CN111943165B - Electrode material based on polyimide mesocarbon microbead structure and preparation method thereof - Google Patents
Electrode material based on polyimide mesocarbon microbead structure and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an electrode material based on a polyimide mesocarbon microbead structure and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing a polyamic acid solution; (2) self-assembly reaction of Polyimide (PI). (3) And (3) carbonizing the polyimide. (4) And (3) preparing a template skeleton agent. (5) And (4) preparing an electrode material. According to the invention, polyimide is used as a matrix, a thermal polycondensation hydrothermal reaction is carried out, sintering process parameters are controlled, the mesocarbon microbeads with porosity, nitrogen enrichment and uniform size are prepared, the graphite interlayer spacing is increased by virtue of the unique 'curved surface effect', more structural defects are provided by virtue of the 'homogeneous nitrogen doping effect' induction, the transmission of lithium ions is facilitated, and lithium storage microporous sites are increased while lithium is embedded between layers, so that the electricity storage performance of the electrode material is improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to an electrode material based on a polyimide mesocarbon microbead structure and a preparation method thereof.
Background
In recent years, with the rapid development of new energy industries, lithium ion batteries are gradually and widely applied to the fields of large-scale power grids, power energy storage, consumer electronics and the like as a preferred scheme of high-energy batteries. The electrode material is an important factor for determining the performance of the battery, and the negative electrode material also directly influences the energy density, the cycle life and the safety performance of the battery. Graphite is widely used in the negative electrode material of commercial lithium ion batteries because of its advantages of wide source, low price, good conductivity, excellent electrochemical inertia, low charge and discharge platform, etc. However, since the graphite material is a layered carbon having highly oriented crystals and has a small interlayer distance, the graphite layer is exfoliated due to the co-intercalation of solvent molecules along with the intercalation of lithium ions during charging, and the structure of the negative electrode material is unstable, which finally causes the degradation of battery performance, and is not favorable for high-rate charge and discharge. Similarly, electrode dusting of tin-based, silicon-based negative electrode materials due to the massive volume effect has also severely impacted their commercialization process. In the aspect of electrode plate preparation process, the lithium battery negative electrode material is usually prepared by active substances, conductive agents and binders through a traditional grinding mode, the grinding process is complex, and electrode plates can be cracked along with the difference of the performances of the binders.
In the previous patent of the applicant, a method for preparing an organic electrode material based on a polyimide structure (chinese patent 201711339230.0) has been to prepare a polyimide-based "rod-like" lithium ion battery cathode material by a one-step solvothermal precipitation method, and has shown electrochemical characteristics of high rate and high cycle stability, but due to the rod-like structure, the lithium storage mechanism is mainly a mechanism of lithium intercalation between carbon layers, and microporous lithium storage is assisted.
Disclosure of Invention
The invention provides an electrode material based on a polyimide mesocarbon microbead structure and a preparation method thereof, aiming at the defects of the prior art, the mesocarbon microbeads with porosity, nitrogen enrichment and uniform size are prepared by taking polyimide as a matrix through thermal polycondensation hydrothermal reaction and sintering process parameter control, the graphite interlayer spacing is increased by virtue of the unique 'curved surface effect', more structural defects are provided by induction of 'homogeneous nitrogen doping effect', the lithium ion transmission is convenient, and lithium storage microporous sites are increased while lithium is intercalated between layers, so that the electricity storage performance of the electrode material is improved. The prepared polyimide mesocarbon microbeads are used as active substances of the lithium ion battery cathode material, and the lithium ion battery cathode material is prepared by directly pumping and filtering under the support of a framework material, and has the electrochemical characteristics of high capacity and high cycle stability.
The invention adopts the following technical scheme:
a preparation method of an electrode material based on a polyimide mesocarbon microbead structure comprises the following steps:
(1) under the protection of nitrogen and under the condition of ice-water bath, adding diamine into a solvent until the diamine is completely dissolved; then adding dianhydride monomer, and stirring for 8-12h to obtain polyamic acid (PAA) solution;
(2) and (2) placing the polyamic acid solution in the step (1) into a hydrothermal reaction kettle, adding a cyclization reaction catalyst, performing high-pressure hydrothermal reaction, naturally cooling to normal temperature, diluting with an isometric solvent, performing ultrasonic treatment for 0.25-0.5h, filtering by using a sand core funnel, washing with ethanol, and performing vacuum drying for 8h to obtain polyimide Powder (PI).
