WO2019174621A1 - 多孔铝宏观体及其制造系统与方法 - Google Patents

多孔铝宏观体及其制造系统与方法 Download PDF

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WO2019174621A1
WO2019174621A1 PCT/CN2019/078190 CN2019078190W WO2019174621A1 WO 2019174621 A1 WO2019174621 A1 WO 2019174621A1 CN 2019078190 W CN2019078190 W CN 2019078190W WO 2019174621 A1 WO2019174621 A1 WO 2019174621A1
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Prior art keywords
aluminum
subsystem
porous
polymer film
vapor
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PCT/CN2019/078190
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English (en)
French (fr)
Inventor
骞伟中
薛济萍
杨周飞
尤伟任
金鹰
顾孙望
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SHANGHAI ZHONGTIAN ALUMINUM WIRE CO Ltd
Tsinghua University
Jiangsu Zhongtian Technology Co Ltd
Original Assignee
SHANGHAI ZHONGTIAN ALUMINUM WIRE CO Ltd
Tsinghua University
Jiangsu Zhongtian Technology Co Ltd
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Priority to EP19768237.0A priority Critical patent/EP3709322B8/en
Priority to JP2020543689A priority patent/JP6945786B2/ja
Publication of WO2019174621A1 publication Critical patent/WO2019174621A1/zh
Priority to US16/893,644 priority patent/US11268187B2/en
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5873—Removal of material
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    • 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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • 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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/668—Composites of electroconductive material and synthetic resins
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
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    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/76—Containers for holding the active material, e.g. tubes, capsules
    • H01M4/762—Porous or perforated metallic containers
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of electrochemical energy storage and metal processing, and in particular relates to a porous aluminum used in an electrochemical energy storage system and a manufacturing system and method thereof.
  • supercapacitors and various secondary batteries are the key research fields of clean electrochemical energy storage in the world. They have the characteristics of reversible charge and discharge, which can store energy and drive various power equipment such as vehicles and lifting equipment. , wind power blades, various circuit switches, and for various power supplies.
  • the common structural characteristic of a supercapacitor and various secondary batteries or a mixture thereof is that it has an active material, has a positive and a negative electrode and a separator, and has a current collector.
  • Conventional processing methods often use a metal foil (such as aluminum foil) that is non-porous, flat, and mechanically strong, and has good conductivity as a current collector (collecting current).
  • the active material and the binder are often fixed to the surface of the macroscopic body by mixing and rolling. This method has achieved great industrialization.
  • active materials for supercapacitors are often various carbon or carbon materials.
  • the active material used for the secondary battery is exemplified by a lithium ion battery, and is often various inorganic lithium compounds.
  • the necessary accessories used in the system such as separators, electrolytes, etc., have an intrinsic density that is mostly less than the intrinsic density of the metal. Therefore, in the year before the pursuit of the mass energy density and volume energy density of the device, the conventional non-porous macroscopic body showed a large proportion of mass in the device and did not contribute energy.
  • the traditional processing method of bonding the active material to the non-porous metal macroscopic body also has the disadvantages of being difficult to disassemble and recover, which is not conducive to the disassembly and recovery of the device after being scrapped, and is disadvantageous for reducing the cost and protecting the environment.
  • porous aluminum macroscopic bodies In view of the importance of aluminum current collectors, various methods for preparing porous aluminum macroscopic bodies have been proposed, including electroplating or physical sputtering using polyurethane templates. After removing the template, these porous hollow aluminum macroscopic bodies have a void ratio of 97%, good electrical conductivity and very low quality.
  • the electrochemical aluminizing method uses an expensive reagent such as an aluminum ion liquid, and requires no water in the system to prevent the ionic liquid from decomposing, forming a strong corrosive substance such as AlCL3 and an acid mist such as HCl. The water removal cost of the porous polyurethane film is also increased.
  • the simple physical sputtering method overcomes the shortcomings of electrochemical aluminum plating, but its equipment is limited in volume, and it is impossible to achieve simultaneous sputtering of large-area samples, and the deposition speed of aluminum is too slow.
  • there is a method of high-temperature physical vapor aluminum in the industry but high-temperature aluminum vapor directly causes the porous polyurethane film to melt, and a qualified sample cannot be obtained.
  • the present invention provides a porous aluminum macroscopic body, a manufacturing system therefor, and a method of making the same, ensuring rapid deposition, maintaining excellent electrochemical stability, and other uses.
  • a porous aluminum macroscopic body wherein the porous aluminum macroscopic body is a three-dimensional all-through pore structure formed by joining hollow aluminum filaments, the wall thickness of the hollow aluminum filament is 7-100 micrometers; and the overall porosity of the porous aluminum macroscopic body is 85- 99%, tensile strength 0.4-2MPa, compressive strength 1-3.5Mpa; hollow holes are closed, not connected to the outside world.
  • a manufacturing system for preparing the porous aluminum macroscopic body comprising a magnetron sputtering subsystem 1, a high temperature aluminum vapor subsystem 2, a low temperature aluminum deposition subsystem 3, an aluminum vapor recovery subsystem 4, and a porous Polymer film transport subsystem 5; porous polymer film transport subsystem 5 and magnetron sputtering subsystem subsystem 1 and low temperature aluminum deposition subsystem 3 are connected to each other to form a porous polymer film moving path; high temperature aluminum vapor subsystem 2 The low temperature aluminum deposition subsystem 3 and the aluminum vapor recovery subsystem 4 are connected to each other to form an aluminum element supply, deposition and recovery path.
