CN117457406A - Lithium ion hybrid supercapacitor based on phosphorus-carbon composite anode material and preparation method thereof - Google Patents
Lithium ion hybrid supercapacitor based on phosphorus-carbon composite anode material and preparation method thereof Download PDFInfo
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- CN117457406A CN117457406A CN202311528584.5A CN202311528584A CN117457406A CN 117457406 A CN117457406 A CN 117457406A CN 202311528584 A CN202311528584 A CN 202311528584A CN 117457406 A CN117457406 A CN 117457406A
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- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000002131 composite material Substances 0.000 title claims abstract description 119
- 239000010405 anode material Substances 0.000 title claims abstract description 76
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 29
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 83
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 35
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 34
- 239000002041 carbon nanotube Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 24
- 239000007970 homogeneous dispersion Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 15
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- 229910052751 metal Inorganic materials 0.000 claims description 13
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- 238000002156 mixing Methods 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 9
- 150000003384 small molecules Chemical class 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 229920001940 conductive polymer Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000006138 lithiation reaction Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 13
- 239000007773 negative electrode material Substances 0.000 abstract description 9
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 description 30
- 239000000843 powder Substances 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- 229920000767 polyaniline Polymers 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 13
- 229910003472 fullerene Inorganic materials 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 229910013870 LiPF 6 Inorganic materials 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 11
- 230000001351 cycling effect Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229920000128 polypyrrole Polymers 0.000 description 11
- 239000012300 argon atmosphere Substances 0.000 description 10
- 239000000498 cooling water Substances 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 9
- 229920001197 polyacetylene Polymers 0.000 description 9
- 229920000123 polythiophene Polymers 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 229920000388 Polyphosphate Polymers 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000001205 polyphosphate Substances 0.000 description 4
- 235000011176 polyphosphates Nutrition 0.000 description 4
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- 229920002125 Sokalan® Polymers 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
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- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a lithium ion hybrid supercapacitor based on a phosphorus-carbon composite negative electrode material and a preparation method thereof. The method comprises the following steps: step 1, stirring and dissolving a phosphorus-carbon composite anode material, a conductive agent, a binder and N-methyl pyrrolidone to obtain mixed slurry; step 2, coating the obtained mixed slurry on a current collector to obtain a negative plate, and pre-lithiating the negative plate; and step 3, assembling the pre-lithiated negative plate, the positive plate and the electrolyte to obtain the lithium ion hybrid supercapacitor. The lithium ion hybrid supercapacitor has high energy density, high power density and excellent long-cycle stability, when the power density is 1200W/kg, the energy density is higher than 175Wh/kg, when the power density is increased to 18kW/kg, the energy density can still be kept above 140Wh/kg, the lithium ion hybrid supercapacitor can be circularly charged and discharged for 2000 times under the current density of 1A/g, and the capacity retention rate is higher than 80%.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a lithium ion hybrid supercapacitor based on a phosphorus-carbon composite negative electrode material and a preparation method thereof.
Background
With the rapid development of world economy, the energy demand is increasing, the problems of shortage of fossil energy and environmental pollution are becoming serious, and the search for a cleaner and more efficient new energy is becoming a topic of common concern for global researchers. The lithium ion hybrid supercapacitor is taken as a novel energy storage device, combines the respective advantages of a lithium ion battery and a supercapacitor, has high energy density, high power density and long cycle life, and is considered as one of the most promising electrochemical energy storage devices. However, the performance of the lithium ion hybrid supercapacitor is limited by the performance of the anode material, and in recent years, the search for a suitable anode material has been a relatively popular problem.
Phosphorus can be combined with 3 lithium to form Li during lithiation reaction 3 P, and the theoretical specific capacity of the graphite cathode can reach 2596mAh/g, which is 7 times of the theoretical capacity (372 mAh/g) of the graphite cathode. Therefore, phosphorus is a cathode material of a lithium ion hybrid supercapacitor with great potential. However, since the conductivity of phosphorus is low and the volume expansion rate is more than 300% in the charge and discharge process, the structure is very unstable after nanocrystallization, and the long-cycle stability of the phosphorus anode material is poor. In order to solve the problems, at present, a ball milling method is often adopted to realize phosphorus nanocrystallization and phosphorus-carbon compounding to obtain a phosphorus-carbon composite anode material so as to improve the structural stability of the phosphorus-containing anode material, and the method can also increase the electronic conductivity of the phosphorus-containing anode material. In addition, the surface of the phosphorus-carbon composite anode material is coated with a layer of conductive polymer, so that direct contact between electrolyte and the phosphorus-carbon composite anode material in the charge and discharge process can be reduced, and further, the dissolution of lithium polyphosphate small molecules and the consumption of the electrolyte are reduced, and the long-cycle performance of the phosphorus-carbon composite anode material is improved.
