CN108365247A - A kind of bromo- half flow battery with ion embedded type solid cathode - Google Patents
A kind of bromo- half flow battery with ion embedded type solid cathode Download PDFInfo
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- CN108365247A CN108365247A CN201810055189.2A CN201810055189A CN108365247A CN 108365247 A CN108365247 A CN 108365247A CN 201810055189 A CN201810055189 A CN 201810055189A CN 108365247 A CN108365247 A CN 108365247A
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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
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention belongs to electrochemical technology field, specially a kind of half flow battery of bromine with ion embedded type solid cathode.The battery system specifically includes：The positive liquid that negative electrode solution that titanium phosphate sodium or titanium phosphate cathode of lithium, the aqueous solution containing one or both of sodium ion or lithium ion are constituted, amberplex, the aqueous solution containing one or both of bromide ion anode and sodium ion or lithium ion are constituted.The present invention is using high potential Br2/Br‑While electricity is to doing flow battery anode, liquid cathode in traditional flow battery is replaced using the solid-state water system negative material titanium phosphate sodium or titanium phosphate lithium of high-energy density, both bromine flow battery voltage height had been maintained, the advantage that energy work rate separately designs, is safe, having extended cycle life, simultaneously because not limited by solute concentration, the energy density of negative side greatly improves, battery impedance substantially reduces, and greatly improves the volume energy density, mass energy density and working efficiency of entire battery module.
Description
Technical field
The invention belongs to battery technology fields, and in particular to a kind of bromo- half liquid stream electricity with ion embedded type solid cathode
Pond.
Background technology
Flow battery can realize electricity by the Reversible redox reaction of the active material in positive and negative anodes electrolyte solution
Energy is mutually converted with chemical energy, while having the characteristics that energy work rate can separate design, high security, long circulation life, special
It is not suitble to do large scale electric network energy storage.The flow battery system developed at present include all-vanadium flow battery, iron/chrome liquor galvanic battery,
Sodium polysulfide/bromine redox flow cell, zinc/bromine flow battery, zinc/iron liquid galvanic battery etc., wherein all-vanadium flow battery tentatively business
Change.However, the concentration limitation due to active material in electrolyte solution, the energy density of flow battery is not generally high, and by
In largely using liquid positive-negative pole, flow battery volume is larger, equipment volume of the volume energy density with respect to other energy storage modes
Energy density is relatively low.What is more important vanadium substance has higher toxicity, can be caused seriously to environment if leakage
Pollution.Flow battery based on zinc solution was got the attention at nearly 2 years, however the solution modeling of zinc load can cause sternly
The dendrite problems of weight can cause battery short circuit, and then influence the safety and stability of equipment after zinc dendrite pierces through diaphragm.
Water system sodium ion or lithium ion battery are equally the Hot spots for development of current energy storage technology.Water system sodium ion or lithium ion
The energy storage principle of battery and organic system sodium, lithium ion battery are essentially identical, have following remarkable advantage：First, water system electricity
Solution matter has many advantages, such as low cost, high security compared to organic electrolyte at high price and inflammable, toxic.Meanwhile lithium ion
Or migration rate faster, therefore can use thicker electrode to sodium ion in aqueous solution in actual production, and realize better
Power characteristic.Titanium phosphate sodium (NaTi2(PO4)3) it is a kind of embedded abjection type water system sodium ion or lithium ion battery negative material,
With typical NASICON structures, tunnel size allows sodium ion or lithium ion free migration, sodium ion can also be allowed embedding
Enter, lithium ion is embedded and lithium sodium ion is embedded in jointly.Titanium phosphate sodium or titanium phosphate lithium have lower current potential, phase in aqueous solution
To the charge and discharge platform of larger capacity, stabilization, splendid high rate performance and outstanding cycle performance.Therefore, titanium phosphate sodium or
Titanium phosphate lithium is considered as a kind of suitable high power, extensive, long-time energy storage water system sodium-ion battery or lithium ion battery
Negative material.Currently, titanium phosphate sodium cathode and titanium phosphate cathode of lithium have realized same sodium manganese oxygen anode (Na respectively0.44MnO2) or
LiMn2O4（LiMn2O4）Anode constitutes novel water system sodium-ion battery system or aquo-lithium ion battery system.However these water
It is the performance of system and unsatisfactory：The dynamic process of sodium manganese oxygen anode and lithium manganate cathode is existed by sodium ion or lithium ion
Diffusion in solid electrode is limited, therefore limits the power density of system.In addition, proton in aqueous solution also can be along with
Sodium ion or lithium ion are embedded into sodium manganese oxygen anode or lithium manganate cathode, cause capacity attenuation.What is more important, this causes
Sodium manganese oxygen anode and lithium manganate cathode are all very sensitive to the pH value of electrolyte, therefore when enclosed type water system battery is analysed when overcharging
When oxygen, proton concentration increase, with sodium, the lithium ion in sodium manganese oxygen or LiMn2O4 exchange reaction will occur for proton, lead to capacity
Decaying.
