CN109103484A - A kind of flow battery and preparation method thereof - Google Patents
A kind of flow battery and preparation method thereof Download PDFInfo
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- CN109103484A CN109103484A CN201810998204.7A CN201810998204A CN109103484A CN 109103484 A CN109103484 A CN 109103484A CN 201810998204 A CN201810998204 A CN 201810998204A CN 109103484 A CN109103484 A CN 109103484A
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- anolyte
- catholyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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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
- 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
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a kind of flow batteries, are related to battery technology field, provide the acid and stannous salt of enough protons since the anolyte group of the flow battery becomes, catholyte group becomes the acid for providing enough protons and contains ferrous salt.Stannous ion in anolyte has higher kinetic constant in acid medium, and reaction rate is big, improves the voltage efficiency of flow battery.The invention also discloses a kind of flow battery preparation methods, when due to using stannous ion as active material in anolyte, the tin that reaction generates rapidly can be deposited and be dissolved in the reaction, and product tin has good electric conductivity, it can make flow battery invertibity with higher, improve the efficiency of flow battery.
Description
Technical field
The present invention relates to battery technology fields more particularly to a kind of flow battery and preparation method thereof.
Background technique
With the development of science and technology, electrochemical energy storage device is more and more concerned by people, wherein liquid stream electricity
Pond possess have extended cycle life, be easy scale, quick response and addressing freely etc. other battery systems hardly matched it is excellent
Gesture, thus flow battery becomes the emphasis of field technical staff research.
Flow battery is a kind of model electrochemical energy storage device, and by battery pile, positive catholyte storage tank and other are auxiliary
Control device is helped to form.There is flow battery energy, power can separate, and design, self discharge is few, have extended cycle life and responds speed
Spend the advantages that fast.In the prior art, the positive catholyte of flow battery uses vanadic salts solution, also referred to as all-vanadium flow
Battery.
But in the above prior art, since the positive catholyte of flow battery is all made of vanadic salts solution, on the one hand,
Vanadium ion in positive catholyte causes the voltage efficiency of flow battery low since kinetic constant is small, on the other hand, positive yin
Reaction product poorly conductive in the electrolyte of pole, causes flow battery electrochemical reaction poorly reversible, inefficiency.
Summary of the invention
The main purpose of the present invention is to provide a kind of flow batteries and preparation method thereof, it is intended to solve in the prior art by
It is all made of vanadic salts solution in the positive catholyte of flow battery, causes the voltage efficiency of flow battery low and flow battery
The technical issues of electrochemical reaction is poorly reversible, inefficiency.
To achieve the above object, first aspect of the embodiment of the present invention provides a kind of flow battery, which includes:
Negative electrode, anode electrode, anolyte fluid reservoir, catholyte fluid reservoir, diaphragm, cathode peristaltic pump with
And positive peristaltic pump；
The negative electrode is separated with the anode electrode by the diaphragm；
Anolyte is stored in the anolyte fluid reservoir, the anolyte is wriggled by the cathode
Pump returns in the anolyte fluid reservoir via the negative electrode；
Catholyte is stored in the catholyte fluid reservoir, the catholyte is wriggled by the anode
Pump returns in the catholyte fluid reservoir via the anode electrode；
The anolyte group, which becomes, provides the acid and stannous salt of enough protons；
The catholyte group becomes the acid for providing enough protons and contains ferrous salt.
Second aspect of the embodiment of the present invention provides a kind of flow battery preparation method, this method comprises:
Configure anolyte and catholyte；
Activate negative electrode and anode electrode；
By the negative electrode, the anode electrode, anolyte fluid reservoir, catholyte fluid reservoir, diaphragm, bear
Pole peristaltic pump and positive peristaltic pump are assembled into flow battery.
