CN112635200A - Preparation method of lithium ion capacitor based on novel positive electrode pre-lithium-intercalation process - Google Patents
Preparation method of lithium ion capacitor based on novel positive electrode pre-lithium-intercalation process Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 61
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- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
Abstract
The invention belongs to the technical field of chemical power supplies, and particularly relates to a preparation method of a lithium ion capacitor based on a novel positive electrode pre-lithium intercalation process. The preparation method comprises the following steps: mixing a positive electrode active material, a positive electrode lithiation organic functional material, a positive electrode conductive agent and a positive electrode binder in a mixed solvent consisting of a strong-polarity solvent and a weak-polarity solvent, processing to obtain positive electrode slurry, heating the positive electrode slurry, coating the positive electrode slurry on the front side and the back side of a positive electrode current collector, and drying, rolling and slicing to obtain a positive electrode piece; mixing a negative electrode active material, a negative electrode conductive agent and a negative electrode binder in N-methyl pyrrolidone, processing to obtain negative electrode slurry, coating the negative electrode slurry on the front and back surfaces of a negative electrode current collector, and drying, rolling and slicing to obtain a negative electrode piece; and step three, manufacturing the positive pole piece, the diaphragm and the negative pole piece into a battery cell, and obtaining the lithium ion capacitor after vacuum drying, electrolyte injection and packaging.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a preparation method of a lithium ion capacitor based on a novel positive electrode pre-lithium intercalation process.
Background
The lithium ion capacitor is a novel energy storage device combining the charge and discharge characteristics of a lithium ion battery and a chemical super capacitor, generally speaking, the capacitor adopts a carbon-based material with an ultra-large specific surface area as a positive active material, and adopts a material with a low-potential reversible lithium desorption characteristic as a negative active material. In the process of charging and discharging, the electrochemical reaction mechanism of the anode is ion surface adsorption and ion exchange reaction, the electrochemical reaction mechanism of the cathode is reversible ion embedding-separating process, and the hybrid electrochemical reaction mechanism is just the electrochemical reaction mechanism, so that the energy density of the lithium ion capacitor is higher than that of the traditional double electric layer capacitor, and the power density is higher than that of the lithium ion battery.
However, in the production process of the lithium ion capacitor, the positive electrode material is a carbon-based material and does not contain a lithium source, so that the capacities of the positive electrode and the negative electrode are seriously mismatched, and the performance of the lithium ion capacitor is obviously lower than the optimal value. Therefore, in the process of manufacturing the lithium ion capacitor, it is important to develop a pre-lithium technology in order to optimize the performance of the lithium ion capacitor. The conventional lithium ion capacitor preparation process generally comprises three types, namely a lithium ion capacitor preparation process based on positive electrode pre-lithium intercalation, a lithium ion capacitor preparation process based on electrolyte pre-lithium intercalation and a lithium ion capacitor preparation process based on negative electrode pre-lithium intercalation. The preparation process of the lithium ion capacitor based on the negative electrode pre-embedded lithium has the advantage of high lithium supplementing efficiency, but the production process has the defects of poor safety, harsh production conditions and the like due to the adoption of the metal lithium foil or the lithium powder, so that the preparation process is also a commonly used preparation process of the conventional lithium ion capacitor, the yield of the lithium ion capacitor is greatly limited, and the production cost of the lithium ion capacitor is greatly increased. The preparation process of the lithium ion capacitor based on the electrolyte pre-lithium intercalation process has the advantages of good safety and simple process, and no redundant components are introduced into an electrode, but the defect is that the cycle stability and the power characteristic of the lithium ion capacitor are lost, so that a larger bottleneck exists in the product application. For the preparation process of the lithium ion capacitor based on the positive electrode pre-embedded lithium, the lithium-rich metal oxide material is widely used at present, and the preparation process has the advantages of good safety and simple process, but has the defects that insoluble metal oxide by-products are introduced into the positive electrode after lithium is supplemented, the electrochemical reaction process on the surface of the positive electrode is not facilitated, the pre-embedded lithium has high potential (more than 4.5V), the electrolyte is easy to decompose and generate gas, and the cycle characteristic of the lithium ion capacitor device is not facilitated. Compared with the prior three lithium ion capacitor preparation processes based on different modes, the technical route of pre-embedding lithium by introducing a lithium-containing material into the positive electrode is more in line with the industrial development trend. However, the existing lithium ion capacitor preparation process based on lithium-rich metal oxide material pre-intercalation can not meet the application requirements.