The present invention combines the concept of traditional flow battery concept and water system sodium ion, lithium ion battery, it is proposed that is based on
Bromo- half flow battery system of inlaid scheme titanium phosphate sodium or titanium phosphate lithium solid cathode.Its anode, which uses, contains bromide ion
And the liquid stream type anode of trace amounts of bromine simple substance.Compared with traditional all-vanadium flow battery, which uses the higher Br of current potential2/Br-
Electricity also compares V to doing anode, cathode potential3+/V2+It is lower, therefore there is higher open-circuit voltage and energy storage capacity.It is born with based on zinc
The flow battery of pole is compared, and there is no the dendrite problems caused by zinc dissolving deposition.In addition, compared with traditional flow battery,
The battery system only has anode to need fluid reservoir, therefore significantly increases the volume ratio and mass-energy density metric density of system.It is another
Aspect, compared with traditional water system sodium-ion battery or water system ion battery, which can show higher power characteristic,
Main reason is that the diffusion velocity of sodium ion or lithium ion in liquid anode far above its solid electrode diffusion velocity,
Therefore system can export higher power.What is more important, the small pH value variation of electrolyte, does not interfere with liquid bromine anode
Stability, large volume liquid stream can also make positive and negative anodes pendular ring border maintain to stablize relatively, therefore proposed by the invention based on embedding
Enter the single flow battery system of compound cathode, more traditional water system sodium ion or lithium ion battery also have the longer cycle longevity
Life.
Invention content
It is an object of the invention to propose that a kind of long-life, high-energy density, high stable have an ion embedded type solid
Bromo- half flow battery of cathode.
Bromo- half flow battery proposed by the present invention with ion embedded type solid cathode comprising：
Titanium phosphate sodium cathode or titanium phosphate cathode of lithium；
The negative electrode solution that aqueous solution containing one or both of sodium ion and lithium ion is constituted；
Amberplex；
Negative one valence bromide ion anode, and
The positive liquid that aqueous solution containing one or both of sodium ion and lithium ion is constituted.
In the present invention, the titanium phosphate sodium cathode or titanium phosphate cathode of lithium, it is necessary to comprising active material titanium phosphate sodium or
Titanium phosphate lithium includes additionally conductive agent, binder and collector.By active material titanium phosphate sodium or titanium phosphate lithium and conductive agent
And binder is bonded cathode by electrode film is made in a manner of roll-in after evenly mixing with collector.Wherein, active matter
The content of matter titanium phosphate sodium or titanium phosphate lithium must be between 30%-90%.In negative electrode film, the loading of active material is
100-2000 mg cm-2 。
In the present invention, the titanium phosphate sodium or titanium phosphate lithium have typical nanoscale（Less than 800 nanometers
Grain）, modified surface has carbon-coating, for improving electronic conductance.Nanoscale and surface-carbon-modified cathode can effectively shorten sodium from
The diffusion path of son or lithium ion and the electronic conductance for enhancing electrode material, so that the negative material has higher multiplying power
Characteristic.
