CN112735841A - Preparation method of novel button cell type super capacitor - Google Patents
Preparation method of novel button cell type super capacitor Download PDFInfo
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- CN112735841A CN112735841A CN202110003692.5A CN202110003692A CN112735841A CN 112735841 A CN112735841 A CN 112735841A CN 202110003692 A CN202110003692 A CN 202110003692A CN 112735841 A CN112735841 A CN 112735841A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 32
- 239000013543 active substance Substances 0.000 claims abstract description 23
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 19
- 239000011267 electrode slurry Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000006258 conductive agent Substances 0.000 claims description 42
- 239000007774 positive electrode material Substances 0.000 claims description 34
- 239000007773 negative electrode material Substances 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 17
- 239000002033 PVDF binder Substances 0.000 claims description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 16
- 238000005096 rolling process Methods 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 14
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 9
- 229910021385 hard carbon Inorganic materials 0.000 claims description 7
- 229910021384 soft carbon Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000011056 performance test Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000006257 cathode slurry Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
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- 238000001311 chemical methods and process Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- H01G11/32—Carbon-based
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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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
- H01G11/84—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
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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
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Abstract
The invention provides a preparation method of a novel button cell type super capacitor, belongs to the technical field of electrochemical energy storage, and can solve the technical problems of complex preparation process, poor consistency and inconvenience for large-scale production in the prior art. The preparation method mainly comprises the following steps: the method comprises the steps of preparing a positive electrode slurry, preparing a positive plate, preparing a negative electrode slurry, preparing a negative plate and the like, wherein the positive electrode active substance is selected from lithium iron phosphate and activated carbon, and the negative electrode active substance is selected from a carbon material. The invention prepares a novel button cell type super capacitor with ultra-long cycle life, ultra-high rate performance and certain energy density by accurately regulating and controlling the capacity ratio of the anode material and the cathode material. The invention can be applied to the aspect of battery type super capacitors.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a preparation method of a novel button cell type super capacitor.
Background
The super capacitor has the advantages of high capacity, high power, long service life, low cost, environmental friendliness and the like, and can partially or completely replace the traditional chemical battery. With the continuous development of super capacitor technology, the application range of super capacitor technology is also expanded from the initial electronic equipment field to the fields of power, energy storage and the like.
The battery type super capacitor is a super capacitor based on the traditional double electric layer, which is added with a small amount of battery materials, such as activated carbon material doped with nitrogen/boron/sulfur, manganese oxide, iron oxide or lithium battery material (the dosage is generally less than 20%), the working principle of the super capacitor is still shallow charge adsorption or reaction based on the double electric layers or pseudocapacitances formed between the two electrodes and the electrolyte, compared with the traditional double electric layer capacitor, the cycle stability, the energy density and the rate capability of the battery type super capacitor are higher, but the current research on the battery type super capacitor of a lithium ion system is less, for example, Chinese patent CN105280394 discloses a new concept super capacitor based on the high power density and the high energy density of a multilayer structure and a preparation method thereof, but the side is more important than the layer structure of the electrodes, but the matching and mechanism research on the battery type super capacitor is less, moreover, because the preparation process of the layered electrode is complicated, the consistency is poor, and the large-scale production is not facilitated, the key for solving the problems is to develop the button cell type super capacitor which has a simple process, an ultra-long cycle life, an ultra-high rate performance and a certain energy density.
