CN103839695A - Graphene electrode plate, and preparation method and application thereof - Google Patents
Graphene electrode plate, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to an electrochemical material and discloses a graphene electrode plate, and a preparation method and application thereof. The preparation method of the graphene electrode plate includes: preparing a conductive layer, which is made of materials of alginate and a conductive agent, on a current collector; and preparing a graphene layer, which is made of materials of graphene, a conductive agent and the alginate, on the surface of the conductive layer which undergoes a drying process and performing a dying process and then obtaining the graphene electrode plate. In the preparation method for the graphene electrode plate, uniform carboxyl groups are distributed evenly on a chain structure of the alginate and the carboxyl groups in the alginate are capable of forming chemical bonds with hydroxyl groups on different graphene-plate layers so that a bonding force between the graphene plate layers is reinforced and conductivity between the graphene plate layers is improved and thus the rate performance is improved; and low reaction activity between the alginate and an electrolyte, and an excellent electrolyte resistance characteristic reduce irreversible consumption of the electrolyte on the surfaces of cathode active material particles in a cyclic process so that the long cyclic performance of a cell is ensured.
Description
Technical field
The present invention relates to electrochemical electrode Material Field, relate in particular to a kind of Graphene electrodes sheet and its preparation method and application.
Background technology
Ultracapacitor (Supercapacitors) claims again electrochemical capacitor (Electrochemical Capacitors) or double electric layer capacitor (Electric Double Layer Capacitors), it is a kind of novel energy-storing element between traditional capacitor and battery, there is more high-specific capacitance super and energy density compared with traditional capacitor, there is higher power density compared with battery; Because ultracapacitor has that the speed of discharging and recharging is fast, environmentally safe and the advantage such as have extended cycle life, promise to be novel green energy resource in this century.Electrode material is the important component part of ultracapacitor, be affect ultracapacitor capacitive character can and the key factor of production cost, therefore research and develop high-performance, electrode material is the important content of ultracapacitor research work cheaply.The electrode material of the ultracapacitor of research mainly contains Carbon Materials, metal oxide and hydrate electrode material thereof and conductive polymer electrodes material at present.
At present the electrode material of double electric layers supercapacitor is mainly material with carbon element, has good heat conduction and electric conductivity, higher specific area, is widely used in electrochemical field and makes electrode material, and material with carbon element is the most successfully one of electrode material of current industrialization.At present, the research of carbon-based electrode material mainly concentrates on research and development and has the research of the aspects such as porous carbon materials that high-specific surface area, internal resistance are less.Graphene has high specific area, fabulous conductivity, good thermal conductivity, and the cost performance of the Graphene obtaining by graphite oxide reducing process is higher, and good stability, is the ideal electrode material of ultracapacitor.The ultracapacitor that use Graphene produces will be all higher than the energy storage density of at present all ultracapacitors.
When Graphene uses as active material, because the layer structure of Graphene has certain rigidity, with the caking property of collector be not fine, coating can there will be dry linting phenomenon after drying and processing, causes the life-span of electrode slice and chemical property to reduce.
Summary of the invention
Problem to be solved by this invention is to provide a kind of doubly forthright and life-span that can improve electrochemical capacitor electrode sheet, can strengthen again the preparation method of the close-burning Graphene electrodes sheet of Graphene and collector simultaneously.
Technical scheme of the present invention is as follows:
A preparation method for Graphene electrodes sheet, comprises the steps:
According to mass percent, the conductive agent of 0.4～4% alginate and 36～39.6% is added in aqueous solvent, stir, obtain conductive layer slurry; Subsequently conductive layer slurry is coated in to collection liquid surface, after drying is processed, obtains the electrode slice of coated with conductive layer; Wherein, in described conductive layer slurry, water accounts for 60% of quality;
According to mass percent, 36～38.4% Graphene, 0.8～2% conductive agent, 0.8～2% alginate are added in aqueous solvent, stir, obtain Graphene slurry; Subsequently Graphene slurry is coated in to the conductive layer surface of electrode slice, drying obtains Graphene electrodes sheet after processing; Wherein, in described Graphene slurry, water accounts for 60% of quality.
The preparation method of described Graphene electrodes sheet, wherein, the coating layer thickness of conductive layer slurry is 3～10 μ m; The coating layer thickness of described Graphene slurry is 50～300 μ m.
