CN114420927B - Negative electrode material, preparation method thereof and negative electrode sheet - Google Patents
Negative electrode material, preparation method thereof and negative electrode sheet Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention provides a negative electrode material, a preparation method thereof and a negative electrode sheet. The nitrogen element in the bulking agent is decomposed, and the generated gas continuously forms holes to enable the carbon-based substrate to be in a loose porous sponge shape, so that the unique honeycomb structure not only has a large specific surface area, is favorable for the infiltration of electrolyte, but also improves the strength and stability of the honeycomb structure through the collocation of nitrate, and can relieve the volume expansion of the cathode material in the circulation process, improve the circulation stability of the material, improve the defect of circulating water, greatly improve the circulation attenuation, and solve the problems of particle breakage, separation from pole pieces and the like of the spherical cathode material in the circulation process.
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 plate.
Background
Among various applicable energy storage technologies, alkali metal ion batteries have become a research hotspot in recent years as a general electrochemical energy storage system 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, and the working principles of the alkali metal ion battery are similar in the same main group, the alkali metal ion battery is a rocking chair type mechanism realized by virtue of ion migration in the charge and discharge process, and the sodium element reserves in the crust are far higher than the lithium element, so that the lithium ion battery has the advantage of being incomparable with the LIB in terms of cost, and has good application prospect in the future.
For example, chinese patent document CN112838197a discloses a negative electrode material, which includes a carbon-doped material, and a part of doping elements in the carbon-doped material form a C-Ma-Mb chemical bond with a carbon base, so that the fast charge performance of the negative electrode material is effectively improved, and the problem that the fast charge and slow discharge performance of the existing negative electrode material is poor is solved to a certain extent. Still far away from practical application, the use requirement of high-function output cannot be met, capacity loss is large under the condition of quick charge and quick discharge, and large-scale cyclic attenuation still occurs.
Disclosure of Invention
Therefore, the invention aims to solve the problems of large capacity loss and serious cycle attenuation of the anode material under the condition of quick charge and quick discharge in the prior art, and provides the anode material, the preparation method thereof and an anode sheet.
To this end, the invention provides a negative electrode material comprising a carbon-based matrix, a source of doping elements comprising nitrate, and a bulking agent.
Further, the mass ratio of the carbon-based matrix, the bulking agent and the nitrate is 20-40:1-10:20-30.
As a more preferred embodiment, the mass ratio of the carbon-based matrix, the bulking agent and the nitrate is 20-40:5-10:20-30.
As a more preferable embodiment, the mass ratio of the carbon-based matrix to the bulking agent is more than 6:1 and less than or equal to 2:1.
Further, the swelling agent is at least one selected from hydrazine hydrate, hydrogen peroxide and ammonia water.
The bulking agent may be a hydrazine hydrate solution, such as a conventional aqueous hydrazine hydrate solution having a volume concentration of 30-50%.
Further, the carbon-based substrate is selected from at least one of sarcosine, cystine, serine, and dicyandiamide.
Further, the nitrate is at least one selected from the group consisting of aluminum nitrate nonahydrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate and copper nitrate trihydrate.
Further, the anode material further satisfies at least one of the following (1) to (4):
(1) The doping element source further 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 includes a sulfur source, preferably, the sulfur source is selected from at least one of thiourea, thiothioamide 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 includes a tin source, preferably, the tin source is selected from at least one of stannous oxalate, tin nitrate, tin methane sulfonate and tin 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 anode material further includes a dispersant, preferably, the dispersant may be at least one of polyvinyl alcohol Ding Quanzhi, polyvinyl alcohol, and polyether; preferably, the mass ratio of the carbon-based matrix to the dispersing agent is 20-40:2-4.
For example, the dispersant may be at least one of polyvinyl alcohol Ding Quanzhi, polyvinyl alcohol, polyether P123 and polyether F127.
Further, the mass ratio of the carbon-based matrix to the tin source is more than 15:1 and less than or equal to 1.5:1.
The invention also provides a preparation method of the anode material, which comprises the following steps:
dispersing the carbon-based matrix, the doping element source and the bulking agent in a solvent, drying and sintering to prepare the anode material.
Further, the method also comprises the step of adding a dispersing agent into the solvent; further, the carbon-based substrate may be mixed with the dispersant before being dispersed in the solvent. For example, the mixing may be carried out by using a deaerator at a rotational speed of 300 to 500r/min for 10 to 20 minutes.
