CN115360354A - Preparation method and application of sodium-ion battery positive electrode material - Google Patents

Preparation method and application of sodium-ion battery positive electrode material Download PDF

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CN115360354A
CN115360354A CN202211285632.8A CN202211285632A CN115360354A CN 115360354 A CN115360354 A CN 115360354A CN 202211285632 A CN202211285632 A CN 202211285632A CN 115360354 A CN115360354 A CN 115360354A
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sodium
graphene
aniline
polyaniline
graphene aerogel
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CN115360354B (en
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吴丽军
李亚辉
王亚峰
龙海涛
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Jiangsu Zhitai New Energy Technology Co ltd
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    • 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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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention discloses a preparation method and application of a sodium-ion battery anode material, wherein the preparation method comprises the following steps: s1, preparing aniline-graphene aerogel; s2, simultaneously adding an oxidant and a vanadium source, a phosphorus source and a sodium source which are dispersed in water into the aniline-graphene aerogel dispersed in water, stirring and heating to generate polyaniline while generating the sodium vanadium phosphate gel, wherein the generated polyaniline covers the sodium vanadium phosphate gel; s3, carrying out high-temperature and high-pressure reaction, wherein the polyaniline-coated sodium vanadium phosphate is distributed on the surface of the polyaniline-loaded graphene aerogel; s4, cleaning, drying and ball-milling the precipitate obtained in the step S3 to obtain a target compound; according to the invention, the particle size of the sodium vanadium phosphate is controlled to be uniformly distributed on the surface of the graphene aerogel, and the conductivity and the structural stability of the anode material are both considered; the obtained compound is applied to the sodium ion battery, the electrochemical consistency of the obtained sodium ion battery is high, and the cycle performance and the rate capability are obviously improved.

Description

Preparation method and application of sodium-ion battery positive electrode material
Technical Field
The invention relates to the technical field of positive electrode materials of sodium-ion batteries, in particular to a preparation method and application of a positive electrode material of a sodium-ion battery.
Background
Compared with lithium batteries, sodium batteries have low raw material cost, wide sources, and physical properties similar to those of lithium, and sodium ions are deintercalated between positive and negative electrodes to form charge transfer, so the sodium ion batteries are considered as the most potential batteries.
The invention patent CN107845796B discloses a carbon-doped sodium vanadium phosphate positive electrode material, a preparation method and an application thereof, and aims to improve the conductivity of sodium vanadium phosphate and solve the problems of poor multiplying power and cycle life of a prepared sodium battery 3 V 2 (PO 4 ) 3 the/C composite particles were carbon coated a second time with dopamine hydrochloride, na 3 V 2 (PO 4 ) 3 the/C composite particles are wrapped in a carbon net serving as a second carbon layer to obtain the carbon-doped vanadium sodium phosphate cathode material with a unique structure, and the electrochemical performance of the carbon-doped vanadium sodium phosphate cathode material is lower than that of Na which is not wrapped by the carbon net 3 V 2 (PO 4 ) 3 the/C composite particles are obviously improved. The specification further indicates that the carbon-doped vanadium sodium phosphate cathode material with excellent effect cannot be obtained without dopamine carbon coating or under the condition of pH value of dopamine carbon coating.
Patent pair Na combining CN107845796B invention 3 V 2 (PO 4 ) 3 The improvement of the conductivity is known, and the prior art is directed to Na 3 V 2 (PO 4 ) 3 The requirement of the conductivity improvement process parameters is strict, and the Na formed after the first carbon layer is coated cannot be effectively controlled 3 V 2 (PO 4 ) 3 The uniformity and the improvement of the conductivity of the/C composite particles are limited.
Disclosure of Invention
The invention aims to provide a preparation method of a positive electrode material of a sodium-ion battery, which controls Na 3 V 2 (PO 4 ) 3 The particle size is uniformly distributed on the surface of the graphene aerogel, and the conductivity and the structural stability of the cathode material are both considered.
In order to solve the technical problem, the technical scheme of the invention is as follows: a preparation method of a positive electrode material of a sodium-ion battery comprises the following steps:
s1, preparing aniline-graphene aerogel;
dispersing graphene in deionized water, performing ultrasonic treatment, stripping and dispersing the graphene in the deionized water;
adding aniline into the graphene-water dispersion liquid, performing ultrasonic dispersion, and dispersing and attaching the aniline to the surface of the graphene;
placing the water dispersion system with aniline uniformly attached to the surface of graphene in a reaction kettle for hydrothermal reaction to prepare aniline-graphene hydrogel;
freezing and drying the obtained aniline-graphene hydrogel to obtain aniline-graphene aerogel;
s2, simultaneously adding an oxidant, a vanadium source compound, a phosphorus source compound and a sodium source compound which are dispersed in water into the aniline-graphene aerogel dispersed in water, heating to 70-90 ℃ under stirring, reacting for 2-6 hours to generate sodium vanadium phosphate gel, and simultaneously carrying out oxidation polymerization on aniline to form polyaniline, wherein the generated polyaniline covers the sodium vanadium phosphate gel;
s3, transferring the dispersion system subjected to the S2 into a reaction kettle for high-temperature and high-pressure reaction, and distributing polyaniline-coated sodium vanadium phosphate on the surface of the polyaniline-loaded graphene aerogel;
and S4, cleaning the precipitate obtained in the step S3, drying and carrying out ball milling to obtain the polyaniline-graphene aerogel-sodium vanadium phosphate compound.
