CN111029158B - Lithium ion supercapacitor lithium pre-embedding method - Google Patents
Lithium ion supercapacitor lithium pre-embedding method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 59
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 51
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
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- 230000008569 process Effects 0.000 claims abstract description 38
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- 238000012360 testing method Methods 0.000 claims description 18
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
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- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- -1 LA series Polymers 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910017251 AsO4 Inorganic materials 0.000 claims description 3
- 229910009740 Li2GeO3 Inorganic materials 0.000 claims description 3
- 229910007522 Li2SeO4 Inorganic materials 0.000 claims description 3
- 229910007562 Li2SiO3 Inorganic materials 0.000 claims description 3
- 229910007367 Li2TeO3 Inorganic materials 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 3
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- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 3
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- NILQLFBWTXNUOE-UHFFFAOYSA-N 1-aminocyclopentanecarboxylic acid Chemical compound OC(=O)C1(N)CCCC1 NILQLFBWTXNUOE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
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- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
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- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a lithium pre-embedding method of a lithium ion super capacitor, which comprises the following steps: preparing a mixed glue solution of a binder and a solvent; adding a high molecular polymer monomer into the mixed glue solution, and uniformly dispersing by adopting a stirring process to obtain a mixed solution of the mixed glue solution and the high molecular polymer monomer; adding inorganic lithium salt into the obtained mixed solution, and preparing a mixed glue solution, a high-molecular polymer monomer and a uniform dispersion solution of the inorganic lithium salt by adopting a stirring process; adding a conductive agent and positive electrode material active carbon into the obtained dispersion liquid, and uniformly dispersing by adopting a stirring process to obtain slurry; and coating the obtained slurry on a current collector to obtain the positive electrode plate. According to the lithium ion super capacitor, the high molecular polymer monomer and the inorganic lithium salt are doped into the positive electrode, so that the low-cost, high-efficiency and controllable lithium pre-embedding process is realized, and the problems of uncontrollable lithium doping amount, potential safety hazard, high environmental cost caused by environmental sensitivity of used materials and the like are solved.
Description
Technical Field
The invention relates to a lithium ion super capacitor technology, in particular to a lithium pre-embedding method of a lithium ion super capacitor.
Background
With the global exhaustion of fossil energy and the increasingly prominent problem of environmental pollution, there is an urgent need to develop new energy storage devices, and among such chemical energy storage devices, lithium ion batteries and super capacitors are favored due to their outstanding excellent performance. The lithium ion battery has the energy density as high as 250Wh/kg, but the power density is relatively low, so that the lithium ion battery cannot be charged and discharged at a large multiplying power, and the low-temperature performance and the cycle performance are poor; supercapacitors have power densities of up to 10kW/kg, can achieve rapid charging and discharging, and have long cycle lives (>104 times), whereas their energy densities are much lower than lithium ion batteries, only 5-10 Wh/kg. Therefore, when the lithium ion battery or the super capacitor is used independently, the requirements of modern vehicles, portable equipment and the like which are rapidly developed at present on the energy storage device cannot be met due to the performance disadvantages of the lithium ion battery or the super capacitor, and the lithium ion super capacitor which has the higher energy density of the lithium ion battery and the higher power density of the super capacitor is in the field of vision of people.
For the activated carbon/lithium titanate system lithium ion super capacitor, the capacity difference between the positive activated carbon and the negative lithium titanate is large, so the capacity of the positive activated carbon needs to be improved as much as possible to reduce the difference, and the improvement mode mainly comprises the following steps: (1) regulating and controlling the microstructure of the activated carbon; and (2) expanding the working voltage range of the activated carbon. In the current state of the art, the preparation process of the activated carbon is relatively stable, and a further remarkable result is difficult to obtain by regulating and controlling the microstructure of the activated carbon to improve the capacity of the activated carbon, so that the activated carbon is in a stable voltage range (1.5V-4.5V, v.Li)+Li, the same below) to expand the voltage window becomes an effective way to increase the capacity of the activated carbon. The open circuit voltage of the active carbon is about 3V, and LiPF is used6When the electrolyte is used, the positive electrode potential adsorbs anions (PF) in the electrolyte at or above the open circuit voltage6-) Provide forCapacity, positive electrode potential, to adsorb cations (Li) below open circuit voltage+) The capacity is provided, and the part of positive ions come from a lithium source pre-embedded in advance, so if a voltage interval below the open circuit potential of the positive electrode is used, an additional lithium source, namely, the negative electrode is pre-embedded in lithium, must be provided.