(3) Carbonizing polyimide: and (2) placing the polyimide powder in a vacuum tube type sintering furnace, sintering for 0.5-1 h at 100 ℃, sintering for 0.5-1 h at 200 ℃, sintering for 0.5-1 h at 300 ℃ and sintering for 1-2 h at 700-900 ℃ in a nitrogen or argon atmosphere to obtain the polyimide-based mesocarbon microbeads MCPI.
(4) Preparing a foam graphene NG template skeleton agent: fully dispersing Graphene Oxide (GO) in deionized water, then soaking foam Nickel (NF) in the graphene suspension, taking out, placing in a drying oven, and performing vacuum drying to obtain an N-GO precursor template; reacting the N-GO precursor template in a hydrochloric acid solution to remove nickel, thereby obtaining a GOF template; washing with deionized water for multiple times, then placing the GOF template in a hydriodic acid solution for reaction, washing with the deionized water, and drying in vacuum to obtain a foam graphene NG template skeleton agent;
(5) preparing an electrode material: adding the template skeleton agent NG and the MCPI powder into ultrapure water, performing ultrasonic dispersion, performing suction filtration to form a membrane, and performing vacuum drying to obtain the membrane electrode material.
In the step (4), the preparation method of the foam graphene NG template skeleton agent comprises the following steps: fully dispersing Graphene Oxide (GO) in deionized water, then soaking foam Nickel (NF) in the graphene suspension for 2 hours, taking out, placing in an oven for vacuum drying at 60 ℃ for 3 hours, and obtaining an N-GO precursor template; reacting the N-GO precursor template in 3mol/L hydrochloric acid solution at 65 ℃ for 4h, and removing nickel to obtain a GOF template; and washing with deionized water for multiple times, then placing the GOF template in 40. wt% hydriodic acid solution for reacting for 8h at 80 ℃, washing with the deionized water, and drying for 8h in vacuum at 100 ℃ to obtain the foam graphene NG template skeleton agent.
In the step (5), the preparation method of the electrode material comprises the following steps: adding template skeleton agent NG and MCPI powder into ultrapure water, performing ultrasonic dispersion for 6 hours, performing suction filtration to form a film, and performing vacuum drying at 75 ℃ for 12 hours to obtain the film-shaped electrode material.
The preparation method is characterized by comprising the following steps: the diamine monomer adopted in the step (1) has the following structure:
the preparation method is characterized by comprising the following steps: the dianhydride monomer adopted in the step (1) has the following structure:
the preparation method is characterized by comprising the following steps: the molar ratio of diamine to dianhydride monomer in the step (1) is 1: 0.98-1.02.
The preparation method is characterized by comprising the following steps: the solvent in the step (1) is dimethylformamide or dimethylacetamide and N-methylpyrrolidone;
the preparation method is characterized by comprising the following steps: the concentration of the polyamic acid (PAA) solution in the step (1) is 0.01-0.04 mol/100 ml; the reaction was carried out under ice-water bath conditions.
The preparation method is characterized by comprising the following steps: the cyclization reaction catalyst adopted in the step (2) is isoquinolinone with the mass fraction of 0.001 wt% of the whole reaction system, and the PAA solution is reacted for 1-2 hours under the condition of 100-130 ℃ and 8-12 hours under the condition of 160-180 ℃ in a hydrothermal reaction kettle.
The preparation method is characterized by comprising the following steps: the filter membrane adopted in the step (3) is made of PU material, and the aperture is 0.22 mu m;
the preparation method is characterized by comprising the following steps: the particle size of the polyimide-based mesocarbon microbeads MCPI prepared in the step (3) is 0.01-50 mu m.
