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CN-121983441-A - High-voltage hybrid electrochemical energy storage capacitor and large-scale mass production manufacturing method thereof

CN121983441ACN 121983441 ACN121983441 ACN 121983441ACN-121983441-A

Abstract

The invention discloses a high-voltage hybrid electrochemical energy storage capacitor and a large-scale mass production manufacturing method thereof, and belongs to the technical field of electrochemical energy storage. The capacitor comprises a plurality of groups of electrode units connected in series, wherein the electrode units take a composite copper-aluminum current collecting foil as a base material, a carbon nano anchoring layer, an active carbon positive electrode layer and a hard carbon negative electrode layer are arranged on the surface of the electrode units, a cellulose insulating diaphragm is arranged between the adjacent electrode units, a flexible heat conduction insulating layer is sprayed on an insulating margin area, a packaging shell, a pressure triggering type exhaust structure and a current collecting lead-out electrode are configured, and rated working voltage is not lower than 800V. The manufacturing method comprises the steps of leveling a base material, coating a carbon nano anchoring layer, coating an electrode carbon layer in a localized manner, nondestructively transferring and positioning an electrode plate, replacing by gradient vacuum nitrogen, vacuum spraying an insulating layer, curing and packaging and the like. The invention does not need rare materials such as lithium, cobalt, nickel and the like, has low cost, long cycle life and no thermal runaway risk, can realize mass stable production by adopting a lossless switching process, is suitable for high-voltage energy storage scenes of 800V and above, and has excellent industrialized popularization value.

Inventors

  • Request for anonymity

Assignees

  • 广西钦州市华源电子有限公司

Dates

Publication Date
20260505
Application Date
20260403

Claims (12)