In the present invention, the titanium phosphate sodium cathode or titanium phosphate cathode of lithium are reversibly embedded in sodium ion and lithium ion,
Or the two is embedded in jointly.
In the present invention, the material of the carbon-coating of the surface modification is the agraphitic carbon of organic carbon formation, carbon nanometer
Pipe, one kind in graphene or several mixtures.
In the present invention, the conductive agent is mesoporous carbon, hard charcoal, graphite, graphene, single wall or multi-walled carbon nanotube, carbon
One kind in the conductive materials such as fiber, acetylene black or carbon black, or in which it is several；The content of conductive agent is between 1% to 30%.
In the present invention, the binder is polytetrafluoroethylene (PTFE), Kynoar, polyolefin, polyvinyl alcohol, butadiene-styrene rubber
One or more of；The content of binder is between 1% -30%.
In the present invention, the collector is the solid network for having high electronic conductance, can be carbon felt, graphite felt, conduction
Graphite cake, electrically conductive graphite net, carbon cloth, titanium net, nickel screen, copper mesh, aluminium net, one kind in stainless (steel) wire or in which several compound
Object.
In the present invention, the negative one valence bromide ion anode, it includes negative one valence bromide ion (Br to be-) and trace amounts of bromine list
Matter (Br2) aqueous solution, negative one valence bromide ion concentration is between 0.1 mol/L to 10 mol/L.
In the present invention, the positive liquid and negative electrode solution are aqueous solution, and contain sodium ion (Na+) and lithium ion (Li+)
One or both of, lithium sodium ion total concentration is between 0.1-10 mol/L.
In the present invention, the positive liquid and negative electrode solution, in addition to containing one or both of sodium ion and lithium ion, also
May include potassium ion (K+), magnesium ion (Mg2+), zinc ion (Zn2+), ammonium ion (NH4 +One or more of), it is dense
Degree is 0.1-2.0 mol/L.
In the present invention, the positive liquid and negative electrode solution, in addition to bromine anion, the anion that can also contain, it is described it is cloudy from
Son is sulfate radical (SO4 2-), nitrate anion (NO3 -), phosphate radical (PO4 3-), one hydrogen radical (HPO of phosphoric acid4 2-), dihydrogen phosphate
(H2PO4 -), chlorion (Cl-) and hydroxyl (OH-One or more of), corresponding ion concentration is in 0.1 mol/L to 10
Between mol/L.
In the present invention, the amberplex is：Nafion（Polytetrafluoroethylene (PTFE)（Teflon®）With perfluor -3,6- bis-
The copolymer of epoxy -4- methyl -7- decene-sulfuric acid）Film and its all kinds of derivative or the cation-exchange membrane of reinforcement（Its thickness
Between 30-200 μm）, there is microporous mesoporous selectivity to penetrate film（Aperture is between 2-200 nm）, it is semi-permeable membrane, anti-
Permeable membrane etc..
In the present invention, bromo- half flow battery with ion embedded type solid cathode, including clamping plate, gasket, stream
Necessity device such as road flow-field plate, graphite plate current collectors, carbon felt enables to be assembled into finished battery.Its structure is as shown in Figure 1.
Bromo- half flow battery of the present invention with ion embedded type solid cathode, operation principle such as Fig. 2 institutes
Show.When playing energy storage effect charging, the negative one valence bromide ion in positive liquid loses electronics and is oxidized to bromo- half flow battery
Bromine simple substance, sodium ion or lithium ion in positive liquid enter negative electrode solution by cation-exchange membrane, negative material titanium phosphate sodium or
Titanium phosphate lithium obtains electronics and embedded sodium ion or lithium ion in reduction process；Then by cathode titanium phosphate when as corona discharge
Sodium or titanium phosphate lithium provide electronics, and bromine simple substance obtains electronics and is converted into negative one valence bromide ion, sodium ion or lithium ion from negative electrode solution
It migrates to positive liquid.
