CN102623668A - Preparation method for grapheme hydrogen storage electrode - Google Patents
Preparation method for grapheme hydrogen storage electrode Download PDFInfo
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- CN102623668A CN102623668A CN2012100937072A CN201210093707A CN102623668A CN 102623668 A CN102623668 A CN 102623668A CN 2012100937072 A CN2012100937072 A CN 2012100937072A CN 201210093707 A CN201210093707 A CN 201210093707A CN 102623668 A CN102623668 A CN 102623668A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a preparation method for a grapheme hydrogen storage electrode, belonging to the fields of preparation technologies and application of nano materials. The preparation method is characterized in that automatic control direct current arc hydrogen plasma equipment is utilized; a pure graphite block is used as a consumption anode, and a carbon rod is used as a cathode; a certain amount of hydrogen is introduced, and then the steps of evaporation, condensation, passivation and the like are carried out to prepare the grapheme material; the grapheme material is used as an active substance and mixed with a binder according to a certain mass ratio; and then an obtained mixture is dried in an extruding mode to manufacture the electrochemical hydrogen storage electrode. The preparation method has the advantages that the grapheme powder material has simple preparation process, high product purity and low cost, and the volume production can be realized; and because the grapheme product has a large quantity of folds, the specific surface area of the grapheme product is increased, and the bonding mismatching between slices is improved; and interlayer polarization is caused so as to form electrochemical hydrogen storage sites, therefore the hydrogen storage quantity of the grapheme electrode is improved.
Description
Technical field
The invention belongs to nano material preparation technology and application.Be a kind ofly to prepare the method for electrochemical electrode as hydrogen storage material, particularly adopt physical vapor method synthesizing graphite alkene powder body material with Graphene.
Background technology
The energy is the basis that human society is depended on for existence and development.In recent years; Because non-renewable fossil energy storage capacitys such as oil, coal constantly reduce; Environmental pollution is more and more serious; Cause negative effects such as energy shortage, greenhouse effect, make the development and utilization of new forms of energy such as solar energy, nuclear energy, wind energy, geothermal energy, oceanic energy, Hydrogen Energy more and more come into one's own.The utilization of Hydrogen Energy comprises production, accumulating, three aspects of application, because hydrogen is gas under normal conditions, so the storage of hydrogen and transportation are the hydrogen energy source key in application.The discovery of hydrogen storage material and be applied as the Hydrogen Energy utilization condition of reality the most is provided.Hydrogen storage material mainly contains at present: metal hydride, hydrogen bearing alloy and material with carbon element etc.Metal hydride and hydrogen bearing alloy have the defective that is difficult to overcome as hydrogen storage material, store promptly that the required condition of hydrogen is harsh, quality is heavy, poor stability and cost an arm and a leg etc.Carbon-based material makes its storage that is more suitable for hydrogen and transportation with characteristics such as its excellent conductivity, light weight, high chemical stability and controllable structure.
After Geim group by Britain graceful Chester university successfully prepared Graphene in 2004, in worldwide, caused research boom.Graphene is a kind of real superficiality solid, and desirable single-layer graphene has super large specific area (2630m
3/ g), also have good electrical conductivity and thermal conductivity simultaneously, be very potential energy storage material.The theoretical research of P.Martin shows that the graphene-structured with multilayer and big sheet interlayer spacing helps Chu Qing more.C.Ataca etc. also draw the conclusion that the graphene-structured that is coated by the Li atom can be used as efficient hydrogen storage media in theory, and its storage hydrogen theoretical capacity can reach 12.8wt.%.G.K.Dimitrakakis utilizes Graphene and CNT to design a three-dimensional storage hydrogenic model, if mix lithium ion in this material, its hydrogen storage ability under normal pressure can reach 41g/L.G.Srinivas etc. utilize the method for reduction-oxidation graphite to prepare Graphene, compare with other carbon nanomaterial (single wall and multi-walled carbon nano-tubes, carbon nano-fiber etc.), and the hydrogen storage property of this Graphene has advantage.K.S.Subrahmanyam etc. have studied the chemical hydrogen storage property of Graphene, utilize the birch reduction method can in multi-layer graphene, add the hydrogen up to 5wt.%.The research of nanometer hydrogen storage material to take off/the hydrogenation excellent performance, cost is low and the direction that can produce in enormous quantities deeply develops.