The polymer coating of the existing phosphorus-carbon composite material is usually carried out by an in-situ polymerization process, for example, chinese patent application No. CN112018363A discloses a black phosphorus-based composite anode material, a preparation method thereof and application thereof in a metal secondary battery, wherein the black phosphorus-carbon modified composite material is obtained by ball milling treatment, and then the conductive polymer is coated on the surface of the modified material by liquid-phase in-situ polymerization. However, the method requires high temperature and high pressure, and the reaction conditions are severe, which is unfavorable for the mass preparation of the phosphorus-carbon composite material and can limit the commercial application of the phosphorus-carbon composite material. In addition, when the surface of the phosphorus-carbon negative electrode material is coated with the conductive polymer layer, the in-situ polymerization degree is also influenced by phosphorus-carbon interface functional groups and pore structures, and the problem that the polymerization uniformity is difficult often exists, so that the problems of low electronic conductivity, serious volume expansion in the charge-discharge process, aggravation of the dissolution behavior of lithium polyphosphate micromolecules and the like of the phosphorus-carbon composite negative electrode material are caused, and the high-rate performance and the long-cycle stability of the lithium ion hybrid supercapacitor are finally not facilitated.
Disclosure of Invention
In order to solve the problems that when the existing phosphorus-carbon composite anode material is used for the anode of a lithium ion hybrid supercapacitor, the rate capability and long cycle performance of the lithium ion hybrid supercapacitor are not excellent enough due to low conductivity, severe volume expansion, dissolution of lithium polyphosphate and the like, the invention provides the lithium ion hybrid supercapacitor based on the phosphorus-carbon composite anode material and a preparation method thereof. The specific technical scheme of the invention is as follows:
the invention provides a preparation method of a lithium ion hybrid supercapacitor based on a phosphorus-carbon composite anode material, which comprises the following steps of:
step 1, stirring and dissolving a phosphorus-carbon composite anode material, a conductive agent, a binder and N-methyl pyrrolidone to obtain mixed slurry;
step 2, coating the obtained mixed slurry on a current collector to obtain a negative plate, and pre-lithiating the negative plate;
and step 3, assembling the pre-lithiated negative plate, the positive plate and the electrolyte to obtain the lithium ion hybrid supercapacitor.
Specifically, in the step 1, the mass ratio of the phosphorus-carbon composite anode material to the conductive agent to the binder is 7-8:1:1-2, and the solid content of the mixed slurry is 40% -60%.
Specifically, the conductive agent in step 1 is at least one of conductive carbon black, carbon nanotubes or graphene.
Specifically, the binder in the step 1 is at least one selected from polyvinylidene fluoride or polytetrafluoroethylene.
Specifically, the current collector in the step 2 is at least one of copper foil, titanium foil, stainless steel foil, copper mesh, titanium mesh, stainless steel mesh or nickel mesh.
Specifically, the pre-lithiation method in step 2 is to directly contact the metal lithium foil with the negative electrode sheet for 0.5-2 hours in the presence of an electrolyte.
Specifically, the positive plate in the step 3 is one of activated carbon, template carbon, graphene, carbon nanotubes or carbon aerogel positive plates.
Specifically, the electrolyte in step 3 is 1M LiPF 6 Dissolved in an EC/DEC (volume ratio 1:1) solution.
Specifically, the preparation method of the phosphorus-carbon composite anode material in the step 1 comprises the following steps:
s1, dispersing and dissolving a polymer and a conductive agent in a solvent to obtain a high polymer solution;
s2, mixing a phosphorus source, graphite, a carbon nano tube and a small molecule modifier, and then ball milling to obtain an interface modified phosphorus-carbon composite material;
s3, dispersing the interface modified phosphorus-carbon composite material in a high polymer solution to obtain a homogeneous dispersion liquid;
s4, performing rotary evaporation on the homogeneous dispersion liquid to obtain the phosphorus-carbon composite anode material coated with the conductive polymer film.
More specifically, the polymer in the step S1 is one of polyacrylic acid, polyimide, polyaniline, polypyrrole, polythiophene, or polyacetylene;
more specifically, in step S1, the conductive agent is one of graphene, carbon black, carbon nanotubes or fullerenes; the addition of the conductive agent can increase the conductivity of the polymer.
More specifically, the solvent in step S1 is water or an organic solvent, and the organic solvent is one of N-methylpyrrolidone, ethanol, acetone, N-dimethylformamide or acetonitrile.
More specifically, in the step S1, the mass fraction of the polymer solution is 1-20%, and the mass ratio of the polymer to the conductive agent in the polymer solution is 2:1-16:1.
More specifically, in step S2, the phosphorus source is black phosphorus or red phosphorus;
more specifically, the small molecule modifier in step S2 is one of urea, melamine, polydimethyldiallylammonium chloride or p-phenylenediamine.
More specifically, the small molecule modifier in the step S2 is one of urea, melamine, polydimethyldiallylammonium chloride or p-phenylenediamine; the small molecule modifier is used for bonding the polymer to the surface of the phosphorus-carbon through a chemical bond, so that the purpose of uniformly coating the phosphorus-carbon negative electrode material is achieved, a coating film formed by the polymer is uniform, controllable and uniformly coated, the conductivity is good, and excellent multiplying power performance and long-cycle stability are shown.
More specifically, the mass ratio of the phosphorus source, graphite, carbon nanotube and small molecule modifier in the interface modified phosphorus-carbon composite material in step S2 is 50-85%, 10-40%, 1-20% and 1-3%, respectively.
More specifically, the dispersion concentration of the phosphorus-carbon composite material in the step S3 in the polymer solution is 0.1-100g/L.
