CN114420927A - Negative electrode material, preparation method thereof and negative electrode plate - Google Patents
Negative electrode material, preparation method thereof and negative electrode plate Download PDFInfo
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Abstract
The invention provides a negative electrode material, a preparation method thereof and a negative electrode plate. The decomposition of nitrogen element in the swelling agent and the continuous pore-forming of generated gas enable the carbon-based matrix to be in a loose and porous spongy state, the unique honeycomb structure not only has a large specific surface area and is beneficial to the infiltration of electrolyte, the strength and the stability of the honeycomb structure are improved by the matching use of nitrate, but also the volume expansion of the negative electrode material in the circulating process can be relieved, the circulating stability of the material is improved, the defect of circulating water jumping is improved, the circulating attenuation is greatly improved, and the problems that the particles of the spherical negative electrode material are broken in the circulating process, the spherical negative electrode material is separated from a pole piece and the like are solved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a negative electrode material, a preparation method thereof and a negative electrode sheet.
Background
Among various applicable energy storage technologies, alkali metal ion batteries have become a hot research in recent years as a general electrochemical energy storage means for portable and large-scale power storage. The alkali metal ion battery mainly comprises a Lithium Ion Battery (LIB), a Sodium Ion Battery (SIB), a Potassium Ion Battery (PIB) and the like, is in the same main group, has similar working principles, is a rocking chair type mechanism realized by means of ion migration in the charging and discharging process, has the advantage that the LIB is difficult to compare in the cost aspect because the storage capacity of sodium element in a ground shell is far higher than that of lithium element, and has good application prospect in the future.
For example, chinese patent document CN112838197A discloses a negative electrode material, which includes a doped carbon material, wherein a part of doped elements in the doped carbon material forms a C-Ma-Mb chemical bond with a carbon-based matrix, thereby effectively improving the fast charging performance of the negative electrode material, and solving the problem of poor fast charging and slow discharging performance of the conventional negative electrode material to a certain extent. But still has a great difference from practical application, cannot meet the use requirement of high-function output, has large capacity loss under the condition of fast charging and fast discharging, and still has large-amplitude cyclic attenuation.
Disclosure of Invention
Therefore, the invention aims to solve the problems of large capacity loss and serious cycle attenuation of the negative electrode material under the condition of quick charge and quick discharge in the prior art, and provides the negative electrode material, the preparation method thereof and the negative electrode sheet.
To this end, the invention provides an anode material, which comprises a carbon-based matrix, a doping element source and a swelling agent, wherein the doping element source comprises nitrate.
Further, the mass ratio of the carbon-based matrix to the expanding agent to the nitrate is 20-40:1-10: 20-30.
In a more preferred embodiment, the mass ratio of the carbon-based matrix to the expanding agent to the nitrate is 20-40:5-10: 20-30.
In a more preferred embodiment, the mass ratio of the carbon-based matrix to the expanding agent is greater than 6:1 and equal to or less than 2: 1.
Further, the swelling agent is at least one selected from hydrazine hydrate, hydrogen peroxide and ammonia water.
The swelling agent can adopt hydrazine hydrate solution, such as currently conventional hydrazine hydrate aqueous solution with the volume concentration of 30-50%.
Further, the carbon-based matrix is selected from at least one of sarcosine, cystine, serine, and dicyanodiamine.
Further, the nitrate is selected from at least one of aluminum nitrate nonahydrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate, and copper nitrate trihydrate.
Further, the anode material also satisfies at least one of the following (1) to (4):
(1) the doping element source also comprises a phosphorus source, preferably, the phosphorus source is selected from at least one of phytic acid, trimethyl phosphate and tributyl phosphate; preferably, the mass ratio of the carbon-based matrix to the phosphorus source is 20-40: 20-40;
(2) the doping element source further comprises a sulfur source, preferably, the sulfur source is selected from at least one of thiourea, thiosulfamide and thioglycolic acid; preferably, the mass ratio of the carbon-based matrix to the sulfur source is 20-40: 3.5-8;
(3) the doping element source further comprises a tin source, preferably, the tin source is selected from at least one of stannous oxalate, stannic nitrate, stannic methane sulfonate and stannic ethane sulfonate; preferably, the mass ratio of the carbon-based matrix to the tin source is 20-40: 2-14;
(4) the doping element source further comprises a lanthanide oxide, preferably, the lanthanide oxide is selected from at least one of lanthanum oxide, cerium oxide, and samarium oxide; preferably, the mass ratio of the carbon-based matrix material to the lanthanide oxide is 20-40: 2-5.