Preferably, the molar ratio of vanadium, phosphorus and sodium in the vanadium source compound, the phosphorus source compound and the sodium source compound is 2:3:3. in the present invention, the vanadium source is vanadate, such as ammonium vanadate, the phosphorus source is phosphate, such as ammonium phosphate, and the sodium source is sodium-containing salt, such as sodium sulfate.
Preferably, the molar ratio of the graphene to the sodium vanadium phosphate is 1: (5 to 10), for example, 1: 5. 1: 6. 1: 7. 1:8. 1:9 or 1:10, etc., but are not limited to the recited values, and other unrecited values within the numerical range are equally applicable; the method comprises the following steps that graphene enters a structure at a high temperature of a hydrothermal reaction to form graphene hydrogel, and aerogel is formed through quick-freezing and drying; the product capacity is reduced by too much the using amount of the graphene aerogel, the using amount of the graphene aerogel is too little, the vanadium sodium phosphate crystal dispersing substrate is insufficient, and the vanadium sodium phosphate is difficult to effectively spread with uniform particles on the surface of the graphene aerogel, so that the aim of nanocrystallization cannot be achieved. The molar ratio of aniline to sodium vanadium phosphate is 1: (8 to 12), for example, 1:8. 1:9. 1:10. 1:11 or 1:12, but not limited to the recited values, and other unrecited values within the range are equally applicable; in the preparation process of the cathode material, aniline originally adsorbed on the surface of the graphene aerogel and adjacent to each other is polymerized to generate polyaniline, the polyaniline effectively covers and surrounds vanadium sodium phosphate gel surrounded by the aniline before polymerization, and the polyaniline regulates and controls the dispersion condition of the vanadium sodium phosphate on the surface of the graphene aerogel; therefore, the product capacity is reduced by using too much aniline, the uniformity and morphology of the vanadium sodium phosphate particles are not effectively regulated by using too little aniline, and the dispersibility of the vanadium sodium phosphate particles on the surface of the graphene aerogel is not good.
The preferred parameters of the hydrothermal reaction in S1 are as follows:
reaction temperature: 330 ℃ to 370 ℃;
reaction time: 10 hours to 14 hours.
According to the invention, the sufficient formation of the graphene hydrogel is effectively ensured, and the graphene aerogel is favorably used as a loading substrate.
The parameters of the high-temperature high-pressure reaction in S3 are preferably as follows:
reaction temperature: 180 ℃ to 300 ℃;
reaction time: 5 to 8 hours.
According to the invention, the high-temperature and high-pressure reaction of S3 is used for promoting the vanadium sodium phosphate in a gel state to be distributed on the surface of the graphene aerogel in a particle form under the limitation of the coating partition of polyaniline, so that the vanadium sodium phosphate nanoparticles in the compound are effectively ensured to be uniform and controllable in size and shape, and the vanadium sodium phosphate nanoparticles are ensured to be uniformly dispersed on the surface of the graphene aerogel.
The concrete process of freeze-drying the aniline-graphene hydrogel in the S1 to obtain the aniline-graphene aerogel is preferably as follows:
the aniline-graphene hydrogel was freeze-dried in liquid nitrogen for 65 to 78 hours.
The aniline-graphene hydrogel is subjected to water sublimation in freeze drying and is converted into the aniline-graphene aerogel.
Preferably, the oxidant for oxidizing and polymerizing aniline into polyaniline in S2 is 98% concentrated sulfuric acid, and the molar ratio of sulfuric acid to aniline is 1:100.
the second purpose of the invention is to provide a positive electrode material of a sodium-ion battery, wherein Na coated and limited by polyaniline is adopted in the invention 3 V 2 (PO 4 ) 3 The particle size is evenly distributed on the surface of the graphene aerogel, the conductivity is obviously improved, the moving path of sodium ions is effectively shortened by the nano particles, and the cycle performance and the rate performance of the battery are effectively improved.
In order to solve the technical problem, the technical scheme of the invention is as follows: the positive electrode material of the sodium-ion battery prepared by the preparation method provided by the invention comprises sodium vanadium phosphate, polyaniline and graphene aerogel, wherein sodium vanadium phosphate nanoparticles are coated by the polyaniline and are uniformly dispersed on the surface of the graphene aerogel.
