CN112735847A - Lithium ion capacitor negative electrode plate with Cu transition layer and preparation method and application thereof - Google Patents
Lithium ion capacitor negative electrode plate with Cu transition layer and preparation method and application thereof Download PDFInfo
- Publication number
- CN112735847A CN112735847A CN202011545205.XA CN202011545205A CN112735847A CN 112735847 A CN112735847 A CN 112735847A CN 202011545205 A CN202011545205 A CN 202011545205A CN 112735847 A CN112735847 A CN 112735847A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ion capacitor
- current collector
- negative electrode
- transition layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 136
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 131
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 230000007704 transition Effects 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 54
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 53
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims description 64
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 28
- 239000011888 foil Substances 0.000 claims description 28
- 238000005470 impregnation Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 238000007789 sealing Methods 0.000 claims description 19
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000004544 sputter deposition Methods 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 56
- 238000012360 testing method Methods 0.000 description 17
- 238000010586 diagram Methods 0.000 description 15
- 239000002002 slurry Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- 238000005096 rolling process Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- -1 lithium titanate Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- 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
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- 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
- H01G11/66—Current collectors
- H01G11/68—Current collectors 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
- H01G11/84—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
- H01G11/84—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
Abstract
The invention provides a lithium ion capacitor negative electrode plate with a Cu transition layer and a preparation method and application thereof, belonging to the field of capacitors. The invention modifies the current collector of the negative pole piece, and forms the Cu transition layer on the two sides of the current collector respectively, so that the contact internal resistance of the lithium titanate coating and the current collector is greatly reduced, thereby realizing the reduction of the whole internal resistance of the lithium ion capacitor, and the lithium ion capacitor can still keep lower contact internal resistance and better electrical property to continue working after being recycled, greatly prolonging the service life of the lithium ion capacitor product, and compared with the Ag transition layer, the invention adopts the Cu transition layer, thereby having lower cost and being more beneficial to batch production.
Description
Technical Field
The invention belongs to the field of capacitors, and particularly relates to a lithium ion capacitor negative electrode plate with a Cu transition layer, and a preparation method and application thereof.
Background
The hybrid lithium ion super capacitor is a new and expensive capacitor family, compared with the super capacitor, the monomer voltage of the hybrid lithium ion super capacitor can reach 3.8V, the super capacitor can only reach 2.7-3.0V, the unique performance of the hybrid lithium ion super capacitor is favored by the industry, the hybrid lithium ion super capacitor is a compact energy source with power density and energy density between the super capacitor and a lithium ion battery, and the hybrid lithium ion super capacitor is expected to become a next generation energy storage device with high performance, safety and superiority such as large capacity, rapid large-current charge and discharge, long cycle life and the like by virtue of an electric double layer structure. In terms of the magnitude of capacitance, the capacitance provided by the hybrid lithium ion super capacitor can reach over farad level, the capacitance leap from the micro farad level of the traditional capacitor to the primary quality of the farad level is realized, and the capacitor is a revolutionary significant innovation with milestone significance in the energy technology history.
With the development of the hybrid lithium ion super capacitor, it can provide good performance indexes such as high voltage, high power and high reliability required by various applications, and thus has wide applications in many fields such as power systems, electric vehicles, portable devices, even military affairs and the like. Nowadays, hybrid lithium ion super capacitors have been widely used in the fields of automotive electronics, intelligent industrial control, smart home, 5G base stations, and even in the field of military electromagnetic guns. Aiming at the application in the field, the hybrid lithium ion super capacitor is in the role of a standby power supply or a starting power supply, and the hybrid lithium ion super capacitor is required to have longer service life, larger discharge current and performance under an extreme temperature environment. Aiming at the requirements, a key index technology, namely lower internal resistance, is provided for the hybrid lithium ion super capacitor. The internal resistance directly affects the service life of the hybrid lithium ion super capacitor, the maximum current carried by the hybrid lithium ion super capacitor and the like. The key core technology of the existing domestic preparation technology of the hybrid lithium ion super capacitor is the preparation of a pole piece, which is mainly realized by wet coating, and the technical level of the preparation of the pole piece directly determines whether the internal resistance of the hybrid lithium ion super capacitor is low enough.
The hybrid lithium ion super capacitor is essentially different from the super capacitor in that one half of the electrode is a lithium battery pole piece material, and the other half of the electrode is a carbon-based super-capacity material, so that the internal resistance increasing effect is more obvious than that of the super capacitor. The positive electrode of the hybrid super capacitor is made of active carbon material, the negative electrode is lithium titanate, belonging to a cubic spinel structure (Fd3m), and the hybrid super capacitor is a composite oxide consisting of transition metal titanium and low-potential metal lithium, belonging to AB2X4Series, structure and spinel LiMn2O4Similarly, Fd3m is the space lattice group, and the unit cell parameter a is 0.836nm as shown in FIG. 1. During the operation of the hybrid lithium ion supercapacitor, only 1mol of Li can be inserted into each mole of lithium titanate, oxygen in the lithium titanate occupies a 32e position, titanium occupies a 16c position of 5/6, and the rest part of the lithium ion supercapacitor is occupied by lithium ions. When discharged, the lithium originally located at the 8a position of the tetrahedron and the intercalated lithium migrate to the adjacent 16c position. Therefore, unlike a super capacitor, a hybrid lithium ion super capacitor is composed of a capacitor and a lithium battery, and has high power density and energy density by taking the advantages of both lithium battery and super capacitor.