From the future industrial application, the preparation of the lithium ion capacitor requires that the pre-lithiation material adopted in the preparation process has good stability, the pre-lithiation process is safe, the residual components of the electrode layer are few, the process for exerting the electrochemical properties of the positive electrode and the negative electrode is not influenced, and the large-scale production is easy.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a lithium ion capacitor based on a novel positive electrode pre-lithium intercalation process, which comprises the following steps: firstly, a mixed solvent with strong polarity and weak polarity in a certain proportion is used as a solvent system of a lithiated organic functional material and a carbon-based positive electrode active material, a low-speed mechanical ball milling method is adopted to fully mix slurry, and the slurry is heated to a certain temperature and then coated in a slit extrusion mode; the cathode electrode coating preparation process adopts a conventional process and a lamination process to prepare the lithium ion capacitor device.
The technical scheme adopted by the invention for solving the technical problems in the prior art is as follows:
the invention relates to a preparation method of a lithium ion capacitor based on a novel positive electrode pre-lithium intercalation process, wherein the lithium ion capacitor comprises a positive electrode and a negative electrode, and the positive electrode comprises a positive electrode current collector, a positive electrode active material coated on the positive electrode current collector and a positive electrode lithiation organic functional material composite material; the negative electrode includes a negative electrode current collector and a negative electrode active material coated on the negative electrode current collector.
The preparation method of the lithium ion capacitor comprises the following steps:
mixing a positive electrode active material, a positive electrode lithiation organic functional material, a positive electrode conductive agent and a positive electrode binder in a mixed solvent consisting of a strong-polarity solvent and a weak-polarity solvent, performing mechanical ball milling treatment, stirring and dispersing to obtain a positive electrode slurry, heating the positive electrode slurry to a certain temperature, coating the positive electrode slurry on the front side and the back side of a positive electrode current collector, and drying, rolling and slicing to obtain a positive electrode piece;
mixing a negative electrode active material, a negative electrode conductive agent and a negative electrode binder in N-methyl pyrrolidone, performing mechanical ball milling, stirring and dispersing to obtain negative electrode slurry, coating the negative electrode slurry on the front and back surfaces of a negative electrode current collector, and drying, rolling and slicing to obtain a negative electrode piece;
and step three, manufacturing the positive pole piece, the diaphragm and the negative pole piece into the battery cell in a multi-layer sandwich type lamination mode, and obtaining the lithium ion capacitor after vacuum drying, electrolyte injection and packaging.
Further, the positive electrode slurry in the first step comprises 50 wt% -70 wt% of a positive electrode active material, 20 wt% -30 wt% of a positive electrode lithiation organic functional material, 5 wt% -10 wt% of a positive electrode conductive agent and 5 wt% -10 wt% of a positive electrode binder.
Further, the positive active material in the first step includes activated carbon and graphene.
Further, the lithiated organic functional material of the positive electrode in the step one comprises one or more of a 3-methyl-1, 2-diphenol lithium-based benzene material, 1-nitro-2, 4, 6-triphenollithium-based benzene, 1-nitro-2, 4-diphenol lithium-based benzene, 1-cyano-2, 4, 6-triphenollithium-based benzene, 1-methyl-2, 4, 6-triphenollithium-based benzene and the like.
Further, the strong polar solvent in the step one is one of ethanol, n-propanol, isopropanol and n-butanol, and the weak polar solvent is one of n-hexane, petroleum ether, cyclohexane, n-heptane and n-octane; the volume ratio of the strong polar solvent to the weak polar solvent is 2: 1-1: 2.
Further, the temperature of the positive electrode slurry heated in the first step is 35-45 ℃.
Further, the ball milling speed of the mechanical ball milling treatment in the first step and the second step is 150-.
Further, the negative electrode slurry in the first step and the second step comprises 80 wt% -90 wt% of a negative electrode active material, 5 wt% -10 wt% of a negative electrode conductive agent and 5 wt% -10 wt% of a negative electrode binder.
Further, the negative active material in the second step is one or more of hard carbon, soft carbon and mesocarbon microbeads.
Further, the electrolyte solvent system in the third step is one or more of EC, DMC, DEC, EMV and VC.
