CN106449160A - High-energy water-system lithium-ion fluid capacitor structure - Google Patents

High-energy water-system lithium-ion fluid capacitor structure Download PDF

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Publication number
CN106449160A
CN106449160A CN201610970901.2A CN201610970901A CN106449160A CN 106449160 A CN106449160 A CN 106449160A CN 201610970901 A CN201610970901 A CN 201610970901A CN 106449160 A CN106449160 A CN 106449160A
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China
Prior art keywords
holding vessel
sizing agent
cathode size
anode sizing
lithium ion
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CN201610970901.2A
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Chinese (zh)
Inventor
刘昊
郝会颖
邢杰
董敬敬
张自力
郑志远
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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Priority to CN201610970901.2A priority Critical patent/CN106449160A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention provides a high-energy water-system lithium-ion fluid capacitor structure which comprises an undischarged positive electrode storage tank, a discharged positive electrode storage tank, a reaction chamber, an undischarged negative electrode storage tank, a discharged negative electrode storage tank and a slurry conveying device. Positive electrode slurry is stored in the undischarged positive electrode storage tank and the discharged positive electrode storage tank, negative electrode slurry is stored in the undischarged negative electrode storage tank and the discharged negative electrode storage tank, and negative electrode slurry and the positive electrode slurry are made of by different raw materials. According to the capacitor structure, lithium-ion battery materials serve as raw materials of the slurry, so that specific capacity of water-system fluid capacitors is remarkably improved. By the aid of asymmetrical fluid electrode configuration, namely, different positive electrode slurry and negative electrode slurry, working voltage of a device can reach 1.8V, so that the specific capacity of the water-system fluid capacitors is greatly higher than that of existing water-system fluid capacitors.

Description

A kind of aquo-lithium ion type fluid capacitor structure of high-energy
Technical field
The present invention relates to electrochemical cell art field, especially relates to a kind of aquo-lithium ion type fluid electricity of high-energy Structure of container.
Background technology
In recent years, with the increasing rapidly of installed capacity of the clean energy resourcies such as solar energy, wind energy, it is adaptable to extensive energy storage The research and development of technology and device become to become more and more important.Electrochemical cell does not have spy because of its higher energy density and to geographical conditions Very require and receive significant attention.Wherein, flow battery is the important representative of such battery.Worldwide, had many Individual country builds up the flow battery electricity storage station that energy storage reaches several megawatts to tens megawatts, and progressively steps into commercialization (Soloveichik 2015).
As shown in figure 1, traditional flow battery adopts the liquid (such as full vitriol electrolyte) with oxidation/reduction ability to make For ergastic substances, these liquid are stored in external bulk storage tank respectively.In battery operation, anode and negative electrode holding vessel Middle liquid is pumped into the reaction that operating room is aoxidized or reduced respectively, realizes filling or discharge process for battery, so as to reach The purpose of energy storage.Flow battery structure very simple.
Importantly, size of the total capacity of this kind of battery depending on external storage tank volume, and power is then depended on The indoor size of working electrode of work and the characteristic of electrolyte active substance.As its accumulation chamber and operating room are to separate , allow for the total capacity of flow battery and power can have great motility and adaptability in the application with independent regulation.
But, charging more slow (a few hours) and the service life limited (typically smaller than 20,000 of traditional flow battery Circulation) limit it need in peak load regulation network etc. quick response occasion application (Presser, Dennison et al.2012).
On the other hand, ultracapacitor has extremely fast charging and discharging capabilities and extra long life, is particularly well-suited to needs The occasion of fast charging and discharging.Therefore, researcher proposes to combine ultracapacitor with traditional flow battery, will be super The materials such as the such as activated carbon of capacitor and electrolyte mixing are made into flowable slurry, and the simple configuration with reference to flow battery Obtain new semisolid fluid capacitor (Hatzell, Boota et al.2015).First generation fluid capacitor adopts mesoporous carbon Ball and safety, inexpensive aqueous electrolyte make slurry, show very high power density with this fluid capacitor for obtaining, But energy density is limited to relatively low ratio electric capacity (～90F/g) of mesoporous carbon spheres and the running voltage that aqueous electrolyte is relatively low (～0.6V) (Presser, Dennison et al.2012).
