CN110790248B - Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof - Google Patents
Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method and application of flower-shaped iron-doped cobalt phosphide (Fe-CoP) microspheres for a sodium ion battery cathode material. The method adopts carbonized cinnamon leaves as a substrate carbon film, the carbon film is immersed in nitrate solution containing iron and cobalt for hydrothermal reaction, and after the hydrothermal kettle is cooled to room temperature for a certain reaction time, a precursor product is washed and dried. The microscopic appearance of the flower-shaped microspheres deposited on the carbon film after the phosphating treatment is kept unchanged. The flower-shaped microspheres are composed of nanosheets, have large specific surface area, are uniform in size, are beneficial to rapid transmission of ions, and can relieve large volume expansion of electrode materials in the charging and discharging processes. The doping of the iron element can increase the sodium storage sites of the electrode material and improve the electrochemical performance of the electrode material. The preparation method provides a new idea for preparing the sodium-ion battery cathode material, is simple in operation process, low in preparation cost and expected to realize large-scale application.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to an iron-doped cobalt phosphide microsphere electrode material with a flower-shaped structure, and a preparation method and application thereof.
Background
Sodium ion batteries have not received much attention since their discovery in 1980. In recent years, due to the early warning of shortage of lithium resources, research on sodium ion batteries is gradually emphasized. The sodium storage mechanism of a sodium ion battery is similar to that of a lithium ion battery, and Na in the battery is filled in the battery during charging + Electrons flow from the positive electrode to the negative electrode in the external circuit. The transport process of electrons and ions is also reversed during discharging. Energy density of sodium ion batteryThe lithium ion battery is high, and can be used for large-scale energy storage equipment such as wind power stations, solar power stations and household energy storage, and can also be used for low-speed vehicles such as logistics vehicles, farm tools, electric vehicles and electric ships. The electrode material of the sodium ion battery is one of the factors determining the electrochemical performance of the sodium ion battery. A great deal of research work has been carried out to obtain electrode materials with high specific capacity, long life and low cost.
At present, due to the transition metal phosphide (NiP) 4 、FeP 2 、CoP、CuP 2 Etc.) have a higher theoretical capacity that has attracted a wide range of attention from researchers. However, there are two fatal drawbacks that severely hinder the practical application of transition metal phosphides in sodium ion batteries. Firstly, the transition metal phosphide undergoes large volume expansion during sodium intercalation and sodium deintercalation, which easily leads to pulverization of the electrode material and rapid capacity fading. Secondly, the lower conductivity severely slows down the electrode reaction kinetics, resulting in a lower utilization of the electrode material. Therefore, in order for transition metal phosphides to overcome these two obstacles, the following three approaches have been mainly adopted: (1) The transition metal phosphide is nanocrystallized to increase the specific surface area of the material and increase the active sites; (2) Compounding the transition metal phosphide with a carbon material to increase the conductivity of the transition metal phosphide and alleviate the problem of volume expansion of the transition metal material; (3) The incorporation of heteroatoms increases defects in the transition metal phosphide, further increasing the active sites for sodium storage.
However, the specific capacity and the cycling stability performance in the existing method are poor, and an electrode material with higher specific capacity and better cycling stability needs to be invented.
Disclosure of Invention
The invention aims to: the invention provides a synthesis method of an iron-doped cobalt phosphide (Fe-CoP) microsphere electrode material with a flower-like structure, which can be produced in batches, and has the advantages of simple and controllable synthesis process, mild conditions, simplicity, convenience, feasibility, uniform appearance and size of the electrode material and stronger application prospect.
The invention also aims to solve the technical problem of providing the iron-doped cobalt phosphide microspheres with the flower-like structure prepared by the preparation method and application thereof.
The invention adopts a hydrothermal method and an in-situ phosphating method to obtain flower-shaped iron-doped cobalt phosphide microspheres consisting of micron sheets, and the flower-shaped iron-doped cobalt phosphide microspheres grow on a carbon film, and the composite micron structure has uniform size. The application of the cobalt phosphide-based electrode material in the self-supporting sodium ion battery cathode material can obviously improve the specific capacity and the cycle life of the cobalt phosphide-based electrode material, and has important significance in developing metal phosphide electrode materials with excellent performance.
