CN114975937B - Cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material and preparation and application thereof - Google Patents
Cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material and preparation and application thereof Download PDFInfo
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Abstract
The application discloses a cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano box composite material, a preparation method thereof and application thereof in preparing a lithium ion battery cathode. The cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material is in a cube shape, is hollow, comprises a nitrogen-doped carbon box-shaped shell and a cobalt chloride particle mixture with crystal water encapsulated in the nitrogen-doped carbon box-shaped shell, and is also provided with a gap in the shell. The preparation method comprises the following steps: firstly, synthesizing Co-Co PBA in a solid cube shape, then coating PDA on the surface of the Co-Co PBA, and further carbonizing and chlorinating the obtained product to obtain the composite material. The composite material has the characteristics of simple structure, stable cycle performance, high specific capacity and excellent multiplying power performance.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano box composite material, a preparation method thereof and application thereof in preparation of a lithium ion battery cathode.
Background
The rapid development of energy storage of automobiles, electrons and renewable energy sources greatly promotes the demand for high-performance energy storage equipment. Lithium ion batteries are one of the important energy storage devices because of their high energy density and long cycle life.
Heretofore, carbonaceous materials have been widely used as negative electrodes for lithium ion batteries, but they are less rationalTheoretical capacity (372 mAh g) -1 ) And safety issues limit further improvement in performance of lithium ion batteries. Much research is devoted to exploring new high performance alternatives to carbonaceous materials.
Materials such as transition metal oxides, sulfides, phosphides and the like have been widely studied for lithium ion battery anode materials. As reported in the patent publication No. CN111924887a, a micron cobalt disulfide composite material is prepared by first synthesizing a carbon nanotube reinforced metal-organic framework ZIF-67 in situ, then performing a low-temperature controllable limited-domain reaction, and then carbonizing and vulcanizing. The patent with publication number CN114229832A reports a nitrogen-carbon doped cobalt phosphide nanocube material containing carbon nanotubes, which is prepared by synthesizing ZIF-67 cubes, calcining at high temperature to obtain Co@NC-CNT nanocube precursor, and finally, phosphorus-forming the nitrogen-carbon doped cobalt phosphide nanocube material containing carbon nanotubes.
However, transition metal chlorides are of less concern. CoCl 2 As early as 2011, it was reported that the material can be used as a negative electrode material of a lithium ion battery, but the development is very limited afterwards, mainly because of CoCl 2 The strong water absorption, there are serious dissolution and shuttling problems in lithium ion battery electrolytes, which lead to rapid capacity fade. Poor cycle performance severely limits CoCl 2 The application of the lithium ion battery is as follows.
Disclosure of Invention
Aiming at the technical problems in the art, the application provides a cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material and a preparation method thereof. The composite material has the characteristics of simple structure, stable cycle performance, high specific capacity and excellent multiplying power performance. In addition, the material has important application value as a lithium ion battery anode material.
A cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material, which is in a cube shape and hollow inside;
the cobalt chloride packaging nitrogen-doped carbon hollow cube nano box composite material comprises a nitrogen-doped carbon box-shaped shell and a cobalt chloride particle mixture with crystal water, wherein the cobalt chloride particle mixture is packaged in the nitrogen-doped carbon box-shaped shell, and a gap is reserved in the shell of the cobalt chloride packaging nitrogen-doped carbon hollow cube nano box composite material;
the cobalt chloride particle mixture with crystal water is CoCl 2 ·2H 2 O particles and CoCl 2 ·6H 2 A mixture of O particles.
Preferably, the nitrogen-doped carbon box-like shell is formed by carbonization of polydopamine.
Preferably, cobalt chloride particles in the cobalt chloride particle mixture with the crystal water are formed by carbonizing and chlorinating a Co-Co PBA precursor;
the preparation method of the Co-Co PBA precursor comprises the following steps: co (NO) 3 ) 2 ·6H 2 O and sodium citrate dihydrate are dissolved in deionized water to obtain solution A; will K 3 [Co(CN) 6 ]Dissolving in deionized water to obtain a solution B; injecting the solution B into the solution A, uniformly stirring the obtained solution at 20-30 ℃, and aging for 18-22 h; and centrifugally separating, washing and drying the aged product to obtain the Co-Co PBA precursor.
