CN110104625B - Preparation method of manganese-doped copper phosphate positive electrode material - Google Patents
Preparation method of manganese-doped copper phosphate positive electrode material Download PDFInfo
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- C01B25/00—Phosphorus; Compounds thereof
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Abstract
A method for preparing manganese-doped copper phosphate anode material. Adding copper oxide into deionized water to obtain a suspension A; dissolving soluble phosphate in the solution A and freezing to obtain solid B(ii) a Freeze-drying the solid B to recrystallize phosphate on the surface of the copper oxide to obtain a mixture C; grinding the mixture C in an agate mortar to uniformly mix the mixture C and the agate mortar to obtain a sample D; dissolving manganese acetate tetrahydrate and manganese chloride tetrahydrate in water, dropwise adding the solution into the sample D, drying, and performing ball milling to obtain a precursor E; placing the precursor E in a magnetic boat for heat treatment to obtain Mn-doped copper phosphate Cu3(PO4)2And (3) a positive electrode material. According to the invention, the copper phosphate is wrapped on the surface of the copper oxide by using a dissolving and re-crystallizing method, so that a precursor with high purity is obtained. Meanwhile, the method does not need to dope with a manganese source in a protective atmosphere (including a vacuum environment), ball-milling is carried out to obtain a product, heat treatment is carried out in a direct heating mode, and the heat preservation time is short, so that the material with the expected morphology can be obtained.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a preparation method of a manganese-doped copper phosphate anode material.
Background
With the concern of various countries on the fossil energy crisis and the environmental pollution problem, research, development and application of high-performance green lithium ion batteries become one of the hot points of research of scientists of various countries [ dianthus superbus, zhang bing, zheng sheng man, four categories of lithium ion battery anode materials progress [ J ] power technology, 2016,40(7): 1515-. The electrochemical performance of lithium ion batteries is greatly related to the electrode materials used, and the development of positive electrode materials is slower than that of negative electrodes. The current research work mainly focuses on layered oxides, spinel structure compounds, polyanion type compounds and other positive electrode materials [ Wanyang, Zhengqiao 20342, Yidun Min. Researchers mainly modify the existing materials by using methods such as surface coating, doping, component design and the like and actively research and develop a composite material with an amorphous or porous structure [ Wanqi, Guo Xianping, Wanmin.
Disclosure of Invention
The invention aims to provide a preparation method of a manganese-doped copper phosphate anode material, namely, trace manganese ions are introduced into copper phosphate, the space of lattice gaps and the internal transmission characteristic can be adjusted by a doping modification method, the ion migration resistance is reduced, the ion conductivity and the electronic conductivity of the phosphate material are improved, and the electrochemical performance of the material is improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
1) adding 1g of copper oxide into 10-30 ml of deionized water, and performing ultrasonic dispersion to uniformly disperse the copper oxide in the water to obtain a suspension A;
2) according to the mass ratio of the soluble phosphate to the copper oxide of 1: 0.6-2, dissolving soluble phosphate in the solution A under magnetic stirring, then dropwise adding phosphoric acid to adjust the pH value to 4-6, and then putting the solution in a refrigerator for freezing to obtain a solid B;
3) freeze-drying the solid B to recrystallize phosphate on the surface of the copper oxide to obtain a mixture C;
4) grinding the mixture C in an agate mortar to uniformly mix the mixture C and the agate mortar to obtain a sample D;
5) according to the molar ratio of copper oxide to manganese acetate tetrahydrate and manganese chloride tetrahydrate of 10-20: dissolving manganese acetate tetrahydrate and manganese chloride tetrahydrate in 5-20 mL of water, dropwise adding the dissolved manganese acetate tetrahydrate and manganese chloride tetrahydrate into a sample D, drying to obtain a mixture of phosphate, copper oxide, manganese acetate and manganese chloride, and drying the mixture for 300-600 r min-1Ball-milling at a rotating speed to fully mix the raw materials to obtain a precursor E;
6) placing the sample E in a magnetic boat, covering the magnetic boat with a cover, and placing the sample E in a box type high-temperature sintering furnace at the temperature of 5-10 ℃ for min-1Heating the mixture from room temperature to 600-800 ℃ at a heating rate to obtain Mn-doped copper phosphate Cu3(PO4)2And (3) a positive electrode material.