The preparation method of described Graphene electrodes sheet, wherein, described alginate comprises sodium alginate and/or potassium alginate.
The preparation method of described Graphene electrodes sheet, wherein, the vertical structure allosome L-guluronic acid in described sodium alginate or potassium alginate and the ratio of D-MANNOSE aldehydic acid are less than or equal to 1.5.
The preparation method of described Graphene electrodes sheet, wherein, the data molecular weight in described sodium alginate or potassium alginate is 500,000～1,000,000.
The preparation method of described Graphene electrodes sheet, wherein, the calcium impurities content in described sodium alginate or potassium alginate is less than or equal to 0.3%.
The preparation method of described Graphene electrodes sheet, wherein, described drying and processing is drying and processing 6～12 hours in the baking oven of 80～10 DEG C.
A kind of Graphene electrodes sheet, this electrode slice adopts above-mentioned either method to make; This Graphene electrodes sheet can be widely used in using as electrode in electrochemical capacitor.
The Graphene electrodes sheet that preparation method provided by the invention makes, has the following advantages:
1, low thermal expansion, because alginate has the good characteristic of high-modulus, low elongation, can fetter the varied in thickness of pole piece on the whole, makes the expansion of Graphene turn to intergranular hole.Thereby reduce cell expansion rate, thereby extend the electrode slice life-span;
2, high rate capability, carboxyl is uniformly distributing in the chain structure of alginate, carboxyl in alginate can form chemical bond from the hydroxyl on different graphene sheet layers, thereby strengthen the adhesion between graphene sheet layer and lamella, strengthen the conductivity between graphene sheet layer, thereby improved high rate performance;
3, good long cycle characteristics, on the one hand, carboxyl in alginate can form chemical bond from the hydroxyl on different graphene sheet layers, thereby strengthen the adhesion between graphene sheet layer and lamella, in the time that electrode part is destroyed, the carboxyl of this strong polarity and the hydroxyl of negative electrode active material show good self-repair effect, thereby have ensured the stability of electrode; On the other hand, due to the low reaction activity between alginate and electrolyte, and good electrolyte resistance characteristic, in cyclic process, bonded dose of covering preferably of part surface of negative electrode active material, the surface that makes to be exposed to the negative electrode active material in electrolyte greatly reduces, thereby has reduced the irreversible consumption of electrolyte on anode active material particles surface, has ensured the long cycle performance of battery.
4, in the middle of Graphene and collector, increase conductive layer, contribute to the contact resistance of less active material layer and collector, carboxyl on the alginate simultaneously adopting can with Graphene on hydroxyl form chemical bond, ensure the close contact of Graphene active layer and conductive layer, can effectively prevent the dry linting problem that Graphene pole piece occurs, increase electrode life.
Brief description of the drawings
Preparation technology's flow chart of the Graphene electrodes sheet that Fig. 1 provides for an embodiment;
The Graphene electrodes chip architecture schematic diagram that Fig. 2 provides for an embodiment.
Embodiment
The preparation method of the Graphene electrodes sheet of an embodiment provided by the invention, as shown in Figure 1, its technological process is as follows:
S1, conductive agent and alginate are added in aqueous solvent, stir, obtain conductive layer slurry, slurry conduction layered material is coated in to collector (as Copper Foil, aluminium foil, nickel foil, a preferably aluminium foil) surface equably upper, coating thickness is 3～10 μ m; Then put it into baking oven, at 80-100 DEG C of drying and processing 6-12h, then adopt same operation coated with conductive layer at the another side of collector again, in this conductive layer, the mass fraction of alginate and conductive agent is respectively 90～99% and 1～10%; Wherein, alginate, conductive agent (as, acetylene black, Ketjen black, SP conductive black, electrically conductive graphite), the mass fraction of aqueous solvent is respectively 0.4～4%, 36～39.6% and 60%;
S2, according to mass percent, by 36～38.4% Graphene, 0.8～2% conductive agent (as, acetylene black, Ketjen black, SP conductive black, electrically conductive graphite), 0.8～2% alginate adds in 60% aqueous solvent, stirs, and obtains Graphene slurry; Subsequently Graphene slurry is coated in to conductive layer one surface of electrode slice, coating thickness is that 50～300 μ m are thick, then puts it into baking oven, at 80-100 DEG C of drying and processing 6-12h, and then adopt the graphene coated slurry of same operation at the another side of conductive layer, obtain Graphene electrodes sheet; In this Graphene electrodes sheet, the mass fraction of Graphene, conductive agent, alginate is respectively 90～96%, 2～5% and 2～5%.
