CN111082034B - Preparation of tin/tin phosphide/carbon composite material of alkali metal ion battery cathode - Google Patents
Preparation of tin/tin phosphide/carbon composite material of alkali metal ion battery cathode Download PDFInfo
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Abstract
The invention discloses a preparation method of a tin/tin phosphide/carbon composite material of an alkali metal ion battery cathode; the method mainly comprises the following steps: firstly, crosslinking sodium alginate and tetravalent tin ions, using sodium chloride as an inhibitor, then freeze-drying a crosslinking product, carbonizing the product in an inert atmosphere, and then phosphorizing the product by using sodium hypophosphite to obtain the tin/tin phosphide/carbon composite material. According to the invention, nano-sized tin oxide particles are generated by a sodium alginate crosslinking method and are wrapped by graphitized carbon, a better pore channel structure is formed in a macromolecule cracking process, and the structure of the tin/tin phosphide/carbon composite material is maintained while the tin/tin phosphide/carbon composite material is obtained by using gaseous phosphorization, so that the prepared composite material has good pore channel and conductivity, can effectively inhibit the expansion of tin, and has good cycle performance and rate capability when being used for an alkali metal ion battery. The method is simple to operate, low in process cost and easy for industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of preparation of an alkali metal ion battery cathode material, in particular to preparation of a tin/tin phosphide/carbon composite material of an alkali metal ion battery cathode.
Background
The lithium ion battery is the best-known alkali metal ion battery, is a secondary battery, and has the advantages of high energy density, environmental friendliness, good safety and the like. The negative electrode used by the lithium ion battery at present is mainly graphite, the cost of the graphite is low, but the capacity is small, and the graphite cannot meet the current requirement along with the improvement of the energy storage requirement. Therefore, the development of new anode materials is imminent.
The tin-based material is a promising alkali metal ion battery negative electrode material due to the advantages of environmental friendliness, high specific capacity and the like, but the volume expansion rate of the tin-based material in the circulating process is high, so that electrodes are pulverized and fall off, and the performance of the battery is degraded. Nanocrystallization and carbon coating are one strategy to effectively alleviate this problem. Nanocrystallization refers to the reduction of the size of a material to the nanometer scale, thereby mitigating the effects of its deformation. And the carbon coating can buffer the volume expansion and improve the overall conductivity of the material. However, some of the existing nanocrystallization and carbon coating methods are complex and cannot be compatible. For example, liujianghong et al invented a method for preparing carbon-coated manganous oxide (patent No. CN 201410666514.0), which uses acrylonitrile oligomer as raw material to perform carbon coating, and needs to perform heating, stirring and drying for many times, and takes a long time. On-line cracking atomization composite precursor for preparing SnO invented by deep and deep dawn 2 Method for preparing amorphous carbon composite material (patent number: CN 201810778802.3), and SnO is used in the method 2 The mixture of alcohol soluble glue and glucose as precursor is converted into aerosol by ultrasonic atomizer and introduced into quartz tube with temperature up to 1100-1200 deg.C by using carrier gas for cracking, and the method is complicated and the temperature is higher than 1000 deg.C to make SnO 2 The particle size of (2) is larger.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a tin/tin phosphide/carbon composite material of an alkali metal ion battery cathode, which comprises the following steps: namely, the characteristic of cross-linking of sodium alginate and tin ions is utilized, the tin ions are subjected to nano-scale local confinement through the macromolecules of the sodium alginate, a nano-scale carbon-coated tin oxide composite material is generated in the high-temperature reaction process, and the structure is maintained by utilizing gaseous phosphorization to obtain the tin and tin phosphide carbon composite material. Specifically, sodium alginate and tin ions can generate a cross-linking reaction to form a uniformly dispersed egg-box (egg-box) structure, the egg-box structure is carbonized through a local confinement effect of the structure to obtain a tin oxide/carbon nano composite material, and then gaseous phosphine energy is utilized to phosphorize tin oxide in situ to generate tin and tin phosphide without damaging the structure of the tin oxide/carbon nano composite material, so that the tin and tin phosphide carbon composite material is prepared.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a preparation method of a tin/tin phosphide/carbon composite material for a negative electrode of an alkali metal ion battery, which comprises the following steps:
s1, under the condition of adding sodium ions as an inhibitor, carrying out a cross-linking reaction on sodium alginate and tetravalent tin ions to generate gel;
s2, calcining and carbonizing the gel in an inert atmosphere after freeze drying to obtain a tin oxide/carbon composite material;
and S3, phosphating the tin oxide/carbon composite material by using sodium hypophosphite in an inert atmosphere to obtain the tin/phosphated tin/carbon composite material.