  • the rear end of the low-temperature aluminum deposition subsystem 3 is provided with an oxygen-containing gas inlet in the direction of the porous polymer film transporting subsystem 5; while depositing aluminum, the porous polymer film is completely burned by using the temperature of the aluminum; When the film exits the low temperature aluminum deposition subsystem 3, it does not contain carbon.
  • the oxygen-containing gas is 2-10% oxygen or argon containing oxygen.
  • the low-temperature aluminum deposition subsystem 3 has a plurality of aluminum deposition channels, so that the porous aluminum film moved by the low-temperature aluminum deposition subsystem 3 to the porous polymer film transport subsystem 5 can contact the oxygen-containing gas, but from the porous polymer film.
  • the transfer subsystem 5 returns the porous aluminum film of the low temperature aluminum deposition subsystem 3, no longer in contact with the oxygen containing gas.
  • the aluminum vapor recovery subsystem 4 includes an air introduction system for introducing a mixed gas of an inert gas, a polymer-burning exhaust gas, and an aluminum vapor in the low-temperature aluminum deposition subsystem 3 into the aluminum vapor recovery subsystem 4;
  • the vapor condenses into a solid and separates from the other gases and returns to the high temperature aluminum vapor subsystem 2, respectively.
  • the high-temperature aluminum vapor subsystem 2 converts the aluminum recovered by the external aluminum and aluminum vapor recovery subsystem 4 into aluminum vapor in the high-temperature aluminum vapor subsystem 2; meanwhile, the mixed gas introduced into the aluminum vapor recovery subsystem 4 The combustion is harmlessly treated, and the exhaust gas is sent to the high-temperature aluminum vapor subsystem 2.
  • a method of preparing the porous aluminum macroscopic body comprising the steps of:
  • a porous polymer film having a thickness of 0.5 to 30 mm, a width of 1 to 500 mm, and an aspect ratio of 400:1 to 400,000:1 is wound around a reel a of the porous polymer film conveying subsystem 5 at 1 to 20 cm.
  • the /min speed is fed into the magnetron sputtering subsystem 1 to control the surface power of the aluminum target to 2-10 W/cm 2 in an argon atmosphere at an absolute pressure of 0.5 to 5 Pa at 25-50 ° C.
  • the preparation method is from the low-temperature aluminum deposition subsystem 3, the aluminum wire is a hollow structure, and the hollow holes are all communicated with the external medium.
  • the porous polymer film transfer subsystem 5 returns to the low temperature aluminum deposition subsystem 3 and the magnetron sputtering subsystem 1, the diameter of the aluminum wire becomes large, and all of the original hollow holes are closed and no longer communicate with the outside.
  • the porous polymer film includes, but is not limited to, polyurethane, polyolefin, PVDF film, and PTFE film.
  • the high temperature aluminum vapor subsystem 2 converts the aluminum recovered by the external aluminum and aluminum vapor recovery subsystem 4 into aluminum vapor in the high temperature aluminum vapor subsystem 2 by a high temperature melting method.
  • the deposition speed is 5 times faster and the cost is reduced by 50%.
  • the obtained product was increased in tensile strength by 50-80% as compared with the product obtained by simply depositing aluminum by sputtering and removing the polymer template.
  • the oxygen content of the sample decreased by 50%.
  • the prepared porous aluminum macro body has the characteristics of high void ratio and high strength.
  • the step of removing the polymer template is reduced by 20%, and the cost is reduced by 50%, which is beneficial to environmental protection.
  • Figure 1 is a schematic view of a porous aluminum macro body manufacturing system of the present invention.
  • a porous polyurethane film having a thickness of 0.5 mm, a width of 1 mm and an aspect ratio of 400,000:1 was wound around the reel a of the subsystem 5, and fed into the magnetron sputtering subsystem 1 at a speed of 1 cm/min.
  • the surface power of the aluminum target is controlled to be 2 W/cm 2 in an inert gas (argon) atmosphere at 25 ° C and an absolute pressure of 5 Pa, and the aluminum layer is continuously deposited by sputtering on one side of the porous polymer film to a thickness of 1nm.
  • the high-temperature aluminum vapor subsystem 2 was activated, and in the molten bath therein, the aluminum particles were always melted at 600 ° C and turned into aluminum vapor (partial pressure of 0.1%) in the presence of an inert gas (nitrogen).
  • the inert gas carries aluminum vapor to the low temperature aluminum deposition subsystem 3.
  • the temperature of the low temperature aluminum deposition subsystem 3 is set to 200 ° C, and the film of the magnetron sputtering subsystem 1 is continuously fed into the low temperature aluminum deposition subsystem 3, and aluminum vapor is directly deposited on the film, and the deposition time is controlled in 30 minutes. .
  • the aluminum-plated film of the low-temperature aluminum deposition subsystem 3 is wound on the reel b of the porous polymer film transporting subsystem 5, automatically flipped, and returned to the low-temperature aluminum deposition subsystem 3 and the magnetron sputtering subsystem 1 in turn.
  • the hollow aluminum wire has a wall thickness of 20 ⁇ m, a macroscopic porosity of 95%, a tensile strength of 1 MPa, and a compressive strength of 1.5 MPa.