At present, the following main implementation schemes are provided for the technical problem of pre-lithium intercalation:
according to the scheme (1), a simple substance lithium source is adopted, and lithium pre-insertion on a negative electrode is realized through modes of electrochemical lithium pre-insertion, internal short circuit, external short circuit and the like;
scheme (2), the positive electrode incorporates conventional lithium ion battery positive electrode materials (including but not limited to LiFePO)4、 LiCoO2、LiMn2O4Lithium rich manganese base, etc.);
scheme (3), the positive electrode incorporates a lithium-rich and irreversibly delithiatable lithium salt (including but not limited to Li)5FeO4、 Li2HBN, etc.) to insert lithium doped with lithium salt irreversibly into the negative electrode during the first cycle, thereby achieving the purpose of pre-inserting lithium.
In the scheme (1), the scheme of pre-embedding lithium by using the elemental lithium source is difficult to control the doping amount of lithium, is easy to generate potential safety hazards such as volume change, short circuit, thermal runaway and the like, and consumes a large amount of time when pre-embedding lithium by using the elemental lithium source; in the scheme (2), the implementation scheme that the anode material of the conventional lithium ion battery is doped into the anode is adopted to form a structure in which the capacitor is connected with the interior of the battery in parallel, and the defect that the multiplying power performance of the device is greatly influenced along with the increase of the proportion of the battery material is overcome; scheme (3) adopts sacrificial lithium salt, the rest part after the first circulation loses activity to become an ineffective component, and some parts escape in a gas form or are dissolved in the electrolyte and do not contribute to capacity any more to cause energy density reduction, the used lithium salt has high requirements on the environment, and if large-scale production is carried out, the environment control cost is relatively high, and in addition, the possibility of side reaction is also existed.
Disclosure of Invention
The present invention aims to solve the above problems in the above solutions.
In order to achieve the above object, in one aspect, the present invention provides a lithium pre-intercalation method for a lithium ion supercapacitor, which comprises a preparation method of a positive electrode plate:
preparing a mixed glue solution of a binder and a solvent; the binder comprises PVdf, CMC, PVA, PTFE, LA series and polyimide; the solvent comprises NMP and water.
Adding a high molecular polymer monomer into the mixed glue solution, and uniformly dispersing by adopting a stirring process to obtain a mixed solution of the mixed glue solution and the high molecular polymer monomer; the high molecular polymer monomer comprises aniline, pyrrole, thiophene, naphthalene, pyrene, phenanthrene, perylene and derivatives thereof.
Adding inorganic lithium salt into the obtained mixed solution, and preparing a mixed glue solution, a high-molecular polymer monomer and a uniform dispersion solution of the inorganic lithium salt by adopting a stirring process; the lithium salt comprises LiAlO2、Li3AsO4、 Li3BO3、Li2CO3、Li2GeO3、Li3PO4、Li2SO4、Li2SeO4、Li2SiO3、Li2TeO3。
Adding a conductive agent and positive electrode material active carbon into the obtained dispersion liquid, and uniformly dispersing by adopting a stirring process to obtain slurry; the conductive agent comprises carbon nano tubes, Ketjen black, acetylene, Super p, ks6 and graphene.
And coating the obtained slurry on a current collector to obtain the positive electrode plate. The current collector comprises foamed nickel, a smooth aluminum foil and a corrosion aluminum foil.
