CN112397681A - Self-supporting electrode and preparation method and application thereof - Google Patents

Self-supporting electrode and preparation method and application thereof Download PDF

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CN112397681A
CN112397681A CN202011328947.7A CN202011328947A CN112397681A CN 112397681 A CN112397681 A CN 112397681A CN 202011328947 A CN202011328947 A CN 202011328947A CN 112397681 A CN112397681 A CN 112397681A
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self
supporting electrode
zinc
electrode
pvdf
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聂赞相
周航
黄媛
普里帖斯·希亚拉
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Shenzhen Xinyuan Flexible Technology Co ltd
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    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/04—Processes of manufacture in general
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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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
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    • 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
    • H01G11/22—Electrodes
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    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
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Abstract

The invention provides a preparation method of a self-supporting electrode, which comprises the following steps: mixing polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and an organic solvent to obtain a mixed solution; mixing the mixed solution with the carbon nano tube and the zinc slurry to obtain mixed slurry; and stripping the mixed slurry after film formation on the surface of the substrate to obtain the self-supporting electrode. The invention adopts polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) with independent film forming capability to firmly fix zinc particles as electrode active substances on a flexible film, and simultaneously improves the conductive capability of a zinc electrode by using the carbon nano tube. The PVDF-HFP adopted by the invention has independent film forming capability, can be directly taken off from a glass substrate after being placed for a period of time after being spin-coated, and the obtained electrode film is a complete self-supporting electrode, and has uniform and stable thickness and quality. The invention also provides a self-supporting electrode and application thereof.

Description

Self-supporting electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a self-supporting electrode and a preparation method and application thereof.
Background
A self-supporting electrode refers to an electrode that does not require a current collector. In general, battery electrodes are required to collect the current generated by the battery active materials to form a large current output, and the carrier of the collected current is called a current collector. The current collector in the energy storage device mainly refers to metal foils such as copper foil, aluminum foil, stainless steel and the like, and as the energy storage device gradually develops to be flexible, the material of the current collector also changes, and conductive media with flexibility such as carbon cloth, carbon paper and the like gradually replace the metal foils. However, the current collectors tend not to participate in the energy storage reaction of the battery, which means that the use of current collectors greatly reduces the mass and volume capacity of the battery. Therefore, in order to satisfy the growing flexible energy storage devices, self-supporting electrodes having high mechanical strength and large capacity are required.
Currently, self-supporting electrodes are still focused on a network structure of carbon-based materials such as carbon nanotubes or carbon nanofibers, which has the advantages of providing nanopores for rapid ion transport and having a high specific surface area. The active substance is attached to the conductive carbon-based material in different ways, the most primitive being a direct coating method. In addition, an electrode film may be prepared by a suction filtration method, an in-situ polymerization method, a vapor deposition method, a spin coating method, or the like. The patent (CN 111628140 a) uses one or more of conductive carbon black, graphite, carbon nanotube, and C60 to prepare on a flexible conductive substrate by a spin coating method, i.e. a flexible negative electrode. The patent (CN 111755255A) uses hydrochloric acid, a titanium source, an antimony source compound and a pyrrole monomer to prepare polypyrrole @ antimony/bisThe titanium oxide composite material is prepared by uniformly mixing polypyrrole @ antimony/titanium dioxide composite material with polyvinylidene fluoride, adding 1-methyl-2-pyrrolidone to prepare slurry, and spin-coating the slurry on the first layer of TiO 2 And drying the film layer, and then calcining to obtain the film electrode material. However, in the above process of preparing the flexible negative electrode, the flexible negative electrode is spin-coated on the flexible conductive substrate, and is not completely independently formed into a film.
At present, self-supporting electrodes are mostly used for super capacitors and lithium ion batteries, and research on the self-supporting electrodes applied to zinc-manganese ion batteries is less. And the problem of active material powder falling off can occur if a binder is not used in the process of preparing the self-supporting electrode.
Disclosure of Invention
In view of this, the present invention aims to provide a self-supporting electrode, a method for preparing the same, and an application of the same.
The invention provides a preparation method of a self-supporting electrode, which comprises the following steps:
mixing PVDF-HFP and an organic solvent to obtain a mixed solution;
mixing the mixed solution with the carbon nano tube and the zinc slurry to obtain mixed slurry;
and stripping the mixed slurry after film formation on the surface of the substrate to obtain the self-supporting electrode.
Preferably, the organic solvent is acetone; the mass ratio of PVDF-HFP to acetone is 1: (8 to 12).
