CN112331836A - Tin oxide-hard carbon composite negative electrode material and preparation method and application thereof - Google Patents
Tin oxide-hard carbon composite negative electrode material and preparation method and application thereof Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention relates to a preparation method of a tin oxide-hard carbon composite negative electrode material, which comprises the steps of mixing and stirring a phenol monomer, an aldehyde monomer, a tin salt, a sacrificial template agent and water to prepare a precursor solution; granulating the precursor solution by a spray drying method to obtain precursor granules; calcining the precursor particles to obtain a tin oxide-hard carbon composite anode material; a tin oxide-hard carbon composite negative electrode material is prepared according to the preparation method; an application of a tin oxide-hard carbon composite negative electrode material in a lithium ion battery. The invention has the beneficial effects that: the hard carbon and the tin oxide with high specific capacity are compounded by using a spray drying method, so that the test specific capacity of the lithium ion battery is improved and is far higher than that of a commercial graphite material; the cycling stability of the lithium ion battery is improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a tin oxide-hard carbon composite negative electrode material and a preparation method and application thereof.
Background
The current 3C products, electric vehicles, energy storage power stations and other application scenes put forward higher requirements on lithium ion batteries, and more electric quantity is expected to be stored by using smaller volume or lighter mass, so that the improvement of the mass/volume energy density of the lithium ion batteries is important for the lithium ion batteries, the improvement of the specific capacity of an electrode material is one of important strategies for improving the energy density of the lithium ion batteries, wherein the negative electrode material takes carbon as a matrix, and an alloy type negative electrode with high specific capacity is compounded in an important mode.
The hard carbon material is a non-graphitizable amorphous carbon material, has a short-range order and a long-range disorder structure, and can be described as amorphous carbon formed by disordered stacking of countless tiny graphite-like nano chips, wherein defects and gaps are filled. The hard carbon material has good physical and chemical stability due to the unique disordered structure, the carbon-based material has good electrical conductivity, and in addition, the hard carbon material can be obtained by pyrolysis of a high polymer material and a biomass material, so that the structural design is easy to carry out, and the hard carbon material is a good composite material substrate.
The alloyed negative electrode material has ultrahigh theoretical specific capacity, such as 4200mAh/g of Si, 992mAh/g of Sn, and tin oxides of SnO and SnO2The high theoretical specific capacity of 875mAh/g and 783mAh/g is far more than 372mAh/g of the graphite material, wherein tin oxide has strong physical and chemical stability, is easy to obtain by salt material conversion, has strong structural design and is a good composite material additive.
Compounding hard carbon materials with high capacity alloyed reactive cathodes is a good strategy in order to increase the specific capacity of hard carbon materials: on one hand, the specific capacity of the material can be greatly increased by introducing the alloying reaction type negative electrode; on the other hand, the hard carbon material can also be used as a buffer matrix of the alloying reaction type negative electrode, so that the damage to an electrode structure caused by volume expansion in the charging and discharging processes is reduced, the conductivity of the electrode is improved, the electrochemical performance of the electrode material is further optimized, however, the problem of expansion caused by the alloying type negative electrode cannot be completely solved by single carbon compounding, and a modification space still exists.
In summary, the prior art still lacks a cathode material which has high specific capacity and high stability and is formed by compounding an alloying cathode and a carbon-based cathode through a precise structural design.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a tin oxide-hard carbon composite negative electrode material, and a preparation method and application thereof, so as to overcome the defects in the prior art.
The technical scheme for solving the technical problems is as follows: a preparation method of a tin oxide-hard carbon composite negative electrode material comprises the following steps:
s100, mixing and stirring a phenol monomer, an aldehyde monomer, a tin salt, a sacrificial template agent and water to prepare a precursor solution;
s200, granulating the precursor liquid to obtain precursor particles;
s300, calcining the precursor particles to obtain the tin oxide-hard carbon composite negative electrode material,
wherein, the generation of the tin oxide comes from carbothermic reduction reaction in the calcining process, the heat treatment temperature is 400-600 ℃, the atmosphere is nitrogen, and the tin oxide comprises one or two of tin, tin monoxide and tin dioxide.
On the basis of the technical scheme, the invention can be further improved as follows.
Furthermore, the sacrificial template agent is polystyrene polymer microspheres, and the polystyrene polymer microspheres can be completely decomposed by calcining in an inert atmosphere at 400-600 ℃, so that pores are formed in the hard carbon matrix.