Hereafter, researchers continuously attempt to increase water system fluid capacitor energy density using new method.For example, exist Add oxidation/reduction material (as the organic molecule of solubility) (Boota, the Hatzell et of solubility in aqueous electrolyte Al.2015) increasing capacitance or lift running voltage (Huang, the Zhang of aqueous electrolyte using asymmetric electrode et al.2014).By these methods, the energy density of fluid capacitor improves about 1.5-3 times.For example, in power density For, under the conditions of～50-100W/kg, energy density is up to 11-14Wh/kg, but the energy density still can not meet application very well Needs.Therefore, how to design and prepare the fluid capacitor with higher energy density just becomes a major issue, and Its energy density depends primarily on the characteristic of the material therefor of anode and cathode slurry.
Content of the invention
It is an object of the invention to provide a kind of aquo-lithium ion type fluid capacitor structure of high-energy, existing to solve The low technical problem of fluid capacitor energy density present in technology.Compare with existing water system fluid capacitor, the present invention's Fluid capacitor slurry has higher energy density, maintains higher power density and cycle life.
For solving above-mentioned technical problem, a kind of aquo-lithium ion type fluid capacitor knot of high-energy that the present invention is provided Structure, positive pole holding vessel, reative cell after its positive pole holding vessel that includes not discharge, electric discharge, the negative pole holding vessel that do not discharge, negative pole after electric discharge Holding vessel and slurry conveying device,
Reative cell includes cathode chamber and anode chamber；
Through pipeline and the cathode chamber, positive pole holding vessel after the electric discharge is connected the positive pole holding vessel that do not discharge；
Through pipeline and the anode chamber, negative pole holding vessel after the electric discharge is connected the negative pole holding vessel that do not discharge；
After do not discharge positive pole holding vessel and the electric discharge, positive pole holding vessel internal memory contains anode sizing agent；
After do not discharge negative pole holding vessel and the electric discharge, negative pole holding vessel internal memory contains cathode size；
Slurry conveying device includes anode sizing agent conveyer device and cathode size conveyer device,
The positive pole that the anode sizing agent conveyer device is used for not discharging after positive pole holding vessel and electric discharge between positive pole holding vessel The conveying of slurry；
The negative pole that the cathode size conveyer device is used for not discharging after negative pole holding vessel and electric discharge between negative pole holding vessel The conveying of slurry；
In course of conveying, anode sizing agent and cathode size are synchronous respectively by cathode chamber and anode chamber；
The cathode size and anode sizing agent are made up of different material.
Further, the anode sizing agent is formulated by lithium ion battery material, conductive agent and Aqueous Lithium Salts；
The cathode size is formulated by porous carbon materials, conductive agent and Aqueous Lithium Salts.
The present invention is by employing lithium ion battery material as the raw material of slurry so that the specific capacity of fluid capacitor is obtained To being obviously improved；Particular, it is important that the present invention is by adopting asymmetrical fluid electrode configuration, i.e., different positive and negative electrodes are starched Material, makes the running voltage of device up to 1.8V so that the water system fluid capacitor specific energy is much higher than existing water system fluid Capacitor.
Further, the lithium ion battery material be spinel lithium manganate, cobalt acid lithium, LiFePO4 and ternary lithium electricity material One or several mixing in material.
Further, the ternary lithium electric material includes nickel-cobalt-manganese ternary lithium electric material or nickel cobalt aluminum ternary lithium electricity material Material.
Further, the conductive agent is Ketjen black, acetylene black, white carbon black, CNT, Graphene and reduction-oxidation graphite The mixing of one or more in alkene.
Further, the lithium salts be lithium sulfate, lithium nitrate, the compositionss of one or more in lithium chloride.
Further, the porous carbon materials are the mixing material of one or more in activated carbon, mesoporous carbon spheres or granule Material.
Further, the lithium ion battery material shared mass percent in the anode sizing agent is 1～80%.
Further, the porous carbon materials shared mass percent in the cathode size is 1～80%.
Further, the conductive agent shared mass percent in anode sizing agent or cathode size is 0.1～30%.
Further, the Aqueous Lithium Salts concentration is 0.2-3mol/L.
Further, the cathode chamber and anode chamber are symmetrical set, and are provided with barrier film between the two.
Further, the cathode chamber includes the outer layer protection plate for setting gradually from left to right, conductive current collector and carries recessed Slot insulation piece；
The anode chamber includes band groove insulation piece, conductive current collector and the outer layer protection plate for setting gradually from left to right.