Preferably, the side length of the cobalt chloride encapsulated nitrogen-doped carbon hollow cubic nano box is 100 nm-5 mu m.
Preferably, the thickness of the nitrogen-doped carbon box-shaped shell is 10-100 nm.
Preferably, in the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material, the mass ratio of cobalt chloride in the cobalt chloride particle mixture with crystal water is 20-79%, the mass ratio of crystal water in the cobalt chloride particle mixture with crystal water is 1-20%, and the balance is carbon.
The application also provides a preparation method of the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano box composite material, which comprises the following steps:
(1) Preparation of solution A Co (NO) 3 ) 2 ·6H 2 O and lemonSodium citrate dihydrate is dissolved in deionized water;
preparing solution B, mixing K 3 [Co(CN) 6 ]Dissolving in deionized water;
injecting the solution B into the solution A, uniformly stirring the obtained solution at 20-30 ℃, and aging for 18-22 h; centrifugally separating, washing and drying the aged product to obtain a Co-Co PBA precursor;
(2) Dispersing the Co-Co PBA precursor obtained in the step (1) in deionized water; adding the tris hydrochloride, fully stirring and dispersing, then adding the dopamine hydrochloride, and stirring for 4-8 hours; centrifugally separating, washing and drying the obtained product to obtain Co-Co PBA@PDA; heating the obtained Co-Co PBA@PDA to 400-700 ℃ under the argon atmosphere, and preserving heat for 1-3 hours to obtain a Co@ carbon hollow cube nano box;
(3) And (3) placing the Co@ carbon hollow cube nano box obtained in the step (2) in a tube furnace, heating to 300-600 ℃, introducing mixed gas of argon and chlorine, and preserving heat for 0.5-2 h to obtain the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano box composite material.
The preparation method of the application comprises the steps of firstly synthesizing Co-Co PBA with a solid cube shape, then coating PDA on the surface of the Co-Co PBA, and further carbonizing and chlorinating the obtained product to obtain the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material.
Preferably, in step (1):
when preparing solution A, the Co (NO 3 ) 2 ·6H 2 The dosage ratio of O, sodium citrate dihydrate and deionized water is 87.5-525 mg:265mg:20mL;
when preparing solution B, the solution K 3 [Co(CN) 6 ]The dosage ratio of the deionized water is 66.5-399 mg:20mL.
Preferably, in the step (2), the deionized water is used in an amount of 144mL, the tris hydrochloride is used in an amount of 174mg, and the dopamine hydrochloride is used in an amount of 18 to 108mg, relative to 120mg of the Co-Co PBA precursor.
The application also provides application of the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano box composite material in preparation of a lithium ion battery cathode.
The cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano box composite material is used for manufacturing the lithium ion battery cathode: respectively weighing cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material, acetylene black conductive agent and polyvinylidene fluoride binder according to the mass ratio of 8:1:1, dissolving polyvinylidene fluoride in a proper amount of N-methylpyrrolidone, stirring until the polyvinylidene fluoride is completely dissolved, adding uniformly grinded active material and acetylene black into the solution, and continuously stirring to ensure uniform slurry mixing. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12 mm), drying at the temperature of 100 ℃ in a vacuum oven, and finally flattening by using the pressure of 10MPa on a tablet press to obtain the lithium ion battery negative plate.
And assembling the prepared electrode plate, the lithium plate and the diaphragm into the CR2025 button-type lithium ion battery in a glove box filled with high-purity argon. Electrolyte is 1mol/L LiPF 6 The charge and discharge performance and the cycling stability of the lithium ion battery are tested by adopting a new-Wei battery test system.
The application can obtain the CoCl with stable cycle performance, high specific capacity and excellent multiplying power performance 2 A base composite material.