In the invention, step S1, sodium alginate and tetravalent tin ions are crosslinked to form gel beads by utilizing the characteristic that sodium alginate can be crosslinked with polyvalent metal ions. The metal component obtained by crosslinking sodium alginate has good uniformity, fine particle size and good carbon coating structure.
And S3, in the phosphorization process, sodium hypophosphite is decomposed under heating to form phosphine gas, the phosphine in situ reduces tin metal tin oxide, and the excessive phosphine continuously reacts with tin to generate tin phosphide.
Further, in step S1, sodium alginate is dissolved in water to prepare a sol with a mass concentration of 1-2%, and the sodium alginate sol is dropped into a tin tetrachloride solution with a concentration of 0.1-0.2 mol/L to perform a crosslinking reaction. Too low a concentration of metal ions will result in incomplete crosslinking, while too high a concentration will result in waste.
Further, in step S1, the crosslinking reaction is performed under the condition of adding sodium ions as an inhibitor. The addition of sodium ions (such as sodium chloride) as an inhibitor can make the concentration of metal ions in the gel more uniform.
Further, tin: sodium molar ratio 1:1-5 sodium chloride is used as an inhibitor to ensure that the metal ions in the gel are distributed more uniformly during crosslinking; too large a proportion of sodium chloride can affect gel strength, leading to failure of crosslinking; the crosslinking reaction time is 24-48 h.
Further, in step S1, the G segment of sodium alginate, i.e., guluronic acid, reacts with tetravalent tin ions to form a gel, and a uniform egg-box (egg-box) structure is formed in sodium alginate.
Further, in step S2, the gel washed with the deionized water is freeze-dried at-70 to-50 ℃ (preferably-60 ℃) for 1 to 3 days.
Further, in step S2, the carbonization method specifically includes: calcining for 1-2 hours at the temperature rising rate of 5-10 ℃ per minute under the protection of inert atmosphere at the temperature of 500-1200 ℃ so as to fully perform the carbonization reaction.
Further, in step S2, after the carbonization, deionized water is used for washing, and then vacuum drying is performed for 12 to 24 hours.
Further, the step S3 includes the step of grinding and mixing the tin oxide/carbon composite material with a molar ratio of tin to phosphorus of 1 to 2-1 with sodium hypophosphite, wherein the grinding and mixing time is 15-30 minutes to ensure that the tin oxide/carbon composite material and the sodium hypophosphite are uniformly mixed, too little sodium hypophosphite will cause incomplete reaction, and too much sodium hypophosphite will cause waste.
Further, in step S3, the phosphating method specifically includes: under an inert atmosphere, sodium hypophosphite (NaH) is used 2 PO 2 ) As a phosphorus source, phosphorizing at 200-400 ℃ for 5-30 minutes at a temperature rise rate of 5-10 ℃ per minute to ensure that the phosphorizing reaction is fully completed. The phosphating process can preserve the structure of the tin oxide/carbon composite material.
Further, in step S3, after the phosphorization is finished, the glass is sequentially washed by deionized water and 0.05mol/L dilute hydrochloric acid, and then is dried in vacuum for 12-24 hours.
