CN1893162A - Double-function liquid flow accumulator with both electric power storage and electrochemical synthesis - Google Patents
Double-function liquid flow accumulator with both electric power storage and electrochemical synthesis Download PDFInfo
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- CN1893162A CN1893162A CNA2005100829735A CN200510082973A CN1893162A CN 1893162 A CN1893162 A CN 1893162A CN A2005100829735 A CNA2005100829735 A CN A2005100829735A CN 200510082973 A CN200510082973 A CN 200510082973A CN 1893162 A CN1893162 A CN 1893162A
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- 238000003860 storage Methods 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 title claims description 43
- 238000003786 synthesis reaction Methods 0.000 title abstract description 4
- 230000015572 biosynthetic process Effects 0.000 title abstract 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 230000005611 electricity Effects 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000004615 ingredient Substances 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 230000005518 electrochemistry Effects 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 230000033116 oxidation-reduction process Effects 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 3
- 238000005341 cation exchange Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000003115 supporting electrolyte Substances 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000003011 anion exchange membrane Substances 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000011231 conductive filler Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 238000005087 graphitization Methods 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 238000004134 energy conservation Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- FYMBCBXJSPPHJQ-UHFFFAOYSA-N [Br].[V] Chemical compound [Br].[V] FYMBCBXJSPPHJQ-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- SKAXWKNRKROCKK-UHFFFAOYSA-N [V].[Ce] Chemical compound [V].[Ce] SKAXWKNRKROCKK-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- -1 alkyl metabolin Chemical compound 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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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- Hybrid Cells (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to a difunctional flow accumulator with both electric power storage and electrochemical synthesis, which reduces high valence ions of an electric pair in a solution flowing through a negative electrode into a low valence state by using input electric energy for use in discharging, and oxidizes oxidizable organic raw materials flowing through a positive electrode into products to be synthesized; during discharging, air (oxygen) is introduced into the positive electrode, oxygen molecules are reduced on the surface of the positive electrode, and the oxygen molecules and reduced electric pairs flowing through the negative electrode solution form a battery to output electric energy. The invention integrates the electric power storage of the flow battery and the electro-oxidation synthesis of organic matters into a whole to form a dual-functional energy-saving and electric power storage system, uses cheap air (oxygen) to ensure that the dual-functional flow battery not only completes the electric power storage-discharge mission, but also can produce organic chemical products, uses one part of electric energy and double functions to achieve the effects of energy saving and gain, and has good application prospect.
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 (claim again liquid stream redox cell), it is long to have a charge and discharge circulation life, and the reliability height does not have discharging and noise, is not subjected to the restriction in geographical position, and the construction period is short, advantage such as moves 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 the devices that a class 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. is proposed, San Francisco, CA.August26-30,1974, 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 by 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 redoxflow battery application as 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 Acta48 (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.of Alloys 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 liquid stream 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 [RemickR J, AngP G P.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 by 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 liquid stream 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 object of the present invention is achieved 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, and 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 by electro-oxidation reaction, in other words, in the charging process, the electric current of input has been finished two things simultaneously, 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.As seen, in each charge and discharge cycle, both carry out the Chemical Manufacture of electroxidation, carried 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 choosing as required) for example, the electrode reaction when then difunctional liquid accumulator cell charges can be expressed as:
Anodal:
(the H of generation
+Remove negative pole by the proton exchange membrane diffusion)
Negative pole:
(with H
+Keep the charge balance of negative solution)
Electrode reaction when difunctional liquid accumulator cell discharges can be expressed as:
Anodal:
, (O
2Reduce required H
+Come by the proton exchange membrane diffusion by negative pole)
Negative pole:
In electrochemical worker, electronics is electricity synthetic " a clean reagent ", both can make " oxidant ", can make " reducing agent " again, and can be under the condition of gentleness with the synthetic many purity height of simple and direct step, product, particularly organic products that added value is high.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 approximately need be with 5 * 10
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 flowing through when charging 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 flowing through when charging 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 flowing through when charging 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 flowing through when charging 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 finish 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
Have the synthetic difunctional liquid accumulator cell of electric power storage-electrochemistry concurrently for the present invention of embodiment brief description below
Embodiment:
With reversible electricity to V
3+/ V
2+Be negative electrode active material, fatty amine is as (C
3H
7)
2NH is anodal reproducibility Organic Ingredients, and the difunctional battery charging/discharging course of reaction of composition is as follows:
The negative pole of battery:
_＝-0.225V
The positive pole of battery:
Charging
_＝1.26V
Discharge
_＝1.229V
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 is not subjected to 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 (as 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, feed compressed air in anodal half-cell, 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 (10)
1, a kind of liquid accumulator cell, it is characterized in that this liquid accumulator cell combines together electric power storage and electrochemistry are synthetic, when charging, with the right high valence ion partial reduction of electricity of will flowing through in the solution of negative pole of the electric energy of input is that lower valency uses when preparing against discharge, and 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 the negative pole of flowing through in the electricity that had been reduced export electric energy to forming battery.