The third purpose of the invention is to provide a sodium-ion battery, and the invention uses nano Na which has uniform particles, is loaded by graphene aerogel and is coated by polyaniline 3 V 2 (PO 4 ) 3 As a positive electrode material, the lithium ion battery effectively improves the cycle performance and rate capability of the battery.
In order to solve the technical problem, the technical scheme of the invention is as follows: a sodium ion battery using the anode material prepared by the invention.
By adopting the technical scheme, the invention has the beneficial effects that:
preparing aniline-graphene aerogel through S1 in time sequence, dispersing graphene in water, adding aniline, and uniformly attaching aniline to the surface of the graphene under the adsorption action of a carbon material; enabling water molecules serving as a solvent to enter a graphene layer structure by utilizing a hydrothermal reaction process to obtain a graphene hydrogel structure, freeze-drying, and sublimating the solvent in the graphene hydrogel to obtain graphene aerogel attached with aniline;
then simultaneously adding concentrated sulfuric acid serving as an oxidant and a vanadium source compound, a phosphorus source compound and a sodium source compound which are dispersed in water into the aniline-graphene aerogel dispersed in water, stirring, heating to 70-90 ℃, reacting for 2-6 hours, and oxidizing and polymerizing aniline to form polyaniline while generating vanadium-sodium phosphate gel; the vanadium sodium phosphate gel is coated in the polyaniline polymerization process, the vanadium sodium phosphate gel and the polyaniline gel are in dynamic balance, and the coated vanadium sodium phosphate can be uniformly dispersed along with the polyaniline and then is applied to the surface of the graphene aerogel to form a composite product with uniform particles;
finally, performing high-temperature and high-pressure reaction on the polyaniline-graphene aerogel-sodium vanadium phosphate gel dispersion system subjected to S2, wherein the polyaniline-coated sodium vanadium phosphate particles are distributed on the surface of the polyaniline-loaded graphene aerogel, and the limitation of the polyaniline on the polyaniline-coated sodium vanadium phosphate prevents the sodium vanadium phosphate from agglomerating in the particle growth process, so that the control on uniform particle size and uniform dispersion of the sodium vanadium phosphate nanoparticles distributed on the surface of the graphene aerogel is realized;
according to the invention, vanadium sodium phosphate nanoparticles are coated by polyaniline and uniformly dispersed on the surface of graphene aerogel, and are coated by polyaniline to prevent particle agglomeration, and the more dispersed the particles, the better the rate capability of the material is;
according to the invention, the particle nanocrystallization shortens the sodium-embedded path of the sodium vanadium phosphate, and simultaneously assists two conductive substances, namely graphene aerogel and polyaniline, so that the conductive capability of the composite material is further improved, and the rate capability of the battery is effectively improved;
polyaniline is synchronously formed along with sodium vanadium phosphate gel to match with the growth conditions of high temperature and high pressure, sodium vanadium phosphate particles form limiting or templating under the uniform distribution of polyaniline, the particle size of the sodium vanadium phosphate particles loaded on the graphene aerogel is uniform, the consistency of the material is improved, the material is applied to a sodium battery, and the consistency of the electrochemical performance of the sodium ion battery is high;
the graphene aerogel used in the invention embodies the excellent performance of graphene under the macroscopic scale, the structure is formed by three-dimensional lapping and assembling of graphene laminas, the graphene aerogel has a three-dimensional continuous porous network structure, the advantages of high specific surface area, high porosity, high electrical conductivity, good thermal conductivity and mechanical strength and the like of graphene and aerogel are inherited, and the three-dimensional network structure is more suitable for a positive electrode material distribution substrate than the simple lamina graphene.
The cycle performance and the rate capability of the sodium ion battery are improved.
Drawings
Fig. 1 is an XRD spectrum of the polyaniline-graphene aerogel-sodium vanadium phosphate composite prepared in example 5 of the present invention;
FIG. 2 is a TEM image of a composite obtained in comparative example 2 and a composite obtained in example 5, wherein a is comparative example 2,b is example 5;
fig. 3 is a rate curve of assembling the cathode materials respectively prepared in examples 1 to 5 and comparative examples 1 and 2 into a finished battery;
fig. 4 is a graph showing cycle performance of the cathode materials respectively prepared in examples 1 to 5 and comparative examples 1 and 2 assembled into a finished battery.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
The embodiment discloses a preparation method of a sodium-ion battery cathode material, which comprises the following steps:
s1, preparing aniline-graphene aerogel;
dispersing graphene in deionized water, wherein the mass of the deionized water is 20 times of that of the graphene, carrying out ultrasonic treatment for 1 hour, and stripping and dispersing the graphene in the deionized water;
adding aniline into the graphene-water dispersion liquid, performing ultrasonic dispersion for 30min, and dispersing and attaching the aniline to the surface of the graphene;
placing the water dispersion system with aniline uniformly attached to the surface of graphene in a reaction kettle for hydrothermal reaction to prepare aniline-graphene hydrogel;
the parameters of the hydrothermal reaction in S1 are as follows:
reaction temperature: 330 ℃; reaction time: for 10 hours.