More specifically, the heating temperature of the rotary evaporation in the step S4 is 50-300 ℃, the rotation speed is 10-280rpm, and the pressure is 50-80kPa; drying is performed by rotary evaporation, so that the polymer has enough time to arrange molecular chains and self-assemble.
In a second aspect of the invention, a lithium ion hybrid supercapacitor prepared by the method is provided.
The beneficial effects that this application technical scheme brought are as follows:
(1) The phosphorus-carbon composite material is prepared by compounding phosphorus and carbon, and a uniform and compact polymer layer is coated on the surface of the phosphorus-carbon composite material, so that a phosphorus-carbon composite negative electrode material with excellent multiplying power performance and long cycle stability is obtained, the phosphorus-carbon composite negative electrode material is used as a negative electrode of a lithium ion hybrid supercapacitor, and the obtained lithium ion hybrid supercapacitor has high energy density, high power density and excellent long cycle stability, particularly when the power density is 1200W/kg, the energy density is higher than 175Wh/kg, and when the power density is increased to 18kW/kg, the energy density can still be kept above 140Wh/kg, the cycle charge and discharge are carried out for 2000 times under the current density of 1A/g, and the capacity retention rate is higher than 80%;
(2) The preparation method is simple and easy to operate, has lower requirements on equipment, is suitable for mass preparation, is favorable for commercial application of the prepared lithium ion hybrid supercapacitor, and has better application prospect.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Example 1
1. Preparing a phosphorus-carbon composite anode material:
(1) Taking 4.5g of polyaniline powder (PANI, conductivity is 10S/cm@200MPa) and 0.5g of carbon nano tube to be dispersed in 95g N-methylpyrrolidone (NMP), and magnetically stirring for 12 hours to obtain an NMP blue solution of polyaniline/carbon nano tube with mass fraction of 5%;
(2) Mixing black phosphorus powder, graphite powder, carbon nano tubes and urea, and performing ball milling for 10 hours at a rotating speed of 600rpm under an argon atmosphere to obtain a phosphorus-carbon composite material, wherein the phosphorus-carbon composite material contains 74% of black phosphorus, 20% of graphite, 5% of carbon nano tubes and 1% of urea in percentage by mass;
(3) Adding 5g of the phosphorus-carbon composite material into an NMP solution of polyaniline/carbon nano tube, performing ultrasonic treatment for 5min, and performing magnetic stirring for 6h to uniformly disperse to obtain a homogeneous dispersion liquid with the phosphorus-carbon composite material dispersion concentration of 54.1 g/L;
(4) And (3) filling the homogeneous dispersion liquid into a 300mL rotary bottle, regulating the temperature of a heating oil bath to 230 ℃, regulating the rotation speed to 50rpm, starting a vacuum pump, regulating the pressure in the rotary bottle to 75kPa, introducing cooling water, and obtaining 5.5g of compact polyaniline-coated phosphorus-carbon anode material after 30 min.
2. Preparation of a lithium ion hybrid supercapacitor:
step 1, stirring and dissolving 8g of phosphorus-carbon composite anode material, 1g of conductive carbon black, 1g of polyvinylidene fluoride and a certain amount of N-methyl pyrrolidone to obtain mixed slurry (the solid content is 50%);
step 2, coating the obtained mixed slurry on a copper foil to obtain a negative plate, directly contacting the metal lithium foil with the negative plate for 1h in the presence of electrolyte, and pre-lithiating the negative plate;
step 3, pre-lithiated negative electrode sheet, active carbon positive electrode sheet and 1M LiPF 6 And (3) assembling an EC/DEC (volume ratio of 1:1) electrolyte to obtain the lithium ion hybrid supercapacitor.
When the power density of the device based on the active mass of the anode and the cathode is 1200W/kg, the energy density is 185Wh/kg; when the power density is increased to 18kW/kg, the energy density can still be kept at 147Wh/kg; the charge and discharge were cycled 2000 times at a current density of 1A/g, with a capacity retention of 91%. The lithium ion hybrid supercapacitor assembled based on the phosphorus-carbon composite anode material has the advantages of high energy density, high power density and excellent cycling stability.
Example 2
1. Preparing a phosphorus-carbon composite anode material:
(1) 4.7g of polypyrrole powder and 0.3g of carbon black are dispersed in 45g N-methyl pyrrolidone (NMP) and magnetically stirred for 12 hours to obtain an NMP blue solution of polypyrrole/carbon black with the mass fraction of 10%;
(2) Mixing black phosphorus powder, graphite powder, carbon nano tubes and p-phenylenediamine, and then ball-milling for 10 hours at a rotating speed of 600rpm under an argon atmosphere to obtain a phosphorus-carbon composite material, wherein the phosphorus-carbon composite material contains 65% of black phosphorus, 20% of graphite, 13% of carbon nano tubes and 2% of p-phenylenediamine in percentage by mass;
(3) Adding 3g of phosphorus-carbon composite material into NMP solution of polypyrrole/carbon black, carrying out ultrasonic treatment for 5min, and magnetically stirring for 6h to obtain homogeneous dispersion liquid with the phosphorus-carbon composite material dispersion concentration of 68.5 g/L;
(4) And (3) filling the homogeneous dispersion liquid into a 300mL rotary bottle, regulating the temperature of a heating oil bath to 210 ℃, regulating the rotation speed to 60rpm, starting a vacuum pump, regulating the pressure in the rotary bottle to 65kPa, introducing cooling water, and obtaining the compact polypyrrole coated phosphorus-carbon negative electrode material after 30 minutes.
