CN113130864B - Chemical bond enhanced silver ear-shaped porous carbon sphere embedded with monodisperse nano alloy particles and preparation and application thereof - Google Patents
Chemical bond enhanced silver ear-shaped porous carbon sphere embedded with monodisperse nano alloy particles and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of battery cathode materials, and discloses a chemical bond enhanced silver ear-shaped porous carbon sphere embedded with monodisperse nano alloy particles, and preparation and application thereof. The method comprises the following steps: 1) preparing organic bismuth salt, organic antimony salt, a water-soluble carbon source and potassium chloride into a solution by using water to obtain a precursor solution; preparing precursor microspheres from the precursor solution by removing the solvent in the precursor solution; 2) calcining the precursor microspheres in a protective atmosphere to obtain precursor carbon spheres; 3) and (3) soaking the precursor carbon sphere in water, washing and drying to obtain the silver ear-shaped porous carbon sphere embedded with the monodisperse bismuth-antimony alloy nano particles. The method is simple, the obtained carbon spheres are porous carbon spheres in the shape of the tremella, and the nano alloy particles are embedded in the two-dimensional carbon sheets of the porous carbon spheres in the shape of the tremella. The carbon sphere has better electrochemical performance. The porous carbon ball with the silver ear shape is used for a negative electrode of a potassium ion battery and/or a negative electrode of a sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of battery cathode materials, and particularly relates to a chemical bond reinforced nano bismuth-antimony alloy particle embedded in a porous carbon sphere in a silver ear shape, and a preparation method and application thereof. The chemical bond reinforced nano bismuth-antimony alloy particles are embedded in the application of the porous carbon spheres in the shape of the ear of silver to potassium ion batteries and/or sodium ion batteries, and are used as negative electrode materials of the potassium ion batteries and/or the sodium ion batteries.
Background
Currently, with the development of socioeconomic and scientific technologies, the consumption of fossil energy by human beings is increasing, and the problems of environmental pollution and energy shortage are currently significant challenges. The rechargeable battery is used as a secondary battery energy storage system, can convert some renewable resources into electric energy to be stored for various electric appliances, has the characteristics of cleanness, portability and the like, and is an important tool expected to replace fossil energy. Compared with the lithium ion battery widely applied at present, the potassium ion battery and the sodium ion battery have lower cost and more abundant resources. However, the potassium ion and sodium ion batteries are difficult to be applied industrially at present, one reason is that the potassium ion and sodium ion negative electrode materials are difficult to combine high capacity and stable cycling performance under large current.
In general, metal-based materials have a higher theoretical capacity than carbon materials, such as: a metal bismuth. The metal bismuth has high theoretical capacity and becomes a very promising negative electrode material. However, it also faces the problems commonly faced by metal-based materials, i.e. the volume change is large during charging and discharging, the material is easy to break and separate from the current collector, resulting in a sharp drop in capacity. Although carbon coating or material nanocrystallization by high temperature calcination is currently a commonly used improvement to metal-based materials. However, in the case of bismuth, which is a low melting point metal (271.4 ℃), the metal particles tend to melt and aggregate during high-temperature calcination, and the metal particles are too large in size and expand greatly in volume during charge and discharge, so that the material is broken, or the molten metal flows out of the carbon matrix and appears on the surface of the carbon material, and the carbon material does not play a role in coating and restraining. On the other hand, the bonding force between the metal particles and the carbon material is weak, and the metal particles are easy to fall off from the carbon matrix in the circulation process, so that the capacity loss of the material is caused. Therefore, the development of a potassium/sodium ion battery cathode material with long service life and high rate performance is of great significance.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a chemical bond enhanced silver ear-shaped porous carbon sphere embedded with monodisperse nano alloy particles and a preparation method thereof. The invention adopts a method combining bismuth-antimony alloying and in-situ carbonization to synthesize the silver ear-shaped porous carbon spheres embedding the monodisperse BiSb alloy nano particles. When the prepared silver ear-shaped porous carbon sphere alloy nano-particles are used for potassium ion and/or sodium ion battery cathodes, the ultra-long cycle life and the excellent rate capability are realized.
Aiming at the problems that the metal bismuth is low in melting point and is easy to melt, aggregate and flow in the carbonization process, the invention compounds the metal bismuth and the metal antimony to inhibit the flow aggregation of the low-melting-point bismuth. Meanwhile, the organic bismuth salt and the organic antimony salt are used as precursors, the organic framework forms a carbon framework around ions in the pyrolysis process, and then metal ions are reduced into simple substances, so that the aggregation of the metal into large particles can be effectively limited, and the nano-scale dispersed bismuth-antimony alloy particles are formed.