The technical scheme is as follows: in order to solve the technical problem, the invention provides a preparation method of iron-doped cobalt phosphide microspheres with flower-like structures, which comprises the following steps:
(1) Immersing the carbonized hydrothermal base material in a solution containing cobalt nitrate (Co (NO) as a base carbon film 3 ) 2 ) Iron nitrate (Fe (NO) 3 ) 3 ) Urea (CO (NH) 2 ) 2 ) Ammonium fluoride (NH) 4 F) Carrying out hydrothermal reaction in a hydrothermal kettle of the mixed solution, and cooling to obtain a product;
(2) And (2) washing and drying the product obtained in the step (1), then carrying out phosphating treatment in a protective atmosphere, and cooling to obtain the iron-doped cobalt phosphide microspheres with flower-like structures.
Wherein the acid treatment hydrothermal base material conditions in the step (1) are as follows: 2-4 mol/L nitric acid solution is treated for 6-10 hours, washed to be neutral and dried at 60 ℃.
Wherein the hydrothermal material subjected to carbonization treatment in the step (1) comprises one or more of copper sheets, carbon cloth or carbonized cassia leaves.
Wherein, the concentration of metal total ions in the mixed solution in the step (1) is kept at 0.1mol/L, and the molar ratio of the cobalt nitrate to the ferric nitrate is 2: 1-6: 1.
Wherein, CO (NH) described in the step (1) 2 ) 2 The concentration range of (A) is 0.4-0.6 mol/L; NH (NH) 4 The concentration range of F is 0.2-0.3 mol/L.
Wherein the hydrothermal reaction conditions in the step (1) are as follows: reacting for 4-8 hours at 100-120 ℃.
Wherein, the phosphating treatment conditions in the step (2) are as follows: and washing and drying the product, and then adding sodium hypophosphite in a protective atmosphere to carry out phosphating treatment, wherein the phosphating treatment temperature is 300-350 ℃, the time is 2-3 hours, and the mass ratio of the sodium hypophosphite to the product is 10: 1-30: 1.
The invention also discloses the iron-doped cobalt phosphide microspheres with the flower-like structure prepared by the preparation method.
The invention also comprises the application of the iron-doped cobalt phosphide microspheres with flower-like structures in serving as self-supporting electrode materials of sodium ion batteries.
Wherein the specific capacity of the self-supporting electrode material is 128.5-515.4 mAh/g after 100-time circulation under the current density of 100 mA/g.
Has the advantages that: compared with the prior art, the invention has the following advantages: the iron-doped cobalt phosphide microsphere disclosed by the invention consists of micron sheets, so that an electrolyte can fully infiltrate an electrode material and provide more surface active sites. The direct growth of the microspheres on the surface of the carbon-based material can enhance the electron transmission between the carbon-based material and the iron-doped cobalt phosphide microsphere multilevel structure, and the synergistic effect between the iron-doped cobalt phosphide microspheres and the carbon film can relieve the larger volume expansion of the electrode material, effectively inhibit the crushing of the electrode material, and finally realize the improvement of the electrochemical stability of the electrode material.
Drawings
Fig. 1 is an X-ray diffraction analysis (XRD) pattern of the iron-doped cobalt phosphide anode material prepared in example 1 of the present invention; the XRD diffraction peak of the iron-doped cobalt phosphide is consistent with the diffraction peak position of the standard card PDF (# 29-0497) of CoP, and the success of iron doping is proved by the fact that no iron phosphide peak appears;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the self-supporting electrode material prepared by the present invention, wherein a is Fe-doped cobalt phosphide in example 1, and SEM can see that the Fe-doped cobalt phosphide is a micrometer flower-like structure formed by nanosheets, and this unique structure can provide higher electrochemical performance; b is the pure cobalt phosphide in comparative example 1, and the microscopic morphology of the pure cobalt phosphide can be seen to be a nanowire array structure;
FIG. 3 is a diagram of electrochemical performance test, the voltage range of the battery charging and discharging test is 3-0.01V, and the whole charging and discharging test is carried out under the condition of the blue test system at room temperature. Fig. 3 is a first-turn charge-discharge curve of the self-supporting iron-doped cobalt phosphide cathode material prepared in example 1 of the present invention at a current density of 100mA/g, and the charge-discharge curve can show that the iron-doped cobalt phosphide electrode has a first-turn coulombic efficiency of about 58.1%;
FIG. 4 is a graph of electrochemical performance tests; the discharge cycle performance of the self-supporting electrode material prepared for different embodiments of the invention under the current density of 100mA/g is shown. It can be seen from the figure that the electrode capacity of the embodiment is between 128.5 and 515.4mA h/g, which is mainly to change the experimental conditions to bring the influence on the electrochemical performance. Wherein the iron-doped cobalt phosphide electrode prepared according to the protocol of example 1 had the highest specific capacity (515.4 mA h/g) after 100 cycles at a current density of 100 mA/g.
