CN102891013B - Method for preparing ruthenium dioxide combination electrode for energy storage - Google Patents
Method for preparing ruthenium dioxide combination electrode for energy storage Download PDFInfo
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Abstract
The invention provides a method for preparing a ruthenium dioxide combination electrode for energy storage. The method is characterized by comprising the following steps of: a) mixing ruthenium dioxide materials with different content, a binder, a thickening agent, carbon and deionized water in shear mixing equipment to prepare a plurality of kinds of slurry with different ruthenium dioxide content and different viscosity; b) coating the slurry with the lowest ruthenium dioxide content on a current collector, drying and forming; and c) coating multi-layer slurry by using the method in the step b). The ruthenium dioxide combination electrode is tightly combined with the current collector, has the characteristics of high capacity and long service life and can be widely applied to the field of energy storage for national defense and civil use.
Description
Technical field
The present invention relates to field of chemical power source, particularly a kind of preparation method of ruthenium dioxide combination electrode for energy storage.
Background technology
Ultracapacitor (Super capacitor, Ultra capacitor) be a kind of new chemical energy storage device between traditional capacitor and battery also known as " electrochemical capacitor (Electrochemical Capacitor, EC) ".Compare traditional capacitor, it has higher energy density, and static capacity can reach hundreds of even thousands of farad; Compare battery, it has higher power density and the cycle life of overlength, therefore it combines the advantage of traditional capacitor and battery, is a kind of chemical power source had a extensive future.It has that specific capacity is high, power is large, the life-span is long, the warm limit for width that works, the feature such as non-maintaining.
According to the difference of energy storage principle, ultracapacitor is generally divided into two large classes: a class is electric double layer (Double Layer) the principle energy storage formed based on electrode/electrolyte interface separation of charge, and another kind of is based on electrode surface faraday's " pseudo-capacitance " principle energy storage of producing of redox reaction fast.Different according to electrode structure classification, ultracapacitor can be divided into again symmetric form (Symmetric) and asymmetric (Asymmetric; Sometimes mixed type is claimed, Hybrid) two classes, the former is the most common with activated carbon-activated carbon (CC), most typical example is the product of Maxwell company of the U.S., the latter is the most common with activated carbon-metal oxide (CMO), and typical example is activated carbon-nickel oxide (CNiO) and tantalum oxide-ruthenic oxide (TaRuO).Wherein, hydration ruthenic oxide (RuO
2.xH
2o) there is high ratio capacitance (large more than 1 times of specific activity carbon) and the general conductivity of metal, therefore, in the national defence such as military aerospace and specific area, there is important application, particularly anode is tantalum pentoxide, negative electrode is the hybrid super capacitor (being commonly referred to " ruthenium tantalum capacitor ") that hydration ruthenic oxide is formed, and monopolizes the world in national defence because it has excellent frequency response characteristic and high/low temperature stability.
As the core component of ruthenium tantalum capacitor, its electrode fabrication is technical barrier always, its reason mainly contains 2 points: one is due to the special surface characteristic of ruthenic oxide material, the electrode surface be made into is caused easily to ftracture, cause contacting with collector not good, final affect active material chemical property performance and the life-span [Liu Hong, Gan Weiping, Guo Guijin etc. RuO
2.nH
2the preparation of O film and thing facies evolution and voltage-current characteristic
. China YouSe Acta Metallurgica Sinica, 2010,20 (3): 522-527]; Two is because the electrochemical reaction of ruthenic oxide mainly concentrates on the accurate three-dimensional space of two peacekeepings, therefore electrode can not make too thick, otherwise can have a strong impact on electrode performance, this just means the application that prior art limits it and requires at some in the occasion of high energy storage density.Through retrieval, not yet there is relevant technology open at present.
Summary of the invention
The object of the invention is to overcome above-mentioned technological difficulties, a kind of preparation method of ruthenium dioxide combination electrode for energy storage is provided, ruthenic oxide combination electrode is combined with collector tightr, there is the feature such as high power capacity and long-life.
The present invention proposes a kind of preparation method of ruthenium dioxide combination electrode for energy storage, it is characterized in that comprising the steps:
A) the ruthenic oxide material of different content is mixed with binding agent, thickener, carbon and deionized water in shear mixing equipment, make the multiple slurry that ruthenic oxide content is different, viscosity is different;
B) slurry minimum for ruthenic oxide content is coated on collector, drying forming;
C) use step b) method coated with multiple layer slurry.
More preferably, described in ground floor, the content of slurry ruthenic oxide is 0-20%.
More preferably, the content of described slurry ruthenic oxide is no more than 85%.
More preferably, the viscosity of described multilayer slurry outwards reduces gradually from inner.