  • the excess aluminum vapor, inert carrier gas and polymer-removing gas in the low-temperature aluminum deposition subsystem 3 are introduced into the aluminum vapor recovery subsystem 4, and the solid aluminum and the gas are separated by cooling and separation, and returned to the high-temperature aluminum vapor subsystem. 2.
  • the recovered aluminum is used together with the raw material aluminum to produce high temperature aluminum vapor.
  • the gas is treated therein and discharged as tail gas.
  • a porous PVDF film having a thickness of 30 mm, a width of 500 mm, and an aspect ratio of 400:1 was wound around the reel a of the subsystem 5, and fed into the magnetron sputtering subsystem 1 at a speed of 20 cm/min.
  • the surface power of the aluminum target was controlled to be 10 W/cm 2 in an inert gas (argon) atmosphere at 50 ° C and an absolute pressure of 0.5 Pa, and the aluminum layer was continuously deposited by sputtering on one side of the porous polymer film to a thickness of 500nm.
  • the high-temperature aluminum vapor subsystem 2 was started, and in the molten bath therein, the aluminum particles were always melted at 800 ° C and turned into aluminum vapor (partial pressure of 10%) in the presence of an inert gas (nitrogen).
  • the inert gas carries aluminum vapor to the low temperature aluminum deposition subsystem 3.
  • the temperature of the low temperature aluminum deposition subsystem 3 is set to 300 ° C, and the film of the magnetron sputtering subsystem 1 is continuously fed into the low temperature aluminum deposition subsystem 3, and the aluminum vapor is directly deposited on the film, and the deposition time is controlled in 1 minute. .
  • the aluminum-plated film of the low-temperature aluminum deposition subsystem 3 is wound on the reel b of the porous polymer film transporting subsystem 5, automatically flipped, and returned to the low-temperature aluminum deposition subsystem 3 and the magnetron sputtering subsystem 1 in turn.
  • the hollow aluminum wire has a wall thickness of 100 ⁇ m, a macroscopic porosity of 85%, a tensile strength of 2 MPa, and a compressive strength of 3.5 MPa.
  • the excess aluminum vapor, inert carrier gas and polymer-removing gas in the low-temperature aluminum deposition subsystem 3 are introduced into the aluminum vapor recovery subsystem 4, and the solid aluminum and the gas are separated by cooling and separation, and returned to the high-temperature aluminum vapor subsystem. 2.
  • the recovered aluminum is used together with the raw material aluminum to produce high temperature aluminum vapor.
  • the gas is treated therein and discharged as tail gas.
  • a porous PTFE film having a thickness of 5 mm, a width of 50 mm, and an aspect ratio of 4000:1 was wound around the reel a of the subsystem 5, and fed into the magnetron sputtering subsystem 1 at a speed of 10 cm/min.
  • the surface power of the aluminum target was controlled to be 5 W/cm 2 in an inert gas (argon) atmosphere at 38 ° C and an absolute pressure of 2 Pa, and an aluminum layer was continuously deposited by sputtering on one side of the porous polymer film to a thickness of 100 nm. .
  • the high-temperature aluminum vapor subsystem 2 was activated, in which the aluminum particles were always melted at 700 ° C and turned into aluminum vapor (divided by 3%) in the presence of an inert gas (argon).
  • the inert gas carries aluminum vapor to the low temperature aluminum deposition subsystem 3.
  • the temperature of the low temperature aluminum deposition subsystem 3 is set to 250 ° C, and the film of the magnetron sputtering subsystem 1 is continuously fed into the low temperature aluminum deposition subsystem 3, and the aluminum vapor is directly deposited on the film, and the deposition time is controlled in 10 minutes. .
  • the aluminum-plated film of the low-temperature aluminum deposition subsystem 3 is wound on the reel b of the porous polymer film transporting subsystem 5, automatically flipped, and returned to the low-temperature aluminum deposition subsystem 3 and the magnetron sputtering subsystem 1 in turn.
  • the hollow aluminum wire has a wall thickness of 7 ⁇ m, a macroscopic porosity of 99%, a tensile strength of 0.8 MPa, and a compressive strength of 1.2 MPa.
  • the excess aluminum vapor, inert carrier gas and polymer-removing gas in the low-temperature aluminum deposition subsystem 3 are introduced into the aluminum vapor recovery subsystem 4, and the solid aluminum and the gas are separated by cooling and separation, and returned to the high-temperature aluminum vapor subsystem. 2.
  • the recovered aluminum is used together with the raw material aluminum to produce high temperature aluminum vapor.
  • the gas is treated therein and discharged as tail gas.
  • a porous polypropylene film having a thickness of 10 mm, a width of 100 mm and an aspect ratio of 9000:1 was wound around the reel a of the subsystem 5, and fed into the magnetron sputtering subsystem 1 at a speed of 10 cm/min.
  • the surface power of the aluminum target was controlled to be 7 W/cm 2 in an inert gas (argon) atmosphere at 40 ° C and an absolute pressure of 3 Pa, and the aluminum layer was continuously deposited by sputtering on one side of the porous polypropylene film to a thickness of 200nm.
  • the high-temperature aluminum vapor subsystem 2 was activated, in which the aluminum particles were always melted at 750 ° C and turned into aluminum vapor (partial pressure of 8%) in the presence of an inert gas (argon).