Further, the negative electrode material further comprises a dispersant, preferably, the dispersant can be at least one of polyvinyl butyral, polyvinyl alcohol and polyether; preferably, the mass ratio of the carbon-based matrix to the dispersant is 20-40: 2-4.
For example, the dispersant may be at least one of polyvinyl butyral, polyvinyl alcohol, polyether P123, and polyether F127.
Further, the mass ratio of the carbon-based matrix to the tin source is greater than 15:1 and less than or equal to 1.5: 1.
The invention also provides a preparation method of any one of the anode materials, which comprises the following steps:
and dispersing the carbon-based matrix, the doping element source and the swelling agent in a solvent, drying and sintering to obtain the cathode material.
Further, the method also comprises the step of adding a dispersing agent into the solvent; further, the carbon-based matrix and the dispersant may be mixed and then dispersed in the solvent. For example, the mixture is mixed by a deaerator, and the rotation speed is 300 to 500r/min, and the mixing time is 10 to 20 minutes.
Further, the material is dispersed in the solvent at a rotation speed of 200-300rpm and a temperature of 50-60 ℃.
Further, the drying process comprises a solvent volatilization step and a sample self-propagating growth step, wherein the solvent is completely volatilized and is in a gel shape in the early stage of drying (for example, drying is carried out for 8-15 hours), and the sample gradually self-propagates and grows in the later stage of drying (for example, drying is continued for 5-15 hours, namely, the drying time is from 8-15 hours to 13-30 hours) until the shape is porous and spongy.
Further, the drying temperature is 80-100 ℃.
Further, sintering is carried out for at least 15h under the inert atmosphere of 700-850 ℃. Preferably, the inert atmosphere is selected from common inert gases such as nitrogen, argon, and the like.
Further, after the temperature of the materials is reduced to room temperature, the materials are taken out of the sintering container.
Further, the solvent is at least one of ethanol, water, toluene, acetonitrile and N, N-dimethylformamide.
Further, the mass ratio of the carbon-based matrix to the solvent is 20-40: 90-110.
The invention also provides a negative plate which comprises any one of the negative electrode materials or the negative electrode material prepared by any one of the preparation methods. The negative electrode sheet may be prepared by a conventional method, such as homogenizing, coating, etc.
The invention also provides a battery, which comprises the negative plate, a battery shell, a positive plate, an isolating membrane and electrolyte. Wherein the battery can be a lithium ion battery, a sodium ion battery, a potassium ion battery, an aluminum ion battery, and the like.
The invention also provides a terminal, which comprises the battery, a terminal shell and a circuit board, wherein the circuit board is electrically connected with the battery. The terminal can be a mobile phone, a tablet, a notebook, an intelligent bracelet and other common electronic equipment.
The technical scheme of the invention has the following advantages:
1. the anode material provided by the invention comprises a carbon-based matrix, a doping element source and a swelling agent, wherein the doping element source comprises nitrate, and the carbon-based matrix, the swelling agent and the nitrate serving as a nitrogen source are matched for use to prepare the honeycomb-shaped composite anode material, so that the conductivity and the charge-discharge capacity of the anode material are greatly improved, the nitrogen element in the swelling agent is decomposed, and the generated gas is continuously subjected to pore forming to ensure that the carbon-based matrix is in a loose and porous sponge shape, and the unique honeycomb-shaped structure not only has a large specific surface area, is beneficial to infiltration of electrolyte and improves the rate capability of the material; the matched use of the nitrate improves the strength and stability of the honeycomb structure, can relieve the volume expansion of the negative electrode material in the circulating process, improves the circulating stability of the material, improves the defect of circulating water jumping, greatly improves the circulating attenuation, and solves the problems of particle crushing, pole piece separation and the like of the spherical negative electrode material in the circulating process.
2. Research on the cathode material provided by the invention finds that at least one of hydrazine hydrate, hydrogen peroxide and ammonia water can be used as a swelling agent, and particularly the effect of the hydrazine hydrate is optimal.