2. Preparation of a lithium ion hybrid supercapacitor:
step 1, stirring and dissolving 8g of the phosphorus-carbon composite anode material, 1g of conductive carbon black, 1g of polytetrafluoroethylene and a certain amount of N-methylpyrrolidone to obtain mixed slurry (the solid content is 40%);
step 2, coating the obtained mixed slurry on a copper foil to obtain a negative plate, directly contacting the metal lithium foil with the negative plate for 1h in the presence of electrolyte, and pre-lithiating the negative plate;
step 3, pre-lithiated negative electrode sheet, active carbon positive electrode sheet and 1M LiPF 6 And (3) assembling an EC/DEC (volume ratio of 1:1) electrolyte to obtain the lithium ion hybrid supercapacitor.
When the power density of the device based on the active mass of the anode and the cathode is 1200W/kg, the energy density is 179Wh/kg; when the power density is increased to 18kW/kg, the energy density can still be kept at 142Wh/kg; the capacity retention rate was 93% by cycling charge and discharge 2000 times at a current density of 1A/g. The lithium ion hybrid supercapacitor assembled based on the phosphorus-carbon composite anode material has the advantages of high energy density, high power density and excellent cycling stability.
Example 3
1. Preparing a phosphorus-carbon composite anode material:
(1) Taking 4.3g of polyaniline powder (PANI, conductivity is 10S/cm@200MPa) and 0.7g of fullerene to be dispersed in 35g of N, N-dimethylformamide, and magnetically stirring for 12 hours to obtain a DMF solution of polyaniline/fullerene with mass fraction of 12.5%;
(2) Mixing black phosphorus powder, graphite powder, carbon nano tubes and polydimethyl diallyl ammonium chloride, and performing ball milling for 10 hours at a rotating speed of 600rpm under an argon atmosphere to obtain a phosphorus-carbon composite material, wherein the phosphorus-carbon composite material contains 80% of black phosphorus, 14% of graphite, 5% of carbon nano tubes and 1% of polydimethyl diallyl ammonium chloride by mass percent;
(3) Adding 1g of the phosphorus-carbon composite material into a DMF solution of polyaniline/fullerene, carrying out ultrasonic treatment for 5min, and magnetically stirring for 6h to obtain a homogeneous dispersion liquid with the phosphorus-carbon composite material dispersion concentration of 27.1 g/L;
(4) And (3) filling the homogeneous dispersion liquid into a 300mL rotary bottle, regulating the temperature of a heating oil bath to 195 ℃, regulating the rotation speed to 80rpm, starting a vacuum pump, regulating the pressure in the rotary bottle to 60kPa, introducing cooling water, and obtaining the compact polyaniline-coated phosphorus-carbon anode material after 30 minutes.
The first coulombic efficiency of the battery constructed using the phosphorus-carbon composite anode material prepared in example 3 was about 84.57%, and the capacity retention of the battery after 100 cycles was 91.52%.
2. Preparation of a lithium ion hybrid supercapacitor:
step 1, stirring and dissolving 8g of the phosphorus-carbon composite anode material, 1g of carbon nano tube, 1g of polyvinylidene fluoride and a certain amount of N-methyl pyrrolidone to obtain mixed slurry (the solid content is 60%);
step 2, coating the obtained mixed slurry on a copper foil to obtain a negative plate, directly contacting the metal lithium foil with the negative plate for 2 hours in the presence of electrolyte, and pre-lithiating the negative plate;
step 3, pre-lithiated negative electrode sheet, active carbon positive electrode sheet and 1M LiPF 6 And (3) assembling an EC/DEC (volume ratio of 1:1) electrolyte to obtain the lithium ion hybrid supercapacitor.
When the power density of the device based on the active mass of the anode and the cathode is 1200W/kg, the energy density is 187Wh/kg; when the power density is increased to 18kW/kg, the energy density can still be kept at 148Wh/kg; the charge and discharge were cycled 2000 times at a current density of 1A/g with a capacity retention of 90%. The lithium ion hybrid supercapacitor assembled based on the phosphorus-carbon composite anode material has the advantages of high energy density, high power density and excellent cycling stability.
Example 4
1. Preparing a phosphorus-carbon composite anode material:
(1) Dispersing 13g of polythiophene and 2g of graphene in 85g of acetone, and magnetically stirring for 12 hours to obtain an acetone solution of the polythiophene/graphene with the mass fraction of 15%;
(2) Mixing black phosphorus powder, graphite powder, carbon nano tubes and melamine, and performing ball milling for 10 hours at a rotating speed of 600rpm under an argon atmosphere to obtain a phosphorus-carbon composite material, wherein the phosphorus-carbon composite material contains 55% of black phosphorus, 33% of graphite, 10% of carbon nano tubes and 2% of melamine in percentage by mass;
(3) Adding 6g of the phosphorus-carbon composite material into an acetone solution of polythiophene/graphene, carrying out ultrasonic treatment for 5min, and magnetically stirring for 6h to obtain a homogeneous dispersion liquid with the phosphorus-carbon composite material dispersion concentration of 55.7 g/L;
(4) And (3) filling the homogeneous dispersion liquid into a 300mL rotary bottle, regulating the temperature of a heating oil bath to 205 ℃, regulating the rotation speed to 100rpm, starting a vacuum pump, regulating the pressure in the rotary bottle to 55kPa, introducing cooling water, and obtaining the polythiophene-coated phosphorus-carbon anode material after 30 min.
