction filtration, and drying at 60 ℃ to obtain the carbon precursor.
(3) Transferring the carbon precursor into a porcelain boat, placing the porcelain boat in a tube furnace, then heating to T1=400 ℃ at a heating rate of 5 ℃/min, keeping the temperature for T1=1h, heating to T2=550 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for T2=2h. And naturally cooling to room temperature, washing for 1h by using 1mol/L HCl, then alternately washing for 5 times by using absolute ethyl alcohol and deionized water, and then drying for 24h at the temperature of 60 ℃ to obtain the nitrogen-phosphorus doped foamed porous carbon material.
< preparation of negative electrode sheet >
Mixing a nitrogen-phosphorus doped foamy porous carbon material, conductive carbon black and polyvinylidene fluoride according to a mass ratio of 8. Uniformly coating the negative electrode slurry on one surface of a negative electrode current collector copper foil with the thickness of 18 mu m, drying at 70 ℃ under a vacuum condition to obtain a negative electrode plate with the coating thickness of 100 mu m and a single-side coated negative electrode active material layer, and cutting into 1.13cm by using a battery plate slicing machine 2 The negative pole piece is ready for use.
< lithium sheet >
The adopted area is 1.91cm 2 And a lithium sheet having a thickness of 0.5mm (provided by municin, xinghua, inc.).
< preparation of electrolyte solution >
In a dry argon atmosphere glove box, organic solvents of dimethyl carbonate (DMC), diethyl carbonate (DEC) and Ethylene Carbonate (EC) were mixed at a volume ratio of =1 6 ) And dissolving and uniformly mixing to obtain electrolyte with the lithium salt concentration of 1 mol/L.
< preparation of separator >
A porous polyethylene film (Celgard 2400, supplied by Celgard corporation) having a thickness of 14 μm was used.
< preparation of button cell >
In the glove box, according to the positive electrode shell (CR 2032), the negative electrode pole piece, the diaphragm, the electrolyte (40 microliter), the lithium piece and the gasket (the area is 1.91 cm) 2 The thickness is 1 mm), the spring plate and the cathode shell (CR 2032) are arranged from bottom to top in sequence, and the button cell is obtained by packaging with a cell packaging machine (provided by Hefei Kejing Co., ltd.) under the pressure of 12.6 MP. The positive casing, the spacer, the spring plate and the negative casing are all provided by kruede co.
Examples 2 to 12
The procedure was as in example 1, except that the relevant production parameters were adjusted as shown in Table 1.
The preparation parameters and performance parameters of the examples are shown in tables 1 to 2.
TABLE 1
TABLE 2
As can be seen from examples 1 to 12, the nitrogen-phosphorus doped foamed porous carbon material provided in the present application was used as the negative electrode active material, in which the mass percentages of carbon, nitrogen, and phosphorus elements and I D /I G The value of (b) is within the range of the application, and the obtained lithium ion battery has higher capacity and good cycle performance.
Specifically, fig. 1 is an XRD spectrum of the nitrogen-phosphorus doped foamed porous carbon material of example 1, and it can be seen from fig. 1 that there is a distinct bulge at 23 °, indicating that the nitrogen-phosphorus doped foamed porous carbon material prepared by the present application is a mainly amorphous carbon material. FIG. 2 is a Raman spectrum of the nitrogen-phosphorus doped porous carbon foam of example 1, I D /I G A value of 0.73 also indicates that the nitrogen-phosphorus doped porous carbon material produced herein is a predominantly amorphous carbon material. Fig. 3 is an SEM photograph of the nitrogen-phosphorus doped foamy porous carbon material in example 1, wherein a-d in fig. 3 are SEM photographs at different magnifications, and it can be seen from a and b in fig. 3 that the nitrogen-phosphorus doped foamy porous carbon material is a porous carbon material assembled by small carbon spheres, has a micron-sized size, and has a three-dimensional porous foam as a whole; as can be seen from c and d in fig. 3, the above porous foam shape is composed of nano-sized beads. FIG. 4 is an SEM-EDX spectrum of the nitrogen-phosphorus doped foamed porous carbon material of example 1 further demonstrating the presence of carbon, nitrogen and phosphorus elements, carbon atomsThe mass percentages of the elements, nitrogen and phosphorus are shown in Table 2. FIG. 5 is a chart of the cycling charge and discharge performance test of the button cell in example 1 at 400mA/g current density, and it can be seen that the irreversible capacity appearing at circle 1 is related to the growth of the solid electrolyte membrane (SEI film), the capacity gradually becomes stable during the subsequent charge and discharge cycles, and the reversible capacity is 360.9mAh g after 300 cycles -1 The coulombic efficiency is 99.9%, namely the coulombic efficiency is good in cycle performance, so that the nitrogen-phosphorus doped foam porous carbon material provided by the application is suitable for serving as a negative electrode material of a lithium ion battery.