Freezing and drying the obtained aniline-graphene hydrogel to obtain aniline-graphene aerogel;
the specific process for obtaining the polyaniline-graphene aerogel by freeze drying of the aniline-graphene hydrogel in the S1 is as follows:
the aniline-graphene hydrogel was freeze-dried in liquid nitrogen for 72 hours.
The molar ratio of graphene to sodium vanadium phosphate is 1:10; the molar ratio of aniline to sodium vanadium phosphate is 1:12.
s2, adding concentrated sulfuric acid serving as an oxidant and a vanadium source compound, a phosphorus source compound and a sodium source compound which are dispersed in water into the aniline-graphene aerogel dispersed in water;
heating to 80 ℃ under stirring, reacting for 2 hours to generate sodium vanadium phosphate gel, and simultaneously oxidizing and polymerizing aniline to form polyaniline, wherein the generated polyaniline covers the sodium vanadium phosphate gel;
wherein, ammonium vanadate as a vanadium source compound is dissolved in water, and ammonium phosphate as a phosphorus source compound and sodium sulfate as a sodium source compound are dissolved in water together;
the molar ratio of vanadium, phosphorus and sodium in the vanadium source compound, the phosphorus source compound and the sodium source compound is 2:3:3.
the specification of the concentrated sulfuric acid is 98% concentrated sulfuric acid, and the molar ratio of the sulfuric acid to the aniline is 1;
s3, transferring the dispersion system subjected to the S2 into an inner liner of a polytetrafluoroethylene reaction kettle, adding a stainless steel shell, transferring into a forced air constant temperature drying box, and carrying out high-temperature and high-pressure reaction, wherein sodium vanadium phosphate is distributed on the surface of polyaniline-loaded graphene aerogel;
the parameters of the high-temperature high-pressure reaction in the S3 are as follows:
reaction temperature: 180 ℃; reaction time: for 5 hours.
And S4, cleaning the precipitate obtained in the step S3, drying, and performing ball milling to obtain a polyaniline-graphene aerogel-sodium vanadium phosphate compound, wherein polyaniline-coated sodium vanadium phosphate nanoparticles are distributed on the surface of the graphene aerogel.
Example 2
The embodiment discloses a preparation method of a sodium-ion battery positive electrode material, which comprises the following steps:
s1, preparing aniline-graphene aerogel;
dispersing graphene in deionized water, wherein the mass of the deionized water is 20 times that of the graphene, and carrying out ultrasonic treatment for 1h to strip and disperse the graphene in the deionized water;
adding aniline into the graphene-water dispersion liquid, performing ultrasonic dispersion for 30min, and dispersing and attaching the aniline to the surface of the graphene;
placing the water dispersion system with aniline uniformly attached to the graphene surface in a reaction kettle for hydrothermal reaction to prepare aniline-graphene hydrogel;
the parameters of the hydrothermal reaction in S1 are as follows:
reaction temperature: 340 ℃; reaction time: for 11 hours.
Freezing and drying the obtained aniline-graphene hydrogel to obtain polyaniline-graphene aerogel;
the specific process for obtaining the polyaniline-graphene aerogel by freeze drying of the aniline-graphene hydrogel in the S1 is as follows:
the aniline-graphene hydrogel was freeze-dried in liquid nitrogen for 72 hours.
The mol ratio of the graphene to the sodium vanadium phosphate is 1:9; the molar ratio of aniline to sodium vanadium phosphate is 1:11.
s2, simultaneously adding concentrated sulfuric acid serving as an oxidant and a vanadium source compound, a phosphorus source compound and a sodium source compound which are dispersed in water into the aniline-graphene aerogel dispersed in water, stirring, heating to 80 ℃, reacting for 3 hours, oxidizing and polymerizing aniline to form polyaniline while generating sodium vanadium phosphate gel, and coating the polyaniline with the sodium vanadium phosphate gel;
wherein, ammonium vanadate as a vanadium source compound is dissolved in water, and ammonium phosphate as a phosphorus source compound and sodium sulfate as a sodium source compound are dissolved in water together;
the specification of the concentrated sulfuric acid is 98% concentrated sulfuric acid, and the molar ratio of the sulfuric acid to the aniline is 1;
the molar ratio of vanadium, phosphorus and sodium in the vanadium source compound, the phosphorus source compound and the sodium source compound is 2:3:3.
s3, transferring the dispersion system subjected to the S2 into an inner liner of a polytetrafluoroethylene reaction kettle, adding a stainless steel shell, transferring into a forced air constant temperature drying box, and carrying out high-temperature and high-pressure reaction, wherein sodium vanadium phosphate is distributed on the surface of polyaniline-loaded graphene aerogel;
the parameters of the high-temperature high-pressure reaction in the S3 are as follows:
reaction temperature: at 210 ℃; reaction time: for 6 hours.
