CN109767861A - A kind of preparation method and plane electrode of plane electrode - Google Patents

A kind of preparation method and plane electrode of plane electrode Download PDF

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CN109767861A
CN109767861A CN201910032227.7A CN201910032227A CN109767861A CN 109767861 A CN109767861 A CN 109767861A CN 201910032227 A CN201910032227 A CN 201910032227A CN 109767861 A CN109767861 A CN 109767861A
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layer
preparation
metal
plane electrode
active material
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CN109767861B (en
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王晓红
徐思行
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Tsinghua University
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Tsinghua University
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Abstract

The embodiment of the present invention provides the preparation method and plane electrode of a kind of plane electrode, and the preparation method includes: to deposit one layer of metal layer on the surface of porous membrane;In the way of atomizing suction filtration, one layer of active material is deposited on the porous membrane for be covered with metal layer, forms the plane electrode.It is combined without mobile filtered film with conductive layer using the embodiment of the present invention, electrically conductive substrate can be directly obtained, use more convenient and quicker.

Description

A kind of preparation method and plane electrode of plane electrode
Technical field
The present embodiments relate to micro Process and electrochemical technology field more particularly to a kind of preparation methods of plane electrode And plane electrode.
Background technique
Miniature electrochemical device, such as micro super capacitor, miniature electrochemical and minitype ion battery etc., Chang Cai The diffusion length of ion between the electrodes is reduced with plane interdigitated structure to increase the thickness of electrode.Usual this type device Electrode includes substrate layer, current collector layer and active layer: substrate layer is often made of insulating materials such as silica or thin polymer film; Current collector layer is then often using with satisfactory electrical conductivity and chemically inert precious metal material, such as gold/platinum;Active material is at present most Advanced is the various nano materials with nanostructure.Active material and current collector layer are deposited on substrate layer and completed graphical To prepare the moulding process of the i.e. so-called miniature planar device of device.Micro element forming method packet common in micro Process field at present Include spin coating/spraying/laser direct-writing/chemical vapor deposition/physical vapour deposition (PVD) etc..This type processing method is on the one hand for work Property material have high requirement, if spin coating/spraying for material viscosity and uniformity have high request, laser direct-writing is limited to Grapheme material, chemical and physical vapor deposition are even more to be only limitted to several semiconductor technology mates, on the other hand its The active material layer of formation is often not compact enough, and inside will form relatively fluffy structure, and active material layer and conductive collection Contact defective tightness between fluid layer, so that such processing method can make device have biggish contact resistance.
It traditionally will use pumping and filtering device to filter the solution of liquid on porous membrane substrate, then use direct carbonization Or take the mode retransferred off, combine the film filtered with conductive layer.It is often limited to using suction filtration film forming porous On the one hand fibrous substrate, shifting process will cause that contact strength is inadequate, on the other hand due to filter the pattern of film forming be similar to it is more Hole fibrous substrate, the feature that there is height to rise and fall how may be used so the contact area of itself and conventional multiplanar conductive substrate reduces With directly and quickly one-step shaping, become urgent problem.
Summary of the invention
For the technical problems in the prior art, the embodiment of the present invention provide a kind of plane electrode preparation method and Plane electrode.
In a first aspect, the embodiment of the present invention provides a kind of preparation method of plane electrode, comprising: on the surface of porous membrane Deposit one layer of metal layer;
In the way of atomizing suction filtration, one layer of active material is deposited on the porous membrane for be covered with metal layer, forms institute State plane electrode.
Second aspect, the embodiment of the present invention provide a kind of plane electrode, comprising: including the use of plane electrode described above Electrode made from preparation method.
