CN1893162B - Liquid accumulator cell with double functions of accumulating and electrochemical synthesizing - Google Patents
Liquid accumulator cell with double functions of accumulating and electrochemical synthesizing Download PDFInfo
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- CN1893162B CN1893162B CN2005100829735A CN200510082973A CN1893162B CN 1893162 B CN1893162 B CN 1893162B CN 2005100829735 A CN2005100829735 A CN 2005100829735A CN 200510082973 A CN200510082973 A CN 200510082973A CN 1893162 B CN1893162 B CN 1893162B
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- accumulator cell
- liquid accumulator
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The dual functional fluid flow accumulator has both functions of storage and electrochemical synthesis. In charging time, using inputted electric energy deoxidizes ion in high valence of electron pair in solution passing through cathode to ion in low valence for use in discharging time. In discharging time, air (oxygen) is passed over anode. Oxygen molecules are deoxidized on surface of anode. The deoxidized oxygen molecules and already deoxidized electron pair in solution passing through cathode constitute battery so as to output electric energy. The invention syncretizes storage and electric oxo synthesis of organic matter so as to form integration with dual functional energy saving and storage system. The invention accomplishes dual functions of charging-discharging target, and producing organic chemically products.
Description
Technical field
The present invention relates to a kind ofly, belong to power engineering and electrochemical industry field the synthetic difunctional liquid accumulator cell that combines together of electric power storage and electrochemistry.Can be widely used in electric energy savings, peak load regulation network and fields such as dynamo-electric synthetic are arranged.
Background technology
Renewable energy power generations such as development and use solar energy and wind energy are the important measures of national economy sustainable development.Improving efficiency of energy utilization (being called for short energy-conservation), is one of eternal important topic in energy research field.Countries in the world are more and more paid attention to regenerative resource and power-saving technology.The energy consumption that China is calculated with GDP at present is 3 times of the U.S., 5 times of Europe, 9 times of Japan, and energy-conservation potentiality are very big, and task is very heavy.Save electric power and in energy-conservation, occupy primary position, not only can improve utilization of power efficient, and can reduce fossil fuel consumption, alleviate air pollution.
Develop extensive electric power storage, be used for the electric power storage of accent " peak ", solar energy and the wind power generation field of electrical network, large electricity consumer's electric power storage, military electric power storage, can make full use of the generating capacity in all kinds of power stations, supply increases electric power.The liquid accumulator cell that had developed in the last few years (claiming the flow redox cell again), advantage such as it is long to have a charge and discharge circulation life, and reliability is high, does not have discharging and noise, does not receive the restriction in geographical position, and the construction period is short, and operation and fees of maintenance are lower.Make analysis-by-synthesis relatively with chemical energy storage such as lithium ion battery, sodium sulphur fusion battery, chromium nickel-based battery, lead-acid battery, liquid accumulator cell and ultracapacitors, property/price ratio and fail safe very have superiority, and are one type of devices that is suitable for extensive electric power storage.