Further, the sacrificial template is prepared by adopting an emulsion polymerization method.
Further, the synthesis process of the sacrificial template agent is as follows:
adding 1-10 parts of sodium dodecyl sulfate and 1-10 parts of sodium bicarbonate into 1000 parts of water at the temperature of 60-100 ℃ and stirring;
and then, dripping 100-150 parts of styrene monomer and 1-10 parts of potassium persulfate into the solution, and stirring for 12-24 hours to obtain the polystyrene polymer sacrificial template.
Further, the phenolic monomer is one of phenol, catechol and resorcinol;
the aldehyde monomer is one of formaldehyde and furfural;
the tin salt is one of tin acetate, stannic chloride and sodium stannate.
Further, step S100 specifically includes:
adding 5-10 parts of phenol monomers, 5-10 parts of aldehyde monomers, 1-5 parts of tin salt and 1-5 parts of sacrificial template agent into 100 parts of water, and stirring for 12-18 hours to obtain a precursor solution.
Further, the precursor liquid granulation adopts a spray drying method, the spray drying is airflow type, the air inlet temperature is 150-200 ℃, the air outlet temperature is 40-60 ℃, and the feeding speed is 1-5 ml/s.
Further, the calcining temperature is 400-600 ℃.
The tin oxide-hard carbon composite negative electrode material is prepared by the preparation method.
An application of a tin oxide-hard carbon composite negative electrode material in a lithium ion battery.
The invention has the beneficial effects that:
the tin oxide-hard carbon composite negative electrode material is a porous micron composite particle with a designed structure, wherein the tin oxide provides high lithium storage specific capacity, the hard carbon material provides high conductivity and a stable matrix, the structure can be completely and controllably adjusted to adapt to various requirements, and a hollow porous composite structure manufactured by a sacrificial template agent in the tin oxide composite negative electrode material can well relieve the problems of expansion and agglomeration of the tin oxide in circulation, so that the composite negative electrode has high specific capacity and high stability, the stable circulation specific capacity after 50 circles of the composite negative electrode is 660mAh/g under the current density of 200mA/g, which is nearly twice of the specific capacity of a commercial graphite material, and the capacity retention rate is 86%;
the preparation process is simple, the operability is strong, and the practical popularization and large-scale application are facilitated.
Drawings
FIG. 1 is an X-ray diffraction pattern of a tin oxide-hard carbon composite anode material prepared by the present invention;
FIG. 2 is a morphology diagram of a tin oxide-hard carbon composite anode material particle prepared by the present invention, wherein the left diagram is a scanning electron microscope diagram, and the right diagram is a transmission electron microscope diagram;
FIG. 3 is a constant current charge-discharge curve and cycle performance diagram of the tin oxide-hard carbon composite negative electrode material prepared by the invention when applied to a lithium ion battery negative electrode, wherein the current density is 200mA/g, and the voltage interval is 0-3V;
FIG. 4 is a graph showing a comparison of the cycle characteristics of example 1, comparative example 1 and comparative example 2, and showing a current density of 200mA/g and a voltage interval of 0 to 3V.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1
A preparation method of a tin oxide-hard carbon composite negative electrode material comprises the following steps:
preparing a sacrificial template agent by an emulsion polymerization method:
adding 0.5g of sodium dodecyl sulfate and 0.2g of sodium bicarbonate into 250ml of deionized water at the temperature of 80 ℃, stirring, then dripping 40ml of styrene monomer and 0.1g of potassium persulfate into the solution, and stirring for 14 hours to obtain a polystyrene polymer sacrificial template;
2g of catechol and 2ml of 37 percent by weight formaldehyde solution are mixed in 80ml of deionized water, 1g of sodium stannate and 20ml of sacrificial template solution are added, and the mixture is mixed and stirred to prepare precursor solution;
granulating the precursor liquid by a spray drying method to obtain precursor granules, wherein the spray drying is of an airflow type, the air inlet temperature is 180 ℃, the air outlet temperature is 60 ℃, and the feeding speed is 2 ml/s;
and calcining the precursor particles for 2 hours at 550 ℃ in a nitrogen atmosphere to obtain the tin monoxide-hard carbon composite anode material.
