CN110880595A - Cu3Preparation method of P-CuO composite flexible lithium ion battery cathode material - Google Patents
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Abstract
The invention provides a Cu3Method for preparing P-CuO composite flexible lithium ion battery cathode material, Cu3P and CuO are compounded in situ and stably grow on the surface of the copper foil, and the method comprises the following specific steps: placing a copper foil in a muffle furnace at 100-300 ℃ for pre-oxidation treatment for 15 min-1 h, weighing sodium hypophosphite, flatly placing the sodium hypophosphite at the bottom of a ceramic material boat, placing the pre-oxidized copper foil right above the ceramic material boat, covering the copper foil with copper foam, placing the ceramic material boat in a tube furnace, under the condition that argon is used as protective gas, heating at the speed of 1-5 ℃/min, sintering at the temperature of 250-350 ℃, keeping the temperature for 15 min-5 h, and naturally cooling to obtain Cu3The P-CuO flexible electrode material is used as a negative electrode of a lithium ion battery and shows good electrochemical performance. The invention prepares Cu with certain flexibility for the first time3P-CuO compositeA lithium ion battery cathode material. The synthesis process is simple and novel, easy to operate and low in synthesis cost; the obtained sample has good conductivity and good crystallization performance; electrochemical performance tests show that the material has obvious charge and discharge platforms and better cycle stability.
Description
Technical Field
The invention relates to a composite lithium ion battery cathode material with flexibility, in particular to Cu3A preparation method of a P-CuO composite flexible lithium ion battery cathode material belongs to the field of electrochemical power sources.
Background
The energy source is the material foundation that supports the entire human civilization. With the rapid development of social economy, the dependence of people on energy is continuously improved. At present, a great deal of traditional fossil energy such as coal, petroleum, natural gas and the like are developed and used, the problems of air pollution, emission of greenhouse gas and the like are increasingly prominent, and the life of people is directly influenced. With the increasingly serious energy crisis and environmental pollution, changing the existing unreasonable energy structure is the first problem facing human sustainable development. Therefore, the search for renewable clean and environment-friendly alternative energy sources is urgent. Renewable clean energy sources such as wind energy, water energy and solar energy which are developed and utilized at present are random and intermittent, so that the development of high-performance energy storage equipment is a new challenge.
As a high-performance energy storage device, the lithium ion battery has advantages of high specific capacity, high cycle performance, environmental friendliness, no memory effect, and the like, and occupies a leading position in the current energy storage market, and is widely applied to portable electronic devices and power vehicles. At present, the commercial lithium ion battery cathode material is mainly a graphite carbon material, the lower theoretical capacity and the potential safety hazard of lithium dendrite precipitation are keys for restricting the development of the lithium ion battery cathode material, and the development of a novel lithium ion battery cathode material is particularly urgent. Copper phosphide is a promising anode material, and is an ideal lithium ion battery cathode material due to a safer charging and discharging voltage platform and a higher volume specific capacity. Cu3P exhibits poor electrochemical performance due to its poor electronic conductivity and volume effects during cycling. Therefore, research has been focused primarily on enhancing Cu3The conductivity of the P material and how to improve the cycling performance of the material. Based on the background, the invention uses sodium hypophosphite as a phosphorus source, uses the pre-oxidized copper foil as a copper source, and prepares the Cu with certain flexibility for the first time by low-temperature gas-solid reaction and controlling the phosphating amount3The P-CuO flexible electrode material is used as a lithium ion battery cathode material, and shows good electrochemical performance and cycling stability.
Disclosure of Invention
The invention aims to use sodium hypophosphite and copper foil as raw materials to prepare the copper-clad copper foilPreoxidation and low-temperature gas-solid reaction are carried out and the phosphorization process is controlled, so that Cu is successfully prepared3P-CuO flexible electrode material is used as the cathode of the lithium ion battery. The principle is that partial copper oxide is obtained on the surface of copper foil by utilizing the pre-oxidation process, and then PH is decomposed by sodium hypophosphite3Gas direct reduction of copper oxide to Cu3P, avoiding complete phosphating of the copper oxide by covering the copper foil with copper foam, the remaining copper matrix giving it a certain flexibility, the Cu obtained3P and CuO are uniformly compositely grown on the surface of the copper foil and have certain stability, and the copper foil used as a current collector and a matrix enhances the conductivity of the material and controls the volume effect of the material, so that the Cu3The P-CuO flexible electrode material has better electrochemical performance when being used as a lithium ion battery cathode material.