The main method of preparation Graphene has mechanical cracking process, graphite oxide pyrolysis reducing process, chemical vapour deposition technique, CNT cracking process, direct current arc method etc. at present.Characteristics such as direct current arc method is a kind of conventional method of preparation carbon nanomaterial (fullerene, CNT etc.), and it is simple to operate that this method has, and controls easily, and it is quick to grow.The Graphene lamella rule that makes, good crystallinity, Stability Analysis of Structures is expected to obtain higher conductivity and better electrochemical performance.The present invention utilize direct current arc method preparation to the Graphene hydrogen storage material, technology is simple, product purity is high, and can the scale volume production.Utilize such grapheme material to prepare electrode, show excellent electrochemical hydrogen storage performance.
China's granted patent: control direct-current arc metal nano powder production equipment (ZL200410021190.1) automatically, its equipment is made up of the powder generation chamber, powder granularity grading room, powder dust trapping chamber, powder handling chamber, pumped vacuum systems, gas circulator, Hydraulic Power Transmission System, water-cooling system, the programming Control system that connect successively; Powder generates installs anode and negative electrode in the chamber, and passes powder and generate locular wall and be connected with the programming Control system with the external hydraulic transmission; The powder granularity grading room is that double-walled water cooled housing and cooled with liquid nitrogen jar constitute; Hydraulic Power Transmission System moves the hydraulic tank and the drive link that move with the anode dimension by the control cathode dimension and constitutes.This equipment is pack into anode and become the part of anode of material, forms the gap of 10～30mm with negative electrode, and integral device vacuumizes, logical cooling water.After feeding active gases and condensed gas, start starting the arc device and power supply, between the yin, yang electrode, form electric arc, the material start vaporizer also forms the nano-powder particle.This equipment can be realized a large amount of productions of Graphene.
To sum up said, utilize automatically control direct-current arc metal nano powder production equipment to prepare grapheme material to have that technology is simple, magnanimity preparation and be beneficial to advantage such as suitability for industrialized production.Graphene with preparation can obtain excellent properties such as height ratio capacity, high cycle life as electrochemical hydrogen bearing material.
Summary of the invention
The invention provides a kind of preparation method of Graphene hydrogen-storage electrode, is a kind of method that adopts the synthetic grapheme material of direct current arc method.
Technical solution concrete operations step of the present invention is following:
(1) utilize control direct-current arc hydrogen plasma equipment automatically, as anode, negative electrode is a carbon-point with graphite block body, two die openings to 10～30mm, and the hydrogen of feeding 0.01～0.07MPa through steps such as pervaporation, condensation, passivation, prepares grapheme material.
(2) with after binding agent PVDF (Kynoar) mixed with mass ratio in 1: 1～7: 1, the best is made electrode slice than being 4: 1 with the mode that is coated with pressure to the grapheme material that utilizes step (1) preparation as active material.This electrode slice in the three-electrode system of electrochemical hydrogen storage test as work electrode.Ni (OH)
2/ NiOOH electrode is as auxiliary electrode, and calomel electrode is as reference electrode.Electrolyte is the saturated KOH solution of 6mol/L.After forming simulated battery it is carried out the test of chemical property.
Advantage of the present invention is:
1. the adding of catalyst-free in the anode, the powder product is pure, need not follow-up purified treatment.The preparation process is simple, and is with low cost, can realize volume production.
2. the sheet interlayer spacing of Graphene product is at 0.355nm～0.356nm, and the hydrogen molecule of diameter for
can be filled between its lamella.
3. there are a large amount of folds in the Graphene product, increase its specific area, increased the not matching property of Cheng Jian between the lamella simultaneously, cause the interlayer polarization, become the electrochemical hydrogen storage site, improved hydrogen storage content.
4. the Graphene product structure is stable, through repeatedly fill/still keep its structure after putting hydrogen.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the Graphene hydrogen storage material that synthesized by embodiment one, embodiment two, embodiment three.
(a, b c) are transmission electron microscope (TEM) figure of the Graphene hydrogen storage material that synthesized by embodiment one, embodiment two, embodiment three respectively to Fig. 2.