Disclosure of Invention
Aiming at the technical problems of complicated preparation process, poor consistency and inconvenience for large-scale production in the prior art, the invention provides the preparation method of the button cell type super capacitor, which has the advantages of simple preparation process, low cost and energy consumption, super long cycle life, super high rate performance and certain energy density.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a novel button cell type super capacitor comprises the following steps:
weighing a certain amount of positive active substances, mixing, adding polyvinylidene fluoride and a conductive agent, stirring, and vacuumizing to obtain positive slurry;
coating the positive electrode slurry on an etched aluminum foil, drying, rolling and slicing to obtain a positive plate;
weighing a certain amount of negative active substances, mixing, adding carboxymethyl cellulose and a conductive agent, stirring, and vacuumizing to obtain negative slurry;
coating the negative electrode slurry on an etched aluminum foil, drying, rolling and slicing to obtain a negative electrode sheet;
the negative plate, the lithium plate and the electrolyte are assembled into a button cell, and pre-buried treatment is carried out to obtain a pre-buried negative plate;
the novel button cell type super capacitor is assembled by taking the positive plate as a positive electrode and the pre-embedded negative plate as a negative electrode and adding electrolyte;
the positive active material is lithium iron phosphate and active carbon, and the negative active material is a carbon material.
Preferably, the mass ratio of the negative electrode active material to the positive electrode active material is (1: 1-2: 1), and the mass ratio of the lithium iron phosphate to the activated carbon is (1: 5-5: 1).
Preferably, the carbon material is at least one selected from the group consisting of hard carbon, soft carbon and graphite.
Preferably, the addition amount of the lithium iron phosphate and the activated carbon accounts for 80-95% of the total mass of the positive electrode material, the addition amount of the polyvinylidene fluoride accounts for 3-10% of the total mass of the positive electrode material, and the addition amount of the conductive agent accounts for 2-10% of the total mass of the positive electrode material.
Preferably, the addition amount of the carbon material accounts for 85-98% of the total mass of the negative electrode material, the addition amount of the carboxymethyl cellulose accounts for 1-8% of the total mass of the negative electrode material, and the addition amount of the conductive agent accounts for 1-7% of the total mass of the negative electrode material.
Preferably, the conductive agent is selected from at least one of graphene, carbon black, graphite, and ketjen ink.
Preferably, in the preparation steps of the cathode slurry and the anode slurry, the stirring speed is 1000-.
Preferably, in the steps of preparing the positive plate and the negative plate, the drying temperatures are 80-120 ℃ and 90-150 ℃ respectively.
Preferably, the diameter of the positive electrode sheet is 16mm, and the diameter of the negative electrode sheet is 18 mm.
Preferably, the pre-embedding treatment is as follows: after the negative plate, the lithium plate and the electrolyte are assembled into the button cell, the button cell is discharged to 2.2-2.5V under the condition of 0.05-0.08C, then the button cell after discharging is placed in a glove box for disassembly, and the pre-buried negative plate is taken out.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the invention provides a preparation method of a novel button cell type super capacitor, which improves the potential of a positive electrode by regulating and controlling the proportion of a cell type material and active carbon in the positive electrode, gives consideration to higher energy density and higher power density, has smaller influence on coating and has less regulating parameters;
2. the invention provides a preparation method of a novel button cell type super capacitor, which realizes the optimization of the capacity of positive and negative electrodes by regulating the mass ratio of the positive and negative electrodes, improves the multiplying power performance of the battery type super capacitor and prolongs the cycle life of the battery type super capacitor;
3. the invention provides a preparation method of a novel button cell type super capacitor, which reduces the irreversible capacity of a negative electrode, improves the lithium ion concentration in a body phase of the battery type super capacitor and reduces the impact on a negative electrode material in the charging and discharging process through a proper pre-physical and chemical process, thereby improving the energy density and the cycling stability;
4. the invention provides a preparation method of a novel button cell type super capacitor, which has obvious improvement on the cycling stability and rate capability of a positive electrode in the aspect of electrode material selection, can improve the rate capability of the whole body by introducing a high-rate lithium iron phosphate electrode material, and simultaneously greatly improves the cycling characteristic of the whole device because lithium iron phosphate and activated carbon have good structural stability and do not generate side reaction with electrolyte in the charging and discharging processes;
5. the invention provides a preparation method of a novel button cell type super capacitor, which is simple in preparation process, controllable in cost and capable of realizing batch production.