Comparative example 1
This example differs from example 1 in that no sacrificial template was added and no pore was formed inside the particles.
Comparative example 2
This example differs from example 1 in that no tin salt was added and no high capacity tin oxide was incorporated into the particles.
Test examples
The morphology and structure tests of example 1 were performed, including scanning electron microscope tests and transmission electron microscope tests, and the structure tests were X-ray diffraction tests.
Electrode tabs were made from the materials prepared in example 1 and comparative examples 1 and 2 and assembled into 2032 button cells for electrochemical testing as described below.
Firstly, preparing an electrode plate, wherein a negative electrode active material is prepared by the materials prepared in the embodiment 1, the comparative embodiment 1 and the comparative embodiment 2, a conductive agent is conductive carbon black (Super P, Timcal Ltd.), a binder is polyvinylidene fluoride (PVDF, HSV 900, Arkema), a dispersant is N-methyl-2-pyrrolidone (NMP), and the weight percentages of the active materials are as follows: super P: mixing and grinding PVDF (polyvinylidene fluoride) in a mass ratio of 7:2:1, coating the mixture on a copper foil, drying, rolling, punching to prepare an electrode plate, and controlling the active substance on the surface of the electrode to be 2mg/cm2；
Then, a 2032 button cell is manufactured in a glove box filled with argon, a lithium sheet is used as a counter electrode, a polypropylene microporous membrane is used as a diaphragm, and electrochemical tests, namely constant current charge and discharge tests, are respectively carried out on the three groups of cells; the voltage window was set at 0-2V, the current density was 200mA/g, and all charge and discharge cycle tests were performed at 25 ℃ at room temperature during the experiment.
Example 1, X-ray diffraction test shows that fig. 1 is obtained, and comparison shows that the known phases of the PDF card are hard carbon and tin monoxide; as can be seen from the scanning electron microscope image of fig. 2, the negative electrode of the tin oxide-hard carbon composite material prepared in example 1 is spherical-like particles with a particle size of 1-5 μm, and it can be clearly observed that the surfaces of the particles are full of pores; as can also be seen from the transmission electron microscope image of fig. 2, the composite material has a porous structure and a plurality of tin oxide particles are supported therein; it is comprehensively proved that the composite material of example 1 is a hollow porous composite structure, the tin oxide particles improve the capacity of the composite material, the hard carbon matrix provides a coating structure and good conductivity, and the sacrificial template agent forms pores in the hard carbon matrix and relieves the volume expansion of the tin oxide particles in the circulation process.
Through constant-current charge-discharge test analysis, in the embodiment 1 shown in fig. 3, under a current density of 200mA/g, the first-cycle charging specific capacity is 770mAh/g, and the stable cycle specific capacity after 50 cycles is 660mAh/g, which is nearly twice of the specific capacity of a commercial graphite material, the capacity retention rate is 86%, and the electrochemical performance is good; further comparison of example 1 with comparative example 1 without pore formation, comparative example 2 without tin oxide addition gave FIG. 4: in comparative example 1, since no expansion space of tin oxide is built inside the particles, although the specific charge capacity of the first cycle is still a high value of 890mAh/g under the current density of 200mA/g, the cycle stability is extremely poor, the cycle capacity fluctuates continuously, the attenuation is fast, and the capacity retention rate is only 53% after 50 cycles; while comparative example 2 had only a first turn charge capacity of 201mAh/g at a current density of 200mA/g due to the absence of tin oxide particles inside the particles.
Example 2
A preparation method of a tin oxide-hard carbon composite negative electrode material comprises the following steps:
preparing a sacrificial template agent by an emulsion polymerization method:
adding 0.5g of sodium dodecyl sulfate and 0.2g of sodium bicarbonate into 250ml of deionized water at the temperature of 80 ℃, stirring, then dripping 40ml of styrene monomer and 0.1g of potassium persulfate into the solution, and stirring for 14 hours to obtain a polystyrene polymer sacrificial template;
2g of catechol and 2ml of 37 percent by weight formaldehyde solution are mixed in 80ml of deionized water, 1g of sodium stannate and 20ml of sacrificial template solution are added, and the mixture is mixed and stirred to prepare precursor solution;
granulating the precursor liquid by a spray drying method to obtain precursor granules, wherein the spray drying is of an airflow type, the air inlet temperature is 180 ℃, the air outlet temperature is 60 ℃, and the feeding speed is 2 ml/s;
calcining the precursor particles for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain a tin dioxide-tin monoxide-hard carbon composite anode material; calcining for 2 hours at 600 ℃ to obtain the tin monoxide-simple substance tin-hard carbon composite cathode material.