Detailed Description
The present invention is further described below with reference to specific examples to enable those skilled in the art to better understand the present invention, but is not limited to the following examples.
The cassia tree leaves adopted in the embodiment of the invention are picked and obtained in the campus of science and university of Jiangsu.
Example 1
Soaking cortex Cinnamomi Japonici leaf (fresh cortex Cinnamomi leaf picked in campus of Jiangsu science and technology) as base carbon film, which is carbonized (calcined at 800 deg.C for 2 hr under nitrogen protection) and then treated in 2mol/L nitric acid solution at 60 deg.C for 6 hr, into carbon film containing 0.08mol/L Co (NO) 3 ) 2 、0.02mol/L Fe(NO 3 ) 3 、0.5mol/L CO(NH 2 ) 2 、0.3mol/L NH 4 Carrying out hydrothermal reaction on the mixed solution F in a hydrothermal kettle at 100 ℃ for 4 hours, and cooling to obtain a precursor product; washing the precursor product, drying at 60 deg.C, adding sodium hypophosphite under nitrogen atmosphere at 350 deg.C for phosphorization for 2 hr, and adding NaH 2 PO 2 The mass ratio of the precursor product to the iron-doped cobalt phosphide microspheres is 30:1, and the iron-doped cobalt phosphide microspheres with flower-like structures are obtained after cooling.
Comparative example 1
Soaking Cinnamomum cassia leaf as substrate carbon film, which has been carbonized (calcined at 800 deg.C for 2 hr under nitrogen protection) and then treated in 2mol/L nitric acid solution at 60 deg.C for 6 hr, into carbon film containing 0.1mol/L Co (NO) 3 ) 2 、0.5mol/L CO(NH 2 ) 2 、0.3mol/LNH 4 Carrying out hydrothermal reaction on the F mixed solution in a hydrothermal kettle at 100 ℃ for 4 hours, and cooling; washing the precursor product, drying at 60 deg.C, adding sodium hypophosphite under nitrogen atmosphere at 350 deg.C for phosphorization for 2 hr, and adding NaH 2 PO 2 The mass ratio of the product to the cobalt phosphide nanowire array is 30:1, and the cobalt phosphide nanowire array with the nanowire structure is obtained after cooling.
Example 2
Soaking cortex Cinnamomi Japonici leaf as substrate carbon film, which has been carbonized (calcined at 800 deg.C for 2 hr under nitrogen protection) and then treated at 60 deg.C for 6 hr in 2mol/L nitric acid solution, into carbon film containing 0.08mol/L Co (NO) 3 ) 2 、0.02mol/L Fe(NO 3 ) 3 、0.5mol/L CO(NH 2 ) 2 、0.3mol/LNH 4 Carrying out hydrothermal reaction on the mixed solution F in a hydrothermal kettle at 100 ℃ for 8 hours, and cooling; washing the precursor product, drying at 60 deg.c, and phosphorizing at 350 deg.c in nitrogen atmosphere for 2 hr, naH 2 PO 2 The mass ratio of the precursor product to the iron-doped cobalt phosphide microspheres is 30:1, and the iron-doped cobalt phosphide microspheres with flower-like structures are obtained after cooling.
Example 3
Soaking Cinnamomum cassia leaf as substrate carbon film, which has been carbonized (calcined at 800 deg.C for 2 hr under nitrogen protection) and then treated in 4mol/L nitric acid solution at 60 deg.C for 10 hr, into carbon film containing 0.08mol/L Co (NO) 3 ) 2 、0.02mol/L Fe(NO 3 ) 3 、0.5mol/L CO(NH 2 ) 2 、0.3mol/LNH 4 Carrying out hydrothermal reaction on the F mixed solution in a hydrothermal kettle at 100 ℃ for 4 hours, and cooling; washing the precursor product, drying at 60 deg.C, and phosphorizing at 350 deg.C under nitrogen atmosphere for 2 hr in NaH 2 PO 2 The mass ratio of the precursor product to the iron-doped cobalt phosphide microsphere is 30:1, and the iron-doped cobalt phosphide microsphere with a flower-shaped structure is obtained after cooling.