  • the inert gas carries aluminum vapor to the low temperature aluminum deposition subsystem 3.
  • the temperature of the low temperature aluminum deposition subsystem 3 is set to 300 ° C, and the film of the magnetron sputtering subsystem 1 is continuously fed into the low temperature aluminum deposition subsystem 3, and aluminum vapor is directly deposited on the film, and the deposition time is controlled in 2 minutes. .
  • the aluminum-plated film of the low-temperature aluminum deposition subsystem 3 is wound on the reel b of the porous polymer film transporting subsystem 5, automatically flipped, and returned to the low-temperature aluminum deposition subsystem 3 and the magnetron sputtering subsystem 1 in turn.
  • the hollow aluminum wire has a wall thickness of 70 ⁇ m, a macroscopic porosity of 97%, a tensile strength of 1.4 MPa, and a compressive strength of 2.5 MPa.
  • the excess aluminum vapor, inert carrier gas and polymer-removing gas in the low-temperature aluminum deposition subsystem 3 are introduced into the aluminum vapor recovery subsystem 4, and the solid aluminum and the gas are separated by cooling and separation, and returned to the high-temperature aluminum vapor subsystem. 2.
  • the recovered aluminum is used together with the raw material aluminum to produce high temperature aluminum vapor.
  • the gas is treated therein and discharged as tail gas.
  • a porous polyethylene film having a thickness of 20 mm, a width of 300 mm and an aspect ratio of 4000:1 was wound around the reel a of the subsystem 5, and fed into the magnetron sputtering subsystem 1 at a speed of 2 cm/min.
  • the surface power of the aluminum target is controlled to be 4 W/cm 2 in an inert gas (argon) atmosphere at 25 ° C and an absolute pressure of 1 Pa, and the aluminum layer is continuously deposited by sputtering on one side of the porous polyethylene film to a thickness of 120nm.
  • the high-temperature aluminum vapor subsystem 2 was activated, and in the molten bath therein, the aluminum particles were always melted at 780 ° C and turned into aluminum vapor (divided by 0.4%) in the presence of an inert gas (nitrogen).
  • the inert gas carries aluminum vapor to the low temperature aluminum deposition subsystem 3.