Further, the barrier film is polypropylene diaphragm, cellulosic separator or ceramic diaphragm.
It is further preferable that the barrier film is 3500 barrier film of polypropylene celgard.
Further, the conductive current collector is by carbon-based material systems such as the metallic plates such as rustless steel, graphite cake, carbon nanotube papers Become.
Further, the band groove insulation thin slice is politef, polyethylene or rubber sheet.
Further, the thickness with groove insulation thin slice is 0.2-10mm.
Further, the slurry conveying device is propeller or peristaltic pump.
In addition, a kind of the invention also discloses energy-storage system for carrying out energy storage using above-mentioned fluid capacitor.Energy-storage system In the power-supply system that charges for the fluid capacitor and the load system for discharging during use can adopt prior art, here Just repeat no more.
Using technique scheme, the present invention has the advantages that：
1st, lithium ion battery material is employed as the raw material of slurry so that the specific capacity of anode sizing agent is significantly carried Rise；
2nd, asymmetrical fluid electrode configuration is employed, and the running voltage of device is made up to 1.8V；
3rd, existing water system stream is far above using the energy density of the type lithium ion fluid capacitor of this kind of positive and negative electrode slurry Bulk capacitor.For example, under the conditions of power density about 50W/kg, energy density reaches 23.4Wh/kg, is approximately the water that has reported It is the twice of fluid capacitor highest energy density.
Description of the drawings
In order to be illustrated more clearly that the specific embodiment of the invention or technical scheme of the prior art below will be to concrete Needed for embodiment or description of the prior art, accompanying drawing to be used is briefly described, it should be apparent that, in describing below Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation of flow battery of the prior art；
Fig. 2 is a kind of structure of the aquo-lithium ion type fluid capacitor structure of high-energy of the offer of the embodiment of the present invention 2 Schematic diagram；
Fig. 3 is the structural representation of reative cell in the fluid capacitor that the embodiment of the present invention 2 is provided；
Fig. 4 is reative cell decomposing schematic representation in the fluid capacitor that the embodiment of the present invention 2 is provided；
Fig. 5 is the scanning electron microscopic picture of L10K4 anode sizing agent in the embodiment of the present invention 3；
Fig. 6 is the scanning electron microscopic picture of A20K2 cathode size in the embodiment of the present invention 3；
Fig. 7 is for L10K4/A20K2 type lithium ion fluid capacitor in the embodiment of the present invention 3 under different current density condition Charging and discharging curve figure；
Fig. 8 is the ratio electric capacity of L10K4/A20K2 type lithium ion fluid capacitor and specific energy figure in the embodiment of the present invention 3；
Fig. 9 is for L10K2.5/A20K2 type lithium ion fluid capacitor in the embodiment of the present invention 4 in different current density condition Under ratio electric capacity and specific energy figure.
Reference：
10- does not discharge positive pole holding vessel；Positive pole holding vessel after 20- electric discharge；
30- does not discharge negative pole holding vessel；Negative pole holding vessel after 40- electric discharge；
50- anode sizing agent conveyer device；60- cathode size conveyer device；
70- reative cell；70a- cathode chamber；
70b- anode chamber；71- barrier film；
72- outer layer protection plate；73- conductive current collector；
74- carries groove insulation piece.
Specific embodiment
Below in conjunction with accompanying drawing, technical scheme is clearly and completely described, it is clear that described enforcement Example is a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill The every other embodiment obtained under the premise of creative work is not made by personnel, belongs to the scope of protection of the invention.
In describing the invention, it should be noted that term " " center ", " on ", D score, "left", "right", " vertical ", The orientation of instruction such as " level ", " interior ", " outward " or position relationship be based on orientation shown in the drawings or position relationship, merely to Be easy to describe the present invention and simplify description, rather than indicate or the hint device of indication or element must with specific orientation, With specific azimuth configuration and operation, therefore it is not considered as limiting the invention.Additionally, term " first ", " second ", " the 3rd " is only used for describing purpose, and it is not intended that indicating or hint relative importance.
In describing the invention, it should be noted that unless otherwise clearly defined and limited, term " installation ", " phase Even ", " connection " should be interpreted broadly, for example, it may be being fixedly connected, or being detachably connected, or be integrally connected；Can To be to be mechanically connected, or electrically connect；Can be joined directly together, it is also possible to be indirectly connected to by intermediary, Ke Yishi The connection of two element internals.For the ordinary skill in the art, above-mentioned term can be understood at this with concrete condition Concrete meaning in invention.