More preferably, the preferred tetrafluoroethene of described binding agent, butadiene-styrene rubber, sodium carboxymethylcellulose.
More preferably, described thickener preferred cellulose ether, polyacrylamide, titanate esters, gum arabic, Silica hydrogel, gelatin and agar etc.
More preferably, the preferred carbon black of described carbon, graphite, Graphene, SuperP, acetylene black, activated carbon, BP2000, VulcanXC-72, VulcanXC-72R, carbon nano-tube and carbon fiber etc.
More preferably, the methods such as spraying, brushing, coating are applied to described in
More preferably, described ruthenic oxide be hydration ruthenic oxide, mixture without the one or both of hydration ruthenic oxide.
More preferably, described collector material is titanium, graphite or stainless steel, and shapes of materials is sheet material, foil or bar.
More preferably, described multilayer slurry is for being greater than 2 layers.
The ruthenic oxide combination electrode that the present invention obtains is combined with collector more closely, has the feature such as high power capacity and long-life, can be widely used in national defence and the energy storage field such as civilian.
Embodiment
The following detailed description of specific embodiments of the invention.
The present invention proposes a kind of preparation method of ruthenium dioxide combination electrode for energy storage, comprises the steps:
A) the ruthenic oxide material of different content is mixed with binding agent, thickener, carbon and deionized water in shear mixing equipment, make the multiple slurry that ruthenic oxide content is different, viscosity is different;
B) slurry minimum for ruthenic oxide content is coated on collector, drying forming;
C) use step b) method coated with multiple layer slurry.
In the combination electrode made, the gradient that is distributed as of ruthenic oxide distributes, and the content away from collector ruthenic oxide raises gradually.Wherein ruthenic oxide be hydration ruthenic oxide, mixture without the one or both of hydration ruthenic oxide.The content of ground floor slurry ruthenic oxide is 0-20%.In slurry, the content of ruthenic oxide is no more than 85%.The viscosity of each layer slurry is different, and ground floor viscosity is maximum, and viscosity is less more outward.The preferred tetrafluoroethene of binding agent, butadiene-styrene rubber, sodium carboxymethylcellulose.Thickener preferred cellulose ether, polyacrylamide, titanate esters, gum arabic, Silica hydrogel, gelatin and agar etc.The preferred carbon black of carbon, graphite, Graphene, SuperP, acetylene black, activated carbon, BP2000, VulcanXC-72, VulcanXC-72R, carbon nano-tube and carbon fiber etc.Be applied to the methods such as spraying, coating.Collector material is titanium, graphite or stainless steel, and shapes of materials is sheet material, foil or bar.
Adopt three-electrode system classical in electrochemistry, capacity and cycle life test (electrolyte is the sulfuric acid solution of 38%, and potential region is 0-1.0V) are carried out, to assess its specific capacity and electrochemical stability to made electrode.
embodiment 1:
Commercially available for 100mg hydration ruthenic oxide is divided into 4 parts by 1:2:3:4 mass ratio, 4 batches, the slurry becoming viscosity different from the SuperP of certain content, sodium carboxymethylcellulose, butadiene-styrene rubber with deionized water shear-mixed respectively, viscosity is respectively 8000, and 6000,4000,2800.Wherein, the dry weight ratio of the SuperP often criticized, sodium carboxymethylcellulose and butadiene-styrene rubber is 4:1:0.2, and total amount is identical.Adopt rock field hand-held spray guns the 1st batch of slurry to be supported the titanium foil (thickness is 100 μm) of the slightly good fortune through oil removing, surface, then on 1000W baking oven, scene is dried 5 minutes.Then, with order, 2-4 is criticized slurry and support on the electrode surface of previous oven dry successively, the composite electrode layers that formation 1-4 layer, ruthenic oxide content increase progressively successively.By combination electrode at diameter be finally 80mm roll forming machine on compacting, dry after 10 hours in 80 DEG C of air dry ovens and carry out electrochemistry capacitance and stability experiment.As a comparison, adopt prior art, disposable 100mg ruthenic oxide material is made electrode, test its capacity and stability under the same conditions.Found that, adopt combination electrode of the present invention surface without microcraking, the ratio capacitance of reactive silica ruthenium be 880F/g, 50mV/s scan round 5000 weeks afterwards its capacity decline and be only 3.5%.There is significantly crack splitting in the electrode of contrast, its capacity is only 600F/g, and under same sweep speed, the capacity attenuation after 5000 weeks reaches 7.3%.