Compared with the prior art, the application has the following remarkable technical effects:
1) The closed and independent nitrogen-doped carbon box-shaped shell is used as a strong protective cover, and can not only inhibit CoCl 2 A large amount of adsorbed water and can effectively prevent CoCl 2 Dissolved and shuttled in the electrolyte. In particular, nitrogen dopes carbon and CoCl in a carbon box-like enclosure 2 There is a strong bond C-Cl bond between, which means that the carbon nanoshell pair CoCl 2 Has strong anchoring effect and can be used for preparing CoCl 2 The effective limit is in the carbon hollow cube nano box, which improves CoCl 2 Has very important effect on the cycle stability of the product.
2) The cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material provides a large hollow interior and can be used forTo well buffer CoCl in charge-discharge reaction 2 Is a volume change of (2); as a storage space, the hollow interior can also contain electrolyte to satisfy CoCl 2 Is required for the electrochemical reaction of (a). These properties can significantly improve CoCl 2 Charge-discharge reaction capability and stability of the battery.
3) The doping of nitrogen element on the nitrogen-doped carbon box-shaped shell improves the conductivity of the material, and the amorphous property and special shell structure of the carbon are beneficial to the diffusion of lithium ions through the nitrogen-doped carbon box-shaped shell so as to meet the requirement of internal CoCl 2 Is required for the electrochemical reaction of (a). These properties can significantly improve CoCl 2 Is a ratio of the rate performance of (2).
4) Since the above 3 aspects are all based on nitrogen-doped carbon box-shaped shells, the above 3 aspects can mutually affect and synergistically act, thereby improving the CoCl more remarkably 2 Is a lithium battery.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a Co-Co PBA precursor prepared in example 1;
FIG. 2 is an SEM photograph of Co-Co PBA@PDA prepared in example 1;
FIG. 3 is an SEM photograph of a Co@ carbon hollow cube nanoshell prepared according to example 1;
FIG. 4 is a Transmission Electron Microscope (TEM) photograph of the Co@ carbon hollow cube nanoshell prepared in example 1;
FIG. 5 is an SEM photograph of a cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material prepared in example 1;
FIG. 6 is a TEM photograph of a cobalt chloride encapsulated nitrogen doped carbon hollow cube nano-box composite prepared in example 1;
FIG. 7 is an XRD pattern of the cobalt chloride encapsulated nitrogen doped carbon hollow cube nano-box composite material prepared in example 1;
FIG. 8 is a high resolution XPS spectrum of Cl 2p of the cobalt chloride encapsulated nitrogen doped carbon hollow cube nano-box composite material prepared in example 1;
FIG. 9 shows the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material prepared in example 1 and the comparative material at a current density of 0.2Ag -1 Is a cyclic performance graph of (2);
FIG. 10 shows the current density of 2Ag for the cobalt chloride-encapsulated nitrogen-doped carbon hollow cube nano-box composite material prepared in example 1 and the comparative material -1 Is a cycle performance chart of (c).
Detailed Description
The application will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Example 1
(1) Preparation of solution A175 mg Co (NO) 3 ) 2 ·6H 2 O and 265mg sodium citrate dihydrate were dissolved in 20ml deionized water. Preparation of solution B133 mg K 3 [Co(CN) 6 ]Dissolve in 20ml deionized water. Solution B was quickly poured into solution A, stirred at room temperature for 5min, and then aged at room temperature for 20h. Centrifugal separation is carried out on the product, deionized water and ethanol are used for thorough washing, and drying is carried out at 70 ℃ to obtain a Co-Co PBA precursor;
(2) 120mg of the Co-Co PBA precursor obtained in the step (1) was dispersed in 144ml of deionized water. 174mg of tris hydrochloride was added, stirred magnetically and dispersed ultrasonically for 10min. Then 36mg of dopamine hydrochloride was added to the solution and stirred for 6h. The product was centrifuged, washed with deionized water and ethanol, and dried at 70 ℃. Heating the obtained Co-Co PBA@PDA to 500 ℃ under argon, and preserving heat for 2 hours to obtain a Co@ carbon hollow cube nano box;
(3) And (3) placing the Co@ carbon hollow cube nano box obtained in the step (2) in a tube furnace, heating to 450 ℃, introducing mixed gas of argon and chlorine, preserving heat for 1h, and cooling to room temperature to obtain the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano box composite material.