The embodiment of the present invention provides a kind of flow battery and preparation method thereof, due to the anolyte group of the flow battery
As the acid and stannous salt of enough protons is provided, catholyte group becomes the acid for providing enough protons and contains ferrous iron
Salt.On the one hand, since the stannous ion in anolyte has higher kinetic constant, reaction rate in acid medium
Greatly, the voltage efficiency of flow battery is improved.On the other hand, when stannous ion is as active material in anolyte, instead
The tin that should be generated rapidly can be deposited and be dissolved in the reaction, and product tin has good electric conductivity, and liquid stream can be made electric
Pond invertibity with higher, improves the efficiency of flow battery.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those skilled in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is a kind of structural schematic diagram of flow battery provided in an embodiment of the present invention；
Fig. 2 is a kind of flow diagram of flow battery preparation method provided in an embodiment of the present invention；
Fig. 3 be in a kind of flow battery preparation method provided in an embodiment of the present invention flow battery under different current densities
Charging and discharging curve figure；
Fig. 4 be in a kind of flow battery preparation method provided in an embodiment of the present invention flow battery under different current densities
Energy efficiency, voltage efficiency and coulombic efficiency datagram.
Specific embodiment
In order to make the invention's purpose, features and advantages of the invention more obvious and easy to understand, below in conjunction with the present invention
Attached drawing in embodiment, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described reality
Applying example is only a part of the embodiment of the present invention, and not all embodiments.Based on the embodiments of the present invention, those skilled in the art
Member's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
Referring to Fig. 1, Fig. 1 is a kind of structural schematic diagram of flow battery provided in an embodiment of the present invention.
As shown in Figure 1, flow battery includes:
Negative electrode 1, anode electrode 2, anolyte fluid reservoir 3, catholyte fluid reservoir 4, diaphragm 5, cathode are compacted
Dynamic pump 6 and positive peristaltic pump 7.
Wherein, it is stored with anolyte in anolyte fluid reservoir 3, is stored with yin in catholyte fluid reservoir 4
Pole electrolyte, cathode peristaltic pump 6 provide power, anode wriggling for the flowing for the circulation for be anolyte in flow battery
Flowing of the pump 7 for the circulation for being catholyte in flow battery provides power.
Further, negative electrode 1 is separated with anode electrode 2 by diaphragm 5, negative electrode 1, diaphragm 5 and anode electrode 2
Two reactive tanks are formed, negative electrode 1 and diaphragm 5 form negative reaction slot, and anode electrode 2 and diaphragm 5 form positive reactive tank.
Further, one end of anolyte fluid reservoir 3 connects the input port of cathode peristaltic pump 6, cathode by pipeline
The delivery outlet of peristaltic pump 6 connects one end of negative reaction slot by pipeline, and the other end of negative reaction slot connects sun by pipeline
The other end of pole electrolyte fluid reservoir 3, anolyte fluid reservoir 3, cathode peristaltic pump 6 and negative reaction slot are sequentially connected composition
Circuit.
The anolyte stored in anolyte fluid reservoir 3 returns to sun via negative electrode 1 by cathode peristaltic pump 6
In pole electrolyte fluid reservoir 3.
Further, one end of catholyte fluid reservoir 4 connects the input port of positive peristaltic pump 7, anode by pipeline
The delivery outlet of peristaltic pump 7 connects one end of positive reactive tank by pipeline, and the other end of positive reactive tank connects yin by pipeline
The other end of pole electrolyte fluid reservoir 4, catholyte fluid reservoir 4, positive peristaltic pump 7 and positive reactive tank are sequentially connected composition
Circuit.
The catholyte stored in catholyte fluid reservoir 4 passes through positive peristaltic pump 7 and returns to yin via anode electrode 2
In pole electrolyte fluid reservoir 4.
Further, negative electrode 1 and anode electrode 2 are separately connected the positive electrode and negative electrode of load 8, and load 8 passes through cathode
By power storage in flow battery, load 8, also i.e. will be electric for by electrical energy transportation to flow battery for electrode 1 and anode electrode 2
It can be stored in flow battery, or obtain electric energy out of flow battery.
Further, anolyte group, which becomes, provides the acid and stannous salt of enough protons.
Further, catholyte group becomes the acid for providing enough protons and contains ferrous salt.