The preparation method of the invention specifically comprises the following steps: cutting a copper foil into certain small pieces, placing the small pieces in a muffle furnace at 100-300 ℃ for preoxidation for 15 min-1 h (as a preferred scheme, the preoxidation temperature is 100 ℃, the preoxidation time is 15 min), weighing a certain amount of sodium hypophosphite, flatly paving the sodium hypophosphite at the bottom of a ceramic material boat, placing the preoxidized copper foil right above the ceramic material boat (the addition amount of the sodium hypophosphite is 10-50 times of the mass of the copper foil), covering the copper foil with foamed copper, placing the ceramic material boat in a tube furnace, under the protection of inert atmosphere of argon or nitrogen, heating up at a speed of 1-5 ℃/min, sintering at a temperature of 250-350 ℃, and preserving heat for 15 min-5 h (as a preferred condition, in the sintering process, the heating up speed is 3 ℃/min, the sintering temperature is 300 ℃, the preserving heat for 30 min), naturally cooling to obtain Cu3The invention discloses a P-CuO flexible electrode material, and Cu with certain flexibility is prepared for the first time3The P-CuO flexible electrode material is used as a lithium ion battery cathode.
According to the above, the present invention also provides Cu3A preparation method of a P-CuO composite flexible lithium ion battery cathode material comprises the steps of preparing a citric acid solution with a certain concentration (the concentration range of the citric acid solution is 1-10 g/L), treating foam copper cut into certain small blocks for 10-30 min by using the citric acid solution, drying the foam copper by blowing, then placing the foam copper in a muffle furnace for pre-oxidation treatment at 100-300 ℃ for 15 min-1 h,weighing a certain amount of sodium hypophosphite, flatly paving the sodium hypophosphite at the bottom of a ceramic material boat, placing pre-oxidized copper foam right above the ceramic material boat, placing the ceramic material boat in a tube furnace, taking inertia as protective gas, heating up at the speed of 1-5 ℃/min, sintering at the temperature of 300-400 ℃, keeping the temperature for 15 min-5 h, and naturally cooling to obtain Cu3P-CuO/C composite electrode material (as a preferred scheme, the inert atmosphere is nitrogen or argon, the heating rate is 3 ℃/min, the sintering temperature is 350 ℃, and the heat preservation time is 1 h)3The P-CuO/C composite electrode material is used as the cathode of the lithium ion battery.
The invention relates to Cu3The P-CuO flexible electrode material and the preparation method thereof have the following remarkable characteristics:
(1) the synthesis method is simple and novel, easy to operate and low in cost;
(2) the obtained sample has good conductivity, good crystallization performance and high purity;
(3) electrochemical performance tests show that the material has obvious charge and discharge platforms and better cycle stability.
Drawings
Figure 1 XRD pattern of the sample prepared in example 1.
FIG. 2 SEM image of sample prepared in example 1.
FIG. 3 Cyclic voltammogram of the sample prepared in example 1.
FIG. 4 is a graph of (a) first charge and discharge curves and (b) cycle performance of samples prepared according to example 1.
FIG. 5 is a graph of (a) first charge and discharge curves and (b) cycle performance for samples prepared according to example 2.
FIG. 6 is a graph of (a) first charge and discharge curves and (b) cycle performance for samples prepared in example 3.
FIG. 7 SEM image of sample prepared in example 4.
FIG. 8 Cyclic voltammogram of the sample prepared in example 4.
FIG. 9 is a graph of (a) first charge and discharge curves and (b) cycle performance for samples prepared according to example 4.
