CN102487142A - Electrode for flow energy storage battery - Google Patents
Electrode for flow energy storage battery Download PDFInfo
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- CN102487142A CN102487142A CN2010105695102A CN201010569510A CN102487142A CN 102487142 A CN102487142 A CN 102487142A CN 2010105695102 A CN2010105695102 A CN 2010105695102A CN 201010569510 A CN201010569510 A CN 201010569510A CN 102487142 A CN102487142 A CN 102487142A
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Abstract
The invention relates to an electrode for a flow energy storage battery. The electrode is prepared by carrying out surface nitrogen mixing and modification on a carbon material, the number of nitrogen atoms of the electrode surface accounts for 2-10 % of the total number of surface atoms, the existing forms of the surface nitrogen contain pyridinic nitrogen, wherein the number of the pyridinic nitrogen atoms accounts for 30-80 % of the total number of surface atoms. According to the invention, lone pair electrons of the pyridinic nitrogen increase the electron density of a graphite layer, thus the electrocatalytic activity of the carbon material is increased; in addition, the introduction of surface nitrogen-containing function groups improves the hydrophilicity of carbon electrode materials; and by doping nitrogen atoms, the conductivity of the electrode material is increased, thus the voltage efficiency and energy efficiency of the flow energy storage battery containing the electrode material are increased. Simultaneously the preparation method is simple and practicable, has no special requirements of devices, has the advantages of convenient operation, low cost, and high practical value, and is easy for batch production.
Description
Technical field
The present invention relates to electrode material, be specifically related to a kind of liquid flow energy storage battery and use electrode material.
Background technology
Liquid flow energy storage battery has power output because of it and capacity is separate, system design is flexible, energy efficiency is high, the life-span is long, the reliability advantages of higher; Has vast potential for future development aspect the scale energy storage; Be considered to solve the effective ways of renewable energy system randomnesss such as solar energy, wind energy and intermittent unstable state characteristic, in renewable energy power generation and intelligent grid construction, great demand arranged.
Electrode is the place of chemical energy-storage system charge and discharge reaction as one of critical component of all-vanadium liquid flow energy storage battery, requires it to have excellent non-oxidizability, conductivity, electrocatalysis characteristic, stability and mechanical strength.Current, liquid flow energy storage battery mainly is divided into metal species electrode material and carbon element class electrode material with electrode material.The metal species electrode material has been proved and has been not suitable for being used as the all-vanadium liquid flow energy storage battery electrode material because the long-time running stability in full vanadium system highly acid electrolyte is generally relatively poor; Carbon element class electrode material mainly comprises carbon paper, charcoal cloth, graphite cake, charcoal felt etc., reveals greater advantage with its good stable gonosome, becomes the emphasis of research and development.Yet if carbon element class material directly is used as electrode material, its electro catalytic activity still is not very good, need carry out activation modification to it and handle.
Present method of modifying mainly comprises metalized and oxidation processes.Wherein,, also make the preparation technology of electrode become complicated, simultaneously owing to use noble metal to cause the cost of electrode higher, so and be not suitable for large-scale application though metalized has improved the electro catalytic activity of electrode material.Oxidation processes is kind and the quantity that increases the electrode material surface oxygen-containing functional group through methods such as gaseous oxidation, liquid phase oxidation or electrochemical oxidations, improves the purpose of vanadium ion at the electrode surface electro-chemical activity to reach.Developed at present the used for all-vanadium redox flow battery electrode material of multiple method for oxidation preparation; Yet though this processing mode has improved the electro catalytic activity of electrode material, the mechanical strength of material and conductivity all obviously descend, and cause battery performance to reduce.
People such as Shao (Nitrogen-doped mesoporous carbon for energy storage in vanadium redox flow batteries. Journal of Power Sources; 2010 (195); 4375-4379.) synthesized meso-porous carbon material through the method for soft template by a trisphenol and nonionic triblock copolymer, after 850 ℃ of NH
3Heat treatment 2h obtains the doped meso-porous material with carbon element of nitrogen under the atmosphere, finds that through contrast nitrogen-containing functional group can improve VO largely
2+/ VO
2 +The reactivity that electricity is right.Yet this material with carbon element is because it exists with powder type, and the carbon element class material that has 3-D solid structure with respect to charcoal felt, graphite felt etc. is all relatively poor at aspects such as mechanical strength, conductivity, and is not suitable for the electrode material of all-vanadium flow battery.