The invention has the advantages and positive effects that:
according to the invention, the anode is prepared by mixing the lithiated organic functional material and the carbon-based capacitor material, and the solvent system in the preparation process of the anode slurry is regulated and controlled, so that the components and the mass percentage of the anode and cathode materials are further regulated and controlled, and the energy storage performance and the safety of the lithium ion capacitor are effectively improved. The patent provides an use lithiation organic functional material as lithium-embedded material, prepare carbon-based capacitance material/lithium-embedded material composite anode in advance, and then prepare the lithium ion capacitor, the lithiation organic functional material that uses has good stability, preparation simple process's advantage, the organic skeleton after utilizing lithiation organic functional material to take off lithium can be dissolved in electrolyte after taking off lithium, make the high porosity of positive pole keep, also ensured good contact and the excellent electric conductivity of electrode between the electrode material simultaneously, accomplish positive pole "no trace" and mend lithium, can realize low cost, high safety and with traditional lithium ion capacitor electrode, device preparation process flow highly compatible's device production.
Description of the drawings:
fig. 1 shows the pre-lithiation design concept of the lithium ion capacitor based on the carbon-based capacitor material/lithiated organic functional material composite electrode of the present invention.
Detailed Description
For a further understanding of the invention, its nature and utility, reference should be made to the following examples, which are set forth in the following detailed description, taken in conjunction with the accompanying drawings, in which:
the preparation method of the cathode material is described in detail by the following 5 examples:
the preparation process of the embodiment 1-15 is as follows:
(1) preparing a device raw material: the components and amounts in examples 1-5 are prepared as in Table 1;
(2) preparing a positive pole piece of the lithium ion capacitor: sequentially dissolving activated carbon, a positive pre-lithiation material, a positive conductive agent and a positive binder in a solvent, stirring for 2-6 hours at a stirring speed of 150-400r/min by using mechanical ball milling equipment to form uniform positive slurry, heating the slurry to a certain temperature, coating the slurry on the front and back surfaces of a positive current collector, controlling the thickness of a positive plate to be 225-250 mu m in the coating process, wherein drying equipment comprises a plurality of drying boxes with different temperatures, the temperatures are respectively set to be 90 ℃, 100 ℃, 110 ℃, 125 ℃, 115 ℃ and 100 ℃, rolling the dried positive plate, controlling the thickness of the rolled positive plate to be 190-210 mu m, and then punching to obtain a positive plate with the thickness of 70mm x 105 mm;
(3) preparing a lithium ion capacitor negative pole piece: sequentially dissolving a negative electrode active material, a negative electrode conductive agent and a negative electrode binder in azomethyl pyrrolidone, stirring for 2-6 hours at a stirring speed of 150-400r/min by using mechanical ball milling equipment to form uniform negative electrode slurry, heating the negative electrode slurry to a certain temperature, coating the positive and negative surfaces of a negative electrode current collector with the negative electrode slurry, controlling the thickness of a negative electrode sheet to be 110-135 mu m in the coating process, wherein the drying equipment consists of a plurality of drying boxes with different temperatures, the temperatures are respectively set to be 110 ℃, 1120 ℃, 125 ℃, 140 ℃, 130 ℃ and 120 ℃, rolling the dried negative electrode sheet, controlling the thickness of the rolled negative electrode sheet to be 85-105 mu m, and then punching to obtain a 67 mm-100 mm negative electrode sheet;
(4) preparing a lithium ion capacitor: separating the positive electrode plate and the negative electrode plate by using a cellulose paper diaphragm, preparing a battery cell in a sandwich type lamination mode, drying the battery cell at 120 ℃ in vacuum for 24h, dissolving electrolyte into an organic solvent to prepare electrolyte, injecting the electrolyte into the battery cell in a glove box, then packaging the battery cell in an aluminum-plastic film, standing for 24h to obtain a lithium ion capacitor, then charging to 4.05V under the condition of 0.05C, and keeping for 12h at constant voltage to realize pre-lithium intercalation of the lithium ion capacitor based on the positive lithiation organic functional material, thereby completing the preparation of the lithium ion capacitor.
Table 1 device fabrication process parameters for examples 1-5
Reference examples 1 and 2 were prepared, respectively, with reference to examples 2 and 4, wherein reference example 1 was a replacement of the organolithiated functional material of example 2 with LiFePO4Reference example 2 is a method in which the organolithiated functional material in example 4 is replaced with Li6CoO4。
TABLE 2 lithium ion capacitor Performance parameters
In conclusion, the invention prepares the positive electrode by mixing the lithiated organic functional material and the carbon-based active material, and simultaneously regulates and controls the solvent system in the preparation process of the positive electrode slurry, so as to further regulate and control the components and the mass percentage of the positive electrode material and the negative electrode material, and effectively improve the energy storage performance and the safety of the lithium ion capacitor.
