CN113955802A - Three-dimensional multilevel structure lithium ion battery V2O5Preparation method of @ C cathode material - Google Patents
Three-dimensional multilevel structure lithium ion battery V2O5Preparation method of @ C cathode material Download PDFInfo
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Abstract
The invention relates to a lithium ion battery V with a three-dimensional multilevel structure2O5The preparation method of the @ C cathode material comprises the following steps of: will V2O5Adding into deionized water, adding H2O2Stirring the solution, adding trisodium citrate, stirring, standing, centrifuging, collecting the product, calcining and cooling; mixing the oxalic acid and the oxalic acid, adding the mixture into deionized water, stirring the mixture at the temperature of between 60 and 70 ℃, adding ethylene glycol and hexadecyl trimethyl ammonium bromide into the mixture, stirring the mixture, and carrying out hydrothermal reaction at the temperature of between 160 and 190 ℃; centrifugally drying and calcining to obtain 3D-V2O5(ii) a Reacting the acidified pitch carbon with aminated 3D-V2O5The powder is added into deionized water, stirred and filtered to obtain the product. The advantages are that: the cheap and easily obtained modified medium-temperature coal pitch is adopted, the process is simplified, and the large-scale production can be realized. Prepared V2O5The positive electrode material composite material effectively solves the problems of reduction of material bulk density and difficult infiltration of electrolyte.
Description
Technical Field
The invention belongs to the field of lithium ion battery manufacturing, and relates to a three-dimensional multi-level structure lithium ion battery V2O5A preparation method of the @ C cathode material.
Background
In recent years, with the continuous consumption of non-renewable resources and the increasing severity of environmental pollution, the development and utilization of renewable energy sources such as wind energy and solar energy are of great importance, and therefore, the development of advanced energy storage devices has become one of the current core problems. Lithium ion batteries are widely used as advanced energy storage devices, such as portable electronic devices (mobile phones and notebook computers) and flexible wearable watches, and play more and more important roles in the fields of electric automobiles, robots, energy storage power grids and the like in recent years. However, with the gradual increase of the power of the device, the market also puts higher and higher requirements on the performance of the lithium ion battery, so that it is urgent to develop an electrode material with high specific capacity, good safety and long cycle life.
Vanadium pentoxide (V)2O5) The lithium ion battery positive electrode material has the advantages of rich storage capacity, low cost, large specific capacity, high lithium intercalation potential and the like, and is considered to be one of ideal Lithium Ion Battery (LIBs) positive electrode materials. However, V2O5When the lithium ion secondary battery is used as a positive electrode material of a lithium ion secondary battery alone, the structural stability is poor, and Li exists+Has low diffusion coefficient and electron conductivity, which will seriously affect its electrochemical performance. To solve this problem, researchers have generally nanocrystallized the raw material, and the nanocrystallized material generally has a large specific surface area to enlarge the electrode/electrolyte interface and shorten Li+The diffusion path of the ions can effectively promote the promotion of the oxidation/reduction reaction kinetics of the ions. However, the surface energy of the low-dimensional nano material is large, and agglomeration is easy to occur, which leads to reduction of material stacking density and difficult infiltration of electrolyte, and greatly limits exertion of nano material performance, so researchers adopt a strategy of assembling two-dimensional nano materials into a three-dimensional porous structure, thereby exerting the advantages of the nano structure, promoting sufficient infiltration of the electrolyte and relieving volume strain in the charge-discharge process of the material, however, the method cannot improve V2O5The conductivity of the material is poor, so that the electrochemical performance of the material is not obviously improved.
Carbon coating is also one of effective strategies for improving the electrochemical performance, and the carbon coated on the surface of the nano material can effectively reduce the charge transfer impedance of the composite material, inhibit the volume expansion of the material and improve the infiltration effect with the electrolyte.
Disclosure of Invention
To overcome the disadvantages of the prior art, the invention aims to provide a three-dimensionalLithium ion battery V with multi-stage structure2O5The preparation method of the @ C cathode material is characterized in that moderate-temperature asphalt is processed by a mixed acid method and then converted into water-soluble coal asphalt which can be dissolved in alkali liquor and organic solvent, and a hydrothermal method is adopted to prepare the high-performance three-dimensional multi-stage structure lithium ion battery V2O5And (3) a positive electrode material.