Further, the materials are dispersed in the solvent under the conditions of the rotating speed of 200-300rpm and the temperature of 50-60 ℃.
Further, the drying process comprises a solvent volatilizing step and a sample self-propagating growth step, wherein the solvent volatilizes completely in the early drying period (for example, 8-15 hours), is in a gel state, and the sample gradually self-propagates and grows in the later drying period (for example, the drying period is 5-15 hours, namely, from 8-15 hours to 13-30 hours), until the appearance is porous and spongy.
Further, the drying temperature is 80-100 ℃.
Further, sintering is carried out in an inert atmosphere at 700-850 ℃ for at least 15h. Preferably, the inert atmosphere is selected from common inert gases such as nitrogen, argon and the like.
Further, after sintering, the material is taken out of the sintering container after the temperature of the material is reduced to room temperature.
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 electrode plate which comprises any one of the negative electrode materials or any one of the negative electrode materials prepared by the preparation method. The negative electrode sheet may be prepared by conventional methods, such as homogenization, coating, and the like.
The invention also provides a battery, which comprises the negative plate, a battery shell, a positive plate, a separation 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 common electronic device such as a mobile phone, a tablet, a notebook, an intelligent bracelet and the like.
The technical scheme of the invention has the following advantages:
1. the anode material provided by the invention comprises a carbon-based matrix, a doped element source and a swelling agent, wherein the doped element source comprises nitrate, the carbon-based matrix, the swelling agent and the nitrate serving as a nitrogen source are used together to prepare the honeycomb composite anode material, so that the conductivity and charge-discharge capacity of the anode material are greatly improved, the nitrogen element in the swelling agent is decomposed, and generated gas is continuously used for making holes to enable the carbon-based matrix to be in a loose porous sponge shape, and a unique honeycomb structure not only has a large specific surface area, but also is beneficial to the infiltration of electrolyte and improves the multiplying power performance of the material; the nitrate is matched for use, so that the strength and stability of the honeycomb structure are improved, the volume expansion of the anode material in the circulation process can be relieved, the circulation stability of the material is improved, the defect of circulating water jump is overcome, the circulating attenuation is greatly improved, and the problems of particle breakage, pole piece separation and the like of the spherical anode material in the circulation process are solved.
2. The negative electrode material provided by the invention can be used by adopting at least one of hydrazine hydrate, hydrogen peroxide and ammonia water as a swelling agent through researches, and especially has the best effect of the hydrazine hydrate.
3. The anode material provided by the invention has the advantages that the phosphorus source is added into the anode material, the deintercalation of sodium ions is facilitated due to the larger ionic radius, the site for embedding sodium is provided, the circulation stability is further improved, and the chelation of the phosphorus source can further improve the strength and the stability of the honeycomb structure and the circulation stability. As an element similar 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 because the material has more extra-nuclear electrons. And the phosphorus and the sulfur can form covalent bonds with carbon, hydrogen and oxygen, so that the structural stability is improved. The tin dioxide has high melting point and boiling point, is an excellent conductive material, the addition of a tin source in the material can improve the conductivity and low-temperature charge-discharge capacity of the material, and the addition of the dispersing agent can uniformly mix the elements and form a unique conductive network by taking the swelling agent and the nitrate as carriers, so that the ionic conductivity and the electronic conductivity of the material are improved, the rate performance of the composite material is enhanced, and the composite material can be used as a high-power anode material; the lanthanide oxide provides that the lanthanide can form a metal organic framework with the carbon-based group, limiting the volume expansion of the material during cycling, and in addition, the addition of nitrogen and phosphorus sources replaces solvent sites in MOFs, which not only enhances the mechanical properties of the carbon framework, but also further improves the conductivity of the material.
4. For the phosphorus source, the negative electrode material provided by the invention is preferably at least one of phytic acid, trimethyl phosphate and tributyl phosphate, and the substances have strong chelating capacity, and negatively charged phosphate groups can be combined with metal cations, and can form ternary complexes by taking multivalent cations on amino acids as bridges, so that the structural stability of the material is improved.