As described above, since the negative electrode material is lithium titanate, during charging and discharging, electrochemical reaction occurs to insert and remove lithium, while the positive electrode only undergoes physical reaction, i.e. simple physical electrostatic adsorption, as shown in fig. 2. Therefore, during the use process of the hybrid lithium ion supercapacitor, the negative electrode undergoes electrochemical reaction for a long time, so that the crystal lattice changes, the internal resistance is increased, and the capacity is attenuated. At present, the initial internal resistance level and the internal resistance level after recycling of the hybrid lithium ion super capacitor are multiplied (the rising rate reaches 250%) due to the collapse of the lithium titanate crystal lattice of the negative electrode, and the service life and the electrical property of the hybrid lithium ion super capacitor are greatly influenced.
The traditional method for improving the internal resistance generally adopts formula adjustment and rolling shrinkage adjustment. If the formula is adjusted, the capacity performance is influenced, so that the stored energy is less; if the rolling shrinkage is adjusted, the production efficiency is affected because rolling is performed a plurality of times (3 times or more) to reduce the internal resistance. Moreover, the above method does not improve the problem of a drastic increase in internal resistance after recycling.
Therefore, how to make the hybrid lithium ion supercapacitor have lower initial internal resistance and still maintain lower internal resistance and better electrical property after being recycled becomes a difficult problem to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a lithium ion capacitor negative electrode plate with a Cu transition layer, and a preparation method and application thereof, so that a hybrid lithium ion capacitor has lower initial internal resistance, and can still keep lower internal resistance and better electrical property to continue working after being recycled.
In order to achieve the above object, in a first aspect, the present invention provides a lithium ion capacitor negative electrode plate with a Cu transition layer, including a negative electrode current collector, both sides of the negative electrode current collector are respectively covered with a Cu transition layer formed by magnetron sputtering, and surfaces of the Cu transition layers facing away from the negative electrode current collector are respectively covered with a lithium titanate coating.
Preferably, the thicknesses of the Cu transition layers are respectively 100-200 nm.
Preferably, the thickness of the negative pole piece is 140-180 μm.
In a second aspect, the invention provides a preparation method of the lithium ion capacitor negative electrode plate, which comprises the following steps: and respectively carrying out magnetron sputtering on two sides of the negative current collector to form Cu transition layers, and then respectively coating lithium titanate coatings to obtain the negative pole piece of the lithium ion capacitor.
Preferably, the process conditions of the magnetron sputtering are as follows: bombarding Cu target with Ar gas, the back vacuum is 6.0-7.0 x 10-4Pa, cavity pressure of 0.4-0.6Pa, Ar gas flow of 20-40sccm, and targetThe base distance is 3-7cm, the sputtering power is 60-70W, and the sputtering time is 5 min.
In a third aspect, the invention provides a lithium ion capacitor comprising the lithium ion capacitor negative electrode plate.
Preferably, the positive electrode plate used in the lithium ion capacitor comprises a positive electrode current collector, and both surfaces of the positive electrode current collector are respectively covered with carbon coatings.
Preferably, the thickness of the positive pole piece is 200-240 μm.
Preferably, the negative electrode current collector and the positive electrode current collector are respectively an aluminum foil current collector or a copper foil current collector.
In a fourth aspect, the invention provides a preparation method of the above lithium ion capacitor, which includes the following steps: after winding the positive and negative pole pieces of the lithium ion capacitor, respectively leading needles on the inner electrode and the outer electrode to form a battery cell, baking, and then carrying out full-automatic impregnation sealing and assembling under the drying condition that the dew point temperature is-55 ℃ to-80 ℃ to obtain the lithium ion capacitor.
To achieve full automation of the impregnation sealing and assembly, it is necessary to perform the impregnation sealing in a drying room (such as a drying workshop) instead of a glove box.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention modifies the current collector of the negative pole piece, and forms a thin Cu transition layer on the two sides of the current collector respectively, so that the contact internal resistance of the lithium titanate coating and the current collector of the negative pole piece is greatly reduced, and the reduction of the integral internal resistance of the lithium ion capacitor is realized.
(2) In the working process of the hybrid lithium ion supercapacitor applying the negative pole piece, the Cu transition layer and the lithium titanate coating can generate electrochemical reaction, and Cu ions can guide Li ions in the electrolyte to be embedded into the crystal lattice of the lithium titanate coating in an accelerated manner, so that the damage of the lithium titanate crystal lattice in the embedding process is reduced, and the effect of stabilizing the crystal lattice framework is achieved; in the process of lithium removal, the Cu transition layer plays a role in buffering, and the stability of a lithium titanate lattice framework is also protected. Therefore, the existence of the Cu transition layer can ensure that the crystal structure of the lithium titanate coating is very stable, the volume is hardly changed, and the increase of internal resistance and the capacity attenuation are effectively avoided, so that the lithium ion capacitor can still keep lower contact internal resistance and better electrical property to continue working after being recycled (such as being recycled for five thousand times), and the service life of the lithium ion capacitor product is greatly prolonged.