Summary of the invention
The present invention seeks to propose a kind of all-vanadium liquid flow energy storage battery with electrode and preparation method thereof, handle, improve the electro catalytic activity of electrode through nitrating modification to material with carbon element in order to solve above-mentioned all-vanadium liquid flow energy storage battery with the problem that electrode material exists.
To achieve these goals, technical scheme of the present invention does,
Said electrode with material with carbon element as matrix; Matrix is through the nitrating modification, in the nitrogenous material with carbon element layer of its surface formation; And N and C atomic ratio are 0.02-0.3 (can be any range among 0.02-0.1,0.03-0.08, the 0.04-0.06) in the nitrogenous material with carbon element layer, and said material with carbon element is charcoal felt, graphite felt, carbon paper or charcoal cloth.
Said nitrogenous material with carbon element is the nitrogen-doped carbon material, and material with carbon element layer thickness >=0.5 nanometer that electrode surface is nitrogenous is preferably the 10-50 nanometer;
The nitrogen element of 5-90% exists with the form of pyridine type nitrogen in the said nitrogenous material with carbon element layer, and valence bond closes between pyridine type nitrogen-atoms and carbon atom; In the said nitrogenous material with carbon element layer preferably the nitrogen element of 30-60% exist with the form of pyridine type nitrogen, valence bond closes between pyridine type nitrogen-atoms and carbon atom.
The preparation of said electrode: as matrix, under the condition that nitrogen-containing compound exists, matrix gets product in 500-1000 ℃ of nitrogen treatment 0.5-3h after the cooling with material with carbon element.
Nitrogen-containing compound is a kind of in ammonia, amine, cyano compound, nitrogen-containing heterocycle compound, diazonium compound, the azo-compound or more than two kinds.Said nitrogen-containing compound is a kind of in melamine, pyridine, acetonitrile, pyrimidine, oxolane, the urea or more than two kinds.Said material with carbon element comprises charcoal felt, graphite felt, carbon paper or charcoal cloth.
As, one of concrete preparation method of said electrode:
Material with carbon element is warming up to reaction temperature 500-1000 ℃ under the protection of inert gas; Feed ammonia atmosphere then and (can be pure ammonia; Or the gaseous mixture of ammonia and inert gas), the ammonia atmosphere flow is regulated and control according to the quality of the electrode material of putting into, and preferred ammonia flow and electrode material mass ratio are 10-80ml/min/g; Isothermal reaction 0.5-3h is cooled to room temperature again under inert atmosphere.
Preferred 700-900 ℃ of said nitrating reaction temperature, preferred 0.5-1h of reaction time.
The another kind of preparation method of said electrode is:
Material with carbon element is warming up to reaction temperature 500-1000 ℃ under inert gas shielding; The reactor that nitrogen-containing compound will be housed then is warming up to 80-300 ℃; Nitrogenous source is brought in the material with carbon element by inert gas, behind the isothermal reaction 0.5-3h, under inert atmosphere, is cooled to room temperature again.
Said nitrogen-containing compound can be selected from amine, acid amides, cyano compound, nitrogen-containing heterocycle compound, diazonium compound, azo-compound or their mixture, and preferred nitrogen-containing compound is melamine, pyridine, acetonitrile, pyrimidine, oxolane, urea or their mixture.
Said inert gas is a kind of in nitrogen, argon gas or the helium or more than two kinds;
Preferred 700-900 ℃ of said nitrating reaction temperature, preferred 0.5-1h of reaction time.