The specific surface area porosity, the pore volume and the pore size distribution of the nitrogen-phosphorus doped foamed porous carbon material generally affect the capacity retention rate and the first coulombic efficiency of the lithium ion battery, and as can be seen from examples 1 to 12, the specific surface area, the porosity and the pore size distribution of the nitrogen-phosphorus doped foamed porous carbon material are within the range of the application, and the obtained lithium ion battery has better capacity retention rate and first coulombic efficiency. Specifically, FIG. 6 is a nitrogen adsorption-degradation graph of the nitrogen-phosphorus doped foamed porous carbon material of example 1, which was calculated to have a specific surface area of 228.2m 2 g -1 . FIG. 7 is a graph showing the distribution of pore sizes of the nitrogen-phosphorus doped porous carbon foam material of example 1, and it can be seen that the pore sizes of the nitrogen-phosphorus doped porous carbon foam material are mainly concentrated between 2nm and 5nm, indicating that it has relatively abundant mesopores.
The temperature and time of the hydrothermal synthesis reaction, and the temperature, temperature rise rate and time of the high-temperature heat treatment during the preparation process generally affect the capacity, specific surface area and content of each element of the nitrogen-phosphorus doped foamed porous carbon material, and it can be seen from examples 1 to 12 that by adjusting the above preparation parameters within the range of the present application, the capacity, specific surface area and content of each element of the obtained nitrogen-phosphorus doped foamed porous carbon material are also within the range of the present application, and the obtained battery also has higher capacity and good cycle performance.
It will be appreciated that the preparation of nitrogen-phosphorus doped porous carbon material from nesteyr whole-house nutritious milk powder in examples 1 to 12 above is merely exemplary and that other milk powders having protein and fat mass percentages within the scope of the present application may be used as long as the objects of the present application are achieved.
It should be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, or article that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, or article.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present application, and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.
Claims (8)
1. A nitrogen-phosphorus doped foamed porous carbon material comprises, based on the total mass of the nitrogen-phosphorus doped foamed porous carbon material, 85% -93% by mass of carbon element, 6% -12% by mass of nitrogen element and 1% -3% by mass of phosphorus element;
in a raman spectrum of the nitrogen-phosphorus doped foamed porous carbon material, the nitrogen-phosphorus doped foamed porous carbon material satisfies: 0<I D /I G <1.5, wherein I D Indicating that the corresponding peak position of the Raman spectrum is 1360cm -1 ±10cm -1 Peak intensity of time I G Indicating that the corresponding peak position of the Raman spectrum is 1590cm -1 ±10cm -1 The peak at time is strong.
2. The nitrogen-phosphorus doped foamed porous carbon material as claimed in claim 1, which has a specific surface area of 150m 2 /g-300m 2 /g。
3. The nitrogen-phosphorus doped foamed porous carbon material of claim 1 comprising pores with a pore size of 1nm-28nm, the nitrogen-phosphorus doped foamed porous carbon material having a porosity of 0.150cm 3 /g-0.250cm 3 /g。
4. A method for producing a nitrogen-phosphorus doped foamed porous carbon material according to any one of claims 1 to 3, comprising the steps of:
(1) Adding the milk powder into deionized water, and uniformly mixing to obtain milk powder emulsion; based on the total mass of the milk powder, the mass percentage of protein is 12% -25%, and the mass percentage of fat is 10% -40%; the solid content of the milk powder emulsion is 1-10 wt%; /
(2) Carrying out hydro-thermal synthesis reaction on the milk powder emulsion, and drying after the reaction is finished to obtain a carbon precursor; wherein the reaction temperature of the hydrothermal synthesis reaction is 100-140 ℃, and the reaction time is 16-20 h;
(3) Carrying out high-temperature heat treatment on the carbon precursor, cooling to room temperature, cleaning, and drying to obtain a nitrogen-phosphorus doped foamy porous carbon material; wherein the high-temperature heat treatment comprises the steps of heating to 390-410 ℃ at a heating rate of 2-8 ℃/min, keeping the temperature for 1.5-2.5 h, heating to 500-650 ℃ at a heating rate of 2-8 ℃/min, and keeping the temperature for 0.5-3 h.
5. The preparation method according to claim 4, wherein the step of washing comprises washing with an acid solution for 0.5-1.5 h, and then washing with absolute ethyl alcohol and deionized water alternately for 3-7 times; the acid in the acid solution is selected from HCl and H 2 SO 4 、HNO 3 At least one of (1).
6. A negative electrode tab comprising a negative electrode material layer comprising a negative electrode material comprising the nitrogen-phosphorus doped foamy porous carbon material of any one of claims 1-3.
7. The negative electrode tab of claim 6, wherein the nitrogen-phosphorus doped foamed porous carbon material is in a mass percentage of 70 to 95% based on the total mass of the negative electrode material layer.
8. A lithium ion battery comprising the negative electrode sheet of any one of claims 6 to 7.
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| CN106601490A (en) * | 2016-06-21 | 2017-04-26 | 中国科学院青岛生物能源与过程研究所 | Preparation method of biomass-based nitrogenous porous carbon, porous carbon prepared by method and use thereof |
| CN110615424A (en) * | 2019-10-25 | 2019-12-27 | 河北省科学院能源研究所 | Nitrogen-phosphorus doped porous carbon material and preparation method and application thereof |
| CN114628683A (en) * | 2022-03-25 | 2022-06-14 | 浙江大学 | Biological carbon/(CuNiCo) for lithium-sulfur battery3P composite material and preparation method thereof |
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| CN110615424A (en) * | 2019-10-25 | 2019-12-27 | 河北省科学院能源研究所 | Nitrogen-phosphorus doped porous carbon material and preparation method and application thereof |
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