In order to achieve the purpose, the invention is realized by the following technical scheme:
three-dimensional multilevel structure lithium ion battery V2O5The preparation method of the @ C cathode material comprises the following steps of:
1) will V2O5Adding into deionized water, and slowly dripping H2O2Stirring the solution for 15-30min, adding trisodium citrate, continuously stirring for 1-2h, standing for 3-5 days, centrifuging to collect the product, drying, calcining in a tube furnace at 400-500 ℃ for 2-3.5h in the air atmosphere, and cooling to obtain the product named NR-V2O5；
2) Reacting NR-V2O5Adding oxalic acid and deionized water according to the mol ratio of 1:2-1:3.5, stirring at 60-70 ℃ until the solution turns to dark blue, adding ethylene glycol and cetyl trimethyl ammonium bromide, continuously stirring for 0.5-1.5h, transferring the solution to a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 190 ℃ for 10-14h under 160-; after the reaction is finished, placing the mixture into a tubular furnace after centrifugal drying, calcining the mixture for 2 to 4 hours at the temperature of 350-450 ℃ in the air atmosphere to obtain a three-dimensional layered multilevel structure V2O5Ball, named 3D-V2O5；
3) Placing the medium-temperature asphalt in a tubular furnace for carbonization at the temperature of 600-750 ℃ to obtain an asphalt carbon material, then performing asphalt carbon acidification treatment, and introducing hydroxyl and carboxyl functional groups on the surface of the asphalt carbon material;
4) will be 3D-V2O5Dispersing the powder into a toluene solution, adding 3-aminopropyltrimethoxysilane, reacting for 30-40h, and filtering to obtain aminated 3D-V2O5And (3) powder.
5) Mixing the acidified pitch carbon obtained in step 3) with the aminated 3D-V obtained in step 4)2O5Adding the powder into deionized water according to the mass ratio of 1:4-1:6, wherein the 3D-V is realized2O5The amino on the surface and the hydroxyl and carboxyl on the surface of the asphalt carbon are subjected to self-assembly reaction under the action of hydrogen bonds, so that the asphalt carbon is uniformly coated on the V2O5Stirring the mixture on the surface of the ball for 0.5 to 1.5 hours, and filtering the mixture to obtain a product of 3D-V2O5@C。
V in step 1)2O51.600g-1.800g, 300-400mL deionized water; h2O2The concentration of (2) is 30%, and the addition amount is 10-20 mL; 0.1-0.2g of trisodium citrate.
The deionized water in the step 2) is 15-25 mL; the ethylene glycol is 55-70 mL; cetyl trimethyl ammonium bromide in an amount of 0.05 to 0.15 g.
The asphalt carbon acidification treatment method comprises the following steps:
1) crushing, grinding and sieving the pitch carbon by a 100-mesh sieve to obtain raw material pitch carbon;
2) adding raw material pitch carbon into a mixed acid solution, stirring in a constant-temperature water bath, pouring a solid-liquid mixture into deionized water after the reaction is finished to terminate the reaction, performing heat filtration after the reaction is terminated, washing a filter cake with water until the pH value is 5-6, mixing the filter cake with 1mol/L NaOH solution until the pH value is greater than 12, stirring in the constant-temperature water bath, filtering and collecting filtrate, then adjusting the pH value to be less than 2 by using dilute hydrochloric acid, performing centrifugal separation to collect black-brown precipitate, drying at constant temperature and grinding into powder of 50-100 mu m.
The mixed acid solution is prepared by mixing the following components in a volume ratio of 7: 3 of concentrated sulfuric acid and concentrated nitric acid.
Step 4) the 3D-V2O5The powder is 0.2-0.4 g; the toluene solution is 10-25 mL; the 3-aminopropyl trimethoxy silane is 0.2-0.4 mL.
The deionized water in the step 5) is 10-20 mL.