Preferably, Graphene electrodes sheet also needs with roll squeezer pole piece compacting, cut-parts, soldering polar ear again.
The structure of this Graphene electrodes sheet as shown in Figure 2, comprises collector 1, and preparation, at 1 liang of surperficial conductive layer 2 of collector, is coated in the graphene layer 3 of two conductive layer surfaces.
Alginate is in water-soluble solvent time, and alginate joins in mixer grinder together with aqueous solvent, under vacuum state, dissolves completely, obtains aqueous high molecular solution.
In the preparation process of above-mentioned Graphene electrodes sheet, alginates are sodium alginate and/or potassium alginate, two kinds of stereoisomer L-guluronic acids (G section) that described alginate comprises and the ratio G/M of D-MANNOSE aldehydic acid (M section) are less than or equal to 1.5, and the calcium impurities that described alginate comprises is less than or equal to 0.3%.If G section content is too high in molecular sequences, on the one hand, the G segment structure of homopolymerization easily with calcium impurities generation huge legendary turtle cooperation use, make alginic acid interchain in conjunction with tight, act synergistically stronger, finally form gel; On the other hand, after sodium alginate (or potassium) film forming of high G/M ratio, fragility strengthens, and pole piece processing is more difficult; Moreover, the pole piece that pole piece impedance prepared by the sodium alginate (or potassium) of high G/M ratio is prepared higher than the sodium alginate (or potassium) of low G/M ratio, and then affect the performance of battery cryogenic property.
The modulus of elasticity of alginate is more than or equal to 3GPa, otherwise its inhibition that circulation is expanded to Graphene is not obvious.
The number-average molecular weight of alginate is 50,000-1,000,000.Correlated results shows, molecular weight is little, and the strand of sodium alginate (or potassium) is shorter, has influence on sodium alginate or the potassium alginate coating function to particle, and then weakens the stability of slurry; And if molecular weight is too large, can cause the dissolubility variation of sodium alginate (or potassium), be difficult for being uniformly dispersed.
In the preparation process of above-mentioned Graphene electrodes sheet, alginate plays binding agent effect, if content of binder very few (mass fraction is less than 0.4%), can cause active material dispersion effect in slurry poor, the Stability of Slurry of making is poor, cause the skewness of the active material in pole piece, thereby cause overcharging and excessively putting of part active material, and then have influence on the cycle performance of battery; In addition, binding agent is very few, and pole piece bonding is poor, and in pole piece manufacturing process, negative electrode active material layer easily comes off.Otherwise if too much (mass fraction is greater than 4%) of content of binder, binding agent may cover most of active material surface, causes pole piece impedance to increase, and easily analyses lithium in battery charging process, affects battery performance; Binding agent is too much in addition, and pole piece is more crisp, cannot adopt coiling form to complete battery core and make.
The Graphene electrodes sheet that preparation method provided by the invention makes, has the following advantages:
1, low thermal expansion, because alginate has the good characteristic of high-modulus, low elongation, can fetter the varied in thickness of pole piece on the whole, makes the expansion of Graphene turn to intergranular hole.Thereby reduce cell expansion rate, thereby extend the electrode slice life-span;
2, high rate capability, carboxyl is uniformly distributing in the chain structure of alginate, carboxyl in alginate can form chemical bond from the hydroxyl on different graphene sheet layers, thereby strengthen the adhesion between graphene sheet layer and lamella, strengthen the conductivity between graphene sheet layer, thereby improved high rate performance;
3, good long cycle characteristics, on the one hand, carboxyl in alginate can form chemical bond from the hydroxyl on different graphene sheet layers, thereby strengthen the adhesion between graphene sheet layer and lamella, in the time that electrode part is destroyed, the carboxyl of this strong polarity and the hydroxyl of negative electrode active material show good self-repair effect, thereby have ensured the stability of electrode; On the other hand, due to the low reaction activity between alginate and electrolyte, and good electrolyte resistance characteristic, in cyclic process, bonded dose of covering preferably of part surface of negative electrode active material, the surface that makes to be exposed to the negative electrode active material in electrolyte greatly reduces, thereby has reduced the irreversible consumption of electrolyte on anode active material particles surface, has ensured the long cycle performance of battery.