Said electrode can be in liquid flow energy storage battery application, electrode is the liquid flow energy storage battery electrode of processing as electrode material with nitrogenous material with carbon element, or prepares the liquid flow energy storage battery electrode that nitrogenous material with carbon element layer constitutes in the base material outer surface; Said nitrogenous material with carbon element is the nitrogen-doped carbon material.Base material can be charcoal felt, graphite felt, carbon paper or charcoal cloth.
The application has disclosed nitrating modification material with carbon element electrode and has been used for all-vanadium liquid flow energy storage battery; But be not limited to only be used for this system; In other system liquid flow energy storage battery, also can use, like zinc bromine flow battery, polyhalide/bromine flow battery, tin vanadium flow battery etc.
Beneficial effect of the present invention:
1. electrode material of the present invention has formed pyridine type nitrogen in electrode material surface, has introduced more room, defective to carbon element class substrate material surface, promptly more reaction active site; And the lone pair electrons of pyridine type nitrogen have also increased the electron density of graphite flake layer; Thereby improved the electro catalytic activity of carbon element class basis material.
2. electrode material of the present invention owing to the introducing of surperficial nitrogen-containing functional group, has improved the hydrophily of carbon element class electrode material; And because mixing of nitrogen-atoms improved the conductivity of electrode material, thereby improved the voltage efficiency and the energy efficiency of the all-vanadium liquid flow energy storage battery that comprises it.
3. electrode material preparation method of the present invention is simple, and equipment is not had specific (special) requirements, and is easy to operate, with low cost, has high value of practical, is easy to produce in batches.
Description of drawings
Fig. 1 is the SEM figure of nitrating charcoal felt in the charcoal felt and the embodiment of the invention 1 of being untreated;
(a) be untreated charcoal felt, (b) nitrating charcoal felt;
Fig. 2 is the XPS spectrum figure of nitrating charcoal felt in the charcoal felt and the embodiment of the invention 1 of being untreated;
Fig. 3 is the cyclic voltammetry curve figure of nitrating charcoal felt in the embodiment of the invention 1;
Fig. 4 is the charging and discharging curve figure of nitrating charcoal felt under the different electric current density in the embodiment of the invention 1;
Fig. 5 is the cyclic voltammetry curve figure of nitrating charcoal felt in the embodiment of the invention 2;
Fig. 6 is the cyclic voltammetry curve figure of nitrating charcoal felt in the embodiment of the invention 3.
Embodiment
Through specific embodiment the present invention is described in detail below.
The charcoal felt of certain size is put into the quartz ampoule middle part, insert then in the tube furnace, make the charcoal felt be positioned at the tube furnace medium position.Heating rate with 10 ℃/min under the nitrogen atmosphere protection makes tube furnace be warming up to 700 ℃, feeds ammonia replacement nitrogen then, and ammonia flow is 100ml/min, and isothermal reaction 1h converts ammonia into nitrogen again, is cooled to room temperature.
The pattern of prepared nitrating charcoal felt is as shown in Figure 1.Through finding that with the charcoal felt contrast of being untreated the carbon fiber surface of the charcoal felt that is untreated exists some little amorphous carbon particles, some gullies are distributing; And nitrating charcoal felt surface is cleaner than the charcoal felt that is untreated, and does not have the amorphous carbon granule to exist, and this is because the etching action of ammonia causes, and the gully showed increased, has improved the specific area of charcoal felt.
The XPS spectrum figure of prepared nitrating charcoal felt is as shown in Figure 2.Leniently scan in the spectrogram and can find out, mainly exist C, N, three kinds of elements of O in the charcoal felt.Calculate and can learn according to narrow scan spectrum peak, the carbon content on nitrating charcoal felt surface obviously improves, and oxygen content then reduces, and relative atom concentration has been reduced to 8.9% from 24.3%.The quantity that from the narrow scan spectrogram of C1s, O1s, can observe oxygen-containing functional groups such as hydroxyl, carboxyl significantly reduces.For the N1s peak, nitrogen mainly is to exist with the form of quaternary nitrogen (graphite mould nitrogen) in the charcoal felt, and in nitrating charcoal felt except quaternary nitrogen, also exist pyridine type nitrogen.Pyridine type nitrogen accounts for 45.3% of surface nitrogen total atom number.