Further, in step S3, the structure of the tin/tin phosphide/carbon composite material is specifically: the metal component of 3-5nm is uniformly distributed in the carbon matrix, and a plurality of graphitized carbon layers are wrapped around the carbon matrix. Under the preparation condition, in the carbonization process, sodium alginate is cracked at high temperature to generate a carbon material with high carbon content to wrap tin oxide, the temperature is continuously increased, the tin oxide is mutually agglomerated and grown up, and carbon is extruded out to wrap the carbon material around particles to form a carbon layer.
Compared with the prior art, the invention has the following beneficial effects:
1) The method uses sodium alginate as a raw material, and obtains the carbon composite material of tin and tin phosphide by a method of crosslinking, carbonizing and re-phosphorizing with tetravalent tin ions; the method has simple operation, low process cost and easy synthesis; in addition, when sodium alginate and tin ions are subjected to crosslinking carbonization, uniform mesopores are introduced, and tin can catalyze graphitization of the carbon layer to a certain degree, so that the conductivity of the material is improved;
2) When the tin/tin phosphide/carbon composite material prepared by the invention is applied to the cathode of an alkali metal ion battery, the uniform pore channels in the tin/tin phosphide/carbon composite material can be used as a transmission path of alkali metal ions, fine metal component particles enable the carbon coating effect to be better, meanwhile, the carbon layer can improve the conductivity of the material and inhibit the volume expansion of tin, and phosphorus can form a matrix to further inhibit the volume expansion of tin, so that the material can show good cycle performance and rate capability.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
fig. 1 is a transmission electron micrograph of a tin-based carbon composite material obtained in example 1 of the present invention: wherein, a and b are electron micrographs of the tin oxide/carbon composite material, and c and d are electron micrographs of the tin/tin phosphide/carbon composite material;
FIG. 2 is an X-ray diffraction pattern of a tin/tin phosphide/carbon composite material obtained in example 1 of the present invention;
FIG. 3 is a Raman spectrum of a tin/tin phosphide/carbon composite material obtained in example 1 of the present invention;
FIG. 4 is a nitrogen adsorption/desorption curve of the tin/tin phosphide/carbon composite material obtained in example 1 of the present invention;
FIG. 5 is a graph showing the pore size distribution of the tin/tin phosphide/carbon composite material obtained in example 1 of the present invention;
FIG. 6 is a comparison of rate capability of the tin/tin phosphide/carbon composite and the tin oxide/carbon composite obtained in example 1 of the present invention in a negative electrode of a lithium ion battery;
FIG. 7 is a comparison of the cycling performance of the tin/tin phosphide/carbon composite and the tin oxide/carbon composite obtained in example 1 of the present invention in a negative electrode of a lithium ion battery, wherein the current density is 0.1A/g;
FIG. 8 is a comparison of the cycling performance of the tin/tin phosphide/carbon composite material and the tin oxide/carbon composite material obtained in example 1 of the present invention in a negative electrode of a lithium ion battery, wherein the current density was 1A/g.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment relates to a preparation method of a tin/tin phosphide/carbon composite material, which comprises the following steps:
step one, crosslinking reaction: dissolving 3g of sodium alginate in 197ml of deionized water to prepare a solution with the mass fraction of 1.5%. Mixing sodium: sodium chloride and crystallized tin tetrachloride with the tin molar ratio of 3. Slowly dripping sodium alginate into the metal ion water solution, stirring and reacting for 24 hours, and waiting for the crosslinking reaction to be completely finished. The crosslinked product was washed with deionized water 3 times, and then put into a freeze-dryer to be freeze-dried at-60 ℃ for 24 hours.
Step two, carbonization: transferring the sodium alginate pellets after freeze drying into a tube furnace, heating to 550 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, and preserving the heat for 1 hour to obtain the tin oxide/carbon composite material.
Step three, phosphorization: cleaning and drying the tin oxide/carbon composite material, and mixing with sodium hypophosphite according to the ratio of tin: mixing the materials according to the molar ratio of phosphorus to 1; and washing the composite material by using deionized water and 0.05mol/L diluted hydrochloric acid, and then drying the composite material in vacuum for 12 hours to obtain the tin/tin phosphide/carbon composite material.