(3) Although the effect of using the Ag transition layer is better compared with the Cu transition layer, the Ag transition layer has higher cost and is not beneficial to batch production, and the cost can be greatly reduced by adopting the Cu transition layer.
(4) When the lithium ion capacitor is prepared, full-automatic impregnation sealing and assembling of the positive and negative pole pieces in the drying room can be selected, and compared with the impregnation sealing and assembling in the traditional glove box, the efficiency is improved by more than 10 times.
Description of the figures
FIG. 1 is a schematic diagram of a lithium titanate crystal structure;
FIG. 2 is a schematic diagram of the structure and operation of the positive and negative electrodes of the hybrid lithium-ion supercapacitor;
FIG. 3 is a schematic structural diagram of the lithium ion capacitor electrode sheet obtained in examples 1 to 3;
FIG. 4 is a performance effect diagram of the lithium ion capacitor obtained in example 1, (a) a charge-discharge curve, (b) a cycle performance curve, (c) a comparison diagram of the initial internal resistance and the internal resistance after the cycle, (d) a comparison diagram of the efficiency of the full-automatic impregnation assembly in the drying room and the impregnation assembly in the conventional glove box;
FIG. 5 is a performance effect diagram of the lithium ion capacitor obtained in example 2, (a) a charge-discharge curve diagram, (b) a cycle performance curve diagram, (c) a comparison diagram of initial internal resistance and internal resistance after cycle, (d) an efficiency comparison diagram of full-automatic impregnation assembly in a drying room and impregnation assembly in a conventional glove box;
FIG. 6 is a performance effect diagram of the lithium ion capacitor obtained in example 3, (a) a charge-discharge curve, (b) a cycle performance curve, (c) a comparison graph of the initial internal resistance and the internal resistance after the cycle, (d) a comparison graph of the efficiency of the full-automatic impregnation assembly in the drying room and the impregnation assembly in the conventional glove box;
FIG. 7 is a graph showing the performance effect of the lithium ion capacitor obtained in comparative example 1, (a) a cycle performance graph, and (b) a comparison of the initial internal resistance and the internal resistance after the cycle;
FIG. 8 is a performance effect graph of the lithium ion capacitor obtained in comparative example 2, wherein (a) a cycle performance graph and (b) an initial internal resistance and a comparison graph of internal resistances after cycle are shown.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
In order to solve the problems of larger initial internal resistance of a hybrid lithium ion capacitor, severe increase of internal resistance and reduction of electrical property after recycling, the invention provides a lithium ion capacitor negative electrode plate with a Cu transition layer. The current collector of the negative pole piece is modified, the Cu transition layers are formed on the two surfaces of the current collector respectively, so that the contact internal resistance of the lithium titanate coating and the current collector is greatly reduced, the reduction of the integral internal resistance of the hybrid lithium ion capacitor is realized, in the working process of the hybrid lithium ion capacitor, the Cu transition layers and the lithium titanate coating can generate electrochemical reaction, Cu ions can guide Li ions in electrolyte to be embedded into crystal lattices of the lithium titanate coating in an accelerated manner, the damage of the embedding process to the lithium titanate crystal lattices is reduced, and the effect of stabilizing a crystal lattice framework is achieved; in the process of lithium removal, the Cu transition layer plays a role in buffering and also protects the stability of a lithium titanate lattice frame, so that the existence of the Cu transition layer can ensure that the crystal structure of a lithium titanate coating is very stable, the volume is hardly changed, the increase of internal resistance and the capacity attenuation are effectively avoided, and therefore, the low contact internal resistance and the good electrical property can be kept to work continuously after the lithium titanate coating is recycled (such as being recycled for five thousand times), and the service life of a lithium ion capacitor product is greatly prolonged.
The thickness of the Cu transition layer is preferably 100-200 nm. In some embodiments, the Cu transition layer has a thickness of 100nm, 120nm, 150nm, 180nm, or 200 nm. The thicknesses of the two Cu transition layers can be the same or different.
The thickness of the negative pole piece is preferably 140-180 mu m. In some embodiments, the negative electrode tab has a thickness of 140nm, 150nm, 160nm, 170nm, or 180 nm. The thicknesses of the two lithium titanate coatings on the negative electrode plate can be the same or different, and are usually selected to be the same.
Preferably, the negative electrode current collector is an aluminum foil current collector or a copper foil current collector. Wherein, the aluminum foil current collector can be selected from a corrosion aluminum foil current collector, a porous aluminum foil current collector and the like; the copper foil current collector may be selected from a corrosion copper foil current collector, a porous copper foil current collector, and the like.
Preferably, the preparation method of the negative electrode plate of the lithium ion capacitor comprises the following steps: and performing magnetron sputtering on two sides of the negative current collector to form Cu transition layers, and then respectively coating lithium titanate coatings to obtain the negative pole piece of the lithium ion capacitor. In some embodiments, rolling is performed after applying the lithium titanate coating layer. Optionally, Ar gas is adopted to bombard the Cu target in the magnetron sputtering. In some embodiments, the process conditions for magnetron sputtering are: the back vacuum is 6.0-7.0 × 10-4Pa, the cavity pressure is 0.4-0.6Pa, the Ar gas flow is 20-40sccm, the target base distance is 3-7cm, the sputtering power is 60-70W, and the sputtering time is 5 min.