embodiment 2
Commercially available for 100mg hydration ruthenic oxide is divided into 4 parts by 1:2:3:4 mass ratio, 4 batches, the slurry becoming viscosity different from the SuperP of certain content, sodium carboxymethylcellulose, polytetrafluoroethylene with deionized water shear-mixed respectively, viscosity is respectively 8000, and 6000,4000,2800.Wherein, the dry weight ratio of the SuperP often criticized, sodium carboxymethylcellulose and polytetrafluoroethylene is 4:1:0.2, and total amount is identical.Adopting manual brushing mode that the 1st batch of slurry is supported thickness is on the graphite cake of 300 μm, and then on 1000W baking oven, scene is dried 3 minutes.Then, with order, 2-4 is criticized slurry and support on the electrode surface of previous oven dry successively, the composite electrode layers that formation 1-4 layer, ruthenic oxide content increase progressively successively.By combination electrode at diameter be finally 80mm roll forming machine on compacting, dry after 10 hours in 80 DEG C of air dry ovens and carry out electrochemistry capacitance and stability experiment.Found that, adopt combination electrode of the present invention surface without microcraking, the ratio capacitance of reactive silica ruthenium be 950F/g, 50mV/s scan round 5000 weeks afterwards its capacity decline and be only 2.8%.
embodiment 3
Commercially available for 150mg hydration ruthenic oxide is divided into 3 parts by 1:2:3 mass ratio, 3 batches, the slurry becoming viscosity different from the SuperP of certain content, sodium carboxymethylcellulose, polytetrafluoroethylene with deionized water shear-mixed respectively, viscosity is respectively 6000, and 5000,3500.Wherein, the dry weight ratio of the SuperP often criticized, sodium carboxymethylcellulose and polytetrafluoroethylene is 4:1:0.2, and total amount is identical.Adopt manual brushing method to be supported by the 1st batch of slurry on graphite cake (thickness is 300 μm), then on 1000W baking oven, scene is dried 3 minutes.Then, with order, 2-3 is criticized slurry and support on the electrode surface of previous oven dry successively, the composite electrode layers that formation 1-3 layer, ruthenic oxide content increase progressively successively.By combination electrode at diameter be finally 80mm roll forming machine on compacting, dry after 10 hours in 80 DEG C of air dry ovens and carry out electrochemistry capacitance and stability experiment.Found that, adopt combination electrode of the present invention surface without microcraking, the ratio capacitance of reactive silica ruthenium be 1000F/g, 50mV/s scan round 5000 weeks afterwards its capacity decline and be only 2.5%.
embodiment 4
Commercially available for 150mg hydration ruthenic oxide is divided into 4 parts by 1:2:3:4 mass ratio, 4 batches, the slurry becoming viscosity different from the SuperP of certain content, sodium carboxymethylcellulose, polytetrafluoroethylene with deionized water shear-mixed respectively, viscosity is respectively 6000, and 5000,3500,2400.Wherein, the dry weight ratio of the SuperP often criticized, sodium carboxymethylcellulose and polytetrafluoroethylene is 4:1:0.2, and total amount is identical.Adopt manual brushing method to be supported by the 1st batch of slurry on graphite cake (thickness is 300 μm), then on 1000W baking oven, scene is dried 3 minutes.Then, with order, 2-3 is criticized slurry and support on the electrode surface of previous oven dry successively, the composite electrode layers that formation 1-4 layer, ruthenic oxide content increase progressively successively.By combination electrode at diameter be finally 80mm roll forming machine on compacting, dry after 10 hours in 80 DEG C of air dry ovens and carry out electrochemistry capacitance and stability experiment.Found that, adopt combination electrode of the present invention surface without microcraking, the ratio capacitance of reactive silica ruthenium be 1100F/g, 50mV/s scan round 5000 weeks afterwards its capacity decline and be only 2.3%.
embodiment 5
Commercially available for 100mg hydration ruthenic oxide is divided into 4 parts by 1:2:3:4 mass ratio, 4 batches, the slurry becoming viscosity different from the SuperP of certain content, sodium carboxymethylcellulose, polytetrafluoroethylene with deionized water shear-mixed respectively, viscosity is respectively 6000, and 5000,3500,2400.Wherein, the dry weight ratio of the SuperP often criticized, sodium carboxymethylcellulose and polytetrafluoroethylene is 4:1:0.2, and total amount is identical.Adopt manual brushing method to be supported to by the 1st batch of slurry on 316 stainless steels (thickness is 400 μm), then on 1000W baking oven, scene is dried 3 minutes.Then, with order, 2-3 is criticized slurry and support on the electrode surface of previous oven dry successively, the composite electrode layers that formation 1-4 layer, ruthenic oxide content increase progressively successively.By combination electrode at diameter be finally 80mm roll forming machine on compacting, dry after 10 hours in 80 DEG C of air dry ovens and carry out electrochemistry capacitance and stability experiment.Found that, adopt combination electrode of the present invention surface without microcraking, the ratio capacitance of reactive silica ruthenium is that within 5000 weeks, its capacity declines afterwards is 4.7% for the scan round of 930F/g, 50mV/s.