Drawings
FIG. 1 is a test chart of electrochemical properties of example 1 provided in an example of the present invention;
FIG. 2 is a test chart of electrochemical performance of example 2 provided in an embodiment of the present invention;
FIG. 3 is a test chart of electrochemical performance of example 3 provided in an embodiment of the present invention;
FIG. 4 is a test chart of electrochemical properties of comparative example 1 provided in an example of the present invention;
fig. 5 is an electrochemical performance test chart of comparative example 2 provided in the example of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a preparation method of a novel button cell type super capacitor, which comprises the following steps:
s1, weighing a certain amount of positive active substances, mixing, adding polyvinylidene fluoride and a conductive agent, stirring, and vacuumizing to obtain positive slurry;
s2, coating the positive electrode slurry on an etched aluminum foil, drying, rolling and slicing to obtain a positive electrode plate;
s3, weighing a certain amount of negative active substances, mixing, adding carboxymethyl cellulose and a conductive agent, stirring, and vacuumizing to obtain negative slurry;
s4, coating the negative electrode slurry on an etched aluminum foil, drying, rolling and slicing to obtain a negative electrode sheet;
s5, assembling the negative plate, the lithium plate and the electrolyte into a button cell, and pre-embedding to obtain a pre-embedded negative plate;
s6, the novel button cell type super capacitor is assembled by taking the positive plate as a positive electrode and the pre-buried negative plate as a negative electrode and adding electrolyte;
the positive active material is lithium iron phosphate and active carbon, and the negative active material is a carbon material.
The invention provides a preparation method of a novel button cell type super capacitor, which realizes the high rate performance and long cycle life of the button cell type super capacitor by reasonably regulating the proportional relation between a capacitive material and a cell type material in an anode and the capacity relative relation between the anode and a cathode.
In a preferred embodiment, the mass ratio of the negative electrode active material to the positive electrode active material is (1: 1-2: 1), and the mass ratio of the lithium iron phosphate to the activated carbon is (1: 5-5: 1).
In the above preferred embodiment, the mass ratio of the lithium iron phosphate to the activated carbon may be selected from 1:5, 2.6:1, 5:1 or any value within the above-mentioned limited range, and the lithium iron phosphate and the activated carbon fall within the protection scope of the present invention.
In a preferred embodiment, the carbon material is selected from at least one of hard carbon, soft carbon, and graphite.
In a preferred embodiment, the addition amount of the lithium iron phosphate and the activated carbon accounts for 80-95% of the total mass of the positive electrode material, the addition amount of the polyvinylidene fluoride accounts for 3-10% of the total mass of the positive electrode material, and the addition amount of the conductive agent accounts for 2-10% of the total mass of the positive electrode material.
In a preferred embodiment, the adding amount of the carbon material accounts for 85-98% of the total mass of the negative electrode material, the carboxymethyl cellulose accounts for 1-8% of the total mass of the negative electrode material, and the adding amount of the conductive agent accounts for 1-7% of the total mass of the negative electrode material.
In a preferred embodiment, the conductive agent is selected from at least one of graphene, carbon black, graphite, and ketjen ink.
In a preferred embodiment, in the preparation steps of the cathode slurry and the anode slurry, the stirring speed is 1000-.
In a preferred embodiment, in the steps of preparing the positive plate and the negative plate, the drying temperatures are respectively 80-120 ℃ and 90-150 ℃.
In a preferred embodiment, the diameter of the positive plate is 16mm, and the diameter of the negative plate is 18 mm.
In a preferred embodiment, the pre-embedding process is as follows: after the negative plate, the lithium plate and the electrolyte are assembled into the button cell, the button cell is discharged to 2.2-2.5V under the condition of 0.05-0.08C, then the button cell after discharging is placed in a glove box for disassembly, and the pre-buried negative plate is taken out.
In order to more clearly and specifically describe the preparation method of the novel button cell type supercapacitor provided in the embodiments of the present invention, the following description will be made with reference to specific embodiments.