5. The preparation method of the anode material provided by the invention is simple and convenient, the material is taken out immediately after the sintering or after the temperature is reduced to 50-80 ℃ in the research process, the composite product of carbon and nitrate and/or phosphorus is burnt when contacting with air, so that the content of the elements is reduced, and the anode material is taken out from a sintering container after the material is cooled to room temperature after the sintering is controlled.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a photograph of a precursor solution of example 1 of the present invention being heated while being stirred;
FIG. 2 is a graph showing the end of stirring the precursor solution of example 1 of the present invention, and the uniform dispersion of all the raw materials;
FIG. 3 is a photograph of a gel-like sample obtained in example 1 of the present invention;
FIGS. 4 and 5 are pictures of the spongy sample obtained in example 1 of the present invention;
FIG. 6 is a photograph showing the sponge-like sample obtained in example 1 of the present invention after mashing and before sintering;
FIG. 7 is a photograph of a honeycomb anode composite obtained in example 1 of the present invention;
fig. 8 is a scanning electron microscope image of the honeycomb anode composite material obtained in example 1 of the present invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a cathode 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: walka, chemical purity) into a mixing box, uniformly mixing by using a deaerator, wherein the working speed of the deaerator is 300r/min, the time is 10 minutes, pouring the mixed sample into the beaker containing the absolute ethyl alcohol, and stirring for 15 minutes while heating at the temperature of 50 ℃ and the rotating speed of 200 r/min; adding 12g of trimethyl phosphate into the beaker, and stirring for 15 minutes while heating at 50 ℃ and a rotating speed of 200 r/min; adding 3g of hydrazine hydrate solution (the hydrazine hydrate solution is 50vt percent of aqueous solution of hydrazine hydrate), 3g of thiothioamide, 1.2g of stannous oxalate, 12g of aluminum nitrate nonahydrate and 1.2g of cerium oxide into the beaker, and stirring for 15 minutes under the conditions of 50 ℃ and 200r/min of rotating speed to obtain a precursor solution;
(2) Preparation of a negative electrode material: placing the beaker containing the precursor in the step (1) in a forced air drying oven, and drying at 80 ℃ for 10 hours to obtain a gel sample; continuously standing the obtained gel sample in a forced air drying oven at 80 ℃ for 10 hours to obtain a spongy sample; and (3) placing the spongy sample in a corundum boat, mashing, 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, stopping heating until the temperature of the tubular sintering furnace is reduced to 24 ℃, and taking out the corundum boat to obtain the honeycomb anode composite material.
Wherein, as shown in fig. 1, a state diagram of heating and stirring the precursor solution is shown, as shown in fig. 2, all raw materials in the solution obtained in the step (1) are uniformly dispersed in ethanol, as shown in fig. 3, after drying for 12 hours, the solvent in the beaker is observed to be completely volatilized, the sample is in gel form, as shown in fig. 4 and 5, in the continuous drying process, the gradual self-propagating growth of the sample is observed until the sample grows to ten times as large as the original volume after 10 hours, and the appearance is porous like a sponge. As shown in fig. 7 and 8, the honeycomb anode composite material obtained by the present invention has a unique honeycomb structure.
Example 2
The embodiment provides a preparation method of a cathode 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: walka, chemical purity) into a mixing box, uniformly mixing by using a deaerator, wherein the working speed of the deaerator is 400r/min for 15 minutes, pouring the mixed sample into the beaker containing the absolute ethyl alcohol, and stirring for 12 minutes while heating at the temperature of 55 ℃ and the rotating speed of 250 r/min; 21g of trimethyl phosphate is added into the beaker and stirred for 12 minutes while being heated at 55 ℃ and the rotating speed of 250 r/min; 3.5g of hydrazine hydrate solution (hydrazine hydrate solution is 50vt percent of aqueous solution of hydrazine hydrate), 3.5g of thiothioamide, 1.4g of stannous oxalate, 21g of aluminum nitrate nonahydrate and 1.4g of cerium oxide are added into the beaker, and the mixture is heated and stirred for 12 minutes under the conditions of 55 ℃ and the rotating speed of 250r/min to obtain a precursor solution;
(2) Preparation of a negative electrode material: placing the beaker filled with the precursor solution in the step (1) in a forced air drying box, and drying for 12 hours at the temperature of 90 ℃ to obtain a gel-like sample; continuously standing the obtained gel sample in a forced air drying oven at 90 ℃ for 11 hours to obtain a spongy sample; and (3) placing the spongy sample in a corundum boat, mashing, placing the corundum boat in a tubular sintering furnace, introducing argon gas with the flow rate of 4ml/s, sintering at the high temperature of 750 ℃ for 21 hours, stopping heating until the temperature of the tubular sintering furnace is reduced to 22 ℃, and taking out the corundum boat to obtain the honeycomb anode composite material.