FIG. 1 is an SEM photograph of a prepared Co-Co PBA precursor, the Co-Co PBA exhibiting a typical microcube morphology, the cube side length being about 1 μm. Microcubes are uniform in size and are separated from each other.
FIG. 2 is an SEM photograph of a prepared Co-Co PBA@PDA, after coating the PDA, the surface and corners of the cube became more rounded and smooth.
Fig. 3 is an SEM photograph of a Co@ carbon hollow cube nano-box, with a transparent film on the surface of the microcube after carbonization. A number of nanoparticles are discretely distributed inside the transparent film. The microcube structure remains intact.
Fig. 4 is a TEM photograph of a Co@ carbon hollow cube nano-box, and it can be seen that the inside of the cube box is hollow. The carbon hollow cube nano box is produced by decomposing PDA, and the wall thickness is 30-50 nm. A number of nanoparticles are attached to the inner surface of the nanoshell, which are the decomposition products of the Co-Co PBA precursor, i.e. metallic Co, with a size of 30-190 nm. There is a significant gap between these nanoparticles.
FIG. 5 is CoCl 2 SEM photographs of the encapsulated nitrogen-doped carbon hollow cube nano-box composite, the nano-box surface obscured, and the nano-particles were replaced with larger particles.
FIG. 6 is CoCl 2 TEM photographs of the encapsulated nitrogen-doped carbon hollow cube nano-box composite material show that the side length and the thickness of the shell of the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box are not greatly changed compared with those of the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box shown in fig. 4, at the moment, the side length of the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box is about 1 mu m, and the thickness of the nitrogen-doped carbon box-shaped shell is 30-50 nm. In the hollow nano-box, a plurality of particles are aggregated, and some irregularly dispersed particles and some long-strip particles are CoCl 2 。
FIG. 7 is CoCl 2 XRD patterns of the encapsulated nitrogen-doped carbon hollow cube nano-box composite material can be calibrated into two groups of diffraction peaks, and CoCl 2 ·2H 2 O (JCPDS 25-0242) and CoCl 2 ·6H 2 O (77-0197). Diffraction peaks for Co-Co PBAs and metallic Co were not found, indicating that both had completed carbonization and chlorination. The diffraction peak intensity is lower, reflecting CoCl 2 The degree of crystallization is low. A short steamed bread peak occurs at 20-30 deg. due to amorphous carbon. By thermogravimetric experiments under air, the CoCl in the composite material can be calculated 2 70% by mass, 18% by mass of crystal water and the balance of carbon.
FIG. 8 is a CoCl 2 High resolution XPS spectrum of Cl 2p of encapsulated nitrogen-doped carbon hollow cube nano-box composite material, with two peaks at 199.9 and 198.1eV, respectively with Cl - 2p 1/2 And Cl - 2p 3/2 Related to the following. The other two peaks at 200.8 and 200.5eV with C-Cl 2p 1/2 And C-Cl 2p 3/2 Related to the following. The presence of C-Cl bond indicates amorphous carbon cube nanoshells and CoCl 2 There is a strong bond coupling between them, which means that the carbon nanoshell pair CoCl 2 Has strong anchoring effect, and improves the CoCl pair of the carbon hollow cubic nano-box 2 Is a limited domain capability of (c).
CoCl of the application 2 Packaging nitrogen-doped carbon hollow cube nano box composite material to manufacture a lithium ion battery anode: coCl with the mass ratio of 8:1:1 is respectively weighed 2 Encapsulating nitrogen-doped carbon hollow cube nano-box composite material, acetylene black conductive agent and polyvinylidene fluoride binder, dissolving polyvinylidene fluoride in proper amount of N-methyl pyrrolidone, stirring until the polyvinylidene fluoride is completely dissolved, adding uniformly grinded active material and acetylene black into the solution, and continuing stirring to ensure uniform slurry mixing. And then uniformly coating the slurry on a wafer copper foil (with the diameter of 12 mm), drying at the temperature of 100 ℃ in a vacuum oven, and finally flattening by using the pressure of 10MPa on a tablet press to obtain the lithium ion battery negative plate.