Wherein, flow battery is in charge and discharge process, and there are valences for the active material in anolyte and catholyte
State variation is electroneutral to keep anolyte and catholyte, and flow battery has proton in charge and discharge process
Directional migration.It include the acid of enough protons in above-mentioned anolyte and catholyte, enough protons refer in proton
Directional migration in, required minimum proton concentration.For example, when the active material of anolyte is stannous ion, and it is sub-
The concentration of tin ion is 0.5 mole every liter (mol/L, mole/litre), and the active material of catholyte is ferrous ion, and
The concentration of ferrous ion is 1mol/L, when variation of valence occurs due to the ferrous ion of 1mol/L, at this time in order to keep electrolyte
Minimum proton concentration needed for electroneutral is 1mol/L, and proton concentration is more than or equal to 1mol/L, then it is assumed that the concentration of proton is enough.
Further, containing stannous salt include: stannous chloride, stannous sulfate and other contain stannous salt；
Containing ferrous salt include: frerrous chloride, ferrous sulfate and other contain ferrous salt；Enough protons can be provided
Acid includes: hydrochloric acid, sulfuric acid and other acid for containing proton.
Further, due to including containing stannous salt in anolyte, so containing two in anolyte
Valence tin ion, the reaction occurred on negative electrode 1 in flow battery energy storage are as follows:
Each divalent tin ion obtains two electronics in reaction it can be seen from reaction equation (1), generates metallic tin.
And due in catholyte include contain ferrous salt, so in catholyte containing ferrous iron from
Son, the reaction occurred on anode electrode 2 in flow battery energy storage are as follows:
Each ferrous ion loses an electronics in reaction it can be seen from the reaction equation (2), generates the iron of trivalent
Ion.
Based on above-mentioned reaction, flow battery detailed process in energy storage are as follows: when energy storage, load 8 positive electrode and negative electrode difference
It is connect with the negative electrode 1 of flow battery with anode electrode 2, the anolyte stored in anolyte fluid reservoir 3 passes through
Cathode peristaltic pump 6 is delivered to negative reaction slot, and the divalent tin ion in negative reaction slot anolyte is on negative electrode 1
It reacts, and obtains in load 8 being electronically generated metallic tin in negative reaction slot under single-sided deposition in input current.Yin
The catholyte stored in pole electrolyte fluid reservoir 4 passes through positive peristaltic pump 7 and is delivered to positive reactive tank, in positive reactive tank
Ferrous ion in catholyte reacts on anode electrode 2 loses electronics.Electric energy in external load 8 passes through upper
It states chemical reaction and is converted into chemical energy, be stored in flow battery.
Similar, when flow battery releases the electric energy of storage, tin dissolves in anolyte, generates Bivalent Tin
Ion and electronics, the flowing of electronics form electric current, export to external loading 8.Ferric ion in catholyte obtains electricity
Son generates the iron ion of divalent.The chemical energy stored in flow battery switchs to electric energy and is transmitted to load 8.
For flow battery in energy storage and electric discharge, tin ion variation of valence is single, wherein react the tin of generation in single-sided deposition,
And tin can react in quickly deposition and dissolution, improve the invertibity of flow battery, and increase following for flow battery
Ring number.On the other hand, iron is as a kind of resourceful metal, have it is cheap, the characteristics of being easy to get, and ferrous ion
Electrochemical reaction mechanism is clear, and kinetic constant with higher is suitble in big electricity for mutually converting between ferric ion
It works under current density.The deposition of tin and dissolution and the oxidation of iron ion divalent and trivalent with high power reaction constant are also
Original reaction pairing is that ideal reaction electricity is right.
In embodiments of the present invention, since the anolyte group of the flow battery becomes the acid of the enough protons of offer and contains
Stannous salt, catholyte group become the acid for providing enough protons and contain ferrous salt.On the one hand, due to anode electrolysis
Stannous ion in liquid has higher kinetic constant in acid medium, and reaction rate is big, improves the voltage of flow battery
Efficiency.On the other hand, when stannous ion is as active material in anolyte, the tin for reacting generation can in the reaction quickly
Ground deposition and dissolution, and product tin has good electric conductivity, can make flow battery invertibity with higher, improve
The efficiency of flow battery.