The electrode reaction of the battery is summarized as follows：
1. bromo- half flow battery system based on titanium phosphate sodium cathode
Charging process：
Anode：2Br- - 2e- à Br2
Cathode：NaTi2(PO4)3 + 2Na+ + 2e- à Na3Ti2(PO4)3
Discharge process：
Anode：Br2 + 2e- à 2 Br-
Cathode：Na3Ti2(PO4)3 - 2Na+ - 2e- à NaTi2(PO4)3
2. bromo- half flow battery system based on titanium phosphate cathode of lithium
Charging process：
Anode：2Br- - 2e- à Br2
Cathode：LiTi2(PO4)3 + 2Li+ + 2e- à Li3Ti2(PO4)3
Discharge process：
Anode：Br2 + 2e- à 2 Br-
Cathode：Li3Ti2(PO4)3 - 2Na+ - 2e- à LiTi2(PO4)3 。
As described above, the anode of the battery is bromide ion in water system anode liquor, redox reaction is in bromo- half liquid
It is carried out in the carbon felt or graphite felt in liquid stream side in galvanic battery；The cathode of the battery is and the collector with high electronic conductance
In conjunction with titanium phosphate sodium or titanium phosphate cathode of lithium electrode, the insertion of sodium ion or lithium ion in cathode occurs in charge and discharge process
Abjection reaction.The invention replaces the negative electrode solution in traditional flow battery to do the negative of battery by using ion embedded type compound
Pole greatly reduces the working volume of battery, by being matched with the higher bromide ion anode of solubility, has been obviously improved battery
Energy density and working efficiency.Embedded compound avoids the dendrite that conventional zinc flow battery is faced and is formed in the use of cathode
The problem of.In addition, the electrode active material operation interval used in this kind of half liquid stream system is wider, more existing all-vanadium flow
Battery system has the characteristics that voltage is high, energy density is big.Compared with traditional water system sodium-ion battery or ion battery, liquid
Sodium ion or lithium ion have compared with faster ion diffusion rates in solid state electrode in anode, therefore this kind of are based on inlaid scheme
The water system sodium-ion battery or aquo-lithium ion battery that bromo- half flow battery system of cathode is more traditional have higher power close
Degree.What is more important, the small pH value variation of electrolyte, does not interfere with the stability of liquid bromine anode, large volume liquid stream
Positive and negative anodes pendular ring border can be made to maintain to stablize relatively.After usage time long enough, regeneration can be realized by replacing electrolyte,
Positive and negative anodes are made to remain at optimum state, therefore the half flow battery body proposed by the invention based on inlaid scheme cathode
System, more traditional water system sodium ion or lithium ion battery also have longer cycle life.
In the present invention, cathode preparation method：Active material titanium phosphate sodium or titanium phosphate lithium and conductive agent and binder is equal
It is bonded cathode by even mixing by the electrode film made by roll-in mode with collector.
In order to verify the electrochemistry of novel bromo- half flow battery with ion embedded type solid cathode in the present invention
Can, we have carried out related electro-chemical test to assembled battery.Wherein positive liquid electrolyte uses 2.0 mol/L
Na2SO4, negative electrode solution is using 2.0 mol/L Na2SO4.Test shows of the present invention with ion embedded type solid cathode
Bromo- half flow battery has good high rate performance and cyclical stability in the operation interval of 0-2 V.In 40 mA cm-2It puts
Coulombic efficiency reaches 99% in the case of electricity, and energy efficiency is up to 90%, and can 2000 cycles of stable operation.In 80 mA cm-2
Coulombic efficiency reaches 97% in the case of electric discharge, energy efficiency 86%.Under precondition of the energy efficiency more than 80%, battery
Working current density can reach 100 mA cm-2.When active material concentration is 1 mol/L in positive liquid, tool of the present invention
There is the bromo- half flow battery energy density of ion embedded type solid cathode up to 42 Wh/L, active material concentration is in positive liquid
When 2 mol/L, the bromo- half flow battery energy density of the present invention with ion embedded type solid cathode up to 80 Wh/L,
Show good scalability.