Any lithium titanate slurry capable of preparing the cathode of the lithium ion capacitor can be selected to prepare the lithium titanate coating.
The lithium ion capacitor negative pole piece can be used for preparing a lithium ion capacitor. When used to make a hybrid lithium ion capacitor, the positive electrode sheet is typically a carbon-based material. Preferably, the positive electrode plate comprises a positive electrode current collector, and the two surfaces of the positive electrode current collector are respectively coated with carbon coatings. In some embodiments, the carbon coating is applied followed by rolling.
Preferably, the thickness of the positive pole piece is 200-240 μm. In some embodiments, the positive pole piece has a thickness of 200nm, 210nm, 220nm, 230nm, or 240 nm. The thicknesses of the two carbon coatings on the positive pole piece can be the same or different, and are usually selected to be the same.
Any carbon slurry capable of preparing the positive electrode of the lithium ion capacitor can be selected to prepare the carbon coating.
Preferably, the positive electrode current collector is an aluminum foil current collector or a copper foil current collector. Wherein, the aluminum foil current collector can be selected from a corrosion aluminum foil current collector, a porous aluminum foil current collector and the like; the copper foil current collector may be selected from a corrosion copper foil current collector, a porous copper foil current collector, and the like.
The method of making a lithium ion capacitor generally comprises the steps of: and winding the positive and negative pole pieces of the lithium ion capacitor to increase the opposite area, leading pins on the inner electrode and the outer electrode respectively to form a battery cell, baking, and then carrying out impregnation sealing and assembly to obtain the lithium ion capacitor. In some embodiments, the impregnation sealing and the assembly are performed under dry conditions with a dew point temperature of 55 ℃ to-80 ℃. In order to improve the production efficiency, it is preferable to automate the impregnation sealing and the assembly; in order to realize the large-scale automation of the impregnation sealing and the assembly, the impregnation sealing and the assembly treatment are preferably carried out in a drying room, such as a drying workshop, compared with the traditional glove box, the drying room is more beneficial to realizing the large-scale automation operation, and the efficiency can be improved by more than 10 times.
In some embodiments, the positive and negative electrode plates of the lithium ion capacitor are cut to desired specifications before being wound.
Example 1
The embodiment provides a lithium ion capacitor pole piece, and a schematic structural diagram of the lithium ion capacitor pole piece is shown in fig. 3. The negative pole piece comprises a negative pole current collector, two surfaces of the negative pole current collector are covered with Cu transition layers, and the surfaces of the Cu transition layers, which are far away from the negative pole current collector, are respectively covered with a lithium titanate coating; the positive pole piece comprises a positive current collector, and both sides of the positive current collector are covered with carbon coatings. The positive and negative current collectors are all corrosion aluminum foil current collectors.
The preparation method of the positive and negative pole pieces comprises the following steps:
negative pole piece: respectively forming a Cu transition layer on the two sides of the aluminum foil current collector by magnetron sputtering, wherein the process conditions of the magnetron sputtering are as follows: the diameter of the Cu target is 60mm, the thickness is 3mm, and the purity is 5N; bombarding the Cu target with Ar gas, the back vacuum is 6.0 multiplied by 10-4Pa, cavity pressure of 0.4Pa, Ar gas flow of 20sccm, no heating, target base distance of 3cm, and sputtering power of60W, sputtering for 5min to obtain a Cu transition layer with the thickness of 100 nm; and coating the composite lithium titanate slurry on two sides of the aluminum foil current collector with the Cu transition layer, baking to prepare a negative electrode plate, and rolling until the thickness of the negative electrode plate is 140 micrometers.
Positive pole piece: coating the carbon slurry on an aluminum foil current collector without a transition layer, baking to prepare a positive pole piece, and then rolling until the thickness of the positive pole piece is 200 mu m.
The lithium ion capacitor pole piece of the embodiment is used for preparing a lithium ion capacitor, and specifically comprises the following steps: cutting the positive and negative electrode plates of the lithium ion capacitor into thin strip electrode plates with the width of 7mm by using a cutting machine, calculating, taking the effective length of 53mm as the negative electrode and the effective length of 62mm as the positive electrode, increasing the opposite area of the positive electrode in a winding mode, leading pins on the inner electrode and the outer electrode to form a battery cell, baking, and then carrying out full-automatic impregnation sealing and assembling under the drying condition that the dew point temperature is-55 ℃ to obtain the lithium ion capacitor with the voltage capacity of 3.8V 2F. And performing subsequent charge and discharge tests, cycle performance tests, comparison of initial internal resistance and internal resistance after circulation and comparison of impregnation sealing and assembly efficiency in the traditional glove box on the obtained lithium ion capacitor, and setting 5 groups of parallel tests, wherein the test results are shown in figure 4.