On the other hand, the invention provides a lithium pre-intercalation method of a lithium ion super capacitor, which comprises the following steps:
preparing a mixed glue solution of a binder and a solvent;
adding a conductive agent and a negative electrode material lithium titanate into the obtained mixed glue solution, and uniformly dispersing by adopting a stirring process to obtain slurry;
and coating the obtained slurry on a current collector to obtain the negative electrode plate.
In another aspect, the present invention provides a lithium pre-intercalation method for a lithium ion supercapacitor, comprising the following steps:
assembling and molding the positive electrode plate, the negative electrode plate and the diaphragm according to the assembling form;
injecting liquid into the sample and sealing the sample according to the assembling form;
standing the assembled sample for 24h, and then carrying out electrochemical activation on the sample under a small-rate current; the small multiplying current comprises 0.1C and 0.5C; and carrying out constant current charge and discharge test on the sample under the higher rate current; the higher rate current includes 3C, 6C, 12C.
Aiming at the lithium ion super capacitor of an activated carbon/lithium titanate system, the high molecular polymer monomer and the inorganic lithium salt are doped into the positive electrode, so that the low-cost, high-efficiency and controllable pre-lithium embedding process is realized, and the problems of uncontrollable lithium doping amount, potential safety hazard, high environmental cost caused by the sensitivity of the used material to the environment and the like are solved.
Drawings
FIG. 1 is a schematic flow chart of a lithium pre-intercalation method for a lithium-ion supercapacitor according to the present invention;
FIG. 2 is a schematic diagram of a test curve after a sample is assembled by a positive electrode added with pyrene and lithium phosphate and a lithium titanate negative electrode;
FIG. 3 is a schematic diagram of a test curve of a sample assembled by a positive electrode added with pyrene and lithium carbonate and a lithium titanate negative electrode.
Detailed Description
Other features, characteristics and advantages of the present invention will become more apparent from the following detailed description of embodiments of the present invention, which is to be read in connection with the accompanying drawings.
Fig. 1 is a schematic flow chart of a lithium pre-intercalation method for a lithium-ion supercapacitor according to the present invention. As shown in fig. 1, the method comprises a preparation method of the positive electrode plate, and the steps comprise:
preparing a mixed glue solution of a binder (the binder comprises but is not limited to PVdf, CMC, PVA, PTFE, LA series, polyimide and the like) and a solvent (the solvent comprises but is not limited to NMP, water and the like) by adopting a stirring process; wherein the content of the binder accounts for 5-8%.
Adding high molecular polymer monomers (including but not limited to aniline, pyrrole, thiophene, naphthalene, pyrene, phenanthrene, perylene and derivatives thereof) into the glue solution, and uniformly dispersing by adopting a stirring process to obtain a mixed solution of the glue solution and the high molecular polymer monomers; the content of the high molecular polymer monomer accounts for 4-15%.
Adding inorganic lithium salt (lithium salt including but not limited to LiAlO) into the mixed solution obtained in the step (2)2、 Li3AsO4、Li3BO3、Li2CO3、Li2GeO3、Li3PO4、Li2SO4、Li2SeO4、Li2SiO3、Li2TeO3Etc.), adopting a stirring process to prepare a uniform dispersion liquid of the glue solution, the high-molecular polymer monomer and the inorganic lithium salt; the content of the inorganic lithium salt is 3-14%.
Adding a conductive agent (the conductive agent comprises but is not limited to carbon nano tubes, Ketjen black, acetylene, Super p, ks6, graphene and the like) and positive electrode material active carbon into the mixed solution obtained in the step (3), and uniformly dispersing by adopting a stirring process to obtain slurry suitable for coating; wherein, the content of the conductive agent accounts for 3-8% and the content of the positive active material accounts for 55-85%.
Coating the slurry obtained in the step (4) on a current collector (the current collector comprises but is not limited to foamed nickel, a smooth aluminum foil and a corrosion aluminum foil) to obtain a positive electrode plate with appropriate surface density for later use;
the embodiment of the invention also provides a preparation method of the negative electrode slice, which comprises the following steps:
preparing a mixed glue solution of a binder (the binder comprises but is not limited to PVdf, CMC, PVA, PTFE, LA series, polyimide and the like) and a solvent (the solvent comprises but is not limited to NMP, water and the like) by adopting a stirring process; wherein the content of the binder accounts for 2-6%.