Comparative example 2
Cu plate was treated in 2mol/L nitric acid solution at 60 ℃ for 6 hours and then immersed as a base carbon film containing 0.08mol/LCo (NO) 3 ) 2 、0.02mol/L Fe(NO 3 ) 3 、0.5mol/L CO(NH 2 ) 2 、0.3mol/L NH 4 Carrying out hydrothermal reaction on the mixed solution F in a hydrothermal kettle at 100 ℃ for 4 hours, and cooling; washing the precursor product, drying at 60 deg.C, and phosphorizing at 350 deg.C under nitrogen atmosphere for 2 hr in NaH 2 PO 2 The mass ratio of the precursor product to the iron-doped cobalt phosphide microsphere is 30:1, and the iron-doped cobalt phosphide microsphere with a sheet structure is obtained after cooling.
Comparative example 3
Carbon cloth was treated in 2mol/L nitric acid solution at 60 ℃ for 6 hours and then dipped as a substrate in a solution containing 0.08mol/L Co (NO) 3 ) 2 )、0.02mol/L Fe(NO 3 ) 3 、0.5mol/L CO(NH 2 ) 2 、0.3mol/LNH 4 Carrying out hydrothermal reaction on the F mixed solution in a hydrothermal kettle at 100 ℃ for 4 hours, and cooling; washing the precursor product, drying at 60 deg.c, and phosphorizing at 350 deg.c in nitrogen atmosphere for 2 hr, naH 2 PO 2 The mass ratio of the precursor product to the iron-doped cobalt phosphide microspheres is 30:1, and the iron-doped cobalt phosphide microspheres with a sheet structure are obtained after cooling.
Example 4
Soaking cortex Cinnamomi Japonici leaf as substrate carbon film, which has been carbonized (calcined at 800 deg.C for 2 hr under nitrogen protection) and then treated at 60 deg.C for 6 hr in 2mol/L nitric acid solution, into carbon film containing 0.08mol/L Co (NO) 3 ) 2 )、0.02mol/L Fe(NO 3 ) 3 、0.4mol/L CO(NH 2 ) 2 、0.2mol/LNH 4 Carrying out hydrothermal reaction on the F mixed solution in a hydrothermal kettle at 100 ℃ for 4 hours, and cooling; washing the precursor product, drying at 60 deg.c, and phosphorizing at 350 deg.c in nitrogen atmosphere for 2 hr, naH 2 PO 2 The mass ratio of the precursor product to the iron-doped cobalt phosphide microspheres is 30:1, and the iron-doped cobalt phosphide microspheres with flower-like structures are obtained after cooling.
Example 5
Taking the Osmanthus tree leaves which are carbonized (calcined for 2 hours at 800 ℃ under the protection of nitrogen) and then treated for 6 hours at 60 ℃ in 2mol/L nitric acid solution as a baseThe bottom carbon film is immersed in a solution containing 0.08mol/L Co (NO) 3 ) 2 )、0.02mol/L Fe(NO 3 ) 3 、0.5mol/L CO(NH 2 ) 2 、0.3mol/LNH 4 Carrying out hydrothermal reaction on the F mixed solution in a hydrothermal kettle at 100 ℃ for 4 hours, and cooling; washing the precursor product, drying at 60 deg.c, and phosphorizing at 300 deg.c in nitrogen atmosphere for 2 hr, naH 2 PO 2 The mass ratio of the precursor product to the iron-doped cobalt phosphide microsphere is 30:1, and the iron-doped cobalt phosphide microsphere with a flower-shaped structure is obtained after cooling.