Further, the active material in anolyte is stannous ion, and the active material in catholyte is Asia
Iron ion.Solvent in anolyte and catholyte is acid solution, and wherein acid solution, which refers to, provides enough protons
Acid plus ionized water dilute the dilute acid soln to be formed, in acid solution sour concentration can in the case where guaranteeing to provide enough protons,
It adjusts according to actual needs.
Further, the ratio of the amount of the substance of the ferrous ion in the stannous ion and catholyte in anolyte
Value preferably 1 to 2.The reason of being arranged in this way is: in the energy storage of flow battery, each divalent tin ion is obtained in reaction
Two electronics need two when each ferrous ion loses an electronics namely a divalent tin ion reaction in reaction
Ferrous ion participates in reaction.So in the ideal situation in order to guarantee battery in reaction process electricity price balance, it is only necessary to will
The ratio of the amount of the substance of the ferrous ion in stannous ion and catholyte in anolyte is preferably 1 to 2.
Further, it can be needed according to the actual situation when practical application, change the stannous ion and yin in anolyte
The ratio of the amount of the substance of ferrous ion in the electrolyte of pole.Such as in order to improve the utilization rate of active material in anolyte
And increase the amount of active material in catholyte, specifically, if the stannous that the active material in anolyte is 1mol/L
Ion, the ferrous ion that the active material in catholyte is 2mol/L have the stannous of 1mol in flow battery charge and discharge
Ion reacts, and due to following conservation of electrons law in reaction process, while having the ferrous ion of 2mol to react, but real
Chemical reaction both in the operation of border mass transfer can occur because the relatively chemical reaction of chemical reaction later period concentration of electrolyte reduces early period
Problem causes the active material in electrolyte that can not react completely, so in order to improve the active matter in anolyte
Matter utilization rate can increase the amount of cathode active material, in order to react the stannous ion in anolyte as far as possible, anode
The ratio of the amount of the substance of the ferrous ion in stannous ion and catholyte in electrolyte can be changed to 1 to 3, i.e., ferrous
It is 3mol/L that concentration, which increases,.Conversely, anode electrolysis can be increased in order to improve the utilization rate of active material in catholyte
The amount of active material in liquid.
Further, negative electrode 1 and anode electrode 2 are the carbon fiber material with multiple holes, 1 He of negative electrode
Anode electrode 2 is the identical pellet electrode of specification, and with a thickness of 1 millimeter to 5 millimeters, maximum two sides of lateralarea are area
1 square centimeter to 4 square centimeters of square, wherein carbon fiber material be graphite felt, carbon felt, carbon cloth, carbon paper, foamy carbon,
And one of other carbon class materials, wherein material used in carbon fibre is commercial carbon fibre, commercial carbon
Fiber is lighter compared to general carbon fibre, more resistant to corrosion and higher intensity.
Further, diaphragm 5 is amberplex or porous septum.
Further, the range of flow of cathode peristaltic pump 6 and positive peristaltic pump 7 10 milliliters per minute to 60 milliliters it
Between.
In embodiments of the present invention, since the anolyte group of the flow battery becomes the acid of the enough protons of offer and contains
Stannous salt, catholyte group become the acid for providing enough protons and contain ferrous salt.On the one hand, due to anode electrolysis
Stannous ion in liquid has higher kinetic constant in acid medium, and reaction rate is big, improves the voltage of flow battery
Efficiency.On the other hand, when stannous ion is as active material in anolyte, the tin for reacting generation can in the reaction quickly
Ground deposition and dissolution, and product tin has good electric conductivity, can make flow battery invertibity with higher, improve
The efficiency of flow battery.
Referring to Fig. 2, Fig. 2 is a kind of flow diagram of flow battery preparation method provided in an embodiment of the present invention.
As shown in figure 3, this method comprises:
S101, configuration anolyte and catholyte.
Wherein, it configures anolyte and catholyte specifically includes:
Prepare anolyte:
Analysis pure hydrochloric acid or the sulfuric acid amount of reordering deionized water are diluted to anode diluted acid.
Further, stannous chloride solid or stannous sulfate solid are quantified in sparse middle be added of anode, obtains anode electrolysis
Liquid, wherein the concentration of anolyte Anodic diluted acid is 1mol/L to 7mol/L, the concentration of stannous chloride or stannous sulfate
For 1mol/L to 6mol/L.