The preparation method is characterized by comprising the following steps: the template skeleton agent in the step (4) is graphene oxide or carboxyl CNT paper, wherein the mass ratio of the template skeleton agent to PIC is 0.01-20: 1.
the film-shaped electrode material obtained by any one of the production methods
The present invention has the following advantageous effects
1. The preparation method disclosed by the invention has the advantages that the polyimide microspheres with uniform sizes and sizes of 0.01-50 mu m are prepared by regulating and controlling the chemical structure and the polymerization concentration, the proportion of carbon and nitrogen elements of the polyimide mesocarbon microspheres is effectively regulated and controlled by regulating and controlling the sintering process, more structural defects are provided by inducing a homogeneous nitrogen doping effect while the graphite interlayer spacing is increased, lithium intercalation and micropore lithium storage are effectively realized, the transmission of lithium ions is facilitated, and the electricity storage performance of the electrode material is improved.
2. The three-dimensional porous structure provided by the polyimide mesocarbon microbeads prepared by the invention shows excellent structural stability after multiple cycles, and the prepared lithium ion battery cathode shows high cycle stability.
3. The template skeleton agent is added to provide support for the mesocarbon microbeads, and the lithium ion battery negative plate is directly obtained by suction filtration without a binder, so that the preparation process is simplified, and the method is more favorable for industrial popularization.
Drawings
FIG. 1 is an SEM image (2000X magnification) of polyimide-based mesocarbon Microbeads (MCPI) prepared in step (3) of example 1;
FIG. 2 is an SEM image (magnification of 50000 times) of polyimide-based mesocarbon Microbeads (MCPI) prepared in step (3) of example 1;
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
(1) Under the protection of nitrogen, 100ml of NMP solvent is added into a 250ml three-neck flask, 2.1628g of diamine monomer PDA is added and stirred for 30min, after the diamine monomer is completely dissolved in the solvent, the reaction system is placed under the condition of ice-water bath, 6.4446g of dianhydride monomer BTDA is added, and the reaction is carried out for 8h under high-speed stirring, so as to obtain a yellowish-brown PAA solution.
(2) Putting 100ml of the PAA solution obtained in the step (1) into a 200ml high-pressure reaction kettle, dripping 1ml of isoquinolone, heating to 120 ℃, reacting for 1.5h, reacting for 8h at 170 ℃, and naturally cooling to normal temperature to obtain heterogeneous PI-NMP suspension; adding 100ml NMP into the suspension, carrying out ultrasonic treatment for 15min, filtering by using a sand core funnel, washing by using ethanol, and carrying out vacuum drying for 8h at 100 ℃ to obtain tawny polyimide Powder (PI).
(3) In the nitrogen atmosphere, the temperature is increased to 100 ℃ at the heating rate of 3 ℃/min for sintering for 0.5-1 h, 200 ℃ for sintering for 1h, 300 ℃ for sintering for 1h and 700 ℃ for sintering for 1.5h to obtain the polyimide-based mesocarbon Microbeads (MCPI), namely the organic electrode active substance based on the polyimide structure.
(4) Fully dispersing Graphene Oxide (GO) in deionized water, then soaking foam Nickel (NF) in the graphene suspension for 2h, taking out, placing in an oven at 60 ℃, and performing vacuum drying for 3h to obtain the N-GO precursor template. And (3) reacting the N-GO precursor template in 3mol/L hydrochloric acid solution at 65 ℃ for 4h to obtain the GOF template. And washing with deionized water for multiple times, then placing the GOF template in 40 wt.% hydriodic acid solution to react for 8 hours at 80 ℃, washing with the deionized water, and drying for 8 hours in vacuum at 100 ℃ to obtain the foam graphene NG template skeleton agent.
(5) Adding the template skeleton agent NG and the MCPI powder into ultrapure water, stirring for 1h at room temperature, carrying out suction filtration to form a film, carrying out vacuum drying for 12h at 75 ℃, and carrying out tabletting under the pressure of 5MPa to obtain the film-shaped electrode material. The organic electrode material based on the polyimide structure obtained in the embodiment is used as a negative electrode material of a lithium ion battery, mixed vinylidene chloride is coated on a copper foil, and the copper foil is rolled into a negative plate; the anode is made of a lithium metal sheet, the diaphragm is made of a PP/PET composite material, the electrolyte is an ester solution of LiPF6, and the lithium ion battery is assembled and has a specific capacity of 206 mAh/g.