Aiming at the problem of weak binding force between metal particles and a carbon matrix, the KCl is adopted to promote the formation of M-O-C bonds between the metal and the carbon matrix, and the binding force between the metal particles and the carbon matrix is greatly improved.
The invention also aims to provide application of the chemical bond enhanced silver-ear-shaped porous carbon spheres embedded with the monodisperse nano alloy particles in potassium ion and/or sodium ion battery negative electrodes.
The purpose of the invention is realized by the following technical scheme:
a preparation method of chemical bond enhanced silver ear-shaped porous carbon spheres embedding monodisperse nano alloy particles comprises the following steps:
1) preparing organic bismuth salt, organic antimony salt, a water-soluble carbon source and potassium chloride into a solution by using water to obtain a precursor solution; preparing precursor microspheres from the precursor solution by removing the solvent in the precursor solution;
2) calcining the precursor microspheres in a protective atmosphere to obtain precursor carbon spheres embedding the monodisperse bismuth-antimony alloy nanoparticles;
3) and (3) soaking the precursor carbon spheres in water, washing and drying to obtain the silver ear-shaped porous carbon spheres (BiSb @ TCS) embedding the monodisperse bismuth-antimony alloy nanoparticles.
The organic bismuth salt is water-soluble organic bismuth salt, and specifically comprises more than one of bismuth potassium citrate, bismuth sodium citrate, bismuth ammonium citrate, bismuth laurate, bismuth sodium tartrate and bismuth potassium tartrate;
the organic antimony salt is water soluble organic antimony salt, and specifically comprises one or more of potassium antimony tartrate, sodium antimony gluconate, and ammonium antimony gluconate.
The water-soluble carbon source is more than one of ammonium citrate, citric acid, sucrose, glucose and polyvinylpyrrolidone.
The molar ratio of the organic bismuth salt to the organic antimony salt is 1: 0.1-10; the mass ratio of the organic bismuth salt to the water-soluble carbon source to the potassium chloride is 1: 1-5: 1-15.
The mass volume ratio of the organic antimony salt to the water is (0.1-10) g: 100mL, which is equivalent to the concentration of the organic antimony salt in the water being 0.1-10 wt%.
The step 1) of preparing the precursor solution into the precursor microspheres by removing the solvent in the precursor solution means that the precursor solution is prepared into the precursor microspheres by spray drying.
The conditions of the spray drying are as follows: the liquid flow rate is 1-10mL/min, the spray drying temperature is 100-.
The protective atmosphere in the step 2) is inert gas such as nitrogen or argon.
The calcining temperature in the step 2) is 400-900 ℃, and the calcining time is 1-10 h (namely the calcining heat preservation time). Heating to the calcining temperature at the heating rate of 1-5 ℃/min.
The dipping time in the step 3) is 1-12 h; the washing times are 3-6 times, and the washing refers to washing with water; the drying temperature is 60-100 ℃, and the drying time is 5-12 h. The drying comprises vacuum drying.
The dipping in step 3) comprises soaking.
The chemical formula of the nano alloy particles in the silver ear-shaped porous carbon spheres embedding the monodisperse bismuth-antimony alloy nano particles is BiSbx, and x is more than or equal to 0.1 and less than or equal to 10; the nano-alloy particles BiSbx are embedded in a two-dimensional carbon sheet of the porous carbon spheres in the shape of the tremella, the size of the nano-alloy particles BiSbx is 6-10nm, the size of the porous carbon spheres in the shape of the tremella is 1-4um, and a chemical bond M-O-C exists between the nano-alloy particles BiSbx and a carbon matrix of the porous carbon spheres in the shape of the tremella.
The chemical bond reinforced silver ear-shaped porous carbon ball embedded with the monodisperse nano alloy particles is used for a potassium ion battery cathode and/or a sodium ion battery cathode.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention adopts potassium chloride (sodium chloride, potassium nitrate and other substances cannot be adopted, and the potassium chloride of the invention is used for promoting the formation of M-O-C bonds) as a specific template agent, not only can play a pore-forming role, but also can promote the formation of the M-O-C bonds between the bismuth-antimony alloy and the carbon matrix, enhance the binding force between the active alloy particles and the carbon matrix, prevent the falling of the active metal particles in the circulating process and prolong the circulating life of the material.