3. According to the cathode material provided by the invention, the phosphorus source is added into the cathode material, so that the anode material has a larger ionic radius, the desorption of sodium ions is facilitated, and meanwhile, the sodium intercalation site is provided, so that the cycle stability is further improved, and the chelating effect of the phosphorus source can further improve the strength and stability of a honeycomb structure and improve the cycle stability. As an element close to phosphorus, the theoretical specific capacity of the lithium ion battery of elemental sulfur is 1675mAh/g, and the addition of sulfur source elements in the material improves the charge and discharge capacity of the material, and can additionally provide a charge and discharge platform due to more extra nuclear electrons. And phosphorus and sulfur can form covalent bonds with carbon, hydrogen and oxygen, so that the structural stability is improved. The tin dioxide is an excellent conductive material with high melting point and boiling point, the addition of a tin source in the material can improve the conductivity and low-temperature charge and discharge capacity of the material, and the addition of a dispersing agent can enable the elements to be uniformly mixed and form a unique conductive network by taking a swelling agent and a nitrate as carriers, so that the ionic conductivity and the electronic conductivity of the material are improved, the rate capability of the composite material is enhanced, and the composite material can be used as a high-power negative electrode material; the lanthanide oxide provides lanthanide which can form a metal organic framework with the carbon-based matrix, can limit the volume expansion of the material during the circulation, and in addition, the addition of a nitrogen source and a phosphorus source replaces solvent sites in MOFs, so that the mechanical property of the carbon framework can be enhanced, and the conductivity of the material can be further improved.
4. The negative electrode material provided by the invention is preferably at least one of phytic acid, trimethyl phosphate and tributyl phosphate as a phosphorus source, the substances have strong chelating capacity, and the phosphate groups with negative charges can be combined with metal cations and can form a ternary compound by taking multivalent cations on amino acid as a bridge, so that the structural stability of the material is improved.
5. The preparation method of the cathode material provided by the invention is simple and convenient, and in the research process, the unexpected discovery that the material is taken out immediately after sintering or after the temperature is reduced to 50-80 ℃, the composite product of carbon and nitrate and/or phosphorus can be burnt by contacting with air, so that the content of the elements is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a picture of a precursor solution of example 1 of the present invention, which is stirred while being heated;
FIG. 2 is a picture of the precursor solution of example 1 of the present invention after stirring and with all raw materials uniformly dispersed;
FIG. 3 is a photograph of a gel-like sample obtained in example 1 of the present invention;
FIGS. 4 and 5 are each a photograph of a sponge-like sample obtained in example 1 of the present invention;
FIG. 6 is a photograph of a sponge-like specimen obtained in example 1 of the present invention after mashing and before sintering;
FIG. 7 is a photograph of a honeycomb negative electrode composite obtained in example 1 of the present invention;
fig. 8 is a scanning electron microscope photograph of the honeycomb negative electrode composite obtained in example 1 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a preparation method of an anode material, which comprises the following steps,
(1) preparing a precursor solution: preparing a 100ml beaker, adding 60g of absolute ethyl alcohol into the beaker, adding 12g of serine and 1.2g of polyether F127 (manufacturer: Vocko, chemical purity) into a mixing box, uniformly mixing by using a defoaming machine, wherein the working rotating speed of the defoaming machine is 300r/min, the time is 10 minutes, then pouring the mixed sample into the beaker containing the absolute ethyl alcohol, and heating and stirring for 15 minutes under the conditions that the temperature is 50 ℃ and the rotating speed is 200 r/min; adding 12g of trimethyl phosphate into the beaker, heating and stirring for 15 minutes under the conditions that the temperature is 50 ℃ and the rotating speed is 200 r/min; adding 3g of hydrazine hydrate solution (the hydrazine hydrate solution is 50vt percent of hydrazine hydrate aqueous solution), 3g of thiosulfamide, 1.2g of stannous oxalate, 12g of aluminum nitrate nonahydrate and 1.2g of cerium oxide into the beaker, heating and stirring for 15 minutes under the conditions that the temperature is 50 ℃ and the rotating speed is 200r/min to obtain precursor solution;
(2) preparing a negative electrode material: placing the beaker containing the precursor in the step (1) in a forced air drying oven, and drying at the temperature of 80 ℃ for 10 hours to obtain a gel sample; continuously standing the obtained gel-like sample in a forced air drying oven at the temperature of 80 ℃ for 10 hours to obtain a sponge-like sample; placing the sponge sample in a corundum boat, mashing, then placing the corundum boat in a tubular sintering furnace, introducing argon gas with the flow rate of 3ml/s, sintering at the high temperature of 700 ℃ for 17 hours, then stopping heating until the temperature of the tubular sintering furnace is reduced to 24 ℃, and then taking out the corundum boat to obtain the honeycomb-shaped cathode composite material.