The Thaller of U.S. NASA Lewis Research Center in 1974; L.H., a kind of electrochemical energy storage device [Ninth Intersoc.Energy Conv.Eng.Conf., San Francisco, CA.August26-30 are proposed; 1974; Pp.924-928 (NASA TM X-71540)], original text is Flow Redox Cell or Redox flow cell energystorage systems, Chinese letter is translated into liquid accumulator cell.The liquid accumulator cell of " chromium-iron system " is in when charging, the right active material of high potential electricity at positive pole by Fe
+ 2Be oxidized to Fe
+ 3On the negative pole of amberplex opposite side, the right active material of electronegative potential electricity is by Cr
+ 3Be reduced into Cr
+ 2During discharge, above-mentioned two processes are reversed.Multinational scholar is right through two OR electricity of conversion over 30 years, has proposed different liquid accumulator cell systems.Recent years, the new system of research was gradually many; Cerium vanadium system [Study of the Ce (III)/Ce (IV) redox couple for redox flowbattery application like propositions such as B.Fang; Electrochimica acta 47 (2002) 3971-3976]; Full chromium system [the Chromium redox couples for application to redox flow batteries that C.H.Bae etc. propose; Eleetro-chimica Acta 48 (2002) 279-287]; Vanadium-bromine system [Novel vanadium chloride/polyhalide redox flow battery that Maria Skyllas-kazacos proposes; J.power sources124 (2003) 299-302], the full uranium system liquid accumulator cells such as [Characterization of tetraketone ligands for active materials of all-uranium redoxflow battery.J.ofAlloys and Compounds (2004)] that T.Yamamura etc. propose.But that has developed into fairly large electric power storage has only vulcanized sodium/bromine system and full vanadium system.Britain Innogy company has built up the large-scale flow electric power storage station of the sodium polysulfide/bromine system of power 15 megawatts in 2002; Can hold 150 megawatt hour electric energy; 10 hours discharge [Remick R J; AngPGP.Electrically rechargeable anionically active reduction-oxidation electricalstorage-supply system [P] .US:4485154,1984.].Built the large-scale electric power storage of the sodium polysulfide/bromine system station that to hold 120 megawatt hour electric energy for the inferior air base of U.S.'s Mississippi taxi driver brother's rival again in 2004.Liquid accumulator cell [the Ch.Fabjan of country's researchs such as Canada, Japan, Germany, Austria and Portugal, the full vanadium system of development; J.Garche; B.Harrer, The vanadium redox-battery:an efficient storage unit for photovoltaic systems.Electrochimica Acta, 47 (2001) 825-831.]; Power reaches hundreds of multikilowatts, and energy efficiency can reach about 80%.
Be included in anode and the negative electrode different with common storage battery active material; Liquid accumulator cell is dissolved in respectively as the right active material of OR electricity and is contained in two solution in the big fluid reservoir; Each makes the both sides of flow of solution through flow battery intermediate ion exchange membrane with a pump, and reduction and oxidation reaction take place on its porous electrode.During charging, it is transformed into chemical energy with direct current and saves in the electrolyte that feeds positive polar region of flow battery and negative pole district.At this moment, the right lower valency ion of high potential electricity that is dissolved with in the anodal electrolyte is oxidized to high valence state; Simultaneously, the right high valence state ion of electronegative potential electricity that is dissolved with in the negative pole electrolyte is reduced to lower valency.During discharge, electrochemical reaction is undertaken by opposite direction, and the ion of positive and negative electrode electrolyte changes lower valency and high valence state respectively into.Cell is connected into pile through bipolar plates, and similar is in fuel cell.Because power and stored energy capacitance can be considered separately, thereby the flexibility of design is big, is easy to module combinations, and fluid reservoir does not have size restrictions, electric power storage on a large scale, and range of application can be wide.
Existing flow electric power storage system has only simple storage function, and does not have the synthetic function of electrochemistry.
Do not found report in the document at home and abroad about the liquid accumulator cell that has the synthetic dual-use function of electric power storage and electrochemistry concurrently.
Summary of the invention
The purpose of this invention is to provide a kind of with electric power storage and the synthetic difunctional liquid accumulator cell that combines together of electrochemistry.
The objective of the invention is to realize like this, during charging, will flow through with the electric energy of input and to use when the right high valence ion of electricity is reduced to lower valency in order to discharge in the solution of negative pole, the anodal oxidable Organic Ingredients of will flowing through simultaneously is oxidized to required synthetic product; During discharge, to anodal bubbling air or oxygen, oxygen molecule is at anodal surface reduction, it with the solution of the negative pole of flowing through in the electricity that had been reduced export electric energy, a electric energy, dual utilization to forming battery.