As can be seen from the data in fig. 4, the obtained lithium ion capacitor has good charge and discharge performance, and the curve symmetry between the charge process and the discharge process is good; since the discharge plateau of lithium titanate is 1.5V, the charge-discharge curve starts from 1.5V up to 3.8V; the initial internal resistance is 549-553 mOmega, after 5000 times of circulation, the capacity retention rate is up to more than 65%, the internal resistance is only about 785-790 mOmega, and the rising rate is only 43%. And, be worth noting that, adopt the full-automatic mode of soaking equipment in dry house to soak and carry out monomer production, soak the equipment contrast in traditional glove box, efficiency obtains promotion more than 10 times, is favorable to mass production very much, can promote efficiency greatly.
Example 2
The embodiment provides a lithium ion capacitor pole piece, and a schematic structural diagram of the lithium ion capacitor pole piece is shown in fig. 3. The negative pole piece comprises a negative pole current collector, two surfaces of the negative pole current collector are covered with Cu transition layers, and the surfaces of the Cu transition layers, which are far away from the negative pole current collector, are respectively covered with a lithium titanate coating; the positive pole piece comprises a positive current collector, and both sides of the positive current collector are covered with carbon coatings. The positive and negative current collectors are all corrosion aluminum foil current collectors.
The preparation method of the lithium ion capacitor pole piece comprises the following steps:
negative pole piece: respectively forming a Cu transition layer on the two sides of the aluminum foil current collector by magnetron sputtering, wherein the process conditions of the magnetron sputtering are as follows: the diameter of the Cu target is 60mm, the thickness is 3mm, and the purity is 5N; bombarding the Cu target with Ar gas, the back vacuum is 6.5 multiplied by 10-4Pa, the cavity pressure is 0.5Pa, the Ar gas flow is 30sccm, heating is not carried out, the target base distance is 5cm, the sputtering power is 65W, and the sputtering time is 5min, so that a Cu transition layer with the thickness of 150nm is obtained; and coating the composite lithium titanate slurry on two sides of the aluminum foil current collector with the Cu transition layer, baking to prepare a negative electrode plate, and rolling until the thickness of the negative electrode plate is 160 mu m.
Positive pole piece: and coating the carbon slurry on an aluminum foil current collector without a transition layer, baking to prepare a positive pole piece, and rolling until the thickness of the positive pole piece is 220 mu m.
The lithium ion capacitor pole piece of the embodiment is used for preparing a lithium ion capacitor, and specifically comprises the following steps: cutting the positive and negative electrode plates of the lithium ion capacitor into thin electrode plates with the width of 18mm by using a cutting machine, calculating to obtain a negative electrode with the effective length of 35mm and a positive electrode with the effective length of 39mm, increasing the opposite area of the positive electrode in a winding manner, leading pins on the inner electrode and the outer electrode to form a battery cell, baking, and then carrying out full-automatic impregnation sealing and assembly under the drying condition that the dew point temperature is-67.5 ℃ to obtain the lithium ion capacitor with the voltage capacity of 3.8V 50F. And performing subsequent charge and discharge tests, cycle performance tests, comparison of initial internal resistance and internal resistance after circulation and comparison of impregnation sealing and assembly efficiency in the traditional glove box on the obtained lithium ion capacitor, and setting 5 groups of parallel tests, wherein the test results are shown in figure 5.
As can be seen from the data in fig. 5, the obtained lithium ion capacitor has good charge and discharge performance, and the curve symmetry between the charge process and the discharge process is good; since the discharge plateau of lithium titanate is 1.5V, the charge-discharge curve starts from 1.5V up to 3.8V; the initial internal resistance is 140-145m omega, after 5000 times of circulation, the capacity retention rate is up to more than 65%, the internal resistance is only about 207-214m omega, and the rising rate is only 48%. And, be worth noting that, adopt the full-automatic mode of soaking equipment in dry house to soak and carry out monomer production, soak the equipment contrast in traditional glove box, efficiency obtains promotion more than 10 times, is favorable to mass production very much, can promote efficiency greatly.
Example 3
The embodiment provides a lithium ion capacitor pole piece, and a schematic structural diagram of the lithium ion capacitor pole piece is shown in fig. 3. The negative pole piece comprises a current collector, two surfaces of the negative pole current collector are covered with Cu transition layers, and the surfaces of the Cu transition layers, which are far away from the negative pole current collector, are respectively covered with a lithium titanate coating; the positive pole piece comprises a positive current collector, and both sides of the positive current collector are covered with carbon coatings. The positive and negative current collectors are all corrosion aluminum foil current collectors.
The preparation method of the lithium ion capacitor pole piece comprises the following steps:
negative pole piece: respectively forming a Cu transition layer on the two sides of the aluminum foil current collector by magnetron sputtering, wherein the process conditions of the magnetron sputtering are as follows: the diameter of the Cu target is 60mm, the thickness is 3mm, and the purity is 5N; bombarding the Cu target with Ar gas, and keeping the back vacuum at 7.0 × 10-4Pa, the cavity pressure is 0.6Pa, the Ar gas flow is 40sccm, heating is not carried out, the target base distance is 7cm, the sputtering power is 70W, and the sputtering time is 5min, so that a Cu transition layer with the thickness of 200nm is obtained; and coating the composite lithium titanate slurry on two sides of the aluminum foil current collector with the Cu transition layer, baking to prepare a negative electrode plate, and rolling until the thickness of the negative electrode plate is 180 mu m.