Wherein, as shown in fig. 1, the precursor solution is heated and stirred, as shown in fig. 2, it is observed that all the raw materials in the solution obtained in step (1) are uniformly dispersed in ethanol, as shown in fig. 3, after drying for 12 hours, it is observed that the solvent in the beaker is completely volatilized, the sample is in a gel state, as shown in fig. 4 and 5, the sample is observed to gradually grow by self-propagating in the continuous drying process, and after 10 hours, the sample grows to ten times as large as the original volume, and has a porous and spongy shape. As shown in fig. 7 and 8, the honeycomb negative electrode composite material obtained by the present invention has a unique honeycomb structure.
Example 2
The embodiment provides a preparation method of an anode material, which comprises the following steps,
(1) preparing a precursor solution: preparing a 150ml beaker, adding 70g of absolute ethyl alcohol into the beaker, adding 21g of serine and 1.4g of polyether F127 (manufacturer: Vocko, chemical purity) into a mixing box, uniformly mixing by using a defoaming machine, wherein the working rotating speed of the defoaming machine is 400r/min, the time is 15 minutes, then pouring the mixed sample into the beaker containing the absolute ethyl alcohol, and heating and stirring for 12 minutes under the conditions that the temperature is 55 ℃ and the rotating speed is 250 r/min; adding 21g of trimethyl phosphate into the beaker, heating and stirring for 12 minutes under the conditions that the temperature is 55 ℃ and the rotating speed is 250 r/min; adding 3.5g of hydrazine hydrate solution (the hydrazine hydrate solution is 50vt percent of hydrazine hydrate aqueous solution), 3.5g of thiosulfamide, 1.4g of stannous oxalate, 21g of aluminum nitrate nonahydrate and 1.4g of cerium oxide into the beaker, heating and stirring for 12 minutes under the conditions that the temperature is 55 ℃ and the rotating speed is 250r/min to obtain precursor solution;
(2) preparing a negative electrode material: placing the beaker filled with the precursor solution in the step (1) in a forced air drying oven, and drying at the temperature of 90 ℃ for 12 hours to obtain a gel sample; keeping the obtained gel-like sample standing for 11 hours in a forced air drying oven at the temperature of 90 ℃ to obtain a sponge-like sample; placing the sponge sample in a corundum boat, mashing the corundum boat, then placing the corundum boat in a tubular sintering furnace, introducing argon gas at the flow rate of 4ml/s, sintering at the high temperature of 750 ℃ for 21 hours, then stopping heating until the temperature of the tubular sintering furnace is reduced to 22 ℃, and then taking out the corundum boat to obtain the honeycomb-shaped cathode composite material.
Example 3
This example provides a method for preparing an anode material, which is different from example 1 only in that the aluminum nitrate nonahydrate described in step (1) is replaced by cobalt nitrate hexahydrate with the same mass, and other conditions and parameters are completely the same as those of example 1.
Example 4
The present example provides a method for preparing a negative electrode material, which is different from example 1 only in that the addition amount of stannous oxalate in step (1) is 0.8g, and other conditions and parameters are completely the same as those in example 1.
Example 5
This example provides a method for preparing a negative electrode material, which is different from example 1 only in that the addition amount of the hydrazine hydrate solution in step (1) is 2g, and the other conditions and parameters are exactly the same as those in example 1.