Example 3
This example provides a method for preparing a negative electrode material, which differs from example 1 only in that aluminum nitrate nonahydrate in step (1) is replaced by cobalt nitrate hexahydrate of the same quality, and other conditions and parameters are identical to those in example 1.
Example 4
This example provides a method for preparing a negative electrode material, which is different from example 1 only in that the stannous oxalate in step (1) is added in an amount of 0.8g, and other conditions and parameters are identical to those in example 1.
Example 5
The present example provides a method for preparing a negative electrode material, which is different from example 1 only in that the hydrazine hydrate solution in step (1) is added in an amount of 2g, and other conditions and parameters are identical to those in example 1.
Example 6
The embodiment provides a preparation method of a negative electrode 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: walker, chemical purity) into a mixing box, uniformly mixing by using a deaerator, wherein the working speed of the deaerator is 400r/min for 15 minutes, pouring the mixed sample into the beaker containing the absolute ethyl alcohol, and stirring for 15 minutes while heating at the temperature of 60 ℃ and the rotating speed of 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 under the conditions of 60 ℃ and the rotating speed of 300r/min to obtain a precursor solution;
(2) Preparation of a negative electrode material: placing the beaker filled with the precursor solution in the step (1) in a forced air drying box, and drying for 12 hours at the temperature of 90 ℃ to obtain a gel-like sample; continuously standing the obtained gel sample in a forced air drying oven at 90 ℃ for 11 hours to obtain a spongy sample; and (3) placing the spongy sample in a corundum boat, mashing, placing the corundum boat in a tubular sintering furnace, introducing argon gas with the flow rate of 4ml/s, sintering at the high temperature of 850 ℃ for 15 hours, stopping heating until the temperature of the tubular sintering furnace is reduced to 22 ℃, and taking out the corundum boat to obtain the nest-shaped negative electrode composite material.
Comparative example 1
Using hard carbon material HC-03 (compaction density of 0.8 g/cm) 3 ) As a negative electrode material.
Experimental example 1
The negative electrode materials of examples 1 to 6 and comparative example 1 were respectively used, and a button cell was assembled in a glove box using a sodium block as a counter electrode, specifically: the current collector used a 9 μm thick copper foil according to the negative electrode material: conductive agent: binder=92:4:4 mass ratio to prepare slurry, coating surface density of the pole piece was 9.2mg/cm 2 Compacting the pole piece to 3.1g/cm 3 The counter electrode adopts sodium sheet made of sodium block, the isolating membrane adopts membrane of Cangzhou pearl 9+3+1+1, and the electrolyte solution is NaPF-containing 6 1M, PC/DMC volume ratio of 3: 7. Electrochemical performance was then tested using a blue electric test system and a Prlington electrochemical workstation, including a specific capacity for initial charge at 0.1C and 1C and an initial discharge at 1CSpecific capacity, capacity retention at 1C at room temperature and 45 ℃ for 100 weeks, and rate capability (i.e., specific capacity at room temperature of 4C discharge, specifically, 0.1C to 2.5V at room temperature, 0.1C to 0V at room temperature, 0.5C to 2.5V,0.5C to 0V,1C to 2.5V,1C to 0V,4C to 2.5V,4C to 0V), test results are shown in table 1:
table 1 battery performance test of anode materials of examples and comparative examples
As can be seen from Table 1, from examples 1 to 6, the initial charge specific capacity of the battery obtained by using the negative electrode composite material of the present invention at 0.1C can reach 652.6 mAh.g -1 The specific capacity of the initial discharge can reach 588.6 mAh.g -1 The specific discharge capacity at room temperature 4C was 205.8mAh g -1 The capacity retention rate of the normal temperature 1C cycle for 100 weeks can reach more than 83.2%, and the capacity retention rate of the 45 ℃ 1C cycle for 100 weeks can reach more than 72.5%.