Positive pole piece: and coating the carbon slurry on an aluminum foil current collector without a transition layer, baking to prepare a positive pole piece, and rolling until the thickness of the positive pole piece is 240 microns.
The lithium ion capacitor pole piece of the embodiment is used for preparing a lithium ion capacitor, and specifically comprises the following steps: cutting the positive and negative pole pieces of the lithium ion capacitor into thin pole pieces with the width of 30mm by using a cutting machine, calculating to obtain a negative pole with the effective length of 30mm and a positive pole with the effective length of 34mm, increasing the opposite area of the positive pole in a winding mode, leading pins on an inner electrode and an outer electrode to form a battery cell, baking, and then carrying out full-automatic impregnation sealing and assembling under the drying condition that the dew point temperature is-80 ℃ to obtain the lithium ion capacitor with the voltage capacity of 3.8V 100F. And performing subsequent charge and discharge tests, cycle performance tests, comparison of initial internal resistance and internal resistance after circulation and comparison of impregnation sealing and assembly efficiency in a traditional glove box on the obtained lithium ion capacitor, and setting 5 groups of parallel tests, wherein the test results are shown in figure 6.
As can be seen from the data in fig. 6, the obtained lithium ion capacitor has good charge and discharge performance, and the curve symmetry between the charge process and the discharge process is good; since the discharge plateau of lithium titanate is 1.5V, the charge-discharge curve starts from 1.5V up to 3.8V; the initial internal resistance is 50-52m omega, after 5000 times of circulation, the capacity retention rate is up to more than 60%, the internal resistance is only about 76-79m omega, and the rising rate is only 52%. And, be worth noting that, adopt the full-automatic mode of soaking equipment in dry house to soak and carry out monomer production, soak the equipment contrast in traditional glove box, efficiency obtains promotion more than 10 times, is favorable to mass production very much, can promote efficiency greatly.
Comparative example 1
This comparative example provides a lithium ion capacitor electrode sheet, which is the same as example 1 except that the negative electrode sheet does not contain a transition layer. The positive and negative current collectors are all corrosion aluminum foil current collectors.
The preparation method of the lithium ion capacitor pole piece comprises the following steps:
(1) coating the composite lithium titanate slurry on two sides of an aluminum foil current collector without a transition layer, and baking to prepare a negative electrode plate; coating the carbon slurry on the two sides of the aluminum foil current collector without the transition layer, baking to prepare a positive pole piece, namely a positive pole piece and a negative pole piece;
(2) and (3) rolling the obtained positive and negative pole pieces by a roller press until the thickness of the positive pole piece is 200 mu m and the thickness of the negative pole piece is 140 mu m to obtain the lithium ion capacitor pole piece.
The lithium ion capacitor pole piece of the comparative example is used for preparing a lithium ion capacitor, and specifically comprises the following steps: cutting the lithium ion capacitor pole piece into thin pole pieces with the width of 7mm by using a splitting machine, calculating to obtain a negative pole with the effective length of 53mm and a positive pole with the effective length of 62mm, increasing the opposite area of the positive pole in a winding mode, leading pins on an inner electrode and an outer electrode to form a battery cell, baking, and then carrying out full-automatic impregnation sealing and assembling under the drying condition that the dew point temperature is-55 ℃ to obtain the lithium ion capacitor with the voltage capacity of 3.8V 2F. And performing subsequent charge and discharge tests, cycle performance tests and comparison of the initial internal resistance and the internal resistance after the cycle on the obtained lithium ion capacitor, and setting 5 groups of parallel tests, wherein the test results are shown in figure 7.
From the test results, it can be determined that, if a lithium titanate negative electrode without a transition layer and a carbon positive electrode plate are used to form the lithium ion supercapacitor, the initial internal resistance is higher and is as high as 800m Ω, and the internal resistance after circulation is changed more and is as high as 2450m Ω, which is more than 3 times of the initial internal resistance. The capacity retention rate is also low, mainly because of the influence on the internal structure after the internal resistance is increased. After 5000 cycles, the capacity was only 0.6F.
Comparative example 2
The comparative example provides a lithium ion capacitor electrode sheet, wherein the negative electrode sheet is the same as that in example 1; the positive pole piece comprises a positive pole current collector, the two surfaces of the positive pole current collector are covered with Cu transition layers, and the surfaces of the Cu transition layers, which are far away from the positive pole current collector, are respectively covered with carbon coatings. The positive and negative current collectors are all corrosion aluminum foil current collectors.