Novel bromo- half flow battery with ion embedded type solid cathode of the present invention, by water system sodium ion electricity
The advantage of pond and flow battery combines, and the characteristics of designing can be separated by maintaining energy work rate, and charge-discharge performance is good, makes
It is safe without risk of explosion on fire with long lifespan.It, which compares traditional flow battery, simultaneously higher-wattage energy density, because
This its be very suitable for carrying out development utilization as next-generation extensive energy storage device.
Description of the drawings
Fig. 1 is the bromo- half flow battery structural exploded view that the present invention has ion embedded type solid cathode.
The bromo- half flow battery fundamental diagram of present invention when Fig. 2 is using titanium phosphate sodium as negative electrode active material.
The bromo- half flow battery fundamental diagram of present invention when Fig. 3 is using titanium phosphate lithium as negative electrode active material.
Fig. 4 is the bromo- half flow battery working efficiency figure that the present invention has ion embedded type solid cathode.
Specific implementation mode
By embodiment, the present invention is further illustrated down.
Embodiment 1：Bromo- half flow battery based on titanium phosphate sodium cathode Yu bromide ion anode, positive and negative anodes liquid are sodium sulphate.
In the example, anode uses 2 mol/L NaBr solution（10 mL）, positive and negative anodes liquid is all made of 2.0 mol/L Na2SO4。
Diaphragm is 115 films of Nafion.Cathode uses carbon-coated titanium phosphate sodium, cathode film preparation as follows：According to active material（Phosphorus
Sour titanium sodium）：Conductive agent（Carbon nanotube）：Binder（Polytetrafluoroethylene (PTFE)）Mass ratio 8:1:1 is rolled into uniformly after evenly mixing
Film is tailored into the electrode of 3 cm*3.5 cm sizes and with titanium net collector with the uniform tabletting of sandwich structure, makes most after drying
For whole finished electrode thickness in 0.5 mm or so, active material loading is 400 mg cm-2Left and right.In 40 mA cm-2Electric discharge
In the case of coulombic efficiency reach 99%, energy efficiency is up to 92%, and can 2000 cycles of stable operation.In 80 mA cm-2It puts
Coulombic efficiency reaches 97% in the case of electricity, energy efficiency 87%.Under precondition of the energy efficiency more than 80%, battery
Working current density can reach 100 mA cm-2.Calculate to obtain 80 Wh/L of energy density.
Embodiment 2：Bromo- half flow battery based on titanium phosphate sodium cathode Yu bromide ion anode, positive and negative anodes liquid are sodium sulphate.
Anode uses 1 mol/L NaBr solution in the example（20 mL）, positive and negative anodes liquid is all made of 2.0 mol/L Na2SO4。
Diaphragm is 115 films of Nafion.Cathode uses carbon-coated titanium phosphate sodium, cathode film preparation as follows：According to active material（Phosphorus
Sour titanium sodium）：Conductive agent（Carbon nanotube）：Binder（Polytetrafluoroethylene (PTFE)）Mass ratio 8:1:1 is rolled into uniformly after evenly mixing
Film is tailored into the electrode of 3 cm*3.5 cm sizes and with titanium net collector with the uniform tabletting of sandwich structure, makes most after drying
For whole finished electrode thickness in 0.5 mm or so, active material loading is 400 mg cm-2Left and right.In 40 mA cm-2Electric discharge
In the case of coulombic efficiency reach 99%, energy efficiency is up to 89%, and can 2000 cycles of stable operation.In 80 mA cm-2It puts
Coulombic efficiency reaches 97% in the case of electricity, energy efficiency 84%.Under precondition of the energy efficiency more than 80%, battery
Working current density can reach 96 mA cm-2.Calculate to obtain 42 Wh/L of energy density.
Embodiment 3：Bromo- half flow battery based on titanium phosphate cathode of lithium Yu bromide ion anode, positive and negative anodes liquid are lithium sulfate.