And assembling the prepared electrode plate, the lithium plate and the diaphragm into the CR2025 button-type lithium ion battery in a glove box filled with high-purity argon. Electrolyte is 1mol/L LiPF 6 The charge and discharge performance and the cycling stability of the lithium ion battery are tested by adopting a new-Wei battery test system.
FIG. 9 is a CoCl 2 Packaging nitrogen-doped carbon hollow cube nano-box composite material and comparison material at current density of 0.2Ag -1 Is a cycle performance chart of (c). Due to electrochemical activation, the discharge capacity gradually increased to 1179mAh g by 19 th cycle -1 . After that, the discharge capacity starts to decrease slowly. After the 55 th cycle, the discharge capacity was substantially stabilized at 904mAh g -1 . At the 120 th cycle, the discharge capacity still reached 920mAh g -1 . In contrast, the control material CoCl 2 (synthesized by the same method, except that the Co-Co PBA of the control material is not coated with PDA) discharge capacity is monotonically decreased, and after 60 cycles, the discharge capacity is only stabilized at 80mAh g -1 . The discharge capacity of the composite material obtained by the application is 800-900 mAh g higher than that of the control material -1 。
FIG. 10 is a CoCl 2 Packaging nitrogen-doped carbon hollow cube nano box composite material and comparison material at current density of 2Ag -1 Is a cycle performance chart of (c). The composite material can provide stable discharge capacity from 150 th cycle to 1500 th cycle, around 402mAh g -1 Wave motion. At 1500 th cycle, the discharge capacity still reached 406mAh g -1 . In contrast, the control material CoCl 2 (synthesized in the same way except that the Co-Co PBA of the control material was not PDA coated) was only stable at 133mAh g in the first 477 cycles -1 Then further reduced to 95mAh g -1 . The composite material obtained by the application is 3-4 times of the comparative material.
CoCl 2 The performance of the lithium battery packaged with the nitrogen-doped carbon hollow cube nano-box composite material is superior to that of composite materials such as cobalt sulfide, cobalt phosphide, cobalt selenide and the like, for example, the performance is superior to that of a micron cobalt disulfide composite material disclosed in patent publication No. CN111924887A (the current density is 0.2Ag -1 Specific capacity of 450mAh g -1 ) Co superior to that disclosed in the publication No. CN110459744A 9 S 8 @ Si/C (at a current density of 0.25Ag -1 Specific capacity of 50 th cycle-900 mAh g -1 ) Nanometer cobalt phosphide embedded nitrogen-phosphorus co-doped porous carbon (with current density of 0.2 Ag) superior to grape pudding model disclosed in patent publication No. CN110459744A -1 Specific capacity of 120 th cycle-600 mAh g -1 ) Superior to the carbon nanotube-containing nitrogen-doped cobalt phosphide nanocubes disclosed in the publication No. CN114229832A (at current density of 0.1Ag -1 Specific capacity of 100 th cycle-600 mAh g -1 ) Better than the nitrogen-doped porous carbon coated diselenide disclosed in the publication No. CN114229805ACobalt composite (at current density 0.2 Ag) -1 Specific capacity of 100 th cycle-400 mAh g -1 )。
Example 2
(1) Preparation of solution A175 mg Co (NO) 3 ) 2 ·6H 2 O and 265mg sodium citrate dihydrate were dissolved in 20ml deionized water. Preparation of solution B133 mg K 3 [Co(CN) 6 ]Dissolve in 20ml deionized water. Solution B was quickly poured into solution A, stirred at room temperature for 5min, and then aged at room temperature for 20h. Centrifugal separation is carried out on the product, deionized water and ethanol are used for thorough washing, and drying is carried out at 70 ℃ to obtain a Co-Co PBA precursor;
(2) 120mg of the Co-Co PBA precursor obtained in the step (1) was dispersed in 144ml of deionized water. 174mg of tris hydrochloride was added, stirred magnetically and dispersed ultrasonically for 10min. 72mg of dopamine hydrochloride was then added to the solution and stirred for 6h. The product was centrifuged, washed with deionized water and ethanol, and dried at 70 ℃. And heating the obtained Co-Co PBA@PDA to 500 ℃ under argon, and preserving heat for 2 hours to obtain the Co@ carbon hollow cube nano box.