Prepare catholyte:
Analysis pure hydrochloric acid or the sulfuric acid amount of reordering deionized water are diluted to cathode diluted acid.
Further, quantitative frerrous chloride or ferrous sulfate solid are added in cathode diluted acid, obtains catholyte,
The concentration of cathode diluted acid is 1mol/L to 7mol/L in middle catholyte, and the concentration of frerrous chloride or ferrous sulfate is 1mol/L
To 3mol/L.
Wherein, the dosage of anolyte and electrolyte liquid can positive and negative electrode electrode active material it is flux matched before
It puts, freely adjusts concentration and dosage, to obtain the battery of different capabilities size.
S102, activation negative electrode and anode electrode.
Wherein, it activates negative electrode and anode electrode specifically includes:
Negative electrode and anode electrode are placed in the heating device filled with protective gas.
Further, the temperature in heating device is heated to 300 degrees Celsius to 600 degrees Celsius, and keeps the temperature 0.5 hour extremely
6 hours.Wherein heating rate when heating devices heat is 1 centigrade per minute to 10 centigrade per minutes, and protective gas is
Oxidizing gas or inert gas.
S103, by negative electrode, anode electrode, anolyte fluid reservoir, catholyte fluid reservoir, diaphragm, cathode
Peristaltic pump and positive peristaltic pump are assembled into flow battery.
Wherein, by negative electrode, anode electrode, anolyte fluid reservoir, catholyte fluid reservoir, diaphragm, cathode
Peristaltic pump and positive peristaltic pump are assembled into flow battery and specifically include:
Utilize the negative electrode and anode electrode after diaphragm isolation activation.
Further, using the thickness of polyethylene gasket control negative electrode and anode electrode, so that the compression ratio of electrode
It is 50% to 70%.
Wherein, negative electrode and anode electrode are the carbon fiber material with multiple holes, negative electrode and anode electricity
The extremely identical pellet electrode of specification, with a thickness of 1 millimeter to 5 millimeters, maximum two sides of lateralarea are 1 square li of area
The square of rice to 4 square centimeters, wherein carbon fiber material is graphite felt, carbon felt, carbon cloth, carbon paper, foamy carbon, Yi Jiqi
One of his carbon class material, wherein material used in carbon fibre is commercial carbon fibre, commercial carbon fibre phase
It is lighter than in general carbon fibre, more resistant to corrosion and higher intensity.
Further, structure is fastened by bolts to negative electrode, anode electrode, anolyte fluid reservoir, cathode electricity
Solution liquid fluid reservoir, diaphragm, cathode peristaltic pump and positive peristaltic pump are fixed, and are assembled into flow battery.
Wherein, the thickness of electrode of negative electrode and anode electrode, electrode size and electrode material can within the above range certainly
By selecting.
Further, the flow battery after being completed also is needed to carry out charge-discharge test.
Wherein, charge-discharge test is carried out to the flow battery after being completed to specifically include:
By the flow velocity for the flow battery Anodic electrolyte that the control of cathode peristaltic pump is completed, and by positive compacted
The flow velocity of catholyte in the flow battery that dynamic pump control is completed.
Further, the charge-discharge test of flow battery is carried out under different current densities using battery tester.
In embodiments of the present invention, flow battery is made by a kind of fluid cell preparation method, due to the flow battery
Anolyte group become the acid and stannous salt of enough protons be provided, catholyte group, which becomes, provides enough protons
Acid and contain ferrous salt.On the one hand, since the stannous ion in anolyte has higher power in acid medium
Constant is learned, reaction rate is big, improves the voltage efficiency of flow battery.On the other hand, stannous ion is as in anolyte
Active material when, the tin for reacting generation rapidly can be deposited and be dissolved in the reaction, and product tin have good electric conductivity,
It can make flow battery invertibity with higher, improve the efficiency of flow battery.
Further, below by a specific embodiment to a kind of flow battery provided in the embodiment of the present invention
Preparation method does step detailed description.