4, in the middle of Graphene and collector, increase conductive layer, contribute to the contact resistance of less active material layer and collector, carboxyl on the alginate simultaneously adopting can with Graphene on hydroxyl form chemical bond, ensure the close contact of Graphene active layer and conductive layer, can effectively prevent the dry linting problem that Graphene pole piece occurs, increase electrode life.
Below the application of above-mentioned Graphene electrodes sheet in electrochemical capacitor:
Get two Graphene electrode slices, be respectively positive plate and negative plate, order stack of laminations according to positive plate, barrier film, negative plate is dressed up battery core, use again battery housing seal battery core, in battery container, inject electrolyte by the liquid injection port being arranged on battery container subsequently, sealing liquid injection port, obtains electrochemical capacitor.
Preferably, in this electrochemical capacitor, its electrolyte adopts BMIMBF
4, EMIMTFSI plasma liquid, also can adopt conventional super electrolyte TEABF
4/ AN.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
According to mass percent, 90% conductive agent, 10% sodium alginate binding agent are added to the water, stir and be configured to conductive layer slurry, conductive layer slurry is coated on an aluminium foil equably, coating thickness is that 3 μ m are thick, then puts it into baking oven, at 80 DEG C of drying and processing 12h, and then adopt same operation coated with conductive layer at the another side of aluminium foil, wherein water accounts for 60% of total slurry weight.
According to mass percent, 90% graphite, 5% conductive agent, 5% alginate binding agent are added to the water, stir and be configured to Graphene slurry, Graphene slurry is coated on conductive layer equably, coating thickness is 50 μ m, then puts it into baking oven, at 80 DEG C of drying and processing 12h, and then adopt the graphene coated pulp layer of same operation at the another side of conductive layer, obtain Graphene electrodes sheet; Wherein water accounts for 60% of total slurry weight.
Wherein, sodium alginate G/M is 1.5, and its number-average molecular weight is about 500,000, and the modulus of elasticity of sodium alginate is 3GPa, and the content of calcium impurities is 0.1%.
According to mass percent, 99% conductive agent, 1% potassium alginate binding agent are added to the water, stir and be configured to conductive layer slurry, conductive layer slurry is coated on a Copper Foil equably, coating thickness is that 10 μ m are thick, then puts it into baking oven, at 100 DEG C of drying and processing 6h, and then adopt same operation coated with conductive layer at the another side of Copper Foil, wherein water accounts for 60% of total slurry weight.
According to mass percent, 96% Graphene, 2% conductive agent, 2% potassium alginate binding agent are added to the water, stir and be configured to Graphene slurry, Graphene slurry is coated on conductive layer equably, and coating thickness is that 300 μ m are thick, then puts it into baking oven, at 100 DEG C of drying and processing 6h, and then adopt the graphene coated pulp layer of same operation at the another side of conductive layer, and obtain Graphene electrodes sheet, wherein water accounts for 60% of total slurry weight.
Wherein, potassium alginate G/M is 1.3, and its number-average molecular weight is about 1,000,000, and the modulus of elasticity of potassium alginate is 4GPa, and the content of calcium impurities is 0.3%.
According to mass percent, 92% conductive agent, 8% sodium alginate binding agent are added to the water, stir and be configured to slurry, slurry is coated on a nickel foil equably, coating thickness is that 5 μ m are thick, then puts it into baking oven, at 85 DEG C of drying and processing 10h, and then adopt same operation coated with conductive layer at the another side of nickel foil, wherein water accounts for 60% of total slurry weight.
According to mass percent, 92% Graphene active material, 3% conductive agent, 5% sodium alginate binding agent are added to the water, stir and be configured to Graphene slurry, Graphene slurry is coated on conductive layer equably, and coating thickness is that 100 μ m are thick, then puts it into baking oven, at 85 DEG C of drying and processing 10h, and then adopt the graphene coated pulp layer of same operation at the another side of conductive layer, and obtain Graphene electrodes sheet, wherein water accounts for 60% of total slurry weight.
Wherein, sodium alginate G/M is 1.1, and its number-average molecular weight is about 600,000, and the modulus of elasticity of sodium alginate is 6GPa, and the content of calcium impurities is 0.2%.