Comparative example 1
The comparative example provides a preparation method of a button cell type super capacitor, which comprises the following specific steps:
(1) weighing a certain amount of lithium iron phosphate (positive active material), polyvinylidene fluoride and a conductive agent (graphite is selected as the conductive agent) at room temperature, mixing, stirring at 3000rpm, and vacuumizing to obtain positive slurry with the viscosity of 10000cps, wherein the addition amount of the lithium iron phosphate accounts for 90% of the total mass of the positive electrode material, the addition amount of the polyvinylidene fluoride accounts for 5.5% of the total mass of the positive electrode material, and the addition amount of the conductive agent accounts for 4.5% of the total mass of the positive electrode material;
(2) coating the above slurry on etched aluminum foil, drying at 80 deg.C, rolling into 80 μm positive electrode, and slicing with slicer
The positive electrode sheet of (1);
(3) weighing a certain amount of negative electrode active substance (the mass ratio of the negative electrode active substance to the positive electrode active substance is 1:1), namely graphite, adding carboxymethyl cellulose and a conductive agent (the conductive agent is graphite), stirring at the rotating speed of 3000rpm, and vacuumizing to prepare negative electrode slurry with the viscosity of 10000cps, wherein the adding amount of a carbon material accounts for 95% of the total mass of the negative electrode material, the adding amount of the carboxymethyl cellulose accounts for 3% of the total mass of the negative electrode material, the adding amount of the conductive agent accounts for 2% of the total mass of the negative electrode material, and the carbon material can specifically select at least one of hard carbon, soft carbon or graphite;
(4) coating the slurry on copper foil by coating machine, drying at 90 deg.C, rolling to obtain 70 μm negative electrode, and cutting with slicer
The negative electrode sheet of (1);
(5) assembling the negative plate, the lithium plate and the electrolyte into a button cell, discharging to 2.2V under the condition of 0.05C, disassembling the button cell in a glove box by using a button cell disassembling tool, and taking out the pre-treated negative plate;
(6) and (3) taking the positive plate as a positive electrode, taking the pre-embedded negative plate as a negative electrode, and adding a proper amount of electrolyte to assemble the button cell type super capacitor.
Comparative example 2
The comparative example provides a preparation method of a button type double electric layer capacitor, which comprises the following specific steps:
(1) weighing a certain amount of active carbon (positive active substance), polyvinylidene fluoride and a conductive agent (graphite is selected as the conductive agent) at room temperature, mixing, stirring at 3000rpm, and vacuumizing to obtain positive slurry with the viscosity of 10000cps, wherein the addition amount of lithium iron phosphate accounts for 90% of the total mass of the positive electrode material, the addition amount of polyvinylidene fluoride accounts for 5.5% of the total mass of the positive electrode material, and the addition amount of the conductive agent accounts for 4.5% of the total mass of the positive electrode material;
(2) coating the above slurry on etched aluminum foil, drying at 80 deg.C, rolling into 80 μm positive electrode, and slicing with slicer
The positive electrode sheet of (1);
(3) the buckled double-electric-layer capacitor is assembled by two cut identical electrodes and electrolyte.