FIG. 10 is a graph of (a) first charge and discharge curves and (b) cycle performance of samples prepared according to example 5.
FIG. 11 is a graph of (a) first charge and discharge curves and (b) cycle performance for samples prepared in example 6.
Detailed Description
Example 1
Cutting copper foil into 1 × 4cm pieces, placing in a muffle furnace at 100 deg.C for pre-oxidation treatment for 15min, weighing 0.4g sodium hypophosphite, spreading at the bottom of a ceramic material boat, placing the pre-oxidized copper foil right above the ceramic material boat, covering with copper foam, placing the ceramic material boat in a tube furnace, heating at a temperature of 3 deg.C/min under the protection of argon gas, sintering at 300 deg.C for 30min, and naturally cooling to obtain Cu3P-CuO flexible electrode material. XRD analysis of the sample was carried out, and it can be seen from FIG. 1 that three diffraction peaks at 44.4 °, 51.7 ° and 76.4 ° correspond to diffraction peaks of Cu (JCPDS, No.04-0836), and diffraction peaks at 36.0 °, 39.0 °, 41.6 °, 45.1 ° and 46.1 ° correspond to diffraction peaks of Cu3Diffraction peak of P (JCPDS, No. 65-3628). Since the copper oxide is too amorphous, no diffraction peak is evident. SEM representation is carried out on a sample, and as can be seen from figure 2, particles of the prepared material are uniformly distributed, the particle size is about 50-100 nm, and the particles successfully grow on the surface of the copper foil. The materials obtained in the examples were made into batteries as follows: the prepared sample was cut into 0.5X 0.5cm pieces and vacuum-dried at 120 ℃ for 12 hours. The lithium metal sheet is taken as a counter electrode, a high polymer film (PE-PP-PE) is taken as a diaphragm, and LiPF is dissolved6The (1 mmol/L) EC + DEC (volume ratio of 1: 1) solution is used as electrolyte and assembled into a CR2025 type battery in a glove box protected by argon. Standing for 8h after the cell is assembled, performing cyclic voltammetry on the cell by using a CHI600 electrochemical workstation, wherein the scanning speed is 0.01mV/s, and the prepared Cu is shown in figure 33The first cyclic voltammetry curve of the P-CuO flexible electrode material, the reduction peaks of about 2.28V, 1.9V, 1.46V and 1.2V and the oxidation peaks of 1.9V and 2.4V correspond to the reduction and oxidation processes of CuO, and the reduction peaks of 0.8V and 0.65V correspond to the oxidation peaks of 0.8V, 1.1V, 1.2V and 1.28VIn Cu3P reduction and oxidation process shows that Cu is successfully prepared3A composite of P and CuO. And performing constant-current charge and discharge test by using a CT2001 battery test system, wherein the test voltage is 0.02-3V, the current density is 125mA/g, and the prepared Cu is shown in figure 43The first charge and discharge curve (a) and the cycle performance graph (b) of the P-CuO flexible electrode material are shown in the figure, the first charge and discharge specific capacities are respectively 325.1 and 699.2mAh/g, an obvious charge and discharge platform is provided, the charge and discharge capacities after 50 times of cycle are respectively 325.2 and 327.8mAh/g, and the P-CuO flexible electrode material shows better electrochemical performance.