2. Preparation of a lithium ion hybrid supercapacitor:
step 1, stirring and dissolving 7.5g of the phosphorus-carbon composite anode material, 1g of conductive carbon black, 1.5g of polyvinylidene fluoride and a certain amount of N-methyl pyrrolidone to obtain mixed slurry (the solid content is 50%);
step 2, coating the obtained mixed slurry on a copper foil to obtain a negative plate, directly contacting a metal lithium foil with the negative plate for 0.5h in the presence of electrolyte, and pre-lithiating the negative plate;
step 3, pre-lithiated negative electrode sheet, active carbon positive electrode sheet and 1M LiPF 6 And (3) assembling an EC/DEC (volume ratio of 1:1) electrolyte to obtain the lithium ion hybrid supercapacitor.
When the power density of the device based on the active mass of the anode and the cathode is 1200W/kg, the energy density is 196Wh/kg; when the power density is increased to 18kW/kg, the energy density can still be kept at 157Wh/kg; the charge and discharge were cycled 2000 times at a current density of 1A/g with a capacity retention of 82%. The lithium ion hybrid supercapacitor assembled based on the phosphorus-carbon composite anode material has the advantages of high energy density, high power density and excellent cycling stability.
Example 5
1. Preparing a phosphorus-carbon composite anode material:
(1) Dispersing 18.5g of polyacetylene powder and 1.5g of fullerene in 95g of acetonitrile, and magnetically stirring for 12 hours to obtain an acetonitrile solution of polyacetylene/fullerene with a mass fraction of 17.4%;
(2) Mixing red phosphorus powder, graphite powder, carbon nano tubes and p-phenylenediamine, and then ball-milling for 10 hours at a rotating speed of 600rpm under an argon atmosphere to obtain a phosphorus-carbon composite material, wherein the phosphorus-carbon composite material contains 60% of red phosphorus, 23.5% of graphite, 15% of carbon nano tubes and 1.5% of p-phenylenediamine by mass percent;
(3) Adding 0.5g of the phosphorus-carbon composite material into an acetonitrile solution of polyacetylene/fullerene, carrying out ultrasonic treatment for 5min, and magnetically stirring for 6h to obtain a homogeneous dispersion liquid with the phosphorus-carbon composite material dispersion concentration of 4.1 g/L;
(4) And (3) filling the homogeneous dispersion liquid into a 300mL rotary bottle, regulating the temperature of a heating oil bath to 85 ℃, regulating the rotation speed to 30rpm, starting a vacuum pump, regulating the pressure in the rotary bottle to 60kPa, introducing cooling water, and obtaining the polyacetylene coated phosphorus-carbon anode material after 30 minutes.
2. Preparation of a lithium ion hybrid supercapacitor:
step 1, stirring and dissolving 7.5g of the phosphorus-carbon composite anode material, 1g of conductive carbon black, 1.5g of polyvinylidene fluoride and a certain amount of N-methyl pyrrolidone to obtain mixed slurry (the solid content is 50%);
step 2, coating the obtained mixed slurry on a copper foil to obtain a negative plate, directly contacting the metal lithium foil with the negative plate for 1h in the presence of electrolyte, and pre-lithiating the negative plate;
step 3, pre-lithiated negative electrode sheet, active carbon positive electrode sheet and active carbon1M LiPF 6 And (3) assembling an EC/DEC (volume ratio of 1:1) electrolyte to obtain the lithium ion hybrid supercapacitor.
When the power density of the device based on the active mass of the anode and the cathode is 1200W/kg, the energy density of the device is 188Wh/kg; when the power density is increased to 18kW/kg, the energy density can still be kept at 150Wh/kg; the charge and discharge were cycled 2000 times at a current density of 1A/g with a capacity retention of 89%. The lithium ion hybrid supercapacitor assembled based on the phosphorus-carbon composite anode material has the advantages of high energy density, high power density and excellent cycling stability.
Example 6
1. Preparing a phosphorus-carbon composite anode material:
(1) Dispersing 0.8g of polyacrylic acid powder and 0.2g of conductive carbon black in 95g of acetone, and magnetically stirring for 12 hours to obtain an acetone solution of polyacrylic acid/carbon black with the mass fraction of 1.04%;
(2) Mixing black phosphorus powder, graphite powder, carbon nano tubes and urea, and performing ball milling for 10 hours at a rotating speed of 600rpm under an argon atmosphere to obtain a phosphorus-carbon composite material, wherein the phosphorus-carbon composite material contains 60% of black phosphorus, 20% of graphite, 18% of carbon nano tubes and 2% of urea in percentage by mass;
(3) Adding 1g of phosphorus-carbon composite material into an acetone solution of polypyrrole/carbon black, carrying out ultrasonic treatment for 5min, and magnetically stirring for 6h to obtain a uniform dispersion liquid with the phosphorus-carbon composite material dispersion concentration of 8.3 g/L;
(4) And (3) filling the homogeneous dispersion liquid into a 300mL rotary bottle, regulating the temperature of a heating oil bath to 150 ℃, regulating the rotation speed to 130rpm, starting a vacuum pump, regulating the pressure in the rotary bottle to 65kPa, introducing cooling water, and obtaining the polypyrrole coated phosphorus-carbon negative electrode material after 30 minutes.