The subsequent steps are the same as in example 1.
Product CoCl 2 The structure of the encapsulated nitrogen-doped carbon hollow cube nano-box composite material is similar to that of example 1, the main difference being that the thickness of the nitrogen-doped carbon box-shaped shell becomes 50-70 nm, and the CoCl in the composite material 2 60% by mass, 15% by mass of crystal water and the balance of carbon.
The same process as in example 1 was used to fabricate a negative electrode for a lithium ion battery, assembled into a lithium ion battery, and the current density was 0.2Ag -1 And (3) performing cyclic charge and discharge test in a voltage range of 0.01-3.0V. CoCl 2 The packaged nitrogen-doped carbon hollow cube nano-box composite material is electrochemically activated, and the discharge capacity is gradually increased to 1004mAh g when the 17 th cycle is reached -1 . After that, the discharge capacity starts to decrease slowly. After the 52 th cycle, the discharge capacity is basically stabilized at 766mAh g -1 . At the 120 th cycle, the discharge capacity still reached 781mAh g -1 。
Example 3
(1) Preparation of solution A350 mg Co (NO) 3 ) 2 ·6H 2 O and 265mg sodium citrate dihydrate were dissolved in 20ml deionized water. Preparation of solution B266 mg K 3 [Co(CN) 6 ]Dissolve in 20ml deionized water. Solution B was quickly poured into solution A, stirred at room temperature for 5min, and then aged at room temperature for 20h. And (3) centrifugally separating the product, thoroughly washing the product with deionized water and ethanol, and drying the product at 70 ℃ to obtain the Co-Co PBA precursor.
The subsequent procedure was the same as in example 1.
Product CoCl 2 The structure of the encapsulated nitrogen-doped carbon hollow cube nano-box composite material is similar to that of example 1, and the main difference is that the side length of the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box is changed to about 1.2 mu m, and the thickness of the nitrogen-doped carbon box-shaped shell is changed to 40-60 nm. CoCl in composite material 2 65% by mass, 17% by mass of crystal water and the balance of carbon.
The same process as in example 1 was used to fabricate a negative electrode for a lithium ion battery, assembled into a lithium ion battery, and the current density was 0.2Ag -1 And (3) performing cyclic charge and discharge test in a voltage range of 0.01-3.0V. CoCl 2 The encapsulated nitrogen-doped carbon hollow cube nano-box composite material gradually increases the discharge capacity to 1094mAh g from 18 th cycle due to electrochemical activation -1 . After that, the discharge capacity starts to decrease slowly. After the 56 th cycle, the discharge capacity is basically stable at 840mAh g -1 . At the 120 th cycle, the discharge capacity still reached 854mAh g -1 。
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (9)
1. The cobalt chloride packaging nitrogen-doped carbon hollow cube nano box composite material is characterized in that the cobalt chloride packaging nitrogen-doped carbon hollow cube nano box composite material is in a cube shape and hollow in the inside;
the cobalt chloride packaging nitrogen-doped carbon hollow cube nano box composite material comprises a nitrogen-doped carbon box-shaped shell and a cobalt chloride particle mixture with crystal water, wherein the cobalt chloride particle mixture is packaged in the nitrogen-doped carbon box-shaped shell, and a gap is reserved in the shell of the cobalt chloride packaging nitrogen-doped carbon hollow cube nano box composite material;
the cobalt chloride particle mixture with crystal water is CoCl 2 ·2H 2 O particles and CoCl 2 ·6H 2 A mixture of O particles;
cobalt chloride particles in the cobalt chloride particle mixture with the crystal water are formed by carbonizing and chlorinating a Co-Co PBA precursor;
the preparation method of the Co-Co PBA precursor comprises the following steps: co (NO) 3 ) 2 ·6H 2 O and sodium citrate dihydrate are dissolved in deionized water to obtain solution A; will K 3 [Co(CN) 6 ]Dissolving in deionized water to obtain a solution B; injecting the solution B into the solution A, uniformly stirring the obtained solution at 20-30 ℃, and aging for 20-22 hours; and centrifugally separating, washing and drying the aged product to obtain the Co-Co PBA precursor.