  1. 1. A high voltage hybrid electrochemical energy storage capacitor comprising at least two sets of electrode units arranged in series, the electrode units comprising: A single-side or double-side surface of the composite copper-aluminum current collecting foil is provided with a carbon nano anchoring layer which is coated continuously and fully; The outer side of the carbon nano anchoring layer is provided with a localized coated electrode carbon layer, wherein one side of the composite copper-aluminum current collecting foil is an active carbon positive electrode layer, the other side of the composite copper-aluminum current collecting foil is a hard carbon negative electrode layer, and an insulating margin area is reserved around the electrode carbon layer; Insulating diaphragms are arranged between adjacent electrode units; a flexible heat conduction insulating layer is arranged between the insulating margin area and the interlayer of the electrode unit; the device also comprises a packaging shell for sealing and accommodating the electrode unit, a pressure triggering type exhaust structure arranged on the packaging shell, and a collecting and leading-out electrode arranged at the end part of the electrode unit; the inside of the packaging shell is filled with organic electrolyte special for the double-carbon electrode, and the electrolyte infiltrates the electrode carbon layer and the insulating diaphragm; the rated working voltage of the energy storage capacitor is more than or equal to 800V, and the number of the electrode units connected in series can be flexibly increased or decreased according to the target working voltage.
  2. 2. The high-voltage hybrid electrochemical energy storage capacitor of claim 1, wherein the carbon nano anchoring layer is a carbon nano tube or graphene oxide layer, and the thickness is 50-100 nm.
  3. 3. The high-voltage hybrid electrochemical energy storage capacitor according to claim 1, wherein the thickness of the electrode carbon layer is 80-120 microns, the width of the insulating margin area is 1.5-3 mm, the flexible heat-conducting insulating layer is a boron nitride modified flexible epoxy layer, and the thickness is 50-80 microns.
  4. 4. The high-voltage hybrid electrochemical energy storage capacitor of claim 1, wherein the insulating membrane is a porous polymer membrane, a cellulose membrane or a ceramic coated membrane, and has a thickness of 15-30 μm.
  5. 5. The high-voltage hybrid electrochemical energy storage capacitor of claim 1, wherein the pressure-triggered exhaust structure is a normally-closed flexible one-way valve with an opening pressure of 0.03-0.08 mpa, and the mounting seat of the one-way valve is a comb-tooth or perforated plate structure.
  6. 6. The high-voltage hybrid electrochemical energy storage capacitor according to claim 1, wherein the current collecting and leading-out electrode is a copper-aluminum composite electrode lug which is respectively and correspondingly connected with a copper layer and an aluminum layer of a composite copper-aluminum current collecting foil and led out of the packaging shell, and the number of the electrode units connected in series is 50-380.
  7. 7. The high-voltage hybrid electrochemical energy storage capacitor according to claim 1, wherein the special organic electrolyte for the double-carbon electrode is tetraethylammonium tetrafluoroborate/propylene carbonate system, and the withstand voltage of a single electrode unit is more than or equal to 3.5V or is high-voltage organic electrolyte, and the withstand voltage of the single electrode unit is more than or equal to 16V.
  8. 8. A method of mass production of the high voltage hybrid electrochemical storage capacitor of any one of claims 1-7, comprising the steps of: S1, preprocessing a base material, namely carrying out constant-tension double-roller leveling stress-relieving treatment on the composite copper-aluminum current collecting foil, and eliminating the rolling internal stress of the base material; s2, coating an anchoring layer, namely continuously spraying carbon nano dispersion liquid in full-width atomization mode on the carbon side to be coated of the composite copper-aluminum current collecting foil, and drying at low temperature to form the carbon nano anchoring layer; s3, coating an electrode layer, namely preparing the electrode carbon layer outside the carbon nano anchoring layer by adopting a localized coating process with a fixed flange, controlling the outline dimension and thickness consistency of the carbon layer, and drying and shaping at a low temperature by three stages of gradients; S4, nondestructive transfer positioning, namely adopting two groups of bearing tooth mechanisms capable of being inserted and combined in a staggered way to only hold the insulating margin area of the electrode plate, and carrying out synchronous nondestructive transfer and accurate positioning arrangement on the electrode plate and the insulating diaphragm which are coated, wherein the whole process is not in contact with the electrode carbon layer; s5, atmosphere replacement, namely placing the electrode assemblies which are arranged in a closed cavity, and carrying out gradient vacuum extraction and repeated buffer replacement of dry nitrogen to form a protective atmosphere; s6, forming an insulating layer, namely carrying out vacuum spraying on a flexible heat conduction insulating material between an insulating margin area of the electrode unit and an interlayer gap in a protective atmosphere to form a continuous insulating layer; S7, solidifying and packaging, namely performing gradient slow pressure release and low-temperature solidification after spraying, then welding and connecting a current collecting lead-out electrode with a composite copper-aluminum current collecting foil, loading the current collecting lead-out electrode into a packaging shell, injecting organic electrolyte special for the double-carbon electrode in a vacuum environment, sealing the packaging shell after the injection, and finally assembling a pressure trigger type exhaust structure, and detecting the air tightness to obtain the finished product.
  9. 9. The method according to claim 8, wherein in the step S2, the carbon nano-dispersion is an aqueous carbon nano-tube dispersion, the solid content is 0.3% -0.8%, the drying temperature is 35-45 ℃, in the step S3, the localized coating process is performed by using a comma doctor blade, the width of a flange is matched with the width of an insulation margin area, and the three-stage gradient low-temperature drying temperature areas are 35-45 ℃, 55-65 ℃ and 70-80 ℃ in sequence.
  10. 10. The manufacturing method of the electrode plate manufacturing device is characterized in that in the step S4, the specific step of nondestructive transfer positioning is that a first supporting tooth mechanism supports an insulating margin area of an electrode plate and a diaphragm and translates to the position above a lamination station, a second supporting tooth mechanism is inserted into a gap of the first supporting tooth mechanism in a staggered mode, the gap is lifted upwards by 0.8-1.2 mm to receive the electrode plate, after the two supporting tooth mechanisms are flush, the first supporting tooth mechanism is horizontally pulled away, the electrode plate is transferred to the second supporting tooth mechanism, and after the side positioning baffle is calibrated, the second supporting tooth mechanism descends, and the electrode plate falls to a preset position.
  11. 11. The manufacturing method according to claim 8, wherein in the step S5, the gradient vacuum extraction rate is 0.01-0.02 MPa/min, the final vacuum degree is-0.06-0.09 MPa, the nitrogen gas buffer substitution is repeated for 2-3 times, and the oxygen content in the final cavity is less than or equal to 50ppm.
  12. 12. The method according to claim 8, wherein in the step S7, the gradient pressure release rate is 0.008-0.015 mpa/min, the low-temperature curing temperature is 55-65 ℃ and the curing time is 90-150 min, the electrolyte is completely absorbed in the pores of the electrode carbon layer and the insulating membrane by vacuum infiltration, and no free flowing effusion exists in the packaging shell.