2. Preparation of a lithium ion hybrid supercapacitor:
step 1, stirring and dissolving 7.5g of the phosphorus-carbon composite anode material, 1g of conductive carbon black, 1.5g of polyvinylidene fluoride and a certain amount of N-methyl pyrrolidone to obtain mixed slurry (the solid content is 50%);
step 2, coating the obtained mixed slurry on a copper foil to obtain a negative plate, directly contacting the metal lithium foil with the negative plate for 1h in the presence of electrolyte, and pre-lithiating the negative plate;
step 3, pre-lithiated negative electrode sheet, active carbon positive electrode sheet and 1M LiPF 6 And (3) assembling an EC/DEC (volume ratio of 1:1) electrolyte to obtain the lithium ion hybrid supercapacitor.
When the power density of the device based on the active mass of the anode and the cathode is 1200W/kg, the energy density is 192Wh/kg; when the power density is increased to 18kW/kg, the energy density can still be kept at 155Wh/kg; the charge and discharge were cycled 2000 times at a current density of 1A/g, with a capacity retention of 84%. The lithium ion hybrid supercapacitor assembled based on the phosphorus-carbon composite anode material has the advantages of high energy density, high power density and excellent cycling stability.
Example 7
1. Preparing a phosphorus-carbon composite anode material:
(1) Dispersing 2.8g of polyimide powder and 0.2g of fullerene in 97g N-methylpyrrolidone, and magnetically stirring for 12 hours to obtain an NMP blue solution of polyimide/fullerene with the mass fraction of 3%;
(2) Mixing black phosphorus powder, graphite powder, carbon nano tubes and p-phenylenediamine, and then ball-milling for 10 hours at a rotating speed of 600rpm under an argon atmosphere to obtain a phosphorus-carbon composite material, wherein the phosphorus-carbon composite material contains 70% of black phosphorus, 24% of graphite, 5% of carbon nano tubes and 1% of p-phenylenediamine in percentage by mass;
(3) Adding 8g of phosphorus-carbon composite material into an NMP solution of polythiophene/fullerene, carrying out ultrasonic treatment for 5min, and magnetically stirring for 6h to obtain a homogeneous dispersion liquid with the phosphorus-carbon composite material dispersion concentration of 84.8 g/L;
(4) And (3) filling the homogeneous dispersion liquid into a 300mL rotary bottle, regulating the temperature of a heating oil bath to 200 ℃, regulating the rotation speed to 60rpm, starting a vacuum pump, regulating the pressure in the rotary bottle to 80kPa, introducing cooling water, and obtaining 5.5g of the compact polythiophene-coated phosphorus-carbon anode material after 30 min.
2. Preparation of a lithium ion hybrid supercapacitor:
step 1, stirring and dissolving 7g of the phosphorus-carbon composite anode material, 1g of conductive carbon black, 2g of polyvinylidene fluoride and a certain amount of N-methyl pyrrolidone to obtain mixed slurry (the solid content is 50%);
step 2, coating the obtained mixed slurry on a copper foil to obtain a negative plate, directly contacting the metal lithium foil with the negative plate for 1h in the presence of electrolyte, and pre-lithiating the negative plate;
step 3, pre-lithiated negative electrode sheet, active carbon positive electrode sheet and 1M LiPF 6 And (3) assembling an EC/DEC (volume ratio of 1:1) electrolyte to obtain the lithium ion hybrid supercapacitor.
When the power density of the device based on the active mass of the anode and the cathode is 1200W/kg, the energy density of the device is 183Wh/kg; when the power density is increased to 18kW/kg, the energy density can still be kept at 146Wh/kg; the charge and discharge were cycled 2000 times at a current density of 1A/g, with a capacity retention of 91%. The lithium ion hybrid supercapacitor assembled based on the phosphorus-carbon composite anode material has the advantages of high energy density, high power density and excellent cycling stability.
Example 8
1. Preparing a phosphorus-carbon composite anode material:
(1) Dispersing 2g of polyacetylene powder and 1g of graphene in 45g of N, N-dimethylformamide, and magnetically stirring for 12 hours to obtain a DMF (dimethyl formamide) solution of polyacetylene/graphene with the mass fraction of 6.25%;
(2) Mixing red phosphorus powder, graphite powder, carbon nano tubes and polydimethyl diallyl ammonium chloride, and performing ball milling for 10 hours at a rotating speed of 600rpm under an argon atmosphere to obtain a phosphorus-carbon composite material, wherein the phosphorus-carbon composite material contains 75% of black phosphorus, 15% of graphite, 8.5% of carbon nano tubes and 1.5% of polydimethyl diallyl ammonium chloride by mass percent;
(3) Adding 4.5g of the phosphorus-carbon composite material into a DMF solution of polyacetylene/graphene, carrying out ultrasonic treatment for 5min, and magnetically stirring for 6h to obtain a homogeneous dispersion liquid with the phosphorus-carbon composite material dispersion concentration of 94.5 g/L;
(4) And (3) filling the homogeneous dispersion liquid into a 300mL rotary bottle, regulating the temperature of a heating oil bath to 205 ℃, regulating the rotation speed to 200rpm, starting a vacuum pump, regulating the pressure in the rotary bottle to 75kPa, introducing cooling water, and obtaining 5.5g of the compact polyacetylene coated phosphorus-carbon anode material after 30 min.