Example 6
The embodiment provides a preparation method of an anode material, which comprises the following steps:
(1) preparing a precursor solution: preparing a 150ml beaker, adding 70g of absolute ethyl alcohol into the beaker, adding 40g of cystine and 2g of polyether P123 (manufacturer: Wolka, chemical purity) into a mixing box, uniformly mixing by using a defoaming machine, wherein the working rotating speed of the defoaming machine is 400r/min, the time is 15 minutes, then pouring the mixed sample into the beaker containing the absolute ethyl alcohol, and heating and stirring for 15 minutes under the conditions that the temperature is 60 ℃ and the rotating speed is 300 r/min; adding 40g of tributyl phosphate, 8g of hydrazine hydrate solution (aqueous solution with the concentration of 40vt percent), 3.5g of thiourea, 5g of tin methane sulfonate, 21g of aluminum nitrate nonahydrate and 5g of lanthanum oxide into the beaker, and stirring for 15 minutes while heating under the conditions that the temperature is 60 ℃ and the rotating speed is 300r/min to obtain precursor solution;
(2) preparing a negative electrode material: placing the beaker filled with the precursor solution in the step (1) in a forced air drying oven, and drying at the temperature of 90 ℃ for 12 hours to obtain a gel sample; keeping the obtained gel-like sample standing for 11 hours in a forced air drying oven at the temperature of 90 ℃ to obtain a sponge-like sample; placing the sponge sample in a corundum boat, mashing the corundum boat, then placing the corundum boat in a tubular sintering furnace, introducing argon at the flow rate of 4ml/s, sintering the corundum boat at the high temperature of 850 ℃ for 15 hours, then stopping heating until the temperature of the tubular sintering furnace is reduced to 22 ℃, and then taking out the corundum boat to obtain the nest-shaped negative electrode composite material.
Comparative example 1
Adopts a hard carbon material HC-03 (the compaction density is 0.8 g/cm) provided by new energy Co., Ltd of Bai Si Ge, Sichuan3) As the anode material.
Experimental example 1
The cathode materials of examples 1-6 and comparative example 1 are respectively adopted, and a sodium block is adopted as a counter electrode to be assembled into a button in a glove boxDetain the battery, specifically do: the current collector used a copper foil 9 μm thick, according to the negative electrode material: conductive agent: preparing slurry by using a binder in a mass ratio of 92:4:4, wherein the coating surface density of the pole piece is 9.2mg/cm2The pole piece is compacted to 3.1g/cm3The counter electrode is a sodium sheet made of sodium blocks, the isolating membrane is a diaphragm made of Cangzhou bright pearl 9+3+1+1, and the electrolyte solution is a membrane containing NaPF61M, PC/DMC volume ratio 3: 7. Then, a blue test system and a Princeton electrochemical workstation are used for testing electrochemical performance, including first charging specific capacity at 0.1C and 1C and first discharging specific capacity at 1C, capacity retention rate of 100 cycles at 1C at normal temperature and 45 ℃, and rate performance (namely normal-temperature 4C discharging specific capacity, the specific method is that at normal temperature, 0.1C is charged to 2.5V, 0.1C is discharged to 0V, then 0.5C is charged to 2.5V, 0.5C is discharged to 0V, 1C is charged to 2.5V, 1C is discharged to 0V, 4C is charged to 2.5V, 4C is discharged to 0V), and the test results are shown in Table 1:
table 1 test of battery performance made of negative electrode materials of each example and comparative example
As can be seen from Table 1, the specific first charge capacity of the battery obtained from examples 1 to 6 using the negative electrode composite material of the present invention at 0.1C was 652.6mAh g-1Above, the specific discharge capacity for the first time can reach 588.6 mAh.g-1Above, the specific discharge capacity at room temperature of 4C is 205.8 mAh.g-1As described above, the capacity retention rate of 100 cycles at room temperature and 1C can reach more than 83.2%, and the capacity retention rate of 100 cycles at 45 ℃ and 1C can reach more than 72.5%.
The ratio of the main materials such as the nitrogen source, the phosphorus source, the tin source and the like can influence the performance of the prepared negative electrode material, and the excessively low ratio of the tin source in the embodiment 4 can reduce the overall particle strength of the composite material, reduce the compaction of a negative electrode plate and reduce the utilization rate of a battery; the hydrazine hydrate of the example 5 can not generate enough pores in the macroscopic structure of the material if the addition amount is less, and the rate capability of the material is reduced.