In " having the synthetic difunctional liquid accumulator cell of electric power storage-electrochemistry concurrently " of the present invention; Electricity is identical with the flow battery of above-mentioned classics to the electrochemical reaction character of ion in the negative pole electrolyte; Anodal reactant and electrochemical reaction are then all different with it: during charging; Feed the solution of oxidable Organic Ingredients to positive polar region, change new product into through electro-oxidation reaction, in other words; In the charging process; The electric current of input has been accomplished two things simultaneously, and it had both made in the negative pole electrolyte electricity that ion is changed into lower valency and energy storage from high valence state, and carried out electrochemistry again in positive polar region synthetic and to be combined to electricity consumption effective equally with the electrochemistry oxygen of general electrochemical factory; During discharge; Do not fill solution in the positive polar region, but to positive polar region bubbling air (oxygen), oxygen is reduced on positive pole; Form battery with the ion pairing that has been reduced to lower valency in the negative pole electrolyte; In other words, utilize the strong oxidability of cheap air (oxygen), the time be reduced to the ion of lower valency and produced electric energy in charging in the oxidation negative pole electrolyte.It is thus clear that, in each charge and discharge cycle, both carried out the Chemical Manufacture of electroxidation, carry out electric power storage and discharge again, thereby improved the utilization ratio of electric energy.
With [OC]
REExpression oxidizable organic compound raw material, [OC]
OXRepresent oxidized organic compound, negative electricity is to temporarily with Cr
3+/ Cr
2+Represent (the actual electricity that uses is to choose as required) for example, the electrode reaction when then difunctional liquid accumulator cell charges can be expressed as:
Anodal: [OC]
RE-e--→ [OC]
OX+ H
+The H that produces
+Remove negative pole through the PEM diffusion) negative pole: Cr
3++ e--→ Cr
2+(with H
+Keep the charge balance of negative solution) electrode reaction during the discharge of difunctional liquid accumulator cell can be expressed as:
Anodal: O
2+ 4e+4H
+--→ 2H
2O (O
2Reduce required H
+Come through the PEM diffusion by negative pole)
Negative pole: Cr
2+-e--→ Cr
3+
In electrochemical worker, electronics is electricity synthetic " a clean reagent ", both can make " oxidant ", can make " reducing agent " again, and can under the condition of gentleness, synthesize the product, particularly organic products that many purity are high, added value is high with simple and direct step.So organic electrochemistry has developed into an important subdiscipline, dynamo-electric compound probability development is arranged rapidly.Usually the synthetic 1 ton of organic products of electricity need use 5 * 10 approximately
3～1 * 10
4The electric energy of kWh is so the synthetic enterprise of electricity is important electric energy user.Improve the utilization of power efficient of the synthetic enterprise of electricity, can alleviate power tense, can reduce cost again, important reality and far-reaching significance are arranged.
In " have concurrently electric power storage-electrochemistry synthetic difunctional liquid accumulator cell " of the present invention, electric right in the solution of the negative pole of when charging, flowing through, its with respect to the standard oxidationreduction potential of standard hydrogen electrode below 1.2 volts.In fact, as long as negative pole is not separated out hydrogen, standard oxidationreduction potential electric right in the solution of the negative pole of flowing through is low more good more.The cell emf that is lower than the pairing of 0 volt of person and oxygen electrode will can be emitted bigger energy during discharge greater than 1.23 volts (standard oxidationreduction potentials of oxygen electrode); Be preferably lower than-0.4 volt, this moment, cell emf will be greater than 1.63 volts, and the energy of emitting will be bigger.
In " having the synthetic difunctional liquid accumulator cell of electric power storage-electrochemistry concurrently " of the present invention, the anodal oxidable Organic Ingredients of when charging, flowing through comprises alkene, aromatic hydrocarbons, alcohols, ethers, aldehydes, monose, polysaccharide and nitrogenous, phosphorous or sulfur-containing compound etc.
In " having the synthetic difunctional liquid accumulator cell of electric power storage-electrochemistry concurrently " of the present invention; The anodal oxidable Organic Ingredients of when charging, flowing through is their liquid own, their aqueous solution, their organic solution, their emulsion or their suspension-turbid liquid.
In " having the synthetic difunctional liquid accumulator cell of electric power storage-electrochemistry concurrently " of the present invention; The anodal used solvent of oxidable Organic Ingredients of when charging, flowing through comprises water, sulfuric acid, methyl alcohol, ethamine etc. for the proton transfer solvent; Aprotic solvent comprises acetonitrile, dimethyl formamide, oxolane, or water and organic solvent such as ethanol, acetonitrile or dimethyl formamide binary or the multiple mixed solvent formed.