Example 1
The embodiment provides a preparation method of a novel button cell type super capacitor, which comprises the following specific steps:
(1) weighing a certain amount of lithium iron phosphate and activated carbon (positive electrode active substance) at room temperature, mixing according to a mass ratio of 5:1, then adding polyvinylidene fluoride and a conductive agent (the conductive agent is graphite), stirring at 3000rpm, and vacuumizing to obtain positive electrode slurry with the viscosity of 10000cps, wherein the addition amount of the lithium iron phosphate and the activated carbon accounts for 80% of the total mass of the positive electrode material, the addition amount of the polyvinylidene fluoride accounts for 10% of the total mass of the positive electrode material, and the addition amount of the conductive agent accounts for 10% of the total mass of the positive electrode material;
(2) coating the above slurry on etched aluminum foil, drying at 80 deg.C, rolling into 80 μm positive electrode, and slicing with slicer
The positive electrode sheet of (1);
(3) weighing a certain amount of negative electrode active substance (the mass ratio of the negative electrode active substance to the positive electrode active substance is 1:1) at room temperature, namely, adding carboxymethyl cellulose and a conductive agent (the conductive agent is graphite), stirring at the rotating speed of 3000rpm, and vacuumizing to prepare negative electrode slurry with the viscosity of 10000cps, wherein the adding amount of the carbon material accounts for 85% of the total mass of the negative electrode material, the adding amount of the carboxymethyl cellulose accounts for 8% of the total mass of the negative electrode material, the adding amount of the conductive agent accounts for 7% of the total mass of the negative electrode material, and the carbon material can specifically select at least one of hard carbon, soft carbon or graphite;
(4) coating the slurry on copper foil by coating machine, drying at 90 deg.C, rolling to obtain 70 μm negative electrode, and cutting with slicer
The negative electrode sheet of (1);
(5) assembling the negative plate, the lithium plate and the electrolyte into a button cell, discharging to 2.2V under the condition of 0.05C, disassembling the button cell in a glove box by using a button cell disassembling tool, and taking out the pre-treated negative plate;
(6) and (3) taking the positive plate as a positive electrode, taking the pre-embedded negative plate as a negative electrode, and adding a proper amount of electrolyte to assemble the novel button cell type super capacitor.
Example 2
The embodiment provides a preparation method of a novel button cell type super capacitor, which comprises the following specific steps:
(1) weighing a certain amount of lithium iron phosphate and activated carbon (positive electrode active substance) at room temperature, mixing according to a mass ratio of 1:5, then adding polyvinylidene fluoride and a conductive agent (the conductive agent is graphite), stirring at 3000rpm, and vacuumizing to obtain positive electrode slurry with the viscosity of 10000cps, wherein the addition amount of the lithium iron phosphate and the activated carbon accounts for 95% of the total mass of the positive electrode material, the addition amount of the polyvinylidene fluoride accounts for 3% of the total mass of the positive electrode material, and the addition amount of the conductive agent accounts for 2% of the total mass of the positive electrode material;
(2) coating the above slurry on etched aluminum foil, drying at 80 deg.C, rolling into 80 μm positive electrode, and slicing with slicer
The positive electrode sheet of (1);
(3) weighing a certain amount of negative electrode active substance (the mass ratio of the negative electrode active substance to the positive electrode active substance is 1:1) at room temperature, namely, adding carboxymethyl cellulose and a conductive agent (the conductive agent is graphite), stirring at the rotating speed of 3000rpm, and vacuumizing to prepare negative electrode slurry with the viscosity of 10000cps, wherein the adding amount of the carbon material accounts for 98% of the total mass of the negative electrode material, the carboxymethyl cellulose accounts for 1% of the total mass of the negative electrode material, the adding amount of the conductive agent accounts for 1% of the total mass of the negative electrode material, and the carbon material can specifically select at least one of hard carbon, soft carbon or graphite;
(4) coating the slurry on copper foil by coating machine, drying at 90 deg.C, rolling to obtain 70 μm negative electrode, and cutting with slicer
The negative electrode sheet of (1);
(5) assembling the negative plate, the lithium plate and the electrolyte into a button cell, discharging to 2.2V under the condition of 0.05C, disassembling the button cell in a glove box by using a button cell disassembling tool, and taking out the pre-treated negative plate;
(6) and (3) taking the positive plate as a positive electrode, taking the pre-embedded negative plate as a negative electrode, and adding a proper amount of electrolyte to assemble the novel button cell type super capacitor.