Be the electro-chemical activity of test vanadium ion on nitrating charcoal felt surface, the nitrating charcoal felt that embodiment 1 is prepared has carried out the cyclic voltammetric test.As work electrode, the conduct of atresia graphite cake is to electrode with nitrating charcoal felt, and saturated calomel electrode is as reference electrode, and the electro-chemical test instrument of employing is the CHI612 type electrochemical workstation of Shanghai occasion China company.Compound concentration is 0.1M V (II)+0.1M V (III)+3M H
2SO
4With 0.1M V (IV)+0.1M V (V)+3M H
2SO
4Electrolyte, to studying respectively at the electro-chemical activity on nitrating charcoal felt surface, sweep limits is respectively-1V～0V and 0.2～1.4V to V (II)/V (III) and V (IV)/V (V) electricity, sweep speed is 10 mV/s.The cyclic voltammetry curve of nitrating charcoal felt is as shown in Figure 3 in the present embodiment; The relatively big I knowledge of electrochemical oxidation, reduction peak position and peak current of V (II)/V (III) and V (IV)/V (V) on nitrating charcoal felt and the charcoal felt that is untreated, the nitrating charcoal felt charcoal felt that is untreated has the electro catalytic activity and the electrochemical reversibility of obvious raising.
From embodiment 1 the nitrating charcoal felt of preparation cut be of a size of 4cm * 3cm * 0.6cm the charcoal felt as electrode, be assembled into monocell, carry out charge-discharge performance test.Its charging and discharging curve under the different electric current density is as shown in Figure 4, therefrom can find out, the nitrating charcoal felt charcoal felt that is untreated has lower initial charge voltage and higher initial discharge voltage, and current density is high more, and it is remarkable more to improve effect.The battery efficiency that contains nitrating charcoal felt monocell is summarised in the table 1.Compare with the charcoal felt that is untreated, the voltage efficiency that contains nitrating charcoal felt monocell is at 80mA/cm
2Current density under brought up to 86.8% from 83.4%, energy efficiency can reach 81.7%; At 160mA/cm
2High current density under voltage efficiency brought up to 73.5% from 68.9%, energy efficiency brings up to 71.3%.
Embodiment 2
The charcoal felt of certain size is put into the quartz ampoule middle part, insert then in the tube furnace, make the charcoal felt be positioned at the tube furnace medium position.Heating rate with 10 ℃/min under the nitrogen atmosphere protection makes tube furnace be warming up to 900 ℃, feeds ammonia replacement nitrogen then, and ammonia flow is 100ml/min, and isothermal reaction 1h converts ammonia into nitrogen again, is cooled to room temperature.
The cyclic voltammetry curve of the prepared nitrating charcoal of present embodiment felt is as shown in Figure 5; The big I of electrochemical oxidation, reduction peak position and peak current by V (II)/V (III) and V (IV)/V (V) among the figure knows that V (II)/V (III) and V (IV)/V (V) electricity all obviously improves electro-chemical activity on nitrating charcoal felt and electrochemical reversibility.
Embodiment 3
Take by weighing the 200mg melamine and be positioned in the reactor, the charcoal felt is positioned over the tube furnace middle part.Earlier tube furnace heating rate with 10 ℃/min under nitrogen atmosphere is warming up to 800 ℃; The Fast Heating reactor makes it to rise to 300 ℃ again; The melamine of this moment distillation behind the isothermal reaction 0.5h, drops to room temperature at nitrogen atmosphere together with the nitrogen charcoal felt of flowing through together again.
The cyclic voltammetry curve of the prepared nitrating charcoal of present embodiment felt is as shown in Figure 6; The big I of electrochemical oxidation, reduction peak position and peak current by V (II)/V (III) and V (IV)/V (V) among the figure knows that V (II)/V (III) and V (IV)/V (V) electricity all obviously improves electro-chemical activity on nitrating charcoal felt and electrochemical reversibility.