And S4, cleaning the precipitate obtained in the step S3, drying, and performing ball milling to obtain a polyaniline-graphene aerogel-sodium vanadium phosphate compound, wherein polyaniline-coated sodium vanadium phosphate nanoparticles are distributed on the surface of the graphene aerogel.
Example 3
The embodiment discloses a preparation method of a sodium-ion battery positive electrode material, which comprises the following steps:
s1, preparing aniline-graphene aerogel;
dispersing graphene in deionized water, wherein the mass of the deionized water is 20 times that of the graphene, and carrying out ultrasonic treatment for 1h to strip and disperse the graphene in the deionized water;
adding aniline into the graphene-water dispersion liquid, performing ultrasonic dispersion for 30min, and dispersing and attaching the aniline to the surface of the graphene;
placing the water dispersion system with aniline uniformly attached to the surface of graphene in a reaction kettle for hydrothermal reaction to prepare aniline-graphene hydrogel;
the parameters of the hydrothermal reaction in S1 are as follows:
reaction temperature: 350 ℃; reaction time: for 12 hours.
Freezing and drying the obtained aniline-graphene hydrogel to obtain polyaniline-graphene aerogel;
the specific process for obtaining the polyaniline-graphene aerogel by freeze drying of the aniline-graphene hydrogel in the S1 is as follows:
the aniline-graphene hydrogel was freeze-dried in liquid nitrogen for 72 hours.
The mol ratio of the graphene to the sodium vanadium phosphate is 1:8; the molar ratio of aniline to sodium vanadium phosphate is 1:10.
s2, adding concentrated sulfuric acid serving as an oxidant and a vanadium source compound, a phosphorus source compound and a sodium source compound which are dispersed in water into aniline-graphene aerogel dispersed in water, heating to 80 ℃ under stirring, reacting for 4 hours to generate sodium vanadium phosphate gel, and simultaneously oxidizing and polymerizing aniline to form polyaniline, wherein the generated polyaniline covers the sodium vanadium phosphate gel;
wherein, ammonium vanadate as a vanadium source compound is dissolved in water, and ammonium phosphate as a phosphorus source compound and sodium sulfate as a sodium source compound are dissolved in water together;
the specification of the concentrated sulfuric acid is 98% concentrated sulfuric acid, and the molar ratio of the sulfuric acid to the aniline is 1;
the molar ratio of vanadium, phosphorus and sodium in the vanadium source compound, the phosphorus source compound and the sodium source compound is 2:3:3.
s3, transferring the dispersed system subjected to the S2 into an inner liner of a polytetrafluoroethylene reaction kettle, adding a stainless steel shell, transferring into a forced air constant-temperature drying oven, and carrying out high-temperature and high-pressure reaction, wherein sodium vanadium phosphate is distributed on the surface of the polyaniline-loaded graphene aerogel;
the parameters of the high-temperature high-pressure reaction in the S3 are as follows:
reaction temperature: 250 ℃; reaction time: for 7 hours.
And S4, cleaning the precipitate obtained in the step S3, drying, and performing ball milling to obtain a polyaniline-graphene aerogel-sodium vanadium phosphate compound, wherein polyaniline-coated sodium vanadium phosphate nanoparticles are distributed on the surface of the graphene aerogel.
Example 4
The embodiment discloses a preparation method of a sodium-ion battery positive electrode material, which comprises the following steps:
s1, preparing aniline-graphene aerogel;
dispersing graphene in deionized water, wherein the mass of the deionized water is 20 times of that of the graphene, carrying out ultrasonic treatment for 1 hour, and stripping and dispersing the graphene in the deionized water;
adding aniline into the graphene-water dispersion liquid, performing ultrasonic dispersion for 30min, and dispersing and attaching the aniline to the surface of the graphene;
placing the water dispersion system with aniline uniformly attached to the surface of graphene in a reaction kettle for hydrothermal reaction to prepare aniline-graphene hydrogel;
the parameters of the hydrothermal reaction in S1 are as follows:
reaction temperature: 360 ℃; reaction time: for 13 hours.
Freezing and drying the obtained aniline-graphene hydrogel to obtain polyaniline-graphene aerogel;
the specific process for obtaining the polyaniline-graphene aerogel by freeze drying of the aniline-graphene hydrogel in the S1 is as follows:
the aniline-graphene hydrogel was freeze-dried in liquid nitrogen for 72 hours.