Description

High-voltage hybrid electrochemical energy storage capacitor and large-scale mass production manufacturing method thereof Technical Field The invention belongs to the technical field of electrochemical energy storage devices and industrial manufacturing, and particularly relates to a hybrid electrochemical energy storage capacitor suitable for high-voltage scenes of 800V and above and a matched lossless manufacturing method capable of realizing large-scale mass production. Background In the existing electrochemical energy storage system, the lithium iron phosphate battery has the problems of short cycle life (3000-6000 times), large price fluctuation of lithium resources, high total life cycle cost, thermal runaway safety risk and the like, and the sodium ion battery has the defects of limited cycle life (5000-10000 times), high hard carbon negative electrode cost, insufficient low-temperature performance and the like although the material cost is reduced. In the scenes of energy storage in a power grid station area, industrial high-voltage standby, new energy matching and the like, the conventional battery scheme needs a large amount of low-voltage serial-parallel connection, and is matched with a complex BMS, a step-up transformer and a fire-fighting system, so that the initial investment and operation and maintenance cost is extremely high, and large-scale popularization and promotion are difficult to realize. The existing double-layer super capacitor has the advantages of high power density, long cycle life and excellent safety performance, but extremely low energy density, cannot meet the requirements of high-voltage large-capacity long-time energy storage scenes, most of the existing hybrid energy storage capacitors are of small buckle structures, single units have low withstand voltage and cannot adapt to industrial-grade high-voltage scenes with the voltage of more than 800V, and the problems of current collector deformation, coating falling, insulating area pollution and the like generally exist in the electrode manufacturing process, so that the mass production yield is low and the manufacturing cost is high. Meanwhile, the existing high-voltage energy storage device has the defects of easy decomposition under high pressure of electrolyte, high leakage risk, uneven interlayer voltage, easy breakdown and the like, and severely restricts the industrialized application of the high-voltage hybrid energy storage device. Meanwhile, in large-scale energy storage scenes such as new energy grid connection, wind power/photovoltaic matching in remote areas, large-data machine room standby power supply, power grid area energy storage and the like, the existing lithium battery/sodium power scheme has the problems of high cost, short service life and high safety risk, has strict requirements on installation sites and temperature control fire-fighting facilities, is difficult to realize large-scale popularization in scenes without matching in remote areas and with large space and low cost, and the existing super capacitor scheme cannot meet long-term energy storage requirements due to low energy density and high capacity expansion cost, so that the construction promotion of new energy industry and novel power systems is severely restricted. Disclosure of Invention 1. Object of the invention Aiming at the defects of the prior art, the invention aims to provide the high-voltage hybrid electrochemical energy storage capacitor which has no rare resources such as lithium, cobalt, nickel and the like, has low cost, strong high-voltage adaptability, long cycle life and safety without thermal runaway risk, and simultaneously provides a manufacturing method which can realize nondestructive transfer of electrode plates, no damage of coating, high mass production yield and adaptation to large-scale continuous production, thereby solving the problems of high cost, high manufacturing difficulty, poor mass production stability and insufficient high-voltage operation reliability of the high-voltage energy storage device in the prior art. 2. Core technical scheme (1) Product technical scheme A high voltage hybrid electrochemical energy storage capacitor comprising at least two sets of electrode units arranged in series, the electrode units comprising: A composite copper-aluminum current collecting foil which is used as an electrode base material and a current collecting structure; The carbon nano anchoring layer is continuously coated on the surface of one side or two sides of the composite copper-aluminum current collecting foil in a full width mode, and is used for improving the binding force between the electrode layer and the current collector and reducing interface contact resistance; The electrode carbon layer is precisely and locally coated on the outer side of the carbon nano anchoring layer, wherein one side of the composite copper-aluminum current collecting foil is an active carbon positive electrode layer, the other