The proportion of main materials such as nitrogen source, phosphorus source, tin source and the like can influence the performance of the prepared anode material, the proportion of the tin source in the embodiment 4 is too low, the overall particle strength of the composite material can be reduced, the compaction of the anode pole piece is reduced, and the utilization rate of a battery is reduced; the hydrazine hydrate of example 5, if added in a small amount, the macrostructure of the material cannot generate enough pores, which would reduce the rate capability of the material.
The invention can be obtained by comparing the embodiment 1 with the comparative embodiment 1, and the elements such as nitrogen, phosphorus, tin, lanthanum salt and the like are uniformly mixed to construct a symmetrical conductive structure, so that the conductive performance of the negative electrode composite material is improved, the multiplying power performance of the material is improved, and the negative electrode material of the sodium ion battery with quick charging capability is obtained; the invention can relieve the volume effect of the conventional anode material, reduce the exposure degree of the silicon surface as much as possible, thereby reducing the irreversible capacity loss, simultaneously reducing the erosion of HF (hydrogen fluoride) generated by the electrolyte to the electrode material, inhibiting the side reaction generated by the interface, forming the optimal SEI film (solid electrolyte interface film), and simultaneously improving the infiltration efficiency of the electrolyte by a larger specific surface area, thereby improving the cycle performance and the multiplying power performance of the material.
Experimental example 2 screening experiments of materials
The purpose of this experiment is to examine the effect of using different kinds of carbon-based matrix, bulking agent, nitrogen source or phosphorus source to the battery cycle stability, respectively using the carbon-based matrix material, bulking agent, nitrogen source and phosphorus source described in the following table, and adopting the following method to prepare the negative electrode material, the specific method includes:
(1) 60g of absolute ethanol was added to a 100ml beaker. Adding 12g of carbon-based matrix and 1.2g of polyether F127 into a mixing box, uniformly mixing by a deaerator, wherein the working speed of the deaerator is 300r/min for 10 minutes, pouring the mixed sample into a beaker containing absolute ethyl alcohol, heating and stirring for 15 minutes at the temperature of 50 ℃ and the rotating speed of 200r/min, directly preparing a precursor solution (test 1), or adding a bulking agent and/or a nitrogen source into the beaker (test 2-8), or adding the bulking agent, the nitrogen source and the phosphorus source into the beaker together (test 9), and heating and stirring for 15 minutes at the temperature of 50 ℃ and the rotating speed of 200r/min, thereby obtaining the precursor solution.
(2) Drying the precursor solution at 80 ℃ for 10 hours, standing at 80 ℃ for 5 hours, sintering under argon atmosphere for 17 hours, wherein the flow rate of argon is 3ml/s, the temperature is 700 ℃, then stopping heating until the temperature of a tubular sintering furnace is reduced to 24 ℃, and taking out the corundum boat to obtain the cathode material.
Batteries were produced by the method of experimental example 1 using each set of negative electrode materials and the cycle performance was examined, as shown in the following table.
Table 2 results of screening experiments on materials
As shown in the table, tests 1-3 show that on the basis of a carbon-based matrix, the circulation capacity retention rate cannot be effectively improved by independently adding the bulking agent and the nitrogen source, and tests 6-9 adopt the cooperation of hydrazine hydrate, ammonia water or hydrogen peroxide, nitrate and serine, so that the gas generated by decomposing the bulking agent continuously forms holes to enable the serine to be in a loose and porous spongy state, the nitrate also enhances the stability of the spongy structure, the capacity retention rate of the battery is obviously improved, and the nitrate and the hydrazine hydrate have the best cooperation use effect.
Experimental example 3
The purpose of this experiment is to examine the effect of doping element sources on battery performance, and the following table doping element sources are adopted respectively, and the following method is adopted to prepare the negative electrode material, and the specific method comprises:
(1) 60g of absolute ethanol was added to a 100ml beaker. Adding 12g of serine and 1.2g of polyether F127 into a mixing box, uniformly mixing by a deaerator, wherein the working speed of the deaerator is 300r/min for 10 minutes, pouring the mixed sample into a beaker containing absolute ethyl alcohol, and stirring for 15 minutes while heating at 50 ℃ and the rotating speed of 200 r/min. 3g of a hydrazine hydrate solution (the hydrazine hydrate solution is an aqueous solution of 50vt% hydrazine hydrate), 12g of aluminum nitrate nonahydrate and other doping element sources were added to the beaker, and the mixture was heated and stirred for 15 minutes at a temperature of 50℃and a rotation speed of 200r/min, to obtain a precursor solution.