The mol ratio of the graphene to the sodium vanadium phosphate is 1:7; the molar ratio of aniline to sodium vanadium phosphate is 1:9.
s2, adding concentrated sulfuric acid serving as an oxidant and a vanadium source compound, a phosphorus source compound and a sodium source compound which are dispersed in water into aniline-graphene aerogel dispersed in water, heating to 80 ℃ under stirring, reacting for 5 hours to generate sodium vanadium phosphate gel, and simultaneously oxidizing and polymerizing aniline to form polyaniline, wherein the generated polyaniline covers the sodium vanadium phosphate gel;
wherein, ammonium vanadate as a vanadium source compound is dissolved in water, and ammonium phosphate as a phosphorus source compound and sodium sulfate as a sodium source compound are dissolved in water together;
the specification of the concentrated sulfuric acid is 98% concentrated sulfuric acid, and the molar ratio of the sulfuric acid to the aniline is 1;
the molar ratio of vanadium, phosphorus and sodium in the vanadium source compound, the phosphorus source compound and the sodium source compound is 2:3:3.
s3, transferring the dispersed system subjected to the S2 into an inner liner of a polytetrafluoroethylene reaction kettle, adding a stainless steel shell, transferring into a forced air constant-temperature drying oven, and carrying out high-temperature and high-pressure reaction, wherein sodium vanadium phosphate is distributed on the surface of the polyaniline-loaded graphene aerogel;
the parameters of the high-temperature high-pressure reaction in the S3 are as follows:
reaction temperature: 280 ℃; reaction time: for 8 hours.
And S4, cleaning the precipitate obtained in the step S3, drying, and performing ball milling to obtain a polyaniline-graphene aerogel-sodium vanadium phosphate compound, wherein polyaniline-coated sodium vanadium phosphate nanoparticles are distributed on the surface of the graphene aerogel.
Example 5
The embodiment discloses a preparation method of a sodium-ion battery cathode material, which comprises the following steps:
s1, preparing aniline-graphene aerogel;
dispersing graphene in deionized water, wherein the mass of the deionized water is 20 times of that of the graphene, carrying out ultrasonic treatment for 1 hour, and stripping and dispersing the graphene in the deionized water;
adding aniline into the graphene-water dispersion liquid, performing ultrasonic dispersion for 30min, and dispersing and attaching the aniline to the surface of the graphene;
placing the water dispersion system with aniline uniformly attached to the surface of graphene in a reaction kettle for hydrothermal reaction to prepare aniline-graphene hydrogel;
the parameters of the hydrothermal reaction in S1 are as follows:
reaction temperature: 370 ℃; reaction time: for 14 hours.
Freezing and drying the obtained aniline-graphene hydrogel to obtain polyaniline-graphene aerogel;
the specific process for obtaining the polyaniline-graphene aerogel by freeze drying of the aniline-graphene hydrogel in the S1 is as follows:
the aniline-graphene hydrogel was freeze-dried in liquid nitrogen for 72 hours.
The mol ratio of the graphene to the sodium vanadium phosphate is 1:5; the molar ratio of aniline to sodium vanadium phosphate is 1:8.
s2, adding concentrated sulfuric acid serving as an oxidant and a vanadium source compound, a phosphorus source compound and a sodium source compound which are dispersed in water into aniline-graphene aerogel dispersed in water, heating to 80 ℃ under stirring, reacting for 10 hours to generate sodium vanadium phosphate gel, and simultaneously oxidizing and polymerizing aniline to form polyaniline, wherein the generated polyaniline covers the sodium vanadium phosphate gel;
wherein, ammonium vanadate as a vanadium source compound is dissolved in water, and ammonium phosphate as a phosphorus source compound and sodium sulfate as a sodium source compound are dissolved in water together;
the specification of the concentrated sulfuric acid is 98% concentrated sulfuric acid, and the molar ratio of the sulfuric acid to the aniline is 1; the molar ratio of vanadium, phosphorus and sodium in the vanadium source compound, the phosphorus source compound and the sodium source compound is 2:3:3.
s3, transferring the dispersion system subjected to the S2 into an inner liner of a polytetrafluoroethylene reaction kettle, adding a stainless steel shell, transferring into a forced air constant temperature drying box, and carrying out high-temperature and high-pressure reaction, wherein sodium vanadium phosphate is distributed on the surface of polyaniline-loaded graphene aerogel;
the parameters of the high-temperature high-pressure reaction in the S3 are as follows:
reaction temperature: 300 ℃; reaction time: for 8 hours.
And S4, cleaning the precipitate obtained in the step S3, drying, and performing ball milling to obtain a polyaniline-graphene aerogel-sodium vanadium phosphate compound, wherein polyaniline-coated sodium vanadium phosphate nanoparticles are distributed on the surface of the graphene aerogel.
Comparative example 1
This comparative example is an unmodified sodium vanadium phosphate prepared by mixing the vanadium source compound, phosphorus source compound and sodium source compound of examples 1 to 5 in a molar ratio of vanadium, phosphorus and sodium of 2:3:3, carrying out hydrothermal reaction, wherein the parameters are as follows:
reaction temperature: 300 ℃; reaction time: for 8 hours.