Claims (10)
1. liquid flow energy storage battery electrode; It is characterized in that: said electrode with material with carbon element as matrix; Matrix is through the nitrating modification, in the nitrogenous material with carbon element layer of its surface formation; And N and C atomic ratio are 0.02-0.3 in the nitrogenous material with carbon element layer, and said material with carbon element is charcoal felt, graphite felt, carbon paper or charcoal cloth.
2. according to the said electrode of claim 1, it is characterized in that: said nitrogenous material with carbon element is the nitrogen-doped carbon material, material with carbon element layer thickness >=0.5 nanometer that electrode surface is nitrogenous.
3. according to claim 1 or 2 said electrodes, it is characterized in that: the material with carbon element layer thickness 10-50 nanometer that electrode surface is nitrogenous.
4. according to the said electrode of claim 1, it is characterized in that:
The nitrogen element of 5-90% exists with the form of pyridine type nitrogen in the said nitrogenous material with carbon element layer, and valence bond closes between pyridine type nitrogen-atoms and carbon atom.
5. according to claim 1 or 4 said electrodes, it is characterized in that:
The nitrogen element of 30-60% exists with the form of pyridine type nitrogen in the said nitrogenous material with carbon element layer, and valence bond closes between pyridine type nitrogen-atoms and carbon atom.
6. the preparation method of a claim 1,2,3,4 or 5 said electrodes is characterized in that: as matrix, under the condition that nitrogen-containing compound exists, matrix is in 500-1000 ℃ of nitrogen treatment 0.5-3h with material with carbon element, after the cooling product.
7. according to the described preparation method of claim 6, it is characterized in that:
Nitrogen-containing compound is a kind of in ammonia, amine, cyano compound, nitrogen-containing heterocycle compound, diazonium compound, the azo-compound or more than two kinds.
8. according to claim 6 or 7 described preparation methods, it is characterized in that:
Said nitrogen-containing compound is a kind of in melamine, pyridine, acetonitrile, pyrimidine, oxolane, the urea or more than two kinds.
9. according to the described preparation method of claim 6, it is characterized in that: said material with carbon element comprises charcoal felt, graphite felt, carbon paper or charcoal cloth.
10. the application of the said electrode of claim 1 in liquid flow energy storage battery; It is characterized in that: said electrode is the liquid flow energy storage battery electrode of processing as electrode material with nitrogenous material with carbon element, or prepares the liquid flow energy storage battery electrode that nitrogenous material with carbon element layer constitutes in the base material outer surface; Said nitrogenous material with carbon element is the nitrogen-doped carbon material.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000910A (en) * | 2012-11-19 | 2013-03-27 | 国网电力科学研究院武汉南瑞有限责任公司 | Processing method of graphite felt electrode for all-vanadium redox flow battery |
| CN104409739A (en) * | 2014-11-14 | 2015-03-11 | 天津大学 | Preparation method of nitrogen doped graphite felt used for direct flow methanol fuel cell cathode |
| CN105680082A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Long-lifetime zinc-bromine flow battery structure and electrolyte |
| CN105742658A (en) * | 2016-01-21 | 2016-07-06 | 湖南农业大学 | Preparation method of electrode material for all-vanadium flow battery |
| CN107026272A (en) * | 2016-02-01 | 2017-08-08 | 台湾奈米碳素股份有限公司 | Method for manufacturing nitrogen-containing carbon electrode and flow battery thereof |
| CN108539210A (en) * | 2017-03-03 | 2018-09-14 | 湖南省银峰新能源有限公司 | Heteroatom doping flow battery electrode material |
| CN108598498A (en) * | 2018-05-08 | 2018-09-28 | 沈阳建筑大学 | The graphite felt electrode and preparation method thereof of N doping redox graphene modification |