Compared with the prior art, the invention has the beneficial effects that:
the method adopts cheap and easily-obtained modified medium-temperature coal pitch, simplifies the process and can realize large-scale production. Prepared V2O5The positive electrode material composite material effectively solves the problems of reduction of material bulk density and difficult immersion of electrolyteThe electrochemical performance of the material is greatly improved, the application of the coal tar pitch in the field of clean energy is expanded, and a new thought and idea are provided for the preparation of other lithium ion anode materials.
Drawings
FIG. 1 is NR-V2O5The preparation process is shown in the figure.
FIG. 2 is a 3D-V2O5The production process route diagram of @ C.
FIG. 3 is a 3D-V2O5The preparation scheme of @ C.
Fig. 4 is an assembly flow diagram of a lithium ion battery.
In FIG. 5(a) is NR-V2O5,3D-V2O5,3D-V2O5XRD spectrum of @ C material;
(b) is 3D-V2O5Raman spectrum of @ C material.
In FIG. 6(a) is NR-V2O5SEM picture of (1); (b) is 3D-V2O5SEM picture of (1); (c) is 3D-V2O5SEM picture of @ C; (d) - (f) is 3D-V2O5EDS element scan of @ C.
FIG. 7(a) shows NR-V2O5、3D-V2O5、3D-V2O5A cycle performance plot of @ C;
(b) is NR-V2O5、3D-V2O5、3D-V2O5Graph of rate performance @ C.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings, but it should be noted that the present invention is not limited to the following embodiments.
Example 1
Three-dimensional multilevel structure lithium ion battery V2O5Preparation of @ C cathode material:
1) nano V2O5See FIG. 1:
a. 1.7733g V will be mixed2O5Adding into 375mL deionized water, and slowly adding 30% dropwiseH2O2Solution 15mL, after stirring for 20min, 0.15g trisodium citrate was added.
b. Stirring for 2h, standing for 3 days, centrifuging to collect the product, drying, calcining in a tube furnace at 500 deg.C for 3h in air atmosphere, and cooling to obtain nanometer V2O5Is named NR-V2O5。
2) Three-dimensional layered multilevel structure V2O5Preparation of spheres, see fig. 2:
a. 0.364g of NR-V2O5And 0.756g oxalic acid in a 1:3 molar ratio to 15mL deionized water and stirred at 70 ℃ until the solution turned dark blue.
b. Adding 60mL of ethylene glycol and 0.1g of hexadecyl trimethyl ammonium bromide into the solution, continuously stirring the mixture for 1 hour, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 12 hours, after the reaction is finished, placing the solution into a tubular furnace after centrifugal drying, and calcining the solution for 3 hours at 400 ℃ in an air atmosphere to obtain a three-dimensional layered multilevel structure V2O5Ball, named 3D-V2O5。
3) Carbon-coated three-dimensional layered multilevel structure V2O5Preparation of spheres, see fig. 3:
a. the medium temperature asphalt is placed in a tube furnace to be carbonized at 700 ℃ to prepare the asphalt carbon material, and then acidification treatment is carried out to introduce hydroxyl and carboxyl functional groups on the surface of the asphalt carbon material.
b. Will be 3D-V2O5(0.3g) the powder was dispersed in toluene (20mL) solution, 3-aminopropyltrimethoxysilane (0.3mL) was added, the reaction was carried out for 36h, and then the aminated 3D-V was obtained by filtration2O5And (3) powder.
c. Reacting the acidified pitch carbon with aminated 3D-V2O5Adding the powder into deionized water (10-20mL) according to the mass ratio of 1:5, wherein the 3D-V is2O5The amino on the surface and the hydroxyl and carboxyl on the surface of the asphalt carbon are subjected to self-assembly reaction under the action of hydrogen bonds, so that the asphalt carbon is uniformly coated on the V2O5Stirring the surface of the ball for 1 hour, filtering the mixture, and naming the obtained product as 3D-V2O5@C。
Wherein, the acidification treatment process comprises the following steps:
1) crushing, grinding and sieving the pitch carbon by a 100-mesh sieve to obtain raw material pitch carbon;
2) adding raw material pitch carbon into a mixed acid solution, wherein the volume ratio of the mixed acid solution is 7: 3, stirring in a constant-temperature water bath, pouring a solid-liquid mixture into deionized water after the reaction is finished to terminate the reaction, performing heat filtration after the reaction is terminated, washing the filter cake with water until the pH value is 5-6, mixing the filter cake with 1mol/L NaOH solution until the pH value is greater than 12, stirring in a constant-temperature water bath, filtering, collecting filtrate, adjusting the pH value to be less than 2 by using dilute hydrochloric acid, performing centrifugal separation, collecting black-brown precipitate, drying at constant temperature, and grinding into powder of 50-100 mu m.