(2) The invention adopts a method of combining bismuth-antimony alloying and in-situ carbonization to inhibit the flowing aggregation of low-melting point bismuth and synthesize the silver ear-shaped porous carbon spheres embedding the monodisperse BiSb alloy nanoparticles. The size range of the alloy nano particles is 6-10nm, and the extremely small size is beneficial to relieving the expansion stress of the material in the charge and discharge process.
(3) The invention adopts a spray drying method, has simple synthesis process and high production efficiency, and can be used for industrial production.
(4) When the porous carbon ball with the ear-shaped silver is applied to the negative electrode of the potassium ion battery, the cycle life is long and the rate performance is excellent: at a current density of 2A/g, 5700 cycles still had a reversible capacity of 181 mAh/g. It still has 119mAh/g reversible capacity even at 6A/g current density, with potential for large scale commercial applications.
Drawings
FIG. 1 XRD spectrum of BiSb @ TCS prepared in example 1;
FIG. 2 SEM image of BiSb @ TCS prepared in example 1;
FIG. 3 TEM image of BiSb @ TCS prepared in example 1 (microsphere part, BiSb particles embedded in carbon flakes);
FIG. 4 FTIR spectrum of BiSb @ TCS prepared in example 1;
FIG. 5 BiSb @ TCS prepared in example 1 is 2A g -1 Long cycle cycling performance at current density; in the figure, BiSb @ TCS was prepared for example 1, Sb @ TCS was prepared for comparative example 2, Bi @ TCS was prepared for comparative example 3, and TCS was prepared for comparative example 4;
FIG. 6 Rate Performance of BiSb @ TCS prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following examples for better understanding of the present invention, but the embodiments of the present invention are not limited thereto.
Example 1
(1) According to the relationship that the molar ratio of potassium bismuth citrate to potassium antimony tartrate is 1: 2, the mass ratio of potassium bismuth citrate, ammonium citrate and potassium chloride is 1: 3.125, and the concentration of potassium antimony tartrate relative to water is 10 wt%, 3.2g of potassium bismuth citrate, 3g of potassium antimony tartrate, 10g of ammonium citrate and 10g of potassium chloride are dissolved in 300mL of deionized water to form a uniform solution;
(2) spray drying the obtained solution to obtain precursor microspheres; the spray drying temperature is 180 ℃, the liquid flow rate is 6mL/min, and the air flow rate is 10L/min;
(3) placing the precursor microspheres in a tube furnace, calcining in an argon atmosphere at 600 ℃, heating at a rate of 5 ℃/min, and keeping the temperature for 3h to obtain precursor carbon spheres;
(4) and (2) soaking the precursor carbon spheres in deionized water for 12h, washing with the deionized water for 5 times, and drying in a vacuum drying oven at 80 ℃ for 12h to obtain the carbon spheres BiSb @ TCS.
Example 2
(1) According to the relationship that the molar ratio of potassium bismuth citrate to potassium antimony tartrate is 1: 2, the mass ratio of potassium bismuth citrate, ammonium citrate and potassium chloride is 1: 3.125, and the concentration of potassium antimony tartrate relative to water is 10 wt%, 6.4g of potassium bismuth citrate, 6g of potassium antimony tartrate, 20g of ammonium citrate and 20g of potassium chloride are dissolved in 600mL of deionized water to form a uniform solution;
(2) spray drying the obtained solution to obtain precursor microspheres; the spray drying temperature is 200 ℃, the liquid flow rate is 6mL/min, and the air flow rate is 10L/min;
(3) placing the precursor microspheres in a tube furnace, calcining in an argon atmosphere at 600 ℃, heating at a rate of 5 ℃/min, and keeping the temperature for 3h to obtain precursor carbon spheres;
(4) and (3) placing the precursor carbon spheres in deionized water for soaking for 12h, washing with the deionized water for 5 times, and drying in a vacuum drying oven at 80 ℃ for 12h to obtain the product.
Example 3
The spray drying temperature was 150 ℃ and the other conditions were the same as in example 1.
Example 4
The molar ratio of the bismuth potassium citrate to the antimony potassium tartrate is 1: 10, and the mass ratio of the bismuth potassium citrate, the ammonium citrate and the potassium chloride is 1: 2: 1. The other conditions were the same as in example 1.