2. The cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite according to claim 1, wherein the nitrogen-doped carbon box-like shell is formed by polydopamine carbonization.
3. The cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material according to claim 1, wherein the side length of the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box is 100 nm-5 mm.
4. The cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material of claim 1, wherein the thickness of the nitrogen-doped carbon box-shaped shell is 10-100 nm.
5. The cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material according to claim 1, wherein in the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material, the mass ratio of cobalt chloride in the cobalt chloride particle mixture with crystal water is 20% -79%, the mass ratio of crystal water in the cobalt chloride particle mixture with crystal water is 1% -20%, and the balance is carbon.
6. The method for preparing the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material according to any one of claims 1-5, which is characterized by comprising the following steps:
(1) Preparation of solution A Co (NO) 3 ) 2 ·6H 2 O and sodium citrate dihydrate are dissolved in deionized water;
preparing solution B, mixing K 3 [Co(CN) 6 ]Dissolving in deionized water;
injecting the solution B into the solution A, uniformly stirring the obtained solution at 20-30 ℃, and aging for 20-22 hours; centrifugally separating, washing and drying the aged product to obtain a Co-Co PBA precursor;
(2) Dispersing the Co-Co PBA precursor obtained in the step (1) in deionized water; adding tris hydrochloride, fully stirring and dispersing, adding dopamine hydrochloride, and stirring for 4-8 hours; centrifugally separating, washing and drying the obtained product to obtain Co-Co PBA@PDA; heating the obtained Co-Co PBA@PDA to 400-700 ℃ in an argon atmosphere, and preserving heat for 1-3 hours to obtain a Co@ carbon hollow cube nano box;
(3) And (3) placing the Co@ carbon hollow cube nano box obtained in the step (2) in a tube furnace, heating to 300-600 ℃, introducing mixed gas of argon and chlorine, and preserving heat for 0.5-2 h to obtain the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano box composite material.
7. The method for preparing the cobalt chloride-encapsulated nitrogen-doped carbon hollow cube nano-box composite material according to claim 6, wherein in the step (1):
when preparing solution A, the Co (NO 3 ) 2 ·6H 2 The dosage ratio of O, sodium citrate dihydrate and deionized water is 87.5-525 mg:265mg:20mL;
when preparing solution B, the solution K 3 [Co(CN) 6 ]The ratio of the deionized water to the deionized water is 66.5-399 mg:20 And (3) mL.
8. The method of claim 6, wherein in the step (2), the deionized water is used in an amount of 144-mL, the tris (hydroxymethyl) aminomethane hydrochloride is used in an amount of 174-mg, and the dopamine hydrochloride is used in an amount of 18-108 mg relative to the Co-Co PBA precursor of 120-mg.