The implementation effect is as follows:
as shown in fig. 1-a (bar =50 nm), 1-b (bar =20 nm), the tin oxide/carbon composite material obtained by the above method has tin oxide particles of about 3 to 5nm uniformly distributed in the carbon matrix. As shown in fig. 1-c (bar =20 nm) and 1-d (bar =5 nm), the tin phosphide around 3-5nm is uniformly distributed in the carbon matrix, and some tin melts and grows to form larger particles. The X-ray diffraction pattern of the tin/tin phosphide/carbon composite material is shown in figure 2, showing a mixture of elemental tin and tin phosphide. A raman ray diagram is shown in fig. 3, which demonstrates the higher degree of graphitization of the composite material. The nitrogen adsorption-desorption curve and pore size distribution curve of this material are shown in fig. 4 and 5, which show its better pore structure. 0.1g of the composite material was taken, and the ratio of 8:1:1, adding the composite material, conductive carbon black and a binder (the component is polyvinylidene fluoride PVDF is dissolved in N-methyl pyrrolidone NMP, the mass concentration is 0.02 g/ml), stirring to form slurry, uniformly coating the slurry on a copper foil, cutting the slurry into a circular electrode slice with the diameter of 11mm after drying, drying and weighing. In a glove box containing argon atmosphere having a water oxygen content of less than 0.5ppm, a lithium metal was used as a counter electrode, a polyolefin porous membrane was used as a separator, and a 1mol/L lithium hexafluorophosphate solution (solvent: 1 by volumeEster, dimethyl carbonate) as an electrolyte, and electrode sheets were assembled into a CR2016 type half cell. The half cell was subjected to charge and discharge, cyclic voltammetry and ac impedance testing. FIG. 6 is a graph showing the rate capability of the composite material, wherein the specific capacity of the composite material is 598mAh/g at a current density of 0.1A/g, and the specific capacity of the composite material is 247mAh/g at a current density of 5A/g, compared with SnO 2 The multiplying power performance of the/C composite material after phosphorization is improved. FIG. 7 is a cycle performance diagram of the composite material, when the current density is 0.1A/g, the first coulombic efficiency is 50%, and the capacity is still 665mAh/g after 100 cycles, compared with SnO 2 The circulation performance of the/C composite material after phosphorization is improved. FIG. 8 shows the cycle performance of the composite material under a current density of 1A/g, the first discharge ratio is 1767mAh/g, the discharge ratio continuously rises after a period of capacity attenuation, the specific capacity is up to 920mAh/g after 500 circles, and compared with SnO 2 The capacity of the/C composite material is obviously higher.
Example 2
The embodiment relates to a preparation method of a tin/tin phosphide/carbon composite material, which comprises the following steps:
step one, crosslinking reaction: 2g of sodium alginate is dissolved in 198ml of deionized water to prepare a solution with the mass fraction of 1%. Sodium chloride and crystallized tin tetrachloride in a molar ratio of 1. Slowly dripping sodium alginate into the metal ion water solution, stirring and reacting for 36 hours, and waiting for the crosslinking reaction to be completely finished. The crosslinked product was washed 3 times with deionized water, and then put into a freeze-dryer to be freeze-dried at-50 ℃ for 24 hours.
Step two, carbonization: transferring the sodium alginate pellets after freeze drying into a tube furnace, heating to 500 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, and preserving heat for 1 hour to obtain the tin oxide/carbon composite material.
Step three, phosphorization: cleaning and drying the tin oxide/carbon composite material, and mixing with sodium hypophosphite according to the ratio of tin: mixing the materials according to the molar ratio of phosphorus of 1. Washing with deionized water and 0.05mol/L diluted hydrochloric acid, and drying in vacuum for 12 hours to obtain the tin/tin phosphide/carbon composite material.