2. Preparation of a lithium ion hybrid supercapacitor:
step 1, stirring and dissolving 7g of the phosphorus-carbon composite anode material, 1g of conductive carbon black, 2g of polyvinylidene fluoride and a certain amount of N-methyl pyrrolidone to obtain mixed slurry (the solid content is 50%);
step 2, coating the obtained mixed slurry on a copper foil to obtain a negative plate, directly contacting the metal lithium foil with the negative plate for 1h in the presence of electrolyte, and pre-lithiating the negative plate;
step 3, pre-lithiated negative electrode sheet, active carbon positive electrode sheet and 1M LiPF 6 And (3) assembling an EC/DEC (volume ratio of 1:1) electrolyte to obtain the lithium ion hybrid supercapacitor.
When the power density of the device based on the active mass of the anode and the cathode is 1200W/kg, the energy density is 178Wh/kg; when the power density is increased to 18kW/kg, the energy density can still be kept at 140Wh/kg; the charge and discharge were cycled 2000 times at a current density of 1A/g with a capacity retention of 94%. The lithium ion hybrid supercapacitor assembled based on the phosphorus-carbon composite anode material has the advantages of high energy density, high power density and excellent cycling stability.
Example 9
1. Preparing a phosphorus-carbon composite anode material:
(1) 17g of polypyrrole powder and 3g of fullerene are dispersed in 180g N-methyl pyrrolidone (NMP) and magnetically stirred for 12 hours to obtain NMP blue solution of polypyrrole/fullerene with the mass fraction of 10%;
(2) Mixing black phosphorus powder, graphite powder, carbon nano tubes and urea, and performing ball milling for 10 hours at a rotating speed of 600rpm under an argon atmosphere to obtain a phosphorus-carbon composite material, wherein the phosphorus-carbon composite material contains 84% of black phosphorus, 10% of graphite, 5% of carbon nano tubes and 1% of urea in percentage by mass;
(3) Adding 13g of phosphorus-carbon composite material into NMP solution of polypyrrole/fullerene, carrying out ultrasonic treatment for 5min, and magnetically stirring for 6h to obtain homogeneous dispersion liquid with the phosphorus-carbon composite material dispersion concentration of 74.2 g/L;
(4) And (3) filling the homogeneous dispersion liquid into a 300mL rotary bottle, regulating the temperature of a heating oil bath to 230 ℃, regulating the rotation speed to 50rpm, starting a vacuum pump, regulating the pressure in the rotary bottle to 75kPa, introducing cooling water, and obtaining 5.5g of the phosphorus-carbon anode material coated with the compact polypyrrole after 30 min.
2. Preparation of a lithium ion hybrid supercapacitor:
step 1, stirring and dissolving 7g of the phosphorus-carbon composite anode material, 1g of conductive carbon black, 2g of polyvinylidene fluoride and a certain amount of N-methyl pyrrolidone to obtain mixed slurry (the solid content is 50%);
step 2, coating the obtained mixed slurry on a copper foil to obtain a negative plate, directly contacting the metal lithium foil with the negative plate for 1h in the presence of electrolyte, and pre-lithiating the negative plate;
step 3, pre-lithiated negative electrode sheet, active carbon positive electrode sheet and 1M LiPF 6 And (3) assembling an EC/DEC (volume ratio of 1:1) electrolyte to obtain the lithium ion hybrid supercapacitor.
When the power density of the device based on the active mass of the anode and the cathode is 1200W/kg, the energy density is 190Wh/kg; when the power density is increased to 18kW/kg, the energy density can still be kept at 153Wh/kg; the charge and discharge were cycled 2000 times at a current density of 1A/g with a capacity retention of 87%. The lithium ion hybrid supercapacitor assembled based on the phosphorus-carbon composite anode material has the advantages of high energy density, high power density and excellent cycling stability.
Comparative example 1
1. Preparing a phosphorus-carbon composite anode material:
(1) Taking 4.5g of polyaniline powder (PANI, conductivity is 10S/cm@200MPa) and 0.5g of carbon nano tube to be dispersed in 95g N-methylpyrrolidone (NMP), and magnetically stirring for 12 hours to obtain an NMP blue solution of polyaniline/carbon nano tube with mass fraction of 5%;
(2) Mixing black phosphorus powder, graphite powder and carbon nano tubes, and performing ball milling for 10 hours at the rotating speed of 600rpm under the argon atmosphere to obtain a phosphorus-carbon composite material, wherein the phosphorus-carbon composite material contains 75% of black phosphorus, 20% of graphite and 5% of carbon nano tubes in percentage by mass;
(3) Adding 5g of the phosphorus-carbon composite material into an NMP solution of polyaniline/carbon nano tube, performing ultrasonic treatment for 5min, and performing magnetic stirring for 6h to uniformly disperse to obtain a homogeneous dispersion liquid with the phosphorus-carbon composite material dispersion concentration of 54.1 g/L;
(4) And (3) filling the homogeneous dispersion liquid into a 300mL rotary bottle, regulating the temperature of a heating oil bath to 230 ℃, regulating the rotation speed to 50rpm, starting a vacuum pump, regulating the pressure in the rotary bottle to 75kPa, introducing cooling water, and obtaining 5.5g of compact polyaniline-coated phosphorus-carbon anode material after 30 min.