Adding a conductive agent (the conductive agent comprises but is not limited to carbon nano tubes, Ketjen black, acetylene, Super p, ks6, graphene and the like) and a negative electrode material lithium titanate into the mixed glue solution obtained in the step (1), and uniformly dispersing by adopting a stirring process to obtain a slurry suitable for coating; the content of the conductive agent is 2-6%, and the content of the lithium titanate serving as the negative electrode material is 88-96%.
Coating the slurry obtained in the step (2) on a current collector (the current collector comprises but is not limited to foamed nickel, a smooth aluminum foil, a corrosion aluminum foil and a copper foil) to obtain a negative electrode plate with proper surface density for later use;
the embodiment of the invention also provides a sample assembling method, which comprises the following steps:
preparing positive and negative electrode plates;
preparing the device for use according to a packaging format (packaging formats include, but are not limited to, button format, soft pack format, cylindrical format, etc.);
prepare the electrolyte for use in the assembly process (electrolyte solutes including but not limited to LiBF)4、 LiAsF6、LiCF3SO3、LiFP6、LiClO4Etc., the electrolyte solvents used include, but are not limited to, PC, DMC, DEC, EC, etc.);
preparing the separator used in the assembly process (separators include but are not limited to PP/PE separators, fiberglass separators, etc.);
assembling and molding the positive plate, the negative plate and the diaphragm according to the assembling form;
injecting liquid into the sample and sealing the sample according to the assembling form;
standing the assembled sample for 24h, and then, activating and testing;
performing electrochemical activation on the sample under a current with a small multiplying power (such as 0.1C, 0.5C and the like);
carrying out constant current charge and discharge test on the sample under the current with higher multiplying power (such as 3C, 6C, 12C and the like);
the embodiment of the invention aims at the lithium ion super capacitor of an activated carbon/lithium titanate system, and the high molecular polymer monomer and the inorganic lithium salt are doped into the positive electrode, so that the low-cost, high-efficiency and controllable pre-lithium embedding process is realized, and the problems of uncontrollable lithium doping amount, potential safety hazard, high environmental cost caused by environmental sensitivity of used materials and the like are solved.
Specifically, the present invention also provides two specific embodiments:
the first embodiment is as follows:
firstly, preparing a positive electrode plate:
preparing a mixed glue solution of a binder PVdf and a solvent NMP by adopting a stirring process;
adding a high-molecular polymer monomer pyrene into the glue solution, and uniformly dispersing by adopting a stirring process to obtain a mixed solution of the glue solution and the high-molecular polymer monomer pyrene;
adding inorganic lithium salt Li into the mixed solution obtained in the step (2)3PO4The glue solution, the high-molecular polymer monomer pyrene and the inorganic lithium salt Li are prepared by adopting a stirring process3PO4The uniform dispersion of (a);
adding conductive agent Keqin black and anode material active carbon into the mixed solution obtained in the step (3), and uniformly dispersing by adopting a stirring process to obtain slurry suitable for coating;
coating the slurry obtained in the step (4) on a corroded aluminum foil to obtain the aluminum foil with the surface density of 3-4 mg/cm2The positive electrode sheet of (1);
cutting the positive electrode plate into a wafer with the diameter of 14mm for later use;
secondly, preparing a negative plate:
preparing a mixed glue solution of a binder PVdf and a solvent NMP by adopting a stirring process;
adding a conductive agent Super p and a negative electrode material lithium titanate into the mixed glue solution obtained in the step (1), and uniformly dispersing by adopting a stirring process to obtain slurry suitable for coating;
coating the slurry obtained in the step (2) on a smooth aluminum foil to obtain the aluminum foil with the surface density of 1-2 mg/cm2The negative electrode sheet of (1);
cutting the negative electrode slice into a wafer with the diameter of 14mm for later use;
third, sample assembly
Preparing positive and negative electrode wafers with the diameter of 14 mm;
preparing a positive and negative electrode shell, a gasket and an elastic sheet which are matched with the CR2025 in the assembling process;
preparing the electrolyte for use in the assembly process, electrolysisThe liquid component is LiPF6/DC+EMC;