In " having the synthetic difunctional liquid accumulator cell of electric power storage-electrochemistry concurrently " of the present invention; The anodal used supporting electrolyte of oxidable Organic Ingredients of when charging, flowing through is big and high acid and its esters of decomposition voltage of solubility; Comprise: sulfuric acid, nitric acid, perchloric acid, acetic acid, tetrafluoro boric acid, and its esters.
In " having the synthetic difunctional liquid accumulator cell of electric power storage-electrochemistry concurrently " of the present invention, the anodal air or oxygen of when discharge, flowing through, its pressure is lower than 1MPa.Oxygen can any ratio be mixed in air or other gas.
In " having the synthetic difunctional liquid accumulator cell of electric power storage-electrochemistry concurrently " of the present invention, diaphragm material is permoselective membrane, cation-exchange membrane or anion-exchange membrane.
In " having the synthetic difunctional liquid accumulator cell of electric power storage-electrochemistry concurrently " of the present invention, the material of used bipolar plates is the stainless steel of graphite, modification flexible graphite, injection mo(u)lding graphite, the composite material based on polymer-conductive filler, titanium or titanium alloy and various electrocorrosion-resistings.
In " have concurrently electric power storage-electrochemistry synthetic difunctional liquid accumulator cell " of the present invention, the material of electrode used therein is graphitization or non-graphitized porous carbon felt, carbon paper, porous carbon slab, POROUS TITANIUM PLATE, surface deposition PbO
2Titanium plate, surface deposition PbO
2Graphite cake.
The electric power storage of liquid accumulator cell is blended in one with synthetic the combining of organic electroxidation; Form bifunctional energy-conservation, an electric power storage system, utilize cheap air (oxygen), make difunctional flow battery both accomplish electric power storage-discharge mission; And can produce organic chemical industry's product; A electric energy, dual utilization reach effect energy-conservation and gain, have a good application prospect.
Embodiment
Lift the present invention of embodiment brief description below and have the synthetic difunctional liquid accumulator cell of electric power storage-electrochemistry concurrently
Embodiment:
With reversible electricity to V
3+/ V
2+Be negative electrode active material, fatty amine C
2H
5CH
2NH
2Be anodal reproducibility Organic Ingredients, the difunctional battery charging and discharging course of reaction of composition is following:
Battery negative:?
The positive pole of battery
Charging (C
2H
5CH
2)
2NH+H
2O-2e=C
2H
5CH
2NH
2+ C
2H
5CHO+2H
+
Discharge O
2+ 4H
++ 2e=2H
2O
The fatty amine betatopic is oxidized, the about 1.48V of theoretical open circuit voltage of electrolytic cell during charging.Adopting the water of high-k is solvent, HClO
4Or H
2SO
4Be supporting electrolyte, the solution potential window of composition is about 2V, and therefore, above-mentioned cell reaction process does not receive liberation of hydrogen/analyse the oxygen side reaction to influence, and negative electricity is to having good invertibity and dynamic characteristic.Adopt the cation-exchange membrane (like the Nafion film) of high selectivity, macroion conductivity, graphite is bipolar plates, and the porous carbon felt of PAN base is an electrode, can realize the charging of difunctional battery.After the charging, fatty amine (C
3H
7)
2NH is by alkylation removal, and the synthetic N-that obtains being applied to complicated medicine removes alkyl metabolin (C
2H
5CH
2NH
2).Then, the technology synthetic as electroxidation is the same, and the material in the anodal fluid reservoir all changes separation, the extraction that subsequent processing carries out product over to; Use when in anodal fluid reservoir, injecting new raw material in order to the next round charging.
During discharge, in anodal half-cell, feed compressed air, at acid medium, reduction reaction then takes place in oxygen on the porous carbon felt of carried catalyst Pt, the V in the negative solution
2+Oxidation reaction takes place, and close about 1.45V when both theoretical open circuit voltages and charging has realized the discharge of difunctional battery.The coulombic efficiency that discharges and recharges of battery depends primarily on negative pole, generally more than 90%.Have dynamo-electric synthetic productive rate about about 80%, current efficiency is about 70%.