With reference to specific embodiment the present invention will be further explained explanation.
Embodiment 1
A kind of fluid capacitor anode and cathode slurry that the present embodiment is provided, which includes anode sizing agent and cathode size；
Anode sizing agent is formulated by lithium ion battery material, conductive agent and Aqueous Lithium Salts；
Cathode size is formulated by porous carbon materials, conductive agent and Aqueous Lithium Salts.
The present invention is by employing lithium ion battery material as the raw material of slurry so that the specific capacity of fluid capacitor is obtained To being obviously improved；Particular, it is important that the present invention is by adopting asymmetrical fluid electrode configuration, i.e., different positive and negative electrodes are starched Material, makes the running voltage of device up to 1.8V so that the water system fluid capacitor specific energy is much higher than existing water system fluid Capacitor.
Lithium ion battery material is spinel lithium manganate, cobalt acid lithium, the one kind in LiFePO4 and ternary lithium electric material or Several mixing of person.
Ternary lithium electric material includes nickel-cobalt-manganese ternary lithium electric material or nickel cobalt aluminum ternary lithium electric material.
Conductive agent is Ketjen black, acetylene black, white carbon black, CNT, the one kind in Graphene and redox graphene or Several mixing.
Lithium salts is lithium sulfate, lithium nitrate, the compositionss of one or more in lithium chloride.
Porous carbon materials are the mixing material of one or more in activated carbon, mesoporous carbon spheres or granule.
Lithium ion battery material shared mass percent in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80% in anode sizing agent is 1～80%.
Porous carbon materials shared mass percent in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80% in cathode size is 1～80%.
Conductive agent shared mass percent in anode sizing agent or cathode size is 0.1～30%.
Aqueous Lithium Salts concentration is 0.2-3mol/L.
Lithium ion battery material be present invention employs as the raw material of slurry so that the specific capacity of fluid capacitor is shown Write lifting；In addition, by asymmetrical fluid electrode configuration is employed, the running voltage of device is made up to 1.8V, be conducive to ratio The lifting of energy.
Embodiment 2
As in Figure 2-4, the invention also discloses in a kind of employing embodiment 1 high-energy of anode and cathode slurry water system lithium Ion-type fluid capacitor structure, positive pole holding vessel 20 after its positive pole holding vessel 10 that includes not discharge, electric discharge, reative cell 70, not Negative pole holding vessel 40 and slurry conveying device after electric discharge negative pole holding vessel 30, electric discharge,
Reative cell 70 includes cathode chamber 70a and anode chamber 70b；
Not discharging, through pipeline and cathode chamber 70a, positive pole holding vessel 20 after electric discharge is connected positive pole holding vessel 10；
Not discharging, through pipeline and anode chamber 70b, negative pole holding vessel 40 after electric discharge is connected negative pole holding vessel 30；
20 internal memory of positive pole holding vessel after positive pole holding vessel 10 and electric discharge that do not discharge contains anode sizing agent；
40 internal memory of negative pole holding vessel after negative pole holding vessel 30 and electric discharge that do not discharge contains cathode size；
Slurry conveying device includes anode sizing agent conveyer device 50 and cathode size conveyer device 60, and slurry conveying device is excellent Selection of land is propeller or peristaltic pump.
Anode sizing agent conveyer device 50 be used for not discharging positive pole holding vessel 10 with discharge after between positive pole holding vessel 20 just The conveying of pole slurry；
Cathode size conveyer device 60 is for negative between negative pole holding vessel 40 after do not discharge negative pole holding vessel 30 and electric discharge The conveying of pole slurry；
In course of conveying, anode sizing agent and cathode size are synchronous respectively by cathode chamber 70a and anode chamber 70b；
Cathode size and anode sizing agent are made up of different material.
Cathode chamber 70a and anode chamber 70b are symmetrical set, and are provided with barrier film 71 between the two.
Cathode chamber 70a includes outer layer protection plate 72, conductive current collector 73 and the band groove insulation for setting gradually from left to right Piece 74；
Anode chamber 70b includes the band groove insulation piece 74, conductive current collector 73 for setting gradually from left to right and outer layer protection Plate 72.