Preferably, the mass ratio of the zinc slurry to the carbon nanotube to the PVDF-HFP is (75-85): (10-15): (6-10).
Preferably, the PVDF-HFP and the organic solvent are mixed under the condition of magnetic stirring, and the time of the magnetic stirring is 1 to 3 hours;
and the mixing of the mixed solution, the carbon nano tube and the zinc slurry is carried out under the condition of magnetic stirring, and the time of the magnetic stirring is 1-3 h.
Preferably, the film forming method includes spin coating;
the spin coating method comprises the following steps:
spin-coating at low speed for 8-10 s, and then spin-coating at high speed for 25-35 s.
The low rotating speed is 600-800 rpm, and the high rotating speed is 1000-2000 rpm.
Preferably, the mixed slurry further comprises, after forming a film on the surface of the substrate:
and (5) standing for 3-5 min, stripping and drying.
Preferably, the temperature of the standing is room temperature; the drying is vacuum drying, and the drying time is 5-15 hours.
The invention provides a self-supporting electrode prepared by the method in the technical scheme.
Preferably, the thickness of the self-supporting electrode is 0.2 to 0.4mm.
The invention provides an application of the self-supporting electrode in the technical scheme in a zinc and/or manganese ion battery.
The invention adopts polyvinylidene fluoride-hexafluoropropylene with independent film forming capability to firmly fix zinc particles as electrode active substances on a flexible film, and simultaneously improves the conductive capability of a zinc electrode by using the carbon nano tube. The PVDF-HFP adopted by the invention has independent film forming capability, can be directly taken off from a glass substrate after being placed for a period of time after being spin-coated, and the obtained electrode film is a complete self-supporting electrode, and has uniform and stable thickness and quality.
In order to reduce the decrease of the energy density of the electrode quality caused by using a current collector, the invention improves the conductivity of the zinc electrode by using the Carbon Nano Tube (CNT), simultaneously adopts polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) which has independent film forming capability, increases the mechanical property and the flexibility of the electrode, and prepares a self-supporting electrode (namely, a film can be used as the electrode without other carriers).
Drawings
Fig. 1 is a flow chart of a process for preparing a self-supporting electrode according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. In the examples, the methods used were all conventional methods unless otherwise specified.
The process flow for preparing the self-supporting electrode in the embodiment of the invention is shown in fig. 1, and the preparation method of the self-supporting electrode comprises the following steps:
mixing PVDF-HFP and an organic solvent to obtain a mixed solution;
mixing the mixed solution with the carbon nano tube and the zinc slurry to obtain mixed slurry;
and stripping the mixed slurry after forming a film on the surface of the glass substrate to obtain the self-supporting electrode.
In the present invention, the PVDF-HFP and the organic solvent are preferably mixed under magnetic stirring for a period of time of preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 2 hours.
In the invention, the PVDF-HFP is polyvinylidene fluoride-hexafluoropropylene; the mass ratio of the PVDF-HFP to the organic solvent is preferably 1: (8 to 12), more preferably 1: (9 to 11), and most preferably 1.
In the present invention, the organic solvent is preferably acetone.
In the present invention, the mixing of the mixed solution, the carbon nanotubes and the zinc slurry is preferably performed under magnetic stirring, and the time of the magnetic stirring is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 2 hours.
In the present invention, the carbon nanotubes are preferably hydroxylated carbon nanotubes.
The invention has no special limitation on the type and source of the Zinc slurry, and the slurry for the Zinc ion battery, which is well known to the technical personnel in the field, can be adopted and can be obtained from the market, for example, ZK1 Zinc past products of Zinergy Shenzhen Ltd can be adopted.
In the present invention, the mass ratio of the zinc paste, the carbon nanotube, and PVDF-HFP is preferably (75 to 85): (10-15): (6 to 10), more preferably (78 to 82): (11-13): (7 to 9), most preferably 80.
The invention optimizes the raw material proportion and the deposition environment, the film forming method is not limited to the spin coating method, and the spin coating method is preferably used according to the viscosity and the curing rate of the solution, and the film forming effect is best. In the present invention, the method of film formation is preferably spin coating; the spin coating is preferably performed on a spin coater, and the spin coating preferably comprises:
spin-coating at low speed for 8-10 s, and then spin-coating at high speed for 25-35 s.
In the present invention, the low rotation speed is preferably 600 to 800rpm, more preferably 650 to 750rpm, and most preferably 700rpm; the high rotation speed is preferably 1000 to 2000rpm, more preferably 1200 to 1600rpm, and most preferably 1400 to 1500rpm. In the present invention, the time for the low-speed spin coating is preferably 9s, and the time for the high-speed spin coating is preferably 30s.