embodiment 6
As different from Example 1, time prepared by combination electrode, be by 100mg ruthenic oxide material in mass ratio 1:2:3:4:5:6:7:8 divide into 8 parts, the slurry viscosity made also changes to 8000:7000:6000:5000:4000:3000:2000:1000 respectively.Electrochemical results shows, its ratio capacitance is 980F/g, and the capacity attenuation of scan round in 5000 weeks is 2.9%.
Just preferred embodiment of the present invention described in this specification, above embodiment is only in order to illustrate technical scheme of the present invention but not limitation of the present invention.All those skilled in the art, all should be within the scope of the present invention under this invention's idea by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (9)
1. a preparation method for ruthenium dioxide combination electrode for energy storage, is characterized in that comprising the steps:
A) the ruthenic oxide material of different content is mixed with binding agent, thickener, carbon and deionized water in shear mixing equipment, make the multiple slurry that ruthenic oxide content is different, viscosity is different;
B) slurry minimum for ruthenic oxide content is coated on collector, drying forming;
C) use step b) method coated with multiple layer slurry;
Wherein, the content of slurry ruthenic oxide described in ground floor is for being greater than 0 and being less than 20%;
The viscosity of described multilayer slurry outwards reduces gradually from inner.
2. the preparation method of ruthenium dioxide combination electrode for energy storage as claimed in claim 1, is characterized in that the content of described slurry ruthenic oxide is no more than 85%.
3. the preparation method of ruthenium dioxide combination electrode for energy storage as claimed in claim 1, is characterized in that the preferred tetrafluoroethene of described binding agent, butadiene-styrene rubber, sodium carboxymethylcellulose.
4. the preparation method of ruthenium dioxide combination electrode for energy storage as claimed in claim 1, is characterized in that described thickener preferred cellulose ether, polyacrylamide, titanate esters, gum arabic, Silica hydrogel, gelatin and agar.
5. the preparation method of ruthenium dioxide combination electrode for energy storage as claimed in claim 1, is characterized in that the preferred carbon black of described carbon, graphite, Graphene, acetylene black, activated carbon, carbon nano-tube and carbon fiber.
6. the preparation method of ruthenium dioxide combination electrode for energy storage as claimed in claim 1, is applied to spraying, brushing, coating process described in it is characterized in that.
7. the preparation method of ruthenium dioxide combination electrode for energy storage as claimed in claim 1, is characterized in that described ruthenic oxide is hydration ruthenic oxide, mixture without the one or both of hydration ruthenic oxide.
8. the preparation method of ruthenium dioxide combination electrode for energy storage as claimed in claim 1, it is characterized in that described collector material is titanium, graphite or stainless steel, shapes of materials is sheet material, foil or bar.
9. the preparation method of ruthenium dioxide combination electrode for energy storage as claimed in claim 1, is characterized in that the number of plies of described multilayer slurry is for being more than or equal to 2 layers.
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| CN103400696B (en) * | 2013-07-31 | 2016-02-03 | 株洲宏达电子股份有限公司 | A kind of conductive polymer ruthenium dioxide membrane electrode and preparation method thereof |
| CN103887077B (en) * | 2014-03-04 | 2016-09-14 | 成都达艾斯电子有限公司 | A kind of ultracapacitor and preparation method thereof |
| CN104021947B (en) * | 2014-06-20 | 2017-04-12 | 贵州中航聚电科技有限公司 | Method for preparing ruthenium oxide electrode for hybrid super capacitor |
| CN107275568B (en) * | 2017-07-04 | 2019-08-09 | 福州大学 | A kind of ruthenic oxide Quito pore electrod and preparation method thereof of graphene doping |
| CN107633953B (en) * | 2017-09-08 | 2019-10-15 | 西安科技大学 | A kind of multi-layered electrode and its supercapacitor of preparation |
| CN112670090B (en) * | 2020-12-24 | 2022-03-29 | 电子科技大学 | Electrode plate and preparation method and application thereof |
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Inventor after: Zhang Xigui Inventor after: Hua Li Inventor after: An Zhongxun Inventor after: Cao Xiaowei Inventor after: Yu Jiafei Inventor before: Zhang Xigui Inventor before: Hua Li Inventor before: An Zhongxun Inventor before: Cao Xiaowei Inventor before: Yu Jiafei |
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