Example 3
The embodiment provides a preparation method of a novel button cell type super capacitor, which comprises the following specific steps:
(1) weighing a certain amount of lithium iron phosphate and activated carbon (positive active material) at room temperature, mixing according to a mass ratio of 2.6:1, then adding polyvinylidene fluoride and a conductive agent (the conductive agent is graphite), stirring at 3000rpm, and vacuumizing to obtain positive slurry with the viscosity of 10000cps, wherein the addition amount of the lithium iron phosphate and the activated carbon accounts for 90% of the total mass of the positive electrode material, the addition amount of the polyvinylidene fluoride accounts for 5.5% of the total mass of the positive electrode material, and the addition amount of the conductive agent accounts for 4.5% of the total mass of the positive electrode material;
(2) coating the positive electrode slurry on an etched aluminum foil by using a coating machine, and then coating the etched aluminum foil on the positive electrode slurryOven drying at 80 deg.C, rolling into 80 μm positive electrode, and slicing with slicer
The positive electrode sheet of (1);
(3) weighing a certain amount of negative electrode active substance (the mass ratio of the negative electrode active substance to the positive electrode active substance is 1.5:1) at room temperature, namely a carbon material, adding carboxymethyl cellulose and a conductive agent (the conductive agent is graphite), stirring at the rotating speed of 3000rpm, and vacuumizing to prepare negative electrode slurry with the viscosity of 10000cps, wherein the adding amount of the carbon material accounts for 95% of the total mass of the negative electrode material, the carboxymethyl cellulose accounts for 3% of the total mass of the negative electrode material, the adding amount of the conductive agent accounts for 2% of the total mass of the negative electrode material, and the carbon material can specifically select at least one of hard carbon, soft carbon or graphite;
(4) coating the slurry on copper foil by coating machine, drying at 90 deg.C, rolling to obtain 70 μm negative electrode, and cutting with slicer
The negative electrode sheet of (1);
(5) assembling the negative plate, the lithium plate and the electrolyte into a button cell, discharging to 2.2V under the condition of 0.05C, disassembling the button cell in a glove box by using a button cell disassembling tool, and taking out the pre-treated negative plate;
(6) and (3) taking the positive plate as a positive electrode, taking the pre-embedded negative plate as a negative electrode, and adding a proper amount of electrolyte to assemble the novel button cell type super capacitor.
Performance testing
The electrochemical performance of the supercapacitor prepared according to the above proportions and the examples is tested, and the test method and the test result are as follows:
(1) the test method comprises the following steps: the test is carried out by adopting a cyclic charge-discharge method, the test current is 5C, and the test voltage range specifically is as follows: the voltage of the embodiment 1-the embodiment 3 and the comparative example 1 is 2.2-3.8V; comparative example 2 is 0-2.7V;
(2) the test results are shown in the following table:
TABLE 1 statistics of electrochemical performance test results of capacitors made in examples and comparative examples
The electrochemical performance test results of the capacitors prepared in the examples and the comparative examples are analyzed in detail in the present invention with reference to the contents of table 1, which are as follows:
fig. 1 shows the electrochemical performance test result of example 1 of the present invention, and it can be seen from fig. 1 that when the mass ratio of lithium iron phosphate to activated carbon is 5:1, the energy density of the battery-type supercapacitor is higher by about 75Wh/kg (the value is calculated based on the mass of the active materials of the positive electrode and the negative electrode), but the cycle life of the battery-type supercapacitor is very poor, mainly because the battery-type material exists in the positive electrode in a large amount to affect the cycle performance of the positive electrode, secondly, the mass of the negative electrode is low, so that the capacity of the negative electrode is low in excess, which causes the cycle life of the button-type supercapacitor to be poor, and the inflection point about 12 th time appearing in the figure may be the performance of the energy storage device significantly reduced due to the lithium dendrite formed on the negative electrode because the remaining amount of the negative;