The preparation method of the lithium ion capacitor pole piece comprises the following steps:
(1) respectively carrying out magnetron sputtering on a Cu transition layer on two side surfaces of an aluminum foil current collector, wherein the magnetron sputtering process conditions are as follows: the diameter of the Cu target is 60mm, the thickness is 3mm, and the purity is 5N; bombarding the Cu target with Ar gas, the back vacuum is 6.0 multiplied by 10-4Pa, the cavity pressure is 0.4Pa, the Ar gas flow is 20sccm, heating is not carried out, the target base distance is 3cm, the sputtering power is 60W, and the sputtering time is 5min, so that Cu transition layers with the thicknesses of 100nm are obtained;
(2) coating the composite lithium titanate slurry on the current collector with the two sides containing the Cu transition layer, and baking to prepare a negative pole piece; coating the carbon slurry on the current collector with the Cu transition layers on the two sides, and baking to prepare a positive pole piece and obtain a positive pole piece and a negative pole piece;
(3) and (3) rolling the obtained positive and negative pole pieces by a roller press until the thickness of the positive pole piece is 200 mu m and the thickness of the negative pole piece is 140 mu m to obtain the lithium ion capacitor pole piece.
The lithium ion capacitor pole piece of the comparative example is used for preparing a lithium ion capacitor, and specifically comprises the following steps: cutting the positive and negative electrode plates of the lithium ion capacitor into thin strip electrode plates with the width of 7mm by using a cutting machine, calculating, taking the effective length of 53mm as the negative electrode and the effective length of 62mm as the positive electrode, increasing the opposite area of the positive electrode in a winding mode, leading pins on the inner electrode and the outer electrode to form a battery cell, baking, and then carrying out full-automatic impregnation sealing and assembling under the drying condition that the dew point temperature is-55 ℃ to obtain the lithium ion capacitor with the voltage capacity of 3.8V 2F. And performing subsequent charge and discharge tests, cycle performance tests and comparison of the initial internal resistance and the internal resistance after the cycle on the obtained lithium ion capacitor, setting 5 groups of parallel tests, and obtaining a test result shown in figure 8.
From the test results, it can be determined that the initial internal resistance is 540-. After 5000 times of circulation, the capacity retention rate is low and is only 0.7F, because the positive pole piece is provided with the Cu transition layer, the leakage current is large, the negative lithium titanate crystal structure is influenced, and the crystal collapse is caused. After 5000 cycles, the internal resistance of the lithium titanate reaches 2750m omega, which is also caused by the damage of leakage current to the structure of the lithium titanate of the negative electrode. Therefore, unlike the super capacitor, the positive electrode of the hybrid lithium ion super capacitor should not have a Cu transition layer, so as to avoid the damage of the negative electrode structure.
The composite lithium titanate slurry, the carbon slurry and the aluminum foil current collector adopted in each of the above examples and comparative examples are the same.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The lithium ion capacitor negative electrode plate with the Cu transition layer is characterized by comprising a negative electrode current collector, wherein the two surfaces of the negative electrode current collector are respectively covered with the Cu transition layer formed by magnetron sputtering, and the surfaces of the Cu transition layers, which are far away from the negative electrode current collector, are respectively covered with a lithium titanate coating.
2. The negative electrode plate of the lithium ion capacitor as claimed in claim 1, wherein the thickness of the Cu transition layer is 100-200 nm.
3. The lithium ion capacitor negative electrode tab of claim 1, wherein the thickness of the negative electrode tab is 140-180 μm.
4. The preparation method of the negative electrode plate of the lithium ion capacitor as claimed in any one of claims 1 to 3, wherein the preparation method comprises the following steps: and respectively carrying out magnetron sputtering on two sides of the negative current collector to form Cu transition layers, and then respectively coating lithium titanate coatings to obtain the negative pole piece of the lithium ion capacitor.
5. The preparation method according to claim 4, wherein the magnetron sputtering process conditions are as follows: bombarding Cu target with Ar gas, the back vacuum is 6.0-7.0 x 10-4Pa, the cavity pressure is 0.4-0.6Pa, the Ar gas flow is 20-40sccm, the target base distance is 3-7cm, the sputtering power is 60-70W, and the sputtering time is 5 min.
6. A lithium ion capacitor, characterized by comprising the lithium ion capacitor negative electrode sheet according to any one of claims 1 to 3.
7. The lithium ion capacitor according to claim 6, wherein the positive electrode sheet adopted by the lithium ion capacitor comprises a positive electrode current collector, and the two surfaces of the positive electrode current collector are respectively covered with carbon coatings.
8. The lithium ion capacitor of claim 7, wherein the thickness of the positive electrode tab is 200-240 μm.
9. The lithium ion capacitor of claim 7, wherein the negative electrode current collector and the positive electrode current collector are respectively aluminum foil current collectors or copper foil current collectors.