  • the temperature of the low temperature aluminum deposition subsystem 3 is set to 200 ° C, and the film of the magnetron sputtering subsystem 1 is continuously fed into the low temperature aluminum deposition subsystem 3, and aluminum vapor is directly deposited on the film, and the deposition time is controlled in 2 minutes. .
  • the aluminum-plated film of the low-temperature aluminum deposition subsystem 3 is wound on the reel b of the porous polymer film transporting subsystem 5, automatically flipped, and returned to the low-temperature aluminum deposition subsystem 3 and the magnetron sputtering subsystem 1 in turn.
  • the hollow aluminum wire has a wall thickness of 35 ⁇ m, a macroscopic porosity of 89%, a tensile strength of 1.5 MPa, and a compressive strength of 3 MPa.
  • the excess aluminum vapor, inert carrier gas and polymer-removing gas in the low-temperature aluminum deposition subsystem 3 are introduced into the aluminum vapor recovery subsystem 4, and the solid aluminum and the gas are separated by cooling and separation, and returned to the high-temperature aluminum vapor subsystem. 2.
  • the recovered aluminum is used together with the raw material aluminum to produce high temperature aluminum vapor.
  • the gas is treated therein and discharged as tail gas.

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Abstract

本发明公开了一种多孔铝宏观体及其制造系统与方法，该多孔铝宏观体为空心铝丝相连接形成的三维全通孔结构，空心铝丝的壁厚为7-100微米；多孔铝宏观体的总体孔隙率为85-99％，拉伸强度0.4-2MPa，抗压强度1-3.5Mpa；该制造系统包括磁控溅射子系统、高温铝蒸气子系统、低温铝沉积子系统、铝蒸气回收子系统以及多孔聚合物薄膜传送子系统；其制备方法包括首先利用磁控溅射的方法在多孔聚合物薄膜上快速溅射1～500nm厚的铝层，然后将其置于低压物理气相沉积器中，继续沉积铝层至7-100微米厚度的同时，原位将聚合物薄膜分解，得到多孔铝宏观体；该产品具有空隙率调节灵活，强度高的优点，制备方法具有制备时间短，对多孔聚合物薄膜要求低，不需要前处理，可连续化操作，成本低等优点。

Description

多孔铝宏观体及其制造系统与方法 技术领域
本发明属于电化学储能与金属加工技术领域，特别涉及一种电化学储能系统所用的多孔铝及制造系统与方法。
背景技术
目前超级电容器与各种二次电池，是国际上清洁电化学储能的重点研究领域，具有可以可逆充放电的特性，从而可以存储能量，用于驱动各种动力设备，如车辆，起重机械，风力发电浆叶，各种电路开关，以及用于各种电源等。超级电容器与各种二次电池或其混合产品的共同结构特性是，具有活性材料，具有正负极及隔膜，具有集流体。传统的加工方法，常以无孔、平整与机械强度好，导电性好的金属箔(如铝箔)作为集流体(收集电流)。并且为了尽可能增加活性材料在器件中的质量份额，常将活性材料与粘接剂等通过混浆、辊压的方式，固定在宏观体表面。该方法已经实现了大工业化。
然而，用于超级电容的活性物质常为各种碳或炭材料。用于二次电池的活性材料，以锂离子电池为例，常为各种无机锂化合物。同时系统中用的必要的附件如隔膜、电解液等，其本征密度大多小于金属的本征密度。因此，在追求器件的质量能量密度与体积能量密度的前年下，传统的无孔宏观体显示出在器件中质量占比大，并不贡献能量的弊端。同时，传统的，将活性材料粘接在无孔金属宏观体上的加工方式，也具有不易拆解回收的弊端，不利于器件报废后的拆解回收， 对于降低成本，保护环境不利。