S201, configuration anolyte.
Taking 25.05 milliliters of mass fractions is that 36% to 38% hydrochloric acid is placed in 100 milliliters of burnings equipped with 40 milliliters of distilled water
In cup.
Further, the beaker equipped with hydrochloric acid is placed on magnetic stirring apparatus, beaker is stirred with 200 rpms of revolving speed
1 minute, obtain anode dilute acid soln.
Further, 11.51 gram of two hydrated stannous chloride solid is weighed, is added in the anode dilute acid soln of aforementioned arrangements,
It places the beaker on magnetic stirring apparatus again, the solid in beaker is stirred to being completely dissolved.
Further, the solution in beaker is transferred in 100 milliliters of volumetric flask by glass bar, by volumetric flask
In solution constant volume after, obtain 100 milliliters include 3mol/L hydrochloric acid and 0.5mol/L stannous chloride mixed solutions, gained mixing
Solution is anolyte.
S202, configuration catholyte.
Taking 25.05 milliliters of mass fractions is that the hydrochloric acid of 36%-38% is placed in 100 milliliters of beakers equipped with 40 milliliters of distilled water
In.
Further, the beaker equipped with hydrochloric acid is placed on magnetic stirring apparatus, beaker is stirred with 200 rpms of revolving speed
1 minute, obtain cathode dilute acid soln.
Further, 28.08 gram of six ferrous sulfate hydrate solid is weighed, is added in the cathode dilute acid soln of aforementioned arrangements,
It places the beaker on magnetic stirring apparatus again, the solid in beaker is stirred to being completely dissolved.
Further, the solution in beaker is transferred in 100 milliliters of volumetric flask with glass bar, by volumetric flask
Solution constant volume after, obtain 100 milliliters include 3mol/L hydrochloric acid and 1mol/L ferrous sulfate mixed solutions, gained mixed solution
As catholyte.
S203, activated electrode.
Untreated carbon felt or carbon cloth are placed in Muffle furnace, in air atmosphere, with 10 centigrade per minutes
Temperature in muffle furnace is warming up to 300 degrees Celsius by heating rate, and keeps the temperature three hours, the carbon felt activated or carbon cloth,
Carbon felt or carbon cloth after activation are by the anode electrode and negative electrode as flow battery.
S204, assembled battery.
Cutting three pieces area respectively is 4 square centimeters and with a thickness of 0.2 millimeter through 300 celsius temperatures in Muffle furnace
Carbon cloth and a piece of area after activation are 4 square centimeters and with a thickness of 2.5 millimeters through 300 degrees Celsius of height in Muffle furnace
Carbon felt after temperature activation.
Further, carbon cloth is placed in side of the positive electrode, and with polyethylene gasket enclosed electrode, coordination electrode thickness.
Further, carbon felt is placed in negative side, in cathode close to a piece of nonconducting carbon cotton of side cushioning of diaphragm, and
With polyethylene gasket enclosed electrode, coordination electrode thickness.
Further, the diaphragm among two lateral electrodes is isolated using proton exchange membrane, is added electrode combination with movable bolt
Gu obtaining flow battery after being completed.
Further, battery is tested.
25 milliliters of electrolyte are respectively taken from the volumetric flask prepared in S201 and S202, are respectively placed in anolyte fluid reservoir
And in catholyte fluid reservoir.Anolyte and cathode are controlled respectively by cathode peristaltic pump and positive peristaltic pump
Electrolyte flow rate is 10 milliliters per minute to 40 milliliters per minute.
Further, the charge-discharge test of flow battery is carried out under different current densities with battery tester.It is preferred that
, the charge-discharge test of flow battery is carried out using new prestige battery tester.
In flow battery provided in an embodiment of the present invention, the negative electrode provided in S204 also contains one in addition to carbon felt
The electrode of layer nonconductive carbon cotton, the actual discharge capacity for the battery for using this method to be assembled into is 535 milliampere hour.In another liquid
Cathode is only made of a piece of carbon felt in galvanic battery, remaining assemble method is identical, and actual discharge capacity is 401 milliampere hour, and cathode removes
The flow battery of electrode outside carbon felt also containing one layer of nonconductive carbon cotton is than the flow battery that cathode is only made of a piece of carbon felt
Discharge capacity increases 33.4%.