Barrier film 71 is polypropylene diaphragm, more preferably, barrier film is polypropylene 3500 barrier film of celgard. to cellulosic separator or ceramic diaphragm.
Conductive current collector 73 is made up of carbon-based materials such as the metallic plates such as rustless steel, graphite cake, carbon nanotube papers.
Band groove insulation thin slice 74 is politef, polyethylene or rubber sheet.
Thickness with groove insulation thin slice 74 is 0.2-10mm.
The energy density of the type lithium ion fluid capacitor in the present embodiment is far above existing water system fluid capacitor.Example Such as, under the conditions of power density about 50W/kg, energy density reaches 23.4Wh/kg, is approximately the water system fluid electric capacity that has reported The twice of device highest energy density.
Embodiment 3
The present embodiment is substantially the same manner as Example 1, and difference is：
During anode sizing agent makes, 1.23g commercialization LiMn2O4 (LiMn is weighed respectively2O4) powder and 0.49g Ketjen black powder, The concentration of 10ml is added after grinding is uniform for the lithium sulfate aqueous solution of 1mol/L.Said mixture is first used magnetic stirrer 1 hour, place into ultrasonic instrument (power 800W) sonic oscillation 30 minutes.Above-mentioned mixed process is repeated twice, and finally makes each Material and solution uniformly mix, disperse.In slurry prepared by said method, LiMn2O410wt% is accounted for, Ketjen black accounts for 4wt%. The slurry is labeled as L10K4.
Wherein, Fig. 5 is the scanning electron microscopic picture of the slurry.
In cathode size making, 2.72g active carbon powder and 0.22g Ketjen black powder being weighed respectively, adds after grinding is uniform Enter the lithium sulfate aqueous solution of the concentration for 1mol/L of 10ml.Said mixture is first used magnetic stirrer 1 hour, is placed into Ultrasonic instrument (power 800W) sonic oscillation 30 minutes.Above-mentioned mixed process is repeated twice, and finally makes each material and solution Uniform mixing, dispersion.In slurry prepared by said method, activated carbon accounts for 20wt%, and Ketjen black accounts for 2wt%.The slurry is labeled as A10K2.Fig. 6 is the scanning electron microscopic picture of the slurry.
Cathode chamber and the anode chamber that above-mentioned positive pole, cathode size are injected simultaneously into two relative separation of reative cell is (positive and negative Pole room size：Long 4cm, wide 0.5cm, high 0.09cm, barrier film constitutes asymmetric microporous polypropylene membrane celgrad 3500) in being Type lithium ion fluid capacitor, i.e. L10K4/A20K2 lithium ion fluid capacitor.
Fig. 7 is the fluid capacitor in the charging/discharging voltage in 0-1.8V voltage range, under different current density condition Curve；Fig. 8 is corresponding than electric capacity and energy density for which.It is 2.5mA/cm in charging and discharging currents density2(corresponding to power density is Under the conditions of 50Wh/kg), the ratio electric capacity of the type lithium ion fluid capacitor be 52F/g, energy density be 23.4Wh/kg (with just, Active substance Mass Calculation in cathode size)；When electric current density increases to 15mA/cm2When (power density 490.9W/kg), should Device still keeps higher energy density, reaches 9.6Wh/kg.
Thus test obtains the positive technique effect that the present invention has protrusion compared with prior art.
Embodiment 4
The present embodiment is substantially the same manner as Example 1, and difference is：
During anode sizing agent makes, 1.21g commercialization LiMn is weighed respectively2O4Powder and 0.30g Ketjen black powder, grinding is uniform The concentration of 10ml is added afterwards for the lithium sulfate solution of 1mol/L.Said mixture is first used magnetic stirrer 1 hour, then is put Enter ultrasonic instrument (power 800W) sonic oscillation 30 minutes.Above-mentioned mixed process is repeated twice, and finally makes each material and molten Liquid uniformly mixes, disperses.In slurry prepared by said method, LiMn2O410wt% is accounted for, Ketjen black accounts for 2.5wt%.The slurry mark It is designated as L10K2.5.
In cathode size makes, 2.72g active carbon powder and 0.22g Ketjen black powder is weighed respectively, after grinding is uniform The concentration of 10ml is added for the lithium sulfate solution of 1mol/L.Said mixture is first used magnetic stirrer 1 hour, is placed into Ultrasonic instrument (power 800W) sonic oscillation 30 minutes.Above-mentioned mixed process is repeated twice, and finally makes each material and solution Uniform mixing, dispersion.In slurry prepared by said method, activated carbon accounts for 20wt%, and Ketjen black accounts for 2wt%.The slurry is labeled as A10K2.