Example 3
A preparation method of a tin oxide-hard carbon composite negative electrode material comprises the following steps:
preparing a sacrificial template agent by an emulsion polymerization method:
adding 0.5g of sodium dodecyl sulfate and 0.2g of sodium bicarbonate into 250ml of deionized water at the temperature of 80 ℃, stirring, then dripping 40ml of styrene monomer and 0.1g of potassium persulfate into the solution, and stirring for 14 hours to obtain a polystyrene polymer sacrificial template;
mixing 2g of phenol and 1ml of 80 wt% furfural solution in 80ml of deionized water, adding 1g of sodium stannate and 20ml of sacrificial template solution, and mixing and stirring to obtain a precursor solution;
granulating the precursor liquid by a spray drying method to obtain precursor granules, wherein the spray drying is of an airflow type, the air inlet temperature is 200 ℃, the air outlet temperature is 60 ℃, and the feeding speed is 2 ml/s;
and calcining the precursor particles for 2 hours at 550 ℃ in a nitrogen atmosphere to obtain the tin oxide-hard carbon composite negative electrode material.
In summary, the tin oxide-hard carbon composite anode material of the present invention can be demonstrated to have excellent electrochemical performance in examples 1, 2 and 3, and comparative examples 1 and 2.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of a tin oxide-hard carbon composite negative electrode material is characterized by comprising the following steps:
s100, mixing and stirring a phenol monomer, an aldehyde monomer, a tin salt, a sacrificial template agent and water to prepare a precursor solution;
s200, granulating the precursor liquid to obtain precursor particles;
and S300, calcining the precursor particles to obtain the tin oxide-hard carbon composite negative electrode material.
2. The preparation method of the tin oxide-hard carbon composite anode material as claimed in claim 1, wherein the sacrificial template is polystyrene polymer microspheres.
3. The method for preparing the tin oxide-hard carbon composite anode material as claimed in claim 2, wherein the sacrificial template is prepared by emulsion polymerization.
4. The preparation method of the tin oxide-hard carbon composite anode material as claimed in claim 3, wherein the synthesis process of the sacrificial template is as follows:
adding 1-10 parts of sodium dodecyl sulfate and 1-10 parts of sodium bicarbonate into 1000 parts of water at the temperature of 60-100 ℃ and stirring;
and then, dripping 100-150 parts of styrene monomer and 1-10 parts of potassium persulfate into the solution, and stirring for 12-24 hours to obtain the polystyrene polymer sacrificial template.
5. The method for preparing the tin oxide-hard carbon composite anode material according to claim 1, wherein the phenolic monomer is one of phenol, catechol and resorcinol;
the aldehyde monomer is one of formaldehyde and furfural;
the tin salt is one of tin acetate, stannic chloride and sodium stannate.
6. The method for preparing a tin oxide-hard carbon composite anode material according to claim 1, wherein the step S100 specifically comprises:
adding 5-10 parts of phenol monomers, 5-10 parts of aldehyde monomers, 1-5 parts of tin salt and 1-5 parts of sacrificial template agent into 100 parts of water, and stirring for 12-18 hours to obtain a precursor solution.
7. The preparation method of the tin oxide-hard carbon composite anode material as claimed in claim 1, wherein the precursor liquid is granulated by a spray drying method, the spray drying is an air flow type, the air inlet temperature is 150-200 ℃, the air outlet temperature is 40-60 ℃, and the feeding speed is 1-5 ml/s.
8. The method for preparing a tin oxide-hard carbon composite anode material according to claim 1, wherein the calcining temperature is 400 ℃ to 600 ℃.
9. A tin oxide-hard carbon composite anode material characterized by being produced by the production method according to any one of claims 1 to 8.
10. Use of the tin oxide-hard carbon composite anode material of claim 9 in a lithium ion battery.
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| CN116799219A (en) * | 2023-08-25 | 2023-09-22 | 浙江华宇钠电新能源科技有限公司 | Tin-based oxide nanocrystalline modified hard carbon, sodium ion battery and vehicle |
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