Further, Fig. 3 and Fig. 4 are please referred to, Fig. 3 is in a kind of flow battery preparation method provided in an embodiment of the present invention
Charging and discharging curve figure of the flow battery under different current densities.Fig. 4 is a kind of flow battery system provided in an embodiment of the present invention
Energy efficiency, voltage efficiency and coulombic efficiency of the flow battery under different current densities in Preparation Method.
In order to further measure the performance of flow battery, respectively 40 milliamperes of current densities every square centimeter, 80 milliamperes it is every
Square centimeter current density, 120 milliamperes of current density, 160 milliamperes of current densities every square centimeter and 200 millis every square centimeter
Pacify the charge and discharge process for testing flow battery under current density every square centimeter, obtains flow battery under different current densities
Charging and discharging curve figure for further details, please refer to Fig. 3.
Further, be also tested for flow battery 40 milliamperes of current densities every square centimeter, 80 milliamperes it is every square centimeter
Current density, 120 milliamperes of current densities every square centimeter, 160 milliamperes of current densities every square centimeter and 200 milliamperes every square
Energy efficiency, voltage efficiency and coulombic efficiency under centimetre current density, for further details, please refer to Fig. 4.
It can be seen that flow battery under 200 milliamperes of current densities every square centimeter in conjunction with Fig. 3 and Fig. 4, still maintain
Higher 74% energy efficiency.
In embodiments of the present invention, flow battery is made by a kind of fluid cell preparation method, due to the flow battery
Anolyte group become the acid and stannous salt of enough protons be provided, catholyte group, which becomes, provides enough protons
Acid and contain ferrous salt.On the one hand, since the stannous ion in anolyte has higher power in acid medium
Constant is learned, reaction rate is big, improves the voltage efficiency of flow battery.On the one hand, due to the stannous ion in anolyte
There is higher kinetic constant in acid medium, reaction rate is big, improves the voltage efficiency of flow battery.On the other hand,
When stannous ion is as active material in anolyte, the tin for reacting generation rapidly can be deposited and be dissolved in the reaction,
And product tin has good electric conductivity, can make flow battery invertibity with higher, improve the effect of flow battery
Rate.
In several embodiments provided herein, it should be understood that disclosed battery and battery preparation method, it can
To realize by another way.For example, battery structure embodiment described above is only schematical.
It should be noted that for the various method embodiments described above, describing for simplicity, therefore, it is stated as a series of
Combination of actions, but those skilled in the art should understand that, the present invention is not limited by the sequence of acts described because
According to the present invention, certain steps can use other sequences or carry out simultaneously.Secondly, those skilled in the art should also know
It knows, the embodiments described in the specification are all preferred embodiments, and related actions and modules might not all be this hair
Necessary to bright.
In the above-described embodiments, it all emphasizes particularly on different fields to the description of each embodiment, there is no the portion being described in detail in some embodiment
Point, it may refer to the associated description of other embodiments.
The above are the descriptions to a kind of flow battery provided by the present invention and preparation method thereof, for the technology of this field
Personnel, thought according to an embodiment of the present invention, there will be changes in the specific implementation manner and application range, to sum up, this
Description should not be construed as limiting the invention.
Claims (10)
1. a kind of flow battery, which is characterized in that the battery includes:
Negative electrode, anode electrode, anolyte fluid reservoir, catholyte fluid reservoir, diaphragm, cathode peristaltic pump and just
Pole peristaltic pump；
The negative electrode is separated with the anode electrode by the diaphragm；
Anolyte is stored in the anolyte fluid reservoir, the anolyte is passed through by the cathode peristaltic pump
It is returned in the anolyte fluid reservoir by the negative electrode；
Catholyte is stored in the catholyte fluid reservoir, the catholyte passes through the positive peristaltic pump warp
It is returned in the catholyte fluid reservoir by the anode electrode；
The anolyte group, which becomes, provides the acid and stannous salt of enough protons；
The catholyte group becomes the acid for providing enough protons and contains ferrous salt.