Example 5
The molar ratio of the bismuth potassium citrate to the antimony potassium tartrate is 1: 0.1, and the mass ratio of the bismuth potassium citrate, the ammonium citrate and the potassium chloride is 1: 5. The other conditions were the same as in example 1.
Comparative example 1
The same procedure as in example 1 was repeated except that sodium chloride was used instead of potassium chloride.
Comparative example 2
Sb @ TCS was obtained under the same conditions as in example 1, except that potassium bismuth citrate was not used and the same amount of potassium antimony tartrate was used instead.
Comparative example 3
Bi @ TCS was obtained without using antimony potassium tartrate, by substituting the same amount of potassium bismuth citrate under the same conditions as in example 1.
Comparative example 4
TCS was obtained by substituting equal amounts of citric acid instead of antimony potassium tartrate and potassium bismuth citrate under the same conditions as in example 1.
And (3) performance testing:
the results of the electrochemical performance test of the carbon spheres prepared in the examples 1 to 5 when the carbon spheres are used for the negative electrode of the potassium ion battery are shown in table 1, and the results of the electrochemical performance test of the carbon spheres 1 to 5 when the carbon spheres are used for the negative electrode of the sodium ion battery are shown in table 2.
TABLE 1 parameters for microsphere preparation and corresponding electrochemical performance of potassium ion batteries of examples 1-5
TABLE 2 parameters for the preparation of the microspheres of examples 1-5 and corresponding electrochemical performance of sodium ion batteries
The electrochemical performance test results of the products prepared in comparative examples 1-4 when used in the negative electrode of the potassium ion battery are shown in Table 3.
TABLE 3 parameters for the preparation of the products of comparative examples 1-4 and corresponding electrochemical performance of potassium ion batteries
FIG. 1 XRD spectrum of BiSb @ TCS prepared in example 1; FIG. 2 SEM image of BiSb @ TCS prepared in example 1; FIG. 3 TEM image of BiSb @ TCS prepared in example 1 (microsphere part, BiSb particles embedded in carbon flakes); FIG. 4 FTIR spectrum of BiSb @ TCS prepared in example 1; FIG. 5 BiSb @ TCS prepared in example 1 is 2A g -1 Long cycle cycling performance at current density; in the figure, BiSb @ TCS was prepared for example 1, Sb @ TCS was prepared for comparative example 2, Bi @ TCS was prepared for comparative example 3, and TCS was prepared for comparative example 4; FIG. 6 Rate Performance of BiSb @ TCS prepared in example 1.
The results show that the chemical bond reinforced silver ear-shaped porous carbon spheres embedded with the monodisperse nano alloy particles prepared by the organic bismuth salt and the antimony salt have better electrochemical performance, and when the carbon spheres are used as a potassium ion battery cathode, the specific capacity of 120-345mAh/g can be kept after circulating for 50-5700 circles at 0.1-6A/g, and the circulating life exceeds 5700 circles. When the lithium ion battery is used as a sodium ion battery, the specific capacity of 150-450mAh/g can be maintained after 50-1000 cycles of cycling at 0.1-10A/g. On the other hand, if the formation of M-O-C chemical bonds is not promoted by potassium chloride or bismuth-antimony alloy is not formed, the material shows poor cycling stability and low specific capacity in the potassium ion battery.
Preparing a battery:
the adhesive is CMC, SBR or PVDF, the conductive agent is carbon black, and the mass ratio is as follows: the material, the adhesive and the carbon black are 8: 1;
testing in a half cell, wherein a counter electrode is a potassium sheet or a sodium sheet;
the solute of the electrolyte is KFSI or KPF 6 ，NaPF 6 And NaClO 4 Etc., the solvent is DME, EC, DEC, DMC, EMC, PC, etc., and the concentration ranges from 0.5M to 7M;
the test voltage window is 0.01-3.0V, and the test temperature is 25 ℃.
The test procedure was as follows:
(1) mixing the materials prepared in the examples or the comparative examples with an adhesive and a conductive agent, adding deionized water for grinding to prepare slurry, and coating the slurry on a copper foil to prepare a pole piece;
(2) and assembling the pole piece and the potassium sheet or the sodium sheet as the positive pole and the negative pole of the battery respectively to form the battery. The battery is filled with electrolyte.
(3) The assembled batteries were left to stand for 12 hours before testing in a battery cabinet.