And 1) ultrasonically dispersing for 10-30 min.
The soluble phosphate in the step 2) is sodium phosphate or ammonium hydrogen phosphate.
And 2) magnetically stirring for 1-3 hours.
And 2) freezing for 12-24 h.
And 3) freeze-drying for 12-24 h.
And 5) adopting a planetary ball mill for ball milling.
And 6) carrying out heat treatment for 10-30 min.
The raw materials adopted by the invention are nontoxic and pollution-free, and the experimental scheme is simple and easy to operate. And coating the copper phosphate on the surface of the copper oxide by using a dissolving and re-crystallizing method to obtain a precursor with high purity. Meanwhile, the method does not need to dope with a manganese source in a protective atmosphere (including a vacuum environment), ball-milling is carried out to obtain a product, heat treatment is carried out in a direct heating mode, and the heat preservation time is short, so that the material with the expected morphology can be obtained.
The beneficial effects are that:
1) according to the invention, by controlling the doping amount of manganese, the shape-controllable rod-shaped and spherical interconnected copper phosphate anode material is obtained;
2) the method prepares the precursor by a liquid phase method, can uniformly mix two phases, has simple and easy experimental operation, and uses environment-friendly raw materials without pollution.
Drawings
Fig. 1 is an SEM image of a manganese-doped copper phosphate cathode material prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of the manganese-doped copper phosphate cathode material prepared in example 1 of the present invention.
FIG. 3 is a graph of the performance of the manganese-doped copper phosphate cathode material prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1:
1) adding 1g of copper oxide into 10ml of deionized water, and performing ultrasonic dispersion for 10min to obtain a suspension A;
2) according to the mass ratio of sodium phosphate to copper oxide of 1: 0.6 taking sodium phosphate, magnetically stirring for 1 hour, dissolving in the solution A, then dropwise adding phosphoric acid to adjust the pH value to 4, and then putting into a refrigerator for freezing for 12 hours to obtain a solid B;
3) freeze-drying the solid B for 12h to recrystallize phosphate on the surface of the copper oxide to obtain a mixture C;
4) grinding the mixture C in an agate mortar to uniformly mix the mixture C and the agate mortar to obtain a sample D;
5) according to the molar ratio of copper oxide to manganese acetate tetrahydrate and manganese chloride tetrahydrate of 10: 1 dissolving manganese acetate tetrahydrate and manganese chloride tetrahydrate in 5mL of water, dropwise adding the solution into a sample D, drying to obtain a mixture of phosphate, copper oxide and manganese acetate, and allowing the mixture to stand for 300r min-1Ball-milling at a rotating speed to fully mix the raw materials to obtain a precursor E;
6) placing sample E in a magnetic boat, covering with a cover, and sintering at 5 deg.C for min in a box-type high-temperature sintering furnace-1The temperature rise rate is increased from room temperature to 600 ℃ for heat treatment for 10min to obtain Mn-doped copper phosphate Cu3(PO4)2And (3) a positive electrode material.
Referring to FIG. 1, when the product prepared in this example is observed by using a JSM-6700F scanning electron microscope manufactured by Japan, it can be seen from SEM image that the copper phosphate is distributed in the shape of rods and spheres, and they are cross-linked to form a conductive network framework
Referring to FIG. 2, the product prepared in this example was analyzed by a Japanese science D/max2000 PCX-ray diffractometer and found to be a sample of Mn-doped copper phosphate Cu3(PO4)2。
See FIG. 3, at 50mA g-1The first-cycle discharge capacity is 306mAh g-1After 30 cycles of circulation, the reversible capacity is 154mAh g-1。
Example 2:
1) adding 1g of copper oxide into 20ml of deionized water, and performing ultrasonic dispersion for 20min to obtain a suspension A;
2) according to the mass ratio of ammonium hydrogen phosphate to copper oxide of 1: 1.2 taking ammonium hydrogen phosphate, magnetically stirring for 2h, dissolving in the solution A, then dropwise adding phosphoric acid to adjust the pH value to 5, and then putting in a refrigerator for freezing for 18h to obtain a solid B;
3) freeze-drying the solid B for 18h to recrystallize phosphate on the surface of the copper oxide to obtain a mixture C;
4) grinding the mixture C in an agate mortar to uniformly mix the mixture C and the agate mortar to obtain a sample D;
5) according to the molar ratio of copper oxide to manganese acetate tetrahydrate and manganese chloride tetrahydrate of 15: 1 dissolving manganese acetate tetrahydrate and manganese chloride tetrahydrate in 12mL of water, dropwise adding the mixture into a sample D, drying to obtain a mixture of phosphate, copper oxide and manganese acetate, and allowing the mixture to react for 450r min-1Ball-milling at a rotating speed to fully mix the raw materials to obtain a precursor E;
6) placing sample E in a magnetic boat, covering with a cover, and sintering at 8 deg.C for min in a box-type high-temperature sintering furnace-1The temperature rise rate is increased from room temperature to 700 ℃ for heat treatment for 20min to obtain Mn-doped copper phosphate Cu3(PO4)2And (3) a positive electrode material.