In the present invention, the thickness of the film is preferably 0.2 to 0.4mm, more preferably 0.3mm; the film is too thin (< 0.15 mm), the mechanical property of the film is poor, and the film is easy to tear in the film uncovering process; the film is too thick (> 0.5 mm), the film is easy to delaminate and is not easy to completely uncover.
In the invention, after the mixed slurry is formed into a film on the surface of a glass substrate, the mixed slurry is preferably kept stand for 3-5 min, then a plastic tweezers are adopted to strip off the obtained film for stripping, and then the film is dried; the standing is preferably carried out in a dry and pollution-free environment, and the temperature of the standing is preferably room temperature, more preferably 20-30 ℃, and most preferably 25 ℃; the zinc is easily oxidized under the high-temperature condition, and the zinc is kept stand at room temperature without an additional annealing process, so that the manufacturing cost is reduced; meanwhile, due to the evaporation of the solvent, the best mechanical property can be obtained after standing for 3-5 min, and the film is favorably stripped.
In the present invention, the drying is preferably a vacuum drying treatment, and the drying time is preferably 5 to 15 hours, and more preferably 10 hours; the vacuum drying can volatilize residual solvent to avoid oxidation caused by long-time contact with a zinc electrode, and is favorable for close contact with zinc and a conductive material; when the drying time is more than 15 hours, the electrode is too dry and easily broken due to embrittlement, thereby reducing the operability and electrochemical properties of the transfer step.
The invention provides a self-supporting electrode prepared by the method in the technical scheme. In the present invention, the thickness of the self-supporting electrode is preferably 0.2 to 0.4mm, and more preferably 0.3mm.
The invention provides an application of the self-supporting electrode in the technical scheme in a zinc and/or manganese ion battery, and the self-supporting electrode can be used as an electrode of the zinc and/or manganese ion battery.
The PVDF-HFP is used as the adhesive of the electrode to firmly attach the zinc particles to the electrode, and meanwhile, the PVDF-HFP can also enhance the mechanical property and flexibility of the electrode to prepare the flexible self-supporting electrode of the zinc ion battery.
PVDF-HFP used in the following embodiments of the invention is a CAS number 9011-17-0 product provided by sigma-aldrich, a CAS number 7440-44-0 product provided by hydroxylated carbon nanotubes as pioneer nanometers, and Zinc slurry is a ZK1 Zinc past product provided by Zinergy Shennzhen Ltd.
Example 1
0.8g of PVDF-HFP is added into a beaker, then acetone is added dropwise, and the mixture is magnetically stirred for about 2 hours until the weight ratio of PVDF-HFP: the acetone ratio is 1: about 10.5 to obtain a mixed solution;
slowly pouring 1.2g of hydroxylated Carbon Nanotubes (CNT) into a beaker, adding the CNT to the center of a mixed solution in the beaker as much as possible in order to avoid the condition that the CNT is suspended on the wall of the beaker, then adding 8g of zinc slurry into the beaker by using a medicine spoon, and then continuously performing magnetic stirring for 2 hours to obtain a mixed slurry;
after stirring, the mixed slurry was pipetted with a rubber head dropper and dropped on a glass substrate for spin coating on a spin coater, followed by spin coating at a low rotation speed of 700rpm for 9s and then at a high rotation speed of 1500rpm for 30s.
After spin coating, placing the glass substrate in a dry and pollution-free environment, standing for 4min, slightly removing the surface film layer by using a plastic forceps to complete stripping, and then performing vacuum drying treatment for 10 hours to obtain the self-supporting electrode.
The thickness of the self-supporting electrode prepared in the embodiment 1 of the present invention is measured by a vernier caliper, the thickness is 0.3mm, and the bending angle of the self-supporting electrode is between 0 ° (unbent) and 180 ° (folding).
Example 2
0.8g of PVDF-HFP is added into a beaker, then acetone is added dropwise, and the mixture is magnetically stirred for about 2 hours until the PVDF-HFP: the acetone ratio is 1: about 10.5 to obtain a mixed solution;
slowly pouring 1.2g of hydroxylated Carbon Nanotubes (CNT) into a beaker, adding the CNT to the center of a mixed solution of the beaker as much as possible in order to avoid the condition that the CNT is suspended on the wall of the beaker, then adding 8g of zinc slurry into the beaker by using a medicine spoon, and then continuing to perform magnetic stirring for 2 hours to obtain a mixed slurry;
after stirring, sucking the mixed slurry by using a rubber-tipped dropper, dropwise adding the mixed slurry into a culture dish, uniformly diffusing the mixed slurry to completely cover the whole culture dish, placing the culture dish in a dry and pollution-free environment, standing for 4min, slightly removing a surface film layer by using a plastic forceps, completing stripping, and then carrying out vacuum drying for 10 hours to obtain the self-supporting electrode.