Example 2
(1) Under the protection of nitrogen, 120ml of DMF solvent is added into a 250ml three-neck flask, 4.4822g of diamine monomer BIA is added and stirred for 30min, after the diamine monomer is completely dissolved in the solvent, the reaction system is placed under the condition of ice-water bath, 6.2002g of dianhydride monomer ODPA is added, and the reaction is carried out for 8h under high-speed stirring, so as to obtain the yellowish-brown PAA solution.
(2) Putting 80ml of PAA solution obtained in the step (1) into a 250ml high-pressure reaction kettle, dripping 1.5ml of isoquinolone, heating to 120 ℃ for reaction for 2h, reacting at 160 ℃ for 12h, and naturally cooling to normal temperature to obtain heterogeneous PI-DMF suspension; adding 120ml DMF into the suspension, carrying out ultrasonic treatment for 15min, filtering by using a sand core funnel, washing by using ethanol, and carrying out vacuum drying for 8h at 100 ℃ to obtain tawny polyimide Powder (PI).
(3) In the nitrogen atmosphere, the temperature is raised to 100 ℃ at the heating rate of 3 ℃/min and sintered for 0.5h, 200 ℃ for 0.5h, 300 ℃ for 1h and 750 ℃ for 2h to obtain the polyimide-based mesocarbon Microbeads (MCPI), namely the organic electrode active substance based on the polyimide structure.
(4) Fully dispersing Graphene Oxide (GO) in deionized water, then soaking foam Nickel (NF) in the graphene suspension for 2h, taking out, placing in an oven at 60 ℃, and performing vacuum drying for 3h to obtain the N-GO precursor template. And (3) reacting the N-GO precursor template in 3mol/L hydrochloric acid solution at 65 ℃ for 4h to obtain the GOF template. And washing with deionized water for multiple times, then placing the GOF template in 40 wt.% hydriodic acid solution to react for 8 hours at 80 ℃, washing with the deionized water, and drying for 8 hours in vacuum at 100 ℃ to obtain the foam graphene NG template skeleton agent.
(5) Adding the template skeleton agent NG and the MCPI powder into ultrapure water, stirring for 1h at room temperature, carrying out suction filtration to form a film, carrying out vacuum drying for 12h at 75 ℃, and carrying out tabletting under the pressure of 5MPa to obtain the film-shaped electrode material. The organic electrode material based on the polyimide structure obtained in the embodiment is used as a negative electrode material of a lithium ion battery, mixed vinylidene chloride is coated on a copper foil, and the copper foil is rolled into a negative plate; the positive electrode is made of a lithium metal sheet, the diaphragm is made of a PP/PET composite material, the electrolyte is an ester solution of LiPF6, and the lithium ion battery is assembled and has the specific capacity of 252 mAh/g.
Example 3
(1) Under the protection of nitrogen, adding 90ml of DMAc solvent into a 250ml three-neck flask, adding 5.2424g of diamine monomer PMR, stirring for 30min, placing a reaction system under an ice-water bath condition after the diamine monomer is completely dissolved in the solvent, adding 5.8844g of dianhydride monomer BPDA, and stirring at a high speed for reaction for 12h to obtain a yellowish-brown PAA solution.
(2) Putting 90ml of PAA solution obtained in the step (1) into a 250ml high-pressure reaction kettle, dripping 1ml of isoquinolone, heating to 120 ℃ for reaction for 2h, reacting at 160 ℃ for 12h, and naturally cooling to normal temperature to obtain heterogeneous PI-DMAc suspension; adding 120ml DMAc into the suspension, carrying out ultrasonic treatment for 20min, filtering by using a sand core funnel, washing by using ethanol, and carrying out vacuum drying for 8h at 100 ℃ to obtain tawny polyimide Powder (PI).
(3) In the nitrogen atmosphere, the temperature is raised to 100 ℃ at the heating rate of 3 ℃/min and sintered for 1h, sintered for 1h at 200 ℃, sintered for 1h at 300 ℃ and sintered for 2h at 750 ℃ to obtain the polyimide-based mesocarbon Microbeads (MCPI), namely the organic electrode active substance based on the polyimide structure.