Fig. 3 is after being prepared into electrode slice according to the Graphene hydrogen storage material that embodiment one, embodiment two, embodiment three are synthesized, the charge/discharge curve under the 100mA/g current density.
Fig. 4 is after being prepared into electrode slice according to the Graphene hydrogen storage material that embodiment one, embodiment two, embodiment three are synthesized, the stable circulation linearity curve under the 100mA/g current density.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further specified.
Embodiment one:
In controlling direct-current arc hydrogen plasma equipment reaction chamber automatically, as anode, be negative electrode with pure graphite block with the pure carbon rod, two die openings after vacuumizing, feed the H of 0.03MPa to 20mm
2, discharge voltage is 40V, discharging current is 90A.Prepare the Graphene hydrogen storage material.Grapheme material behind the bonding state of comparison composite sample and matrix nickel foam, confirms that the The Best Mixed ratio is 4: 1 with after knot agent PVDF mixed with mass ratio in 1: 1～7: 1.This grapheme material is processed electrode slice as work electrode, Ni (OH)
2/ NiOOH electrode is as auxiliary electrode, and calomel electrode is as reference electrode, and electrolyte is the saturated KOH solution of 6mol/L, behind the composition simulated battery it is carried out the test of chemical property.
Embodiment two:
After vacuumizing, feed the H of 0.05MPa
2, discharge voltage is 40V, discharging current is 90A.Prepare the Graphene hydrogen storage material.Grapheme material is processed electrode slice as work electrode with this grapheme material, Ni (OH) with after knot agent PVDF mixes with mass ratio at 4: 1
2/ NiOOH electrode is as auxiliary electrode, and calomel electrode is as reference electrode, and electrolyte is the saturated KOH solution of 6mol/L, behind the composition simulated battery it is carried out the test of chemical property.Other experiment conditions are identical with embodiment one, and two die openings that different is are to 10mm, the H of feeding
2Be 0.05MPa.
Embodiment three:
Other experiment conditions are identical with embodiment 1, and different is: two die openings are to 30mm, the H of feeding
2Be 0.07MPa.
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the grapheme material that synthesized according to embodiment one, embodiment two, embodiment three.There is an obvious wideization peak in the bright Graphene sample of XRD figure stave in 20～30 ° of scopes, show that it is a disordered state.(002) peak occurs and show that obtained Graphene is the multilayer chip structure.
Fig. 2 (a) (b), (c) is transmission electron microscope (TEM) figure of the grapheme material that synthesized according to embodiment one, embodiment two, embodiment three respectively.TEM schemes (a) and (b) and (c) shows, the graphene film interlamellar spacing of embodiment one preparation is less, and its size is about 0.2 μ m.And the graphene film interlamellar spacing of embodiment two, embodiment three preparations is bigger, and its size has better continuity at 0.5 μ m～1 mu m range, has a large amount of folds simultaneously.
Fig. 3 is after being prepared into electrode slice according to the grapheme material that embodiment one, embodiment two, embodiment three are synthesized, the charge/discharge curve under the 100mA/g current density.Can be drawn by figure, the discharge capacity first of these electrodes is respectively: 6.3mAh/g, 103mAh/g, 143.8mAh/g.The former does not almost have capacity, and then both then show better, and this is relevant with its graphene-structured characteristics.Afterwards the Graphene continuity among both is good, many folds, and big sheet interlayer spacing and bigger characteristics such as the interior crystallite dimension of face are of value to the electrochemical hydrogen storage performance.
Fig. 4 is after being prepared into electrode slice according to the grapheme material that embodiment one, embodiment two and embodiment three are synthesized, the stable circulation linearity curve under the 100mA/g current density.By drawing the good cycling stability of these electrodes among the figure.The Graphene electrodes capacity that embodiment three makes is the highest, and after 50 circulations, capacity still maintains more than the 60mAh/g.