And (3) cleaning, drying and ball-milling the precipitate obtained by the hydrothermal reaction to obtain the unmodified sodium vanadium phosphate.
Comparative example 2
The raw material addition ratio of the graphene aerogel modified sodium vanadium phosphate only disclosed by the comparative example is as follows:
the dosage of ammonium vanadate, ammonium phosphate and sodium sulfate is as follows: phosphorus: the molar ratio of sodium is 2:3:3, using;
the molar ratio of graphene to sodium vanadium phosphate is 1:10.
the preparation method comprises the following steps:
s1, preparing graphene aerogel for distributing sodium vanadium phosphate
Dispersing graphene in deionized water of 20 times, and performing ultrasonic treatment on the graphene by using 1h to strip and fully disperse the graphene in the water, wherein the solution is marked as a solution a;
adding the solution a into a hydrothermal kettle, and treating at 350 ℃ for 12 hours to prepare graphene hydrogel; putting the prepared graphene hydrogel into liquid nitrogen for freezing, and carrying out freeze drying for 72h to obtain high-strength graphene aerogel;
s2, distributing sodium vanadium phosphate on the surface of the graphene aerogel
Dissolving ammonium vanadate into 5 times of deionized water to obtain a solution b;
dissolving ammonium phosphate and sodium sulfate into 5 times of deionized water to obtain a solution c;
adding the solution b and the solution c into the solution a under stirring to obtain a solution d;
heating the solution d to 80 ℃ under stirring, and reacting for 2h to obtain lithium vanadium phosphate gel distributed on the surface of the graphene aerogel;
s3, transferring the dispersion system subjected to the S2 into the inner liner of a polytetrafluoroethylene reaction kettle, adding a stainless steel shell, transferring into a forced air constant temperature drying oven, and reacting for 5 hours at 180 ℃;
and S4, drying and ball-milling the product to obtain the target product graphene aerogel-sodium vanadium phosphate compound.
An XRD (X-ray diffraction) spectrum of the compound obtained in the example 5 of the invention is shown in figure 1, a broad peak of 2 theta in a range of 15-30 degrees is a diffraction packet formed by amorphous polyaniline, and the diffraction packet also comprises a characteristic peak of graphene aerogel; at the positions of 13 degrees, 32 degrees, 49 degrees and 54-56 degrees of 2 theta, characteristic peaks of sodium vanadium phosphate crystals (012), (116), (226), (137) and (138) appear, and the product obtained by the method contains sodium vanadium phosphate and polyaniline; in order to further determine the composition of the obtained composite, the product is subjected to TEM characterization as shown in fig. 2, wherein a in fig. 2 is a TEM image of the product prepared in comparative example 2, and b in fig. 2 is a TEM image of the product obtained in example 5, it is clearly seen from a and b in fig. 2 that the graphene aerogel substrate exists, and the vanadium sodium phosphate crystals are distributed on the surface of the graphene aerogel, and the product prepared by the invention is a polyaniline-graphene aerogel-vanadium sodium phosphate composite by combining XRD data in fig. 1. In addition, the problem of material agglomeration is effectively improved by adding polyaniline, and the vanadium sodium phosphate anode material which is uniformly dispersed and has small particles is formed.
The positive electrode is applied to a sodium ion battery and specifically comprises the following components:
positive electrode (mass fraction): 96% of polyaniline-graphene aerogel-sodium vanadium phosphate compound, 3% of binder PVDF and 1% of dispersant CMC;
negative electrode (mass fraction): 95% of hard carbon material, 2% of conductive agent SP,1% of dispersant CMC and 2% of binder SBR;
conventional sodium electrowinning solutions: 2mol/L sodium hexafluorophosphate, and the solvent comprises the following components in a volume ratio of 1:1: EC, DMC and EMC of 1;
stirring, coating, rolling, flaking, winding, injecting and forming to obtain the 2Ah soft package finished battery.
The rate discharge and cycle performance of the obtained full battery is tested, and the specific test method comprises the following steps:
rate capability:
the rate discharge capacity differences of the full cells corresponding to examples 1 to 5 and comparative examples 1 and 2 at 1C, 2C, 3C and 4C rates were respectively tested, the rate discharge capacity differences of each rate and the 1C capacity differences were compared, and the rate performance of the positive electrode was evaluated, and the details are shown in FIG. 3.
Cycle performance:
examples 1 to 5 and comparative examples 1 and 2 were tested for cycle curves corresponding to 100 full cell cycles, respectively, under the following cycle conditions: 0.5C charged, 1C discharged, and the test is shown in fig. 4.
From the magnification data in fig. 3, it can be seen that, compared with the sodium vanadium phosphate in comparative example 1, the composite material provided by the invention effectively improves the magnification performance, and compared with examples 1 to 5, in comparative example 2, the product obtained by adding the polyaniline-coated limiting matched graphene aerogel as a distribution substrate is better in magnification performance than the product obtained by modifying pure graphene aerogel.