鉴于铝集流体的重要性，前人提出了多种多孔铝宏观体的制备方法，包括利用聚氨酯模板进行电镀或物理溅射。去除模板后，这些多孔空心铝宏观体空隙率可达97％，导电性也很好，质量也非常轻。然而，电化学镀铝法使用含铝离子液体等昂贵试剂，且要求系统中不含任何水份，以避免离子液体分解，形成AlCL3等强腐蚀性物质及HCl等酸雾。也使得多孔聚氨酯薄膜的除水成本上升。单纯的物理溅射法，克服了电化学镀铝的缺点，但其设备体积有限，不能够实现大面积样品的同时溅射，同时铝沉积速度过于缓慢。另外，工业上有高温物理蒸汽铝的方法，但高温铝蒸气会直接导致多孔聚氨酯薄膜熔化，得不到合格样品。
发明内容
鉴于已有方法的不足，本发明提供一种多孔铝宏观体，及其制造系统及制备方法，保证快速沉积，保持优异的电化学稳定性以及其他用途。
为了达到上述目的，本发明采用如下技术方案：
一种多孔铝宏观体，所述多孔铝宏观体为空心铝丝相连接形成的三维全通孔结构，空心铝丝的壁厚为7-100微米；多孔铝宏观体的总体孔隙率为85-99％，拉伸强度0.4-2MPa，抗压强度1-3.5Mpa；空心孔被封闭，不与外界相通。
制备所述的多孔铝宏观体的制造系统，该系统包括一个磁控溅射子系统1、一个高温铝蒸气子系统2、一个低温铝沉积子系统3、一个铝蒸气回收子系统4以及一条多孔聚合物薄膜传送子系统5；多 孔聚合物薄膜传送子系统5与磁控溅射子系统子系统1和低温铝沉积子系统3相互相连，形成多孔聚合物薄膜运动路径；高温铝蒸气子系统2、低温铝沉积子系统3及铝蒸气回收子系统4相互连接，形成铝元素供应、沉积与回收路径。
所述低温铝沉积子系统3后端靠近多孔聚合物薄膜传送子系统5的方向设有含氧气体进口；在沉积铝的同时，利用铝的温度，使多孔聚合物薄膜完全燃烧；使多孔聚合物薄膜出低温铝沉积子系统3时，不含碳元素。
所述的含氧气体为含氧2-10％的氮气或氩气。
所述低温铝沉积子系统3具有多个铝沉积通道，使低温铝沉积子系统3向多孔聚合物薄膜传送子系统5运动的多孔铝薄膜能够接触到含氧气体，但使从多孔聚合物薄膜传送子系统5返回低温铝沉积子系统3的多孔铝薄膜，不再与含氧气体接触。
所述铝蒸气回收子系统4含有引风系统，将低温铝沉积子系统3中的含惰性气体、燃烧聚合物后的尾气和铝蒸气的混合气体引入铝蒸气回收子系统4；通过冷却使铝蒸气凝结为固体，与其他气体分离后，分别返回高温铝蒸气子系统2。
所述高温铝蒸气子系统2将外界的铝及铝蒸气回收子系统4回收的铝，在高温铝蒸气子系统2中变为铝蒸气；同时，将铝蒸气回收子系统4通入的混合气体进行燃烧无害化处理，变为尾气，送出高温铝蒸气子系统2。
制备所述的多孔铝宏观体的方法，包括如下步骤：
(1)将厚度为0.5-30mm，宽度为1-500mm，长宽比400:1～400000:1的多孔聚合物薄膜绕在多孔聚合物薄膜传送子系统5的卷轴a上，以1-20cm/min速度送入磁控溅射子系统1中，在25-50℃下，绝对压力为0.5-5Pa的氩气环境中，控制铝靶材的表面功率为2-10W/cm 2，向多孔聚合物薄膜的一面上通过溅射沉积1-500nm厚的 铝层；
(2)启动高温铝蒸气子系统2，在其中的溶融池中，始终将铝颗粒在600-800℃下熔融，并在惰性气体氮气或氩气存在条件下，变成分压为0.1-10％的铝蒸气；惰性气体携带铝蒸气向低温铝沉积子系统3移动；
(3)将出磁控溅射子系统1的薄膜持续送入低温铝沉积子系统3中，将低温铝沉积子系统3的温度设置为200-300℃，铝蒸气直接沉积在薄膜上，沉积时间控制在1-30分钟；
(4)出低温铝沉积子系统3的镀铝薄膜，卷绕在多孔聚合物薄膜传送子系统5的卷轴b上，自动翻面，再次依次返回低温铝沉积子系统3及磁控溅射子系统1中，保证薄膜上下两面镀铝厚度均匀；
(5)将低温铝沉积子系统3中多余的铝蒸气经过铝蒸气回收子系统4后，循环至高温铝蒸气子系统2，使铝与惰性气体实现循环利用。
所述的制备方法，从低温铝沉积子系统3出来，铝线为空心结构，且空心的孔全部与外界的介质相通。经过多孔聚合物薄膜传送子系统5返回低温铝沉积子系统3与磁控溅射子系统1后，铝线直径变大，且原来所有的空心孔被封闭，不再与外界相通。
所述多孔聚合物薄膜包含但不限于聚氨酯、聚烯烃、PVDF膜和PTFE膜。
所述高温铝蒸气子系统2将外界的铝及铝蒸气回收子系统4回收的铝，在高温铝蒸气子系统2中通过高温熔融方法变为铝蒸气。
本发明的有益效果为：
(1)与纯化学电镀的方法沉积铝相比，该方法速度快20倍，成本低90％。
(2)与单纯的溅射技术相比，沉积速度快5倍，而且成本降低50％。所得产品与单纯溅射法沉积铝，再除去聚合物模板后的产品相 比，拉伸强度提高50-80％。样品含氧量下降50％。制备的多孔铝宏观体具有高空隙率、高强度的特点。
(3)与单纯的高温物理蒸镀法相比，解决了其不能直接适用于多孔聚合物模板的难题。且产品表面的光洁度比单纯的高温蒸镀法，提高10-20％。
(4)有效地利用了高温铝蒸气产生子系统的热源与设备，使得除去聚合物模板的步骤减化20％，成本降低50％，有利于环保。
附图说明
图1本发明多孔铝宏观体制造系统示意图。
具体实施方式
下面结合附图和具体的实施例对本发明做进一步详细的说明：
实施例1：