Preparing a PP/PE septum for use in an assembly process;
assembling a sample according to the sequence of the positive electrode shell, the positive electrode plate, the electrolyte, the diaphragm, the electrolyte, the negative electrode plate, the gasket, the elastic sheet and the negative electrode shell;
sealing the assembled sample using a CR2025 button sealer;
standing the assembled sample for 24h, and then, activating and testing;
fourth, sample activation and testing
Electrochemically activating the sample using a 0.1C current;
carrying out constant-current charge and discharge test on the sample by using 3C current;
FIG. 2 shows the results of the sample testing: the thin lines in the figure show a test curve of a sample assembled by an activated carbon anode and a lithium titanate cathode (represented by AC/LTO), the thick lines in the figure show a test curve of a sample assembled by the anode and a lithium titanate cathode (represented by ACPP/LTO) after pyrene and lithium phosphate are added, according to the mass calculation of the anode coating, after pyrene and lithium phosphate are introduced, the gram capacity is increased from the initial 30.16mAh/g to 44.94mAh/g, the capacity is increased by 49%, and the purpose of pre-embedding lithium into the lithium ion super capacitor is realized.
Example two:
firstly, preparing a positive electrode plate:
preparing a mixed glue solution of a binder PVdf and a solvent NMP by adopting a stirring process;
adding a high-molecular polymer monomer pyrene into the glue solution, and uniformly dispersing by adopting a stirring process to obtain a mixed solution of the glue solution and the high-molecular polymer monomer pyrene;
adding inorganic lithium salt Li into the mixed solution obtained in the step (2)2CO3The glue solution, the high-molecular polymer monomer pyrene and the inorganic lithium salt Li are prepared by adopting a stirring process2CO3The uniform dispersion of (a);
adding conductive agent Keqin black and anode material active carbon into the mixed solution obtained in the step (3), and uniformly dispersing by adopting a stirring process to obtain slurry suitable for coating;
coating the slurry obtained in the step (4) on a corroded aluminum foil to obtain the aluminum foil with the surface density of 3-4 mg/cm2The positive electrode sheet of (1);
cutting the positive electrode plate into a wafer with the diameter of 14mm for later use;
secondly, preparing a negative plate:
preparing a mixed glue solution of a binder PVdf and a solvent NMP by adopting a stirring process;
adding a conductive agent Super p and a negative electrode material lithium titanate into the mixed glue solution obtained in the step (1), and uniformly dispersing by adopting a stirring process to obtain slurry suitable for coating;
coating the slurry obtained in the step (2) on a smooth aluminum foil to obtain the aluminum foil with the surface density of 1-2 mg/cm2The negative electrode sheet of (1);
cutting the negative electrode slice into a wafer with the diameter of 14mm for later use;
third, sample assembly
Preparing positive and negative electrode wafers with the diameter of 14 mm;
preparing a positive and negative electrode shell, a gasket and an elastic sheet which are matched with the CR2025 in the assembling process;
preparing electrolyte used in the assembly process, wherein the electrolyte comprises LiPF6/DC+EMC;
Preparing a PP/PE septum for use in an assembly process;
assembling a sample according to the sequence of the positive electrode shell, the positive electrode plate, the electrolyte, the diaphragm, the electrolyte, the negative electrode plate, the gasket, the elastic sheet and the negative electrode shell;
sealing the assembled sample using a CR2025 button sealer;
standing the assembled sample for 24h, and then, activating and testing;
fourth, testing under sample activation
Electrochemically activating the sample using a 0.1C current;
carrying out constant-current charge and discharge test on the sample by using 3C current;
FIG. 3 shows the results of the sample testing: the dotted line in the figure shows a test curve of a sample assembled by an activated carbon positive electrode and a lithium titanate negative electrode (represented by AC/LTO), the solid line in the figure shows a test curve of a sample assembled by the positive electrode and a lithium titanate negative electrode (represented by ACPC/LTO) after pyrene and lithium carbonate are added, according to the mass calculation of a positive electrode coating, the gram capacity is increased to 47.09mAh/g from the initial 30.16mAh/g after pyrene and lithium carbonate are introduced, the capacity is increased by 56%, and the purpose of pre-lithium intercalation of the lithium ion super capacitor is realized.