From the cycle data of fig. 4, it can be seen that the capacity of comparative example 1 is only 84% remained after 100 weeks of full cell cycle, the cycle decay rate is fast, and the life is short, the invention proposes that the residual capacity of the composite material after 100 weeks of full cell cycle is significantly higher than that of comparative example 1 and comparative example 2, wherein the residual capacity of example 5 can reach 98%, and the cycle life is significantly improved compared with that of comparative example 1 and comparative example 2; further analysis of the cycle data shows that, in the cycle process, the cycle data of the sodium-ion batteries corresponding to the embodiments 1 to 5 have small fluctuation up and down and high consistency of electrochemical performance, and the main reason is that the nano-particle vanadium sodium phosphate uniformly dispersed on the surface of the graphene aerogel shortens a sodium insertion path, and simultaneously assists two conductive substances, namely the graphene aerogel and polyaniline, to further improve the electron conductivity of the composite material; polyaniline is synchronously formed along with sodium vanadium phosphate gel to match with the growth conditions of high temperature and high pressure, sodium vanadium phosphate particles form limiting or templating under the uniform distribution of polyaniline, the particle size of the sodium vanadium phosphate particles loaded on the graphene aerogel is uniform, the consistency of the material is improved, the material is applied to a sodium battery, and the consistency of the electrochemical performance of the sodium ion battery is high; the polyaniline-graphene aerogel-sodium vanadium phosphate compound provided by the invention can be applied to a sodium ion battery, and the cycle performance and the rate capability can be effectively improved.

Claims (9)

1. A preparation method of a positive electrode material of a sodium-ion battery is characterized by comprising the following steps:
the method comprises the following steps:
s1, preparing aniline-graphene aerogel;
dispersing graphene in deionized water, performing ultrasonic treatment, stripping and dispersing the graphene in the deionized water;
adding aniline into the graphene-water dispersion liquid, performing ultrasonic dispersion, and dispersing and attaching the aniline to the surface of graphene;
placing the water dispersion system with aniline uniformly attached to the graphene surface in a reaction kettle for hydrothermal reaction to prepare aniline-graphene hydrogel;
freezing and drying the obtained aniline-graphene hydrogel to obtain aniline-graphene aerogel;
s2, simultaneously adding an oxidant, a vanadium source compound, a phosphorus source compound and a sodium source compound which are dispersed in water into the aniline-graphene aerogel dispersed in water, heating to 70-90 ℃ under stirring, reacting for 2-6 hours to generate sodium vanadium phosphate gel, and simultaneously carrying out oxidative polymerization on aniline under the action of the oxidant to form polyaniline, wherein the generated polyaniline covers the sodium vanadium phosphate gel;
s3, transferring the dispersion system subjected to the S2 into a reaction kettle for high-temperature and high-pressure reaction, and distributing polyaniline-coated sodium vanadium phosphate on the surface of the polyaniline-loaded graphene aerogel;
and S4, cleaning the precipitate obtained in the step S3, drying and carrying out ball milling to obtain the polyaniline-graphene aerogel-sodium vanadium phosphate compound.
2. The production method according to claim 1, characterized in that: the molar ratio of vanadium, phosphorus and sodium in the vanadium source compound, the phosphorus source compound and the sodium source compound is 2:3:3.
3. the method of claim 1, wherein: the mol ratio of the graphene to the sodium vanadium phosphate is 1: (5 to 10); the molar ratio of aniline to sodium vanadium phosphate is 1: (8 to 12).
4. The method of claim 1, wherein:
the parameters of the hydrothermal reaction in S1 are as follows:
reaction temperature: 330 ℃ to 370 ℃;
reaction time: 10 hours to 14 hours.
5. The production method according to claim 1, characterized in that:
the parameters of the high-temperature high-pressure reaction in the S3 are as follows:
reaction temperature: 180 ℃ to 300 ℃;
reaction time: 5 hours to 8 hours.
6. The production method according to claim 1, characterized in that: the concrete process of freezing and drying the aniline-graphene hydrogel in the S1 to obtain the aniline-graphene aerogel is as follows:
the aniline-graphene hydrogel was freeze-dried in liquid nitrogen for 65 to 78 hours.
7. The production method according to claim 1, characterized in that: in S2, the oxidant for oxidizing and polymerizing the aniline into polyaniline is 98% concentrated sulfuric acid, and the molar ratio of sulfuric acid to aniline is 1:100.
8. a positive electrode material for a sodium-ion battery, produced by the production method according to any one of claims 1 to 7, characterized in that: the positive electrode material comprises sodium vanadium phosphate, polyaniline and graphene aerogel, and the sodium vanadium phosphate nanoparticles are coated by the polyaniline and are uniformly dispersed on the surface of the graphene aerogel.
9. Applying the positive electrode material of claim 8 to a sodium ion battery.
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