Claims (7)
1. liquid accumulator cell; It is characterized in that this liquid accumulator cell combines together electric power storage and electrochemistry are synthetic; When charging; Use the right high valence ion partial reduction of electricity in the solution of negative pole of will flowing through of the electric energy of input to use during in order to discharge as lower valency, the anodal oxidable Organic Ingredients of will flowing through simultaneously is oxidized to required synthetic product; During discharge; Form oxygen electrode to anodal bubbling air or oxygen; It with the solution of negative pole of flowing through in the electricity that had been reduced export electric energy to forming battery, wherein said oxidable Organic Ingredients comprises alkene, aromatic hydrocarbons, alcohols, ethers, aldehydes, monose, polysaccharide and nitrogenous, phosphorous or sulfur-containing compound; The used solvent of said Organic Ingredients is binary or the multiple mixed solvent that water, sulfuric acid, methyl alcohol, ethamine, acetonitrile, dimethyl formamide, oxolane, ethanol or water and ethanol, acetonitrile, dimethyl formamide are formed; The used supporting electrolyte of said Organic Ingredients is sulfuric acid, nitric acid, perchloric acid, acetic acid, tetrafluoro boric acid, and its esters.
2. liquid accumulator cell according to claim 1 is characterized in that electric right in the solution of negative pole the time is flowed through in charging, its with respect to the standard oxidationreduction potential of standard hydrogen electrode below 1.2 volts.
3. liquid accumulator cell according to claim 1 is characterized in that the form input liquid accumulator cell of this Organic Ingredients with the aqueous solution, organic solution, emulsion or suspension-turbid liquid.
4. liquid accumulator cell according to claim 1 is characterized in that being mixed in the mist of air or other gas at the time flow through anodal air, oxygen or oxygen of discharge with any ratio, and its pressure is lower than 1MPa.
5. liquid accumulator cell according to claim 1 is characterized in that used diaphragm material is permoselective membrane, cation-exchange membrane or anion-exchange membrane.
6. liquid accumulator cell according to claim 1, the material that it is characterized in that used bipolar plates are the stainless steel of graphite, the composite material based on polymer-conductive filler, titanium or titanium alloy and various electrocorrosion-resistings.
7. liquid accumulator cell according to claim 1, the material that it is characterized in that electrode used therein are graphitization or non-graphitized porous carbon felt, carbon paper, porous carbon slab, POROUS TITANIUM PLATE, surface deposition PbO
2Titanium plate, surface deposition PbO
2Graphite cake.
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| CN102832363B (en) * | 2011-12-29 | 2016-03-02 | 苏州久润能源科技有限公司 | The application of anion-exchange membrane in iron-chromium system liquid phase fluid battery |
| CN104064781B (en) * | 2014-06-18 | 2017-01-04 | 许昌学院 | A kind of β-PbO2the method of particle modifying carbon fibers and application thereof |
| CN107996007A (en) * | 2015-06-16 | 2018-05-04 | 镀铬电力有限公司 | Based on CrIII/CrVIThe high power redox flow batteries of oxidation-reduction pair and its regeneration of mediation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404181A (en) * | 2002-09-26 | 2003-03-19 | 上海交通大学 | Electrochemical synthesis of propanol in protein exchange film fuel cell |
| CN1545161A (en) * | 2003-11-27 | 2004-11-10 | 上海交通大学 | Method for electrochemical hydrogenation and electric energy symbiosis of water-soluble unsaturated organic acid |
| CN1545160A (en) * | 2003-11-27 | 2004-11-10 | 上海交通大学 | Method for electrochemical hydrogenation and electric energy symbiosis of water-soluble unsaturated alcohol |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1404181A (en) * | 2002-09-26 | 2003-03-19 | 上海交通大学 | Electrochemical synthesis of propanol in protein exchange film fuel cell |
| CN1545161A (en) * | 2003-11-27 | 2004-11-10 | 上海交通大学 | Method for electrochemical hydrogenation and electric energy symbiosis of water-soluble unsaturated organic acid |
| CN1545160A (en) * | 2003-11-27 | 2004-11-10 | 上海交通大学 | Method for electrochemical hydrogenation and electric energy symbiosis of water-soluble unsaturated alcohol |
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