In order to the beneficial effect using this kind of slurry is further demonstrated that, positive pole, cathode size are injected simultaneously into reative cell Positive and negative pole room (the tract size of two relative separation：Long 4cm, wide 0.5cm, high 0.09cm, barrier film is microporous polypropylene membrane Celgrad 3500) in, constitute asymmetric L10K2.5/A10K2 lithium ion fluid capacitor.
Fig. 9 is ratio electric capacity and the corresponding energy density of the present embodiment.It is 2.5mA/cm in charging and discharging currents density2(right Power density is answered for 47Wh/kg) under the conditions of, the ratio electric capacity of the type lithium ion fluid capacitor is 49.6F/g, and energy density is 21.9Wh/kg.
The present embodiment is also demonstrated that the present invention has prominent positive technique effect compared with prior art.
Embodiment 5
The present embodiment is substantially the same manner as Example 1, and difference is using CNT as conductive agent, specially：
Anode sizing agent makes：1.21g commercialization LiMn is weighed respectively2O4Powder and 0.30g carbon nanotube powder, grinding is uniform The concentration of 10ml is added afterwards for the lithium sulfate solution of 1mol/L.Said mixture is first used magnetic stirrer 1 hour, then is put Enter ultrasonic instrument (power 800W) sonic oscillation 30 minutes.Above-mentioned mixed process is repeated twice, and finally makes each material and molten Liquid uniformly mixes, disperses to obtain anode sizing agent.
Cathode size makes：Weigh 2.72g active carbon powder and 0.22g carbon nanotube powder respectively, add after grinding is uniform Enter the lithium sulfate solution of the concentration for 1mol/L of 10ml.Said mixture is first used magnetic stirrer 1 hour, is placed into super Acoustic wave apparatus (power 800W) sonic oscillation 30 minutes.Above-mentioned mixed process is repeated twice, and finally makes each material and solution equal Even mixing, dispersion obtain cathode size.
Above-mentioned positive pole, cathode size are injected simultaneously into (tract size in two detached tracts of reative cell：Long 4cm, wide 0.5cm, high 0.09cm, barrier film is microporous polypropylene membrane celgrad 3500) the asymmetric lithium ion fluid capacitor of composition.Borrow The excellent conductive ability of CNT is helped, the power density of the fluid capacitor is improved, and it is close to maintain higher energy Degree.
Embodiment 6
The present embodiment is substantially the same manner as Example 1, and difference essentially consists in the original using cobalt acid lithium as anode sizing agent Material, specially：
Anode sizing agent makes：1.21g commercialization cobalt acid lithium (LiCoO is weighed respectively2) powder and 0.30g carbon nanotube powder, The concentration of 10ml is added after grinding is uniform for the lithium sulfate solution of 1mol/L.Said mixture is first used magnetic stirrer 1 Hour, place into ultrasonic instrument (power 800W) sonic oscillation 30 minutes.Above-mentioned mixed process is repeated twice, and finally makes each material Material and solution uniformly mix, disperse to obtain anode sizing agent.
Cathode size makes：Weigh 2.72g active carbon powder and 0.22g carbon nanotube powder respectively, add after grinding is uniform Enter the lithium sulfate solution of the concentration for 1mol/L of 10ml.Said mixture is first used magnetic stirrer 1 hour, is placed into super Acoustic wave apparatus (power 800W) sonic oscillation 30 minutes.Above-mentioned mixed process is repeated twice, and finally makes each material and solution equal Even mixing, dispersion obtain cathode size.
Above-mentioned positive pole, cathode size are injected simultaneously into (tract size in two detached tracts of reative cell：Long 4cm, wide 0.5cm, high 0.09cm, barrier film is microporous polypropylene membrane celgrad 3500) the asymmetric lithium ion fluid capacitor of composition.Should Water system fluid capacitor is due to employing the LiCoO of stratiform2Material, also has higher energy while high power density is kept Metric density.