The implementation effect is as follows: the material prepared by the method retains the porous characteristic and the nanometer size characteristic. 0.1g of the composite material was taken, and the ratio of 8:1:1, adding the composite material, conductive carbon black and a binder (the component is polyvinylidene fluoride PVDF is dissolved in N-methyl pyrrolidone NMP, the mass concentration is 0.02 g/ml), stirring to form slurry, uniformly coating the slurry on a copper foil, cutting the slurry into a circular electrode slice with the diameter of 11mm after drying, drying and weighing. In a glove box with an argon atmosphere with the water oxygen content lower than 0.5ppm, metal sodium is used as a counter electrode, glass fiber is used as a diaphragm, 1mol/L sodium perchlorate solution (a solvent is ethylene carbonate and propylene carbonate in a volume ratio of 1. The half cell was subjected to charge and discharge, cyclic voltammetry and ac impedance testing. The composite material shows better electrochemical performance.
Example 3
The embodiment relates to a preparation method of a tin/tin phosphide/carbon composite material, which comprises the following steps:
step one, crosslinking reaction: 3g of sodium alginate is dissolved in 147ml of deionized water to prepare a solution with the mass fraction of 2%. Sodium chloride and crystallized tin tetrachloride in a molar ratio of 5. Slowly dripping sodium alginate into the metal ion water solution, stirring and reacting for 48 hours, and waiting for the crosslinking reaction to be completely finished. The crosslinked product was washed 3 times with deionized water, and then placed in a lyophilizer for freeze-drying at-70 ℃ for 72 hours.
Step two, carbonization: transferring the sodium alginate pellets after freeze drying into a tube furnace, heating to 1200 ℃ at the speed of 10 ℃/min under the atmosphere of nitrogen, and preserving heat for 1 hour to obtain the tin oxide/carbon composite material.
Step three, phosphorization: cleaning and drying the tin oxide/carbon composite material, and mixing with sodium hypophosphite according to the ratio of tin: mixing the materials according to the molar ratio of phosphorus of 1. Washing with deionized water and 0.05mol/L diluted hydrochloric acid, and drying in vacuum for 12 hours to obtain the tin/tin phosphide/carbon composite material.
The implementation effect is as follows: the material prepared by the method retains the porous characteristic and the nanometer size characteristic. 0.1g of the composite material was taken, and the ratio of 8:1:1, adding the composite material, conductive carbon black and a binder (the component is polyvinylidene fluoride PVDF is dissolved in N-methyl pyrrolidone NMP, the mass concentration is 0.02 g/ml), stirring to form slurry, uniformly coating the slurry on a copper foil, cutting the slurry into a circular electrode slice with the diameter of 11mm after drying, drying and weighing. In a glove box of an argon atmosphere with the water oxygen content of less than 0.5ppm, metal potassium is used as a counter electrode, glass fiber is used as a diaphragm, 1mol/L potassium hexafluorosilicate solution (the solvent is ethylene carbonate and propylene carbonate with the volume ratio of 1). The half cell was subjected to charge and discharge, cyclic voltammetry and ac impedance testing. The composite material has better electrochemical performance.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (7)
1. A method of preparing a tin/tin phosphide/carbon composite for use in an alkali metal ion battery anode, said method comprising the steps of:
s1, carrying out a crosslinking reaction on sodium alginate and tetravalent tin ions to generate gel;
s2, calcining and carbonizing the gel in an inert atmosphere after freeze drying to obtain a tin oxide/carbon composite material;
s3, phosphating the tin oxide/carbon composite material by using sodium hypophosphite in an inert atmosphere to obtain the tin/phosphated tin/carbon composite material;
in step S1, the crosslinking reaction is carried out under the condition of adding sodium ions as an inhibitor;
in step S1, tin is added: sodium chloride with a sodium molar ratio of 1; the crosslinking reaction time is 24-48 h;
in step S3, the phosphating method specifically includes: under the inert atmosphere, using sodium hypophosphite as a phosphorus source, and phosphorizing at 200-400 ℃ for 5-30 minutes at the heating rate of 5-10 ℃ per minute;
in step S3, the structure of the tin/tin phosphide/carbon composite material is specifically: the metal components with the particle size of 3-5nm are uniformly distributed in the carbon matrix, and a plurality of graphitized carbon layers are wrapped around the carbon matrix.