It should be noted that the above embodiments are only used for illustrating the structure and the working effect of the present invention, and are not used for limiting the protection scope of the present invention. Modifications and adaptations to the above-described embodiments may occur to one skilled in the art without departing from the spirit and scope of the present invention and are intended to be covered by the following claims.
Claims (7)
1. A lithium ion super capacitor lithium pre-embedding method is characterized by comprising a preparation method of a positive electrode plate:
preparing a mixed glue solution of a binder and a solvent;
adding a high molecular polymer monomer into the mixed glue solution, and uniformly dispersing by adopting a stirring process to obtain a mixed solution of the mixed glue solution and the high molecular polymer monomer;
adding inorganic lithium salt into the obtained mixed solution, and preparing a mixed glue solution, a high-molecular polymer monomer and a uniform dispersion solution of the inorganic lithium salt by adopting a stirring process;
adding a conductive agent and positive electrode material active carbon into the obtained dispersion liquid, and uniformly dispersing by adopting a stirring process to obtain slurry;
coating the obtained slurry on a current collector to obtain a positive electrode plate;
the high molecular polymer monomer comprises aniline, pyrrole, thiophene, naphthalene, pyrene, phenanthrene, perylene and derivatives thereof; the content of the high molecular polymer monomer accounts for 4-15%,
the inorganic lithium salt includes LiAlO2、Li3AsO4、Li3BO3、Li2CO3、Li2GeO3、Li3PO4、Li2SO4、Li2SeO4、Li2SiO3、Li2TeO3(ii) a The content of the inorganic lithium salt accounts for 3-14%,
the conductive agent comprises carbon nano tubes, Ketjen black, acetylene, Superp, ks6 and graphene, wherein the content of the conductive agent accounts for 3-8%, and the content of the positive electrode active material accounts for 55-85%.
2. The method of claim 1, wherein the binder comprises PVdf, CMC, PVA, PTFE, LA series, and polyimide; the solvent comprises NMP and water; the content of the binder accounts for 5-8%.
3. The method of claim 1, wherein the current collector comprises nickel foam, plain aluminum foil, etched aluminum foil.
4. The method according to any one of claims 1 to 3, characterized by further comprising a method of preparing a negative electrode sheet:
preparing a mixed glue solution of a binder and a solvent;
adding a conductive agent and a negative electrode material lithium titanate into the obtained mixed glue solution, and uniformly dispersing by adopting a stirring process to obtain slurry;
and coating the obtained slurry on a current collector to obtain the negative electrode plate.
5. The method of claim 4, wherein the binder comprises PVdf, CMC, PVA, PTFE, LA series, and polyimide; the solvent comprises NMP and water; the content of the binder accounts for 2-6%.
6. The method of claim 4, wherein the conductive agent comprises carbon nanotubes, ketjen black, acetylene, Superp, ks6, graphene; the content of the conductive agent is 2-6%, and the content of the lithium titanate serving as the negative electrode material is 88-96%.
7. The method according to claim 4, characterized in that it comprises the following steps:
assembling and molding the positive electrode plate, the negative electrode plate and the diaphragm according to an assembling form;
injecting liquid into the sample and sealing the sample according to the assembling form;
standing the assembled sample for 24h, and then carrying out electrochemical activation on the sample under a small-rate current; the small multiplying current comprises 0.1C and 0.5C; and carrying out constant current charge and discharge test on the sample under the higher rate current; the higher rate current includes 3C, 6C, 12C.
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