The thickness of the self-supporting electrode prepared in the embodiment 2 of the present invention is measured by a vernier caliper, the thickness is 0.3mm, and the bending angle of the self-supporting electrode is from 0 ° (unbent) to 90 ° (folding).
Example 3
Adding 1.0g of PVDF-HFP into a beaker, then dropwise adding 20g of acetone, and magnetically stirring for about 2 hours to obtain a mixed solution;
slowly pouring 1.0g of hydroxylated Carbon Nanotubes (CNT) into a beaker, adding the CNT to the center of a mixed solution of the beaker as much as possible in order to avoid the condition that the CNT is suspended on the wall of the beaker, then adding 8g of zinc slurry into the beaker by using a medicine spoon, and then continuing to perform magnetic stirring for 2 hours to obtain a mixed slurry;
after stirring, sucking the mixed slurry by using a rubber-tipped dropper, dropwise adding the mixed slurry into a culture dish, uniformly diffusing the mixed slurry to completely cover the whole culture dish, placing the culture dish in a dry and pollution-free environment, standing for 4min, slightly removing a surface film layer by using a plastic forceps, completing stripping, and then carrying out vacuum drying for 10 hours to obtain the self-supporting electrode.
The thickness of the self-supporting electrode prepared in the embodiment 3 of the present invention is measured by a vernier caliper, the thickness is 0.3mm, and the bending angle of the self-supporting electrode is between 0 ° (unbent) and 90 ° (folding).
Performance detection
CV testing:
0.35g of manganese dioxide, 0.1g of super-p and 0.05g of PVDF are mixed and stirred for four hours, then the mixture is uniformly coated on carbon paper, and after drying is carried out for 6 hours at 60 ℃, the carbon paper and the self-supporting electrode prepared by the embodiment of the invention are assembled into a zinc-manganese battery, and a cyclic voltammetry test is carried out on an electrochemical workstation, wherein the voltage is set to be 1-1.9V, and the scanning rate is set to be 1mV/s.
As a result, the oxidation peak of the self-supporting electrode prepared in example 1 of the present invention was 1.64V, the oxidation peak of the self-supporting electrode prepared in example 2 was 1.70V, and the oxidation peak of the self-supporting electrode prepared in example 3 was 1.62V.
And (3) rate testing:
0.35g of manganese dioxide, 0.1g of super-p and 0.05g of PVDF are mixed and stirred for four hours, then the mixture is uniformly coated on carbon paper, after being dried for 6 hours at 60 ℃, the mixture is assembled with the self-supporting electrode prepared by the embodiment of the invention into a zinc-manganese battery, and a constant current multiplying power test with the voltage of 1-1.9V is carried out in a blue battery test system(Current step: 0.3,0.6,1.2,1.8,2.4, 3.0A g -1 Five turns per step).
The results of the test were that the results of the rate test of the self-supporting electrode prepared in example 1 of the present invention were 0.3,0.6,1.2,1.8,2.4 and 3.0A g- 1 The specific discharge capacity is 318.5,261.1,200.2,170.7,151.3 and 138.0mAh g -1 When the current returns to 0.3A g -1 Specific discharge capacity of 291.5mAh g -1 (ii) a The results of the rate test of the self-supporting electrode prepared in example 2 were 0.3,0.6,1.2,1.8,2.4, and 3.0A g- 1 The specific discharge capacity is 300.3,251.5,200.2,160.8,136.3 and 125.6mAh g -1 When the current returns to 0.3A g -1 The specific discharge capacity is 255.5mAh g -1 (ii) a The results of the rate test of the self-supporting electrode prepared in example 3 were 0.3,0.6,1.2,1.8,2.4, and 3.0A g- 1 The specific discharge capacity is 270.5,228.6,175.4,150.7,136.5 and 123.4mAh g respectively -1 When the current returns to 0.3A g -1 The specific discharge capacity is 234.5mAh g -1 。
And (3) cycle testing:
0.35g of manganese dioxide, 0.1g of super-p and 0.05g of PVDF are mixed and stirred for four hours, then the mixture is uniformly coated on carbon paper, after the mixture is dried for 6 hours at 60 ℃, the mixture and the self-supporting electrode prepared by the embodiment of the invention are assembled into a zinc-manganese battery, and a constant current circulation test (small current activation is 1.5A g) with the voltage of 1-1.9V is carried out on a blue battery test system -1 Run 10 rounds of activation before 3.0A g -1 Run 500 turns).