Example 2
Cutting copper foil into 1 × 4cm pieces, placing in a muffle furnace at 100 deg.C for pre-oxidation treatment for 30min, weighing 0.2g sodium hypophosphite, spreading at the bottom of a ceramic material boat, placing the pre-oxidized copper foil right above the ceramic material boat, covering with copper foam, placing the ceramic material boat in a tube furnace, heating at 5 deg.C/min under the protection of argon gas at 350 deg.C for 15min, and naturally cooling to obtain Cu3P-CuO flexible electrode material. The materials obtained in the examples were made into batteries as follows: the prepared sample was cut into 0.5X 0.5cm pieces and vacuum-dried at 120 ℃ for 12 hours. The lithium metal sheet is taken as a counter electrode, a high polymer film (PE-PP-PE) is taken as a diaphragm, and LiPF is dissolved6The (1 mmol/L) EC + DEC (volume ratio of 1: 1) solution is used as electrolyte and assembled into a CR2025 type battery in a glove box protected by argon. Standing for 8h after the battery is assembled, and performing constant-current charge and discharge test by using a CT2001 battery test system, wherein the test voltage is 0.02-3V, the current density is 125mA/g, and the prepared Cu is shown in figure 53The first charge and discharge curve (a) and the cycle performance graph (b) of the P-CuO flexible electrode material are shown in the figure, the first charge and discharge specific capacities are 336.7 mAh/g and 701.1mAh/g respectively, an obvious charge and discharge platform is provided, the charge and discharge capacities after 50 times of cycle are 223.1 mAh/g and 225.6mAh/g respectively, and the good electrochemical performance is shown.
Example 3
Cutting copper foil into 1 × 4cm pieces, pre-oxidizing at 200 deg.C in muffle furnace for 15min, weighing 0.6g sodium hypophosphite, and spreadingPlacing a pre-oxidized copper foil right above the ceramic material boat at the bottom of the ceramic material boat, covering the ceramic material boat with copper foam, placing the ceramic material boat in a tube furnace, under the condition of argon as protective gas, heating at the speed of 3 ℃/min, sintering at the temperature of 350 ℃, keeping the temperature for 1h, and naturally cooling to obtain Cu3P-CuO flexible electrode material. The materials obtained in the examples were made into batteries as follows: the prepared sample was cut into 0.5X 0.5cm pieces and vacuum-dried at 120 ℃ for 12 hours. The lithium metal sheet is taken as a counter electrode, a high polymer film (PE-PP-PE) is taken as a diaphragm, and LiPF is dissolved6The (1 mmol/L) EC + DEC (volume ratio of 1: 1) solution is used as electrolyte and assembled into a CR2025 type battery in a glove box protected by argon. Standing for 8h after the battery is assembled, and performing constant-current charge and discharge test by using a CT2001 battery test system, wherein the test voltage is 0.02-3V, the current density is 125mA/g, and the prepared Cu is shown in figure 63The first charge and discharge curve (a) and the cycle performance graph (b) of the P-CuO flexible electrode material are shown in the figure, the first charge and discharge specific capacities are respectively 320.3 mAh/g and 789.1mAh/g, an obvious charge and discharge platform is provided, the charge and discharge capacities after 50 times of cycle are respectively 183.1 mAh/g and 180.6mAh/g, and the good electrochemical performance is shown.
Example 4
Preparing 1g/L citric acid solution, processing 2.5 multiplied by 4cm of foam copper cut into 2.5 cm with the citric acid solution for 10min, drying the foam copper, then placing the foam copper in a muffle furnace for preoxidation treatment at 150 ℃ for 1h, weighing 0.2g of sodium hypophosphite, flatly paving the sodium hypophosphite at the bottom of a ceramic material boat, placing the preoxidized foam copper right above the ceramic material boat, placing the ceramic material boat in a tube furnace, taking argon as protective gas, heating at the speed of 3 ℃/min, sintering at the temperature of 350 ℃, keeping the temperature for 1h, and naturally cooling to obtain Cu3P-CuO/C composite electrode material. The sample was subjected to SEM characterization, and as can be seen from FIG. 7, a layer of material with uniform thickness was grown on the surface of the copper foam, and hundreds of nanometers of pores were uniformly distributed on the surface. The materials obtained in the examples were made into batteries as follows: the prepared sample was cut into 0.5X 0.5cm pieces and vacuum-dried at 120 ℃ for 12 hours. The lithium metal sheet is taken as a counter electrode, a high polymer film (PE-PP-PE) is taken as a diaphragm, and LiPF is dissolved6The (1 mmol/L) EC + DEC (volume ratio of 1: 1) solution is used as electrolyte and assembled into a CR2025 type battery in a glove box protected by argon. After the cell was assembled, the cell was left to stand for 8 hours, and subjected to cyclic voltammetry by using CHI600 electrochemical workstation at a scanning speed of 0.01mV/s, FIG. 8 shows the Cu prepared3The first cyclic voltammetry curve of the P-CuO/C composite electrode material has obvious CuO redox peak and Cu3P oxidation reduction peak, indicating successful Cu preparation3A composite of P and CuO. Performing constant-current charge and discharge test by using a CT2001 battery test system, wherein the test voltage is 0.02-3V, the current density is 200mA/g, and the prepared Cu is shown in figure 93The first charge and discharge curve (a) and the cycle performance graph (b) of the P-CuO/C composite electrode material. As shown in the figure, the first charging and discharging specific capacities are 411.3 and 924.2mAh/g respectively, the charging and discharging platforms are obvious, the charging and discharging capacities after 50 times of circulation are 192.2 and 197.8mAh/g respectively, and the good electrochemical performance is shown.