Anode uses 2 mol/L LiBr solution in the example（10 mL）, positive and negative anodes liquid is all made of 2.0 mol/L Li2SO4。
Diaphragm is 115 films of Nafion.Cathode uses carbon-coated titanium phosphate lithium, cathode film preparation as follows：According to active material（Phosphorus
Sour titanium lithium）：Conductive agent（Carbon nanotube）：Binder（Polytetrafluoroethylene (PTFE)）Mass ratio 8:1:1 is rolled into uniformly after evenly mixing
Film is tailored into the electrode of 3 cm*3.5 cm sizes and with titanium net collector with the uniform tabletting of sandwich structure, makes most after drying
For whole finished electrode thickness in 0.5 mm or so, active material loading is 400 mg cm-2Left and right.In 40 mA cm-2Electric discharge
In the case of coulombic efficiency reach 99%, energy efficiency is up to 91%, and can 2000 cycles of stable operation.In 80 mA cm-2It puts
Coulombic efficiency reaches 97% in the case of electricity, energy efficiency 87%.Under precondition of the energy efficiency more than 80%, battery
Working current density can reach 98 A cm-2。
Embodiment 4：Bromo- half flow battery based on titanium phosphate sodium cathode Yu bromide ion anode, positive and negative anodes liquid are lithium sulfate.
Anode uses 2 mol/L LiBr solution in the example（10 mL）, positive and negative anodes liquid is all made of 2.0 mol/L Li2SO4。
Diaphragm is 115 films of Nafion.Cathode uses carbon-coated titanium phosphate sodium, cathode film preparation as follows：According to active material（Phosphorus
Sour titanium sodium）：Conductive agent（Carbon nanotube）：Binder（Polytetrafluoroethylene (PTFE)）Mass ratio 8:1:1 is rolled into uniformly after evenly mixing
Film is tailored into the electrode of 3 cm*3.5 cm sizes and with titanium net collector with the uniform tabletting of sandwich structure, makes most after drying
For whole finished electrode thickness in 0.5 mm or so, active material loading is 400 mg cm-2Left and right.In 40 mA cm-2Electric discharge
In the case of coulombic efficiency reach 99%, energy efficiency is up to 91, and can 2000 cycles of stable operation.In 80 mA cm-2Electric discharge
In the case of coulombic efficiency reach 97%, energy efficiency 86%.Under precondition of the energy efficiency more than 80%, the work of battery
98 mA cm can be reached by making current density-2。
Embodiment 5：Bromo- half flow battery based on titanium phosphate cathode of lithium Yu bromide ion anode, positive and negative anodes liquid are sodium sulphate.
Anode uses 2 mol/L NaBr solution in the example（10 mL）, positive and negative anodes liquid is all made of 2.0 mol/L Na2SO4。
Diaphragm is 115 films of Nafion.Cathode uses carbon-coated titanium phosphate sodium, cathode film preparation as follows：According to active material（Phosphorus
Sour titanium lithium）：Conductive agent（Carbon nanotube）：Binder（Polytetrafluoroethylene (PTFE)）Mass ratio 8:1:1 is rolled into uniformly after evenly mixing
Film is tailored into the electrode of 3 cm*3.5 cm sizes and with titanium net collector with the uniform tabletting of sandwich structure, makes most after drying
For whole finished electrode thickness in 0.5 mm or so, active material loading is 400 mg cm-2Left and right.In 40 mA cm-2Electric discharge
In the case of coulombic efficiency reach 99%, energy efficiency is up to 91, and can 2000 cycles of stable operation.In 80 mA cm-2Electric discharge
In the case of coulombic efficiency reach 97%, energy efficiency 86%.Under precondition of the energy efficiency more than 80%, the work of battery
97 A cm can be reached by making current density-2。
Table 1. uses the bromo- half flow battery performance of different positive and negative anodes and positive and negative anodes liquid
。
Claims (10)
1. a kind of bromo- half flow battery with ion embedded type solid cathode, which is characterized in that including：
Titanium phosphate sodium cathode or titanium phosphate cathode of lithium；
The negative electrode solution that aqueous solution containing one or both of sodium ion and lithium ion is constituted；
Amberplex；
Negative one valence bromide ion anode, and
The positive liquid that aqueous solution containing one or both of sodium ion and lithium ion is constituted.