The preparation method and plane electrode of plane electrode provided in an embodiment of the present invention are sunk using on the surface of porous membrane One layer of metal layer of product;And in the way of atomizing suction filtration, one layer of active material is deposited on the porous membrane for be covered with metal layer, Form the plane electrode.It can be combined, can directly be obtained with conductive layer without mobile filtered film using the embodiment of the present invention To electrically conductive substrate, more convenient and quicker is used.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is this hair Bright some embodiments for those of ordinary skill in the art without creative efforts, can be with root Other attached drawings are obtained according to these attached drawings.
Fig. 1 is the flow diagram of the preparation method of plane electrode provided in an embodiment of the present invention;
Fig. 2 is the processing of the straight forming flexible flat interdigital device provided in an embodiment of the present invention on porous, electrically conductive substrate Production process;
Fig. 3 a is the sectional view of the porous-substrates provided in an embodiment of the present invention that deposited conductive gold layer;
Fig. 3 b is the sectional view for not depositing the original porous substrate of conductive layer;
Fig. 3 c is the amplification sectional view of the porous-substrates provided in an embodiment of the present invention that deposited conductive gold layer;
Fig. 3 d is the perspective, cut-away view of the porous-substrates provided in an embodiment of the present invention that deposited conductive gold layer;
Fig. 4 a is the sectional view of plane electrode provided in an embodiment of the present invention;
Fig. 4 b is the sectional view for the plane electrode that one embodiment of the invention provides;
In the state of bending, machinery does not occur plane electrode provided in an embodiment of the present invention shown in Fig. 5 for aobvious and visible its The schematic diagram of damage.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art Every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
Fig. 1 is the flow diagram of the preparation method of plane electrode provided in an embodiment of the present invention, as shown in Figure 1, described Method includes:
S101, one layer of metal layer is deposited on the surface of porous membrane;
S102, by atomizing filter in the way of, on the porous membrane for be covered with metal layer deposit one layer of active material, shape At the plane electrode.
The embodiment of the present invention provides a kind of preparation method of plane electrode, and in aperture, the fiber multihole greater than 0.2 micron is filtered On film, one layer of nano-metal particle is deposited, forms a conductive structure.Since the size of metallic particles is distributed in 30~50nm, It, still can be with so that the filter membrane is while with good electric conductivity so the nano-pore of porous membrane is not plugged up For filtering technique.Next, can be according to the hydrophilic or hydrophobicity for being intended to position activity material, to decide whether to make filter membrane Corona treatment.
In the conductive substrates of deposited metal layer, the suction filtration deposition of electrode active material is realized.Conduction will be deposited The filter membrane of layer is placed within vacuum filtration equipment, meanwhile, the electrode active material of unlimited type is evenly dispersed in pair It answers among solution, is subsequently filled among commercial nebulizer.Pumping and filtering device is opened, is being led active material even application with sprayer On the filter membrane of electric layer, active material can be filtered on conductive substrates to obtain plane electrode.In the process, using spraying The purpose of equipment is the horizontal proliferation for preventing active material solution in filter membrane, to avoid electric pole short circuit.The thickness of active material It is decided by the concentration of solution and filters the time.
The preparation method of plane electrode provided in an embodiment of the present invention deposits one layer of metal using on the surface of porous membrane Layer;And in the way of atomizing suction filtration, one layer of active material is deposited on the porous membrane for be covered with metal layer, is formed described flat Face electrode.It can be combined without mobile filtered film with conductive layer using the embodiment of the present invention, electrically conductive lining can be directly obtained Bottom uses more convenient and quicker.
Optionally, the surface in porous membrane sputters one layer of metal layer, specifically:
On fiber multihole filter membrane, one layer of metal particle layer is deposited using the method for sputtering or vapor deposition, forms a conduction Structure.
On the basis of the above embodiments, using sputtering or vapor deposition by the way of by metal particles deposition in fiber multihole filter membrane On, thickness is optional between 30~200 nanometers, and then forms a conductive structure.
Optionally, described on fiber multihole filter membrane, one layer of metal particle layer, shape are deposited using the method for sputtering or vapor deposition At a conductive structure, further includes:
It will be attached on the fiber multihole filter membrane with figuratum metal mask plate fixing compact, and use sputtering or vapor deposition Method deposit one layer of metal particle layer, formed have mask pattern conductive structure.
On the basis of the above embodiments, to before carrying out deposited metal layer on fiber multihole filter membrane, it is also necessary to will be The figuratum metal mask plate of a tool is first attached on filter membrane, after fixing mask plate, in the method using sputtering or vapor deposition One layer of metal particle layer is deposited, so that forming the conductive structure with mask pattern can obtain using figuratum mask plate To the response speed and shorter ion diffusion path of more block.,
Optionally, the pattern of the metal mask plate is the pattern of interdigital structure and hollow out.
On the basis of the above embodiments, it is preferable that the pattern and size of metal mask plate, which can according to need, to be set Fixed, preferably the pattern of metal mask plate is interdigital structure and hollow out state is presented in embodiments of the present invention.
Optionally, described to be attached on the fiber multihole filter membrane with figuratum metal mask plate fixing compact, tool Body are as follows:
Metal mask plate with interdigital structure and hollow out is closely attached to by the fiber multihole filter membrane using PI glue band On.
On the basis of the above embodiments, the permanent mask plate on fiber multihole filter membrane of the aperture greater than 0.2 micron, can adopt It is not made in embodiments of the present invention specific of other adhesive tapes of PI glue band or glue stick as long as can be closely adhered to It limits.
Optionally, described in the way of atomizing suction filtration, one layer of activity is deposited on the porous membrane for be covered with metal layer Material forms the plane electrode, specifically:
After active material solution ultrasonic treatment, it is placed into atomizer;
The porous membrane for being covered with metal layer with mask plate is placed on Vacuum filtration device, using the atomization Device and the Vacuum filtration device carry out the spraying of the active material solution to the porous membrane;
The porous membrane after spraying is removed and dried, the plane electrode for having mask pattern is formed.
On the basis of the above embodiments, in the conductive substrates of deposited interdigitated, by the mask not peeled Version realizes the suction filtration deposition of electrode active material.It will attach and vacuum filtration be placed in by mask plate, the filter membrane that deposited conductive layer Within equipment, meanwhile, the electrode active material of unlimited type is evenly dispersed among corresponding solution, commercialization is subsequently filled into Among sprayer.
Pumping and filtering device is opened, with sprayer by active material even application in mask hollowed out area, active material Filtered on conductive substrates and kept the structure of interdigitation.It in the process, the use of the purpose of spraying apparatus is to prevent activity Horizontal proliferation of the material solution in filter membrane, to avoid electric pole short circuit.The thickness of active material be decided by solution concentration and Filter the time.
After the deposition for completing active material, filter membrane is removed into vacuum filtration equipment, spontaneously dries, then goes at normal temperature Except the adhesive tape of adhesion removes mask plate, plane electrode can be obtained.
Optionally, the active material solution is the mixed solution of metal alkene and carbon nanotube.
Optionally, the metal layer is gold, platinum or chromium.
On the basis of the above embodiments, the metal layer deposited on filter membrane can be the inert metals such as gold, platinum or chromium.
The plane electrode that preparation method provided in an embodiment of the present invention using above-mentioned plane electrode obtains has almost Shape and structure identical with mask hollow-out part, will not occur the short circuit between electrode.Active material and conductive current collector layer it Between will form conformal and close attaching, according to test, contact resistance will be less than 1 ohm.Active material itself will have very High volume density, when especially with two-dimension nano materials as active material, can produce closely and rule nano junction Structure.