As a result of the measurement, the self-supporting electrode prepared in example 1 of the present invention showed a cycle test result of initial capacity of 139.7mAh g -1 The capacity of 500 th turn is 126.4mAh g -1 The capacity retention rate is 90.47%; the result of the cycle test of the self-supporting electrode prepared in example 2 was that the initial capacity was 87.4mAh g -1 Capacity of 74.6mAh g at 500 th turn -1 The capacity retention rate is 85.35%; the result of the cycle test of the self-supporting electrode prepared in example 3 was that the initial capacity was 125.8mAh g -1 Capacity of 72.2mAh g at 500 th turn -1 The capacity retention ratio was 57.4%.
From the above examples, in order to reduce the decrease of the energy density of the electrode mass caused by the use of the current collector, the invention uses the Carbon Nanotube (CNT) to improve the conductivity of the zinc electrode, and simultaneously, the polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) has the independent film forming capability, so that the mechanical property and the flexibility of the electrode are increased, and the self-supporting electrode (i.e., the film itself can be used as the electrode without other carriers) is prepared.
While only the preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.

Claims (10)

1. A method of making a self-supporting electrode comprising:
mixing polyvinylidene fluoride-hexafluoropropylene and an organic solvent to obtain a mixed solution;
mixing the mixed solution with the carbon nano tube and the zinc slurry to obtain mixed slurry;
and stripping the mixed slurry after film formation on the surface of the substrate to obtain the self-supporting electrode.
2. The method of claim 1, wherein the organic solvent is acetone; the mass ratio of the PVDF-HFP to the organic solvent is 1: (8 to 12).
3. The method according to claim 1, wherein the mass ratio of the zinc paste, the carbon nanotubes and the PVDF-HFP is (75-85): (10-15): (6-10).
4. The method according to claim 1, wherein the mixing of PVDF-HFP and the organic solvent is performed under magnetic stirring for 1 to 3 hours;
and the mixing of the mixed solution, the carbon nano tube and the zinc slurry is carried out under the condition of magnetic stirring, and the time of the magnetic stirring is 1-3 h.
5. The method according to claim 1, wherein the method for forming a film comprises spin coating;
the spin coating method comprises the following steps:
spin-coating at low rotation speed for 8-10 s, and then spin-coating at high rotation speed for 25-35 s;
the low rotating speed is 600-800 rpm, and the high rotating speed is 1000-2000 rpm.
6. The method according to claim 1, wherein the step of forming the film on the surface of the substrate with the mixed slurry further comprises:
and (5) standing for 3-5 min, stripping and drying.
7. The method of claim 6, wherein the temperature of the standing is room temperature; the drying is vacuum drying, and the drying time is 5-15 hours.
8. A self-supporting electrode prepared by the method of claim 1.
9. The self-supporting electrode according to claim 8, wherein the thickness of the self-supporting electrode is 0.2 to 0.4mm.
10. Use of a self-supporting electrode according to claim 8 in a zinc and/or manganese ion battery.
CN202011328947.7A 2020-11-24 2020-11-24 Self-supporting electrode and preparation method and application thereof Pending CN112397681A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114614021A (en) * 2022-03-30 2022-06-10 珠海中科先进技术研究院有限公司 Current collector with polymer coating and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107845774A (en) * 2016-09-21 2018-03-27 中国科学院大连化学物理研究所 Self-supporting porous electrode preparation method and its electrode and application
CN109192852A (en) * 2018-08-15 2019-01-11 成都新柯力化工科技有限公司 A kind of flexible piezoelectric film and preparation method for road surface power generation
CN111785898A (en) * 2020-07-13 2020-10-16 南京林业大学 Cellulose-based integrated zinc ion battery and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107845774A (en) * 2016-09-21 2018-03-27 中国科学院大连化学物理研究所 Self-supporting porous electrode preparation method and its electrode and application
CN109192852A (en) * 2018-08-15 2019-01-11 成都新柯力化工科技有限公司 A kind of flexible piezoelectric film and preparation method for road surface power generation
CN111785898A (en) * 2020-07-13 2020-10-16 南京林业大学 Cellulose-based integrated zinc ion battery and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114614021A (en) * 2022-03-30 2022-06-10 珠海中科先进技术研究院有限公司 Current collector with polymer coating and preparation method and application thereof

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Application publication date: 20210223