9. Use of the cobalt chloride encapsulated nitrogen-doped carbon hollow cube nano-box composite material according to any one of claims 1-5 in preparing a lithium ion battery anode.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103928676A (en) * | 2014-04-25 | 2014-07-16 | 云南大学 | Hollow nano cubic NiCo2O4 dual-metal oxide material and preparation method thereof |
| CN110459744A (en) * | 2019-08-01 | 2019-11-15 | 华南师范大学 | A kind of silicon-carbon cobalt sulfide compound, lithium ion battery negative material and preparation method thereof |
| CN111564613A (en) * | 2020-04-29 | 2020-08-21 | 首都师范大学 | Tin-cobalt @ carbon @ manganous manganic oxide yolk-shell structured lithium ion battery cathode composite material and preparation method thereof |
| CN111924887A (en) * | 2020-07-20 | 2020-11-13 | 北京科技大学 | Preparation method of micron cobalt disulfide composite material |
| CN111987315A (en) * | 2020-09-02 | 2020-11-24 | 扬州大学 | Preparation method of carbon nano-box encapsulated NiCoP nano-particle composite material and lithium ion battery cathode material thereof |
| CN112366298A (en) * | 2020-10-19 | 2021-02-12 | 杭州职业技术学院 | Carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material and preparation and application thereof |
| CN112701284A (en) * | 2020-12-29 | 2021-04-23 | 杭州职业技术学院 | Carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material and preparation and application thereof |
| CN113410440A (en) * | 2021-05-14 | 2021-09-17 | 华南理工大学 | Cobalt diselenide @ porous nitrogen-doped carbon nanocomposite, potassium ion battery and preparation method of cobalt diselenide @ porous nitrogen-doped carbon nanocomposite |
| CN113690422A (en) * | 2021-08-31 | 2021-11-23 | 安徽师范大学 | Hollow nanocube multi-element metal compound composite material with layered structure, preparation method and application in lithium ion battery |
| CN114229832A (en) * | 2022-01-05 | 2022-03-25 | 扬州大学 | Preparation method of carbon-nanotube-containing nitrogen-carbon-doped cobalt phosphide nanocube material and lithium ion battery cathode material thereof |
-
2022
- 2022-06-06 CN CN202210634499.6A patent/CN114975937B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103928676A (en) * | 2014-04-25 | 2014-07-16 | 云南大学 | Hollow nano cubic NiCo2O4 dual-metal oxide material and preparation method thereof |
| CN110459744A (en) * | 2019-08-01 | 2019-11-15 | 华南师范大学 | A kind of silicon-carbon cobalt sulfide compound, lithium ion battery negative material and preparation method thereof |
| CN111564613A (en) * | 2020-04-29 | 2020-08-21 | 首都师范大学 | Tin-cobalt @ carbon @ manganous manganic oxide yolk-shell structured lithium ion battery cathode composite material and preparation method thereof |
| CN111924887A (en) * | 2020-07-20 | 2020-11-13 | 北京科技大学 | Preparation method of micron cobalt disulfide composite material |
| CN111987315A (en) * | 2020-09-02 | 2020-11-24 | 扬州大学 | Preparation method of carbon nano-box encapsulated NiCoP nano-particle composite material and lithium ion battery cathode material thereof |
| CN112366298A (en) * | 2020-10-19 | 2021-02-12 | 杭州职业技术学院 | Carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material and preparation and application thereof |
| CN112701284A (en) * | 2020-12-29 | 2021-04-23 | 杭州职业技术学院 | Carbon-coated zinc sulfide @ carbon special-shaped hollow nano polyhedral material and preparation and application thereof |
| CN113410440A (en) * | 2021-05-14 | 2021-09-17 | 华南理工大学 | Cobalt diselenide @ porous nitrogen-doped carbon nanocomposite, potassium ion battery and preparation method of cobalt diselenide @ porous nitrogen-doped carbon nanocomposite |
| CN113690422A (en) * | 2021-08-31 | 2021-11-23 | 安徽师范大学 | Hollow nanocube multi-element metal compound composite material with layered structure, preparation method and application in lithium ion battery |
| CN114229832A (en) * | 2022-01-05 | 2022-03-25 | 扬州大学 | Preparation method of carbon-nanotube-containing nitrogen-carbon-doped cobalt phosphide nanocube material and lithium ion battery cathode material thereof |
Non-Patent Citations (1)
| Title |
|---|
| Sn−Co Nanoalloys Encapsulated in N‑Doped Carbon Hollow Cubes as a High-Performance Anode Material for Lithium-Ion Batteries;Juan Yang et al.;《ACS Appl. Mater. Interfaces》;35216-35223 * |
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