如图1所示，将厚度为0.5mm，宽1mm,长宽比400000：1的多孔聚氨酯薄膜绕在子系统5的卷轴a上，以1cm/min速度送入磁控溅射子系统1中，在25℃、绝对压力为5Pa的惰性气体(氩气)环境中，控制铝靶材的表面功率为2W/cm 2，向多孔聚合物薄膜的一面上通过溅射连续沉积铝层，厚度为1nm。启动高温铝蒸气子系统2，在其中的溶融池中，始终将铝颗粒在600℃下熔融，并在惰性气体(氮气)存在条件下，变成铝蒸气(分压为0.1％)。惰性气体携带铝蒸气向低温铝沉积子系统3移动。将低温铝沉积子系统3的温度设置为200℃，将出磁控溅射子系统1的薄膜持续送入低温铝沉积子系统3中，铝蒸气直接沉积在薄膜上，沉积时间控制在30分钟。在低温铝沉积子系统3的出口端通入含2％氧气的氮气，将聚合物氧化燃烧除去，并使去铝蒸气回收子系统4的气体中氧含量低于1％。出低温铝沉积子系统3的镀铝薄膜，卷绕在多孔聚合物薄膜传送子系统5的卷轴b上，自动翻面，再次依次返回低温铝沉积子系统3及磁控溅射子系统1中，保证薄膜上下两面镀铝厚度均匀。空心铝丝的壁厚为20 微米，宏观体孔隙率为95％，拉伸强度1MPa,抗压强度1.5MPa。
将低温铝沉积子系统3中多余的铝蒸气、惰性载气及去除聚合物的气体引入铝蒸气回收子系统4，通过冷却与分离，分固体铝与气体两路，返回至高温铝蒸气子系统2，回收的铝与原料铝同时用于产生高温铝蒸气。气体在其中经过处理，以尾气形式排放。
实施例2：
如图1所示，将厚度为30mm，宽500mm,长宽比400:1的多孔PVDF薄膜绕在子系统5的卷轴a上，以20cm/min速度送入磁控溅射子系统1中，在50℃、绝对压力为0.5Pa的惰性气体(氩气)环境中，控制铝靶材的表面功率为10W/cm 2，向多孔聚合物薄膜的一面上通过溅射连续沉积铝层，厚度为500nm。启动高温铝蒸气子系统2，在其中的溶融池中，始终将铝颗粒在800℃下熔融，并在惰性气体(氮气)存在条件下，变成铝蒸气(分压为10％)。惰性气体携带铝蒸气向低温铝沉积子系统3移动。将低温铝沉积子系统3的温度设置为300℃，将出磁控溅射子系统1的薄膜持续送入低温铝沉积子系统3中，铝蒸气直接沉积在薄膜上，沉积时间控制在1分钟。在低温铝沉积子系统3的出口端通入含10％氧气的氮气，将聚合物氧化燃烧除去，并使去铝蒸气回收子系统4的气体中氧含量低于1％。出低温铝沉积子系统3的镀铝薄膜，卷绕在多孔聚合物薄膜传送子系统5的卷轴b上，自动翻面，再次依次返回低温铝沉积子系统3及磁控溅射子系统1中，保证薄膜上下两面镀铝厚度均匀。空心铝丝的壁厚为100微米，宏观体孔隙率为85％，拉伸强度为2MPa,抗压强度3.5MPa。
将低温铝沉积子系统3中多余的铝蒸气、惰性载气及去除聚合物的气体引入铝蒸气回收子系统4，通过冷却与分离，分固体铝与气体两路，返回至高温铝蒸气子系统2，回收的铝与原料铝同时用于产生高温铝蒸气。气体在其中经过处理，以尾气形式排放。
实施例3：
如图1所示，将厚度为5mm，宽50mm,长宽比4000:1的多孔PTFE薄膜绕在子系统5的卷轴a上，以10cm/min速度送入磁控溅射子系统1中，在38℃、绝对压力为2Pa的惰性气体(氩气)环境中，控制铝靶材的表面功率为5W/cm 2，向多孔聚合物薄膜的一面上通过溅射连续沉积铝层，厚度为100nm。启动高温铝蒸气子系统2，在其中的溶融池中，始终将铝颗粒在700℃下熔融，并在惰性气体(氩气)存在条件下，变成铝蒸气(分压为3％)。惰性气体携带铝蒸气向低温铝沉积子系统3移动。将低温铝沉积子系统3的温度设置为250℃，将出磁控溅射子系统1的薄膜持续送入低温铝沉积子系统3中，铝蒸气直接沉积在薄膜上，沉积时间控制在10分钟。在低温铝沉积子系统3的出口端通入含5％氧气的氩气，将聚合物氧化燃烧除去，并使去铝蒸气回收子系统4的气体中氧含量低于1％。出低温铝沉积子系统3的镀铝薄膜，卷绕在多孔聚合物薄膜传送子系统5的卷轴b上，自动翻面，再次依次返回低温铝沉积子系统3及磁控溅射子系统1中，保证薄膜上下两面镀铝厚度均匀。空心铝丝的壁厚为7微米，宏观体孔隙率为99％，拉伸强度为0.8MPa,抗压强度1.2MPa。
将低温铝沉积子系统3中多余的铝蒸气、惰性载气及去除聚合物的气体引入铝蒸气回收子系统4，通过冷却与分离，分固体铝与气体两路，返回至高温铝蒸气子系统2，回收的铝与原料铝同时用于产生高温铝蒸气。气体在其中经过处理，以尾气形式排放。
实施例4：
如图1所示，将厚度为10mm，宽100mm,长宽比9000:1的多孔聚丙烯薄膜绕在子系统5的卷轴a上，以10cm/min速度送入磁控溅射子系统1中，在40℃、绝对压力为3Pa的惰性气体(氩气)环 境中，控制铝靶材的表面功率为7W/cm 2，向多孔聚丙烯薄膜的一面上通过溅射连续沉积铝层，厚度为200nm。启动高温铝蒸气子系统2，在其中的溶融池中，始终将铝颗粒在750℃下熔融，并在惰性气体(氩气)存在条件下，变成铝蒸气(分压为8％)。惰性气体携带铝蒸气向低温铝沉积子系统3移动。将低温铝沉积子系统3的温度设置为300℃，将出磁控溅射子系统1的薄膜持续送入低温铝沉积子系统3中，铝蒸气直接沉积在薄膜上，沉积时间控制在2分钟。在低温铝沉积子系统3的出口端通入含10％氧气的氩气，将聚合物氧化燃烧除去，并使去铝蒸气回收子系统4的气体中氧含量低于1％。出低温铝沉积子系统3的镀铝薄膜，卷绕在多孔聚合物薄膜传送子系统5的卷轴b上，自动翻面，再次依次返回低温铝沉积子系统3及磁控溅射子系统1中，保证薄膜上下两面镀铝厚度均匀。空心铝丝的壁厚为70微米，宏观体孔隙率为97％，拉伸强度为1.4MPa,抗压强度2.5MPa。
将低温铝沉积子系统3中多余的铝蒸气、惰性载气及去除聚合物的气体引入铝蒸气回收子系统4，通过冷却与分离，分固体铝与气体两路，返回至高温铝蒸气子系统2，回收的铝与原料铝同时用于产生高温铝蒸气。气体在其中经过处理，以尾气形式排放。
实施例5：