2. bromo- half flow battery according to claim 1 with ion embedded type solid cathode, which is characterized in that institute
The titanium phosphate sodium cathode or titanium phosphate cathode of lithium stated, including：Active material titanium phosphate sodium or titanium phosphate lithium, conductive agent, binder
And collector；By active material titanium phosphate sodium or titanium phosphate lithium with conductive agent and binder by after evenly mixing with the side of roll-in
Electrode film made of formula is bonded cathode with collector；The content of active material titanium phosphate sodium or titanium phosphate lithium is 30%-90%；
The loading of active material in negative electrode film is 100-2000 mg cm-2。
3. bromo- half flow battery according to claim 2 with ion embedded type solid cathode, which is characterized in that institute
There is the titanium phosphate sodium or titanium phosphate lithium stated the particle scale less than 800 nanometers, surface modification to have by carbon-coating.
4. bromo- half flow battery according to claim 3 with ion embedded type solid cathode, which is characterized in that institute
The carbon layer material for the modification stated is one or more of the agraphitic carbon of organic carbon formation, carbon nanotube, graphene.
5. bromo- half flow battery according to claim 1 with ion embedded type solid cathode, which is characterized in that institute
The conductive agent stated is mesoporous carbon, hard charcoal, graphite, graphene, single wall or multi-walled carbon nanotube, carbon fiber, acetylene black or charcoal unlicensed tour guide
The content of one or more of electric material, conductive agent is 1%--30%；
The binder is polytetrafluoroethylene (PTFE), Kynoar, polyolefin, polyvinyl alcohol, one kind in butadiene-styrene rubber or several
Kind, the content of binder is 1% -30%；
The collector is the solid network for having high electronic conductance, selected from carbon felt, graphite felt, electrically conductive graphite plate, electrically conductive graphite
One kind in net, carbon cloth, titanium net, nickel screen, copper mesh, aluminium net, stainless (steel) wire or in which several compounds.
6. bromo- half flow battery according to claim 1 with ion embedded type solid cathode, which is characterized in that institute
The negative one valence bromide ion anode stated includes the aqueous solution of negative one valence bromide ion and trace amounts of bromine simple substance, and negative one valence bromide ion concentration is
0.1mol/L--10 mol/L。
7. bromo- half flow battery according to claim 1 with ion embedded type solid cathode, which is characterized in that institute
The positive liquid and negative electrode solution stated are aqueous solution, and contain one or both of sodium ion and lithium ion, and lithium sodium ion is always dense
Degree is 0.1-10 mol/L.
8. bromo- half flow battery according to claim 7 with ion embedded type solid cathode, which is characterized in that institute
The positive liquid and negative electrode solution stated further include potassium ion in addition to containing one or both of sodium ion and lithium ion, magnesium ion,
One or more of zinc ion, ammonium ion, a concentration of 0.1-2.0 mol/L.
9. bromo- half flow battery according to claim 8 with ion embedded type solid cathode, which is characterized in that institute
The positive liquid and negative electrode solution stated, the anion also contained, the anion be sulfate radical, nitrate anion, phosphate radical, one hydrogen radical of phosphoric acid,
One or more of dihydrogen phosphate, chlorion and hydroxyl, corresponding ion concentration are 0.1mol/L--10mol/L.
10. bromo- half flow battery according to claim 1 with ion embedded type solid cathode, which is characterized in that institute
The amberplex stated is selected from：The cation-exchange membrane of Nafion membrane, all kinds of derivatives or reinforcement has microporous mesoporous selectivity
Through film, semi-permeable membrane, reverse osmosis membrane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111137870A (en) * | 2018-11-06 | 2020-05-12 | 宁波氟创新能源科技有限公司 | Lithium difluorophosphate, preparation method thereof and lithium ion battery electrolyte |
| CN111326778A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院大连化学物理研究所 | Neutral lithium-bromine flow battery |
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