The assembly of the lithium ion battery includes the preparation of electrode plates and the process of assembling the lithium ion battery, as shown in fig. 4, specifically as follows:
(1) dry grinding: 3D-V2O5The material @ C, the conductive agent (acetylene black, SP) and the binder (polyvinylidene fluoride, PVDF) are uniformly ground in an agate mortar according to the mass ratio of 8:1: 1.
(2) Wet grinding and size mixing: nitrogen Methyl Pyrrolidone (NMP) is dripped into an agate mortar, and the mixture is continuously ground until the mixture becomes uniform and sticky slurry.
(3) Smearing: the viscous slurry is evenly coated on the aluminum foil.
(4) And (3) drying: and (3) placing the electrode slice in the air, drying at 80 ℃ for 1h, and then transferring to a vacuum drying oven to dry at 120 ℃ for 12 h.
(5) Cutting: the electrode sheet was cut into a circular piece having a diameter of 11mm using a sheet cutter.
(6) After the electrode plate is prepared, a CR2032 button cell is adopted to assemble a lithium ion battery in a vacuum glove box (the water concentration is less than 0.1ppm, and the oxygen concentration is less than 0.1 ppm). The lithium ion battery counter electrode is a lithium sheet, the specific assembly sequence is a negative electrode shell, the lithium sheet, a diaphragm, 100ul of electrolyte, an electrode plate, a steel sheet, an elastic sheet and a positive electrode shell, and after the battery is assembled, the battery is kept stand for 12 hours and then is subjected to related electrochemical performance tests.
See fig. 5(a), XRD pattern of the sample. As can be seen from the figure, all the samplesThe diffraction peaks of the product are relatively sharp, which indicates that the crystallinity of the material is better, and all the characteristic diffraction peaks of the sample are equal to V2O5The characteristic peaks correspond to each other, and the three main peaks are respectively positioned at 20.3 degrees, 26.1 degrees and 31.0 degrees and correspond to the orthogonal phase V2O5The (010), (101) and (310) crystal planes of (a). No diffraction peaks for other materials were observed in the XRD patterns, indicating that the prepared material was pure and free of other impurities. FIG. 5(b) is a 3D-V diagram2O5Raman spectrum analysis of the/C composite material. As can be seen, the distance is 1350cm-1And 1590cm-1The characteristic Raman peak of the carbon appears, which respectively corresponds to the D peak and the G peak of the pitch carbon, the D peak is obviously stronger than the G peak, the pitch carbon is amorphous carbon and is 140cm-1、283cm-1、407cm-1、480cm-1、527cm-1And 992cm-1At the same time appear V2O5Typical characteristic peak of (A), which indicates that pitch carbon is uniformly coated on V2O5A surface.
As shown in FIG. 6(a), NR-V2O5Consists of a rod-shaped cluster body with the width of 500nm and the length of 0.4 mu m to 2.5 mu m, and part V2O5The nanorods are agglomerated into an irregular blocky structure. As can be seen from FIG. 6(b), the nano-V2O5Obtaining 3D-V after hydrothermal reaction2O5The appearance of the sample is changed greatly, and the sample is of a silver ear-shaped spherical structure formed by assembling ultrathin nano sheets. As can be seen from FIG. 6(c), 3D-V2O5The nano-sheet structure can still be observed on the surface of the @ C sample. As can be seen from the EDS scans of FIGS. 6(d) - (f), the element C, O, V is distributed more uniformly.