Compared with the comparative example 1, the invention can obtain that the invention uniformly mixes the elements of nitrogen, phosphorus, tin, lanthanum salt and the like to construct a symmetrical conductive structure, thereby improving the conductive performance of the cathode composite material, improving the rate performance of the material and obtaining the cathode material of the sodium ion battery with quick charging capability; the invention can relieve the volume effect of the conventional negative electrode material, reduce the exposure degree of the silicon surface as much as possible, thereby reducing the irreversible capacity loss, simultaneously reducing the corrosion of HF (hydrogen fluoride) generated by the electrolyte on the electrode material, inhibiting the side reaction generated by the interface, forming the best SEI film (solid electrolyte interface film), and simultaneously improving the infiltration efficiency of the electrolyte by larger specific surface area, thereby improving the cycle performance and the rate capability of the material.
Experimental example 2 screening experiment of materials
The purpose of this experiment is to investigate the influence of using different types of carbon-based matrix, swelling agent, nitrogen source or phosphorus source on the battery cycle stability, and the following carbon-based matrix material, swelling agent, nitrogen source and phosphorus source are respectively used to prepare the negative electrode material, and the specific method includes:
(1) 60g of absolute ethanol are added to a 100ml beaker. Adding 12g of carbon-based matrix and 1.2g of polyether F127 into a mixing box, uniformly mixing by using a defoaming machine, wherein the working speed of the defoaming machine is 300r/min, the time is 10 minutes, then pouring the mixed sample into a beaker filled with absolute ethyl alcohol, heating and stirring for 15 minutes under the conditions of 50 ℃ and 200r/min to directly prepare a precursor solution (test 1), or adding a swelling agent and/or a nitrogen source into the beaker (tests 2-8) or adding the swelling agent, the nitrogen source and a phosphorus source into the beaker (test 9), heating and stirring for 15 minutes under the conditions of 50 ℃ and 200r/min to obtain the precursor solution.
(2) And drying the precursor solution at the temperature of 80 ℃ for 10 hours, standing at the temperature of 80 ℃ for 5 hours, sintering for 17 hours in an argon atmosphere at the flow rate of 3ml/s and the temperature of 700 ℃, stopping heating until the temperature of the tubular sintering furnace is reduced to 24 ℃, and taking out the corundum boat to obtain the cathode material.
Batteries were prepared using the respective groups of negative electrode materials according to the method of experimental example 1 and the cycle performance was examined, and the following table was recorded.
Table 2 results of screening experiments of materials
As can be seen from the above table, tests 1 to 3 find that, on the basis of a carbon-based substrate, the retention rate of the circulating capacity cannot be effectively improved by adding a swelling agent and a nitrogen source alone, and tests 6 to 9 adopt the cooperation of hydrazine hydrate, ammonia water or hydrogen peroxide with nitrate and serine, so that gas generated by decomposition of the swelling agent is continuously subjected to pore forming, the serine is in a loose and porous sponge shape, the nitrate enhances the stability of the sponge structure, the capacity retention rate of the battery is remarkably improved, and the cooperation use effect of the nitrate and the hydrazine hydrate is the best.
Experimental example 3
The experiment aims to investigate the influence of the doping element source on the battery performance, the following table doping element sources are respectively adopted, and the following method is adopted to prepare the cathode material, and the specific method comprises the following steps:
(1) 60g of absolute ethanol are added to a 100ml beaker. Adding 12g of serine and 1.2g of polyether F127 into a mixing box, uniformly mixing by using a defoaming machine, wherein the working speed of the defoaming machine is 300r/min, the time is 10 minutes, pouring the mixed sample into a beaker containing absolute ethyl alcohol, and heating and stirring for 15 minutes under the conditions that the temperature is 50 ℃ and the rotating speed is 200 r/min. Adding 3g of hydrazine hydrate solution (the hydrazine hydrate solution is 50vt percent of hydrazine hydrate aqueous solution), 12g of aluminum nitrate nonahydrate and other doping element sources into the beaker, and stirring for 15 minutes while heating under the conditions that the temperature is 50 ℃ and the rotating speed is 200r/min to obtain precursor solution.
(2) And drying the precursor solution at the temperature of 80 ℃ for 10 hours, standing at the temperature of 80 ℃ for 5 hours, sintering for 17 hours in an argon atmosphere at the flow rate of 3ml/s and the temperature of 700 ℃, stopping heating until the temperature of the tubular sintering furnace is reduced to 24 ℃, and taking out the corundum boat to obtain the cathode material.