The embodiments described herein are only some, and not all, embodiments of the invention. Based on the above explanations and guidance, those skilled in the art can make modifications, improvements, substitutions, and the like on the embodiments based on the present invention and examples, but all other embodiments obtained without innovative research fall within the scope of the present invention.
Claims (10)
1. A preparation method of a lithium ion capacitor based on a novel positive electrode pre-lithium intercalation process is characterized by comprising the following steps: the lithium ion capacitor comprises a positive electrode and a negative electrode, wherein the positive electrode comprises a positive electrode current collector, a positive electrode active material coated on the positive electrode current collector and a positive electrode lithiation organic functional material composite material; the negative electrode comprises a negative electrode current collector and a negative electrode active material coated on the negative electrode current collector;
the preparation method comprises the following steps:
mixing a positive electrode active material, a positive electrode lithiation organic functional material, a positive electrode conductive agent and a positive electrode binder in a mixed solvent consisting of a strong-polarity solvent and a weak-polarity solvent, performing mechanical ball milling treatment, stirring and dispersing to obtain a positive electrode slurry, heating the positive electrode slurry to a certain temperature, coating the positive electrode slurry on the front side and the back side of a positive electrode current collector, and drying, rolling and slicing to obtain a positive electrode piece;
mixing a negative electrode active material, a negative electrode conductive agent and a negative electrode binder in N-methyl pyrrolidone, performing mechanical ball milling, stirring and dispersing to obtain negative electrode slurry, coating the negative electrode slurry on the front and back surfaces of a negative electrode current collector, and drying, rolling and slicing to obtain a negative electrode piece;
and step three, manufacturing the positive pole piece, the diaphragm and the negative pole piece into the battery cell in a multi-layer sandwich type lamination mode, and obtaining the lithium ion capacitor after vacuum drying, electrolyte injection and packaging.
2. The preparation method of the lithium ion capacitor based on the novel positive electrode pre-lithium intercalation process as claimed in claim 1, wherein: the positive electrode slurry in the first step comprises 50 wt% -70 wt% of positive electrode active material, 20 wt% -30 wt% of positive electrode lithiation organic functional material, 5 wt% -10 wt% of positive electrode conductive agent and 5 wt% -10 wt% of positive electrode binder.
3. The preparation method of the lithium ion capacitor based on the novel positive electrode pre-lithium intercalation process as claimed in claim 1, wherein: the positive active material in the first step comprises active carbon and graphene.
4. The preparation method of the lithium ion capacitor based on the novel positive electrode pre-lithium intercalation process as claimed in claim 1, wherein: in the first step, the lithium-containing organic functional material of the positive electrode comprises one or more of 3-methyl-1, 2-diphenol lithium-based benzene material, 1-nitro-2, 4, 6-triphenol lithium-based benzene, 1-nitro-2, 4-diphenol lithium-based benzene, 1-cyano-2, 4, 6-triphenol lithium-based benzene, 1-methyl-2, 4, 6-triphenol lithium-based benzene and the like.
5. The preparation method of the lithium ion capacitor based on the novel positive electrode pre-lithium intercalation process as claimed in claim 1, wherein: the strong polar solvent in the first step is one of ethanol, n-propanol, isopropanol and n-butanol, and the weak polar solvent is one of n-hexane, petroleum ether, cyclohexane, n-heptane and n-octane; the volume ratio of the strong polar solvent to the weak polar solvent is 2: 1-1: 2.
6. The preparation method of the lithium ion capacitor based on the novel positive electrode pre-lithium intercalation process as claimed in claim 1, wherein: the temperature of the positive electrode slurry heated in the first step is 35-45 ℃.
7. The preparation method of the lithium ion capacitor based on the novel positive electrode pre-lithium intercalation process as claimed in claim 1, wherein: the ball milling speed of the mechanical ball milling treatment in the first step and the second step is 150-.
8. The preparation method of the lithium ion capacitor based on the novel positive electrode pre-lithium intercalation process as claimed in claim 1, wherein: the cathode slurry in the first step and the second step comprises 80-90 wt% of cathode active material, 5-10 wt% of cathode conductive agent and 5-10 wt% of cathode binder.
9. The preparation method of the lithium ion capacitor based on the novel positive electrode pre-lithium intercalation process as claimed in claim 1, wherein: and in the second step, the negative active material is one or more of hard carbon, soft carbon and mesocarbon microbeads.
10. The preparation method of the lithium ion capacitor based on the novel positive electrode pre-lithium intercalation process as claimed in claim 1, wherein: the electrolyte solvent system in the third step is one or more of EC, DMC, DEC, EMC and VC.
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