Embodiment 4
According to mass percent, 95% conductive agent, 5% sodium alginate and potassium alginate binding agent are added to the water, stir and be configured to slurry, slurry is coated on an aluminium foil equably, coating thickness is that 7 μ m are thick, then puts it into baking oven, at 90 DEG C of drying and processing 9h, and then adopt same operation coated with conductive layer at the another side of aluminium foil, wherein water accounts for 60% of total slurry weight.
According to mass percent, 94% Graphene, 3% conductive agent, 3% sodium alginate and potassium alginate binding agent are added to the water, stir and be configured to Graphene slurry, Graphene slurry is coated on conductive layer equably, and coating thickness is that 200 μ m are thick, then puts it into baking oven, at 90 DEG C of drying and processing 9h, and then adopt the graphene coated pulp layer of same operation at the another side of conductive layer, and obtain Graphene electrodes sheet, wherein water accounts for 60% of total slurry weight.
Wherein, sodium alginate and potassium alginate G/M are 1.0, and its number-average molecular weight is about 700,000, and the modulus of elasticity of sodium alginate and potassium alginate is 8GPa, and the content of calcium impurities is 0.1%.
Embodiment 5
According to mass percent, 97% conductive agent, 3% sodium alginate binding agent are added to the water, stir and be configured to conductive layer slurry, conductive layer slurry is coated on an aluminium foil equably, coating thickness is that 8 μ m are thick, then puts it into baking oven, at 95 DEG C of drying and processing 7h, and then adopt same operation coated with conductive layer at the another side of aluminium foil, wherein water accounts for 60% of total slurry weight.
According to mass percent, 95% Graphene, 2% conductive agent, 3% sodium alginate binding agent are added to the water, stir and be configured to Graphene slurry, Graphene slurry is coated on conductive layer equably, and coating thickness is that 200 μ m are thick, then puts it into baking oven, at 90 DEG C of drying and processing 8h, and then adopt the graphene coated pulp layer of same operation at the another side of conductive layer, and obtain Graphene electrodes sheet, wherein water accounts for 60% of total slurry weight.
Wherein, sodium alginate G/M is 1.2, and its number-average molecular weight is about 800,000, and the modulus of elasticity of potassium alginate is 10GPa, and the content of calcium impurities is 0.15%.In slurry layoutprocedure, solvent is water, and water accounts for 60% of total slurry.
Embodiment 6
The present embodiment is electrochemical capacitor, and its Graphene electrodes sheet that adopts that embodiment 1 makes is electrode slice.
Get the Graphene electrodes sheet that two embodiment 1 make, be respectively positive plate and negative plate; Order stack of laminations according to positive plate, barrier film, negative plate is dressed up battery core, then uses battery housing seal battery core, injects TEABF subsequently by the liquid injection port being arranged on battery container in battery container
4/ AN electrolyte, sealing liquid injection port, obtains electrochemical capacitor.
Comparative example 1
The preparation of Graphene electrodes sheet:
Formula of size is pressed siccative weight percent meter, and by 1%PTFE, (polytetrafluoroethylene, 99% Graphene two parts form, and in slurry layoutprocedure, solvent is water, and water accounts for 60% of total slurry.
First by above formula, water and PTFE are joined in de-airing mixer, under vacuum state, dissolve completely, obtain aqueous high molecular solution, then by filling a prescription adding Graphene, vacuum low rate mixing is even.Make required Graphene slurry with 150 order stainless steel sift net filtrations.
This slurry is coated in to the aluminium foil two sides that thickness is 12um equably, then with roll squeezer by pole piece compacting, cut-parts, soldering polar ear, obtains Graphene electrodes sheet.
The assembling of electrochemical capacitor
Get two Graphene electrode slices, be respectively positive plate and negative plate, order stack of laminations according to positive plate, barrier film, negative plate is dressed up battery core, then uses battery housing seal battery core, injects BMIMBF subsequently by the liquid injection port being arranged on battery container in battery container
4il electrolyte, sealing liquid injection port, obtains electrochemical capacitor.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for Graphene electrodes sheet, is characterized in that, comprises the steps:
According to mass percent, the conductive agent of 0.4～4% alginate and 36～39.6% is added in aqueous solvent, stir, obtain conductive layer slurry; Subsequently conductive layer slurry is coated in to collection liquid surface, after drying is processed, obtains the electrode slice of coated with conductive layer; Wherein, in described conductive layer slurry, water accounts for 60% of quality;
According to mass percent, 36～38.4% Graphene, 0.8～2% conductive agent, 0.8～2% alginate are added in aqueous solvent, stir, obtain Graphene slurry; Subsequently Graphene slurry is coated in to the conductive layer surface of electrode slice, drying obtains Graphene electrodes sheet after processing; Wherein, in described Graphene slurry, water accounts for 60% of quality.