(4) Fully dispersing Graphene Oxide (GO) in deionized water, then soaking foam Nickel (NF) in the graphene suspension for 2h, taking out, placing in an oven at 60 ℃, and performing vacuum drying for 3h to obtain the N-GO precursor template. And (3) reacting the N-GO precursor template in 3mol/L hydrochloric acid solution at 65 ℃ for 4h to obtain the GOF template. And washing with deionized water for multiple times, then placing the GOF template in 40 wt.% hydriodic acid solution to react for 8 hours at 80 ℃, washing with the deionized water, and drying for 8 hours in vacuum at 100 ℃ to obtain the foam graphene NG template skeleton agent.
(5) Adding the template skeleton agent NG and the MCPI powder into ultrapure water, stirring for 1h at room temperature, carrying out suction filtration to form a film, carrying out vacuum drying for 12h at 75 ℃, and carrying out tabletting under the pressure of 5MPa to obtain the film-shaped electrode material. The organic electrode material based on the polyimide structure obtained in the embodiment is used as a negative electrode material of a lithium ion battery, mixed vinylidene chloride is coated on a copper foil, and the copper foil is rolled into a negative plate; the positive electrode is made of a lithium metal sheet, the diaphragm is made of a PP/PET composite material, the electrolyte is an ester solution of LiPF6, and the lithium ion battery is assembled, and the specific capacity is 267 mAh/g.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (9)
1. A preparation method of an electrode material based on a polyimide mesocarbon microbead structure comprises the following steps:
adding diamine into a solvent under the protection of nitrogen and under the condition of ice-water bath until the diamine is completely dissolved; then adding dianhydride monomer, and stirring for 8-12h to obtain polyamic acid (PAA) solution;
step (2) placing the polyamic acid solution obtained in the step (1) into a hydrothermal reaction kettle, adding a cyclization reaction catalyst, performing high-pressure hydrothermal reaction, naturally cooling to normal temperature, diluting with an isometric solvent, performing ultrasonic treatment for 0.25-0.5h, filtering by using a sand core funnel, washing with ethanol, and performing vacuum drying for 8h to obtain polyimide Powder (PI);
and (3) carbonizing the polyimide: putting the polyimide powder into a vacuum tube type sintering furnace, sintering for 0.5-1 h at 100 ℃, sintering for 0.5-1 h at 200 ℃, sintering for 0.5-1 h at 300 ℃ and sintering for 1-2 h at 700-900 ℃ in a nitrogen or argon atmosphere to obtain polyimide-based mesocarbon Microbeads (MCPI);
step (4), preparation of a foam graphene template skeleton agent: fully dispersing Graphene Oxide (GO) in deionized water, then soaking foam Nickel (NF) in the graphene suspension, taking out, placing in a drying oven, and performing vacuum drying to obtain an N-GO precursor template; reacting the N-GO precursor template in a hydrochloric acid solution to remove nickel, thereby obtaining a GOF template; washing with deionized water for multiple times, then placing the GOF template in a hydriodic acid solution for reaction, washing with the deionized water, and drying in vacuum to obtain a foamed graphene template skeleton agent;
preparing an electrode material in the step (5): adding the template skeleton agent foam graphene and the MCPI powder into ultrapure water, performing ultrasonic dispersion, performing suction filtration to form a membrane, and performing vacuum drying to obtain the membrane electrode material.
2. The method of claim 1, wherein: the diamine monomer adopted in the step (1) has the following structure:
3. the method of claim 1, wherein: the dianhydride monomer adopted in the step (1) has the following structure:
4. the method of claim 1, wherein: the molar ratio of diamine to dianhydride monomer in the step (1) is 1: 0.98-1.02.
5. The method of claim 1, wherein: the solvent in the step (1) is dimethylformamide, dimethylacetamide or N-methylpyrrolidone.
6. The method of claim 1, wherein: the concentration of the polyamic acid (PAA) solution in the step (1) is 0.01-0.04 mol/100 ml; the reaction was carried out under ice-water bath conditions.
7. The method of claim 1, wherein: the cyclization reaction catalyst adopted in the step (2) is isoquinolinone with the mass fraction of 0.001 wt% of the whole reaction system, and the PAA solution is reacted for 1-2 hours under the condition of 100-130 ℃ and 8-12 hours under the condition of 160-180 ℃ in a hydrothermal reaction kettle.
8. The method of claim 1, wherein: the filter membrane adopted in the step (3) is made of PU material, and the aperture is 0.22 μm.
9. A film-like electrode material obtained by the production method according to any one of claims 1 to 8.
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