Example 6
Soaking cortex Cinnamomi Japonici leaf as substrate carbon film, which has been carbonized (calcined at 800 deg.C for 2 hr under nitrogen protection) and then treated at 60 deg.C for 6 hr in 2mol/L nitric acid solution, into carbon film containing 0.08mol/L Co (NO) 3 ) 2 )、0.02mol/L Fe(NO 3 ) 3 、0.5mol/L CO(NH 2 ) 2 、0.3mol/LNH 4 Carrying out hydrothermal reaction on the F mixed solution in a hydrothermal kettle at 100 ℃ for 4 hours, and cooling; washing the precursor product, drying at 60 deg.c, and phosphorizing at 350 deg.c in nitrogen atmosphere for 2 hr, naH 2 PO 2 The mass ratio of the precursor product to the iron-doped cobalt phosphide microsphere is 10:1, and the iron-doped cobalt phosphide microsphere with a flower-shaped structure is obtained after cooling.
Example 7
Soaking cortex Cinnamomi Japonici leaf as substrate carbon film, which has been carbonized (calcined at 800 deg.C for 2 hr under nitrogen protection) and then treated at 60 deg.C for 6 hr in 2mol/L nitric acid solution, into carbon film containing 0.08mol/L Co (NO) 3 ) 2 )、0.02mol/L Fe(NO 3 ) 3 、0.5mol/L CO(NH 2 ) 2 、0.3mol/LNH 4 Carrying out hydrothermal reaction on the F mixed solution in a hydrothermal kettle at 100 ℃ for 4 hours, and cooling; washing the precursor product, drying at 60 deg.c, phosphorizing at 350 deg.c in nitrogen atmosphere for 3 hr, and adding NaH 2 PO 2 The mass ratio of the precursor product to the iron-doped cobalt phosphide microsphere is 30:1, and the iron-doped cobalt phosphide microsphere with a flower-shaped structure is obtained after cooling.
Application examples
The cells of this experimental example were assembled in a glove box filled with argon gas, and flower-like structures were obtained in examples 1 to 7, respectivelyThe iron-doped cobalt phosphide microspheres or the cobalt phosphide nanowire array with the nanowire structure prepared in the comparative example 1, the iron-doped cobalt phosphide microspheres with the sheet structure prepared in the comparative examples 2 to 3 are directly used as a cathode material, the sodium sheet is used as a counter electrode, and the electrolyte is 1.0M NaPF 6 The additive is dissolved in a mixed solution of ethylene carbonate and diethyl carbonate (volume ratio = 1: 1), the volume percentage of the additive is 5 percent fluoroethylene carbonate, and the diaphragm is a glass fiber membrane. The voltage range of the battery charge and discharge test is 3-0.01V, and the whole charge and discharge test is carried out under the condition of the blue test system at room temperature. The experimental results are as follows: experimental data show that example 1 is the best scheme of the cycle performance in all experiments, and fig. 1 is an XRD (X-ray diffraction) pattern of the iron-doped cobalt phosphide microsphere material obtained in example 1; FIG. 2 is an SEM image of the Fe-doped cobalt phosphide microspheres of example 1, and it can be seen that the diameter of the material is about 10 μm; fig. 3 is a first cycle charge and discharge test curve of example 1, and it can be seen that the first cycle coulombic efficiency of the electrode prepared according to this scheme is about 58.1%.
It can also be seen from fig. 4 that the solution of example 1, which yields the highest coulombic efficiency compared to the other examples, has the highest electrochemical performance with a capacity of 515.4mA h/g after 100 cycles at a current density of 100 mA/g;
the coulombic efficiency of the electrode material prepared in comparative example 1 is about 45.8%, and the capacity after 100 circles of circulation under the current density of 100mA/g is 345.2 mA/g, which shows that the pure cobalt phosphide nanowire array has lower capacity compared with the iron doping;
the coulombic efficiency of the electrode material prepared in example 2 was about 52.8%, and the capacity after 100 cycles at a current density of 100mA/g was 400.7mA h/g, which was low due to the long hydrothermal reaction time and the large amount of deposited active material;
the coulombic efficiency of the electrode material prepared in example 3 is about 44.7%, and the capacity of the electrode material after 100 cycles under the current density of 100mA/g is 320.8 mA/g, which is probably that the electrochemical performance of the material is reduced by treating the carbon film substrate under a larger acidic condition;
the electrode material prepared in comparative example 2 had a coulombic efficiency of about 47.8% and had a capacity of 236.7mA h/g after 100 cycles at a current density of 100 mA/g;
the electrode material prepared in comparative example 3 had a coulombic efficiency of about 47.6%, and had a capacity of 301.3mA h/g after 100 cycles at a current density of 100 mA/g;
the coulombic efficiency of the electrode material prepared in example 4 was about 42.5%, and the capacity after 100 cycles at a current density of 100mA/g was 128.5mA h/g, indicating that the capacity of the electrode material was greatly affected by changing the amount of the reactant;
the coulombic efficiency of the electrode material prepared in example 5 is about 47.6%, and the capacity after 100 cycles of circulation under the current density of 100mA/g is 301.3mA h/g, which shows that the phosphating temperature has a large influence on the capacity of the electrode;
the coulombic efficiency of the electrode material prepared in example 6 was about 43.8%, and the capacity after 100 cycles at a current density of 100mA/g was 350.5mA h/g, indicating that a lower phosphorus content was insufficient to provide a better capacity;
the coulombic efficiency of the electrode material prepared in example 7 was about 56.8%, and the capacity after 100 cycles at a current density of 100mA/g was 426.1mA h/g, indicating that the performance of the electrode material was not greatly affected by the extension of the phosphating time.