fig. 2 shows the electrochemical performance test result of example 2 of the present invention, and it can be seen from fig. 2 that when the mass ratio of lithium iron phosphate to activated carbon is 1:5, the energy density of the battery-type supercapacitor is lower than about 45Wh/kg (the value is calculated based on the mass of the active materials of the positive electrode and the negative electrode), which is mainly due to the lower specific capacity of the activated carbon, the energy source of the whole battery-type supercapacitor is mainly from the absorption and desorption of the activated carbon to the anions and cations, although the addition of the lithium iron phosphate increases the potential of the positive electrode, the energy contributed by the lithium iron phosphate is less, so when the addition of the lithium iron phosphate is less, the energy density of the whole device is not too high, but from the viewpoint of cycle performance, because the absorption and desorption of the electric double layers mainly occur, the impact on the negative electrode material is less, the cycle performance is better, and in the case of about 100 cycles, the electrical performance of the button cell type supercapacitor is hardly attenuated;
fig. 3 shows the results of the electrochemical performance test of example 3 of the present invention, and it can be seen from fig. 3 that when the mass ratio of lithium iron phosphate to activated carbon is 2.6:1, the energy density of the battery-type supercapacitor is lower by about 60Wh/kg (the value is calculated based on the mass of the active materials of the positive and negative electrodes), and has better cycle performance because: the lithium iron phosphate and the activated carbon in the proportion can respectively exert the maximum performance advantages, so that the energy improvement advantage of the lithium iron phosphate can be embodied, and the power density maintenance advantage of the activated carbon on the battery type super capacitor can be embodied. In addition, because the mass ratio of the cathode to the anode is 1.5:1, the cathode has enough margin relative to the anode, and the margin does not influence the energy density of the whole device, the electrochemical performance of the embodiment is optimized;
fig. 4 shows the electrochemical performance test results of comparative example 1 of the present invention, and it can be seen from fig. 4 that when the positive electrode material is completely lithium iron phosphate and the negative electrode is pre-physical and chemical graphite, the energy density of the button cell reaches 150Wh/kg (the value is calculated based on the active material), but the cycle characteristics are also poor because: the cathode material adopts a battery material with poor cycle characteristics and the capacity of the cathode is excessive and insufficient, so that the attenuation of the whole device is fast;
fig. 5 shows the result of the electrochemical performance test of comparative example 2 of the present invention, and it can be seen from fig. 5 that, when the positive and negative electrode materials are completely activated carbon, the whole device becomes a pure physical process with only anion and cation desorption and no charge transfer, so the cycle characteristics of the device have obvious advantages, and about 100% of the initial value can be maintained after 120 cycles, but the energy density of the whole device is low due to the absence of chemical reaction.
Based on the experimental results, the embodiment of the invention realizes the high rate performance and the long cycle life of the button cell type super capacitor by reasonably regulating the proportional relation between the capacitive material and the cell type material in the anode and the capacity relative relation between the anode and the cathode, and the method has the advantages of simple preparation process, controllable cost, realization of batch production and very wide application prospect in the field of the cell type super capacitor.
Claims (10)
1. A preparation method of a novel button cell type super capacitor is characterized by comprising the following steps:
weighing a certain amount of positive active substances, mixing, adding polyvinylidene fluoride and a conductive agent, stirring, and vacuumizing to obtain positive slurry;
coating the positive electrode slurry on an etched aluminum foil, drying, rolling and slicing to obtain a positive plate;
weighing a certain amount of negative active substances, mixing, adding carboxymethyl cellulose and a conductive agent, stirring, and vacuumizing to obtain negative slurry;
coating the negative electrode slurry on an etched aluminum foil, drying, rolling and slicing to obtain a negative electrode sheet;
the negative plate, the lithium plate and the electrolyte are assembled into a button cell, and pre-buried treatment is carried out to obtain a pre-buried negative plate;
the novel button cell type super capacitor is assembled by taking the positive plate as a positive electrode and the pre-embedded negative plate as a negative electrode and adding electrolyte;
the positive active material is lithium iron phosphate and active carbon, and the negative active material is a carbon material.
2. The preparation method of the novel button cell type supercapacitor according to claim 1, wherein the mass ratio of the negative electrode active material to the positive electrode active material is (1: 1-2: 1), and the mass ratio of the lithium iron phosphate to the activated carbon is (1: 5-5: 1).