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, the anodal oxidable Organic Ingredients that it is characterized in that flowing through when charging comprises alkene, aromatic hydrocarbons, alcohols, ethers, aldehydes, monose, polysaccharide and nitrogenous, phosphorous or sulfur-containing compound etc.
4, according to the described anodal oxidable Organic Ingredients of when charging, flowing through of claim 3, it is characterized in that this Organic Ingredients is with liquid, the aqueous solution, organic solution, the form of emulsion or suspension-turbid liquid input liquid accumulator cell.
5, according to the described anodal oxidable Organic Ingredients of when charging, flowing through of claim 3, it is characterized in that the used solvent of this Organic Ingredients comprises water, sulfuric acid, methyl alcohol, ethamine etc. for the proton transfer solvent, aprotic solvent comprises acetonitrile, dimethyl formamide, oxolane etc., or binary or the multiple mixed solvent formed such as water and organic solvent such as ethanol, acetonitrile, dimethyl formamide.
6, according to the described anodal oxidable Organic Ingredients of when charging, flowing through of claim 3, it is characterized in that the used supporting electrolyte of this Organic Ingredients is sulfuric acid, nitric acid, perchloric acid, acetic acid, tetrafluoro boric acid, and its esters.
7, liquid accumulator cell according to claim 1 is characterized in that the anodal air or oxygen of flowing through when discharge, its pressure is lower than 1MPa.
8, liquid accumulator cell according to claim 1 is characterized in that used diaphragm material is permoselective membrane, cation-exchange membrane or anion-exchange membrane.
9, liquid accumulator cell according to claim 1, the material that it is characterized in that used bipolar plates are 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.
10, 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013097594A1 (en) * | 2011-12-29 | 2013-07-04 | Ma Zhiqi | Use of anion-exchange membrane in iron-chromium liquid fluid battery |
| CN104064781A (en) * | 2014-06-18 | 2014-09-24 | 许昌学院 | Method for modifying carbon fibers by using beta-PbO2 particles and application of method |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172394C (en) * | 2002-09-26 | 2004-10-20 | 上海交通大学 | Electrochemical synthesis of propanol in protein exchange film fuel cell |
| 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 |
| 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 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013097594A1 (en) * | 2011-12-29 | 2013-07-04 | Ma Zhiqi | Use of anion-exchange membrane in iron-chromium liquid fluid battery |
| CN104064781A (en) * | 2014-06-18 | 2014-09-24 | 许昌学院 | Method for modifying carbon fibers by using beta-PbO2 particles and application of method |
| 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 |
| US10862153B2 (en) | 2015-06-16 | 2020-12-08 | Chrome Plated Power Llc | High-power redox flow battery based on the CrIII/CrVI redox couple and its mediated regeneration |
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| CN1893162B (en) | 2012-03-28 |
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