10. The method for preparing a lithium ion capacitor according to any one of claims 6 to 9, comprising the steps of: after winding the positive and negative electrode plates of the lithium ion capacitor, respectively leading needles on the inner electrode and the outer electrode to form a battery cell, baking, and then carrying out full-automatic impregnation sealing and assembling under the drying condition that the dew point temperature is-55 ℃ to-80 ℃ to obtain the lithium ion capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011545205.XA CN112735847A (en) | 2020-12-23 | 2020-12-23 | Lithium ion capacitor negative electrode plate with Cu transition layer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011545205.XA CN112735847A (en) | 2020-12-23 | 2020-12-23 | Lithium ion capacitor negative electrode plate with Cu transition layer and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112735847A true CN112735847A (en) | 2021-04-30 |
Family
ID=75605030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011545205.XA Pending CN112735847A (en) | 2020-12-23 | 2020-12-23 | Lithium ion capacitor negative electrode plate with Cu transition layer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112735847A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100127983A (en) * | 2009-05-27 | 2010-12-07 | 양점식 | Negative current collector for secondary battery with reduced weight |
| CN105186004A (en) * | 2015-10-09 | 2015-12-23 | 南阳师范学院 | Copper current collector for lithium-ion battery anodes as well as preparation method and application of copper current collector |
| CN205487766U (en) * | 2016-03-07 | 2016-08-17 | 辽宁博艾格电子科技有限公司 | Lithium ion capacitor |
| CN108666579A (en) * | 2017-03-28 | 2018-10-16 | 通用汽车环球科技运作有限责任公司 | The electrode of lithium cell of copper foil current collector is modified using surface |
| CN110828195A (en) * | 2019-12-12 | 2020-02-21 | 广东风华高新科技股份有限公司 | Super capacitor pole piece with Cu transition layer and preparation method thereof |
| CN111524713A (en) * | 2020-04-23 | 2020-08-11 | 西南科技大学 | Cylindrical lithium ion capacitor and preparation method thereof |
-
2020
- 2020-12-23 CN CN202011545205.XA patent/CN112735847A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100127983A (en) * | 2009-05-27 | 2010-12-07 | 양점식 | Negative current collector for secondary battery with reduced weight |
| CN105186004A (en) * | 2015-10-09 | 2015-12-23 | 南阳师范学院 | Copper current collector for lithium-ion battery anodes as well as preparation method and application of copper current collector |
| CN205487766U (en) * | 2016-03-07 | 2016-08-17 | 辽宁博艾格电子科技有限公司 | Lithium ion capacitor |
| CN108666579A (en) * | 2017-03-28 | 2018-10-16 | 通用汽车环球科技运作有限责任公司 | The electrode of lithium cell of copper foil current collector is modified using surface |
| CN110828195A (en) * | 2019-12-12 | 2020-02-21 | 广东风华高新科技股份有限公司 | Super capacitor pole piece with Cu transition layer and preparation method thereof |
| CN111524713A (en) * | 2020-04-23 | 2020-08-11 | 西南科技大学 | Cylindrical lithium ion capacitor and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5049565B2 (en) | All-solid-state electric double layer capacitor | |
| KR20140010057A (en) | Electrode foil, current collector, electrode, and energy storage element using same | |
| CN111129573B (en) | Heat treatment method of all-solid-state lithium metal battery | |
| CN105226258A (en) | A kind of lithium ion battery negative composite film material and preparation method thereof | |
| CN103971933A (en) | Solid state thin film capacitor and preparation method thereof | |
| WO2017145657A1 (en) | All-solid secondary battery, method for producing all-solid secondary battery, stacked green sheet for all-solid secondary battery, stacked green sheet with current collector foil for all-solid secondary battery, and continuous stacked green sheet for all-solid secondary battery | |
| WO2017124715A1 (en) | Lithium-ion battery separator and preparation method therefor | |
| CN110828195B (en) | Super capacitor pole piece with Cu transition layer and preparation method thereof | |
| CN102054590B (en) | Technology for preparing nickel positive electrode serving as key component of high-power super capacitor | |
| CN211404658U (en) | High-flatness lithium ion battery winding structure | |
| CN112735847A (en) | Lithium ion capacitor negative electrode plate with Cu transition layer and preparation method and application thereof | |
| CN112768254A (en) | Lithium ion capacitor negative electrode plate with Ag transition layer and preparation method and application thereof | |
| CN112735846A (en) | Has Li4Ti5O12Lithium ion capacitor negative pole piece of transition layer and preparation method and application thereof | |
| CN110783112B (en) | Super capacitor pole piece with Ag transition layer and preparation method thereof | |
| WO2018023321A1 (en) | Preparation method for positive electrode sheet containing lithium-ion conductive polymer coating | |
| CN109390575A (en) | Anode material | |
| CN112735845B (en) | Lithium ion capacitor negative electrode plate with latticed transition layer and preparation method and application thereof | |
| KR102628054B1 (en) | Seperator for super capacitor, manufacturing method thereof and super capacitor comprising the same | |
| CN114464771A (en) | Battery cell | |
| CN115842091A (en) | Battery pole piece, battery core, battery module, battery pack and electric device | |
| KR20050015491A (en) | Supercapacitor with reduced internal resistance | |
| CN110797213B (en) | Super capacitor pole piece with C transition layer and preparation method thereof | |
| CN111816843A (en) | Solid-state battery and manufacturing method thereof | |
| CN218215015U (en) | Film electrode super capacitor battery | |
| CN104599866A (en) | Hybrid electrolytic capacitor and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210813 Address after: Fenghua Electronic Industry City, No.18 Fenghua Road, Zhaoqing City, Guangdong Province Applicant after: Guangdong Fenghua Advanced Technology Holding Co.,Ltd. Applicant after: Guangdong Fenghua Chaorong Technology Co.,Ltd. Address before: Fenghua Electronic Industry City, No.18 Fenghua Road, Zhaoqing City, Guangdong Province Applicant before: Guangdong Fenghua Advanced Technology Holding Co.,Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210430 |