Finally it should be noted that：Various embodiments above only in order to technical scheme to be described, rather than a limitation；To the greatest extent Pipe has been described in detail to the present invention with reference to foregoing embodiments, it will be understood by those within the art that：Its according to So the technical scheme described in foregoing embodiments can be modified, or which part or all technical characteristic are entered Row equivalent；And these modifications or replacement, do not make the essence of appropriate technical solution depart from various embodiments of the present invention technology The scope of scheme.

Claims (10)

1. the aquo-lithium ion type fluid capacitor structure of a kind of high-energy, it is characterised in which includes positive pole storage of not discharging Tank, electric discharge after positive pole holding vessel, reative cell, the negative pole holding vessel that do not discharge, electric discharge after negative pole holding vessel and slurry conveying device,
Reative cell includes cathode chamber and anode chamber；
Through pipeline and the cathode chamber, positive pole holding vessel after the electric discharge is connected the positive pole holding vessel that do not discharge；
Through pipeline and the anode chamber, negative pole holding vessel after the electric discharge is connected the negative pole holding vessel that do not discharge；
After do not discharge positive pole holding vessel and the electric discharge, positive pole holding vessel internal memory contains anode sizing agent；
After do not discharge negative pole holding vessel and the electric discharge, negative pole holding vessel internal memory contains cathode size；
Slurry conveying device includes anode sizing agent conveyer device and cathode size conveyer device,
The anode sizing agent that the anode sizing agent conveyer device is used for not discharging after positive pole holding vessel and electric discharge between positive pole holding vessel Conveying；
The cathode size that the cathode size conveyer device is used for not discharging after negative pole holding vessel and electric discharge between negative pole holding vessel Conveying；
In course of conveying, anode sizing agent and cathode size are synchronous respectively by cathode chamber and anode chamber；
The cathode size and anode sizing agent are made up of different material.
2. the aquo-lithium ion type fluid capacitor structure of high-energy according to claim 1, it is characterised in that described just Pole slurry is formulated by lithium ion battery material, conductive agent and Aqueous Lithium Salts；
The cathode size is formulated by porous carbon materials, conductive agent and Aqueous Lithium Salts.
3. the aquo-lithium ion type fluid capacitor structure of high-energy according to claim 1, it is characterised in that described just Pole room and anode chamber are symmetrical set, and are provided with barrier film between the two.
4. the aquo-lithium ion type fluid capacitor structure of high-energy according to claim 3, it is characterised in that described just Pole room includes outer layer protection plate, conductive current collector and the band groove insulation piece for setting gradually from left to right；
The anode chamber includes band groove insulation piece, conductive current collector and the outer layer protection plate for setting gradually from left to right.
5. the aquo-lithium ion type fluid capacitor structure of high-energy according to claim 3, it is characterised in that described every Film is polypropylene diaphragm, cellulosic separator or ceramic diaphragm.
6. the aquo-lithium ion type fluid capacitor structure of high-energy according to claim 4, it is characterised in that described lead Electrojet body is made up of metallic plate, graphite cake or carbon nanotube paper carbon-based material.
7. the aquo-lithium ion type fluid capacitor structure of high-energy according to claim 4, it is characterised in that the band Groove insulation thin slice is politef, polyethylene or rubber sheet.
8. the aquo-lithium ion type fluid capacitor structure of high-energy according to claim 4, it is characterised in that the band The thickness of groove insulation thin slice is 0.2-10mm.
9. the aquo-lithium ion type fluid capacitor structure of high-energy according to claim 1, it is characterised in that the slurry Material conveying device is propeller or peristaltic pump.
10. a kind of aquo-lithium ion type fluid capacitor structure using high-energy described in any one of claim 1-9 is stored up The energy-storage system of energy.
CN201610970901.2A 2016-10-28 2016-10-28 High-energy water-system lithium-ion fluid capacitor structure Pending CN106449160A (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102315473A (en) * 2011-06-28 2012-01-11 北京好风光储能技术有限公司 Lithium ion flow redox battery
CN206236549U (en) * 2016-10-28 2017-06-09 中国地质大学（北京） A kind of aquo-lithium ion type fluid capacitor structure of high-energy

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Publication number Priority date Publication date Assignee Title
CN102315473A (en) * 2011-06-28 2012-01-11 北京好风光储能技术有限公司 Lithium ion flow redox battery
CN206236549U (en) * 2016-10-28 2017-06-09 中国地质大学（北京） A kind of aquo-lithium ion type fluid capacitor structure of high-energy

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Application publication date: 20170222