It should be noted that the embodiments of the present invention are not limited by the above-mentioned examples, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (6)
1. A preparation method of chemical bond enhanced silver-ear-shaped porous carbon spheres embedding monodisperse nano alloy particles is characterized by comprising the following steps: the method comprises the following steps:
1) preparing organic bismuth salt, organic antimony salt, a water-soluble carbon source and potassium chloride into a solution by using water to obtain a precursor solution; preparing precursor microspheres from the precursor solution by removing the solvent in the precursor solution; the organic bismuth salt is water-soluble organic bismuth salt; the organic antimony salt is water-soluble organic antimony salt;
2) calcining the precursor microspheres in a protective atmosphere to obtain precursor carbon spheres embedding the monodisperse bismuth-antimony alloy nanoparticles;
3) dipping the precursor carbon spheres in water, washing and drying to obtain the silver-ear-shaped porous carbon spheres embedded with the monodisperse bismuth-antimony alloy nano particles;
the mol ratio of the organic bismuth salt to the organic antimony salt is 1: (0.1 to 10); the mass ratio of the organic bismuth salt to the water-soluble carbon source to the potassium chloride is 1: (1-5): (1-15);
the organic bismuth salt specifically comprises more than one of bismuth potassium citrate, bismuth sodium citrate, bismuth ammonium citrate, bismuth laurate, bismuth sodium tartrate and bismuth potassium tartrate;
the organic antimony salt specifically comprises one or more of potassium antimony tartrate, sodium antimony gluconate, and ammonium antimony gluconate;
the water-soluble carbon source is more than one of ammonium citrate, citric acid, sucrose, glucose and polyvinylpyrrolidone;
the step 1) of preparing the precursor solution into the precursor microspheres by removing the solvent in the precursor solution means that the precursor solution is prepared into the precursor microspheres by spray drying;
the calcining temperature in the step 2) is 400-900 ℃, and the calcining time is 1-10 h; the protective atmosphere in the step 2) is nitrogen or argon;
the chemical formula of the nano alloy particles is BiSb x And x is more than or equal to 0.1 and less than or equal to 10; the nano alloy particles BiSb x Embedded in a two-dimensional carbon sheet of a porous carbon sphere in the shape of a silver ear, and the nano alloy particles BiSb x Is 6-10nm, the size of the porous carbon spheres of the silver ear shape is 1-4um, and the nano alloy particles BiSb x And a chemical bond M-O-C exists between the carbon substrate and the carbon substrate of the porous carbon ball with the shape of the auricle, wherein the M-O-C represents Bi-O-C and Sb-O-C.
2. The method for preparing chemical bond enhanced monodisperse nano-alloy particle embedded porous carbon tremella-like spheres as claimed in claim 1, wherein the chemical bond enhanced monodisperse nano-alloy particle embedded porous carbon tremella-like spheres comprises the following steps: the conditions of the spray drying are as follows: the liquid flow rate is 1-10mL/min, the spray drying temperature is 100-.
3. The method for preparing chemical bond enhanced monodisperse nano-alloy particle embedded porous carbon tremella-like spheres as claimed in claim 1, wherein the chemical bond enhanced monodisperse nano-alloy particle embedded porous carbon tremella-like spheres comprises the following steps:
the dipping time in the step 3) is 1-12 h.
4. The method for preparing chemical bond enhanced monodisperse nano-alloy particle embedded porous carbon tremella-like spheres as claimed in claim 1, wherein the chemical bond enhanced monodisperse nano-alloy particle embedded porous carbon tremella-like spheres comprises the following steps:
the mass volume ratio of the organic antimony salt to water is (0.1-10) g: 100 mL;
heating to the calcining temperature in the step 2), wherein the heating rate is 1-5 ℃/min;
the dipping time in the step 3) is 1-12 h; the washing in the step 3) is performed for 3-6 times, wherein the washing refers to washing with water; the drying temperature is 60-100 ℃, and the drying time is 5-12 h.
5. A chemically bond-enhanced monodispersed nano-alloy particle-embedded porous carbon sphere in the form of a porous Tremella-shaped carbon sphere obtained by the preparation method according to any one of claims 1 to 4.
6. The use of chemically-enhanced, monodisperse nanoalloy particle-embedded porous carbon sphere of the claims 5, wherein: the chemical bond reinforced silver ear-shaped porous carbon ball embedded with the monodisperse nano alloy particles is used for a potassium ion battery cathode and/or a sodium ion battery cathode.
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