3. The method for preparing a novel button cell type supercapacitor according to claim 1, wherein the carbon material is selected from at least one of hard carbon, soft carbon and graphite.
4. The preparation method of the novel button cell type supercapacitor according to claim 1, wherein the addition amount of the lithium iron phosphate and the activated carbon accounts for 80-95% of the total mass of the positive electrode material, the addition amount of the polyvinylidene fluoride accounts for 3-10% of the total mass of the positive electrode material, and the addition amount of the conductive agent accounts for 2-10% of the total mass of the positive electrode material.
5. The method for preparing the novel button cell type supercapacitor according to claim 1, wherein the addition amount of the carbon material accounts for 85-98% of the total mass of the negative electrode material, the addition amount of the carboxymethyl cellulose accounts for 1-8% of the total mass of the negative electrode material, and the addition amount of the conductive agent accounts for 1-7% of the total mass of the negative electrode material.
6. The method for manufacturing a novel button cell type supercapacitor according to claim 4 or 5, wherein the conductive agent is selected from at least one of graphene, carbon black, graphite, and ketjen ink.
7. The method for preparing a button cell type supercapacitor as claimed in claim 1, wherein in the step of preparing the positive electrode slurry and the negative electrode slurry, the stirring speed is 1000-3000rpm, and the viscosities of the positive electrode slurry and the negative electrode slurry are 1000-10000 cps.
8. The method for preparing a novel button cell type supercapacitor according to claim 1, wherein in the steps of preparing the positive electrode tab and the negative electrode tab, the drying temperatures are 80-120 ℃ and 90-150 ℃ respectively.
9. The method for preparing the novel button cell type supercapacitor according to claim 1, wherein the diameter of the positive plate is 16mm, and the diameter of the negative plate is 18 mm.
10. The method for preparing the novel button cell type supercapacitor according to claim 1, wherein the pre-embedding treatment is: after the negative plate, the lithium plate and the electrolyte are assembled into the button cell, the button cell is discharged to 2.2-2.5V under the condition of 0.05-0.08C, then the button cell after discharging is placed in a glove box for disassembly, and the pre-buried negative plate is taken out.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113921295A (en) * | 2021-09-29 | 2022-01-11 | 海南大学 | Preparation method of novel button cell type supercapacitor based on carbon hybridization |
| CN114613614A (en) * | 2022-04-11 | 2022-06-10 | 浙江浙能技术研究院有限公司 | All-solid-state lithium ion capacitor and preparation method thereof |
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|---|---|---|---|---|
| US20120321913A1 (en) * | 2010-02-26 | 2012-12-20 | Shanghai Aowei Technology Development Co., Ltd. | Manufacturing method for long-lived negative electrode and capacitor battery adopting the same |
| CN109961967A (en) * | 2017-12-26 | 2019-07-02 | 广州汽车集团股份有限公司 | Lithium-ion capacitor and preparation method thereof |
| CN111312526A (en) * | 2019-11-11 | 2020-06-19 | 中国科学院福建物质结构研究所 | Battery-super capacitor hybrid energy storage device and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120321913A1 (en) * | 2010-02-26 | 2012-12-20 | Shanghai Aowei Technology Development Co., Ltd. | Manufacturing method for long-lived negative electrode and capacitor battery adopting the same |
| CN109961967A (en) * | 2017-12-26 | 2019-07-02 | 广州汽车集团股份有限公司 | Lithium-ion capacitor and preparation method thereof |
| CN111312526A (en) * | 2019-11-11 | 2020-06-19 | 中国科学院福建物质结构研究所 | Battery-super capacitor hybrid energy storage device and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113921295A (en) * | 2021-09-29 | 2022-01-11 | 海南大学 | Preparation method of novel button cell type supercapacitor based on carbon hybridization |
| CN114613614A (en) * | 2022-04-11 | 2022-06-10 | 浙江浙能技术研究院有限公司 | All-solid-state lithium ion capacitor and preparation method thereof |
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