2. Preparation of a lithium ion hybrid supercapacitor:
step 1, stirring and dissolving 8g of the phosphorus-carbon composite anode material, 1g of conductive carbon black, 1g of polyvinylidene fluoride and a certain amount of N-methyl pyrrolidone to obtain mixed slurry (the solid content is 50%);
step 2, coating the obtained mixed slurry on a copper foil to obtain a negative plate, directly contacting the metal lithium foil with the negative plate for 1h in the presence of electrolyte, and pre-lithiating the negative plate;
step 3, pre-lithiated negative electrode sheet, active carbon positive electrode sheet and 1M LiPF 6 And (3) assembling an EC/DEC (volume ratio of 1:1) electrolyte to obtain the lithium ion hybrid supercapacitor.
When the power density of the device based on the active mass of the anode and the cathode is 1200W/kg, the energy density is 168Wh/kg; when the power density is increased to 18kW/kg, the energy density can only be kept at 112Wh/kg; the capacity retention rate is only 65% after 2000 times of cyclic charge and discharge under the current density of 1A/g. The lithium ion hybrid supercapacitor assembled based on the phosphorus-carbon composite anode material has low energy density (particularly under high power density) and poor cycling stability.
The reason is that the phosphorus-carbon composite anode material prepared in the comparative example 1 is difficult to realize uniform coating of the polymer layer on the surface of the phosphorus-carbon anode material due to the lack of the strong chemical bonding effect of the small molecular modifier, and the phosphorus-carbon composite anode material has low electronic conductivity, serious charge-discharge volume expansion and aggravated lithium polyphosphate dissolution behavior, so that the lithium ion hybrid supercapacitor prepared based on the anode material has low energy density (particularly under high power density) and poor long-cycle stability.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the lithium ion hybrid supercapacitor based on the phosphorus-carbon composite anode material is characterized by comprising the following steps of:
step 1, stirring and dissolving a phosphorus-carbon composite anode material, a conductive agent, a binder and N-methyl pyrrolidone to obtain mixed slurry;
step 2, coating the obtained mixed slurry on a current collector to obtain a negative plate, and pre-lithiating the negative plate;
and step 3, assembling the pre-lithiated negative plate, the positive plate and the electrolyte to obtain the lithium ion hybrid supercapacitor.
2. The preparation method of the lithium ion hybrid supercapacitor based on the phosphorus-carbon composite anode material, which is disclosed in claim 1, is characterized in that the mass ratio of the phosphorus-carbon composite anode material to the conductive agent to the binder in step 1 is 7-8:1:1-2, and the solid content of the mixed slurry is 40% -60%.
3. The method for preparing a lithium ion hybrid supercapacitor based on a phosphorus-carbon composite anode material according to claim 1, wherein the conductive agent in the step 1 is at least one of conductive carbon black, carbon nanotubes or graphene.
4. The method for preparing a lithium ion hybrid supercapacitor based on a phosphorus-carbon composite anode material according to claim 1, wherein the binder in the step 1 is at least one selected from polyvinylidene fluoride and polytetrafluoroethylene.
5. The method for preparing a lithium ion hybrid supercapacitor based on a phosphorus-carbon composite anode material according to claim 1, wherein the pre-lithiation method in the step 2 is to directly contact a metal lithium foil with an anode sheet for 0.5-2 h in the presence of an electrolyte.
6. The method for preparing a lithium ion hybrid supercapacitor based on a phosphorus-carbon composite anode material according to claim 1, wherein the method for preparing the phosphorus-carbon composite anode material in step 1 comprises the following steps:
s1, dispersing and dissolving a polymer and a conductive agent in a solvent to obtain a high polymer solution;
s2, mixing a phosphorus source, graphite, a carbon nano tube and a small molecule modifier, and then ball milling to obtain an interface modified phosphorus-carbon composite material;
s3, dispersing the interface modified phosphorus-carbon composite material in a high polymer solution to obtain a homogeneous dispersion liquid;
s4, performing rotary evaporation on the homogeneous dispersion liquid to obtain the phosphorus-carbon composite anode material coated with the conductive polymer film.
7. The method for preparing a lithium ion hybrid supercapacitor based on a phosphorus-carbon composite anode material according to claim 6, wherein the small molecule modifier in the step S2 is one of urea, melamine, polydimethyl diallyl ammonium chloride or p-phenylenediamine.
8. The method for preparing a lithium ion hybrid supercapacitor based on a phosphorus-carbon composite anode material according to claim 6, wherein the mass ratio of the polymer to the conductive agent in the high molecular solution in the step S1 is 2:1-16:1.
9. The method for preparing a lithium ion hybrid supercapacitor based on a phosphorus-carbon composite anode material according to claim 6, wherein the mass ratio of the small molecule modifier in the phosphorus-carbon composite material modified by the interface in the step S2 is 1-3%.
10. A lithium ion hybrid supercapacitor made by the method of any one of claims 1 to 9.
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