Example 3:
1) adding 1g of copper oxide into 30ml of deionized water, and performing ultrasonic dispersion for 25min to obtain a suspension A;
2) according to the mass ratio of sodium phosphate to copper oxide of 1: 2, taking sodium phosphate, magnetically stirring for 3 hours, dissolving the sodium phosphate in the solution A, then dropwise adding phosphoric acid to adjust the pH value to 6, and then putting the solution into a refrigerator to freeze for 24 hours to obtain a solid B;
3) freeze-drying the solid B for 24 hours to recrystallize phosphate on the surface of the copper oxide to obtain a mixture C;
4) grinding the mixture C in an agate mortar to uniformly mix the mixture C and the agate mortar to obtain a sample D;
5) according to the molar ratio of copper oxide to manganese acetate tetrahydrate and manganese chloride tetrahydrate of 20: 1 dissolving manganese acetate tetrahydrate and manganese chloride tetrahydrate in 20mL of water, dropwise adding the solution into a sample D, drying to obtain a mixture of phosphate, copper oxide and manganese acetate, and allowing the mixture to react for 600r min-1Ball-milling at a rotating speed to fully mix the raw materials to obtain a precursor E;
6) placing sample E in a magnetic boat, covering with a cover, and sintering at 10 deg.C for min in a box-type high-temperature sintering furnace-1The rate of temperature rise is from room temperatureHeating to 800 ℃ for 30min to obtain Mn-doped copper phosphate Cu3(PO4)2And (3) a positive electrode material.
Example 4:
1) adding 1g of copper oxide into 15ml of deionized water, and performing ultrasonic dispersion for 15min to obtain a suspension A;
2) according to the mass ratio of ammonium hydrogen phosphate to copper oxide of 1: 1, taking ammonium hydrogen phosphate, magnetically stirring for 3 hours, dissolving the ammonium hydrogen phosphate in the solution A, then dropwise adding phosphoric acid to adjust the pH value to 6, and then putting the solution into a refrigerator to freeze for 20 hours to obtain a solid B;
3) freeze-drying the solid B for 15h to recrystallize phosphate on the surface of the copper oxide to obtain a mixture C;
4) grinding the mixture C in an agate mortar to uniformly mix the mixture C and the agate mortar to obtain a sample D;
5) according to the molar ratio of copper oxide to manganese acetate tetrahydrate and manganese chloride tetrahydrate of 13: 1 dissolving manganese acetate tetrahydrate and manganese chloride tetrahydrate in 13mL of water, dropwise adding the solution into a sample D, drying to obtain a mixture of phosphate, copper oxide and manganese acetate, and allowing the mixture to react for 500r min-1Ball-milling at a rotating speed to fully mix the raw materials to obtain a precursor E;
6) placing sample E in a magnetic boat, covering with a cover, and sintering at 6 deg.C for min in a box-type high-temperature sintering furnace-1The temperature rise rate is increased from room temperature to 750 ℃ for heat treatment for 15min to obtain Mn-doped copper phosphate Cu3(PO4)2And (3) a positive electrode material.