(2) Drying the precursor solution at 80 ℃ for 10 hours, standing at 80 ℃ for 5 hours, sintering under argon atmosphere for 17 hours, wherein the flow rate of argon is 3ml/s, the temperature is 700 ℃, then stopping heating until the temperature of a tubular sintering furnace is reduced to 24 ℃, and taking out the corundum boat to obtain the cathode material.
Batteries were produced by the method of experimental example 1 using each set of negative electrode materials and the coating resistivity on the electrode sheet foil and the specific capacity of normal-temperature 4C discharge were measured (specifically, at normal temperature, 0.1C charge to 2.5V,0.1C discharge to 0V, then 0.5C charge to 2.5V,0.5C discharge to 0V,1C charge to 2.5V,1C discharge to 0V,4C charge to 2.5V,4C discharge to 0V), and the results are shown in the following table.
TABLE 3 coating resistivity on Pole piece foil and specific discharge capacity at Normal temperature 4C
Compared with the experiment No. 6 which only adopts serine, a bulking agent and nitrate, other experiments can form a conductive framework with a carbon base 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 improved, the resistivity of the prepared negative electrode plate is reduced, and the rate performance of the battery is improved.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (16)
1. A negative electrode material comprising a carbon-based matrix, a source of doping elements, and a bulking agent, the source of doping elements comprising a nitrate, a phosphorus source, a sulfur source, a tin source, and a lanthanide oxide.
2. The anode material of claim 1, wherein the mass ratio of carbon-based matrix, bulking agent to 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 substrate is selected from at least one of sarcosine, cystine, serine, and dicyandiamide; 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 phosphorus source is at least one of phytic acid, trimethyl phosphate and tributyl phosphate;
(2) The sulfur source is selected from at least one of thiourea, thiothioamide or thioglycollic acid;
(3) The tin source is at least one selected from stannous oxalate, tin nitrate, tin methane sulfonate and tin ethane sulfonate;
(4) The lanthanide oxide is at least one selected from lanthanum oxide, cerium oxide and samarium oxide.
5. The anode material according to claim 4, wherein the mass ratio of the carbon-based matrix to the phosphorus source is 20-40:20-40.
6. The anode material according to claim 4, wherein the mass ratio of the carbon-based matrix to the sulfur source is 20-40:3.5-8.
7. The anode material according to claim 4, wherein the mass ratio of the carbon-based matrix to the tin source is 20-40:2-14.
8. The anode material according to claim 4, wherein a mass ratio of the carbon-based matrix to the lanthanide oxide is 20-40:2-5.
9. The anode material according to any one of claims 1 to 4, further comprising a dispersant.
10. The anode material according to claim 9, wherein the dispersant is at least one selected from the group consisting of polyvinyl alcohol Ding Quanzhi, polyvinyl alcohol, and polyether.
11. The anode material according to claim 9, wherein the mass ratio of the carbon-based matrix to the dispersant is 20-40:2-4.
12. A method for producing the anode material according to any one of claims 1 to 11, comprising the steps of: dispersing the carbon-based matrix, the doping element source and the bulking agent in a solvent, drying and sintering to prepare the anode material.
13. The method for producing a negative electrode material according to claim 12, further comprising the step of adding a dispersant to the solvent; and/or dispersing the materials in a solvent at a rotation speed of 200-300rpm and a temperature of 50-60 ℃; and/or, the drying temperature is 80-100 ℃; and/or sintering in an inert atmosphere at 700-850 ℃ for at least 15 hours; and/or taking out the material from the sintering container after the temperature of the material is reduced to room temperature after sintering; 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.
14. A negative electrode sheet comprising the negative electrode material according to any one of claims 1 to 11 or the negative electrode material produced by the production method according to claim 12 or 13.
15. A battery comprising the negative electrode sheet of claim 14, further comprising a battery housing, a positive electrode sheet, a separator, and an electrolyte.
16. A terminal comprising the battery of claim 15, further comprising a terminal housing and a circuit board, the circuit board being electrically connected to the battery.
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