Example 5
Preparing 2g/L citric acid solution, processing 2.5 multiplied by 4cm of foam copper cut into 2.5 cm with the citric acid solution for 10min, drying the foam copper, then placing the foam copper in a muffle furnace for preoxidation at 100 ℃ for 10min, weighing 0.4g of sodium hypophosphite, flatly paving the sodium hypophosphite at the bottom of a ceramic material boat, placing the preoxidized foam copper right above the ceramic material boat, placing the ceramic material boat in a tube furnace, taking argon as protective gas, heating at the speed of 3 ℃/min, sintering at the temperature of 400 ℃, keeping the temperature for 2h, and naturally cooling to obtain Cu3P-CuO/C composite electrode material. The materials obtained in the examples were made into batteries as follows: the prepared sample was cut into 0.5X 0.5cm pieces and vacuum-dried at 120 ℃ for 12 hours. The lithium metal sheet is taken as a counter electrode, a high polymer film (PE-PP-PE) is taken as a diaphragm, and LiPF is dissolved6The (1 mmol/L) EC + DEC (volume ratio of 1: 1) solution is used as electrolyte and assembled into a CR2025 type battery in a glove box protected by argon. Standing for 8 hours after the battery is assembled, and performing constant-current charge and discharge test by using a CT2001 battery test system, wherein the test voltage is 0.02-3V, the current density is 200mA/g, and the prepared Cu is shown in figure 103First charge and discharge curve (a) and cycle of P-CuO/C composite electrode materialRing performance graph (b). As shown in the figure, the first charging and discharging specific capacities are 395.1 mAh/g and 789.2mAh/g respectively, the charging and discharging platforms are obvious, the charging and discharging capacities after 50 times of circulation are 165.2 mAh/g and 177.8mAh/g respectively, and the good electrochemical performance is shown.
Example 6
Preparing 5g/L citric acid solution, processing 2.5 multiplied by 4cm of foam copper cut into 2.5 cm with the citric acid solution for 10min, drying the foam copper, then placing the foam copper in a muffle furnace for pre-oxidation treatment at 100 ℃ for 15min, weighing 0.4g of sodium hypophosphite, flatly paving the sodium hypophosphite at the bottom of a ceramic material boat, placing the pre-oxidized foam copper right above the ceramic material boat, placing the ceramic material boat in a tube furnace, taking argon as protective gas, heating at the speed of 3 ℃/min, sintering at the temperature of 350 ℃, keeping the temperature for 1h, and naturally cooling to obtain Cu3P-CuO/C composite electrode material. The materials obtained in the examples were made into batteries as follows: the prepared sample was cut into 0.5X 0.5cm pieces and vacuum-dried at 120 ℃ for 12 hours. The lithium metal sheet is taken as a counter electrode, a high polymer film (PE-PP-PE) is taken as a diaphragm, and LiPF is dissolved6The (1 mmol/L) EC + DEC (volume ratio of 1: 1) solution is used as electrolyte and assembled into a CR2025 type battery in a glove box protected by argon. Standing for 8 hours after the battery is assembled, and performing constant-current charge and discharge test by using a CT2001 battery test system, wherein the test voltage is 0.02-3V, the current density is 200mA/g, and the prepared Cu is shown in figure 113The first charge and discharge curve (a) and the cycle performance graph (b) of the P-CuO/C composite electrode material. As shown in the figure, the first charging and discharging specific capacities are respectively 252.6 and 559.1mAh/g, the charging and discharging platforms are obvious, the charging and discharging capacities after 50 times of circulation are respectively 319.4 and 328.1mAh/g, and the electrochemical performance is better.