Example 5:
1) adding 1g of copper oxide into 25ml of deionized water, and performing ultrasonic dispersion for 30min to obtain a suspension A;
2) according to the mass ratio of sodium phosphate to copper oxide of 1: 1.8 taking sodium phosphate, magnetically stirring for 2h, dissolving in the solution A, then dropwise adding phosphoric acid to adjust the pH value to 5, and then putting in a refrigerator for freezing for 15h to obtain a solid B;
3) freeze-drying the solid B for 20h to recrystallize phosphate on the surface of the copper oxide to obtain a mixture C;
4) grinding the mixture C in an agate mortar to uniformly mix the mixture C and the agate mortar to obtain a sample D;
5) according to the molar ratio of copper oxide to manganese acetate tetrahydrate and manganese chloride tetrahydrate of 18: 1 getDissolving manganese acetate tetrahydrate and manganese chloride tetrahydrate in 18mL of water, dropwise adding the mixture into the sample D, drying to obtain a mixture of phosphate, copper oxide and manganese acetate, and allowing the mixture to react for 400r min-1Ball-milling at a rotating speed to fully mix the raw materials to obtain a precursor E;
6) placing sample E in a magnetic boat, covering with a cover, and sintering at 9 deg.C for min in a box-type high-temperature sintering furnace-1Heating the mixture from room temperature to 650 ℃ at the heating rate for 25min to obtain Mn-doped copper phosphate Cu3(PO4)2And (3) a positive electrode material.
Claims (8)
1. A preparation method of a manganese-doped copper phosphate cathode material is characterized by comprising the following steps:
1) adding 1g of copper oxide into 10-30 ml of deionized water, and performing ultrasonic dispersion to uniformly disperse the copper oxide in the water to obtain a suspension A;
2) according to the mass ratio of the soluble phosphate to the copper oxide of 1: 0.6-2, dissolving soluble phosphate in the solution A under magnetic stirring, then dropwise adding phosphoric acid to adjust the pH value to 4-6, and then putting the solution in a refrigerator for freezing to obtain a solid B;
3) freeze-drying the solid B to recrystallize phosphate on the surface of the copper oxide to obtain a mixture C;
4) grinding the mixture C in an agate mortar to uniformly mix the mixture C and the agate mortar to obtain a sample D;
5) according to the molar ratio of copper oxide to manganese acetate tetrahydrate and manganese chloride tetrahydrate of 10-20: dissolving manganese acetate tetrahydrate and manganese chloride tetrahydrate in 5-20 mL of water, dropwise adding the dissolved manganese acetate tetrahydrate and manganese chloride tetrahydrate into a sample D, drying to obtain a mixture of phosphate, copper oxide, manganese acetate and manganese chloride, and drying the mixture for 300-600 r min-1Ball-milling at a rotating speed to fully mix the raw materials to obtain a precursor E;
6) placing the sample E in a magnetic boat, covering the magnetic boat with a cover, and placing the sample E in a box type high-temperature sintering furnace at the temperature of 5-10 ℃ for min-1Heating the mixture from room temperature to 600-800 ℃ at a heating rate to obtain Mn-doped copper phosphate Cu3(PO4)2And (3) a positive electrode material.
2. The method for preparing the manganese-doped copper phosphate cathode material according to claim 1, wherein the method comprises the following steps: and 1) ultrasonically dispersing for 10-30 min.
3. The method for preparing the manganese-doped copper phosphate cathode material according to claim 1, wherein the method comprises the following steps: the soluble phosphate in the step 2) is sodium phosphate or ammonium hydrogen phosphate.
4. The method for preparing the manganese-doped copper phosphate cathode material according to claim 1, wherein the method comprises the following steps: and 2) magnetically stirring for 1-3 hours.
5. The method for preparing the manganese-doped copper phosphate cathode material according to claim 1, wherein the method comprises the following steps: and 2) freezing for 12-24 h.
6. The method for preparing the manganese-doped copper phosphate cathode material according to claim 1, wherein the method comprises the following steps: and 3) freeze-drying for 12-24 h.
7. The method for preparing the manganese-doped copper phosphate cathode material according to claim 1, wherein the method comprises the following steps: and 5) adopting a planetary ball mill for ball milling.
8. The method for preparing the manganese-doped copper phosphate cathode material according to claim 1, wherein the method comprises the following steps: and 6) carrying out heat treatment for 10-30 min.
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