In FIG. 7(a), (b), NR-V2O5、3D-V2O5、3D-V2O5The capacity of the/C sample after circulating for 10 circles under the current density of 0.1A/g is 281mAh/g, 265mAh/g and 270mAh/g respectively. NR-V when the current density increases from 0.1A/g by a factor of 50 to 5.0A/g2O5、3D-V2O5、3D-V2O5The @ C samples had capacities of 85mAh/g, 100mAh/g and 113mAh/g, capacity retention rates of 30.2%, 37.7% and 41.9%, respectively, and 3D-V2O5The @ C sample had the highest capacity retention. When the current returns to the current density of 0.1A/g, 3D-V2O5The @ C sample still has a lithium storage capacity of 200mAh/g, which is higher than that of the other two groups of samples, and the excellent rate capability of the @ C sample is attributed to that carbon coating provides good conductivity for the composite material and a smooth conductive network is constructed; on the other hand, due to the fact that the ultrathin nanosheets effectively shorten the transmission radius of lithium ions and increase the diffusion rate of the ions, the factors promote the increase of the rate capability of the material. In group 3 samples, V2O5The rate capability of the sample is poor, which is probably because the nanorods are agglomerated more seriously, which not only prolongs the diffusion path of lithium ions, but also is not beneficial to the infiltration of electrolyte, and limits the exertion of the material capacity. When the nano-material is assembled into a three-dimensional multi-fold nano-sheet structure, the agglomeration of low-dimensional nano-materials is relieved, so that the nano-material is in a 3D-V shape2O5The cycle performance and the rate performance of the sample are improved. The cycling performance of the three sets of samples at a current density of 100mA/g is shown in FIG. 7(a), 3D-V2O5The @ C sample has a relatively good capacity retention rate, the first circle of the sample has a lithium storage capacity of 289mAh/g, the first circle still has a capacity of 234mAh/g after 50 circles of circulation, and the capacity retention rate is 81.0%.
3D-V2O5The @ C material has a reversible capacity of 270mAh/g at a current density of 0.1A/g, and still has a specific capacity of 113mAh/g at a current density of 5.0A/g. Kinetic analysis showed that surface pitch carbon and ultra-thin V2O5The synergistic effect of the nano-sheets effectively improves the dynamics of heterogeneous reaction of the material, and the composite material has a rapid pseudocapacitance lithium storage mechanism. This is because 3D-V2O5The three-dimensional multilevel structure, the good conductive network and the short lithium ion diffusion path of the @ C composite material greatly promote V2O5And (4) exertion of capacity.
The invention adopts a sol-gel method to prepare the rod-shaped nano vanadium pentoxide (NR-V)2O5) And further synthesize the vanadium pentoxide (3D-V) with a three-dimensional layered multilevel structure by taking the vanadium pentoxide as a raw material2O5) Finally, the asphalt is taken as a carbon source, and uniform carbon coating is carried out on the surface of the asphalt by an electrostatic adsorption method to prepare the 3D-V2O5The @ C composite material can be used as a lithium ion battery anode material assembled battery. The electrochemical results show that the ultrathin 3D-V2O5The unique structure of the nano-sheet and the synergistic effect of the asphalt carbon enhance the electron/ion conduction rate of the composite material, and show a rapid pseudocapacitance lithium storage mechanism. Compared with NR-V2O5And 3D-V2O5Ball, 3D-V2O5The @ C composite material has excellent rate capability and cycle performance, has a specific capacity of 113mAh/g under a large current density of 5.0A/g, and has a capacity retention rate of more than 81% after 50 cycles of circulation under a current density of 0.1A/g.