如图1所示，将厚度为20mm，宽300mm,长宽比4000:1的多孔聚乙烯薄膜绕在子系统5的卷轴a上，以2cm/min速度送入磁控溅射子系统1中，在25℃、绝对压力为1Pa的惰性气体(氩气)环境中，控制铝靶材的表面功率为4W/cm 2，向多孔聚乙烯薄膜的一面上通过溅射连续沉积铝层，厚度为120nm。启动高温铝蒸气子系统2，在其中的溶融池中，始终将铝颗粒在780℃下熔融，并在惰性气体(氮气)存在条件下，变成铝蒸气(分压为0.4％)。惰性气体携带铝蒸气向低温铝沉积子系统3移动。将低温铝沉积子系统3的温度设置为 200℃，将出磁控溅射子系统1的薄膜持续送入低温铝沉积子系统3中，铝蒸气直接沉积在薄膜上，沉积时间控制在2分钟。在低温铝沉积子系统3的出口端通入含3.5％氧气的氮气，将聚乙烯氧化燃烧除去，并使去铝蒸气回收子系统4的气体中氧含量低于1％。出低温铝沉积子系统3的镀铝薄膜，卷绕在多孔聚合物薄膜传送子系统5的卷轴b上，自动翻面，再次依次返回低温铝沉积子系统3及磁控溅射子系统1中，保证薄膜上下两面镀铝厚度均匀。空心铝丝的壁厚为35微米，宏观体孔隙率为89％，拉伸强度为1.5MPa,抗压强度3MPa。
将低温铝沉积子系统3中多余的铝蒸气、惰性载气及去除聚合物的气体引入铝蒸气回收子系统4，通过冷却与分离，分固体铝与气体两路，返回至高温铝蒸气子系统2，回收的铝与原料铝同时用于产生高温铝蒸气。气体在其中经过处理，以尾气形式排放。

Claims (10)

  1. 一种多孔铝宏观体，其特征在于：所述多孔铝宏观体为空心铝丝相连接形成的三维全通孔结构，空心铝丝的壁厚为7-100微米；多孔铝宏观体的总体孔隙率为85-99％，拉伸强度0.4-2MPa，抗压强度1-3.5Mpa；空心孔被封闭，不与外界相通。
  2. 一种制备权利要求1所述的多孔铝宏观体的制造系统，其特征在于：该系统包括一个磁控溅射子系统1、一个高温铝蒸气子系统2、一个低温铝沉积子系统3、一个铝蒸气回收子系统4以及一条多孔聚合物薄膜传送子系统5；多孔聚合物薄膜传送子系统5与磁控溅射子系统子系统1和低温铝沉积子系统3相互相连，形成多孔聚合物薄膜运动路径；高温铝蒸气子系统2、低温铝沉积子系统3及铝蒸气回收子系统4相互连接，形成铝元素供应、沉积与回收路径。
  3. 如权利要求2所述的制造系统，其特征在于：所述低温铝沉积子系统3后端靠近多孔聚合物薄膜传送子系统5的方向设有含氧气体进口；在沉积铝的同时，利用铝的温度，使多孔聚合物薄膜完全燃烧；使多孔聚合物薄膜出低温铝沉积子系统3时，不含碳元素。
  4. 如权利要求2所述的制造系统，其特征在于：所述低温铝沉积子系统3具有多个铝沉积通道，使低温铝沉积子系统3向多孔聚合物薄膜传送子系统5运动的多孔铝薄膜能够接触到含氧气体，但使从多孔聚合物薄膜传送子系统5返回低温铝沉积子系统3的多孔铝薄膜，不再与含氧气体接触。
  5. 如权利要求2所述的制造系统，其特征在于：所述铝蒸气回收子系统4含有引风系统，将低温铝沉积子系统3中的含惰性气体、燃烧聚合物后的尾气和铝蒸气的混合气体引入铝蒸气回收子系统4；通过冷却使铝蒸气凝结为固体，与其他气体分离后，分别返回高温铝蒸气子系统2。
  6. 如权利要求2所述的制造系统，其特征在于：所述高温铝蒸气子系统2将外界的铝及铝蒸气回收子系统4回收的铝，在高温铝蒸气子系统2中变为铝蒸气；同时，将铝蒸气回收子系统4通入的混合气体进行燃烧无害化处理，变为尾气，送出高温铝蒸气子系统2。
  7. 一种制备权利要求1所述的多孔铝宏观体的方法，其特征在于：包括如 下步骤：
    (1)将厚度为0.5-30mm，宽度为1-500mm，长宽比400:1～400000:1的多孔聚合物薄膜绕在多孔聚合物薄膜传送子系统5的卷轴a上，以1-20cm/min速度送入磁控溅射子系统1中，在25-50℃下，绝对压力为0.5-5Pa的氩气环境中，控制铝靶材的表面功率为2-10W/cm 2，向多孔聚合物薄膜的一面上通过溅射沉积1-500nm厚的铝层；
    (2)启动高温铝蒸气子系统2，在其中的溶融池中，始终将铝颗粒在600-800℃下熔融，并在惰性气体氮气或氩气存在条件下，变成分压为0.1-10％的铝蒸气；惰性气体携带铝蒸气向低温铝沉积子系统3移动；
    (3)将出磁控溅射子系统1的薄膜持续送入低温铝沉积子系统3中，将低温铝沉积子系统3的温度设置为200-300℃，铝蒸气直接沉积在薄膜上，沉积时间控制在1-30分钟；
    (4)出低温铝沉积子系统3的镀铝薄膜，卷绕在多孔聚合物薄膜传送子系统5的卷轴b上，自动翻面，再次依次返回低温铝沉积子系统3及磁控溅射子系统1中，保证薄膜上下两面镀铝厚度均匀；
    (5)将低温铝沉积子系统3中多余的铝蒸气经过铝蒸气回收子系统4后，循环至高温铝蒸气子系统2，使铝与惰性气体实现循环利用。
  8. 如权利要求7所述的制备方法，其特征在于：从低温铝沉积子系统3出来，铝线为空心结构，且空心的孔全部与外界的介质相通。经过多孔聚合物薄膜传送子系统5返回低温铝沉积子系统3与磁控溅射子系统1后，铝线直径变大，且原来所有的空心孔被封闭，不再与外界相通。
  9. 如权利要求7所述的制备方法，其特征在于：所述多孔聚合物薄膜包含但不限于聚氨酯、聚烯烃、PVDF膜和PTFE膜。
  10. 如权利要求7所述的制备方法，其特征在于：所述高温铝蒸气子系统2将外界的铝及铝蒸气回收子系统4回收的铝，在高温铝蒸气子系统2中通过高温熔融方法变为铝蒸气。
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