2. battery according to claim 1, which is characterized in that active material in the anolyte be stannous from
Son, the active material in the catholyte are ferrous ion；
The ratio of the amount of the substance of the ferrous ion in stannous ion and the catholyte in the anolyte is 1
Than 2.
3. battery according to claim 1, which is characterized in that the negative electrode and the anode electrode is with multiple
The carbon fiber material of hole, the negative electrode and the anode electrode are the identical pellet electrode of specification, with a thickness of 1 millimeter
To 5 millimeters, square that maximum two sides of lateralarea are 1 square centimeter to 4 square centimeters of area, wherein the carbon
Cellulose fiber material is one of graphite felt, carbon felt, carbon cloth, carbon paper and foamy carbon.
4. battery according to claim 3, which is characterized in that the diaphragm is amberplex or porous septum.
5. battery according to claim 4, which is characterized in that the flow of the cathode peristaltic pump and the positive peristaltic pump
Range is per minute between 10 milliliters to 60 milliliters.
6. a kind of flow battery preparation method, which is characterized in that the described method includes:
Configure anolyte and catholyte；
Activate negative electrode and anode electrode；
The negative electrode, the anode electrode, anolyte fluid reservoir, catholyte fluid reservoir, diaphragm, cathode is compacted
Dynamic pump and positive peristaltic pump are assembled into flow battery.
7. according to the method described in claim 6, it is characterized in that, the configuration anolyte and catholyte packet
It includes:
Prepare the anolyte:
Analysis pure hydrochloric acid or the sulfuric acid amount of reordering deionized water are diluted to anode diluted acid；
Quantitative stannous chloride solid or stannous sulfate solid are added in the anode diluted acid, obtains the anolyte,
Described in anode diluted acid described in anolyte concentration is 1 mole and often rises to 7 moles every liter, stannous chloride or sulfuric acid are sub-
The concentration of tin is 1 mole and often rises to 6 moles every liter.
Prepare the catholyte:
Analysis pure hydrochloric acid or the sulfuric acid amount of reordering deionized water are diluted to cathode diluted acid；
Quantitative frerrous chloride or ferrous sulfate solid are added in the cathode diluted acid, obtains the catholyte, wherein institute
The concentration for stating cathode diluted acid described in catholyte is 1 mole and often rises to 7 moles every liter, frerrous chloride or ferrous sulfate it is dense
Degree often rises to 3 moles every liter for 1 mole.
8. the method according to the description of claim 7 is characterized in that the activation negative electrode and anode electrode include:
The negative electrode and the anode electrode are placed in the heating device filled with protective gas；
Temperature in the heating device is heated to 300 degrees Celsius to 600 degrees Celsius, and keeps the temperature 0.5 hour to 6 hours,
Described in heating devices heat when heating rate be 1 centigrade per minute to 10 centigrade per minutes, the protective gas is
Oxidizing gas or inert gas.
9. according to the method described in claim 8, it is characterized in that, described by the negative electrode, the anode electrode, anode
Electrolyte fluid reservoir, catholyte fluid reservoir, diaphragm, cathode peristaltic pump and positive peristaltic pump are assembled into flow battery packet
It includes:
Utilize the negative electrode and the anode electrode after diaphragm isolation activation；
The thickness of the negative electrode and the anode electrode is controlled using polyethylene gasket so that the compression ratio of electrode be 50 to
70%；
Structure is fastened by bolts to the negative electrode, the anode electrode, the anolyte fluid reservoir, the cathode
Electrolyte fluid reservoir, the diaphragm, the cathode peristaltic pump and the positive peristaltic pump are fixed, and are assembled into the liquid
Galvanic battery.
10. according to the described in any item methods of claim 6 to 9, which is characterized in that the method also includes:
The flow velocity of anolyte described in the flow battery being completed by cathode peristaltic pump control, Yi Jitong
Cross the flow velocity of catholyte described in the flow battery that the positive peristaltic pump control is completed；
The charge-discharge test of the flow battery is carried out under different current densities using battery tester.
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Cited By (1)
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|---|---|---|---|---|
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