Claims (7)
1. Three-dimensional multilevel structure lithium ion battery V2O5A preparation method of a @ C positive electrode material is characterized by comprising the following steps of:
1) will V2O5Adding into deionized water, and slowly dripping H2O2Stirring the solution for 15-30min, adding trisodium citrate, continuously stirring for 1-2h, standing for 3-5 days, centrifuging to collect the product, drying, calcining in a tube furnace at 400-500 ℃ for 2-3.5h in the air atmosphere, and cooling to obtain the product named NR-V2O5；
2) Reacting NR-V2O5Adding oxalic acid and deionized water according to the mol ratio of 1:2-1:3.5, stirring at 60-70 ℃ until the solution turns to dark blue, adding ethylene glycol and cetyl trimethyl ammonium bromide, continuously stirring for 0.5-1.5h, transferring the solution to a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction at 190 ℃ for 10-14h under 160-; after the reaction is finished, placing the mixture into a tubular furnace after centrifugal drying, calcining the mixture for 2 to 4 hours at the temperature of 350-450 ℃ in the air atmosphere to obtain a three-dimensional layered multilevel structure V2O5Ball, named 3D-V2O5；
3) Placing the medium-temperature asphalt in a tubular furnace for carbonization at the temperature of 600-750 ℃ to obtain an asphalt carbon material, then performing asphalt carbon acidification treatment, and introducing hydroxyl and carboxyl functional groups on the surface of the asphalt carbon material;
4) will be 3D-V2O5Dispersing the powder into a toluene solution, adding 3-aminopropyltrimethoxysilane, reacting for 30-40h, and filtering to obtain aminated 3D-V2O5And (3) powder.
5) Mixing the acidified pitch carbon obtained in step 3) with the aminated 3D-V obtained in step 4)2O5Adding the powder into deionized water according to the mass ratio of 1:4-1:6, wherein the 3D-V is realized2O5The amino on the surface and the hydroxyl and carboxyl on the surface of the asphalt carbon are subjected to self-assembly reaction under the action of hydrogen bonds, so that the asphalt carbon is uniformly coated on the V2O5Stirring the mixture on the surface of the ball for 0.5 to 1.5 hours, and filtering the mixture to obtain a product of 3D-V2O5@C。
2. The three-dimensional multilevel structure lithium ion battery V according to claim 12O5A method for producing a @ C positive electrode material, characterized in that V in step 1)2O51.600g-1.800g, 300-400mL deionized water; h2O2The concentration of (2) is 30%, and the addition amount is 10-20 mL; 0.1-0.2g of trisodium citrate.
3. The three-dimensional multilevel structure lithium ion battery V according to claim 12O5The preparation method of the @ C cathode material is characterized in that the deionized water in the step 2) is 15-25 mL; the ethylene glycol is 55-70 mL; cetyl trimethyl ammonium bromide in an amount of 0.05 to 0.15 g.
4. The three-dimensional multilevel structure lithium ion battery V according to claim 12O5The preparation method of the @ C cathode material is characterized in that the asphalt carbon acidification treatment method comprises the following steps:
1) crushing, grinding and sieving the pitch carbon by a 100-mesh sieve to obtain raw material pitch carbon;
2) adding raw material pitch carbon into a mixed acid solution, stirring in a constant-temperature water bath, pouring a solid-liquid mixture into deionized water after the reaction is finished to terminate the reaction, performing heat filtration after the reaction is terminated, washing a filter cake with water until the pH value is 5-6, mixing the filter cake with 1mol/L NaOH solution until the pH value is greater than 12, stirring in the constant-temperature water bath, filtering and collecting filtrate, then adjusting the pH value to be less than 2 by using dilute hydrochloric acid, performing centrifugal separation to collect black-brown precipitate, drying at constant temperature and grinding into powder of 50-100 mu m.
5. The three-dimensional multilevel structure lithium ion battery V according to claim 42O5The preparation method of the @ C cathode material is characterized in that the mixed acid solution is prepared by mixing the following components in a volume ratio of 7: 3 of concentrated sulfuric acid and concentrated nitric acid.
6. The three-dimensional multilevel structure lithium ion battery V according to claim 12O5A method for producing a @ C positive electrode material, characterized in that the 3D-V in step 4)2O5The powder is 0.2-0.4 g; the toluene solution is 10-25 mL; the 3-aminopropyl trimethoxy silane is 0.2-0.4 mL.
7. The three-dimensional multilevel structure lithium ion battery V according to claim 12O5The preparation method of the @ C cathode material is characterized in that the deionized water in the step 5) is 10-20 mL.
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