Optionally, the fiber multihole filter membrane is Nylon, PVDF, PTFE.
On the basis of the above embodiments, the fiber multihole filter membrane can be Nylon, PVDF, PTFE, but be not limited to this Several, different types of filter membrane corresponds to different types of electrolyte.
Fig. 2 is the processing of the straight forming flexible flat interdigital device provided in an embodiment of the present invention on porous, electrically conductive substrate Production process, the specific method is as follows:
1) porous membrane of the aperture at 0.2 micron or more is got out, it will using PI glue band (or other adhesive tapes or glue stick) Filter membrane is closely pasted on silicon wafer (or other planar materials);
2) metallic mask is pasted onto filter membrane surface using PI glue band (or other adhesive tapes or glue stick);
3) together with silicon chip substrate, the layer gold of 100 nano thickness is sputtered on filter membrane;
4) it uses oxygen plasma treatment five minutes, so that layer gold has better hydrophily;
5) active material solution (being the mixed solution of metal alkene and carbon nanotube used in this example) is ultrasonically treated 2 Hour, although being placed in commercial atomizer;
6) filter membrane for having pasted mask is placed on Vacuum filtration device, opens Suction filtration device, while will be active Material spraying is in the region that mask is open, depending on spray time is according to required thickness of electrode;
7) turn off Vacuum filtration device and atomizer, filter membrane is removed and spontaneously dried, mask is then taken, can obtain Obtain plane interdigitated structure electrode.
Fig. 3 a is the sectional view of the porous-substrates provided in an embodiment of the present invention that deposited conductive gold layer;Fig. 3 b is not deposit The sectional view of the original porous substrate of conductive layer.Pass through the comparison of Fig. 3 a-3b, it is seen that layer gold has uniformly conformally been deposited on fiber On, the conductive network of connection is formd, while not blocking the gap of filter membrane, Fig. 3 c and Fig. 3 d are respectively that deposited conductive layer Enlarged drawing and perspective view.
By Fig. 4 a and Fig. 4 b it can be confirmed that active material layer, closely attaches between conductive current collector layer and substrate layer.From figure 4b can be seen that when using two-dimensional material as active material, and the active material layer of acquisition has very close structure.
The embodiment of the present invention also provides a kind of plane electrode, is made using the preparation method of above-mentioned plane electrode, such as Fig. 5 Shown, in the state of bending, mechanical damage does not occur plane electrode provided in an embodiment of the present invention shown in Fig. 5 for aobvious and visible its Schematic diagram.Thus the plane electrode prepared has good flexibility, is embodied in when bending to 180 degree, electrochemistry Obviously decaying will not occur in performance.
The apparatus embodiments described above are merely exemplary, wherein described, unit can as illustrated by the separation member It is physically separated with being or may not be, component shown as a unit may or may not be physics list Member, it can it is in one place, or may be distributed over multiple network units.It can be selected according to the actual needs In some or all of the modules achieve the purpose of the solution of this embodiment.Those of ordinary skill in the art are not paying creativeness Labour in the case where, it can understand and implement.
Through the above description of the embodiments, those skilled in the art can be understood that each embodiment can It realizes by means of software and necessary general hardware platform, naturally it is also possible to pass through hardware.Based on this understanding, on Stating technical solution, substantially the part that contributes to existing technology can be embodied in the form of software products in other words, should Computer software product may be stored in a computer readable storage medium, such as ROM/RAM, magnetic disk, CD, including several fingers It enables and using so that a computer equipment (can be personal computer, server or the network equipment etc.) executes each implementation Method described in certain parts of example or embodiment.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations;Although Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features; And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and Range.