Claims (4)
1. A preparation method of iron-doped cobalt phosphide microspheres with flower-like structures is characterized by comprising the following steps:
(1) Performing acid treatment on the carbonized hydrothermal base material, immersing the carbonized hydrothermal base material serving as a base carbon film into a hydrothermal kettle containing a mixed solution of cobalt nitrate, ferric nitrate, urea and ammonium fluoride for hydrothermal reaction, and cooling to obtain a precursor product;
(2) Washing and drying the precursor product obtained in the step (1), then carrying out phosphating treatment in a protective atmosphere, and cooling to obtain the iron-doped cobalt phosphide microspheres with flower-like structures;
the acid treatment hydrothermal substrate material conditions in the step (1) are as follows: treating the mixture for 6 to 10 hours in 2 to 4mol/L nitric acid solution, and washing the mixture to be neutralAnd drying at 60 ℃, wherein the hydrothermal substrate material subjected to carbonization treatment in the step (1) comprises one or more of a copper sheet, a carbon cloth or a carbonized bay leaf, the total metal ion concentration in the mixed solution in the step (1) is kept at 0.1mol/L, the molar ratio of cobalt nitrate to ferric nitrate is (2) 2 ) 2 The concentration range of (A) is 0.4 to 0.6mol/L; NH (NH) 4 The concentration range of F is 0.2 to 0.3mol/L, and the hydrothermal reaction conditions in the step (1) are as follows: reacting for 4 to 8 hours at the temperature of 100 to 120 ℃, wherein the phosphating conditions in the step (2) are as follows: washing and drying the precursor product, and then adding sodium hypophosphite in a protective atmosphere to carry out phosphating treatment, wherein the phosphating treatment temperature is 300-350 ℃, the phosphating treatment time is 2-3 hours, and the mass ratio of the sodium hypophosphite to the product is (10).
2. The iron-doped cobalt phosphide microspheres with a flower-like structure prepared by the preparation method of claim 1.
3. The use of the iron-doped cobalt phosphide microspheres with a flower-like structure as claimed in claim 2 as a self-supporting electrode material of a sodium-ion battery.
4. The use according to claim 3, wherein the self-supporting electrode material has a specific capacity of 128.5 to 515.4mAh/g when cycled 100 times at a current density of 100 mA/g.
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| CN108793111A (en) * | 2018-07-10 | 2018-11-13 | 南京邮电大学 | A kind of method and products thereof of quick preparation phosphatization cobalt |
| CN109599542A (en) * | 2018-11-15 | 2019-04-09 | 江苏科技大学 | A kind of phosphatization cobalt biomass carbon composite material and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108793111A (en) * | 2018-07-10 | 2018-11-13 | 南京邮电大学 | A kind of method and products thereof of quick preparation phosphatization cobalt |
| CN109599542A (en) * | 2018-11-15 | 2019-04-09 | 江苏科技大学 | A kind of phosphatization cobalt biomass carbon composite material and preparation method and application |
Non-Patent Citations (1)
| Title |
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| 过渡金属化合物基三维电极及其电催化分解水性能研究;刘志贺;《中国优秀硕士论文数据库》;20190131;第25-32页 * |
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