| CN108878900A (en) * | 2018-06-20 | 2018-11-23 | 湖南国昶能源科技有限公司 | A kind of preparation method of the modified carbon felt of nitrogen-doped graphene |
| CN110534757A (en) * | 2019-09-11 | 2019-12-03 | 上海交通大学 | High performance carbon electrode and preparation method thereof |
| CN110620244A (en) * | 2019-09-24 | 2019-12-27 | 福州大学 | Glucose hydrothermal carbon and nitrogen co-doped graphite felt electrode and preparation method and application thereof |
| CN111244489A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Application of electrode material in zinc-bromine single flow battery |
| CN114249398A (en) * | 2020-09-23 | 2022-03-29 | 中国科学院金属研究所 | Construction method of efficient electro-Fenton cathode material and application of efficient electro-Fenton cathode material in water treatment |
| WO2022186043A1 (en) | 2021-03-05 | 2022-09-09 | 旭化成株式会社 | Electrode for redox flow battery, and method for producing electrode for redox flow battery |
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| CN103000910B (en) * | 2012-11-19 | 2015-03-04 | 国网电力科学研究院武汉南瑞有限责任公司 | Processing method of graphite felt electrode for all-vanadium redox flow battery |
| CN103000910A (en) * | 2012-11-19 | 2013-03-27 | 国网电力科学研究院武汉南瑞有限责任公司 | Processing method of graphite felt electrode for all-vanadium redox flow battery |
| CN104409739A (en) * | 2014-11-14 | 2015-03-11 | 天津大学 | Preparation method of nitrogen doped graphite felt used for direct flow methanol fuel cell cathode |
| CN105680082A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Long-lifetime zinc-bromine flow battery structure and electrolyte |
| CN105742658A (en) * | 2016-01-21 | 2016-07-06 | 湖南农业大学 | Preparation method of electrode material for all-vanadium flow battery |
| CN107026272B (en) * | 2016-02-01 | 2020-04-21 | 台湾奈米碳素股份有限公司 | Method for manufacturing nitrogen-containing carbon electrode and flow battery thereof |
| CN107026272A (en) * | 2016-02-01 | 2017-08-08 | 台湾奈米碳素股份有限公司 | Method for manufacturing nitrogen-containing carbon electrode and flow battery thereof |
| CN108539210A (en) * | 2017-03-03 | 2018-09-14 | 湖南省银峰新能源有限公司 | Heteroatom doping flow battery electrode material |
| CN108598498A (en) * | 2018-05-08 | 2018-09-28 | 沈阳建筑大学 | The graphite felt electrode and preparation method thereof of N doping redox graphene modification |
| CN108598498B (en) * | 2018-05-08 | 2020-09-29 | 沈阳建筑大学 | Graphite felt electrode modified by nitrogen-doped reduced graphene oxide and preparation method thereof |
| CN108878900A (en) * | 2018-06-20 | 2018-11-23 | 湖南国昶能源科技有限公司 | A kind of preparation method of the modified carbon felt of nitrogen-doped graphene |
| CN108878900B (en) * | 2018-06-20 | 2021-06-11 | 湖南国昶能源科技有限公司 | Preparation method of nitrogen-doped graphene modified carbon felt |
| CN111244489A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Application of electrode material in zinc-bromine single flow battery |
| CN111244489B (en) * | 2018-11-28 | 2020-12-15 | 中国科学院大连化学物理研究所 | Application of electrode material in zinc-bromine single flow battery |
| CN110534757A (en) * | 2019-09-11 | 2019-12-03 | 上海交通大学 | High performance carbon electrode and preparation method thereof |
| CN110620244A (en) * | 2019-09-24 | 2019-12-27 | 福州大学 | Glucose hydrothermal carbon and nitrogen co-doped graphite felt electrode and preparation method and application thereof |
| CN114249398A (en) * | 2020-09-23 | 2022-03-29 | 中国科学院金属研究所 | Construction method of efficient electro-Fenton cathode material and application of efficient electro-Fenton cathode material in water treatment |
| CN114249398B (en) * | 2020-09-23 | 2024-06-28 | 中国科学院金属研究所 | Construction method of high-efficiency electro-Fenton cathode material and application of high-efficiency electro-Fenton cathode material in water treatment |
| WO2022186043A1 (en) | 2021-03-05 | 2022-09-09 | 旭化成株式会社 | Electrode for redox flow battery, and method for producing electrode for redox flow battery |
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Application publication date: 20120606 |