Claims (10)

1. a kind of preparation method of plane electrode characterized by comprising
One layer of metal layer is deposited on the surface of porous membrane;
In the way of atomizing suction filtration, one layer of active material is deposited on the porous membrane for be covered with metal layer, is formed described flat Face electrode.
2. preparation method according to claim 1, which is characterized in that the surface in porous membrane sputters one layer of metal Layer, specifically:
On fiber multihole filter membrane, one layer of metal particle layer is deposited using the method for sputtering or vapor deposition, forms a conductive mechanism.
3. preparation method according to claim 2, which is characterized in that it is described on fiber multihole filter membrane, using sputtering or The method of vapor deposition deposits one layer of metal particle layer, forms a conductive mechanism, further includes:
It will be attached on the fiber multihole filter membrane with figuratum metal mask plate fixing compact, and use sputtering or the side of vapor deposition Method deposits one layer of metal particle layer, forms the conductive mechanism for having mask pattern.
4. preparation method according to claim 3, which is characterized in that the pattern of the metal mask plate be interdigital structure simultaneously The pattern of hollow out.
5. the preparation method according to claim 4, which is characterized in that described to be fixed tightly with figuratum metal mask plate It is closely connected to be attached on the fiber multihole filter membrane, specifically:
The metal mask plate with interdigital structure and hollow out is closely attached on the fiber multihole filter membrane using PI glue band.
6. preparation method according to claim 3, which is characterized in that it is described in the way of atomizing suction filtration, it is being covered with One layer of active material is deposited on the porous membrane of metal layer, forms the plane electrode, specifically:
After active material solution ultrasonic treatment, it is placed into atomizer;
To be placed on Vacuum filtration device with the porous membrane for being covered with metal layer of mask plate, using the atomizer and The Vacuum filtration device carries out the spraying of the active material solution to the porous membrane;
The porous membrane after spraying is removed and dried, the plane electrode for having mask pattern is formed.
7. preparation method according to claim 6, which is characterized in that the active material solution is metal alkene and carbon nanometer The mixed solution of pipe.
8. preparation method according to claim 1, which is characterized in that the metal layer is gold, platinum or chromium.
9. preparation method according to claim 1, which is characterized in that the fiber multihole filter membrane be Nylon, PVDF, PTFE。
10. a kind of plane electrode, which is characterized in that including the use of the preparation side of any one of the claim 1-9 plane electrode Method is made.
CN201910032227.7A 2019-01-14 2019-01-14 Preparation method of planar electrode and planar electrode Active CN109767861B (en)

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Citations (7)

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CN1577916A (en) * 2003-07-02 2005-02-09 三星Sdi株式会社 Microporous film containing nano particles and its forming method, and fuel cell containing the same
CN102568865A (en) * 2012-02-22 2012-07-11 华中科技大学 Preparation method of flexible super capacitor based on paper and application thereof
CN103021663A (en) * 2012-12-20 2013-04-03 同济大学 Novel method for preparing counter electrode material of carbon nanotube thin-film solar cell
US20150214551A1 (en) * 2012-07-13 2015-07-30 Furukawa Electric Co., Ltd. Current collector foil, electrode structure, lithium secondary battery, or electrical double layer capacitor
CN106910897A (en) * 2017-03-02 2017-06-30 宁德时代新能源科技股份有限公司 Current collector, pole piece thereof and battery
CN108641482A (en) * 2018-05-28 2018-10-12 中国科学技术大学 A kind of high-performance can ink-jet ink and preparation method thereof and the application in flexible all-solid-state supercapacitor
CN109036858A (en) * 2017-11-28 2018-12-18 中国科学院大连化学物理研究所 A kind of all solid state plane interdigitation lithium-ion capacitor of flexibility and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1577916A (en) * 2003-07-02 2005-02-09 三星Sdi株式会社 Microporous film containing nano particles and its forming method, and fuel cell containing the same
CN102568865A (en) * 2012-02-22 2012-07-11 华中科技大学 Preparation method of flexible super capacitor based on paper and application thereof
US20150214551A1 (en) * 2012-07-13 2015-07-30 Furukawa Electric Co., Ltd. Current collector foil, electrode structure, lithium secondary battery, or electrical double layer capacitor
CN103021663A (en) * 2012-12-20 2013-04-03 同济大学 Novel method for preparing counter electrode material of carbon nanotube thin-film solar cell
CN106910897A (en) * 2017-03-02 2017-06-30 宁德时代新能源科技股份有限公司 Current collector, pole piece thereof and battery
CN109036858A (en) * 2017-11-28 2018-12-18 中国科学院大连化学物理研究所 A kind of all solid state plane interdigitation lithium-ion capacitor of flexibility and preparation method thereof
CN108641482A (en) * 2018-05-28 2018-10-12 中国科学技术大学 A kind of high-performance can ink-jet ink and preparation method thereof and the application in flexible all-solid-state supercapacitor

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