Batteries were prepared using the respective groups of negative electrode materials according to the method of experimental example 1 and the resistivity of the coating layer on the electrode foil and the normal-temperature 4C specific discharge capacity were measured (specifically, the battery was charged to 2.5V at 0.1C, to 0V at 0.1C, to 2.5V at 0.5C, to 0V at 0.5C, to 2.5V at 1C, to 0V at 1C, to 2.5V at 4C, and to 0V at 4C), and the results are shown in the following table.
TABLE 3 specific coating resistivity and specific discharge capacity at room temperature 4C of the pole piece foil
As can be seen from the above table, compared with the experiment No. 6 which only uses serine, swelling agent and nitrate, other experiments can form a conductive framework with a carbon-based matrix by additionally adding a sulfur source, a tin source, a lanthanum source and a phosphorus source, so that the ionic conductivity and the electronic conductivity of the material are increased, the resistivity of the manufactured negative electrode plate is reduced, and the rate capability of the battery is improved.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The negative electrode material is characterized by comprising a carbon-based matrix, a doping element source and a swelling agent, wherein the doping element source comprises nitrate.
2. The negative electrode material of claim 1, wherein the mass ratio of the carbon-based matrix to the expanding agent to the nitrate is 20-40:1-10: 20-30; and/or the swelling agent is at least one selected from hydrazine hydrate, hydrogen peroxide and ammonia water.
3. The anode material according to claim 1 or 2, wherein the carbon-based matrix is selected from at least one of sarcosine, cystine, serine, and dicyanodiamine; and/or the nitrate is selected from at least one of aluminum nitrate nonahydrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate and copper nitrate trihydrate.
4. The anode material according to any one of claims 1 to 3, wherein the anode material further satisfies at least one of the following (1) to (4):
(1) the doping element source also comprises a phosphorus source, preferably, the phosphorus source is selected from at least one of phytic acid, trimethyl phosphate and tributyl phosphate; preferably, the mass ratio of the carbon-based matrix to the phosphorus source is 20-40: 20-40;
(2) the doping element source further comprises a sulfur source, preferably, the sulfur source is selected from at least one of thiourea, thiosulfamide or thioglycolic acid; preferably, the mass ratio of the carbon-based matrix to the sulfur source is 20-40: 3.5-8;
(3) the doping element source further comprises a tin source, preferably, the tin source is selected from at least one of stannous oxalate, stannic nitrate, stannic methane sulfonate and stannic ethane sulfonate; preferably, the mass ratio of the carbon-based matrix to the tin source is 20-40: 2-14;
(4) the doping element source further comprises a lanthanide oxide, preferably, the lanthanide oxide is selected from at least one of lanthanum oxide, cerium oxide, and samarium oxide; preferably, the mass ratio of the carbon-based matrix to the lanthanide oxide is 20-40: 2-5.
5. The negative electrode material of any one of claims 1 to 4, further comprising a dispersant, preferably the dispersant is selected from at least one of polyvinyl butyral, polyvinyl alcohol and polyether; preferably, the mass ratio of the carbon-based matrix to the dispersant is 20-40: 2-4.
6. A method for preparing the anode material according to any one of claims 1 to 5, comprising the steps of: and dispersing the carbon-based matrix, the doping element source and the swelling agent in a solvent, drying and sintering to obtain the cathode material.
7. The method for producing the anode material according to claim 6, further comprising a step of adding a dispersant to the solvent; and/or, the material is dispersed in the solvent under the conditions of the rotation speed of 200-300rpm and the temperature of 50-60 ℃; and/or, the drying temperature is 80-100 ℃; and/or, sintering at 700-850 ℃ inert atmosphere for at least 15 h; and/or after the temperature of the materials is reduced to room temperature after sintering, taking the materials out of the sintering container; and/or the solvent is one of ethanol, water, toluene, acetonitrile and N, N-dimethylformamide; and/or the mass ratio of the carbon-based matrix to the solvent is 20-40: 90-110.
8. A negative electrode sheet, characterized by comprising the negative electrode material according to any one of claims 1 to 5 or the negative electrode material produced by the production method according to claim 6 or 7.
9. A battery comprising the negative electrode sheet according to claim 8, further comprising a battery case, a positive electrode sheet, a separator, and an electrolyte.
10. A terminal comprising the battery of claim 9, and further comprising a terminal housing and a circuit board, the circuit board being electrically connected to the battery.
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