2. The method for preparing the tin/tin phosphide/carbon composite material for the negative electrode of the alkali metal ion battery as claimed in claim 1, wherein in step S1, sodium alginate is dissolved in water to prepare a sol with a mass concentration of 1-2%, and the sodium alginate sol is dropped into a tin tetrachloride solution with a concentration of 0.1-0.2 mol/L to perform a crosslinking reaction.
3. The method for preparing the tin/tin phosphide/carbon composite material for the negative electrode of the alkali metal ion battery as recited in claim 1, wherein in the step S1, a G segment in sodium alginate, i.e., guluronic acid, undergoes a spontaneous crosslinking reaction with tetravalent tin ions to form a gel, and a uniform "egg-box" structure is formed in sodium alginate.
4. The method for preparing the tin/tin phosphide/carbon composite material for the negative electrode of the alkali metal ion battery as claimed in claim 1, wherein in the step S2, the freeze-drying is to freeze-dry the gel washed with deionized water at-70 to-50 ℃ for 1 to 3 days.
5. The method for preparing the tin/tin phosphide/carbon composite material for the negative electrode of the alkali metal ion battery as claimed in claim 1, wherein in the step S2, the carbonization method is specifically: calcining for 1-2 hours at the temperature rising rate of 5-10 ℃ per minute and under the condition of 500-1200 ℃ under the protection of inert atmosphere.
6. The method for preparing a tin/tin phosphide/carbon composite material for an alkali metal ion battery negative electrode as recited in claim 1, wherein the step S3 comprises the step of subjecting the tin oxide/carbon composite material having a molar ratio of tin to phosphorus of 1 to 2 to 1.
7. The method for preparing the tin/tin phosphide/carbon composite material for the anode of the alkali metal ion battery as recited in claim 1, wherein in the step S3, after the completion of the phosphating, the composite material is washed with deionized water and 0.05mol/L diluted hydrochloric acid in sequence, and then vacuum-dried for 12 to 24 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107403911A (en) * | 2017-06-20 | 2017-11-28 | 江苏大学 | Graphene/transition metal phosphide/C-base composte material, preparation method and lithium ion battery negative electrode |
| CN108511714A (en) * | 2018-03-27 | 2018-09-07 | 燕山大学 | A kind of transition metal phosphide-carbon composite and its preparation method and application |
| CN108539197A (en) * | 2018-03-13 | 2018-09-14 | 上海交通大学 | The preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon |
| CN109346332A (en) * | 2018-10-17 | 2019-02-15 | 上海交通大学 | Lithium ion mixed capacitor and preparation method thereof based on alginic acid cross-linked structure |
| CN110034283A (en) * | 2018-09-17 | 2019-07-19 | 南方科技大学 | Phosphorization tin composite material and preparation method and application |
-
2019
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107403911A (en) * | 2017-06-20 | 2017-11-28 | 江苏大学 | Graphene/transition metal phosphide/C-base composte material, preparation method and lithium ion battery negative electrode |
| CN108539197A (en) * | 2018-03-13 | 2018-09-14 | 上海交通大学 | The preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon |
| CN108511714A (en) * | 2018-03-27 | 2018-09-07 | 燕山大学 | A kind of transition metal phosphide-carbon composite and its preparation method and application |
| CN110034283A (en) * | 2018-09-17 | 2019-07-19 | 南方科技大学 | Phosphorization tin composite material and preparation method and application |
| CN109346332A (en) * | 2018-10-17 | 2019-02-15 | 上海交通大学 | Lithium ion mixed capacitor and preparation method thereof based on alginic acid cross-linked structure |
Non-Patent Citations (1)
| Title |
|---|
| Salt effects on the cross-linking mechanism of cupric-induced sol-gel transition in alginate solutions;Honghe Zheng 等;《Carbohydrate Polymers》;19980430(第35期);第215-221页 * |
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