Claims (2)
1. the preparation method of a Graphene hydrogen-storage electrode uses control direct-current arc hydrogen plasma equipment automatically, and as anode, negative electrode is a carbon-point with pure graphite block body, feeds active gases, through steps such as pervaporation, condensation, passivation, prepares grapheme material; Utilize this material as active material, evenly mix with bonding agent in proportion, after oven dry, be made into the electrochemical hydrogen storage electrode with the mode that is coated with pressure; Its characteristic may further comprise the steps:
(1) utilize control direct-current arc hydrogen plasma equipment automatically, as anode, negative electrode is a carbon-point with graphite block body, two die openings to 10～30mm, and the hydrogen of feeding 0.01～0.07MPa through pervaporation, condensation, passivation, prepares grapheme material;
(2) Graphene that utilizes step (1) preparation with after binding agent PVDF mixed with mass ratio in 1: 1～7: 1, is made electrode slice with the mode that is coated with pressure as active material; This electrode slice in the three-electrode system of electrochemical hydrogen storage test as work electrode, Ni (OH)
2/ NiOOH electrode is as auxiliary electrode, and calomel electrode is as reference electrode, and electrolyte is the saturated KOH solution of 6mol/L, behind the composition simulated battery it is carried out the test of chemical property.
2. the preparation method of a kind of Graphene hydrogen-storage electrode as claimed in claim 1 is characterized in that, the mass ratio of Graphene and bonding agent is 4: 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037666A (en) * | 2018-08-02 | 2018-12-18 | 盐城市新能源化学储能与动力电源研究中心 | Metal hydride graphene battery and graphene battery |
| CN109545572A (en) * | 2018-11-30 | 2019-03-29 | 北方民族大学 | A kind of Ni1-xCox(OH)2The preparation method of/graphene composite material |
| CN111661843A (en) * | 2020-05-27 | 2020-09-15 | 富耐克超硬材料股份有限公司 | Activated nano graphite powder and preparation method thereof |
| CN115458729A (en) * | 2022-10-28 | 2022-12-09 | 天津普兰能源科技有限公司 | Graphene-coated silicon material, and electric arc preparation method and application thereof |
| CN116334539A (en) * | 2023-05-29 | 2023-06-27 | 深圳市汉嵙新材料技术有限公司 | Preparation method of graphene hydrogen storage membrane material, graphene hydrogen storage membrane material and hydrogen storage tank |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153076A (en) * | 2011-05-04 | 2011-08-17 | 上海大学 | Method for preparing graphene with high crystallinity |
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2012
- 2012-03-31 CN CN2012100937072A patent/CN102623668A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153076A (en) * | 2011-05-04 | 2011-08-17 | 上海大学 | Method for preparing graphene with high crystallinity |
Non-Patent Citations (1)
| Title |
|---|
| 吕维强: "石墨烯的电化学储氢性能及其理论计算", 《哈尔滨工业大学硕士学位论文》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037666A (en) * | 2018-08-02 | 2018-12-18 | 盐城市新能源化学储能与动力电源研究中心 | Metal hydride graphene battery and graphene battery |
| CN109037666B (en) * | 2018-08-02 | 2020-08-07 | 盐城市新能源化学储能与动力电源研究中心 | Metal hydride graphene battery and graphene battery |
| CN109545572A (en) * | 2018-11-30 | 2019-03-29 | 北方民族大学 | A kind of Ni1-xCox(OH)2The preparation method of/graphene composite material |
| CN109545572B (en) * | 2018-11-30 | 2020-07-31 | 北方民族大学 | Ni1-xCox(OH)2Preparation method of/graphene composite material |
| CN111661843A (en) * | 2020-05-27 | 2020-09-15 | 富耐克超硬材料股份有限公司 | Activated nano graphite powder and preparation method thereof |
| CN111661843B (en) * | 2020-05-27 | 2022-12-13 | 富耐克超硬材料股份有限公司 | Activated nano graphite powder and preparation method thereof |
| CN115458729A (en) * | 2022-10-28 | 2022-12-09 | 天津普兰能源科技有限公司 | Graphene-coated silicon material, and electric arc preparation method and application thereof |
| CN116334539A (en) * | 2023-05-29 | 2023-06-27 | 深圳市汉嵙新材料技术有限公司 | Preparation method of graphene hydrogen storage membrane material, graphene hydrogen storage membrane material and hydrogen storage tank |
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Application publication date: 20120801 |