2. the preparation method of Graphene electrodes sheet according to claim 1, is characterized in that, the coating layer thickness of described conductive layer slurry is 3～10 μ m.
3. the preparation method of Graphene electrodes sheet according to claim 1, is characterized in that, the coating layer thickness of described Graphene slurry is 50～300 μ m.
4. the preparation method of Graphene electrodes sheet according to claim 1, is characterized in that, described alginate comprises sodium alginate and/or potassium alginate.
5. the preparation method of Graphene electrodes sheet according to claim 3, is characterized in that, the vertical structure allosome L-guluronic acid in described sodium alginate or potassium alginate and the ratio of D-MANNOSE aldehydic acid are less than or equal to 1.5.
6. the preparation method of Graphene electrodes sheet according to claim 3, is characterized in that, the data molecular weight in described sodium alginate or potassium alginate is 50,000～1,000,000.
7. the preparation method of Graphene electrodes sheet according to claim 3, is characterized in that, the calcium impurities content in described sodium alginate or potassium alginate is less than or equal to 0.3%.
8. the preparation method of Graphene electrodes sheet according to claim 1, is characterized in that, described drying and processing is drying and processing 6～12 hours in the baking oven of 80～10 DEG C.
9. a Graphene electrodes sheet, is characterized in that, this electrode slice is made by the arbitrary described method of claim 1 to 8.
Graphene electrodes sheet in electrochemical capacitor as the application in electrode field.
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| CN104391030A (en) * | 2014-12-17 | 2015-03-04 | 济南大学 | Preparation method and application of sensor for heavy metal ions Cd2+, Pb2+ and Cu2+ built based on alginic acid functionalized graphene |
| CN105862377A (en) * | 2016-06-16 | 2016-08-17 | 无锡市翱宇特新科技发展有限公司 | Electric heating clothes hanger |
| CN106362290A (en) * | 2016-09-06 | 2017-02-01 | 彭博 | Novel endocardial pacing or defibrillation device |
| CN108330296A (en) * | 2018-03-26 | 2018-07-27 | 赣州市赤鼎再生资源有限公司 | The recovery process of tin in a kind of stanniferous waste material |
| EP3428941A4 (en) * | 2016-03-18 | 2019-03-27 | Shinshu University | Lithium composite negative electrode and hybrid capacitor, and manufacturing methods thereof |
| WO2019153907A1 (en) * | 2018-02-07 | 2019-08-15 | 宁波中车新能源科技有限公司 | Low internal resistance and high power graphene supercapacitor electrode sheet and preparation method therefor |
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| CN104391030A (en) * | 2014-12-17 | 2015-03-04 | 济南大学 | Preparation method and application of sensor for heavy metal ions Cd2+, Pb2+ and Cu2+ built based on alginic acid functionalized graphene |
| EP3428941A4 (en) * | 2016-03-18 | 2019-03-27 | Shinshu University | Lithium composite negative electrode and hybrid capacitor, and manufacturing methods thereof |
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| CN105862377A (en) * | 2016-06-16 | 2016-08-17 | 无锡市翱宇特新科技发展有限公司 | Electric heating clothes hanger |
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| WO2019153907A1 (en) * | 2018-02-07 | 2019-08-15 | 宁波中车新能源科技有限公司 | Low internal resistance and high power graphene supercapacitor electrode sheet and preparation method therefor |
| CN108330296A (en) * | 2018-03-26 | 2018-07-27 | 赣州市赤鼎再生资源有限公司 | The recovery process of tin in a kind of stanniferous waste material |
| CN110933782A (en) * | 2019-10-21 | 2020-03-27 | 珠海烯蟀科技有限公司 | Method and device for using flexible graphene electrode as high borosilicate graphene conducting layer |
| CN110980889A (en) * | 2019-12-17 | 2020-04-10 | 北京丰舜通环保科技有限公司 | Electrode and preparation method thereof |
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Application publication date: 20140604 |