Claims (8)
1. Cu3The preparation method of the P-CuO composite flexible lithium ion battery cathode material is characterized in that the preparation process of the material is as follows:
(1) placing the copper foil in a muffle furnace for preoxidation treatment at 100-300 ℃ for 15 min-1 h;
(2) weighing sodium hypophosphite, flatly paving the sodium hypophosphite at the bottom of the ceramic material boat, and placing the copper foil treated in the step (1) right above the ceramic material boat and covering the copper foil with foamed copper;
(3) placing the ceramic material boat in the step (2) in a tube furnace, under the condition of inert atmosphere, heating at the speed of 1-5 ℃/min, sintering at the temperature of 250-350 ℃, keeping the temperature for 15 min-5 h, and naturally cooling to obtain Cu3P-CuO flexible electrode material.
2. Cu according to claim 13The preparation method of the P-CuO composite flexible lithium ion battery negative electrode material is characterized in that a copper foil block is placed in a muffle furnace for pre-oxidation treatment, the length of the copper foil is 2-4 cm, and the width of the copper foil is 0.5-2 cm; the treatment temperature is 100 deg.C, and the treatment time is 15 min.
3. Cu according to claim 13The preparation method of the P-CuO composite flexible lithium ion battery cathode material is characterized in that the mass of sodium hypophosphite at the bottom of a ceramic material boat is 10-50 times of that of copper foil, and the copper foil positioned right above ceramic is covered by copper foam.
4. Cu according to claim 13The preparation method of the P-CuO composite flexible lithium ion battery cathode material is characterized in that the inert atmosphere comprises argon or nitrogen, the heating speed is 3 ℃/min, the sintering temperature is 300 ℃, and the heat preservation time is 30 min.
5. Cu according to any of claims 1 to 43The preparation method of the P-CuO composite flexible lithium ion battery negative electrode material is characterized in that the copper foil in the step (1) can also be foam copper, the foam copper is treated by citric acid solution for 10-30 min and then dried, and then pre-oxidized for 15 min-1 h at 100-300 ℃ in a muffle furnace.
6. Cu according to claim 53The preparation method of the P-CuO composite flexible lithium ion battery cathode material is characterized in that the concentration range of the citric acid solution is 1-10 g/L.
7. Cu according to claim 53The preparation method of the P-CuO composite flexible lithium ion battery cathode material is characterized in that in the step (3), the ceramic material boat is placed in a tube furnace, under the condition of inert atmosphere, the temperature rise speed is 1-5 ℃/min, the sintering temperature is 300-400 ℃, the heat preservation time is 15 min-5 h, and Cu is obtained after natural cooling3P-CuO/C flexible electrode material.
8. Cu according to claim 73The preparation method of the P-CuO composite flexible lithium ion battery cathode material is characterized in that the inert atmosphere is nitrogen or argon, the heating speed is 3 ℃/min, the sintering temperature is 350 ℃, and the heat preservation time is 1 h.
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CN114464814A (en) * | 2022-01-26 | 2022-05-10 | 南京航空航天大学 | Modified copper current collector for lithium metal battery cathode and preparation method thereof |
CN114824295A (en) * | 2022-03-15 | 2022-07-29 | 黑龙江大学 | Method for preparing anode material for assembling hybrid zinc-air battery |
NL2030456B1 (en) * | 2021-11-05 | 2023-01-03 | Advanced Mat Institute Shandong Academy Of Sciences | Cathode Material Coated In situ by Copper Foam/lithium Metal Battery |
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